US 2011 01 05333A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0105333 A1 Israels et al. (43) Pub. Date: May 5, 2011

(54) SEED TREATMENT COMPOSITIONS AND (30) Foreign Application Priority Data METHODS Aug. 16, 2007 (EP) ...... O7114464.6 (76) Inventors: Rafel Israels, Koeln (DE); Andreas O O Landes, Roemerberg (DE); Dirk Publication Classification Voeste, Limburgerhof (DE); Doris (51) Int. Cl. Stephan, Limburgerhof (DE); AOIN 25/24 (2006.01) Christian Sowa, Neustadt (DE); A6IR 9/00 (2006.01) Bernd Bruchmann, Ereinsheim (52) U.S. Cl...... 504/360; 514/772; 514/772.7; (DE): Daniel Schoenfelder, 504/358: 424/484 Mannheim (DE); Joachim Clauss, s Darmstadt (DE) (57) ABSTRACT (21) Appl. No.: 12/673,538 The present invention relates to seed treatment compositions comprising active ingredient and hyperbranched polymer. (22) PCT Filed: Apr. 17, 2008 The hyperbranched polymer is used as seed coating agent, especially as a binder to promote adhesion of the active ingre (86). PCT No.: PCT/USO8/60673 dient(s) to the seeds. S371 (c)(1), The present invention also relates to methods of treating seed (2), (4) Date: Feb. 15, 2010 with Such a composition. US 2011/O 105333 A1 May 5, 2011

SEED TREATMENT COMPOSITIONS AND 0011. The invention therefore relates to seed treatment METHODS compositions comprising active ingredient and hyper branched polymer. Particular embodiments of the compos tions are defined in the claims and are disclosed herein. 0001. The present invention relates to seed treatment com 0012. The compositions of the present invention show positions and methods of treating seed. The present invention also relates to the use of hyperbranched polymers in seed good adhesion of active ingredient(s) to the seeds and seeds treatment compositions. treated with the compositions of the present invention show 0002 Seed treatment is the process of applying active good flowability. Germination of the treated seeds is not ingredients to seeds in order to Support the germination and/ affected. or the growth of a large variety of crops. Typical examples 0013 As used herein, a “composition' comprises at least include the application of pesticides such as fungicides, one active ingredient and at least one auxiliary agent. insecticides and plant growth regulators. 0014 AS used herein, ingredients comprise active ingre 0003 Being an alternative to traditional broadcast spray dients and auxiliary agents. ing of pesticides, seed treatment compositions must fulfil a 0015. In the present invention, an “active ingredient' is a number of special requirements which include their applica compound which directly exerts a biologically relevant bility to seeds in commercial equipment, the adhesion of the effect, preferably a pesticidal effect as described herein. active ingredients to the treated seeds, and good flowability of 0016. The term “auxiliary agent” refers to a compound or the treated seeds. Of course, the treated seeds must still be combination of compounds which do not exert a biologically capable of germination. relevant effect of their own, but support the effects of the 0004. In order to improve adhesion of the active ingredi active ingredient(s). When auxiliary agents are used, their ents to the seed, water-soluble or water-dispersable film choice will depend on the active ingredients and on the pro forming polymers may be added to a seed treatment compo cedures selected for seed treatment. sition. EP-A 1139 738 describes a number of such polymers. 0005. According to U.S. Pat. No. 6,121,193, treatment of 0017. Usually, the compositions thus comprise an active rice seeds is particularly challenging because rice seeds are ingredient component (A') and an auxiliary agent compo sprinkled with water for 24 to 48 hours before sowing. This nent (“B”). The active ingredient component (A') of the phase of sprinkling with water exhibits the disadvantage of composition comprises one or more than one active ingredi leaching out the agrochemical active material attached to the ent(s). The auxiliary agent component (“B”) comprises one or seed. To address this problem U.S. Pat. No. 6,121,193 pro more auxiliary agent(s). poses the use of hyperbranched polyethyleneimines to 0018. As used herein, the term “at least one' refers to 1, 2, improve the adhesion of active ingredients to the rice seeds. 3, or more members from a group and include mixtures of 2. 0006. In a seed coating, polymers may also have an effect 3, or more different members from the group. on the bioavailability of the active ingredient and thus provide 0019. Unless indicated otherwise, all amounts in % by a slow-release effect. This effect may be desirable if it results weight refer to the weight of the total composition (or formu in a prolonged efficacy of the active ingredient(s). Also, slow lation). release coatings may improve germination of seeds by reduc 0020. In general, the compositions comprise from 0.005% ing the release of phytotoxic active ingredients in the early by weight to 95% by weight, preferably from 0.1% by weight stages of plant development. Slow-release effects may be to 90% by weight, in particular from 5% by weight to 50% by modulated by combining film-forming polymers with inert weight, of the active ingredient component 'A', the balance carriers such as clay. These effects may be further fine-tuned being formed by component “B”. In this context, the active by applying a multi-layered coating (WO 2004/049778). ingredients are employed in a purity of 90% to 100%, pref 0007. A disadvantage of using polymers to adhere active erably 95% to 100% (according to NMR spectrum). ingredients to seeds is that the seeds often become sticky. 0021. According to the invention, the active ingredient is Sticky seeds will show a reduced flowability. This can be especially selected from plant protection active agents (pes problematic, e.g. during sowing. ticides). Such an agent has the purpose or effect of preventing 0008 Although the use of polymers in seed treatment infection of a plant by any pest or of repelling, deterring or compositions is well-known in the art, commonly used poly destroying the pest or of reducing in another way the damage mers tend to provide seed treatment compositions which are caused by it. Plant pests can belong to different groups of not entirely satisfactory. It is especially the combination of organisms; the higher animals, in particular insects and acar seed-specific and general requirements for seed treatment ids, include numerous important pests, as do nematodes and compositions that remains hard to achieve. Snails; vertebrates. Such as mammals and birds, are today of 0009. It was an object of the present invention to provide secondary importance in industrialized countries. Numerous seed treatment compositions which are effective in adhering groups of microbes, including fungi, bacteria, inclusive of active ingredient(s) to seeds, with the treated seeds still show mycoplasmas, viruses and viroids, comprise pests, and even ing good flowability and germination. weeds, which compete with useful plants for limited habitat 0010. It was now found that certain hyperbranched poly and other resources, can be classed as pests in the broad sense. mers can be advantageously used in seed treatment compo Pesticides comprise in particular aphicides, acaricides, des sitions. Such compositions are very effective in Sticking iccants, bactericides, chemosterilants, defoliants, antifeed active ingredients to seeds. Still the treated seeds show ants, fungicides, herbicides, herbicide Safeners, insect attrac acceptable flowability and germination properties. The tants, insecticides, insect repellents, molluscicides, hyperbranched polymers can be incorporated in standard nematicides, mating disrupters, plantactivators, plant growth seed treatment compositions or mixed with them shortly regulators, rodenticides, mammal repellents, synergists, bird before application. repellents and virucides. US 2011/O 105333 A1 May 5, 2011

0022. The following list of pesticides which can be used A.7. Macrocyclic lactone insecticides: abamectin, emamec according to the invention, is intended to illustrate the pos tin, milbemectin, lepimectin, spinosad, the compound of for sible active ingredients, but not to impose any limitation: mula (I) (CAS No. 187166-40-1) A. Insecticides and Acaricides 0023 A.1. Organo (thio)phosphates: acephate, azame thiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, (T) chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isox athion, malathion, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phos OMe phamidon, phorate, phoxim, pirimiphos-methyl, profenofos, H prothiofos, Sulprophos, tetrachlorvinphos, terbufos, triazo OEt R n Y phos, trichlorfon; R R A.2. Carbamates: alanycarb, aldicarb, bendiocarb, benfura O. S S carb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathio OMe, carb, methiocarb, methomyl, oxamyl, pirimicarb, propoXur, Me thiodicarb, triazamate; A.3. Pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalo thrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta cypermethrin, Zeta-cypermethrin, deltamethrin, esfenvaler ate, etofenproX, fempropathrin, fenvalerate, imiprothrin, A.8. METI I compounds: fenazaquin, pyridaben, tebufen lambda-cyhalothrin, gamma-cyhalothrin, permethrin, pral pyrad, tolfenpyrad, flufenerim; lethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvali A.9. METI II and III compounds: acequinocyl, fluacyprim. nate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, hydramethylnon, profluthrin, dimefluthrin; A.10. Uncoupler compounds: chlorfeinapyr; A.4. Growth regulators: a) chitin synthesis inhibitors: ben A.11. Oxidative phosphorylation inhibitor compounds: Zoylureas: chlorfluaZuron, diflubenzuron, flucycloXuron, cyhexatin, diafenthiuron, fenbutatin oxide, propargite; flufenoxuron, hexaflumuron, lufenuron, novaluron, tefluben A.12. Moulting disruptor compounds: cyromazine; Zuron, triflumuron; buprofezin, diofenolan, hexythiazox, A.13. Mixed Function Oxidase inhibitor compounds: pipero etoxazole, clofentazine; b) ecdysone antagonists: nyl butoxide: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; A. 14. Sodium channel blocker compounds: indoxacarb, c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid metaflumizone; biosynthesis inhibitors: Spirodiclofen, spiromesifen, Spirotet A.15. Various: benclothiaz, bifenazate, cartap, flonicamid, ramat, pyridalyl pymetrozine, Sulfur, thiocyclam, flubendiamide, A.5. Nicotinic receptor agonists/antagonists compounds: cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, the clothianidin, dinotefuran, imidacloprid, thiamethoxam, aminoquinazolinone compound of formula (I) nitenpyram, acetamiprid, thiacloprid; the thiazol compound of formula (I) (T) CF 21 (Tl) CF N

N—R'-2,2-dihalo-1-R"cyclo-propanecarboxamide-2-(2,6- dichloro-C.C.C.-tri-fluoro-p-tolyl)hydrazone or N R-2,2-di A.6. GABA antagonist compounds: acetoprole, endosulfan, (R")propionamide-2-(2,6-dichloro-O.O.C.-trifluoro-p-tolyl)- ethiprole, fipronil, Vaniliprole, pyrafluprole, pyriprole, the hydrazone, wherein R' is methyl or ethyl, halo is chloro or phenylpyrazole compound of formula () bromo, R" is hydrogen or methyl and R" is methyl or ethyl, anthranilamide compounds of formula (I) (T2) O S (T5) CF1 NH2, B2, ( \, Al y (1 HN N1 Bl N N-N H C C x^ Yi R-N S

Y it US 2011/O 105333 A1 May 5, 2011 wherein A' is CH, Cl, Br, I, X is C. H. C. C1, C-F or N, chloro-3'-fluorobiphenyl-2-yl)-4-difluoromethyl-2- Y is F, Cl, or Br. Y" is H, F, C1, CF, B' is hydrogen, Cl, Br, methylthiazole-5-carboxamide, N-(3',4'-dichloro-4- I, CN, B' is C1, Br, CF, OCHCF. OCF.H, and R is hydro fluorobiphenyl-2-yl)-3-difluoromethyl-1- gen, CH or CH(CH), and malononitrile compounds as methylpyrazole-4-carboxamide, N-(2-cyanophenyl)-3, described in JP 2002 284608, WO 02/89579, WO 02/90320, 4-dichloroisothiazole-5-carboxamide: WO 02/90321, WO 04/06677, WO 04/20399, JP 2004.99597, 0028 carboxylic acid morpholides: dimethomorph, WO 05/68423, WO 05/68432, or WO 05/63694, especially flumorph; the malononitrile compounds CF (CH),C(CN)-CH(CF) 0029 benzamides: flumetover, fluopicolide (picoben CFH, CF (CH),C(CN),CH (CF)CFH, CF (CH),C Zamid), Zoxamide; (CN)(CH2)C(CF)F, CF (CH2)C(CN)2(CH2)(CF) 0030 other carboxamides: carpropamid, diclocymet, CF, CFH(CF),CHC(CN),CH (CF)CFH, CF (CH) mandipropamid, N-(2-(4-3-(4-chlorophenyl)prop-2- C(CN)2CH (CF)CF, CF (CF). CHC(CN)CH (CF) ynyloxy-3-methoxyphenyl)ethyl)-2-methanesulfony CFH, and CFCFCHC(CN),CH (CF)CF.H. lamino-3-methylbutyramide, N-(2-(4-3-(4-chlorophe 0024. The commercially available compounds of the nyl)prop-2-ynyloxy-3-methoxyphenyl)ethyl)-2- group A may be found in The Pesticide Manual, 13" Edition, ethanesulfonylamino-3-methylbutyramide: British Crop Protection Council (2003) among other publi B.3. Azoles such as cations. Thioamides of formula (I) and their preparation 0.031 triazoles: bitertanol, bromuconazole, cyprocona have been described in WO 98/28279. Lepimectin is known Zole, difenoconazole, diniconazole, enilconazole, from Agro Project, PJB Publications Ltd, November 2004. epoxiconazole, fenbuconazole, flusilaZole, fluguin Benclothiaz and its preparation have been described in EP-A1 conazole, flutriafol, hexaconazole, imibenconazole, 454621. Methidathion and Paraoxon and their preparation ipconazole, metconazole, myclobutanil, penconazole, have been described in Farm Chemicals Handbook, Volume propiconazole, prothioconazole, Simeconazole, tebu 88, Meister Publishing Company, 2001. Acetoprole and its conazole, tetraconazole, triadimenol, triadimefon, triti preparation have been described in WO 98/28277. Metaflu conazole; mizone and its preparation have been described in EP-A1 462 0032) imidazoles: cyazofamid, imazalil, pefurazoate, 456. Flupyrazofos has been described in Pesticide Science prochloraz, triflumizole; 54, 1988, p. 237-243 and in U.S. Pat. No. 4,822,779. Pyraf 0033 benzimidazoles: benomyl. carbendazim, luprole and its preparation have been described in JP fuberidazole, thiabendazole; 2002 193709 and in WO 01/00614. Pyriprole and its prepara 0034 others: ethaboxam, etridiazole, hymexazole; tion have been described in WO98/.45274 and in U.S. Pat. No. B.4. Nitrogenous heterocyclyl compounds Such as 6,335,357. Amidoflumet and its preparation have been 0035 pyridines: fluazinam, pyrifenox, 3-5-(4-chlo described in U.S. Pat. No. 6,221,890 and in JP 21.010907. rophenyl)-2,3-dimethylisoxazolidin-3-yl-pyridine: Flufenerim and its preparation have been described in WO 0.036 pyrimidines: bupirimate, cyprodinil, ferimZone, 03/007717 and in WO 03/007718. Cyflumetofen and its fenarimol, mepanipyrim, nuarimol, pyrimethanil; preparation have been described in WO 04/080180. 0037 piperazines: triforine; I0025) Anthranilamides of formula (I) and their prepara 0.038 pyrroles: fludioxonil, fenpiclonil; tion have been described in WO 01/70671: WO 02/48137; 0.039 morpholines: aldimorph, dodemorph, fenpropi WO 03/24222, WO 03/15518, WO 04/67528: WO 04/33468; morph, tridemorph; and WO 05/118552. The malononitrile compounds CF, 0040 dicarboximides: iprodione, procymidone, Vinclo Zolin; 0041 others: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomeZine, fenoxanil, folpet, fen CH(CF)CFH, CF (CH),C(CN)-CH(CF)CF, CF propidin, famoxadone, fenamidone, octhillinone, (CF). CHC(CN),CH (CF)CFH, and CFCFCHC probenazole, produinazid, pyroquilon, quinoxyfen, tri (CN),CH (CF)CFH have been described in WO cyclazole, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4, O5/63694. 6-trifluorophenyl)-1,2,4-triazolo 1.5-alpyrimidine, 2-butoxy-6-iodo-3-propyl-chromen-4-one, N,N-dim B. Fungicides: ethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfo 0026. B.1. Strobilurins such as azoxystrobin, dimox nyl)-1.2.4 triazole-1-sulfonamide; yStrobin, enestroburin, fluoxastrobin, kresoxim-methyl, B.5. Carbamates and dithiocarbamates such as metominostrobin, picoxystrobin, pyraclostrobin, triflox 0042 dithiocarbamates: ferbam, mancozeb, maneb, ystrobin, orysastrobin, methyl (2-chloro-5-1-(3-methylben metiram, metam, propineb, thiram, Zineb, Ziram; Zyloxyimino)ethylbenzyl)carbamate, methyl (2-chloro-5- 0043 carbamates: diethofencarb, flubenthiavalicarb, 1-(6-methylpyridin-2-ylmethoxyimino)ethylbenzyl) iprovalicarb, propamocarb, methyl 3-(4-chlorophenyl)- carbamate, methyl 2-(ortho-((2.5- 3-(2-isopropoxycarbonylamino-3-methylbutyry dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate; lamino)propionate, 4-fluorophenyl N-(1-(1-(4-cy B.2. Carboxamides such as anophenyl)ethanesulfonyl)but-2-yl)carbamate; 0027 carboxanilides: benalaxyl, benodanil, boscalid, B.6. Other fungicides such as carboxin, mepronil, fenfuram, fenhexamid, flutolanil, 0044 guanidines: dodine, iminoctadine, guaZatine; furametpyr, metalaxyl, ofurace, oxadixyl, oxycarboxin, 0045 antibiotics: kasugamycin, polyoxins, Streptomy penthiopyrad, thifluzamide, tiadinil, N-(4-bromobiphe cin, validamycin A; nyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-car 0046 organometallic compounds: fentin salts: boxamide, N-(4-trifluoromethylbiphenyl-2-yl)-4-dif 0047 sulfur-containing heterocyclyl compounds: iso luoromethyl-2-methylthiazole-5-carboxamide, N-(4- prothiolane, dithianon; US 2011/O 105333 A1 May 5, 2011

0048 organophosphorus compounds: edifenphos, fos loxyfen, halosafen, lactofen, nitrofen, nitrofluorfen, oxyfluo etyl, fosetyl-aluminum, iprobenfos, pyrazophos, tolclo rfen, fluaZolate, pyraflufen, cinidon-ethyl, flumiclorac, flumi fos-methyl, phosphorous acid and its salts; oxazin, flumipropyn, fluthiacet, thidiazimin, oxadiazon, 0049 organochlorine compounds: thiophanate-methyl, oxadiargyl, azafenidin, carfentraZone, SulfentraZone, pentox chlorothalonil, dichlofluanid, tolylfluanid, flusulfamide, aZone, benzfendizone, butafenacil, pyraclonil, profluaZol. phthalide, hexachlorbenzene, pencycuron, quintoZene; flufenpyr, flupropacil, nipyraclofen and etnipromid; 0050 nitrophenyl derivatives: binapacryl, dinocap, C.5 Bleacher herbicides such as metflurazon, norflurazon, dinobuton; flufenican, diflufenican, picolinafen, beflubutamid, fluridone, 0051 inorganic active compounds: Bordeaux mixture, fluorochloridone, flurtamone, mesotrione, Sulcotrione, isox copper acetate, copper hydroxide, copper oxychloride, achlortole, isoxaflutole, benzofenap, pyrazolynate, pyra basic copper Sulfate, Sulfur, ZOxyfen, benzobicyclon, amitrole, clomaZone, aclonifen, 0.052 others: spiroxamine, cyflufenamid, cymoxaniil, 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl) metrafenone. pyrimidine, and also 3-heterocyclyl-substituted benzoyl derivatives of the formula II (see in WO 96/26202, WO C. Herbicides: 97/41116, WO 97/41117 and WO 97/41118) 0053 C. 1 Lipid biosynthesis inhibitors such as chlorazi fop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop, fenoxaprop-p, fenthiaprop, fluazifop, fluaZifop-Phaloxyfop, R13 O R8 haloxyfop-P, isoxapyrifop, metamifop, propaquizafop, R9 quizalofop, quizalofop-P trifop, alloxydim, butroxydim, clethodim, cloproxydim, cycloxydim, profoxydim, Sethoxy NN dim, tepraloxydim, tralkoxydim, butylate, cycloate, diallate, N OH R10 dimepiperate, EPTC, esprocarb, ethiolate, isopolinate, 2 methiobencarb, molinate, orbencarb, pebulate, prosulfocarb, R R11 sulfallate, thiobencarb, tiocarbazil, triallate, Vernolate, ben furesate, ethofumesate and bensulide; in which the variables R to R' areas defined below: C.2 ALS inhibitors such as amidosulfuron, azimsulfuron, R. R" are hydrogen, halogen, C1-Co-alkyl, C-C-ha benSulfuron, chlorimuron, chlorSulfuron, cinosulfuron, loalkyl, C-C-alkoxy, C-C-haloalkoxy, C-C-alkylthio. cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flazasul C-C-alkylsulfinyl or C-C-alkylsulfonyl: furon, flupyrsulfuron, foramsulfuron, halosulfuron, imaZo R is a heterocyclic radical selected from the group consisting Sulfuron, iodosulfuron, mesosulfuron, metSulfuron, nicosul of such as thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3- furon, oxasulfuron, primisulfuron, prosulfuron, yl, isoxazol-4-yl, isoxazol-5-yl 4.5-dihydroisoxazol-3-yl, pyrazosulfuron, rimsulfuron, Sulfometuron, Sulfosulfuron, 4,5-dihydroisoxazol-4-yl and 4,5-dihydroisoxazol-5-yl, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, tri where the nine radicals mentioned may be unsubstituted or fluSulfuron, tritosulfuron, imazamethabenZ, imaZamox, mono- or poly Substituted, e.g. mono-, di-, tri- or tetrasubsti imaZapic, imazapyr, imaZaquin, imaZethapyr, cloranSulam, tuted, by halogen, C-C-alkyl, C-C-alkoxy, C-C-ha dicloSulam, florasulam, flumetSulam, metoSulam, penoXSu loalkyl, C-Ca-haloalkoxy or C-C-alkylthio; lam, bispyribac, pyriminobac, propoxycarbazone, flucarba R'' is hydrogen, halogen or C-C-alkyl; Zone, pyribenzoxim, pyriftalid and pyrithiobac; R" is C1-Co-alkyl: C.3 Photosynthesis inhibitors such as atraton, atrazine, ametryne, aziprotryne, cyanazine, cyanatryn, chlorazine, R" is hydrogen or C-C-alkyl. cyprazine, desmetryne, dimethametryne, dipropetryn, egli C.7 EPSP synthase inhibitors such as glyphosate: nazine, ipazine, mesoprazine, methometon, methoprotryne, C.8 glutamine synthase inhibitors such as glufosinate and procyazine, proglinazine, prometon, prometryne, propazine, bilanaphos; Sebuthylazine, secbumeton, Simazine, simeton, simetryne, C.9 DHP synthase inhibitors such as asulam: terbumeton, terbuthylazine, terbutryne, trietazine, ametridi C. 10 Mitose inhibitors such as benfluralin, butralin, dinitra one, amibuzin, hexaZinone, isomethiozin, metamitron, mine, ethalfluralin, fluchioralin, isopropalin, methaipropalin, metribuzin, bromacil, isocil, lenacil, terbacil, brompyrazon, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, tri chloridazon, dimidazon, desmedipham, phenisopham, phen fluralin, amiprofoS-methyl, butamifos, dithiopyr, thiazopyr, medipham, phenmedipham-ethyl, benzthiaZuron, buthiuron, propyZamide, tebutam, chlorthal, carbetamide, chlorbufam, ethidimuron, isouron, methabenzthiaZuron, monoisouron, chlorpropham and propham; tebuthiuron, thiazafluoron, anisuron, buturon, chlorbromu C.11 VLCFA inhibitors such as acetochlor, alachlor, ron, chloreturon, chlorotoluron, chloroXuron, difenoXuron, butachlor, butenachlor, delachior, diethatyl, dimethachlor, dimefuron, diuron, fenuron, fluometuron, fluothiuron, iso dimethenamid, dimethenamid-P, metaZachlor, metolachlor, proturon, linuron, methiuron, metobenzuron, metobromuron, S-metolachlor, pretilachlor, propachlor, propisochlor, metoxuron, monolinuron, monuron, neburon, parafluoron, prynachlor, terbuchlor, thenylchlor, xylachlor, allidochlor, phenobenzuron, siduron, tetrafluoron, thidiaZuron, cyper CDEA, epronaz, diphenamid, napropamide, naproanilide, quat, diethamquat, difenZoquat, diguat, morfamquat, pethoxamid, flufenacet, mefenacet, fentraZamide, anilofos, paraquat, bromobonil, bromoxynil, chloroxynil, iodobonil. piperophos, cafenstrole, indanofan and tridiphane; ioxynil, amicarbazone, bromofenoxim, flumezin, methazole, C.12 Cellulose biosynthesis inhibitors such as dichiobenil, bentaZone, propanil, pentanochlor, pyridate, and pyridafol; chlorthiamid, isoxaben and flupoxam, C.4 Protoporphyrinogen-IX oxidase inhibitors such as acif C.13 Decoupler herbicides such as dinofenate, dinoprop, luorfen, bifenox, chlomethoxyfen, chlornitrofen, ethoxyfen, dinosam, dinoseb, dinoterb, DNOC, etinofen and medinot fluorodifen, fluoroglycofen, fluoronitrofen, fomesafen, fury erb: US 2011/O 105333 A1 May 5, 2011

