(12) United States Patent (10) Patent No.: US 7,943,644 B2 Uhr Et Al

USOO794364.4B2

(12) United States Patent (10) Patent No.: US 7,943,644 B2 Uhr et al. (45) Date of Patent: May 17, 2011

(54) STABILIZATION OF IODINE-CONTAINING (56) References Cited BOCDES BY MEANS OF SPECIAL AZOLE COMPOUNDS U.S. PATENT DOCUMENTS 2,739,922 A * 3/1956 Shelanski ...... 524,548 (75) Inventors: Hermann Uhr, Leverkusen (DE); 4,276,211 A 6/1981 Singer et al. ... 260/29.6 MN Johannes Kaulen, Odenthal (DE); 4.297.258 A 10/1981 Long, Jr...... 260f29.6 MN

Thomas Jaetsch, Köln (DE); Peter 4,552,885. A 1 1/1985 Gabriele et al...... 514/316 Spetmann, Leverkusen (DE) 5,051,256 A * 9/1991 Barnes ...... 424/402 6,143,204. A 1 1/2000 Lutz et al...... 252/384 rsr rr 6.353,021 B1 3/2002 Gaglani et al. . ... 514,478 (73) Assignee: NNESS putschland GmbH, 6,472,424 B1 10/2002 Gaglani et al. . ... 514,478 everkusen (DE) 6,946,427 B2* 9/2005 Lutz et al...... 504,140 c - 2006/00 13833 A1 1/2006 Bartko ...... 424/400 (*) Notice: Subject to any disclaimer, the term of this 2007/0128246 A1* 6/2007 Hossainy et al...... 424/423 patent is extended or adjusted under 35 U.S.C. 154(b) by 18 days. FOREIGN PATENT DOCUMENTS WO 98.22543 5, 1998 (21) Appl. No.: 12/281,163 WO 99.291.76 6, 1999 WO OOf 16628 3, 2000 (22) PCT Filed: Feb. 21, 2007 WO 2007 O28527 3, 2007 (86). PCT No.: PCT/EP2007/001480 OTHER PUBLICATIONS S371 (c)(1), Nomiya, Kenji, et al. “Synthesis and Crystal Structure of Coinage (2), (4) Date: Nov. 10, 2008 Metal (I) Complexes with Tetrazole (Htetz) and Triphenylphospine Ligands, and Their Antimicrobial Activities. A Helical Polymer of (87) PCT Pub. No.: WO2007/101549 Silver (I) Complex Ag(tetz)(PPh3)2n and Monomeric Gold (I) Complex Au(tetz)(PPh3)].” Inorganica Chimica Acta, vol. 298, pp. PCT Pub. Date: Sep. 13, 2007 24-32 (2000).* Abstract of CS Patent No. 276253 B6 (Apr. 11, 1991) STN Search (65) Prior Publication Data Notes at L3, Answer 15.* US 2009/O192219 A1 Jul. 30, 2009 * cited by examiner (30) Foreign Application Priority Data Primary Examiner — Raymond J Henley, III Mar. 6, 2006 (DE) ...... 10 2006 O1 O 199 (74) Attorney, Agent, or Firm — Nicanor A. Kohncke (51) Int. Cl. (57) ABSTRACT A6 IK3I/4I (2006.01) A6 IK 47/00 (2006.01) Specific azole compounds are outstandingly suitable for sta (52) U.S. Cl...... 514/359; 514/361; 514/381: 514/769 bilizing iodine-containing biocides in industrial materials, (58) Field of Classification Search ...... 514/359, more particularly in paints based on alkyd resin. 514/361, 381,769 See application file for complete search history. 14 Claims, No Drawings US 7,943,644 B2 1. 2 STABILIZATION OF ODNE-CONTAINING Also known are transition metal-containing alkyd resin BOCDES BY MEANS OF SPECIAL AZOLE paints in which halopropargyl compounds are stabilized by COMPOUNDS means of organic epoxides (cf. WO 00/16628). There have also already been descriptions of processes for CROSS REFERENCE TO RELATED PATENT 5 Suppressing the light-induced degradation of active antifun APPLICATIONS gal compounds, such as iodopropargyl butylcarbamate among others, by addition of tetraalkylpiperidine compounds The present patent application claims the right of priority and/or UV absorbers (cf. EP-A 0083 308). under 35 U.S.C. S 119 (a)-(d) and 35 U.S.C. S365 of Interna The addition of epoxy compounds is intended to reduce the tional Application No. PCT/EP2007/001480, filed 21 Feb. 10 discoloration of iodoalkyne compounds, such as IPBC (cf. 2007, which was published in German as International Patent U.S. Pat. No. 4,276.211 and U.S. Pat. No. 4,297.258). Publication No. WO 2007/101549 A1 on 13 Sep. 2007, which Also described, furthermore, have been synergistic mix is entitled to the right of priority of German Patent Applica tures of epoxides with UV absorbers (cf. WO99/29.176) and tion DE 10 2006 01 0199.5 filed on 6 Mar. 2006. with benzylidenecamphor derivatives (cf. U.S. Pat. No. The invention