C.14 Auxin herbicides such as clomeprop, 2,4-D, 2,4,5-T. atom or a group of atoms. “Dendrimers’ (cascade polymers, MCPA, MCPA thioethyl, dichlorprop, dichlorprop-P, meco isotropically branched polymers, isobranched polymers, star prop, mecoprop-P, 2,4-DB, MCPB, chloramben, dicamba, burst polymers) are molecularly uniform macromolecules 2.3.6-TBA, tricamba, quinclorac, quinmerac, clopyralid, flu with a highly symmetrical structure. Dendrimers are derived oroxypyr, picloram, triclopyr and benazolin; structurally from the star polymers in which the individual C.15 Auxin transport inhibitors such as naptalam, diflufen chains are each for their part branched in a star-like way. They Zopyr; arise starting from Small molecules through a continually C.16 Benzoylprop, flamprop, flamprop-M, bromobutide, repeating reaction sequence, resulting in ever higher branch chlorflurenoli, cinmethylin, methyldymron, etobenzanid, ings, at the ends of which are each time found functional fosamine, metam, pyributicarb, oxaziclomefone, dazomet, groups which are in turn starting points for further branch triaziflam and methyl bromide. ings. Thus, the number of the monomer end groups grows D. Safeners: exponentially with each reaction step, resulting at the end in a spherical tree structure. A characteristic feature of the den 0054 Benoxacor, clog uintocet, cyometrinil, dichlormid, drimers is the number of the reaction stages (generations) dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, carried out to construct them. Due to their uniform structure, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, dendrimers as a rule exhibit a defined molar mass. Molecu naphthalic anhydride, 2.2.5-trimethyl-3-(dichloroacetyl)-1, larly and structurally nonuniform hyperbranched polymers 3-oxazolidine (R-29148), 4-(dichloroacetyl)-1-oxa-4-aza spiro[4.5 decane (AD-67: MON 4660) and oxabetrinil are dendrimer-like, but they exhibit side chains of varying Preferred insecticides are selected from: length and branching, as well as a molar mass distribution. 0055 acetamiprid, alpha-cypermethrin, beta-cyper 0059 Molecularly and structurally nonuniform hyper methrin, bifenthrin, carbofuran, carbosulfan, clothianidin, branched polymers are preferably used according to the cycloprothrin, cyfluthrin, cypermethrin, deltamethrin, present invention. These are as a rule simple and conse diflubenzuron, dinotefuran, etofemprox, fenbutatin-oxide, quently more economical to prepare than dendrimers. How fenpropathrin, fipronil, flucythrinate, imidacloprid, lambda ever, of course, structurally and molecularly uniform den cyhalothrin, nitenpyram, pheromones, spinosad, teflubenZu drimeric polymers and star polymers can also be used. ron, tefluthrin, terbufos, thiacloprid, thiamethoxam, thiodi 0060 A hyperbranched polymer according to the present carb, tralomethrin, triazamate, Zeta-cypermethrin, invention is any polymer that (i) has a weight average molecu spirotetramat, flupyrazofos, NC 512, tolfenpyrad, flubendia lar weight (M) of more than 500 g/mol and (ii) a degree of mide, bistrifluoron, benclothiaz, DPX-E2Y45, HGW86, branching (DB) of more than 5%. pyrafluprole, pyriprole, F-7663, F-2704, amidoflumet, 0061 Preferably, the hyperbranched polymers used flufenerim, cyflumetofen. Particular preference is given to according to the invention exhibit a weight-average molecu clothianidin, fipronil, imidacloprid and thiamethoxam. lar weight (M) of more than 1000 g/mol, preferably of more Preferred fungicides are selected from: than 1500 g/mol. Particular preference is given to polymers 0056 metalaxyl, oxadixyl, guazatline, pyrimethanil, strep which exhibit a weight-average molecular weight in the range tomycin, difenoconazole, epoxiconazole, fluquiconazole, of approximately 500 to 200000 g/mol, preferably 750 to 150 flutriafol, hymexazole, imazalil, metconazole, prochloraZ. 000 g/mol, in particular 1000 to 100 000 g/mol. prothioconazole, tebuconazole, thiabendazole, triadimenol, 0062. The number-average molecular weight (M) of the triticonazole, iprodion, maneb, mancoZeb, metiram, thiram, hyperbranched polymers used according to the invention is benomyl, boscalid, carbendazim, carboxin, dazomet, silthio generally higher than 400 g/mol, preferably higher than 500 fam, copper fungicides, fludioxonil, Sulfur, dazomet, aZOX g/mol. Particular preference is given to polymers which yStrobin, kresoxim-methyl, orysastrobin, pyraclostrobin, tri exhibit a number-average molecular weight in the range of floxystrobin, captain dimethomorph. Particular preference is approximately 400 to 100 000 g/mol, preferably 500 to 80 given to pyraclostrobin, triticonazole and fluguinconazole. 000 g/mol, in particular 1000 to 50 000 g/mol. 0057. In a particular embodiment of the invention, the composition may comprise one or more repellents for warm 0063. The polydispersity of the hyperbranched polymers blooded animals, e.g. birds, dogs and hedgehogs, for example used according to the invention is in general from 1.2 to 50, nonanoic acid vanillyl amide. The amount of repellent will preferably from 1.4 to 40, particularly preferably from 1.5 to preferably range from 0.1 to 5% by weight, based on the total 30 and very particularly preferably from 2 to 30. weight of the composition. 0064. The data on the polydispersity and on the number 0058. In the context of the present invention, the term average and weight average molecular weight M, and M. “hyperbranched polymer refers very generally to polymers relate here to gel permeation chromatography measurements, which are distinguished by a branched structure and a high polymethyl methacrylate having been used as a standard and functionality. Reference may also be made, for the general tetrahydrofuran, dimethylformamide, dimethylacetamide or definition of hyperbranched polymers, to P. J. Flory, J. Am. hexafluoroisopropanol as an eluent. The method is described Chem. Soc., 1952, 74,2718, and H. Frey et al., Chem. Eur. J., in Analytiker Taschenbuch Vol. 4, pages 433 to 442, Berlin 2000, 6, No. 14, 2499, which are incorporated herein by 1984. reference in their entirety. The “hyperbranched polymers' 0065. The degree of branching (DB) reflects the average within the meaning of the invention include star polymers, number of dendritic linkages and terminal units per molecule. dendrimers, both molecularly and structurally nonuniform Preferably, the hyperbranched polymers used according to hyperbranched polymers, and high molecular weight poly the invention exhibit a degree of branching (DB) of at least 10, mers different therefrom, Such as, e.g., comb polymers. "Star 20, 30 or even 35%. Preference is given to polymers which polymers' are polymers in which three or more chains start at preferably exhibit a DB from 20 to 99%, preferably 30 to 95% one center. The center can in this connection be an individual and in particular 35 to 75%. Reference may be made, for the US 2011/O 105333 A1 May 5, 2011 definition of the “Degree of Branching, to H. Frey et al., Acta carbonate and/or OH groups; in the case of hyperbranched Polym., 1997, 48, 30, which is incorporated herein in its polyesters, OH and/or carboxyl groups; in the case of hyper entirety. branched polyether, OH groups, and the like). Moreover, the 0066. According to one aspect, the hyperbranched poly hyperbranched polymers may comprise further functional mers usually have a glass transition temperature of -80°C. or groups in addition to the functional groups already obtained higher, -70° C. or higher, or -60° C. or higher. According to by the polymerization reaction. another aspect, the glass transition temperature of the hyper 0075. In principle, there is no upper limit to the number of branched polymers usually is at most 150°C., at most 100° C. functional terminal or side groups, but products having a very or at most 50° C. The glass transition temperature is deter large number of functional groups may have undesired prop mined according to the ASTM-method D3418-03 using DSC. erties, such as, for example, high viscosity or poor solubility. 0067. The acid number of the hyperbranched polymers The hyperbranched polymers of the present invention gener according to the present invention is usually from 0 to 500, ally have not more than 500 functional terminal or side preferably from 0 to 400, more preferably from 0 to 300 and groups, preferably not more than 100, in particular not more in particular from 0 to 200 mg KOH/g, as determined accord than 30, functional terminal or side groups. The amount of ing to DIN 53240, part 2. functional terminal or side groups is preferably 4 to 100, 0068. The hydroxyl number of the hyperbranched poly especially 5 to 30 and more especially 6 to 20 per molecule. mers according to the present invention is usually from 0 to 0076. The term “functionality” represents, here and sub 1000, preferably from 0 to 750 and in particular from 0 to 500 sequently, the average number of the respective functional mg KOH/g, as determined according to DIN 53240, part 2. terminal or side groups per molecule or per polymer chain. 0069. The hyperbranched polymers according to the (0077. The hyperbranched polymers are preferably present invention are typically soluble or dispersible in water, selected from hyperbranched polycarbonates, hyperbranched i.e. it is possible to prepare clear Solutions (without gel par polyesters, hyperbranched polyethers and mixed forms ticles being detectable with the naked eye) or dispersions thereof Such as hyperbranched polyestercarbonates, hyper comprising at least 1% by weight, preferably at least 5% by branched polyethercarbonates, hyperbranched polyetherest weight and in particular at least 10% by weight, of hyper ers and hyperbranched polyetherestercarbonates. Especially branched polymer in water at about 23° C. and about 1 atm. preferred hyperbranched polymers are selected from hyper 0070 According to a particularembodiment of the present branched polycarbonates, hyperbranched polyesters, hyper invention, the viscosity of a 10% by weight solution of hyper branched polyethercarbonates, hyperbranched polyetherest branched polymer in water at about 23°C. is lower than 1000 ers, hyperbranched polyestercarbonates and hyperbranched mPas, preferably lower than 750 mPas and especially lower polyetherestercarbonates, with hyperbranched polycarbon than 500 mPas, as determined on a TA Instruments CSL 500 ates, hyperbranched polyesters, hyperbranched polyethercar Carri Med Rheometer with a cone-plate system at a shear rate bonates and hyperbranched polyestercarbonates being par of 100 1/s. ticularly preferred. Further, hyperbranched polymers 0071. The hyperbranched polymers according to the selected from hyperbranched polyurethanes, hyperbranched present invention are preferably amphiphilic polymers. polyureas, hyperbranched polyamides, hyperbranched Amphilic hyperbranched polymers usually have an HLB polyamines and mixed forms thereof Such as hyperbranched value from 1 to 20, preferably 3 to 20 and in particular 4 to 20. polyureaurethanes, hyperbranched polyesteramides, hyper 0072 The HLB value is a measure for the hydrophilic and branched polyesteramines and especially hyperbranched lipophilic portion of a compound. The determination of the polyetheramines, may be suitable according to the present HLB value is described, for instance, in W. C. Griffin, Journal invention, with an emphasis on hyperbranched polyure of the Society of Cosmetic Chemists, 1949, 1,311 and W. C. thanes, hyperbranched polyureas, hyperbranched polyureau Griffin, Journal of the Society of Cosmetic Chemists, 1954, 5, rethanes, hyperbranched polyesteramides, and optionally 249, which are incorporated herein by reference in their hyperbranched polyetheramines. In a further aspect, the entirety. To this end, 1 g of sample material is dissolved in a hyperbranched polymer according to the present invention is mixture of 4% benzene and 96% dioxane and water is added not a hyperbranched polyethyleneamine, polyamidoamide, until the occurrence of cloudiness. The value thus determined polyethyleneimine or polyether, or a copolymer thereof. is generally proportional to the HLB value. 0078. The hyperbranched polymers include in particular 0073. In the case of a hyperbranched polymer having eth those which are disclosed below and/or are obtainable by the ylene oxide groups (polyethylene glycol) the HLB value can methods disclosed below. be determined in accordance with a method described by C. 0079 So-called AB, preferably AB or AB, monomers D. Moore, M. Bell, SPC Soap, Perfum. Cosmet. 1956, 29.893 are particularly suitable for the synthesis of the hyper (which is incorporated herein by reference in its entirety) as branched polymers. These have two different functional follows: HLB-(number of ethylene oxide groups)* 100/ groups A and B in a molecule, which can undergo an inter (number of carbon atoms in the lipophilic portion of the molecular reaction with one another with formation of a link. molecule). The functional group A is comprised only once per molecule 0074. In the context of this invention, the hyperbranched and the functional group B twice or more. The reaction of said polymer is to be understood as meaning a product which, in AB monomers with one another results in the formation of addition to the functional groups which are part of the poly uncrosslinked polymers having regularly arranged branching mer skeleton (e.g. in the case of hyperbranched polycarbon points. The polymers have virtually exclusively B groups at ates, carbonate groups; in the case of hyperbranched polyes the chain ends. ters, ester groups; in the case of hyperbranched polyether, 0080 Furthermore, hyperbranched polymers can be pre ether groups, and the like), furthermore comprises at least pared via the A+B, Synthesis route. Here, A and B, are two four, preferably at least eight, functional terminal or side different monomers having the functional groups A and Band groups (e.g. in the case of hyperbranched polycarbonates, the indices X and y for the number of functional groups per US 2011/O 105333 A1 May 5, 2011 monomer. In the case of the A+B, Synthesis, presented here incorporated in the form of polymerized units while increas by way of example for an A+B synthesis, a difunctional ing the molecular weight. For this purpose, for example, monomer A is reacted with a trifunctional monomer B. A difunctional or higher-functional alcohols, difunctional or 1:1 adduct of A and Bhaving on average one functional group higher-functional amines, difunctional or higher-functional A and two functional groups B first forms and can then isocyanates, difunctional or higher-functional carboxylic likewise react to give a hyperbranched polymer. The hyper acids, difunctional or higher-functional epoxides, which branched polymers thus obtained also have predominantly B carry aromatic radicals or long-chain alkane, alkene oralkyne groups as terminal groups. radicals in addition to the reactive groups, can be used. 0081. The originally present functional groups (in particu I0089. Examples of such monomers are alcohols, such as lar A and B groups) can be transfunctionalized by polymer glyceryl monostearate, glyceryl monooleate, hexanediol. analogous reaction with Suitable compounds. In this way, octanediol, decanediol, dodecanediol, octadecanediol or particularly well-adapted hyperbranched polymers are dimeric fatty alcohols, amines, such as hexamethylenedi obtainable for use according to the present invention. amine, octanediamine or dodecanediamine, isocyanates, 0082. The transfunctionalization of the hyperbranched Such as aromatic or aliphatic di- and polyisocyanates, for polymers can be effected during the preparation of the poly example diphenylmethane diisocyanate and the more highly mers, immediately after the polymerization reaction or in a oligomeric species thereof, tolylene diisocyanate, naphthyl separate reaction. ene diisocyanate, Xylylene diisocyanate, hexamethylene 0083. If components which have further functional groups diisocyanate, hexamethylene diisocyanate trimers, isophor in addition to A and B groups are added before or during the one diisocyanate, bis(diisocyanatocyclohexyl)methane orbis polymer synthesis, a hyperbranched polymer having ran (isocyanatomethyl)-cyclohexane, and acids, Such as adipic domly distributed further functional groups, i.e. functional acid, octanedioic acid, dodecanedioic acid, octadecanedioic groups differing from A or B groups, is obtained. acid and dimeric fatty acids. 0084 Compounds used for the transfunctionalization may 0090. Furthermore, the polymers according to the inven firstly comprise the desired functional group newly to be tion can be rendered hydrophilic by converting, for example, introduced and a second group which is capable of reacting hyperbranched polymers comprising hydroxyl groups or with the B groups of the hyperbranched polymer used as amino groups into highly functional polymer polyols by reac starting material, with formation of a bond. An example of tion with alkylene oxides, for example ethylene oxide, pro this is the reaction of an isocyanate group with a hydroxycar pylene oxide or butylene oxide, ethylene oxide preferably boxylic acid or an aminocarboxylic acid with formation of an being used. As a further option, however, difunctional or acid functionality or the reaction of an OH group with acrylic higher-functional alkylene oxide-alcohols or alkylene oxide anhydride with formation of a reactive acrylic double bond. amines can also be used as synthesis components for the 0085 Examples of suitable functional groups which can polymer. be introduced by means of Suitable reactants comprise in 0091. It is also possible to produce hyperbranched poly particular acidic or basic groups having H atoms and deriva mers which have different types of functionalities. This can tives thereof, such as OC(O)OR, -COOH, -COOR, be effected, for example, by reaction with a mixture of dif CONHR, CONH, OH, -SH, NH, NHR, ferent compounds for transfunctionalization, or by reacting NR, SOH, -SOR, NHCOOR, NHCONH, only some of the originally present functional groups. —NHCONHR, without there being any intention to limit the 0092. Furthermore, compounds having mixed functional list thereto. If appropriate, the functional groups can also be ity can be produced by using monomers of the type ABC or converted into the corresponding salts with the aid of suitable ABC for the polymerization, where C is a functional group acids or bases. Furthermore, for example, alkyl halides can which is not reactive with A or B under the chosen reaction also be used for quaternizing existing primary, secondary or conditions. tertiary amino groups. In this way, for example, water-soluble (0093 OH -, COOH- and/or —OC(O)OR-terminated or water-dispersible hyperbranched polymers can be hyperbranched polymers have proven to be particularly obtained. advantageous for use according to the present invention. The I0086. The radicals R of said groups are as a rule straight use of hyperbranched polymers which have OH and COOH chain or branched alkyl radicals or are aryl radicals which groups or OH and —OC(O)OR groups or OH, COOH and may also furthermore be substituted. For example, they are —OC(O)OR groups is very particularly advantageous. C-Coo-alkyl radicals or are C-C-aryl radicals. It is also possible to use other functional groups, such as, for example, 0094) Hyperbranched polycarbonates and their prepara - CN or - OR. tion are disclosed, for instance, in WO 2005/026234 and DE 0087. For using the hyperbranched polymers according to 102005009166, which are incorporated herein by reference the present invention, it may be advantageous if hydrophilic in their entirety. and hydrophobic molecule moieties have a certain ratio to one 0095. In particular, hyperbranched polycarbonates are another. A hyperbranched polymer can be rendered hydro obtainable by phobic, for example, by using monofunctional hydrophobic a) reaction of at least one organic carbonate (A) of the general compounds with which existing reactive groups are modified formula RO(CO)OR with at least one aliphatic alcohol (B) before, during or after the polymerization. Thus, the polymers which has at least 30H groups, with elimination of alcohols according to the invention can be rendered hydrophobic, for ROH to give one or more condensates (K), R, in each case example, by reaction with monofunctional, Saturated or independently of one another, being a straight-chain or unsaturated aliphatic or aromatic amines, alcohols, carboxy branched aliphatic, araliphatic or aromatic hydrocarbon radi lic acids, epoxides or isocyanates. cal having 1 to 20 carbon atoms, and 0088. Furthermore, for example, difunctional or higher b) intermolecular reaction of the condensates (K) to give a functional monomers having hydrophobic groups can also be hyperbranched polycarbonate, US 2011/O 105333 A1 May 5, 2011

the ratio of the OH groups to the carbonates in the reaction 0104. In the preparation of the hyperbranched polycarbon mixture being chosen so that the condensates (K) have on ates, it is necessary to adjust the ratio of the compounds average either one carbonate group and more than one OH comprising OH groups to the carbonate so that the resulting group or one OH group and more than one carbonate group. simplest condensate (referred to below as condensate (K)) 0096. The radicals R of the organic carbonates (A) of the comprises on average either one carbonate group and more general formula RO(CO)OR which are used as a starting than one OH group or one OH group and more than one material are, in each case independently of one another, a carbonate group. The simplest structure of the condensate (K) straight-chain or branched aliphatic, araliphatic or aromatic from a carbonate (A) and a di- or polyalcohol (B) gives the hydrocarbon radical having 1 to 20 carbon atoms. The two arrangement XY or YX, where X is a carbonate group, Y is radicals R may also be linked to one another with formation of a ring. It is preferably an aliphatic hydrocarbon radical and a hydroxyl group and n is as a rule a number from 1 to 6. particularly preferably a straight-chain or branched alkyl preferably from 1 to 4, particularly preferably from 1 to 3. The radical having 1 to 5 carbon atoms. reactive group which results as an individual group is referred 0097 Dialkyl or diaryl carbonates can be prepared, for to below generally as “focal group'. example, from the reaction of aliphatic, araliphatic or aro 0105. If, for example, the reaction ratio is 1:1 in the prepa matic alcohols, preferably monoalcohols, with phosgene. ration of the simplest condensate (K) from a carbonate and a Furthermore, they can also be prepared by oxidative carbo dihydric alcohol, a molecule of the type XY results on aver nylation of the alcohols or phenols by means of CO in the age, illustrated by the general formula 1. presence of noble metals, oxygen or NO. Regarding methods of preparation of diary1 or dialkyl carbonates, also see “Ull mann's Encyclopedia of Industrial Chemistry’, 6th Edition, 2000 Electronic Release, Verlag Wiley-VCH. 0098. Examples of suitable carbonates comprise aliphatic * - - -- HO-R-OH - ROH,- or aromatic carbonates, such as ethylene carbonate, 1.2- or 1,3-propylene carbonate, diphenyl carbonate, ditolyl carbon O ate, dixylyl carbonate, dinaphthyl carbonate, ethyl phenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl R No ls O-R-OH carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclo hexylcarbonate, diheptyl carbonate, dioctyl carbonate, dide 0106. In the preparation of the condensate (K) from a cyl carbonate and didodecyl carbonate. carbonate and a trihydric alcohol with a reaction ratio of 1:1, 0099 Aliphatic carbonates are preferably used, in particu a molecule of the type XY, results on average, illustrated by lar those in which each of the radicals independently com the general formula 2. The focal group here is a carbonate prises 1 to 5 carbon atoms, such as, for example, dimethyl group. carbonate, diethyl carbonate, dipropylcarbonate, dibutyl car bonate or diisobutyl carbonate. 0100. The organic carbonates are reacted with at least one O OH aliphatic alcohol (B) which has at least 30H groups. A 0101 Examples of aliphatic alcohols having at least three * - - + HO-R - ROH,- O O V OH groups are glycerol, trimethylolmethane, trimethylole OH thane, trimethylolpropane, 1,2,4-butanetriol, tris(hydroxym O ethyl)amine, tris(hydroxyethyl)amine, tris(hydroxypropyl) amine, pentaerythritol, bis(trimethylolpropane) or Sugars, R ls pH Such as, for example, glucose, trifunctional or higher-func No o–R tional polyetherols based on trifunctional or higher-func OH tional alcohols and ethylene oxide, propylene oxide or buty lene oxide, or polyesterols. Glycerol, trimethylolethane, 0107. In the preparation of the condensate (K) from a trimethylolpropane, 1,2,4-butanetriol, pentaerythritol and carbonate and a tetrahydric alcohol, likewise with the reac polyetherols thereof based on ethylene oxide or propylene tion ratio of 1:1, a molecule of the type XY results on aver oxide are particularly preferred. age, illustrated by the general formula3. The focal group here 0102 These polyfunctional alcohols can also be used as a is a carbonate group. mixture with difunctional alcohols (B'), with the proviso that the average OH functionality of all alcohols used is altogether greater than 2. Examples of Suitable compounds having two OH groups comprise ethylene glycol, diethylene glycol, tri O HQ OH ethylene glycol, 1.2- and 1,3-propanediol, dipropylene gly R ls -R + RI - ROH,- col, tripropylene glycol, neopentylglycol. 1.2-, 1.3- and 1,4- O O MV butanediol. 1.2-, 1.3- and 1.5-pentanediol, hexanediol. HO OH cyclopentanediol, cyclohexanediol, cyclohexanedimethanol O and difunctional polyetherols or polyesterols. 0103. The reaction of the carbonate with the alcohol or Rul. " alcohol mixture to give the hyperbranched polycarbonate is No o-R-OH effected with elimination of the monofunctional alcohol or phenol from the carbonate molecule. US 2011/O 105333 A1 May 5, 2011

0108. In the formulae 1 to 3, R has the meaning defined at 0114. In a preferred embodiment, the condensation reac the outset and R' is a, preferably aliphatic, hydrocarbon radi tion is carried out in the absence of a solvent. The monofunc cal. tional alcohol ROH or the phenol liberated in the reaction can 0109 Furthermore, the preparation of the condensate (K) be removed from the reaction equilibrium by distillation, if can also be effected, for example, from a carbonate and a appropriate under reduced pressure, in order to accelerate the trihydric alcohol, illustrated by the general formula 4, the reaction. molar reaction ratio being 2:1. Here, a molecule of the type 0115 If it is intended to distill off, it is usually advisable to XY results on average, and the focal group here is an OH use Such carbonates which liberate, during the reaction, alco group. In the formula 4, Rand R' have the same meaning as hols ROH having a boiling point of less than 140°C. in the formulae 1 to 3. 0116. In order to accelerate the reaction, catalysts or cata lyst mixtures may also be added. Suitable catalysts are com pounds which catalyze foresterification or transesterification 4 reactions, for example alkali metal hydroxides, alkali metal O pH carbonates, alkali metal bicarbonates, preferably of Sodium, 2 is 1 - + HO-R - 2 ROH of potassium or of cesium, tertiary amines, guanidines, O O ammonium compounds, phosphonium compounds, organic OH aluminum, tin, Zinc, titanium, Zirconium or bismuth com O-R pounds, and furthermore so-called double-metal cyanide (DMC) catalysts, as described, for example, in DE 101.38216 p or in DE 10147712, which are incorporated herein by refer HO-R- Pl O ence in their entirety. 0117 Potassium hydroxide, potassium carbonate, potas O sium bicarbonate, diazabicyclooctane (DABCO), diazabicy O-R clononene (DBN), diazabicycloundecene (DBU), imida Zoles, such as imidazole, 1-methylimidazole or 1.2- dimethylimidazole, titanium tetrabutylate, titanium 0110. If difunctional compounds, for example a dicarbon tetraisopropylate, dibutyltin oxide, dibutyltin dilaurate, tin ate or a diol, are added in addition to the components, this results in a lengthening of the chains, as illustrated, for dioctoate, Zirconium acetylacetonate or mixtures thereof are example, in the general formula 5. Once again, a molecule of preferably used. the type XY results on average, and the focal group is a 0118. The addition of the catalyst is generally effected in carbonate group. an amount of from 50 to 10 000, preferably from 100 to 5000, ppm by weight, based on the amount of the alcohol or alcohol mixture used. 5 0119 Furthermore, it is also possible to control the inter OH A molecular polycondensation reaction by addition of a Suitable - Pl catalyst, as well as by the choice of a suitable temperature. O HO R Furthermore, the average molecular weight of the polymer 2 RN ls -R + OH 3 ROH (P) can be established by the composition of the starting O O components and via the residence time. HO-R-OH 0.120. The condensates (K) or the polycondensates (P) O which are prepared at elevated temperature are usually stable over a relatively long period at room temperature. O O ls O -R-OH I0121 Owing to the characteristics of the condensates (K), it is possible that polycondensates (P) having different struc R ulR tures, which have branches but no crosslinks, can result from No O1 No the condensation reaction. Furthermore, the polycondensates (P) ideally have either a carbonate group as the focal group 0111. In formula 5, R is an organic, preferably aliphatic, and more than two OH groups or an OH group as the focal radical, and Rand R' are defined as described above. group and more than two carbonate groups. The number of 0112 The simple condensates (K) described by way of reactive groups arises from the characteristics of the conden example in the formulae 1-5 preferably undergo, according to sates (K) used and the degree of polycondensation. the invention, an intermolecular reaction with formation of 0.122 For example, a condensate (K) according to the hyperbranched polycondensates, referred to below as poly general formula 2 can react by intermolecular tricondensation condensates (P). to give two different polycondensates (P) which are repro 0113. The reaction to give the condensate (K) and to give duced in the general formulae 6 and 7. the polycondensate (P) is usually effected at a temperature of from 0 to 250° C., preferably at from 60 to 160° C., in the absence of a solvent or in solution. In general, it is possible to use all solvents which are inert to the respective starting materials. Organic solvents, such as, for example, decane, dodecane, benzene, toluene, chlorobenzene, Xylene, dimeth ylformamide, dimethylacetamide or solvent naphtha, are preferably used. US 2011/O 105333 A1 May 5, 2011 10

further functional groups or functional elements, such as mer -continued capto groups, primary, secondary or tertiary amino groups, O ether groups, derivatives of carboxylic acids, derivatives of O ls /OH Sulfonic acids, derivatives of phosphonic acids, aryl radicals O ls p O-R or long-chain alkyl radicals in addition to hydroxyl groups or carbonate groups. For modification by means of carbamate R ls p O-R OH groups, for example ethanolamine, propanolamine, isopro No O-R OH panolamine, 2-(butylamino)ethanol, 2-cyclohexylamino) OH ethanol, 2-amino-1-butanol, 2-(2-aminoethoxy)ethanol and 7 higher alkoxylation products of ammonia, 4-hydroxypiperi O dine, 1-hydroxyethylpiperazine, diethanolamine, dipropano OH lamine, diisopropanolamine, tris(hydroxymethyl)-ami 3 R n O lsO-R A He-2 ROH V nomethane, tris(hydroxyethyl)aminomethane, OH ethylenediamine, propylenediamine, hexamethylenediamine O OH A or isophoronediamine can be used. X-0-R I0131 For the modification with mercapto groups, for O example, mercaptoethanol can be used. Tertiary amino isO - O-R? OH groups can be produced, for example, by incorporation of V N-methyldiethanolamine, N-methyldipropanolamine or O O-R N,N-dimethylethanolamine. Ether groups can be generated, 1 Y. for example, by incorporating difunctional or higher-func O tional polyetherols by condensation. By reaction with long chain alkanediols, it is possible to introduce long-chain alkyl (0123. In formulae 6 and 7. RandR' are as defined above. radicals, and the reaction with alkyl or aryl diisocyanates 0.124. There are various possibilities for terminating the generates polycarbonates having alkyl, aryl and urethane intermolecular polycondensation reaction. For example, the groups. temperature can be reduced to a range in which the reaction I0132) Subsequent functionalization can be obtained by stops and the product (K) or the polycondensate (P) is stor reacting the resulting hyperbranched polycarbonate with a age-stable. suitable functionalizing reagent which can react with OH 0.125. In a further embodiment, a product having groups and/or carbonate groups of the polycarbonate. reactive toward the focal group of (P) can be added to the product (P) for terminating the reaction as soon as a polycon 0.133 Hyperbranched polycarbonates comprising densate (P) having the desired degree of polycondensation is hydroxyl groups can be modified, for example, by adding present as a result of the intermolecular reaction of the con molecules comprising acid groups or isocyanate groups. For densate (K). Thus, in the case of a carbonate group as the focal example, polycarbonates comprising acid groups can be group, for example, a mono-, di- or polyamine can be added. obtained by reaction with compounds comprising anhydride In the case of a hydroxyl group as the focal group, for groups. example, a mono-, di- or polyisocyanate, a compound com I0134) Furthermore, hyperbranched polycarbonates com prising epoxide groups oran acid derivative reactive with OH prising hydroxyl groups can also be converted into highly groups can be added to the product (P). functional polycarbonate-polyetherpolyols by reaction with 0126 The preparation of the polycarbonates according to alkylene oxides, for example ethylene oxide, propylene oxide the invention is generally effected in a pressure range of from or butylene oxide. 0.1 mbar to 20 bar, preferably at from 1 mbar to 5 bar, in reactors or reactor cascades which are operated in the batch 0.135 The hyperbranched polycarbonates formed by the mode, semicontinuously or continuously. process described are readily soluble in various solvents, for 0127. By the abovementioned adjustment of the reaction example in water, alcohols, such as methanol, ethanol or conditions and, if appropriate, by the choice of the Suitable butanol, alcohol/water mixtures, acetone, 2-butanone, ethyl solvent, the products can be further processed after the prepa acetate, butyl acetate, methoxypropyl acetate, methoxyethyl ration without further purification. acetate, tetrahydrofuran, dimethylformamide, dimethylac 0128. In a further preferred embodiment, the polycarbon etamide, N-methylpyrrolidone, ethylene carbonate or propy ates may comprise further functional groups in addition to the lene carbonate. functional groups already obtained by the reaction. The func 0.136. According to a particular embodiment, the hyper tionalization can be effected during the increase in molecular branched polycarbonate of the invention is a hyperbranched weight or Subsequently, i.e. after the end of the actual poly polycarbonate obtainable by reacting a dialkyl carbonate, e.g. condensation. diethylcarbonate, and a polyoxyethylene triol. The polyoxy 0129. If components which have further functional groups ethylene triol preferably is an ethoxylation product of trim or functional elements in addition to hydroxyl or carbonate ethylolpropane with 2 to 25, e.g. 3 or 12, units of ethylene groups are added before or during the increase in molecular oxide. weight, a polycarbonate polymer having randomly distrib 0.137 Hyperbranched polyesters and their preparation are uted functionalities differing from the carbonate or hydroxyl disclosed, for instance, in WO 93/17060, WO 01/46296, WO groups is obtained. 03/54204, WO 03/93343, WO 05/037893, WO 04/020503, 0130. Such effects can be achieved, for example, by add WO 05/118677, which are incorporated herein by reference ing, during the polycondensation, compounds which carry in their entirety. US 2011/O 105333 A1 May 5, 2011

0.138. In particular, hyperbranched polyesters are obtain mono- or dimethyl esters and the corresponding mono- or able by reacting at least one aliphatic, cycloaliphatic, diethyl esters, and furthermore mono- and divinyl esters and araliphatic or aromatic dicarboxylic acid (A) or a derivative mixed esters, preferably mixed esters having different C-C- thereof with alkyl components, particularly preferably mixed methyl ethyl a) at least one at least trifunctional aliphatic, cycloaliphatic, esters, as well as their anhydrides. araliphatic or aromatic alcohol (B), or 0.143 Furthermore, mixtures of two or more of the above b) with at least one dihydric aliphatic, cycloaliphatic, mentioned dicarboxylic acids can be used. araliphatic or aromatic alcohol (B) and at least one X-func 0144. It is also possible to use a mixture of a dicarboxylic tional aliphatic, cycloaliphatic, araliphatic or aromatic alco acid and one or more of its derivatives. It is equally possible hol (C) which has more than two OH groups, where x is a to use a mixture of a plurality of different derivatives of one or number greater than 2, preferably from 3 to 8, particularly more dicarboxylic acids. preferably from 3 to 6, very particularly preferably 3 or 4 and 0145 Particularly preferably, malonic acid, succinic acid, in particular 3, glutaric acid, adipic acid, 1.2-, 1.3- or 1.4-cyclohexanedicar or by reacting at least one aliphatic, cycloaliphatic, boxylic acid (hexahydrophthalic acids), phthalic acid, isoph araliphatic or aromatic carboxylic acid (D) or a derivative thalic acid, terephthalic acid or mono- or dialkyl esters thereof which has more than two acid groups, where y is a thereof are used. number greater than 2, preferably from 3 to 8, particularly (0146 Tricarboxylic acids or polycarboxylic acids (D.) preferably from 3 to 6, very particularly preferably 3 or 4 and which can be reacted are, for example, aconitic acid, 1.3.5- in particular 3, with cyclohexanetricarboxylic acid, 1,2,4-benzenetricarboxylic c) at least one at least difunctional aliphatic, cycloaliphatic, acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetra araliphatic or aromatic alcohol (B), or carboxylic acid (pyromellitic acid) and mellitic acid and low d) with at least one dihydric aliphatic, cycloaliphatic, molecular weight polyacrylic acids. araliphatic or aromatic alcohol (B) and at least one X-func 10147 Tricarboxylic acids or polycarboxylic acids (D) tional aliphatic, cycloaliphatic, araliphatic or aromatic alco can be used either as such or in the form of derivatives. hol (C) which has more than two OH groups, where x is a 0.148. It is also possible to use a mixture of a tri- or poly number greater than 2, preferably from 3 to 8, particularly carboxylic acid and one or more of its derivatives, for preferably from 3 to 6, very particularly preferably 3 or 4 and example a mixture of pyromellitic acid and pyromellitic in particular 3, anhydride. It is also possible to use a mixture of a plurality of e) if appropriate in the presence of further functionalized different derivatives of one or more tri- or polycarboxylic building blocks E and acids, for example a mixture of 1,3,5-cyclohexanetricarboxy f) optionally Subsequent reaction with a monocarboxylic acid lic acid and pyromellitic dianhydride. or a monocarboxylic acid derivative F. I0149 Examples of diols (B) used are ethylene glycol, the ratio of the reactive groups in the reaction mixture being propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane chosen so that a molar ratio of OH groups to carboxyl groups 1,3-diol, butane-1,4-diol, butane-2,3-diol, pentane-1,2-diol. or derivatives thereof of from 5:1 to 1:5, preferably from 4:1 pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pen to 1:4, particularly preferably from 3:1 to 1:3 and very par tane-2,3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3- ticularly preferably from 2:1 to 1:2 results. diol, hexane-1,4-diol, hexane-1,5-diol, hexane-1,6-diol, hex 0.139. The dicarboxylic acids (A) include, for example, ane-2,5-diol, heptane-1,2-diol. 1,7-heptanediol, 1.8- aliphatic dicarboxylic acids, Such as oxalic acid, malonic octanediol. 1.2-octanediol. 1.9-nonanediol. 1,2-decanediol. acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1.5- Suberic acid, azelaic acid, sebacic acid, undecane-am-dicar hexadiene-3,4-diol. 1.2- and 1.3-cyclopentanediols, 1.2-, 1.3- boxylic acid, dodecane-O.()-dicarboxylic acid, cis- and trans and 1.4-cyclohexanediols, 1,1-, 1.2-, 1.3- and 1,4-bis(hy cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohex droxymethyl)cyclohexanes, 1,1-, 1.2-, 1.3- and 1,4-bis(hy ane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4- droxyethyl)cyclohexanes, neopentylglycol, (2)-methyl-2,4- dicarboxylic acid, cis- and trans-cyclopentane-1,2- pentanediol. 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3- dicarboxylic acid, cis- and trans-cyclopentane-1,3- hexanediol. 2,5-dimethyl-2.5-hexanediol. 2,2,4-trimethyl-1, dicarboxylic acid. Furthermore, aromatic dicarboxylic acids, 3-pentanediol, pinacol, diethylene glycol, triethylene glycol, Such as, for example, phthalic acid, isophthalic acidortereph dipropylene glycol, tripropylene glycol, polyethylene glycols thalic acid, can also be used. Unsaturated dicarboxylic acids, HO(CH2CH2O), H or polypropylene glycols HO(CH Such as maleic acid or fumaric acid, can also be used. CHICH2O), H, where n is an integer and n is 4, polyeth 0140 Said dicarboxylic acids may also be substituted by ylenepolypropylene glycols, it being possible for the one or more radicals selected from C-Cs-alkyl groups, sequence of the ethylene oxide of the propylene oxide units to C-C2-cycloalkyl groups, C-Co-alkenyl groups or Cs-Ca be block-by-block or random, polytetramethylene glycols, aryl groups. The following may be mentioned as typical preferably up to a molecular weight up to 5000 g/mol, poly examples of substituted dicarboxylic acids: 2-methylmalonic 1,3-propanediols, preferably having a molecular weight up to acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methyl 5000 g/mol, polycaprolactones or mixtures of two or more Succinic acid, 2-ethylsuccinic acid, Cis-alkenylsuccinic members of the above compounds. One or both hydroxyl acid, 2-phenylsuccinic acid, itaconic acid and 3.3-dimethyl groups in the abovementioned diols can be substituted by SH glutaric acid. groups. Preferably used diols are ethylene glycol, 1,2-pro 0141. The dicarboxylic acids can be used either as such or panediol. 1,3-propanediol. 1,4-butanediol. 1.5-pentanediol. in the form of their derivatives. 1.6-hexanediol. 1.8-octanediol. 1.2-, 1.3- and 1,4-cyclohex 0142. Derivatives are the relevant anhydrides in mono anediol. 1.3- and 1,4-bis(hydroxymethyl)cyclohexane and meric or polymeric form, mono- or dialkyl esters, preferably diethylene glycol, triethylene glycol, dipropylene glycol, mono- or di-C-C-alkyl esters, particularly preferably tripropylene glycol, polyethylene glycols HO(CH2CH2O) US 2011/O 105333 A1 May 5, 2011

H or polypropylene glycols HO(CHICHCHO), H. crosslinked polymers with regularly arranged branching where n is an integer and n is 24, polyethylenepolypropylene positions. The polymers exhibit almost exclusively B groups glycols, it being possible for the sequence of the ethylene at the chain ends. Further details will be found, for example, oxide of the propylene oxide units to be block-by-block or in Journal of Molecular Science, Rev. Macromol. Chem. random, or polytetramethylene glycols, preferably up to a Phys. C37(3), 555-579 (1997), which is incorporated herein molecular weight up to 5000 g/mol. by reference in its entirety. 0150. The dihydric alcohols B can optionally also com 0155 The reaction can be carried out in the presence or prise further functionalities, such as, for example, carbonyl, absence of a solvent. Suitable solvents are, for example, carboxyl, alkoxycarbonyl or Sulfonyl functions, such as, for hydrocarbons, such as paraffins, aromatics, ethers and example, dimethylolpropionic acid or dimethylolbutyric ketones. The reaction is preferably carried out in the absence acid, and C-C-alkyl esters thereof, glyceryl monostearate or of solvents. The reaction can be effected in the presence of a glyceryl monooleate. dehydrating agent as an additive, which is added at the begin 0151. Alcohols (C) having 3 or more OH groups com ning of the reaction. For example, molecular sieves, in par prise glycerol, trimethylolmethane, trimethylolethane, trim ticular molecular sieve 4A, MgSO and NaSO are suitable. ethylolpropane, 1,2,4-butanetriol, tris(hydroxymethyl) Water or alcohol formed during the reaction can also be amine, tris(hydroxyethyl)amine, tris(hydroxypropyl)amine, distilled off and it is possible to use, for example, a water pentaerythritol, diglycerol, triglycerol or higher condensates separator in which the water is removed with the aid of an of glycerol, di(trimethylolpropane), di(pentaerythritol), entraining agent. trishydroxymethyl isocyanurate, tris(hydroxyethyl) isocya 0156 The reaction can be carried out in the absence of a nurate (THEIC), tris(hydroxypropyl) isocyanurate, inositols catalyst. Preferably, however, the procedure is effected in the or Sugars, such as, for example, glucose, fructose or Sucrose, presence of at least one catalyst. Acidic inorganic, organome Sugar alcohols, such as, for example, Sorbitol, mannitol, threi tallic or organic catalysts or mixtures of a plurality of acidic tol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, inorganic, organometallic or organic catalysts are preferred. dulcitol (galactitol), maltitol, isomalt, trifunctional or higher functional polyetherols based on trifunctional or higher-func 0157 For example, sulfuric acid, sulfates and hydrogen tional alcohols and ethylene oxide, propylene oxide and/or Sulfates, such as Sodium hydrogensulfate, phosphoric acid, butylene oxide. phosphonic acid, hypophosphorous acid, aluminum Sulfate 0152 Glycerol, diglycerol, trig lycerol, trimethylole hydrate, alum, acidic silica gel (having a pH in water of sG. thane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, in particular sS) and acidic alumina may be used. It is also tris(hydroxyethyl) isocyanurate and polyetherols thereof possible, for example, to use aluminum compounds of the based on ethylene oxide and/or propylene oxide are particu general formula A1(OR), and titanates of the general for larly preferred. mula Ti(OR) as acidic inorganic catalysts, where the R radicals may each be the same or different and are indepen 0153. According to a particular embodiment, the hyper dently selected from butyl, isopropyl or 2-ethylhexyl. Pre branched polymer is a hyperbranched polyester that is obtain ferred acidic organometallic catalysts are, for example, able by reacting C.B-unsaturated carboxylic acids and deriva selected from dialkyltin oxides RSnO or dialkyltin esters tives thereof with a multifunctional alcohol. The C.B- RSn(OR), where RandR may be selected from C, -Co unsaturated carboxylic acids and their derivatives are alkyl or C-C2-cycloalkyl and may be the same or different. preferably dicarboxylic acids and their derivatives. Particular Particularly preferred representatives of acidic organometal preference is given to dicarboxylic acids and derivatives lic catalysts are dibutyltin oxide and dibutyltin dilaurate. wherein the double bond is in vicinity to both carboxylic acid groups. These preferred C. B-unsaturated carboxylic acids 0158. The reaction is carried out at temperatures of from and their derivatives include maleic acid, maleic acid anhy 60 to 250° C. dride, maleic acid dichloride, furmaric acid, furmaric acid 0159. According to a particular embodiment, the hyper dichloride, itaconic acid, and itaconic acid dichloride. Maleic branched polyester of the invention is a hyperbranched poly acid anhydride is particularly preferred. Said C. B-unsatur ester obtainable by reacting an optionally substituted Succinic ated carboxylic acids and their derivatives may be used alone acid anhydride and a polyoxyethylene triol. The optionally or in combination or together with further carboxylic acids Substituted Succinic acid anhydride is preferably a C-Cs and their derivatives, preferably di- or polycarboxylic acids alkenyl Succinic acid anhydride, e.g. Cis-alkenyl Succinic and their derivatives, for example adipic acid, for preparing acid anhydride The polyoxyethylene triol preferably is an the hyperbranched polyesters. Hyperbranched polyesters ethoxylation product of trimethylolpropane with 2 to 25, e.g. based on maleic acid anhydride are disclosed in, for instance, 3 or 12, units of ethylene oxide. WO 05/037893, which is incorporated herein by reference in 0160 Hyperbranched polyethers and their preparation are its entirety. disclosed, for instance, in WO 03/062306, WO 00/56802, DE 0154 According to a further particular embodiment, the 102 11664 or DE 19947631, which are incorporated herein hyperbranched polymer is a hyperbranched polyester that is by reference in their entirety. obtainable by using an AB monomer Such as dihydroxycar 0.161 Mixed forms of hyperbranched polycarbonates, boxylic acids, e.g. dimethylolpropionic acid. “AB mono polyesters and polyethers, such as hyperbranched polyester mers' are particularly suitable for the synthesis of hyper carbonates, hyperbranched polyethercarbonates, polyether branched polymers. These AB monomers exhibit two esters, polyetherestercarbonates, can be prepared in analogy different functional groups A and B which can react with one to the hyperbranched polycarbonates, polyesters and poly anotherfor the formation of a linkage. The functional group A ethers by combining reactants in a suitable manner. For is in this connection only present once per molecule and the instance, polyestercarbonates and their preparation are dis functional group B twice or several times. Reaction of said closed in DE 102005009166, which is incorporated herein by AB, monomers with one another produces essentially non reference in its entirety. US 2011/O 105333 A1 May 5, 2011

0162 Hyperbranched polyurethanes and their preparation with compounds exhibiting at least two groups which react are disclosed, for instance, in WO 97/02304 or DE 19904 with isocyanate groups. At least one of the reaction partners 444, which are incorporated herein by reference in their exhibits groups with varying reactivity with regard to the entirety. other reaction partner. Preferably, both reaction partners 0163 Hyperbranched polyureas and their preparation are exhibit groups with varying reactivity with regard to the other disclosed, for instance, in WO 03/066702, DE 10351401.5 or reaction partner. The reaction conditions are chosen so that DE 102004006304.4, which are incorporated herein by ref only certain reactive groups can react with one another. erence in their entirety. 0172. In addition, AB molecules can be prepared as dis 0164. Hyperbranched polyureapolyurethanes and their closed in the German patent application P 102 04 979.3. preparation are disclosed, for instance, in WO 97/02304 or which is incorporated herein by reference in their entirety. In DE 19904 444, which are incorporated herein by reference in this instance, isocyanate groups protected by blocking agents their entirety. are reacted with polyamines to give polyureas. 0.165. The term “polyurethanes' comprises, in the context 0173 Possible di- or polyisocyanates are the aliphatic, of this invention, not only those polymers whose repeat units cycloaliphatic, araliphatic and aromatic di- or polyisocyan are bonded to one another via urethane groups but very gen ates known as state of the art and mentioned Subsequently by erally polymers which can be obtained by reaction of at least way of example. Mention may preferably be made, in this one di- and/or polyisocyanate with at least one compound connection, of 4,4'-diphenylmethane diisocyanate, the mix exhibiting at least one group which is reactive with regard to tures of monomeric diphenylmethane diisocyanates and oli isocyanate groups. These include polymers whose repeat gomeric diphenylmethane diisocyanates (polymer MDI), tet units, in addition to urethane groups, are also bonded by urea, ramethylene diisocyanate, tetramethylene diisocyanate allophanate, biuret, carbodiimide, amide, uretonimine, uret trimers, hexamethylene diisocyanate, hexamethylene diiso dione, isocyanurate or oxazolidone (oxazolidinone) groups cyanate trimers, isophorone diisocyanate trimer, 4,4'-methyl (see, for example, Plastics Handbook, Saechtling, 26th edi enebiscyclohexane diisocyanate, Xylylene diisocyanate, tet tion, p. 491 ff. Carl Hanser Verlag, Munich, 1995, which is ramethylxylylene diisocyanate, dodecane diisocyanate, incorporated herein in their entirety by reference The term lysine alkyl ester diisocyanate, alkyl representing C-Co "polyurethanes' comprises in particular polymers exhibiting alkyl, 1,4-diisocyanatocyclohexane or 4-isocyanatomethyl urethane and/or urea groups. 1.8-octamethylene diisocyanate. 0166 Their content ofurethane and/or urea groups (and, if 0.174 Di- or polyisocyanates exhibiting NCO groups of present, additional groups obtained by reaction of an isocy varying reactivity are suitable particularly preferably for the anate group with a correspondingly reactive group with an synthesis of polyurethanes and polyureas. Mention may be active hydrogen atom) preferably lies in a range of 0.5 to 10 made in this connection of 2,4-toluoylene diisocyanate (2,4- mol/kg, particularly preferably 1 to 10 mol/kg, especially 2 to TDI), 2,4'-diphenylmethane diisocyanate (2.4-MDI), triiso 8 mol/kg. cyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl-2- 0167. The synthesis of hyperbranched polyurethanes and ethylpentamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl polyureas which can be used in accordance with the invention 1,6-hexamethylene diisocyanate, can, for example, be carried out as described below. 2-isocyanatopropylcyclohexane isocyanate, 3(4)-isocy 0168 Use is preferably made, in the synthesis of the anatomethyl-1-methylcyclohexane isocyanate, 1,4-diisocy hyperbranched polyurethanes and polyureas, of AB mono anato-4-methylpentane, 2,4'-methylenebiscyclohexane mers exhibiting both isocyanate groups and groups which can diisocyanate and 4-methylcyclohexane 1,3-diisocyanate react with isocyanate groups for the formation of a linkage. X (H-TDI). is a natural number between 2 and 8. X is preferably 2 or 3. 0.175 Isocyanates, the NCO groups of which are first Either A relates to the isocyanate groups and B relates to equally reactive, in which, however, the first addition of a groups which react with them or vice versa. reactant to an NCO group can induce a fall in reactivity in the 0169. The groups which react with isocyanate groups are second NCO group, are furthermore suitable for the synthesis preferably OH, NH, NRH, SH or COOH groups. of the polyurethanes and polyureas. Examples thereof are (0170 The AB-monomers can be prepared in a knownway isocyanates, the NCO groups of which are coupled via a using various techniques. AB monomers can, for example, delocalized p-electron system, e.g. 1.3- and 1,4-phenylene be synthesized according to the method disclosed in WO diisocyanate, 1.5-naphthalene diisocyanate, biphenyl diiso 97/02304, which is incorporated herein by reference in their cyanate, tolidine diisocyanate or 2.6-toluoylene diisocyanate. entirety, with the use of protective group techniques. By way 0176 Furthermore, use may be made, for example, of of example, this technique was illustrated by the preparation oligo- or polyisocyanates which can be prepared from the of an AB monomer from 2,4-toluoylene diisocyanate (TDI) abovementioned di- or polyisocyanates or mixtures thereof and trimethylolpropane. First, one of the isocyanate groups of by linking by means of urethane, allophanate, urea, biuret, the TDI is blocked in a known way, for example by reaction uretdione, amide, isocyanurate, carbodiimide, uretonimine, with an oxime. The remaining free NCO group is reacted with oxadiazinetrione or iminooxadiazinedione structures. trimethylolpropane, one of the three OH groups reacting with 0177 Use is preferably made, as compounds with at least the isocyanate group. After cleavage of the protective group, two groups which are reactive with isocyanates, of di-, tri- or a molecule with one isocyanate group and 20H groups is tetrafunctional compounds, the functional groups of which obtained. exhibit a varying reactivity with regard to NCO groups. (0171 In a particularly advantageous way, the AB mol 0.178 Preference is given, for the preparation of polyure ecules can be synthesized according to the method disclosed thanes and polyurea-polyurethanes, to compounds with at in DE-A 19904 444, which is incorporated herein by refer least one primary and at least one secondary hydroxyl group, ence in its entirety, in which no protective groups are required. at least one hydroxyl group and at least one mercapto group, In this method, di- or polyisocyanates are used and are reacted particularly preferably with at least one hydroxyl group and at US 2011/O 105333 A1 May 5, 2011

least one amino group in the molecule, in particular aminoal isocyanate groups and which, as described, can be converted cohols, aminodiols and aminotriols, since the reactivity of the at higher temperatures to give a hyperbranched polyurethane. amino group is clearly higher in comparison with the There is produced first a hyperbranched polymer which hydroxyl group in the reaction with isocyanate. exhibits one free OH group and, depending on the degree of 0179 Examples of the abovementioned compounds with polymerization, a more or less large number of NCO groups. at least two groups which react with isocyanates are propy 0185. The preparation of the hyperbranched polyure lene glycol, glycerol, mercaptoethanol, ethanolamine, N-me thanes and polyureas can in principle be carried out without thylethanolamine, diethanolamine, ethanolpropanolamine, solvent but is preferably carried out in solution. All com dipropanolamine, diisopropanolamine, 2-amino-1,3-pro pounds liquid at the reaction temperature and inert with panediol, 2-amino-2-methyl-1,3-propanediol or tris(hy regard to the monomers and polymers are Suitable in principle droxymethyl)aminomethane. Furthermore, mixtures of the as solvent. above-mentioned compounds can also be used. 0186. Other products are accessible by additional alterna 0180 Isocyanate-reactive products exhibiting at least two tive synthetic forms. Mention may be made here, for example, amino groups in the molecule are preferably used for the of: preparation of polyureas. 0187. AB molecules can, for example, be obtained by 0181. These are, for example, ethylenediamine, N-alkyl reaction of diisocyanates with compounds with at least 4 ethylenediamine, propylenediamine, N-alkylpropylenedi groups which are reactive with respect to isocyanates. Men amine, hexamethylenediamine, N-alkylhexamethylenedi tion may be made, by way of example, of the reaction of amine, diaminodicyclohexylmethane, phenylenediamine, toluoylene diisocyanate with tris(hydroxymethyl)ami isophoronediamine, amine-terminated polyoxyalkylenep nomethane. olyols (referred to as Jeffamines), bis(aminoethyl)amine, bis 0188 Polyfunctional compounds can also be used to ter (aminopropyl)amine, bis(aminohexyl)amine, tris(aminoet minate the polymerization, which compounds can react with hyl)amine, tris(aminopropyl)amine, tris(aminohexyl)amine, the respective A groups. In this way, several Small hyper trisaminohexane, 4-aminomethyl-1,8-octamethylenedi branched molecules can be linked together to give a large amine, N'-(3-aminopropyl)-N,N-dimethyl-1,3-propanedi hyperbranched molecule. amine, trisaminononane or melamine. Furthermore, mixtures 0189 Hyperbranched polyurethanes and polyureas with of the above-mentioned compounds can also be used. chain-extended branches can, for example, be obtained by 0182. The preparation of an AB molecule for the prepa additionally using, in the polymerization reaction, in addition ration of a polyurethane from a diisocyanate and an aminodiol to the AB molecules, in the molar ratio 1:1, a diisocyanate is illustrated here by way of example. In this connection, first and a compound which exhibits two groups which react with one mole of a diisocyanate is reacted with one mole of an isocyanate groups. These additional AA or BB compounds aminodiol at low temperatures, preferably in the range can also even have available additional functional groups between -10 and 30°C. In this temperature range, the ure which, under the reaction conditions, may not, however, be thane formation reaction is virtually completely suppressed reactive with regard to the A or B groups. In this way, addi and the NCO groups of the isocyanate react exclusively with tional functionalities can be introduced into the hyper the amino group of the aminodiol. The AB-molecule formed, branched polymer. in this instance an AB type, exhibits a free NCO group and 0190. Hyperbranched polyamides and their preparation two free OH groups and can be used for the synthesis of a are disclosed, for instance, in U.S. Pat. No. 4507 466, U.S. hyperbranched polyurethane. Pat. No. 6,541,600, US-A-2003055209, U.S. Pat. No. 6,300, 0183 This AB molecule can react intermolecularly, by 424, U.S. Pat. No. 5,514,764, WO 92/08749, and DE warming and/or addition of catalyst, to give a hyperbranched 10200403.9101.7, which are incorporated herein by reference polyurethane. The synthesis of the hyperbranched polyure in their entirety. thane can advantageously take place at elevated temperature, 0191) A suitable procedure for the preparation of hyper preferably in the range between 30 and 80°C., without prior branched polyamides starts out from polyfunctional amines isolation of the AB molecule in an additional reaction step. and polycarboxylic acids, use being made of at least one On using the AB molecule with two OH groups and one polyfunctional compound exhibiting three or more than three NCO group described, a hyperbranched polymer is produced (e.g. 4, 5, 6, and the like) functional groups. Formally, in this which, per molecule, exhibits one free NCO group and, procedure, a first class of monomers with two identical func depending on the degree of polymerization, a more or less tional groups A (e.g., a dicarboxylic acid or a diamine) is large number of OH groups. The reaction can be carried out then reacted with a second class of monomers B, this second up to high conversions, through which very high molecular class comprising at least one compound with more than equal weight structures are obtained. However, it can also, for functional groups (e.g., at least one tricarboxylic acid (n-3) or example, be terminated by addition of suitable monofunc a higher than trivalent carboxylic acid or at least one triamine tional compounds or by addition of one of the starting com (n-3) or a higher than trivalent amine). Preferably, the second pounds for the preparation of the AB molecule on reaching class of monomers comprises at least one divalent monomer the desired molecular weight. Depending on the starting com B which exhibits two functional groups complementary to pound used for the termination, either completely NCO-ter the monomers A. Preferably, the monomers B, exhibit a minated or completely OH-terminated molecules are pro mean functionality of at least 2.1 (n=2.1). Preferably, for the duced. preparation of hyperbranched polyamides according to this 0184 Alternatively, an AB molecule can also be pre alternative form, the monomers A are used in a molar excess pared, for example, from 1 mol of glycerol and 2 mol of with regard to the monomers B. Preferably, the molar ratio of 2,4-TDI. At low temperature, the primary alcohol groups and monomers A to monomers B, lies in a range from 1:1 to 20:1, the isocyanate group in the 4-position preferably react and an particularly preferably of 1.1:1 to 10:1, in particular 1.2:1 to adduct is formed which exhibits one OH group and two 5:1. In a preferred embodiment, a hyperbranched prepolymer US 2011/O 105333 A1 May 5, 2011