relates to the use of specific known azole 15 6,472,424) which likewise exhibit reduced yellowing. compounds as Stabilizers of iodine-containing biocides, and The stabilizing activity of the aforementioned stabilizers, also to active compound formulations, concentrates and however, is not always Sufficient, and is hampered by perfor industrial products comprising iodine-containing biocide and mance drawbacks. Thus it is observed in particular that the specific azole compounds. drying times of the paints are significantly prolonged, which Iodine-containing biocides are generally employed in in many cases is unacceptable to the user. Moreover, the order to protect industrial materials from decomposition/de inhibition of the coloration is not always satisfactory. struction and visual alteration by fungi, bacteria and algae, The present invention accordingly provides active com preferably by fungi. Also used here besides iodoalkynyl com pound mixtures comprising at least one iodine-containing pounds are active compounds in which one or more iodine biocide and at least one azole compound of the general for atoms are attached at double bond systems, but also to singly 25 mula (I) or tautomer thereof, bonded carbon atoms. Features common to all iodine-containing biocides are firstly that on exposure to light they lead to a yellowing (I) accompanied by loss of active compound and activity and X secondly that in many application forms, but especially in 30 j\ Solvent-based formulations, paints, stains or varnishes, even RI Y without exposure to light, they are chemically unstable, H which is manifested in a degradation of the active compound, with the result of reduced biological activity. in which The chemical degradation is particularly severe in the pres 35 R" is hydrogen, hydroxyl, mercapto or optionally substituted ence of transition metal compounds, which are used prefer amino entially as dryers (siccatives) in paints containing alkyd resin. and Particularly noteworthy here are cobalt-containing dryers, X, Y and Zindependently of one another are N or C R. although the alternatively and in some cases additionally used in which lead, manganese and Vanadium dryers also lead to severe 40 R is hydrogen, hydroxyl, mercapto or optionally substituted active compound degradation. amino. As well as the dryers, there are a series of further constitu Preference is given to mixtures comprising at least one ents leading, in varying intensities, to degradation of iodine iodine-containing biocide and at least one azole compound of containing biocides in paints, varnishes, primers, impregnat the formula (I) or tautomer thereof ing systems, stains and active compound formulations. While 45 in which the destabilizing effect is still relatively weak in the case of R" is hydrogen, hydroxyl, mercapto, amino, C1-C3-alky the solvents typically used, the other typical components of a lamino or di-C-C-alkylamino paint formulation, such as in-process additives, plasticizers, and colour pigments, anti-settling agents, thixotropic agents, cor X, Y and Z independently of one another are N or C R. rosion inhibitors, anti-skinning agents and binders, for 50 and example, show more or less strongly pronounced destabiliz R is hydrogen, hydroxyl, mercapto, amino, C1-C3-alky ing effects. lamino or di-C-C-alkylamino. Surprisingly it has now been found that through the use of The radicals indicated in the respective definitions and particular azole compounds, in particular from the group of preferred and particularly preferred definitions may, indepen imidazoles, triazoles and tetrazoles, it is possible to stabilize 55 dently of the particular combination indicated, be replaced in iodine-containing biocides both from chemical and light any desired way, including replacement by radical definitions induced degradation, thereby making it possible to prevent of other combinations. Moreover, radical definitions from the above-described drawbacks such as colour changes and each preference range may also be omitted. chemical degradation. Particular preference is given to mixtures of the invention The azoles for use in accordance with the invention, in 60 which comprise at least one of the following imidazoles, particular from the group of imidazoles, triazoles and tetra triazoles or tetrazoles: Zoles, are known; however, their use for stabilizing iodine 2-aminoimidazole, containing biocides has not previously been described. 