with terminal groups A is first prepared and is further reacted 1.9-diaminononane, 1,10-diaminodecane, 1,11-diaminoun Subsequently with at least one monomer B and/or B. To decane, 1,12-diaminododecane, N-alkylethylenediamine, prepare the prepolymer, use is preferably made of monomers such as N-methylethylenediamine and N-ethylethylenedi A and monomers B, in a molar ratio of 1:1 to 20:1, particu amine, N,N'-dialkylethylenediamine, such as N,N'-dimeth larly preferably of 1.1:1 to 10:1, especially 1.2:1 to 5:1. ylethylenediamine, N-alkylhexamethylenediamine, such as 0.192 An additional suitable procedure for the preparation N-methylhexamethylenediamine, piperazine, bis(4-ami of hyperbranched polyamides starts out from polyfunctional nocyclohexyl)methane, phenylenediamine, isophoronedi aminocarboxylic acids, use being made of at least one poly amine, bis(2-aminoethyl)ether, 1.2-bis(2-aminoethoxy) functional compound exhibiting three or more than three ethane and amine-terminated polyoxyalkylenepolyols (e.g., 4, 5, 6 and the like) functional groups, i.e. what is (“Jeffamines' or C,c)-diaminopolyethers), which can be pre referred to as an AB monomer (X is greater than or equal to pared, e.g., by amination of polyalkylene oxides with ammo 2). These can then be reacted with additional monomers AB, 18. A and/or B. 0200 Suitable triamines are, e.g. bis(2-aminoethyl)amine 0193 Suitable dicarboxylic acids are, for example, oxalic (diethylenetriamine), N,N'-diethyldiethylenetriamine, bis acid, malonic acid, Succinic acid, glutaric acid, adipic acid, (3-aminopropyl)amine, bis(6-aminohexyl)amine, 4-ami pimelic acid, Suberic acid, azelaic acid, sebacic acid, unde nomethyl-1,8-octamethylenediamine, N'-(3-aminopropyl)- cane-O.()-dicarboxylic acid, dodecane-O.co-dicarboxylic N,N-dimethyl-1,3-propanediamine, melamine, and the like. acid, cis- and transcyclohexane-1,2-dicarboxylic acid, cis 0201 Suitable amines of higher valency are N,N'-bis(2- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans aminoethyl)ethylenediamine (triethylenetetramine), N,N'- cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopen bis(2-aminoethyl)-1,3-diaminopropane, N,N'-bis(3-amino tane-1,2-dicarboxylic acid, cis- and trans-cyclopentane-1,3- propyl)-1,4-diaminobutane (spermine), N,N'-bis(2- dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic aminoethyl)piperazine, N,N'-bis(3-aminopropyl) acid and mixtures thereof. piperazine, tris(2-aminoethyl)amine, tris(3-aminopropyl) 0194 The abovementioned dicarboxylic acids can also be amine, tris(6-aminohexyl)amine, and the like. substituted. Suitable substituted dicarboxylic acids can 0202 Polymeric polyamines are also suitable. These gen exhibit one or more residues preferably chosen from alkyl, erally exhibit a number-average molecular weight of approxi cycloalkyl and aryl as defined at the start. Suitable substituted mately 400 to 10 000, preferably approximately 500 to 8000. dicarboxylic acids are, for example, 2-methylmalonic acid, These include, e.g., polyamine with terminal primary or sec 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuc ondary amino groups, polyalkyleneimines, preferably poly cinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, ita ethyleneimines, vinylamides obtained by hydrolysis of poly conic acid, 3.3-dimethylglutaric acid, and the like. N-Vinylamides, such as, e.g., poly-N-vinylacetamide, the 0.195 The dicarboxylic acids can be used either as such or abovementioned C. ()-diamines based on aminated polyalky in the form of derivatives. Suitable derivatives are anhydrides lene oxides, and copolymers comprising, copolymerized, and their oligomers and polymers, mono- and diesters, pref a(3-ethylenically unsaturated monomers with appropriate erably mono- and dialkyl esters, and acid halides, preferably functional groups, e.g. aminomethyl acrylate, aminoethyl chlorides. Suitable esters are mono- or dimethyl esters, acrylate, (N-methyl)aminoethyl acrylate, (N-methyl)amino mono- or diethyl esters, and mono- and diesters of higher ethyl methacrylate, and the like. alcohols, such as, for example, n-propanol, isopropanol, 0203 The above-described hyperbranched polyamides n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, can generally already be used as in the compositions of the and the like, also mono- and divinyl esters and mixed esters, present invention. In an additional embodiment, the above preferably methyl ethyl ester. described hyperbranched polyamides are additionally also 0196. In the context of the present invention, it is also Subjected to a polymer-analogous reaction, as is described possible to use a mixture of a dicarboxylic acid and one or Subsequently. Suitable for this are, for example, monocar more of its derivatives. Likewise, it is, in the context of the boxylic acids, monoamines, mono- or polyols, and also present invention, possible to use a mixture of several differ mono- and polycarboxylic acids, aminocarboxylic acids, ent derivatives of one or more dicarboxylic acids. mono- and polyamines, and mono- and polyols with special 0197) Use is made particularly preferably of succinic acid, functional groups for the modification of the properties of the glutaric acid, adipic acid, phthalic acid, isophthalic acid, hyperbranched polyamides. terephthalic acid or their mono- or dimethyl esters. Use is 0204 The preparation of the hyperbranched polyamides made very particularly preferably of adipic acid. can be carried out in the presence of a conventional catalyst. 0198 Suitable polyfunctional amines for the preparation These include, e.g., metal oxides and carbonates, strong of hyperbranched polyamides exhibit 2 or more than 2 (e.g. 3, acids, terephthalates, titanium halides, alkoxides and car 4, 5, 6, and the like) primary or secondary amino groups boxylates, and the like. Suitable catalysts are disclosed, for capable of amide formation. example, in U.S. Pat. No. 2,244,192, U.S. Pat. No. 2,669,556, 0199 Suitable diamines are straight-chain and branched SU 775 106 and U.S. Pat. No. 3,705,881. Additional suitable aliphatic and cycloaliphatic amines with generally approxi catalysts are mentioned Subsequently with the polyesteram mately 2 to 30, preferably about 2 to 20, carbon atoms. Suit ides. able diamines are, for example, those of the general formula 0205 Hyperbranched polyesteramides and their prepara R" NH R NH-R, in which R" and R represent, tion are disclosed, for instance, in WO 99/16810, EP 1 036 independently of one another, hydrogen, alkyl, cycloalkyl or 106, WO 00/56804 and WO 06/018126, which are incorpo aryl and R represents alkylene, cycloalkylene or arylene. rated herein by reference in their entirety. These include ethylenediamine, 1,2-diaminopropane, 1,3-di 0206 Polyesteramides are very generally polymeric com aminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1.6- pounds exhibiting estergroups and amide groups. Use may be diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, made, to prepare hyperbranched polyesteramides, in prin US 2011/O 105333 A1 May 5, 2011 ciple of at least divalent compounds chosen from polycar 0213 Suitable polyfunctional amines for the preparation boxylic acids, hydroxycarboxylic acids, aminocarboxylic of hyperbranched polyesteramides are those described above acids, aminoalcohols, polyamines, polyols and derivatives of for the preparation of hyperbranched polyamides. Reference the abovementioned compounds. In this connection, first, the may be made in their entirety to the suitable and preferred condition applies that the compounds are chosen in Such a embodiments mentioned therein. way that the polymers obtained exhibit both ester groups and 0214 Suitable polyfunctional alcohols for the preparation amide groups. In this connection, in addition, the condition of hyperbranched polyesteramides exhibit two or more than applies that the compounds are chosen in Such a way that at two (e.g., 3, 4, 5, 6, and the like) hydroxyl groups. In this least one polyfunctional compound is used which exhibits connection, the hydroxyl groups can also be partially or com three or more than three (e.g., 4, 5, 6, and the like) functional pletely replaced by mercapto groups. groups. 0215 Suitable diols are straight-chain and branched ali 0207. A suitable procedure to prepare hyperbranched phatic and cycloaliphatic alcohols with generally approxi polyesteramides starts out from polyfunctional aminoalco mately 2 to 30, preferably approximately 2 to 20, carbon hols and polycarboxylic acids, use being made of at least one atoms. These include 1.2-ethanediol. 1,2-propanediol, 1.3- polyfunctional compound exhibiting three or more than three propanediol. 1.2-butanediol. 1,3-butanediol. 1,4-butanediol. (e.g., 4, 5, 6, and the like) functional groups. 2,3-butanediol. 1.2-pentanediol. 1,3-pentanediol. 1.4-pen 0208. An additional suitable procedure to prepare hyper tanediol. 1.5-pentanediol. 2,3-pentanediol. 2.4-pentanediol branched polyesteramides starts out from polyfunctional 1.2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1.5-hex amines, polyfunctional alcohols and polycarboxylic acids, anediol, 1.6-hexanediol. 2.5-hexanediol. 1.2-heptanediol. use being made of at least one polyfunctional compound 1,7-heptanediol. 1.2-octanediol. 1.8-Octanediol. 1.2- exhibiting three or more than three (e.g., 4, 5, 6, and the like) nonanediol, 1.9-nonanediol. 1.2-decanediol. 1,10-de functional groups. canediol. 1,12-dodecanediol, 2-methyl-1,3-propanediol. 0209 Suitable polyfunctional aminoalcohols for the 2-methyl-2-butyl-1,3-propanediol. 2,2-dimethyl-1,3-pro preparation of hyperbranched polyesteramides exhibit two or panediol. 2,2-dimethyl-1,4-butanediol, pinacol, 2-ethyl-2- more than two (e.g., 3, 4, 5, 6, and the like) functional groups butyl-1,3-propanediol, diethylene glycol, triethylene glycol, chosen from hydroxyl groups and primary and secondary dipropylene glycol, tripropylene glycol, polyalkylene gly amino groups. As defined, aminoalcohols in this connection cols, cyclopentanediols, cyclohexanediols, and the like. always exhibit at least one hydroxyl group and at least one 0216 Suitable triols are, e.g., glycerol, butane-1,2,4-triol, primary or secondary amino group. Suitable aminoalcohols n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6- are straight-chain and branched aliphatic and cycloaliphatic triol, n-hexane-1,2,5-triol, trimethylolpropane and trimethy aminoalcohols with generally 2 to 30, preferably 2 to 20, lolbutane. Suitable triols are furthermore the triesters of carbon atoms. hydroxycarboxylic acids with trivalent alcohols. Preferably, 0210 Suitable divalent aminoalcohols are, e.g., 2-amino in this connection, they are triglycerides of hydroxycarboxy ethanol (monoethanolamine), 3-amino-1-propanol, lic acids, such as, e.g., lactic acid, hydroxyStearic acid and 2-amino-1-propanol, 1-amino-2-propanol, 2-amino-3-phe ricinoleic acid. Naturally occurring mixtures comprising nylpropanol, 2-amino-2-methyl-1-propanol, 2-amino-1-bu hydroxycarboxylic acid triglycerides, in particular castor oil, tanol, 4-amino-1-butanol, 2-aminoisobutanol, 2-amino-3- are also suitable. Suitable polyols of higher Valency are, e.g., methyl-1-butanol, 2-amino-3,3-dimethylbutanol, 1-amino-1- Sugar alcohols and their derivatives, such as erythritol, pen pentanol, 5-amino-1-pentanol, 2-amino-1-pentanol, taerythritol, dipentaerythritol, threitol, inositol and sorbitol. 2-amino-4-methyl-1-pentanol, 2-amino-3-methyl-1-pen Reaction products of the polyols with alkylene oxides, such tanol, 2-aminocyclohexanol, 4-aminocyclohexanol, 3-(ami as ethylene oxide and/or propylene oxide, are also suitable. nomethyl)-3.5.5-trimethylcyclohexanol, 2-amino-1,2-diphe Relatively high molecular weight polyols with a number nylethanol, 2-amino-1,1-diphenylethanol, 2-amino-2- average molecular weight in the range of approximately 400 phenylethanol, 2-amino-1-phenylethanol, 2-(4- to 6000 g/mol, preferably 500 to 4000 g/mol, can also be aminophenyl)ethanol, 2-(2-aminophenyl)ethanol. 1-(3- used. These include, e.g., polyesterols based on aliphatic, aminophenyl)ethanol, 2-amino-1-hexanol, 6-amino-1- cycloaliphatic and/or aromatic di-, tri- and/or polycarboxylic hexanol, 6-amino-2-methyl-2-heptanol, acids with di-, tri- and/or polyols, and also the polyesterols N-methylisopropanolamine, N-ethylisopropanolamine, based on lactone. These furthermore include polyetherols N-methylethanolamine, 1-ethylaminobutan-2-ol. 4-methyl which can be obtained, e.g., by polymerization of cyclic 4-aminopentan-2-ol. 2-(2-aminoethoxy)ethanol, N-(2-hy ethers or by reaction of alkylene oxides with an initiator droxyethyl)piperazine, 1-amino-2-indanol, N-(2-hydroxy molecule. These furthermore also include conventional poly ethyl)aniline, amino Sugars, such as D-glucosamine, carbonates with terminal hydroxyl groups known to a person D-galactosamine, 4-amino-4,6-dideoxy-C-D-glucopyra skilled in the art which can be obtained by reaction of the diols nose, and mixtures thereof. described above or also bisphenols, such as bisphenol A, with 0211 Suitable trivalentaminoalcohols and aminoalcohols phosgene or carbonic diesters. Co-Polyamidols, poly(methyl of higher Valency are, e.g., N-(2-hydroxyethyl)ethylenedi (meth)acrylate) C,c)-diols and/or poly(butyl(meth)acrylate amine, diethanolamine, dipropanolamine, diisopropanola C.co-diols, such as, e.g., MD-1000 and BD-1000 from Gold mine, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol. Schmidt, are also Suitable. and the like. 0217. The preparation of hyperbranched polyesteramides 0212 Suitable polycarboxylic acids for the preparation of can be carried out according to conventional processes known hyperbranched polyesteramides are those described above to a person skilled in the art. In a first embodiment, the for the preparation of hyperbranched polyamides. Reference preparation of hyperbranched polyesteramides is carried out may be made in their entirety to the suitable and preferred in a single-stage one-pot process starting from polyfunctional embodiments mentioned therein. aminoalcohols and dicarboxylic acids, use being made of at US 2011/O 105333 A1 May 5, 2011

least one polyfunctional aminoalcohol exhibiting three or 0221 Suitable acidic catalysts are, e.g., Sulfuric acid, more than three (e.g., 4, 5, 6, and the like) functional groups. phosphoric acid, phosphonic acid, hypophosphorous acid, The molar ratio of dicarboxylic acid to aminoalcohol prefer aluminum sulfate hydrate, alum, acidic silica gel and acidic ably lies in a range of 2:1 to 1.1:1, particularly preferably of alumina. Suitable catalysts are furthermore organoaluminum 1.5:1 to 1.2:1. If, in a suitable embodiment of this single-stage compounds of the general formula Al(OR) and organotita process, only dicarboxylic acids, i.e. monomers of type A, nium compounds of the general formula Ti(OR), the R resi and trifunctional aminoalcohols, i.e. monomers of type B, dues representing, independently of one another, alkyl or are used, it is advisable to interrupt the reaction before the gel cycloalkyl according to the definition given at the start. Pre point is reached. For the definition of the gel point, see Flory, ferred R residues are, for example, chosen from isopropyland Principles of Polymer Chemistry, Cornell University Press, 2-ethylhexyl. 1953, pp. 387-398, which is incorporated herein by reference 0222 Preferred acidic organometallic catalysts are, for in its entirety. The gel point can both be calculated according example, chosen from dialkyltin oxides of the general for to the theory of Flory and determined by monitoring the mula R2SnO, R representing, independently of one another, viscosity of the reaction mixture. It is practicable to interrupt alkyl or cycloalkyl according to the definition given at the the reaction as soon as a rapid rise in the Viscosity is observed. start. These preferably include di-n-butyltin oxide, which can 0218. In a second embodiment, the preparation of hyper be obtained as commercial "Oxo-Tin'. branched polyesteramides is carried out in a two-stage one 0223 Suitable acidic organic catalysts are furthermore pot process. In this connection, in the first stage, a prepolymer acidic organic compounds exhibiting at least one acid group with free carboxylic acid groups is first prepared and this is chosen from phosphoric acid groups, phosphonic acid Subsequently reacted in a second stage with polyfunctional groups, Sulfoxyl groups, Sulfonic acid groups, and the like. compounds exhibiting functional groups capable of ester or p-Toluenesulfonic acid is preferred, for example. Suitable amide formation. In a suitable embodiment, the carboxylic catalysts are furthermore acidic ion-exchange materials, for acids A and aminoalcohols B are used for the preparation of example polystyrene resins modified with Sulfonic acid the prepolymers in the first stage. The molar ratio of dicar groups, which are crosslinked in the usual way, e.g. with boxylic acid to aminoalcohol preferably lies in a range of 2:1 divinylbenzene. to 10:1, particularly preferably of 2.5:1 to 5:1 and especially 0224 Hyperbranched polyamines and their preparation 2.7:1 to 4:1. In this procedure, the gelling of the reaction are disclosed, for instance, in: U. Steuerle, R. Feuerhake, mixture can generally easily be avoided, even at high reaction “AZiridines, Ullmann's Encyclopedia of Industrial Chemis rates. Use may be made, for the further reaction of the pre try, Wiley-VCH and in: G. Scherr, U. Steuerle, R. polymers in the second stage, of the abovementioned poly Fikentscher, “Imines, Cyclic”. Kirk-Othmer Encyclopedia of functional amines, aminoalcohols and polyamines, if appro Chemical Technology, Wiley and Sons, 2004-2007, which is priate in combination with additional polycarboxylic acids. incorporated herein by reference in its entirety. Reference is made, for suitable and preferred embodiments of these compounds, to what was said above. Preferably, in the 0225 Hyperbranched polyetheramines and their prepara second reaction stage, use is predominantly or exclusively tion are disclosed, for instance, in DE 10331770.8, which is made of divalent compounds in accordance with a chain incorporated herein by reference in its entirety. lengthening. 0226 Polyetheramines (also referred to as polyetheram 0219 Comparable polymers to those obtained after the ine polyols) will be typically obtained from trialkanolamines, two-stage one-pot process can also be obtained if the hyper e.g. triethanolamine, tripropanolamine, triisopropanolamine, branched polyesteramides obtained after the single-stage optionally as a mixture with mono- or dialkanolamines, by one-pot process described above are Subjected to a Subse catalytic etherification, for example acid or basic catalysis, quent modification in accordance with a polymer-analogous under elimination of water. reaction, it being possible for the above-mentioned polyfunc 0227 Preparation of these polymers is described, for tional amines, alcohols, aminoalcohols and carboxylic acids example, in U.S. Pat. No. 2,178,173, U.S. Pat. No. 2.290,415, then to be used for this polymer-analogous reaction. A poly U.S. Pat. No. 2,407,895 and DE 4003 243, which are incor mer-analogous reaction, both of the hyperbranched polyes porated herein by reference in their entirety. The polymeriza teramides obtained after the single-stage process and of the tion process can be carried out statistically, or alternatively hyperbranched polyesteramides obtained after the two-stage block-like structures from single alkanolamines may be pre process, with monofunctional compounds, e.g. monoalco pared, which will be linked with each other in a further step. hols, monoamines and monocarboxylic acids, as described See also U.S. Pat. No. 4,404,362, which is incorporated more specifically below, is naturally also possible. These herein by reference in its entirety. monofunctional compounds can exhibit additional functional 0228. The starting material may be triethanolamine, groups for additional modification of the polymer properties. tripropanolamine, triisopropanolamine or tributanolamine, Suitable stoppers are, for example, fatty acids, fatty acid optionally in combination with dialkanolamines like dietha derivatives, such as anhydrides and esters, fatty alcohols, nolamine, dipropanolamine, diisopropanolamine, dibutano acids and acid derivatives, which exhibit additional func lamine, N.N"-dihydroxyalkylpiperidine (alkyl-C-C), or in tional groups, and alcohols and amines, which exhibit addi combination with di- or higher functional polyetheroles tional functional groups. based on ethylenoxide and/or propylenoxide. The use of tri 0220. The esterification and amidation reaction for the ethanolamine and triisopropanolamine or a mixture thereofas preparation of hyperbranched polyesteramides, as well as the starting material is preferred. amidation reaction for the preparation of hyperbranched 0229. After the reaction, thus without further modifica polyamides, can be carried out in the presence of at least one tion, the hyperbranched polyetheramine polyols formed in catalyst. Suitable catalysts are, for example, acidic catalysts, the process described above are hydroxyl group terminated. organometallic catalysts, enzymes, and the like. They are well soluble in various solvents. US 2011/O 105333 A1 May 5, 2011

0230. Examples of such solvents include aromatic and/or 0240. It is further possible to stop the reaction by diluting (cyclo)aliphatic hydrocarbons and mixtures thereof, haloge with a precooled solvent. This is especially preferred if the nated hydrocarbons, ketones, esters and ethers. viscosity of the reaction mixture has to be adjusted by addi 0231. The preparation of the polyetheramine polyols is tion of a solvent. carried out in the absence of a solvent or in solution. Solvents 0241 Preparation of the polyetheramine polyols is usually to be considered have been mentioned above. In a preferred made at pressures from 0.1 mbar to 20 bar, preferably from 1 embodiment the reaction will be carried out in the absence of mbar to 5 bar, in reactors or reactor cascades using batch, a solvent. semi-batch or continuous processes. 0242. Due to the above-mentioned setting of reaction con 0232. The temperature during preparation should be high ditions and selection of a suitable solvent, if necessary, the enough to allow the aminoalkanol to react. Typically a tem products of the present invention can be processed after perature range of 100-350° C., preferably 150-300° C., more preparation without further purification. preferably 180-280° C. and particular 200-250° C. will be 0243 The reaction mixture may be subjected to a deco needed. lourisation, if necessary, Such as treatment with charcoal or 0233. In a preferred embodiment the condensation reac metal oxides, e.g. aluminium oxide, silicon oxide, magne tion is carried out in the absence of a solvent. Water or low sium oxide, Zirconium oxide, boron oxide or mixtures molecular reaction products formed during the reaction may thereof, in an amount of for example, 0.1 to 50% by weight, be removed, for instance by distillation, if appropriate under preferably 0.5 to 25% by weight, more preferably 1 to 10% by reduced pressure, to increase the speed of the reaction. weight, at temperatures from, for example, 10 to 100° C. 0234. The separation of water or low-molecular reaction preferably from 20 to 80° C. and more preferably from 30 to products may be promoted by passing through (stripping) a 60° C. 0244. The reaction mixture also may be filtered to remove stream of a gas that is Substantially inert under the reaction precipitates, if necessary. conditions, e.g. nitrogen, or a noble gas, e.g. helium, neon or 0245. In another preferred embodiment the product will be argon. Catalysts or mixtures of catalysts may be added to stripped, i.e., low-molecular volatile compounds are increase the speed of the reaction. Suitable catalysts are com removed. For that purpose the catalyst optionally may be pounds that catalyse etherification and reetherification reac deactivated after the desired degree of conversion has been tions, for example alkali metal hydroxides, alkali metal car achieved, and the low-molecular volatile components, e.g. bonates, alkali metal bicarbonates, preferably sodium water, the aminoalkanols used as starting material, or volatile bicarbonate, potassium bicarbonate or cesium bicarbonate, oligomeric or cyclic compounds may be removed by distilla acidic compounds, like iron chloride or Zinc chloride, formic tion, optionally with introduction of a gas, preferably nitro acid, oxalic acid, or phosphorus-containing acidic com gen or noble gases, under reduced pressure, if necessary. pounds, like phosphoric acid, polyphosphoric acid, phospho 0246. After the reaction, thus without further modifica nic acid or phosphinic acid. It is preferred to use phosphoric tion, the hyperbranched polyetheramines prepared according acid, phosphonic acid or phosphinic acid, optionally diluted to the method are hydroxyl group terminated. They are well with water. soluble in various solvents, e.g. in water, alcohols, like metha 0235. The addition of the catalyst is generally effected in nol, ethanol, butanol, mixtures of alcohol/water, acetone, an amount of from 0.001 to 10, preferably from 0.005 to 7, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl more preferably from 0.01 to 5 mole percent, based on the acetate, methoxyethyl acetate, tetrahydrofuran, dimethyl for amount of the alkanolamine or alkanolamine mixture used. mamide, dimethyl acetamide, N-methylpyrrolidone, ethyl 0236. It is furthermore possible to carry out the intramo ene carbonate or propylene carbonate. lecular polycondensation reaction as well by addition of a 0247. Hyperbranched polyesteramines and their prepara Suitable catalyst as by selecting an appropriate temperature. It tion are disclosed, for instance, in DE 10331770, which is is also possible to adjust the average molecular mass of the incorporated herein by reference in its entirety. 0248. In the context of the present invention, the expres polymer by carrying out the composition of the starting com sion “polyesteramines' describes very generally polymeric ponents and the retention time. compounds exhibiting ester groups and amino groups in the 0237. The polymers, which are prepared at elevated tem chain, amino groups not being part of an amide group. In perature, are usually stable at room temperature over a longer principle, at least divalent compounds exhibiting one amino period, e.g. at least for 6 weeks, without showing clouding, group, preferably no longer available for a Subsequent reac precipitation and/or rise in Viscosity. tion, and at least two additional functional groups, capable of 0238. There are several ways to terminate the intramolecu an addition or condensation reaction, can be used for the lar polycondensation reaction. The temperature may be, for preparation of hyperbranched polyesteramines. These example, reduced to a range that stops the reaction and gives include, for example, N-alkyl-N-(hydroxyalkyl)aminoalkan a storage-stable polycondensation product. That typically ecarboxylic acids and carboxylic acid derivatives, N,N-di happens at a temperature lower than 60°C., preferably lower (hydroxyalkyl)anninoalkanecarboxylic acids and carboxylic than 50° C., more preferably lower than 40° C. and in par acid derivatives, N-alkyl-N-(aminoalkyl)aminoalkanecar ticular at room temperature. boxylic acids and carboxylic acid derivatives, N,N-di(ami 0239 Furthermore the catalyst may be desactivated, in the noalkyl)aminoalkanecarboxylic acids and carboxylic acid case of basic catalysts for example by adding of an acid derivatives, and the like. In addition to these monomers, the component, such as a lewis acid or an organic or inorganic hyperbranched polyesteramines used according to the inven proton acid, as well as by adding of a basic component in the tion can comprise additional polyfunctional compounds case of an acidic catalyst, for instance a lewis base or an incorporated exhibiting two or more than two (e.g., 3, 4, 5, 6, organic or inorganic base. and the like) functional groups. These include the above US 2011/O 105333 A1 May 5, 2011

described polycarboxylic acids, polyfunctional amines, poly 0257 The reaction according to the Michael addition type functional alcohols and polyfunctional aminoalcohols, refer is preferably carried out in bulk or in a solvent which is inert ence to which is made here in their entirety. under the reaction conditions. Suitable solvents are, e.g., high 0249. The preparation of hyperbranched polyesteramines boiling alcohols, such as glycerol, aromatic hydrocarbons, is preferably carried out with the use of AB, and/or AB Such as benzene, toluene, Xylene, and the like. The reaction is monomers which can be obtained by a reaction according to preferably carried out at a temperature in the range of 0 to the Michael addition type. 100° C., particularly preferably 5 to 80° C. and especially 10 (0250. In a first embodiment for the preparation of an AB to 70°C. The reaction is preferably carried out in the presence monomer by Michael addition, an aminoalcohol exhibiting a ofaninert gas, Such as nitrogen, helium or argon, and/or in the secondary amino group and two hydroxyl groups is reacted presence of a radical inhibitor. General procedures for the with a compound with an activated double bond, e.g. a viny addition of aminoalcohols to activated double bonds are logous carbonyl compound. known to a person skilled in the art. In a preferred embodi 0251 Suitable aminoalcohols exhibiting a secondary ment, the preparation of the monomers by Michael addition amino group and two hydroxyl groups are, e.g., diethanola and their Subsequent reaction in a polycondensation are car mine, dipropanolamine, diisopropanolamine, 2-amino-1,3- ried out in the form of a one-pot reaction. propanediol, 3-amino-1,2-propanediol, diisobutanolamine, 0258. The preparation of the hyperbranched polyesteram ines from the abovementioned or from other AB monomers dicyclohexanolamine, and the like. is carried out according to conventional processes known to a 0252 Suitable compounds with an activated double bond person skilled in the art. In a suitable procedure, the prepara are preferably chosen from esters of C.B-ethylenically unsat tion of suitable polyesteramines according to the invention is urated mono- and dicarboxylic acids with monovalent alco carried out with the use of the above-described AB mono hols. The C.f3-ethylenically unsaturated mono- and dicar mers which can be obtained by Michael addition. These can boxylic acids are preferably chosen from acrylic acid, additionally be reacted in the presence of additional poly methacrylic acid, fumaric acid, maleic acid, itaconic acid, functional monomers. Suitable polyfunctional monomers are crotonic acid, maleic anhydride, monobutyl maleate and mix the polyfunctional aminoalcohols, polyfunctional amines, tures thereof. Preferably, acrylic acid, methacrylic acid and polyfunctional alcohols and polycarboxylic acids mentioned their mixtures are used as acid component. Preferred vinylo above in the preparation of the hyperbranched polyesteram gous compounds are methyl (meth)acrylate, methyl ethacry lates, ethyl (meth)acrylate, ethyl ethacrylate, n-butyl (meth) ides, reference to which is made here in their entirety. If acrylate, tert-butyl (meth)acrylate, tert-butyl ethacrylate, desired, hydroxycarboxylic acids can additionally be used as n-octyl (meth)acrylate, 1,1,3,3-tetramethylbutyl (meth)acry chain extenders. These include, for example, lactic acid, gly late, ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, colic acid, and the like. n-decyl (meth)acrylate, n-undecyl (meth)acrylate, tridecyl 0259. In a suitable embodiment, the preparation of hyper (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth) branched polyesteramines is carried out in the presence of an acrylate, palmityl (meth)acrylate, heptadecyl(meth)acrylate, AB monomer. This is preferably chosen from 2-amino-2- nonadecyl (meth)acrylate, arachidyl (meth)acrylate, behenyl ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol. (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acry 1-amino-2,3-propanediol, 2-amino-1,3-propanediol or late, n-myricyl (meth)acrylate, palmitoleyl (meth)acrylate, 2-amino-1-phenyl-1,3-propanediol. oleyl (meth)acrylate, linoleyl (meth)acrylate, linolenyl 0260. In an additional suitable embodiment, the prepara (meth)acrylate, Stearyl (meth)acrylate, lauryl (meth)acrylate tion of the hyperbranched polyesteramines is carried out in the presence of a “core molecule'. Suitable core molecules and mixtures thereof. Methyl acrylate and n-butyl acrylate are are, for example, trimethyloipropane, pentaerythritol, particularly preferred. alkoxylated polyols, such as ethoxylated trimethyloipropane, 0253) In a second embodiment for the preparation of an ethoxylated glycerol, propoxylated trimethylolpropane or AB monomer by Michael addition, an aminoalcohol exhib propoxylated glycerol, polyamines, such as tris(2-aminoet iting a primary amino group and a hydroxyl group is reacted hyl)amine, ethylenediamine or hexamethylenediamine, with a compound with an activated double bond. diethanolamine, diisopropanolamine, and the like. The addi 0254 Suitable aminoalcohols exhibiting a primary amino tion of the core-forming monomers can be carried out at the group and a hydroxyl group are the divalent aminoalcohols beginning or in the course of the reaction. mentioned above for the preparation of hyperbranched poly 0261. In an additional suitable embodiment, the prepara esteramides, reference to which is made here in their entirety. tion of the hyperbranched polyesteramines is carried out with Suitable compounds with activated double bond are those the use of an aromatic AB2 monomer. Suitable aromatic AB mentioned above in the first embodiment for the preparation monomers are, e.g., amidol, aminobenzyl alcohol, 2-amino of an AB monomer by Michael addition. 5-chlorobenzyl alcohol, 2-amino-9-fluorenol, and the like. 0255. In a third embodiment for the preparation of an AB 0262 The polycondensation reaction for the preparation monomer by Michael addition, an aminoalcohol exhibiting a of hyperbranched polyesteramines can be carried out in the primary amino group, a secondary amino group and a presence of a catalyst. Suitable catalysts are the catalysts hydroxyl group is reacted with a compound with three acti described above for the preparation of the hyperbranched vated double bonds. polyesteramides, reference to which is made here in their 0256 A suitable aminoalcohol exhibiting a primary amino entirety. Enzymes, such as lipases or esterases, are also Suit group, a secondary amino group and a hydroxyl group is able catalysts. Suitable lipases or esterases can be obtained hydroxyethylethylenediamine. Suitable compounds with from Candida cylindracea, Candida lipolytica, Candida rug activated double bonds are those mentioned above in the first Osa, Candida antartica, Candida utilis, Chronobacterium embodiment for the preparation of an AB monomer by viscosum, Geotrichum viscosum, Geotrichum candidum, Michael addition. Mucor javanicus, Mucor mihei, pig pancreas, Pseudomonas US 2011/O 105333 A1 May 5, 2011 20 spp., Pseudomonas fluorescens, Pseudomonas cepacia, The essentially primary, straight-chain and even-numbered Rhizopus arrhizus, Rhizopus deleimar, Rhizopus niveus, Ziegler alcohols obtainable by organoaluminum synthesis are Rhizopus Oryzae, Aspergillus niger; Penicillium roquefortii, furthermore suitable. Penicillium camembertii, esterases from Bacillus spp. and 0269 Suitable monovalent alcohols for the polymer Bacillus thermoglucosidasius. Preferred enzymes are Can analogous reaction are, e.g., monofunctional alcohols, such dida antarticalipases B and particularly preferably immobi as, e.g., octanol, nonanol, decanol, undecanol, dodecanol, lized Candida antartica lipases B, as can be obtained com tridecanol, tetradecanol, pentadecanol, hexadecanol, hepta mercially from Novozymes Biotech Inc. under the decanol, octadecanol, and the like, and mixtures thereof. designation Novozyme 435. 0270. According to a preferred embodiment, the hyper 0263 Advantageously, with enzymatic catalysis, the reac branched polymer comprises hydrophobic moieties and is tion is possible at low temperatures in a range of approxi obtainable by mately 40 to 90° C., preferably 60 to 70° C. Preferably, the 0271 a) either reacting at least one dicarboxylic acid (A) enzymatic reaction is carried out in the presence of an inert having at least one polyisobutylene group or a derivative gas, Such as carbon dioxide, nitrogen, argon or helium. thereof, if appropriate in a mixture with a further dicar 0264. According to a preferred embodiment of the present boxylic acid (D) or a derivative thereof, with at least one invention, the hyperbranched polymers comprise hydropho aliphatic or aromatic compound (C) which has at least 3 bic moieties. identical or different groups reactive toward acid groups or 0265 Hydrophobic moieties include in particular long derivatives thereof, chain aliphatic hydrocarbon radicals such as long-chain alkyl 0272 or or alkenyl radicals, aromatic hydrocarbon radicals or 0273 b) reacting at least one dicarboxylic acid (A) hav araliphatic hydrocarbon radicals. These can be incorporated ing at least one polyisobutylene group or a derivative into the hyperbranched polymers during their synthesis by thereof, if appropriate in a mixture with a further dicar using suitable reactants, or Subsequent to the synthesis of the boxylic acid (D) or derivatives thereof, with at least one hyperbranchend skeleton, e.g. in a polymer-analogous reac aliphatic or aromatic compound (B) which has 2 identical tion. or different groups reactive toward acid groups or deriva 0266 For instance, long chain aliphatic carboxylic acids tives thereof, and at least one aliphatic or aromatic com Such as octanoic acid, decanoic acid, dodecanoic acid and pound (C) which has more than two identical or different tetraundecanoic acid; fatty acids Such as Stearic acid, oleic groups reactive toward acid groups or derivatives thereof, acid, lauric acid, palmitic acid, linolic acid and linolenic acid; with elimination of water or alcohols ROH where R' is a aromatic carboxylic acids Such as phthalic acid, isophthalic straight-chain or branched, aliphatic, cycloaliphatic, acid, terephthalic acid and trimellitic acid; cycloaliphatic car araliphatic or aromatic hydrocarbon radical having from 1 boxylic acids such as cyclohexane dicarboxylic acid; dicar to 20 carbon atoms, and X is greater than 2, preferably boxylic acids such as octanedioic acid, decanedioic acid, between 3 and 8, dodecanedioic acid, tetradecanedioic acid and dimeric fatty 0274 or acids are Suitable for preparing hyperbranched polymers hav 0275 c) reacting at least one aliphatic or aromatic com ing hydrophobic moieties. Likewise aliphatic alcohols such pound (B) which has two identical or different groups as octanols, decanols, dodecanols and tetradecanols; fatty reactive toward acid groups or a derivative thereof with at alcohols such as Stearyl alcohol and oleyl alcohol; unsatur least one dicarboxylic acid (A) having polyisobutylene ated alcohols such as allyl alcohol and crotyl alcohol; aro groups or a derivative thereof, if appropriate in a mixture matic alcohols such as benzyl alcohol; cycloaliphatic alco with a further dicarboxylic acid (D) or a derivative thereof, hols such as cyclohexanol; mono fatty acidgylcerides such as and at least one aliphatic or aromatic carboxylic acid (D) glyceryl monostearate, glyceryl monooleate and glyceryl or a derivative thereof which has more than two acid monopalmitate are Suitable for preparing hyperbranched groups, with elimination of water or alcohols ROH where polymers having hydrophobic moieties. R" is a straight-chain or branched, aliphatic, cycloaliphatic, 0267 Suitable hydrophobic groups for a polymer-analo araliphatic or aromatic hydrocarbon radical having from 1 gous reaction are preferably chosen from Saturated or unsat to 20 carbon atoms, and y is greater than 2, preferably urated hydrocarbon residues with 8 to 40, preferably 9 to 35, between 3 and 8, in particular 10 to 30, carbon atoms. They are preferably the ratio of the reactive partners in the reaction mixture being alkyl, alkenyl, cycloalkyl or aryl residues. The cycloalkyl or selected so as to establish a molar ratio of molecules having aryl residues can exhibit 1, 2 or 3 substituents, preferably groups reactive toward acid groups to molecules having acid alkyl or alkenyl substituents. groups of from 2:1 to 1:2, preferably from 1.5:1 to 1:2, more 0268 For instance, for the polymer-analogous reaction, preferably from 0.9:1 to 1:1.5 and most preferably of 1:1. monovalent alcohols exhibiting one of the hydrophobic moi (0276. The compounds (A) are compounds which have at eties mentioned herein can be used. Such alcohols and alco least one, preferably exactly one, polyisobutenegroup and at hol mixtures can, e.g., be obtained by hydrogenation of fatty least two, preferably exactly two, carboxylic acid groups or acids from natural fats and oils or of synthetic fatty acids, e.g. derivatives thereof. from the catalytic oxidation of paraffins. Suitable alcohols 0277 Reaction products of an ene reaction between poly and alcohol mixtures can furthermore be obtained by hydro isobutene and fumaryl chloride, fumaric acid, itaconic acid, formylation of olefins with simultaneous hydrogenation of itaconyl chloride, maleyl chloride, maleic anhydride and/or the aldehydes, generally resulting in mixtures of straight maleic acid, and/or the esters of the acids, are preferred. chain and branched primary alcohols (oxo alcohols). Suitable 0278. In a preferred embodiment, they are 1: 1 (mol/mol) alcohols and alcohol mixtures can furthermore be obtained by reaction products of an ene reaction between a polyisobutene partial oxidation of n-paraffins according to known pro and fumaryl chloride, fumaric acid, itaconic acid, itaconyl cesses, producing predominantly linear secondary alcohols. chloride, maleyl chloride, maleic anhydride and/or maleic US 2011/O 105333 A1 May 5, 2011 acid, and/or the esters of the acids, preferably with maleic 10295) Compounds (D) have more than two carboxyl anhydride or of maleyl chloride, more preferably with maleic groups or derivatives thereof, preferably from 3 to 8, more anhydride. preferably from 3 to 6. These compounds may be aliphatic, 0279. The polyisobutenes are preferably those which have cycloaliphatic, araliphatic or aromatic and have preferably up end groups formed from vinyl isomer and/or vinylidene iso to 20 carbon atoms, more preferably up to 12 carbon atoms. mer to an extent of at least 60 mol%. 0296 Convertible tricarboxylic acids or polycarboxylic 0280. The number-average molar mass M, of the com acids (D) are, for example, aconitic acid, 1,3,5-cyclohexan pounds (A) is preferably at least 100 g/mol, more preferably etricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5- at least 800 g/mol. In general, the number-average molar benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic mass Mn of the compounds (A) is up to 5000 g/mol, more acid (pyromellitic acid) and mellitic acid, and low molecular preferably up to 2000 g/mol. weight polyacrylic acids, for example up to a molar mass up 0281. In a particularly preferred embodiment, the com to 2000 g/mol, preferably up to 1000 g/mol and more prefer pounds (A) have a number-average molar mass M, of ably up to 500 g/mol. 1000+/-500 g/mol. (0297 Tricarboxylic acids or polycarboxylic acids (D.) 0282 Dicarboxylic acids (D) have exactly two carboxyl can be used in the reaction either as such or else in the form of groups or derivatives thereof. These compounds may be ali derivatives. phatic, cycloaliphatic, araliphatic or aromatic and have pref 0298 Derivatives are preferably understood to mean erably up to 20 carbonatoms, more preferably up to 12 carbon 0299 the anhydrides in question, in monomeric or else atOmS. polymeric form, (0283) The dicarboxylic acids (D) include, for example, 0300 mono-, di- or trialkyl esters, preferably mono-, di aliphatic dicarboxylic acids Such as oxalic acid, malonic acid, or trimethyl esters or the corresponding mono-, di- or Succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic triethyl esters, but also the mono-, di- and triesters acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, derived from higher alcohols, for example n-propanol, dodecanedicarboxylic acid, cis- and trans-cyclohexane-1,2- isopropanol, n-butanol, isobutanol, tert-butanol, n-pen dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxy tanol, n-hexanol, and also mono-, di- or trivinyl esters, lic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, 0301 and mixed methyl ether esters. cis- and transcyclopentane-1,2-dicarboxylic acid, cis- and 0302. It is also possible to use a mixture of a tri- or poly trans-cyclopentane-1,3-dicarboxylic acid. It is also possible carboxylic acid and one or more of its derivatives, for to use aromatic dicarboxylic acids, for example phthalic acid, example a mixture of pyromellitic acid and pyromellitic dian isophthalic acid or terephthalic acid. Unsaturated dicarboxy hydride. It is equally possible in the context of the present lic acids Such as maleic acid or fumaric acid can also be used. invention to use a mixture of a plurality of different deriva 0284. The dicarboxylic acids mentioned may also be sub tives of one or more tri- or polycarboxylic acids, for example stituted by one or more radicals selected from a mixture of 1,3,5-cyclohexanetricarboxylic acid and pyrom 0285 Examples of representatives of substituted dicar ellitic dianhydride. boxylic acids include: 2-methylmalonic acid, 2-ethylmalonic 0303 Groups reactive toward acid groups or derivatives acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl thereof are preferably hydroxyl ( OH), primary amino Succinic acid, 2-phenylsuccinic acid, itaconic acid, 3.3-dim ( NH), secondary amino ( NHR) or thiol groups ( SH), ethylglutaric acid. more preferably hydroxyl or primary amino groups and most 0286. It is also possible to use mixtures of two or more of preferably a hydroxyl group. the aforementioned dicarboxylic acids. 0304 Secondary amino groups can be substituted by 0287. The dicarboxylic acids can be used either in proto C-Co-alkyl, C-C-cycloalkyl, aralkyl or C-C-aryl as R nated or unprotonated form, preferably in protonated form as radicals. such or in the form of derivatives. 0305 The compounds reactive toward acid groups (B) used according to the present invention are, for example, 0288 Derivatives are preferably understood to mean difunctional alcohols such as ethylene glycol, propane-1,2- 0289 the anhydrides in question, in monomeric or else diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol. polymeric form, butane-1,4-diol, butane-2,3-diol, pentane-1,2-diol, pentane 0290 mono- or dialkyl esters, preferably mono- or dim 1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2,3- ethyl esters or the corresponding mono- or diethyl esters, diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol. but also the mono- and dialkyl esters derived from higher hexane-1,4-diol, hexane-1,5-diol, hexane-1,6-diol, hexane-2, alcohols, for example n-propanol, isopropanol, n-bu 5-diol, heptane-1,2-diol, 1,7-heptanediol, 1,8-octanediol, tanol, isobutanol, tert-butanol, n-pentanol, n-hexanol, 1.2-octanediol, 1.9-nonanediol. 1,2-decanediol. 1,10-de 0291 and also mono- and divinyl esters and canediol. 1.2-dodecanediol. 1,12-dodecanediol. 1.5-hexadi 0292 mixed esters, preferably methyl ether esters. ene-3,4-diol, 1.2- or 1.3-cyclopentanediol, 1.2-, 1.3- or 1,4- 0293. In the context of the present invention, it is also cyclohexanediol. 1.2-, 1.3- or 1,4-bis(hydroxymethyl) possible to use a mixture of a dicarboxylic acid and one or cyclohexane, bis(hydroxyethyl)cyclohexanes, neopentyl more of its derivatives. It is equally possible in the context of glycol, 2-methyl-2,4-pentanediol. 2,4-dimethyl-2,4-pen the present invention to use a mixture of two or more different tanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, derivatives of one or more dicarboxylic acids. 2-propyl-1,3-heptanediol. 2,4-diethyloctane-1,3-diol, 2.5- 0294 Particular preference is given to using malonic acid, dimethyl-2.5-hexanediol. 2,2,4-trimethyl-1,3-pentanediol, Succinic acid, glutaric acid, adipic acid, 1.2-, 1.3- or 1,4- pinacol, diethylene glycol, triethylene glycol, dipropylene cyclohexanedicarboxylic acid (hexahydrophthalic acids), glycol, tripropylene glycol, polyethylene glycols phthalic acid, isophthalic acid, terephthalic acid or their HO(CH2CH2O), H or polypropylene glycols HO(CH mono- or dialkyl esters. CHICH2O), H, where n is an integer and n 4, polytetrahy US 2011/O 105333 A1 May 5, 2011 22 drofurans having a molar mass up to 2000, polycaprolactones 0310. However, preferred compounds (B) do not bear any or mixtures of two or more representatives of the above com further functional groups apart from carboxyl groups or pounds. It is possible for one or even both hydroxyl groups in derivatives thereof. the aforementioned diols to be substituted by SH groups. 0311 Preferred compounds (B) are alcohols or amino Preference is given to ethylene glycol, 1.2-propanediol. 1.3- alcohols, more preferably alcohols. propanediol, 1,4-butanediol. 1.5-pentanediol, 1.6-hex 0312 Compounds (CO have an average of more than 2, anediol. 1.8-octanediol, 1.3- and 1,4-bis(hydroxymethyl)cy preferably from 3 to 8, more preferably from 3 to 6 groups clohexane, and also diethylene glycol, triethylene glycol, reactive toward acid groups and derivatives thereof. dipropylene glycol and tripropylene glycol. 0313 They may be aliphatic, cycloaliphatic, araliphatic or 0306 The compounds (B) used may also be molecules aromatic and have generally not more than 100, preferably having one hydroxyl and one amino group, for example etha not more than 50, more preferably not more than 20 carbon nolamine, 2-aminopropanol, 3-aminopropanol, isopropano atOmS. lamine, 2-, 3- or 4-amino-1-butanol, 6-amino-1-hexanol, 0314. At least trifunctional compounds having groups N-methyl-ethanolamine, 2-(ethylamino)ethanol, 1-(ethy reactive toward acid groups (C) comprise trifunctional or lamino)-2-propanol 2-(butylamino)ethanol, 2-(cyclohexy higher-functionality alcohols such as glycerol, trimethylol lamino)ethanol, 2-amino-2-methyl-1-propanol, 2-(2-amino methane, trimethylolethane, trimethylolpropane, 1,2,4-bu ethoxy)ethanol, 9-amino-3,6-dioxanonan-1-ol O tanetriol, tris(hydroxymethyl) isocyanurate, tris(hydroxy 2-(phenylamino)ethanol. ethyl) isocyanurate (THEIC), pentaerythritol, diglycerol, 0307 The compounds (B) used are also difunctional triglycerol or higher condensation products of glycerol, di(t- amines, for example ethylenediamine, N-alkylethylenedi rimethylolpropane), di(pentaerythritol), inositols, Sorbitol or amine, the propylenediamines (1,2-diaminopropane and 1.3- Sugars, for example glucose, fructose or Sucrose, trifunctional diaminopropane), 2,2-dimethyl-1,3-propylenediamine, or higher-functionality polyetherols based on trifunctional or N-alkylpropylenediamine, piperazine, tetramethylenedi higher-functionality alcohols and ethylene oxide, propylene amine (1,4-diaminobutane), N-alkylbutylenediamine, N,N'- oxide or butylene oxide. Particular preference is given to dimethylethylenediamine, pentanediamine, hexamethylene glycerol, diglycerol, triglycerol, trimethylolethane, trimethy diamine, N-alkylhexamethylenediamine, heptanediamine, lolpropane, 1,2,4-butanetriol, pentaerythritol, and their poly octanediamine, nonanediamine, decanediamine, dode etherols based on ethylene oxide or propylene oxide. canediamine, hexadecanediamine, 1,3-diamino-2,2-diethyl 0315 Preference is given to compounds (B) or (C) com propane, 1,3-bis(methylamino)propane, 1,5-diamino-2-me pounds of the formula (Ia) to (Id), thylpentane, 3-(propylamino)propylamine, N,N'-bis(3- aminopropyl)piperazine, N,N'-bis(3-amino-propyl) piperazine, isophoronediamine (IPDA), tolylenediamine, (Ia) Xylylenediamine, diaminodiphenylmethane, cyclohexylene R7 R8 diamine, bis(aminomethyl)cyclohexane, diaminodiphenyl Sulfone, 2-butyl-2-ethyl-1,5-pentamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylenediamine, 2-aminopro pylcyclohexylamine, 3(4)-aminomethyl-1-methylcyclo H O O H hexylamine, 1,4-diamino-4-methylpentane, amine-termi nated polyoxyalkylene polyols (so-called Jeffamines from (Ib) Huntsmann Corp., Houston, Tex.) or amine-terminated poly tetramethylene glycols. 0308 Examples of such diamines are the so-called Jef famines(R D or ED series. The D series is amino-functional ized polypropylenediols composed of 3-4 1,2-propylene units (Jeffamine(R) D-230, mean molar mass 230), 6-7 1,2- (Ic) propylene units (JeffamineR D-400, mean molar mass 400), an average of approx. 34 12-propylene units (Jeffamine(R) D-2000, mean molar mass 2000) or an average of approx. 69 1,2-propylene units (JeffamineR XTJ-510 (D-4000), mean molar mass 4000). These products may in part also be present in the form of amino alcohols. The ED series is diamines (Id) based on polyethylene oxides which have ideally been pro poxylated on both sides, for example Jeffamine(R). HK-511 (XTJ-511) composed of 2 ethylene oxide and 2 propylene oxide units with a mean molar mass of 220, Jeffamine(R) XTJ-500 (ED-600) composed of 9 ethylene oxide and 3.6 propylene oxide units with a mean molar mass of 600 and Jeffamine(RXTJ-502 (ED-2003) composed of 38.7 ethylene oxide and 6 propylene oxide units with a mean molar mass of where 2OOO. R7 and Rare each independently hydrogen or C-C-alkyl 0309 The compounds (B) may also have further func optionally substituted by aryl, alkyl, aryloxy, alkyloxy, het tional groups, for example carboxyl groups or ester groups. eroatoms and/or heterocycles, Examples of such compounds are dimethylolpropionic acid, k, I, m, q are each independently an integer from 1 to 15, dimethylolbutyric acid or neopentylglycol hydroxypivalate. preferably from 1 to 10 and more preferably from 1 to 7 and US 2011/O 105333 A1 May 5, 2011