4-aminoimidazole, There are already known methods of preventing the deg 2-hydroxyimidazole, radation of halopropargyl compounds in transition metal 65 4-hydroxyimidazole, containing alkyd resin paints. WO 98/22543, for example, 2-mercaptoimidazole, describes the use of chelating reagents. 4-mercaptoimidazole, US 7,943,644 B2 3 4 2-imidazolin-4-one, Examples of microorganisms which may bring about deg 4-amino-2-hydroxyimidazole, radation or alteration of the industrial materials include bac 4-amino-2-mercaptoimidazole, teria, fungi, yeasts, algae and slime organisms. The active 3-amino-1,2,4-triazole, compounds of the invention act preferably against fungi, 3-hydroxy-1,2,4-triazole, more particularly moulds, wood-discolouring and wood-de 3-mercapto-1,2,4-triazole, stroying fungi (Basidiomycetes) and also against Slime 3-amino-5-hydroxy-1,2,4-triazole, organisms and bacteria. 3-amino-5-mercapto-1,2,4-triazole, Microorganisms of the following genera may be men 3,5-diamino-1,2,4-triazole, tioned by way of example: 3-hydroxy-5-mercapto-1,2,4-triazole, 10 Alternaria. Such as Alternaria tenuis, 3,5-dihydroxy-1,2,4-triazole, Aspergillus, Such as Aspergillus niger; Chaetomium Such as Chaetomiurn globosum, 3,5-dimercapto-1,2,4-triazole, Coniophora, such as Coniophora puetana, 5-amino-1,2,3,4-tetrazole, 5-hydroxy-1,2,3,4-tetrazole, Lentinus, Such as Lentinus tigrinus, 15 Penicillium, Such as Penicillium glaucum, 5-mercapto-1,2,3,4-tetrazole. Polyporus, such as Polyporus versicolor; The iodine-containing biocides present in the mixtures of Aureobasidium, Such as Aureobasidium pullulans, the invention are preferably iodoalkynyl compounds or com Sclerophoma, such as Sclerophoma pityophila, pounds in which one or more iodine atoms are attached to Trichoderma, such as Trichoderma viride, double bond systems, or compounds in which one or more Escherichia, such as Escherichia coli, iodine atoms are attached to singly bonded carbon atoms. Pseudomonas, such as Pseudomonas aeruginosa, With particular preference the iodine-containing active Staphylococcus, such as Staphylococcus aureus. compounds are the following compounds: 3-iodo-2-propy Depending on their respective physical and/or chemical nylpropyl carbamate, 3-iodo-2-propynylbutyl carbamate properties, the mixtures of the invention can furthermore be (IPBC), 3-iodo-2-propynyl-m-chlorophenyl carbamate, 25 converted into the typical formulations, such as Solutions, 3-iodo-2-propynylphenyl carbamate, 3-iodo-2-propynyl 2.4. emulsions, Suspensions, powders, foams, pastes, granules, 5-trichloro-phenyl ether, 3-iodo-2-propynyl 4-chlorophenyl aerosols and ultrafine encapsulations in polymeric Sub formal (IPCF), di(3-iodo-2-propynyl)hexyl dicarbamate, StanceS. 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-pro These formulations can be prepared in a known manner, for pynyloxyethanol phenyl carbamate, 3-iodo-2-propynylth 30 example by mixing the active compounds with extenders, that ioXothioethyl carbamate, 3-iodo-2-propynylcarbamic ester is, liquid solvents, liquefied gases underpressure, and/or solid (IPC), N-iodpropargyloxycarbonylalanine, N-iodopropargy carriers, if appropriate with the use of surfactants, that is loxycarbonylalanine ethyl ester, 3-(3-iodo-propargyl)ben emulsifiers and/or dispersants and/or foam-formers. If the ZOxazol-2-one, 3-(3-iodopropargyl)-6-chlorobenzoxazol-2- extender used is water, it is also