each X, for i=1 to k, 1 to 1, 1 to m and 1 to q may each Suitable aromatics are toluene, ortho-Xylene, meta-xylene, independently be selected from the group of CH2—CH2— para-Xylene, Xylene as an isomer mixture, ethylbenzene, O—, —CH2—CH(CH)—O—, —CH(CH)—CH2—O , chlorobenzene and ortho- and meta-dichlorobenzene. Also —CH2—C(CH), O , —C(CH)—CH2—O—, Suitable as solvents are ethers, for example dioxane or tet —CH2—CHVin-O , —CHVin-CH O—, —CH2— rahydrofuran and ketones, for example methyl ethyl ketone CHPh-O- and —CHPh-CH-O-, preferably from the and methyl isobutyl ketone. group of —CH2—CH2—O—, —CH2—CH(CH)—O— 0323. As already detailed above, unconverted poly and —CH(CH)—CH2—O , and more preferably isobutenes may also be present as inert diluents. —CH2—CH2—O—, 0324 Further usable aromatic hydrocarbon mixtures are where Phis phenyl and Vin is vinyl. those which comprise predominantly aromatic C7- to Ca 0316. In these formulae, C-Cls-alkyl optionally substi hydrocarbons and may comprise a boiling range from 110 to tuted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or 300° C., more preferably toluene, o-, m- or p-xylene, trim heterocycles is, for example, methyl, ethyl, propyl, isopropyl. ethylbenzene isomers, tetramethylbenzene isomers, ethyl n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, benzene, cumene, tetrahydronaphthalene and mixtures com 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetrade prising them. cyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimeth 0325 Examples of these are the Solvesso(R) brands from ylbutyl, 1,1,3,3-tetramethylbutyl, preferably methyl, ethyl or ExxonMobil Chemical, particularly Solvesso(R) 100 (CAS n-propyl, most preferably methyl or ethyl. No. 64742-95-6, predominantly C and Caromatics, boiling 0317 Preference is given to one- to thirtyfold and particu range about 154-178°C.), 150 (boiling range about 182-207 lar preference to three- to twentyfold ethoxylated, propoxy C.) and 200(CAS No. 64742-94-5), and the Shellsol R brands lated or mixed ethoxylated and propoxylated and especially from Shell. Hydrocarbon mixtures of paraffins, cycloparaf exclusively ethoxylated neopentyl glycol, trimethylolpro fins and aromatics are also commercially available under the pane, trimethylolethane or pentaerythritol or glycerol. names Kristallól (for example Kristallól 30, boiling range 0318. At least trifunctional compounds having groups about 158-198° C., or Kristallól 60: CAS No. 64742-82-1), reactive toward acid groups (C) further comprise trifunc petroleum spirit (for example likewise CAS No. 64742-82-1) tional or higher-functionality amino alcohols such as tris or Solvent naphtha (light: boiling range about 155-180°C., (hydroxymethyl)amine, tris(hydroxyethyl)amine, tris(hy heavy: boiling range about 225-300° C.). The aromatics con droxypropyl)amine, diethanolamine, dipropanolamine, tent of Such hydrocarbon mixtures is generally more than diisopropanolamine, di-sec-butanolamine, tris(hydroxym 90% by weight, preferably more than 95% by weight, more ethyl)aminomethane, tris(hydroxyethyl)aminomethane, preferably more than 98% by weight and most preferably 3-amino-1,2-propanediol, 1-amino-1-deoxy-D-Sorbitol and more than 99% by weight. It may be sensible to use hydro 2-amino-2-ethyl-1,3-propanediol. carbon mixtures with a particularly reduced content of naph 0319. At least trifunctional compounds having groups thalene. reactive toward acid groups (C) further comprise trifunc 0326. The amount of solvent added is at least 0.1% by tional or higher-functionality amines such as tris(2-aminoet weight based on the mass of the starting materials to be hyl)amine, tris(3-aminopropyl)amine, tris(aminohexyl) converted which are used, preferably at least 1% by weight amine, trisaminohexane, 4-aminomethyl-1.8- and more preferably at least 10% by weight. It is also possible octamethylenediamine, trisaminononane, to use excesses of Solvents based on the mass of starting diethylenetriamine (DETA), dipropylenetriamine, dibutylen materials to be converted which are used, for example from etriamine, dihexylenetriamine, N-(2-aminoethyl)propanedi 1.01- to 10-fold. Amounts of solvent of more than 100 times amine, melamine, triethylenetetramine (TETA), tetraethyl the mass of starting materials to be converted which are used enepentamine (TEPA), isopropylenetriamine, are not advantageous because the reaction rate declines sig dipropylenetriamine and N,N'-bis(3-aminopropylethylenedi nificantly in the case of significantly lower concentrations of amine), oligomeric diaminodiphenylmethanes, N,N'-bis(3- the reactants, which leads to uneconomic long reaction times. aminopropyl)ethylenediamine, N,N'-bis(3-aminopropyl)bu 0327. To carry out this process, it is possible to work in the tanediamine, N.N.N',N'-tetra(3-aminopropyl) presence of a dehydrating agent as an additive, which is added ethylenediamine, N.N.N',N'-tetra(3-aminopropyl) at the start of the reaction. Suitable examples are molecular butylenediamine, trifunctional or higher-functionality sieves, especially 4A molecular sieve, MgSO and NaSO. It amine-terminated polyoxyalkylene polyols (so-called Jef is also possible to add further dehydrating agent during the famines), trifunctional or higher-functionality polyethylene reaction or to replace dehydrating agent with fresh dehydrat imines or trifunctional or higher-functionality polypropyle ing agent. It is also possible to distill off alcohol or water neimines. formed during the reaction and, for example, to use a water 0320 Examples of triamines are Jeffamine(RT-403, a tri separator, in which case the water is removed with the aid of amine based on a trimethylolpropane modified with 5-6 1.2- an azeotroping agent. propylene units, JeffamineR T-5000, a triamine based on a 0328. The process can be carried out in the absence of glycerol modified with approx. 85 12-propylene units, and catalysts. However, when catalysts are employed, preference Jeffamine(RXTJ-509 (T-3000), a triamine based on a glycerol is given to using acidic inorganic, organometallic or organic modified with 501,2-propylene units. catalysts or mixtures of a plurality of acidic inorganic, orga 0321 Preferred compounds (C) are alcohols or amino nometallic or organic catalysts. alcohols, more preferably alcohols. 0329. In the context of the present invention, acidic inor 0322 The process is carried out in substance or in the ganic catalysts are, for example, Sulfuric acid, Sulfates and presence of a solvent. Suitable solvents are, for example, hydrogensulfates, such as Sodium hydrogensulfate, phospho hydrocarbons such as paraffins or aromatics. Particularly ric acid, phosphonic acid, hypophosphorous acid, aluminum Suitable paraffins are n-heptane and cyclohexane. Particularly Sulfate hydrate, alum, acidic silica gel (having a pH in water US 2011/O 105333 A1 May 5, 2011 24 of 56, in particular 55) and acidic alumina. It is also possible, which form the polymer skeleton, terminally or laterally, also for example, to use aluminum compounds of the general at least three, preferably at least six, more preferably at least formula Al(OR), and titanates of the general formula ten functional groups. The functional groups are acid groups Ti(OR), as acidic inorganic catalysts, where the R radicals and/or amino or hydroxyl groups. There is in principle no may each be the same or different and are independently upper limit on the number of terminal or pendant functional selected from butyl, isopropyl or 2-ethylhexyl. Preferred groups, but products with a very high number of functional acidic organometallic catalysts are, for example, selected groups can have undesired properties, for example high vis from dialkyltin oxides RSnO or dialkyltin esters RSn cosity. The hyperbranched polyesters that are useful in the (OR), where R and R* may be selected from C-Co-alkyl present invention usually have not more than 500 terminal or or C-C2-cycloalkyl and may be the same or different. Par pendant functional groups, preferably not more than 100 ticularly preferred representatives of acidic organometallic terminal or pendant functional groups. catalysts are dibutyltin oxide and dibutyltin dilaurate. 0340. In a further preferred embodiment, the inventive 0330 Preferred acidic organic catalysts are acidic organic polymers, in addition to the functional groups already compounds having, for example, phosphate groups, Sulfonic obtained by the reaction, may obtain further functional acid groups, Sulfate groups or phosphonic acid groups. Par groups. The functionalization can be effected during the ticular preference is given to Sulfonic acids, for example molecular weight buildup or else Subsequently, i.e. after the para-toluenesulfonic acid. The acidic organic catalysts used actual polycondensation has ended. may also be acidic ion exchangers, for example Sulfonic 0341 When components which have further functional acid-containing polystyrene resins which have been groups or functional elements in addition to hydroxyl, amino crosslinked with about 2 mol % of divinylbenzene. or carboxyl groups are added before or during the molecular 0331. It is also possible to use combinations of two or weight buildup, a polymer is obtained with randomly distrib more of the aforementioned catalysts. It is also possible to use uted functionalities other than the carboxyl, amino or Such organic or organometallic or else inorganic catalysts hydroxyl groups. which are present in the form of discrete molecules in immo 0342. Such effects can be achieved, for example, by addi bilized form, for example on silica gel or on Zeolites. tion of compounds during the polycondensation which, in 0332. When the use of acidic inorganic, organometallic or addition to hydroxyl groups, primary or secondary amino organic catalysts is desired, from 0.1 to 10% by weight, groups or carboxyl groups, bear further functional groups or preferably from 0.2 to 2% by weight of catalyst is used in functional elements such as mercapto groups, tertiary amino accordance with the invention. groups, ether groups, in particular polyethylene oxide and/or 0333. The process according to the invention is preferably propylene oxide groups, carbonyl groups, Sulfonic acids or carried out under an inert gas atmosphere, i.e., for example, derivatives of sulfonic acids, sulfinic acids or derivatives of under carbon dioxide, nitrogen or noble gas, among which Sulfinic acids, phosphonic acids or derivatives of phosphonic particular mention should be made of argon. acids, phosphinic acids or derivatives of phosphonic acids, 0334. A gas inert under the reaction conditions can pref silane groups, siloxane groups, aryl radicals or long-chain erably be passed through the reaction mixture, so that volatile alkyl radicals, or fluorinated or perfluorinated aryl or alkyl compounds are stripped out of the reaction mixture. radicals. 0335 The process according to the invention is carried out 0343 For modification with mercapto groups, it is pos attemperatures of from 60 to 250° C. Preference is given to sible, for example, to use mercaptoethanol. Tertiary amino working at temperatures of from 80 to 200°C., more prefer groups can be obtained, for example, by incorporating N-me ably at from 100 to 180° C. thyldiethanolamine, N-methyldipropanolamine or N,N-dim 0336. The pressure conditions of the process according to ethylethanolamine. Ether groups can be generated, for the invention are uncritical per se. It is possible to work at distinctly reduced pressure, for example at from 1 to 500 example, by incorporating difunctional or higher-functional mbar. The process according to the invention can also be ity polyetherols by condensation. Reaction with long-chain carried out at pressures above 500 mbar. For reasons of sim alkanediols allows long-chain alkyl radicals to be introduced; plicity, preference is given to reaction at atmospheric pres the reaction with alkyl or aryl diisocyanates generates poly sure; but it is also possible to perform it at slightly elevated mers having alkyl, aryland urethane or urea groups. pressure, for example up to 1200 mbar. It is also possible to 0344. For a modification, it is advantageously also pos work under distinctly elevated pressure, for example at pres sible to use compounds which bear at least one primary and/or sures up to 10 bar. Preference is given to reaction at atmo secondary amino group and at least one carboxyl, Sulfonic spheric pressure and at reduced pressures. acid or phosphonic acid group. 0337 The reaction time of the process according to the 0345 Examples of these are amino acids, hydroxyalkyl invention is typically from 10 minutes to 48 hours, preferably or -arylsulfonic acids, for example taurine or N-methyltau from 30 minutes to 24 hours and more preferably from 1 to 12 rine, or N-cyclohexylaminopropane- and -ethanesulfonic hours. acid. 0338 After the reaction has ended, the hyperbranched 0346 Examples of amino acids are glycine, alanine, B-ala polymers can be isolated easily, for example by filtering off nine, Valine, lysine, leucine, isoleucine, tert-leucine, pheny the catalyst and, if appropriate, removing the solvent, the lalanine, tyrosine, tryptophan, proline, aspartic acid, glutamic removal of the solvent being carried out typically at reduced acid, asparagine, glutamine, serine, threonine, cysteine, pressure. Further suitable workup methods are, for example, methionine, arginine, histidine, 4-aminobutyric acid, cystine, precipitation of the polymer after addition of water and sub citrulline, theanine, homocysteine, 4-hydroxyproline, alliin sequent washing and drying. or ornithine. 0339. These hyperbranched polymers have, in addition to 0347 Subsequent functionalization can be obtained by the polyisobutylene groups and the ester or amide groups reacting the hyperbranched polymer obtained, in an addi US 2011/O 105333 A1 May 5, 2011 tional process step, with a suitable functionalizing reagent 0359 The compositions of the present invention comprise which can react with the OH and/or NH and/or carboxyl an agent Suitable for seed coating materials, i.e. a hyper groups of the polymer. branched polymer. The compositions may comprise further 0348 Hyperbranched polymers comprising hydroxyl seed treatment auxiliary agents which are in particular groups or amino groups can be modified, for example, by selected from the group consisting of agents Suitable for Solid adding molecules comprising isocyanate groups. For matrix priming materials, penetration enhancers Suitable for example, polymers comprising urethane groups or urea promoting seed imbibition, colorants, antifreezes, and gelling groups can be obtained by reacting with alkyl or aryl isocy agents. anates. 0360 According to the invention, the seed coating mate 0349. In addition, hyperbranched polymers comprising rial of the compositions of the present invention comprises hydroxyl groups or amino groups may also be converted to the hyperbranched polymeras binder (or sticker). Therefore, high-functionality polyether polyols by reacting with alky usually no further binders need to be added to the composi lene oxides, for example ethylene oxide, propylene oxide or tion. However, combinations of the hyperbranched polymers butylene oxide. These compounds can then be obtained, for with one or more than one conventional binder may be expe example, in water-soluble form. dient. 0350. It is also possible to incorporate additional hydro 0361 Further binders (or stickers) are all customary bind philic resudues into a hyperbranched polymer of the inven ers (or Stickers) which can be employed in seed treatment tion. For instance, monovalent polyetheralcohols with a num compositions. Further binders (or stickers) that are useful in ber-average molecular weight in the range of approximately the present invention preferably comprise an adhesive poly 500 to 10000 g/mol, preferably of 1000 to 5000 g/mol may be mer that may be natural or partly or wholly synthetic and is used. Monovalent polyetheralcohols can be obtained by without phytotoxic effect on the seed to be coated. Preferably, alkoxylation of monovalent initiator molecules. Such as, for the further binder (or sticker) is biodegradable. example, methanol, ethanol or n-butanol, ethylene oxide or 0362. The further binder (or sticker) may be selected from mixtures or ethylene oxide with other alkylene oxides, in polyesters, polyether esters, polyanhydrides, polyester ure particular propylene oxide, being used as alkoxylating agent. thanes, polyester amides; polyvinyl acetates; polyvinyl 0351. The compositions of the present invention may con acetate copolymers; polyvinyl alcohols and tylose; polyvinyl tain one kind of hyperbranched polymer or a blend of two or alcohol copolymers; polyvinylpyrolidones; polysaccharides, more than two different hyperbranched polymers. including starches, modified Starches and Starch derivatives, 0352. According to a particular embodiment, the seed dextrins, maltodextrins, alginates, chitosanes and celluloses, treatment composition of the present invention comprises at cellulose esters, cellulose ethers and cellulose ether esters least 1% by weight, preferably at least 2% by weight, and in including ethylcelluloses, methylcelluloses, hydroxymethyl particular at least 5% by weight of hyperbranched polymer. celluloses, hydroxypropylcelluloses and carboxymethylcel lulose; fats; oils; proteins, including casein, gelatin and Zeins; 0353. According to a further particular embodiment, the gum arabics; shellacs: vinylidene chloride and vinylidene seed treatment composition comprises at most 50% by chloride copolymers; lignoSulfonates, in particular calcium weight, preferably at most 30% by weight, and in particular at lignoSulfonates; polyacrylates, polymethacrylates and most 20% by weight of hyperbranched polymer. acrylic copolymers; polyvinylacrylates; polyethylene oxide; 0354 According to one aspect, the weight ratio of hyper polybutenes, polyisobutenes, polystyrene, polyethyleneam branched polymer to the active ingredient(s) is at least 0.1:1. ines, polyethylenamides; acrylamide polymers and copoly preferably at least 0.2:1, and in particular at least 0.5:1. mers; polyhydroxyethyl acrylate, methylacrylamide mono 0355 According to another aspect, the weight ratio of mers; and polychloroprene. hyperbranched polymer to the active ingredient(s) is at most 0363 Typically, the amount of further binders will not 50:1, preferably at most 10:1, and in particular at most 5:1. exceed 10% by weight. Preferably, it does not exceed 5% by 0356. In the compositions of the present invention, the weight and in particular 1% by weight, based on the total hyperbranched polymer is used as seed coating agent, espe weight of the composition. According to a particular embodi cially as a binder to promote adhesion of the active ingredient ment, the compositions of the present invention do not con (s) to the seeds. Adhesion of active ingredient(s) to the seeds tain significant amounts of further binders, i.e. they contain can be determined by shearing the treated seeds and deter no further binder or the amount is below 0.5% by weight and mining the active ingredient loading before and after shear preferably below 0.1% by weight, based on the total weight of 1ng. the composition. 0357 The present invention thus also relates to the use of 0364 Optionally, the coating material also comprises one a hyperbranched polymer as defined herein as seed coating or more additional seed treatment auxiliary agents selected agent. from the group consisting of fillers and plasticizers. 0358. The composition of the invention is a seed treatment 0365. The filler can be an absorbent or an inert filler, such composition. A seed treatment composition according to the as are known in the art, and may include wood flours, cereal present invention comprises at least one auxiliary agent that is flours, tree bark mill, wood meal and nutshell meal, Sugars, in specifically Suited for the seed treatment, i.e. an auxiliary particular polysaccharides, activated carbon, fine-grain inor agent which in particular promotes adhesion of the active ganic Solids, silica gels, silicates, clays, chalk, diatomaceous ingredient to and/or penetration into the seeds and/or other earth, calcium carbonate, magnesium carbonate, dolomite, wise improves stability and/or manageability of the compo magnesium oxide, calcium sulfate and the like. Clays and sition or the seeds treated therewith. Thus, the seed treatment inorganic Solids which may be used include calcium bento composition the present invention comprises at least one seed nite, kaolin, china clay, talc, perlite, mica, Vermiculite, sili treatment auxiliary agent(s), and optionally one or more fur cates, quartz powder, montmorillonite, attapulgite, bole, ther auxiliary agents. loess, limestone, lime and mixtures thereof. Sugars which US 2011/O 105333 A1 May 5, 2011 26 may be useful include dextrin and maltodextrin. Cereal flours material should be chosen so that it can release the active include wheat flour, oat flour and barley flour. The filler may ingredient(s)at areasonable rate, for example overa period of also comprise fertilizer Substances such as, for example, minutes, hours, or days. ammonium Sulfate, ammonium phosphate, ammonium 0371 Penetration enhancers suitable for promoting seed nitrate, ureas and mixtures thereof. imbibition include agriculturally acceptable surface active 0366. The filler is selected so that it will provide a proper compounds. The amount of penetration enhancers will usu microclimate for the seed, for example the filler is used to ally not exceed 20% by weight, based on the total weight of increase the loading rate of the active ingredients and to adjust the composition. Preferably, the amount of penetration the control-release of the active ingredients. The filler can aid enhancers, if present, will be in the range from 2% to 20% by in the production or process of coating the seed. The amount weight. of filler can vary, but generally the weight of the filler com 0372 Colorants according to the invention are all dyes and ponents, if present, will be in the range of about 0.05 to about pigments which are customary for Such purposes. In this 75% of the total weight, more preferably about 0.1 to about context, both pigments, which are sparingly soluble in water, 50%, and even more preferably about 0.5% to 15%. and dyes, which are soluble in water, may be used. Examples 0367. It is preferred that the binder (or sticker) be selected which may be mentioned are the colorants, dyes and pigments so that it can serve as a matrix for the active ingredient(s). known under the names Rhodamin B. C. I. Pigment Red 112 While the binders disclosed above may all be useful as a and C. I. Solvent Red 1, Pigment Blue 15:4, Pigment Blue matrix, it is preferred that a continuous Solid phase of one or 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue more binder compounds is formed throughout which is dis 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 48:2, tributed as a discontinuous phase the active ingredient(s). Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, Optionally, a filler and/or other components can also be Pigment Orange 43, Pigment Orange 34, Pigment Orange 5. present in the matrix. The term “matrix’ is to be understood to Pigment Green 36, Pigment Green 7, Pigment White 6, Pig include what may be viewed as a matrix system, a reservoir ment Brown 25, Basic Violet 10, Basic Violet 49, Acid Red system or a microencapsulated system. In general, a matrix 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, system consists of the active ingredient(s) and a filler uni Basic Red 10, Basic Red 108. The amount of colorants, if formly dispersed within a polymer, while a reservoir system present, will usually not exceed 20% by weight of the com consists of a separate phase comprising the active ingredient position and preferably ranges from 1 to 15% by weight, (s) that is physically dispersed within a Surrounding, rate based on the total weight of the composition. It is generally limiting, polymeric phase. Microencapsulation includes the preferred if the colorants are also active as repellents for coating of Small particles or droplets of liquid, but also to warm-blooded animals, e.g. iron oxide, TiO, Prussian blue, dispersions in a solid matrix. anthraquinone dyes, azo dyes and metal phtalocyanine dyes. 0368 Especially if the active ingredient(s) used in the 0373 Antifreezes which can be employed especially for coating is an oily type composition and little or no inert filler aqueous compositions are in principle all those substances is present, it may be useful to hasten the drying process by which lead to a depression of the melting point of water. drying the composition. This optional step may be accom Suitable antifreezes comprise alcohols such as methanol, plished by means well known in the art and can include the ethanol, isopropanol, butanols, glycol, glycerine, diethyleng addition of fillers such as calcium carbonate, kaolin or ben lycol and the like. Typically, the amount of antifreeze will not tonite clay, perlite, diatomaceous earth, or any absorbent exceed 20% by weight and, if present, frequently ranges from material that is added preferably concurrently with the active 1 to 15% by weight, based on the total weight of the compo ingredient(s) coating layer to absorb the oil or excess mois sition. ture. The amount of absorbent necessary to effectively pro 0374 Gelling agents which are suitable are all substances vide a dry coating will be in the range of about 0.5 to about which can be employed for Such purposes in agrochemical 10% of the weight of the seed. compositions, for example cellulose derivatives, polyacrylic 0369 Optionally, the coating material comprises a plasti acid derivatives, Xanthan, modified clays, in particular cizer. Plasticizers are typically used to make the film that is organically modified phyllosilicates and highly-dispersed formed by the coating layer more flexible, to improve adhe silicates. A particularly Suitable gelling agent is carrageen sion and spreadability, and to improve the speed of process (Satiagel(R). Usually, the amount of gelling agent will not ing. Improved film flexibility is important to minimize chip exceed 5% by weight of the composition and, if present, ping, breakage or flaking during storage, handling or sowing preferably ranges from 0.5 to 5% by weight, based on the total processes. Many plasticizers may be used; however, useful weight of the composition. plasticizers include polyethylene glycol, oligomeric poly 0375. Further auxiliary agents that may be present in the alkylene glycols, glycerol, alkylbenzylphthalates, in particu seed treatment composition include solvents, wetters, dis lar butylbenzylphthalate, glycol benzoates and related com persants, emulsifiers, Surfactants, thickeners, protective col pounds. The range of plasticizer, if present, in the coating loids, antifoams, and preservatives. layer will be in the range of from about 0.1% by weight to 0376 Water is a preferred solvent. According to a particu about 20% by weight. lar embodiment, the compositions of the present invention 0370 Agents suitable for solid matrix priming materials comprise at least 5% by weight, preferably at least 10% by which are useful in the present invention include polyacryla weight and in particular at least 30% by weight of water. On mide, starch, clay, silica, alumina, Soil, sand, polyurea, poly the other hand, the compositions of the present invention acrylate, or any other material capable of absorbing or usually comprise at most 99% by weight, preferably at most adsorbing the active ingredient(s) and releasing the active 90% by weight and in particular at most 80% by weight of ingredient(s) into or onto the seed. It is useful to make Sure Water. that active ingredient(s) and the Solid matrix material are 0377. Further examples of suitable solvents are organic compatible with each other. For example, the solid matrix Solvents such as aromatic Solvents (for example Solves.So US 2011/O 105333 A1 May 5, 2011 27 products, Xylene), paraffins (for example mineral oil frac cellulose sulfate salt. Xanthan gum is preferred. Usually, the tions), alcohols (for example methanol, butanol, pentanol, amount of thickener will not exceed 20% by weight and, if benzyl alcohol), ketones (for example cyclohexanone, present, frequently ranges from 1 to 15% by weight, based on gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates the total weight of the composition. (glycol diacetate), glycols, fatty acid dimethylamides, fatty 0384 Protective colloids are typically water soluble, acids and fatty acid esters. In principle, Solvent mixtures may amphiphilic polymers. Examples include proteins and dena also be used. However, according to aparticular embodiment, tured proteins such as casein, polysaccharides such as water the compositions of the present invention contain less than soluble starch derivatives and cellulose derivatives, in par 15% by weight and preferably less than 6% by weight of said ticular hydrophobic modified starch and celluloses, further organic solvents. more polycarboxylates such as polyacrylic acid and acrylic 0378 Surface active compounds are all those surfactants acid copolymers, polyvinylalcohol, polyvinylpyrrolidone, which are Suitable for formulating agrochemical actives, in vinylpyrrolidone copolymers, polyvinyl amines, polyethyl particular for active ingredient(s), and which may be non ene imines and polyalkylene ethers. Usually, the amount of ionic, cationic, anionic or amphoteric. According to their protective colloid will not exceed 3% by weight of the com action, Surfactants—sometimes referred to as “additives' - position and, if present, preferably ranges from 0.1 to 2% by may be divided into wetters, dispersants, emulsifiers or pro weight, based on the total weight of the composition. tective colloids; however, these particular groups may over 0385 Antifoams which can be employed are all those lap and cannot be divided strictly. Typically, the amount of substances which inhibit the development of foam and which surfactants will not exceed 20% by weight and, if present, are conventionally used for formulating agrochemical active frequently ranges from 1 to 15% by weight, based on the total ingredients. Silicone antifoams, i.e. aqueous silicon emul weight of the composition. sions (e.g. Silikon R. SRE by Wacker or Rhodorsil R by 0379 Suitable wetters are all those substances which pro Rhodia), long chain alcohols, fatty acids and salts thereof, e.g. mote wetting and which are conventionally used for formu and magnesium Stearate are particularly Suitable. Usually, the lating agrochemical active ingredients. Alkylnaphthalene amount of antifoam will not exceed 3% by weight of the Sulfonates Such aS diisopropyl- O composition and, if present, preferably ranges from 0.1 to 2% disobutylnaphthalenesulfonates can be used preferably. by weight, based on the total weight of the composition. 0380 Dispersants and/or emulsifiers which are suitable 0386 Preservatives which can be employed are all preser are all nonionic, anionic and cationic dispersants or emulsi Vatives used for Such purposes in agrochemical compositions. fiers conventionally used for formulating agrochemical active Examples which may be mentioned are dichlorophene, ingredients. The following can preferably be used: nonionic isothiazolenes and isothiazolones such as 1,2-benzisothiazol or anionic dispersants and/or emulsifiers or mixtures of non 3(2H)-one, 2-methyl-2H-isothiazol-3-one-hydrochloride, ionic or anionic dispersants and/or emulsifiers. 5-chloro-2-(4-chlorobenzyl)-3(2H)-isothiazolone, 5-chloro 0381 Suitable nonionic dispersants and/or emulsifiers 2-methyl-2H-isothiazol-3-one, 5-chloro-2-methyl-2H which may be employed are, in particular, ethylene oxide/ isothiazol-3-one, 5-chloro-2-methyl-2H-isothiazol-3-one alkylene oxide block copolymers, alkylphenol polyglycol hydrochloride, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3- ethers and tristryrylphenol polyglycol ethers, for example one, 4,5-dichloro-2-octyl-2H-isothiazol-3-one, 2-methyl polyoxyethylene octylphenol ether, ethoxylated isooctylphe 2H-isothiazol-3-one, 2-methyl-2H-isothiazol-3-one-calcium nol, octylphenol, nonylphenol, alkylphenol polyglycol ether, chloride complex, 2-octyl-2H-isothiazol-3-one and benzyl tributylphenyl polyglycol ether, tristearylphenyl polyglycol alcohol hemiformal. Usually, the amount of preservatives ether, alkylaryl-polyether alcohols, alcohol and fatty alcohol will not exceed 2% by weight of the composition and, if ethylene oxide condensates, ethoxylated castor oil, polyoxy present, preferably ranges from 0.01 to 1% by weight, based ethylene alkyl ether, ethoxylated polyoxypropylene, lauryl on the total weight of the composition. alcohol polyglycol ether acetal, Sorbitol esters and methyl 0387. The skilled person is essentially familiar with agri cellulose. cultural compositions of active ingredients (see, for instance, 0382 Suitable anionic dispersants and/or emulsifiers Ullmann's Encyclopedia of Industrial Chemistry, Fungicides which may be employed are, in particular, alkali metal, alka Chapter 4, 5th ed. on CD-ROM, Wiley-VCH, 1997 and Mol line earth metal and ammonium salts of ligninsulfonic acid, let, H., Grubemann, A., Formulation technology, Wiley VCH naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaph Verlag GmbH. Weinheim (Federal Republic of Germany), thalenesulfonic acid, alkylarylsulfonates, alkyl Sulfates, 2001, which is incorporated herein by reference in its alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated entirety). Examples include water-soluble concentrates (SL, fatty alcohol glycol ethers, furthermore arylsulfonate/form LS), dispersible concentrates (DC), emulsifiable concen aldehyde condensates, for example condensates of sulfonated trates (EC), emulsions (EW, EO, ES), suspensions (SC, OD, naphthalene and naphthalene derivatives with formaldehyde, FS), water-dispersible granules (WG, SG), water-dispersible condensates of naphthalene or of naphthalenesulfonic acid or water-soluble powders (WP, SPSS, WS), dusts or dustable with phenol and formaldehyde, ligninsulfonates, lignin powders (DP, DS), granules (GR, FG, GG, MG), ULV solu sulfite waste liquors, phosphated or sulfated derivatives of tions (UL) and gel formualtions (GF). For seed treatment methylcellulose, and salts of polyacrylic acid. purposes, such compositions may be applied as such or after 0383. Thickeners are typically water-soluble polymers addition of a Suitable liquid, in particular water, in order to which exhibit Suitable plastic properties in an aqueous dissolve, emulsify, disperse, Supend or dilute the composi medium. Examples include gum arabic, gum karaya, gum tion. The type of the ready-to-use preparation applied to the tragacanth, guar gum, locust bean gum, Xanthan gum, carra seeds thus depends on the type of composition used and the geenan, alginate salt, casein, dextran, pectine, agar, 2-hy method used for treating the seeds. droxyethyl starch, 2-aminoethyl starch, 2-hydroxyethyl cel 0388. The compositions can be prepared in the known lulose, methyl cellulose, carboxymethyl cellulose salt, manner, for example by extending the active ingredient com US 2011/O 105333 A1 May 5, 2011 28 ponent with one or more auxiliary agents (see e.g. for review ant(s) and/or wetter(s) and made as water-dispersible or U.S. Pat. No. 3,060,084, EP-A 707445 (for liquid concen water-soluble granules by means oftechnical appliances (for trates), Browning, "Agglomeration’, Chemical Engineering, example extrusion, spray tower, fluidized bed), whereby a Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Hand formulation with 50% (w/w) of the active ingredient(s) is book, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and obtained. Dilution with water gives a stable dispersion or et seq., WO 91/13546, U.S. Pat. No. 4,172,714, U.S. Pat. No. Solution of the active compound(s). 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587, G Water-dispersible and water-soluble powders (WP, SPSS, U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095, WS) 558, U.S. Pat. No. 3.299,566, Klingman, Weed Control as a 0396 75 parts by weight of the active ingredient(s) are Science, John Wiley and Sons, Inc., New York, 1961, Hance ground in a rotor-stator mill with addition of 25 parts by et al., Weed Control Handbook, 8th Ed., Blackwell Scientific weight of dispersant(s) and/or wetter(s), and silica gel. Publications, Oxford, 1989 and Mollet, H., Grubemann, A., whereby a formulation with 75% (w/w) of the active ingre Formulation technology, Wiley VCH Verlag GmbH. Wein dient(s) is obtained. Dilution with water gives a stable disper heim (Germany), 2001, 2. D. A. Knowles, Chemistry and sion or solution of the active ingredient(s). Technology of Agrochemical Formulations, Kluwer Aca H Gel formulation (GF) demic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), 0397. In an agitated ball mill, 20 parts by weight of the all of which being incorporated by reference in their entirety). active ingredient(s) are comminuted with addition of 10 parts 0389. The following formulations simply illustrate said by weight of dispersant(s), 1 part by weight of a gelling agent compositions, with a Suitable amount of hyperbranched poly and 70 parts by weight of water or of an organic solvent to mer being added to the formulation: give a fine active compound(s) suspension, whereby a formu A Water-soluble concentrates, solutions (SL, LS) lation with 20% (w/w) of the active ingredient(s) is obtained. 0390 10 parts by weight of the active ingredient(s) and, Dilution with water gives a stable suspension of the active optionally, wetters or other auxiliaries are dissolved in 90 ingredient(s). parts by weight of water or a water-soluble solvent, whereby I Dusts and dustable powders (DP, DS) a formulation with 10% (w/w) of the active ingredient(s) is 0398 5 parts by weight of the active ingredient(s) are obtained. Dilution with water gives a solution. ground finely and mixed intimately with 95 parts by weight of B Dispersible concentrates (DC) finely divided kaolin. This gives a dustable product having 0391 20 parts by weight of the active ingredient(s) are 5% (w/w) of the active ingredient(s). dissolved in 70 parts by weight of cyclohexanone with addi tion of 10 parts by weight of dispersant(s), for example poly JGranules (GR, FG, GG, MG), vinylpyrrolidone, whereby a formulation with 20% (w/w) of the active ingredient(s) is obtained. Dilution with water gives 0399 0.5 parts by weight of the active ingredient(s) is a dispersion. ground finely and associated with 95.5 parts by weight of C Emulsifiable concentrates (EC) carriers, whereby a formulation with 0.5% (w/w) of the active 0392 15 parts by weight of the active ingredient(s) are ingredient(s) is obtained. Current methods are extrusion, dissolved in 70 parts by weight of an organic solvent with spray-drying or the fluidized bed. addition of calcium dodecylbenzenesulfonate and castor oil KULV solution (UL) ethoxylate (in each case 5 parts by weight), whereby a for 0400 10 parts by weight of the active ingredient(s) are mulation with 15% (w/w) of the active ingredient(s) is dissolved in 90 parts by weight of an organic solvent. This obtained. Dilution with water gives an emulsion. gives a product having 10% (w/w) of the active ingredient(s). 0401 Formulations A-K can be diluted with water before D Emulsions (EW, EO ES) application or directly applied. 0402 For the seed treatment according to the present 0393 25 parts by weight of the active ingredient(s) are invention, Suspensions are preferred. Further, gel formula dissolved in 35 parts by weight of an organic solvent with tions are Suitable. addition of calcium dodecylbenzenesulfonate and castor oil 0403. According to a particular embodiment of present ethoxylate (in each case 5 parts by weight). This mixture is invention, the seed treatment composition is a liquid or is introduced into 30 parts by weight of water by means of an applied as a liquid. Preference is given to a Suspension and emulsifier machine (e.g. Ultraturrax) and made into a homo especially an aqueous Suspension. The Suspended particles geneous emulsion, whereby a formulation with 25% (w/w) of are active ingredient(s) or auxiliary agents having a melting the active ingredient(s) is obtained. Dilution with water gives point above 30° C. an emulsion. 0404 According to the present invention, the following E Suspensions (SC, OD, FS) formulations are particularly preferred: flowable concen trates (especially FS). This formulation can be applied to the 0394. In an agitated ball mill, 20 parts by weight of the seed diluted or undiluted. active ingredient(s) are comminuted with addition of 10 parts 04.05 According to a particular embodiment, the inven by weight of dispersant(s) and/or wetter(s) and 70 parts by tion relates to a FS formulation. Typcially, an FS formulation weight of water or of an organic solvent to give a fine active may comprise 1-800 g/l of the active ingredient(s), 1-200 g/1 compound(s) suspension, whereby a formulation with 20% dispersant, 0 to 200 g/l antifreezing agent, 1 to 400 g/l of a (w/w) of the active ingredient(s) is obtained. Dilution with hyperbranched polymer, 0 to 200 g/l of a colorant and up to 1 water gives a stable Suspension of the active ingredient(s). liter of a solvent, preferably water. F Water-dispersible granules (WG, SG) 0406 According to a further particular embodiment, the 0395 50 parts by weight of the active ingredient(s) are seed treatment composition of the present invention is a seed ground finely with addition of 50 parts by weight of dispers coating formulation. US 2011/O 105333 A1 May 5, 2011 29

04.07 Such seed coating formulations comprise the active stage of the plant also flowers and/or fruits, all of which are ingredient(s), at least one binder (or Sticker), i.e., a hyper physically connected to form an individual which is, under branched polymer as defined herein, and optionally at least reasonable conditions, viable without the need for artificial one further auxiliary agent that is selected from the group measures. The term may also refer to an entire plantharvested consisting of fillers and plasticizers. as such. 0408. Seed coating formulations comprising binders, fill 0418. The term “plant parts” refers to roots, shoots, foli ers and/or plasticizers are well-known in the art. Seedcoating age, flowers or other parts of the vegetative stage of the plant, formulations are disclosed, for example, in U.S. Pat. Nos. which, when dislodged and disconnected from the rest, are 5,939,356, 5,882,713, 5,876,739, 5,849,320, 5,834,447, incapable of Survival, unless Supported by artificial measures 5,791,084, 5,661,103, 5,622,003, 5,580,544, 5,328,942, orable to re-grow the missing parts to forman entire plant. As 5,300,127, 4,735,015, 4,634,587, 4,383,391, 4,372,080, used herein, fruits are also considered as plant parts. 4.339,456, 4,272.417 and 4.245,432, among others. 0419. As used herein, the term “root” refers to parts of a 04.09. The amount of the active ingredient(s) that is plant which are normally, in order to fulfill their physiological included in the coating formulation will vary depending upon functions, located beneath the soil surface. Preferably, the the type of seed, but the coating formulation will contain an term denotes the parts of a plant which are below the seed and amount of the active ingredient(s) that is pesticidally effec have directly emerged from the latter, or from other roots, but tive. In general, the amount of the active ingredient(s) in the not from shoots or foliage. coating formulation will range from about 0.005 to about 0420. As used herein, the “shoots and foliage' of a plant 75% of the total weight. A more preferred range for the active are to be understood to be the shoots, stems, branches, leaves ingredient(s) is from about 0.01 to about 40%; more preferred and other appendages of the stems and branches of the plant is from about 0.05 to about 20%. after the seed has sprouted, but not including the roots of the 0410 The exact amount of the active ingredient(s) that is plant. It is preferable that the shoots and foliage of a plant be included in the coating formulation is easily determined by understood to be those non-root parts of the plant that have one skilled in the art and will vary depending upon the size grown from the seed and are located a distance of at least one and other characteristics (surface structure etc.) of the seed to inch away from the seed from which they emerged (outside be coated. The active ingredient(s) of the coating formulation the region of the seed), and more preferably, to be the non must not inhibit germination of the seed and should be effi root parts of the plant that are at or above the surface of the cacious in protecting the seed and/or the plant during that time soil. in the target pest’s life cycle in which it causes injury to the 0421. As used herein, “fruits’ are considered to be the seed or plant. In general, the coating will be efficacious for parts of a plant which contain seeds and/or serve to spread approximately 0 to 120 days, preferably for approximately 0 seeds, and/or which may be removed from a plant without to 60 days, after Sowing. impairing its viability. 0411. The coating formulations formed with the active 0422. According to the present invention, the seed treat ingredient(s) are capable of effecting a slow rate of release of ment comprises applying a composition of the invention to a the active ingredient(s) by diffusion or movement through the seed. Although the present method can be applied to a seed in matrix into the seed or to the Surrounding medium. any physiological state, it is preferred that the seed be in a 0412. The present invention also relates to the use of a Sufficiently durable state that it incurs no significant damage composition as defined herein for treating seed. during the treatment process. Typically, the seed is a seed that 0413. The present invention also relates to a method of has been harvested from the field; removed from the plant; treating seed with a composition described herein, which and/or separated from the fruit and any cob, pod, stalk, outer comprises applying an effective amount of a composition as husk, and Surrounding pulp or other non-seed plant material. defined herein to a lot of seeds. The seed is preferably also biologically stable to the extent 0414. The term “batch' or “lot' means a group of seeds that the treatment would cause no biological damage to the that are undergoing the seed treatment. The amount and seed. In one embodiment, for example, the treatment can be weight of the seeds can vary depending on the treatment. applied to seed that has been harvested, cleaned and dried to 0415. The term “loading refers to the actual amount of an a moisture content below about 15% by weight. In an alter active ingredient or a hyperbaranched polymer that is adhered native embodiment, the seed can be one that has been dried onto each seed, based on bulk amount of seed. and then primed with water and/or another material and then 0416. As used herein, the term “seed' denotes any resting re-dried before or during the treatment with a composition of stage of a plant that is physically detached from the vegetative the invention. stage of a plant and/or may be stored for prolonged periods of 0423. According to a preferred embodiment of the inven time and/or can be used to re-grow another plant individual of tion, the seed to be treated is thus substantially dry. “Substan the same species. Here, the term “resting refers to a state tially dry” seed includes seed that has a moisture content wherein the plant retains viability, within reasonable limits, in which results if the seed is allowed to equilibrate in an air spite of the absence of light, water and/or nutrients essential atmosphere at 20 to 30° C. and 30-90% relative humidity, e.g. for the vegetative (i.e. non-seed) state. In particular, the term at 25° C. and 50% relative humidity. refers to true seeds but does not embraces plant propagules 0424 The term seed treatment comprises all suitable seed Such as Suckers, corms, bulbs, fruit, tubers, grains, cuttings treatment and especially seed dressing techniques known in and cut shoots. the art, such as seed coating (e.g. seed pelleting), seed dusting 0417. As used herein, the term “plant’ means an entire and seed imbibition (e.g. seed soaking). Here, “seed treat plant or parts thereof. The term “entire plant” refers to a ment” refers to all methods that bring seeds and a composition complete plant individual in its vegetative, i.e. non-seed of the invention into contact with each other, and “seed dress stage, characterized by the presence of an arrangement of ing to methods of seed treatment which provide the seeds roots, shoots and foliage, depending on the developmental with an amount of the active ingredient, i.e. which generate a US 2011/O 105333 A1 May 5, 2011 30 seed comprising the active ingredient. In principle, the treat seeds partially or completely with a layer or layers of non ment can be applied to the seed at any time from the harvest plant material, and “imbibition any process that results in of the seed to the sowing of the seed. The seed can be treated penetration of the active ingredient(s) into the germinable immediately before, or during, the planting of the seed, for parts of the seed and/or its natural sheath, (inner) husk, hull, example using the “hopper-box” or “planter-box” method. shell, pod and/or integument. The invention therefore also However, the treatment may also be carried out several weeks relates to a treatment of seeds which comprises providing or months, for example up to 12 months, before planting the seeds with a coating that comprises the active ingredient(s), seed, for example in the form of a seed dressing treatment, and to a treatment of seeds which comprises imbibition of without a substantially reduced efficacy being observed. seeds with the active ingredient(s). 0425 Expediently, the treatment is applied to unsown 0432 Coating is particularly effective in accommodating seed. As used herein, the term "unsown seed' is meant to high loads of the active ingredient(s), as may be required to include seed at any period from the harvest of the seed to the treat typically refractory pests, while at the same time pre Sowing of the seed in the ground for the purpose of germina venting unacceptable phytotoxicity due to the increased load tion and growth of the plant. Preferably, the seed is not a of the active ingredient(s). pregerminated seed Such as a pregerminated rice seed. 0433 Coating may be applied to the seeds using conven 0426. When it is said that unsown seed is “treated’, such tional coating techniques and machines, such as fluidizedbed treatment is not meant to include those practices in which the techniques, the roller mill method, rotostatic seed treaters, pesticide is applied to the soil, rather than directly to the seed. and drum coaters. Other methods such as the spouted beds 0427 By applying the treatment to the seed prior to the technique may also be useful. The seeds may be pre-sized Sowing of the seed the operation is simplified. In this manner, before coating. After coating, the seeds are typically dried and seeds can be treated, for example, at a central location and then transferred to a sizing machine for sizing. then dispersed for planting. This permits the person who 0434. Such procedures are known in the art. Seed coating plants the seeds to avoid the handling and use of the active methods and apparatus for their application are disclosed in, ingredient and to merely handle and plant the treated seeds in for example, U.S. Pat. Nos. 5,918,413, 5,891,246, 5,554,445, a manner that is conventional for regular untreated seeds, 5,389,399, 5,107,787, 5,080,925, 4,759,945 and 4,465,017. which reduces human exposure. 0435. In another particular embodiment, the solid the 0428 Specifically, the seed treatment follows a procedure active ingredient(s), for instance as a solid fine particulate in which the seed is exposed to the specifically desired formulation, e.g. a powder or dust, can be mixed directly with amount of a preparation comprising the active ingredient(s). seeds. Optionally, a sticking agent can be used to adhere the The preparation may be a composition of the present inven Solid, e.g. the powder, to the seed surface. For example, a tion that is applied as such or after previously diluting it, e.g. quantity of seed can be mixed with a sticking agent (which with water; for instance, it may be expedient to dilute seed increases adhesion of the particles on the surface of the seed) treatment compositions 2-10 fold leading to concentrations in and optionally agitated to encourage uniform coating of the the ready-to-use compositions of 0.01 to 60% by weight seed with the sticking agent. For example, the seed can be active compound by weight, preferably 0.1 to 40% by weight. mixed with a sufficient amount of sticking agent, which leads In some instances, it may be expedient to add the hyper to a partial or complete coating of the seed with Sticking branched polymers of the present invention to a composition agent. The seed pretreated in this way is then mixed with a that has no or insufficient amounts of binder. Upon addition of Solid formulation containing the active ingredient(s) to the hyperbranched polymers and optional dilution with water achieve adhesion of the solid formulation on the surface of the the resulting composition is suitable for seed treatment. seed material. The mixture can be agitated, for example by 0429 Thus, the active ingredient concentrations in ready tumbling, to encourage contact of the Sticking agent with the to-use preparation can be varied within Substantial ranges. In active ingredient(s), thereby causing the solid the active general, they are in the range from 0.01 and 80% by weight, ingredient(s) to Stick to the seed. frequently in the range from 0.1 to 50% by weight, preferably 0436 Another particular method of treating seed with the in the range from 0.5 and 20% by weight, based on the total active ingredient(s) is imbibition. For example, seed can be weight of the preparation. The active ingredients can also combined for a period of time with an aqueous solution com Successfully be used in concentrated form, it being possible to prising from about 1% by weight to about 75% by weight of apply, to the seed, preparations with more than 80% by weight the active ingredient(s) in a solvent such as water. Preferably of active ingredient, or even the active ingredient without the concentration of the solution is from about 5% by weight additions. The amount of additives will generally not exceed to about 50% by weight, more preferably from about 10% by 30% by weight, preferably 20% by weight, and is, in particu weight to about 25% by weight. During the period that the lar, in the range of from 0.1 to 20% by weight, in each case seed is combined with the solution, the seed takes up (im based on the total weight of the preparation. bibes) at least a portion of the active ingredient(s). Optionally, 0430. Usually, a device which is suitable for seed treat the mixture of seed and solution can be agitated, for example ment, for example a mixer for Solid or Solid/liquid compo by shaking, rolling, tumbling, or other means. After the imbi nents, is employed until the preparation is distributed uni bition process, the seed can be separated from the Solution formly on the seed. Thus, the preparation can be applied to and optionally dried in a suitable manner, for example by seeds by any standard seed treatment methodology, including patting or air-drying. but not limited to mixing in a container (e.g., a bottle, bag or 0437. In yet another particular embodiment of the present tumbler), mechanical application, tumbling, spraying, and invention, the active ingredient(s) can be introduced onto or immersion. If appropriate, this is followed by drying. into a seed by use of Solid matrix priming. For example, a 0431 Particular embodiments of the present invention quantity of the active ingredient(s) thereof can be mixed with comprise seed coating and imbibition (e.g. soaking). "Coat a solid matrix material, and then the seed can be placed into ing denotes any process that endows the outer Surfaces of the contact with the solid matrix material for a period to allow the US 2011/O 105333 A1 May 5, 2011

active ingredient(s) to be introduced to the seed. The seed can trees and evergreens, e.g. C. ulmi (Dutch elm disease) on then optionally be separated from the solid matrix material elms; Cercospora spp. (Cercospora leaf spots) on corn, rice, and stored or used, or, preferably, the mixture of solid matrix Sugar beets (e.g. C. beticola), Sugar cane, vegetables, coffee, material plus seed can be stored or planted/sown directly. Soybeans (e.g. C. Sojina or C. kikuchii) and rice; Cladospo 0438. In each embodiment of the invention, it is preferred rium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, that the composition of the invention is applied to a seed in an e.g. C. herbarum (black ear) on wheat; Claviceps purpurea effective amount, that is, an amount Sufficient to provide (ergot) on cereals; Cochliobolus (anamorph: Helminthospo Sufficient active ingredient, e.g. for protection against pests, rium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), to the seed and the plant that grows from the seed. A seed cereals (e.g. C. sativus, anamorph: B. Sorokiniana) and rice treatment according to the present invention is therefore for (e.g. C. miyabeanus, anamorph: H. Otyzae); Colletotrichum protecting not only the seed but also the plant that grows from (teleomorph: Glomerella) spp. (anthracnose) on cotton (e.g. the seed. C. gossypii), corn (e.g. C. graminicola), soft fruits, potatoes 0439. As used herein, “protection' is achieved if the per (e.g. C. coccodes: black dot), beans (e.g. C. lindemuthianum) cent offeeding damage to the seed and/or the plant at 10 days and Soybeans (e.g. C. truncatum or C. gloeosporioides); Cor after infestation (DAI) with the pest is significantly reduced ticium spp., e.g. C. Sasakii (sheath blight) on rice; for treated seeds or plants grown from treated seeds as com Corynespora cassicola (leaf spots) on Soybeans and orna pared to untreated seeds or plants grown from untreated mentals; Cycloconium spp., e.g. C. Oleaginum on olive trees; seeds. In order to be effective, the active ingredient is gener Cylindrocarpon spp. (e.g. fruit tree canker or young vine ally employed in an amount of from 0.1 to 500 g, preferably decline, teleomorph: Nectria or Neonectria spp.) on fruit 0.5 to 200 g, and in particular 0.75 to 100 g, per 100 kilograms trees, vines (e.g. C. liriodendri, teleomorph: Neonectria liri of seed. Odendri: Black Foot Disease) and ornamentals; Demato 0440 According to the present invention one purpose of phora (teleomorph: Rosellinia) necatrix (root and stem rot) said seed treatment is to control a pest. Such a seed treatment on Soybeans; Diaporthe spp., e.g. D. phaseolorum (damping thus involves a pesticidal effect or a pesticidal activity pro off) on soybeans: Drechslera (syn. Helminthosporium, teleo viding protection against damage done by the pest to a seed morph: Pyrenophora) spp. on corn, cereals, such as barley and/or a plant grown from the seed. Seed treatment can espe (e.g. D. teres, net blotch) and wheat (e.g. D. tritici-repentis: cially be used to protect seeds and seedlings from early season tan spot), rice and turf. Esca (dieback, apoplexy) on vines, disease and insect pests affecting crop emergencVee and caused by Formitiporia (syn. Phellinus) punctata, F. mediter growth. ranea, Phaeomoniella chlamydospora (earlier Phaeoacre 0441. As used herein, the terms “pesticidal effect” and monium chlamydosporum), Phaeoacremonium aleophilum "pesticidal activity” mean any director indirect action on the and/or Bottyosphaeria obtusa, Elsinoe spp. on pome fruits target pest that results in reduction offeeding damage on the (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. treated seeds as well as on the fruits, roots, shoots and/or ampelina: anthracnose); Entvloma Oryzae (leaf Smut) on rice; foliage of plants grown from treated seeds as compared Epicoccum spp. (black mold) on wheat; Erysiphe spp. (pow untreated seeds or to plants grown from untreated seeds, dery mildew) on Sugar beets (E. betae), vegetables (e.g. E. respectively. The terms 'active against a (first or second) pisi). Such as cucurbits (e.g. E. cichoracearum), cabbages, pest also have the same meaning. Such direct or indirect rape (e.g. E. cruciferarum); Eutypalata (Eutypa canker or actions include killing of the pest, repelling the pest from the dieback, anamorph: Cytosporina lata, syn. Libertella ble plant seeds, fruits, roots, shoots and/or foliage, inhibiting pharis) on fruit trees, vines and ornamental woods: Exsero feeding of the pest on, or the laying of its eggs on, the plant hilum (syn. Helminthosporium) spp. on corn (e.g. E. turci seeds, fruits, roots, shoots and/or foliage, and inhibiting or cum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or preventing reproduction of the pest. stem rot) on various plants, such as F graminearum or F. 0442 Pests in particular include soil-borne and soil-dwell culmorum (root rot, Scab or head blight) on cereals (e.g. wheat ing, shoot and foliage pests. or barley), F. Oxysporum on tomatoes, F. Solani on Soybeans 0443 Particular fungi to be controlled include the follow and F. verticifloides on corn; Gaeumannomyces graminis 1ng: (take-all) on cereals (e.g. wheat or barley) and corn; Gibber 0444 Albugo spp. (white rust) on ornamentals, vegetables ella spp. on cereals (e.g. G. Zeae) and rice (e.g. G. fijikuroi: (e.g. A. Candida) and Sunflowers (e.g. A. tragopogonis); Bakanae disease); Glomerella cingulata on vines, pome fruits Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. and other plants and G. gossypii on cotton; Grainstaining brassicola or brassicae), Sugar beets (A. tenuis), fruits, rice, complex on rice; Guignardia bidwellii (black rot) on vines; Soybeans, potatoes (e.g. A. Solani or A. alternata), tomatoes Gymnosporangium spp. on rosaceous plants and junipers, (e.g. A. Solani or A. alternata) and wheat; Aphanomyces spp. e.g. G. Sabinae (rust) on pears; Helminthosporium spp. (syn. on Sugar beets and vegetables; Ascochyta spp. on cereals and Drechslera, teleomorph: Cochliobolus) on corn, cereals and Vegetables, e.g. A. tritici (anthracnose) on wheat and A. hor rice: Hemileia spp., e.g. H. vastatrix (coffee leaf rust) on dei on barley; Bipolaris and Drechslera spp. (teleomorph: coffee; isariopsis clavispora (syn. Cladosporium vitis) on Cochliobolus spp.) on corn (e.g. D. maydis), cereals (e.g. B. vines; Macrophomina phaseolina (syn. phaseoli) (root and Sorokiniana: spot blotch), rice (e.g. B. Oryzae) and turfs; stem rot) on Soybeans and cotton; Microdochium (syn. Blumeria (formerly Erysiphe) graminis (powdery mildew) on Fusarium) nivale (pink Snow mold) on cereals (e.g. wheat or cereals (e.g. on wheat or barley); Botrytis cinerea (teleo barley); Microsphaera diffusa (powdery mildew) on Soy morph: Botryotinia fickeliana: grey mold) on fruits and ber beans; Monilinia spp., e.g. M. laxa, M. fructicola and M. ries (e.g. Strawberries), vegetables (e.g. lettuce, carrots, cel fructigena (bloom and twig blight, brown rot) on Stone fruits ery and cabbages), rape, flowers, vines, forestry plants and and other rosaceous plants; Mycosphaerella spp. on cereals, wheat; Bremia lactucae (downy mildew) on lettuce; Cerato bananas, soft fruits and ground nuts, such as e.g. M. gramini cystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved cola (anamorph: Septoria tritici, Septoria blotch) on wheat or US 2011/O 105333 A1 May 5, 2011 32

M.fijiensis (black Sigatoka disease) on bananas; Peronospora diseases; Stagonospora spp. on cereals, e.g. S. nodorum spp. (downy mildew) on cabbage (e.g. P. brassicae), rape (e.g. (Stagonospora blotch, teleomorph: Leptosphaeria syn. P parasitica), onions (e.g. P. destructor), tobacco (P taba Phaeosphaerial nodorum) on wheat; Synchytrium endobioti cina) and soybeans (e.g. P. manshurica); Phakopsora cum on potatoes (potato wart disease); Taphrina spp., e.g. T. pachyrhizi and P. meibomiae (soybean rust) on Soybeans; deformans (leaf curl disease) on peaches and T. pruni (plum Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P pocket) on plums; Thielaviopsis spp. (black root rot) on tetraspora) and Soybeans (e.g. P. gregata: stem rot); Phoma tobacco, pome fruits, vegetables, soybeans and cotton, e.g. T. lingam (root and stem rot) on rape and cabbage and P betae basicola (syn. Chalara elegans); Tilletia spp. (common bunt (root rot, leaf spot and damping-off) on Sugar beets; Phomop or Stinking Smut) on cereals, such as e.g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarfbunt) on wheat; sis spp. on Sunflowers, vines (e.g. P. viticola: can and leaf Tiphula incarnata (grey Snow mold) on barley or wheat; spot) and Soybeans (e.g. stem rot: P phaseoli, teleomorph: Urocystis spp., e.g. U. occulta (stem Smut) on rye; Uromyces Diaporthe phaseolorum); Physoderma maydis (brown spots) spp. (rust) on vegetables, such as beans (e.g. U. appendicu on corn; Phytophthora spp. (wilt, root, leaf fruit and stem latus, syn. U. phaseoli) and Sugar beets (e.g. U. betae); Usti root) on various plants, such as paprika and cucurbits (e.g. P lago spp. (loose Smut) on cereals (e.g. U. nuda and U. avae capsid), soybeans (e.g. P. megasperma, syn. P. Soiae), pota nae), corn (e.g. U. maydis: corn Smut) and Sugar cane; toes and tomatoes (e.g. P infestans: late blight) and broad Venturia spp. (scab) on apples (e.g. V, inaequalis) and pears; leaved trees (e.g. Pramorum: Sudden oak death); Plasmodio and Verticillium spp. (wilt) on various plants, such as fruits phora brassicae (club root) on cabbage, rape, radish and other and ornamentals, vines, Soft fruits, vegetables and field crops, plants; Plasmopara spp., e.g. P. viticola (grapevine downy e.g. V. dahliae on Strawberries, rape, potatoes and tomatoes. mildew) on vines and P. halstedii on Sunflowers: Podosphaera spp. (powdery mildew) on rosaceous plants, 0445 Particular insects to be controlled include the fol hop, pome and soft fruits, e.g. P. leucotricha on apples; Poly lowing: myxa spp., e.g. on cereals, such as barley and wheat (P 0446 lepidopterans (Lepidoptera), for example Agrotis graminis) and Sugar beets (P. betae) and thereby transmitted Ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia viral diseases; Pseudocercosporella herpotrichoides (eyes gemmatalis, Argyresthia Conjugella, Autographa gamma, pot, teleomorph: Tapesia vallundae) on cereals, e.g. wheat or Bupalus piniarius, Cacoecia murinana, Capua reticulana, barley, Pseudoperonospora (downy mildew) on various Chematobia brumata, Choristoneura funiferana, Choristo plants, e.g. P. cubensis on cucurbits or P. humili on hop; neura Occidentalis, Cirphis unipuncta, Cydia pomonella, Pseudopezicula tracheiphila (redfire disease or, rotbrenner, Dendrolimus pint Diaphania initidalis, Diatraea grandi anamorph: Phialophora) on vines; Puccinia spp. (rusts) on Osella, Earias insulana, Elasmopalpus lignosellus, Eupo various plants, e.g. P. triticina (brown or leafrust), P. Striifor ecilia ambiguella, Evetria bouliana, Feltia subterranea, Gal mis (stripe or yellow rust), P hordei (dwarfrust), P graminis leria mellonella, Grapholitha finebrana, Grapholitha (stem or black rust) or P recondita (brown or leaf rust) on molesta, Heliothis armigera, Heliothis virescens, Heliothis cereals, such as e.g. wheat, barley or rye, and asparagus (e.g. zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, P asparagi); Pyrenophora (anamorph: Drechslera) tritici Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina repentis (tan spot) on wheat or P. teres (net blotch) on barley; fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucop Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe tera scitella, Lithocolletis blancardella, Lobesia botrana, grisea, rice blast) on rice and P grisea on turf and cereals; Loxostege Sticticalis, Lymantria dispar; Lymantria monacha, Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, Lyonetia clerkella, Malacosoma neustria, Mamestra brassi rape, Sunflowers, soybeans, Sugar beets, vegetables and Vari cae, Orgvia pseudotsugata, Ostrinia nubilalis, Panolis flam ous other plants (e.g. P. ultimum or P aphanidermatum); mea, Pectinophora gossypiella, Peridroma Saucia, Phalera Ranularia spp., e.g. R. collo-Cygni (Ranularia leaf spots, bucephala, Phthorimaea operculella, Phyllocnistis citrella, Physiological leaf spots) on barley and R. beticola on Sugar Pieris brassicae, Plathypena scabra, Plutella xylostella, beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, Pseudoplusia includens, Rhyacionia frustrana, Scrobi rape, potatoes, Sugar beets, vegetables and various other palpula absoluta, Sitotroga cerealella, Sparganothis pilleri plants, e.g. R. Solani (root and stem rot) on Soybeans, R. Solani ana, Spodoptera frugiperda, Spodoptera littoralis, (sheath blight) on rice or R. cerealis (Rhizoctonia Spring Spodoptera litura, Thaumatopoea pitvocampa, Tortrix viri blight) on wheat or barley; Rhizopus stolonifer (black mold, dana, Trichoplusia ni and Zeiraphera Canadensis, Soft rot) on Strawberries, carrots, cabbage, vines and toma 0447 beetles (Coleoptera), for example Agrilus sinuatus, toes; Rhynchosporium secalis (Scald) on barley, rye and triti Agriotes lineatus, Agriotes obscurus, Amphimallus solstitia cale; Sarocladium Oryzae and S. attenuatum (sheath rot) on lis, Anisandrus dispar, Anthonomus grandis, Anthononus rice, Sclerotinia spp. (stem rot or white mold) on vegetables pomorum, Aphthona euphoridae, Althous haemorrhoidalis, and field crops, such as rape, Sunflowers (e.g. S. Scierotiorum) Atomaria linearis, Blastophagus piniperda, Blitophaga and soybeans (e.g. S. rolfsii or S. Sclerotiorum); Septoria spp. undata, Bruchus rufimanus, Bruchus pisorum, Bruchus len on various plants, e.g. S. glycines (brown spot) on Soybeans, tis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifur S. tritici (Septoria blotch) on wheat and S. (syn. Stagono cata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthor spora) nodorum (Stagonospora blotch) on cereals; Uncinula rhynchus mapi, Chaetocnema tibialis, Conoderus (syn. Erysiphe) necator (powdery mildew, anamorph: vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on longicornis, Diabrotica semipunctata, Diabrotica 12-punc corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and tata Diabrotica speciosa, Diabrotica virgifera, Epillachna turf Sphacelotheca spp. (Smut) on corn, (e.g. S. reiliana: head varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Smut), Sorghum and Sugar cane; Sphaerotheca fuliginea Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips (powdery mildew) on cucurbits; Spongospora subterranea typographus, Lema bilineata, Lema melanopus, Leptinotarsa (powdery scab) on potatoes and thereby transmitted viral decemlineata, Limonius Californicus, Lissorhoptrus Oryzo US 2011/O 105333 A1 May 5, 2011

philus, Melanotus communis, Melligethes aeneus, Melolontha rus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, hippocastani, Melolontha melolontha, Oulema Oryzae, Otio Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia rrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochle piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, ariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllo Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hva phaga sp., Phyllopertha horticola, Phyllotreta memorum, lopterus pruni, Hyperomyzus lactucae, Macrosiphun ave Phyllotreta striolata, Popillia japonica, Sitona lineatus and nae, Macrosiphum euphorbiae, Macrosiphon rosae, Sitophilus granaria, Megoura viciae, Melanaphis pyrarius, Metopolophium 0448 flies, mosquitoes (Diptera), e.g. Aedes aegypti, dirhodium, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anoph Myzus varians, Nasonovia ribisnigri, Nilaparvata lugens, eles maculipennis, Anopheles crucians, Anopheles albi manus, Anopheles gambiae, Anopheles freeboni, Anopheles Pemphigus bursarius, Perkinsiella saccharicida, Phorodon leucosphyrus, Anopheles minimus, Anopheles quadrimacu humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, latus, Caliphora vicina, Ceratitis capitata, Chrysomya bez Rhopalosiphum maidis, Rhopalosiphum path, Rhopalosi Ziana, Chrysomya hominivorax, Chrysomya macellaria, phum insertum, Sappaphis mala, Sappaphis mali, Schizaphis Chrysops discalis, Chrysops silacea, Chrysops atlanticus, graminum, Schizoneura lanuginosa, Sitobion avenae, Tri Cochliomyia hominivorax, Contarinia sorghicola Cordylo aleurodes vaporariorum, Toxoptera aurantiand, Viteus viti bia anthropophaga, Culicoides firens, Culex pipiens, Culex folii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta Triatoma spp., and Arilus critatus, inornata, Culiseta melanura, Dacus cucurbitae, Dacus 0453 ants, bees, wasps, sawflies (Hymenoptera), e.g. Oleae, Dasineura brassicae, Delia antique, Delia coarctata, Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephal Delia platura, Delia radicum, Dermatobia hominis, Fannia otes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, canicularis, Geomyza Tripunctata, Gasterophilus intestina Crematogaster spp., Hoplocampa minuta, Hoplocampa lis, Glossina morsitans, Glossina palpalis, Glossina fiscipes, testudinea, Lasius niger; Monomorium pharaonis, Solenopsis Glossina tachinoides, Haematobia irritans, Haplodiplosis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis equestris, Hippelates spp., Hyllemyia platura, Hypoderma xyloni, Pogonomyrmex barbatus, Pogonomyrmex Californi lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza cus, Pheidole megacephala, Dasy mutila Occidentalis, Bom trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, bus spp., Vespula squamosa, Paravespula vulgaris, Lycoria pectoralis, Mansonia titillanus, Mayetiola destruc Paravespula pennsylvanica, Paravespula germanica, Doli tor, Musca autumnalis, Musca domestica, Muscina stabu chovespula maculata, Vespa crabro, Polistes rubiginosa, lans, Oestrus ovis, Opomyza forum, Oscinella frit, Pegomya Camponotus floridanus, and Linepithema humile, hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia 0454 crickets, grasshoppers, locusts (Orthoptera), e.g. coarctata, Phlebotomus argentipes, Psorophora columbiae, Acheta domestica, Gryllotalpa gryllotalpa, Locusta migrato Psila rosae, Psorophora discolor, Prosimulium mixtum, ria, Melanoplus bivittatus, Melanoplus femurrubrum, Mel Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haem anoplus mexicanus, Melanoplus sanguinipes, Melanoplus orrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxy's spretus, Nomadacris Septemfasciata, Schistocerca ameri calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus line cana, Schistocerca gregaria, Dociostaurus maroccanus, Ola, and Tabanus similis, Tipula oleracea, and Tipula palu Tachycines asynamorus, Oedaleus Senegalensis, Zonozerus dosa, variegatus, Hieroglyphus daganensis, Kraussaria angu 0449 thrips (Thysanoptera), e.g. Dichromothrips cor lifera, Calliptamus italicus, Chortoicetes terminifera, and betti, Dichromothrips ssp., Frankliniella fisca, Frankliniella Locustana pardalina, occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips 0455 arachnoidea, Such as arachnids (Acarina), e.g. of the Oryzae, Thrips palmi and Thrips tabaci, families Argasidae. Ixodidae and Sarcoptidae, Such as 0450 termites (Isoptera), e.g. Calotermes flavicollis, Leu Amblyomma americanum, Amblyomma variegatum, cotermes flavipes, Heterotermes aureus, Reticulitermes fia Ambryomma maculatum, Argas persicus, Boophilus annula vipes, Reticulitermes virginicus, Reticulitermes lucifigus, tus, Boophilus decoloratus, Boophilus microplus, Dermacen Reticulitermes Santonensis, Reticulitermes grassei, Termes tor silvarum, Dermacentor andersoni, Dermacentor variabi natalensis, and Coptotermes formosanus, lis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, 0451 cockroaches (Blattaria-Blattodea), e.g. Blattella Ixodes Scapularis, Ixodes holocyclus, Ixodes pacificus, Orni germanica, Blattella asahinae, Periplaneta americana, thodorus moubata, Ornithodorus hermsi, Ornithodorus turi Periplaneta japonica, Periplaneta brunnea, Periplaneta cata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus filigginosa, Periplaneta australasiae, and Blatta Orientalis, gallinae, Psoroptes ovis, Rhipicephalus sang uineus, Rhipi 0452 bugs, aphids, leafhoppers, whiteflies, scale insects, cephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes cicadas (Hemiptera), e.g. Acrosternum hilare, Blissus leu Scabiei, and Eriophyidae spp. Such as Aculus Schlechtendali, copterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysder Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemi cus intermedius, Eutygaster integriceps, Euschistus impic dae spp. Such as Phytonemus pallidus and Polyphagotarson tiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus emus latus; Tenuipalpidae spp. Such as Brevipalpus phoeni pratensis, Nezara viridula, Piesma quadrata, Solubea insu cis; Tetranychidae spp. Such as Tetranychus cinnabarinus, laris, Thyanta perditor, Acyrthosiphon Onobrychis, Adelges Tetranychus kanzawai, Tetranychus pacificus, Tetranychus laricis, Aphidula masturtii, Aphis fabae, Aphis forbesi, Aphis telarius and Tetranychus urticae, Panonychus ulmi, Panony pomi, Aphis gossypii, Aphis grossulariae, Aphis Schneideri, chus citri, and Oligonychus pratensis; Araneida, e.g. Latro Aphis spiraecola, Aphis Sambuci, Acyrthosiphon pisum, dectus mactans, and Loxosceles reclusa; Aulacorthum Solani, Bemisia argentifolii, Brachycaudus car 0456 fleas (Siphonaptera), e.g. Ctenocephalides felis, dui, Brachycaudus helichrysi, Brachycaudus persicae, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Brachycaudus prunicola, Brevicoryne brassicae, Capitopho Tunga penetrans, and Nosopsyllus fasciatus, US 2011/O 105333 A1 May 5, 2011 34

0457 silverfish, firebrat (Thysanura), e.g. Lepisma sac 0465. In one aspect, if the seed is rice the hyperbranched charina and Thermobia domestica, polymer is not a hyperbranched polyethyleneamine, polya 04.58 centipedes (Chilopoda), e.g. Scutigera coleoptrata, midoamide, polyethyleneimine or polyether, or a copolymer thereof. 0459 millipedes (Diplopoda), e.g. Narceus spp., 0466 According to the present invention, it is particularly 0460 Earwigs (Dermaptera), e.g. forficula auricularia, advantageous to treat seeds from corn, wheat, barley, oat, rye, 0461 lice (Phthiraptera), e.g. Pediculus humanus capitis, spelt, soybeans, rape, or vegetables with the claimed compo Pediculus humanus corporis, Pthirus pubis, Haematopinus sitions, with an emphasis on seeds from corn, wheat, barley, eutystemus, Haematopinus suis, Linognathus vituli, Bovicola Soybeans, or rape. bovis, Menopon gallinae, Menacanthus stramineus and Sole 0467. The present invention also provides a seed that has nopotes Capillatus. been treated by the method described herein. It also provides 0462 Collembola (springtails), e.g. Onychiurus ssp. a seed obtainable by the method described herein. 0463. The compositions of the present invention are also 0468. Further, the present invention also provides a seed Suitable for controlling Nematodes: plant parasitic nematodes that has been treated with the seed treatment composition Such as root knot nematodes, Meloidogyne hapla, Meloid described herein, and in particular that is coated with the ogyne incognita, Meloidogyne javanica, and other Meloid composition or contains it. It also provides a seed obtainable ogyne species; cyst-forming nematodes, Globodera ros by using the composition described herein. to chiensis and other Globodera species; Heterodera avenae, 0469 According to a particular embodiment, the seeds Heterodera glycines, Heterodera Schachtii, Heterodera tri treated with the composition of the present invention have a folii, and other Heterodera species; Seed gall nematodes, loading of active ingredient(s) of 0.1 to 500 g, preferably 0.5 Anguina species; Stem and foliar nematodes, Aphelenchoides to 200 g, and in particular 0.75 to 100 g, per 100 kilograms of species; Sting nematodes, Belonolaimus longicaudatus and seed. other Belonolaimus species; Pine nematodes, Bursaphelen 0470 According to a further particular embodiment, the chus xylophilus and other Bursaphelenchus species; Ring seeds treated with the composition of the present invention nematodes, Criconema species, Criconemella species, Cri have a loading of hyperbranchend polymer of 1 to 1000 g, conenoides species, Mesocriconema species; Stem and bulb preferably 2 to 500 g, and in particular 5 to 250 g, per 100 nematodes, Dity lenchus destructor, Dity lenchus dipsaci and kilograms of seed. other Dity lenchus species; Awl nematodes, Dolichodorus 0471. The term “coated with and/or contains' here signi species; Spiral nematodes, Heliocotylenchus multicinctus fies that the active ingredient(s) is for the most part on the and other Helicotylenchus species; Sheath and sheathoid Surface of the seed at the time of application, although a nematodes, Hemicycliophora species and Hemiciri greater or lesser part of the active ingredient(s) may penetrate conenoides species; Hirshmanniella species; Lance nema into the seed, depending on the method of application. When todes, Hoploaimus species; false rootknot nematodes, the said seed is (re)planted, it may absorb the active ingredient Nacobbus species; Needle nematodes, Longidorus elongatus (s). and other Longidorus species: Lesion nematodes, Pratylen 0472. According to one embodiment, such a seed com chus neglectus, Pratylenchus penetrans, Pratylenchus curvi prising the active ingredient(s) has a coating, wherein the tatusi, Pratylenchus goodevi and other Pratylenchus species; coating comprises the active ingredient(s). According to a Burrowing nematodes, Radopholus similis and other Radop further embodiment, such a seed comprising the active ingre holus species: Reniform nematodes, Rotylenchus robustus dient(s) is a seed whose germinable part and/or natural and other Rotylenchus species; Scutellonema species; Stubby sheath, shell, pod and/or integument comprise(s) the active root nematodes, Trichodorus primitivus and other Tri ingredient(s). Also, the active ingredient(s) can be present in chodorus species, Paratrichodorus species; Stunt nematodes, both the coating and the germinable part and/or natural Tvlenchorhynchus claytoni, Tilenchorhynchus dubius and sheath, shell, pod and/or integument of the seed. other Tilenchorhynchus species; Citrus nematodes, Tvlen 0473 Preferably, such seeds comprise an effective amount chulus species; Dagger nematodes, Xiphinema species; and of the active ingredient(s). Accordingly, the seeds are coated, other plant parasitic nematode species. impregnated or coated and impregnated in Such a manner that 0464. The compositions of the present invention are also pest damage during germination and emergence is reduced. useful for controlling arachnids (Arachnoidea). Such as acar 0474 The seeds treated with the composition of the ians (Acarina), e.g. of the families Argasidae. Ixodidae and present invention may also be enveloped with a film overcoat Sarcoptidae, such as Amblyomma americanum, Amblyo ing to protect the coating containing the active ingredient(s). mma variegatum, Argas persicus, Boophilus annulatus, Boo Such overcoatings are known in the art and may be applied philus decoloratus, Boophilus microplus, Dermacentor Silva using conventional fluidized bed and drum film coating tech rum, Hyalomma truncatum, Ixodes ricinus, Ixodes niques. rubicundus, Ornithodorus moubata, Otobius megnini, Der 0475. The seeds of the present invention can be used for manySSuS gallinae, Psoroptes ovis, Rhipicephalus appendicu the propagation of plants. The seeds can be stored, handled, latus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophy planted/sowed and tilled. idae spp. Such as Aculus Schlechtendali, Phyllocoptrata 0476. In the context of the present invention, aliphatic oleivora and Eriophyes sheldoni; Tarsonemidae spp. Such as hydrocarbon radicals include in particular alkyl, alkylene, Phytonemus pallidus and PolyphagotarSonemus latus; Tenui alkenyl and cycloalkyl radicals. Aromatic hydrocarbon radi palpidae spp. Such as Brevipalpus phoenicis; Tetranychidae cals include in particular aryl and arylene radicals. spp. Such as Tetranychus cinnabarinus, Tetranychus kanza Araliphatic hydrocarbon radicals include in particular aralkyl wai, Tetranychus pacificus, Tetranychustelarius and Tetrany radicals. chus urticae, Panonychus ulmi, Panonychus citri, and oligo 0477 The expression “alkyl comprises straight-chain nychus pratensis. and branched alkyl groups. Suitable short-chain alkyl groups US 2011/O 105333 A1 May 5, 2011

are, e.g., Straight-chain or branched C-C-alkyl, preferably 0485. In a 6 L flask, equipped with stirrer, internal ther C-C alkyl and particularly preferably C-C alkyl groups. mometer and reflux condenser, diethylcarbonate (1183 g, These include in particular methyl, ethyl, propyl, isopropyl. 10.0 moles) was reacted with a triol (2700 g, 10.0 moles: n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, prepared by ethoxylation of trimethyloipropane with 3 units 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dim ethylene oxide) at 145° C. and normal pressure under nitro ethylpropyl. 2.2-dimethylpropyl, 1-ethylpropyl, n-hexyl, gen atmosphere in the presence of potassium carbonate (0.4 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, g). Ethanol was constantly formed during the reaction as a 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, by-product of the condensation, thus lowering the boiling 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3.3-dimethylbutyl, point to about 100°C. within 5hrs. After the boiling tempera 1,1,2-trimethylpropyl, 1.2.2-trimethylpropyl, 1-ethylbutyl, ture remained constant, the reflux condenser was substituted 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, by a distillation unit, comprising a 20 cm packed column, a 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl, and the like. cooler directed downwards and a receiver, and the ethanol Suitable long-chain Cs-Co alkyl groups are straight-chain formed during the reaction was distilled off continuously. and branched alkyl or alkenyl groups. In this connection, they After about 810 g ethanol (overall) had been removed, corre are preferably mainly linear alkyl residues, such as those also sponding to a conversion of about 88% based on ethanol, the present in natural or synthetic fatty acids and fatty alcohols reaction mixture was cooled down to 100° C. and adjusted and also oxo alcohols, which, if appropriate, in addition can with 85% phosphoric acid to a pH value <7 to neutralise be mono-, di- or polyunsaturated. These include, e.g., potassium carbonate. The mixture was stirred at 140°C. for 1 n-hexyl, n-heptyl. n-octyl, n-nonyl, n-decyl. n-undecyl hr. Then the reaction apparatus was equipped with a gas inlet n-dodecyl, n-tridecyl, n-tetradecyl. n-pentadecyl, n-hexade tube and the mixture was stripped with nitrogen at 180° C. for cyl, n-heptadecyl. n-octadecyl. n-nonadecyl, and the like. 3 hrs. In this way further residual ethanol or low-molecular 0478. The expression “alkylene' within the meaning of compounds (about 10 g overall) were removed. the present invention represents straight-chain or branched 0486 Subsequently, the product was cooled and analysed. alkanediyl groups with 1 to 7 carbon atoms (short chain), e.g. The OH number was found to be 265 mg KOH/g. Molecular methylene, 1.2-ethylene, 1,3-propylene, and the like, or with masses, determined by GPC (eluent=DMAC, 8 to 40 carbon atoms (long chain). calibration=PMMA): Mn=2150 g/mole, Mw =7400 g/mole. 0479. Alkenyl preferably represents straight-chain and A 10% by weight solution of the product in water had a branched alkenyl groups having 2 to 40 carbon atoms, which viscosity of 13 mPas, as determined on a TA Instruments CSL can be monounsaturated, diunsaturated or polyunsaturated. 500 Carri Med Rheometer with a cone-plate system at a shear They are preferably Co-Cs, in particular Co-Co and espe rate of 100 1/s. cially C-C alkenyl groups. These include in particular octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, Reference Example 2 tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octa 0487. Hyperbranched polyester from alkenyl succinic decenyl, nonadecenyl, linolyl, linoleyl, eleostearyl, and the acid anhydride (Pentasize 8) and polyoxyethylene triol, hav like, and in particular oleyl (9-octadecenyl). ing an OH number of 70 mg KOH/g and an acid number of 28 0480 Cycloalkyl preferably represents C-C-cycloalkyl mg KOH/g. radicals, for example cyclopropyl, cyclobutyl, cyclopentyl, 0488 698 g (2 moles) of a C-s-alkenylsuccinic acid anhy cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl dride (Pentasize 8, Trigon Chemie GmbH) with a molecular cycloundecyl and cyclododecyl; preference is given to cyclo mass of 349 g/mole, 1340 g (2.0 moles) of a trimethylolpro pentyl, cyclohexyland cycloheptyl. Cs-Cs cycloalkyl, Such as pane-based polyetherol, grafted Statistically with 12 units cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, are usu ethylene oxide, and 0.1 g dibutyltindilaureate were weighed ally preferred. in to a 4 L. glass flask, equipped with stirrer, internal ther 0481 Aryl comprises unsubstituted and substituted aryl mometer, a cooler directed downwards with a tubular vacuum groups usually having 6 to 14 carbon atoms and preferably connector, and heated slowly to 180° C. under stirring. represents phenyl, tolyl, Xylyl, mesityl, naphthyl, fluorenyl, Vacuum was applied continuously and the internal pressure anthracenyl, phenanthrenyl, naphthacenyl and in particular of the apparatus was reduced up to 40 mbar. Due to the gas phenyl, tolyl, Xylyl or mesity1. bubbles formed the mixture foamed slightly. The reaction 0482 Aralkyl comprises unsubstituted and substituted mixture was stirred at 180° C. for 4 hrs. at 40 mbar and aryl groups usually having 6 to 14 carbon atoms bound to additional for 2 hrs. at 180° C. at 20 mbar while the water alkylene usually having 1 to 7 carbon atoms. formed during the reaction was distilled of continuously. 0489 Decrease in acid number was checked periodically EXAMPLES until a value under 30 mg KOH/g was found. Subsequently, the product was cooled and analysed. The OH number was 0483 The invention will be illustrated by the following found to be 70 mg KOH/g, the acid number was 28 mg examples, which should not be construed as limiting the KOH?g. Molecular masses determined by GPC invention. (eluent=DMAC, calibration=PMMA): Mn=3400 g/mole, Mw-21000 g/mole. A 10% by weight solution of the product REFERENCE EXAMPLES in water had a viscosity of 216 mPas, as determined on a TA Preparation of Hyperbranched Polymers Instruments CSL 500 CarriMed Rheometer with a cone-plate system at a shear rate of 100 1/s. Reference example 1 Reference Example 3 0484 Hyperbranched polycarbonate from diethylcarbon 0490 Hyperbranched polycarbonate from diethylcarbon ate and polyoxyethylene triol, having an OH number of 265 ate and polyoxyethylene triol, having an OH number of 150 mg KOH/g. mg KOH/g. US 2011/O 105333 A1 May 5, 2011 36

0491. In a 6 L flask, equipped with stirrer, internal ther 2. The composition according to claim 1, wherein the mometer and reflux condenser, diethylcarbonate (590.7g, 5.0 hyperbranched polymer has a degree of branching (DB) from moles) was reacted with a polyoxyethylene triol (3350 g, 5.0 20 to 99%. moles; prepared by ethoxylation of trimethylolpropane with 3. The composition according to claim 1 or 2, wherein the 12 units ethylene oxide) at 145° C. at normal pressure under hyperbranched polymer has a weight-average molecular nitrogen atmosphere in the presence of potassium carbonate weight of more than 1000 g/mol. (0.5 g). Ethanol was constantly formed during the reaction as 4. The composition according to any one of claims 1 to 3. a by-product of the condensation, thus lowering the boiling wherein the hyperbranched polymer has a glass transition point to about 120°C. within 6 hrs. After the boiling tempera temperature of -80° C. to 50° C. ture remained constant, the reflux condenser was substituted 5. The composition according to any one of claims 1 to 4. by a distillation unit, comprising a 20 cm packed column, a wherein the hyperbranched polymer is soluble in water or cooler directed downwards and a receiver, and the ethanol water-dispersible. formed during the reaction was distilled off continuously. 6. The composition according to any one of claims 1 to 5. After about 405 g ethanol (overall) had been removed, corre wherein the viscosity of a 10% by weight solution of hyper sponding to a conversion of about 88% based on ethanol, the branched polymer in water is lower than 1000 mPas. reaction mixture was cooled down to 100° C. and adjusted 7. The composition according to any one of claims 1 to 6. with 85% phosphoric acid (about 1.2 g) to a pH value <7 to wherein the hyperbranched polymer is selected from hyper neutralise the potassium carbonate. The mixture was stirred at branched polycarbonates, hyperbranched polyesters, hyper 140° C. for 1 hr. Then the reaction apparatus was equipped branched polyethers, hyperbranched polyestercarbonates, with a gas inlet tube and the mixture was stripped with nitro hyperbranched polyethercarbonates, hyperbranched poly gen at 180°C. for 3 hrs. In this way, further residual of ethanol etheresters, hyperbranched polyetherestercarbonates, hyper or low-molecular compounds (about 10 g overall) were branched polyurethanes, hyperbranched polyureas, hyper removed. branched polyamides, hyperbranched polyamines, 0492 Subsequently, the product was cooled and analysed. hyperbranched polyureaurethanes, hyperbranched polyes The OH number was found to be 150 mg KOH/g. Molecular teramides, hyperbranched polyesteramines and hyper masses determined by GPC (eluent=DMAC, calibration branched polyetheramines. —PMMA): Mn=2750 g/mole, Mw =5700 g/mole. A 10% by 8. The composition according to any one of claims 7. weight solution of the product in water had a viscosity of 2 wherein the hyperbranched polymer is selected from hyper mPas, as determined on a TA Instruments CSL 500 Carri Med branched polycarbonates, hyperbranched polyesters, hyper Rheometer with a cone-plate system at a shear rate of 100 1/s. branched polyestercarbonates, hyperbranched polyethercar bonates, hyperbranched polyetheresters, hyperbranched Examples 1 to 3 polyetherestercarbonates, hyperbranched polyurethanes, Seed Treatment Compositions hyperbranched polyureas, hyperbranched polyureaure thanes, hyperbranched polyesteramides, and hyperbranched 0493 Ready-to-use treatment slurries were prepared by polyesteramines. mixing all ingredients as indicated. 9. The composition according to claim 7, wherein the hyperbranched polymer is selected from hyperbranched polycarbonates, hyperbranched polyesters, hyperbranched polyethercarbonates, hyperbranched polyetheresters, hyper 1 2 3 Control branched polyestercarbonates and hyperbranched polyether REGENT 500 FS 40 g 40 g 40 g 40 g estercarbonates. Poylmer of Ref, ex. 1 10 g Poylmer of Ref, ex. 2 10g 10. The composition according to any one of claims 1 to 9, Poylmer of Ref, ex. 3 10 g wherein hyperbranched polymer comprises hydrophobic WATER 50 g 50 g 50 g 60 g moieties. Loss of ai. 16 19 18 41 11. The composition according to any of claims 1 to 10, flowability 24.0 23 19.5 2O.S comprising at least 1% by weight, preferably at least 2% by weight and in particular at least 5% by weight of hyper REGENT 500 FS is a commercial seed treatment product branched polymer. from BASF containing 500 g/L of the insecticide fipronil. 12. The composition according to any of claims 1 to 11, 0494. Seed treatment experiments were carried out with comprising at most 50% by weight, preferably at most 30% the slurries by applying 10 g slurry to 2 kg untreated maize in by weight and in particular at most 20% by weight of hyper a mini-Rotostatbatch treater from SATEC. The flowability of branched polymer. treated maize was determined as the time required for 2 kg 13. The composition according to any of claims 1 to 12, maize to flow through a vibrated metal funnel with the fol further comprising a solid matrix material. lowing dimensions: 290 mm (diameter), 30 mm (outlet), 290 14. The composition according to any of claims 1 to 13, mm (length). further comprising a penetration enhancer. 0495 Adhesion to the seed was determined 24 hours after 15. The composition according to any of claims 1 to 14, treatment by shearing the treated seed for 30 seconds in a further comprising a colorant. “dummy” treatment in the same Rotostat and determining the 16. The composition according to any of claims 1 to 15, loading with Fipronil before and after shearing. The loss of further comprising an anti-freeze agent. a.i. is determined as the difference between these two values. 17. The composition according to any of claims 1 to 16, We claim: further comprising a gelling agent. 1. A seed treatment composition comprising active ingre 18. The composition according to any of claims 1 to 17, dient and hyperbranched polymer. further comprising water. US 2011/O 105333 A1 May 5, 2011 37

19. The composition according to claim 18, comprising at 23. A method of treating seed, which comprises applying least 5% by weight, preferably at least 10% by weight and in an effective amount of a composition of any one of claims 1 to particular at least 30% by weight of water. 20 to a lot of seeds. 24. The method of claim 23, wherein the seeds are substan 20. The composition according to claim 18 or 19, compris tially dry before the effective amount of the composition is ing at most 99% by weight, preferably at most 90% by weight applied. and in particular at most 80% by weight of water. 25. The method of claim 23 or 24, wherein the seeds are 21. The use of a hyperbranched polymer as seed coating corn, wheat, barley, oat, rye, spelt, vegetable, soybean or rape agent. seeds. 22. The use according to claim 21, wherein the hyper branched polymer is defined as in any one of claims 1 to 20.