possible to use for example one, diiodomethyl p-tolyl sulphone, diiodomethyl 35 organic solvents as auxiliary solvents. Essentially, Suitable p-chlorophenyl Sulphone, 3-iodo-2-propynyl alcohol, 4-chlo liquid solvents are: aromatics, such as Xylene, toluene or rophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2- alkylnaphthalenes, chlorinated aromatics or chlorinated ali propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, phatic hydrocarbons, such as chlorobenzenes, chloroethylene 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl or methylene chloride, aliphatic hydrocarbons, such as cyclo n-hexylcarbamate, 3-iodo-2-propynyl cyclohexylcarbamate. 40 hexane or paraffins, for example mineral oil fractions, alco The mixtures of the invention in general contain 0.01%- hols, such as butanol or glycol and their ethers and esters, 70% by weight of at least one iodine-containing biocide and ketones, such as acetone, methyl ethyl ketone, methyl isobu 0.001%-50% by weight of at least one azole compound of the tyl ketone or cyclohexanone, strongly polar solvents, such as formula (I), preferably 0.05%-60% by weight of at least one dimethylformamide and dimethylsulphoxide, and water. By iodine-containing biocide and 0.005%-40% by weight of at 45 liquefied gaseous extenders or carriers are meant liquids least one azole compound of the formula (I), and with par which are gaseous at ambient temperature and under atmo ticular preference 0.1%-50% by weight of at least one iodine spheric pressure, for example aerosol propellants. Such as containing biocide and 0.01%-30% by weight of at least one halogenated hydrocarbons and butane, propane, nitrogen and azole compound of the formula (I). carbon dioxide. Suitable solid carriers are: for example The mixtures of the invention can be prepared by mixing 50 ground natural minerals, such as kaolins, clays, talc, chalk, together the individual components as a function of their quartz, attapulgite, montmorillonite or diatomaceous earth, respective physical and/or chemical properties, without addi and ground synthetic minerals, such as finely divided silica, tives, or converting them into the typical formulations, such alumina and silicates. Suitable solid carriers for granules are: as solutions, emulsions, Suspensions, powders, foams, pastes, for example crushed and fractionated natural rocks Such as granules, aerosols and ultra-fine encapsulations in polymeric 55 calcite, marble, pumice, Sepiolite and dolomite, and synthetic Substances. granules of organic and inorganic meals, and granules of The mixtures of the invention are suitable for protecting organic material Such as sawdust, coconut shells, maize cobs industrial materials. Industrial materials in the present con and tobacco stalks. Suitable emulsifiers and/or foam-formers text are non-living materials which have been prepared for are: for example nonionic and anionic emulsifiers, such as use in industry. The industrial materials are, for example, 60 polyoxyethylene fatty acid esters, polyoxyethylene fatty adhesives, sizes, paper and cardboard, textiles, leather, wood, alcohol ethers, for example alkylaryl polyglycol ethers, alkyl wood-based materials, coating materials and plastics articles, Sulphonates, alkyl Sulphates, arylsulphonates and protein cooling lubricants and other materials which may be infested hydrolysates. Suitable dispersants are: for example lignoSul or decomposed by microorganisms. phite waste liquors and methylcellulose. Additionally provided is the use of the mixtures of the 65 Tackifiers such as carboxymethylcellulose and natural and invention for protecting industrial materials against infesta synthetic polymers in the form of powders, granules or lati tion and/or destruction by microorganisms. ces, such as gum arabic, polyvinyl alcohol and polyvinyl US 7,943,644 B2 5 6 acetate, and natural phospholipids, Such as cephalins and benzimidazoles such as: lecithins, and synthetic phospholipids, can be used in the carbendazim, benomyl, fuberidazole, thiabendazole or their formulations. Other possible additives are mineral and veg salts; etable oils. morpholine derivatives such as: It is possible to use colourants such as inorganic pigments, aldimorph, dimethomorph, dodemorph, fallimorph, fenpropi for example iron oxide, titanium oxide and Prussian blue, and din, fenpropimorph, tridemorph, trimorphamid and their organic dyes, such as alizarin dyes, azo dyes and metal phtha arylsulphonate salts such as, for example, p-toluenesulphonic locyanine dyes, and trace nutrients such as salts of iron, acid and p-dodecylphenylsulphonic acid; manganese, boron, copper, cobalt, molybdenum and zinc. benzothiazoles Such as: 10 2-mercaptobenzothiazole; The formulations generally comprise between 0.1 and 95 benzothiophene dioxides such as: percent by weight of active compound, preferably between 2 N-cyclohexyl-benzobthiophenecarboxamide S.S.-dioxide: and 75 percent by weight. benzamides such as: The present invention further provides microbicidal com 2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide, positions based on the mixtures of the invention and compris 15 tecloftalam: ing at least one solvent or diluent and also, if appropriate, boron compounds such as: processing auxiliaries and, if appropriate, further antimicro boric acid, boric esters, borax: bially active compounds. In this case, the active compounds formaldehyde and formaldehyde-releasing compounds Such may be present herein either in dissolved form or as Suspen aS sions or emulsions. The solvents or diluents are either water benzyl alcohol mono (poly)hemiformal, 1,3-bis(hydroxym or all customary organic solvents. ethyl)-5,5-dimethylimidazolidine-2,4-dione (DMDMH), The efficacy and the activity spectrum of the mixtures of bisoxazolidine, n-butanol hemiformal, cis-1-(3-chloroallyl)- the invention and of the compositions preparable therefrom 3,5,7-triaza-1-azoniaadamantane chloride, 1-1,3-bis(hy can be increased by adding, if appropriate, further antimicro droxymethyl-2,5-dioxoimidazolidin-4-yl-1,3-bis-(hy bial compounds, fungicides, bactericides, herbicides, insec 25 droxymethyl)urea, dazomet, dimethylolurea, 4.4- ticides or other active compounds, so as to widen the spec dimethyloxazolidine, ethylene glycol hemiformal, trum of activity or to obtain particular effects. These mixtures 7-ethylbicyclooxazolidine, hexahydro-S-triazine, hexameth may have an even wider activity spectrum. ylenetetramine, N-hydroxymethyl-N'-methylthiourea, meth In many cases, synergistic effects are obtained, i.e. the ylenebismorpholine, Sodium N-(hydroxymethyl)glycinate, 30 N-methylolchloroacetamide, oxazolidine, paraformalde activity of the mixture is greater than the activity of the hyde, taurolin, tetrahydro-1,3-oxazine, N-(2-hydroxypropyl) individual components. The following compounds, for aminemethanol, tetramethylolacetylenediurea (TMAD): example, are found to be particularly favorable co-compo isothiazolinones such as: nents: N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazo triazoles such as: 35 lin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, 5-chloro aZaconazole, azocyclotin, bitertanol, bromuconazole, cypro N-octylisothiazolinone, N-octylisothiazolin-3-one, 4.5-trim conazole, diclobutrazole, difenoconazole, diniconazole, ethyleneisothiazolinone, 4.5-benzoisothiazolinone; epoxyconazole, etaconazole, fenbuconazole, fenchlorazole, aldehydes such as: fenethanil, fluguinconazole, flusilaZole, flutriafol, furcona cinnamaldehyde, formaldehyde, glutardialdehyde, B-bromo Zole, hexaconazole, imibenconazole, ipconazole, isozofos, 40 cinnamaldehyde, o-phthaldialdehyde; myclobutanil, metconazole, paclobutrazole, penconazole, thiocyanates Such as: propioconazole, prothioconazole, Simeconazole, (+)-cis-1- thiocyanatomethylthiobenzothiazole, methylenebisthiocy (4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol, anate, 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl) quaternary ammonium compounds and guanidines such as: propan-2-ol, tebuconazole, tetraconazole, triadimefon, tri 45 benzalkonium chloride, benzyldimethyltetradecylammo adimenol, triapenthenol, triflumizole, triticonazole, unicona nium chloride, benzyldimethyl-dodecylammonium chloride, Zole and their metal salts and acid adducts; dichlorobenzyldimethylalkylammonium chloride, dide imidazoles Such as: cyldimethyl-ammonium chloride, dioctyldimethylammo clotrimazole, bifonazole, climbazole, econazole, fenapamil, nium chloride, N-hexadecyltrimethylammonium chloride, imazalil, isoconazole, ketoconazole, lombazole, miconazole, 50 1-hexadecylpyridinium chloride, iminoctadine tris(albesi pefurazoate, prochloraZ, triflumizole, thiazolcar, 1-imida late); Zolyl-1-(4-chloro-phenoxy)-3.3-dimethylbutan-2-one, and iodine derivatives such as: their metal salts and acid adducts; diiodomethyl p-tolyl Sulphone, 3-iodo-2-propynyl alcohol, pyridines and pyrimidines such as: 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-di ancymidol, buthiobate, fenarimol, mepanipyrin, nuarimol, 55 iodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, pyVoxyfur, triamirol; 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl Succinate dehydrogenase inhibitors such as: n-butylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate, benodanil, carboxim, carboxim Sulphoxide, cyclafluramid, 3-iodo-2-propynyl cyclohexylcarbamate, 3-iodo-2-propynyl fenfuram, flutanil, furcarbanil, furmecyclox, mebenil, phenylcarbamate; mepronil, methfuroxam, metSulfovax, nicobifen, pyracar 60 phenols such as: bolid, oxycarboxin, Shirlan, Seedvax: tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophe naphthalene derivatives such as: nol. 3,5-dimethyl-4-chlorophenol, dichlorophene, 2-benzyl terbinafine, naftifine, butenafine, 3-chloro-7-(2-aza-2,7,7-tri 4-chlorophenol, triclosan, diclosan, hexachlorophene, methyloct-3-en-5-yne); methyl p-hydroxy-benzoate, ethyl p-hydroxybenzoate, pro Sulphenamides Such as: 65 pyl p-hydroxybenzoate, butyl p-hydroxybenzoate, octyl dichlofluanid, tolylfluanid, folpet, fluorofolpet, captan, p-hydroxybenzoate, o-phenylphenol, m-phenylphenol, captofol; p-phenylphenol, 4-(2-tert-butyl-4-methylphenoxy)phenol, US 7,943,644 B2 7 8 4-(2-isopropyl-4-methylphenoxy)phenol, 4-(2,4-dimeth thyl, furametpyr, thifluzamide, methalaxy-M, benthiavali ylphenoxy)-phenol and their alkali metal salts and alkaline carb, metrafenon, cyflufenamid, tiadinil, tea tree oil, phe earth metal salts; noxyethanol, microbicides with an activated halogen group Such as: Ag., Zn or Cu-containing Zeolites alone or incorporated into bronopol, bronidox, 2-bromo-2-nitro-1,3-propanediol. polymeric materials. 2-bromo-4'-hydroxyacetophenone, 1-bromo-3-chloro-44.5, Very especially preferred are mixtures with 5-tetramethyl-2-imidazolidinone, B-bromo-3-nitrostyrene, aZaconazole, bromuconazole, cyproconazole, dichlobutra chloracetamide, chloramine T, 1,3-dibromo-4,4,5,5-tetram Zol, diniconazole, diuron, hexaconazole, metaconazole, pen ethyl-2-imidazolidinone, dichloramine T., 3,4-dichloro-(3H)- conazole, propiconazole, tebuconazole, dichlofluanid, 10 tolylfluanid, fluorfolpet, methfuroxam, carboxin, N-cyclo 1,2-dithiol-3-one, 2,2-dibromo-3-nitrilepropionamide, 1,2- hexyl-benzobthiophenecarboxamide S.S.-dioxide, fempi dibromo-2,4-dicyanobutane, halane, halazone, mucochloric clonil, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3- acid, phenyl (2-chlorocyanovinyl) sulphone, phenyl (1.2- carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3- dichloro-2-cyanovinyl) Sulphone, trichloroisocyanuric acid; One, 5-chloro-N-methylisothiazolin-3-one, pyridines such as: 15 N-octylisothiazolin-3-one, dichloro-N-octylisothiazolinone, 1-hydroxy-2-pyridinethione (and their Cu, Na, Fe, Mn, Zn mercaptobenzothiazole, thiocyanatomethylthioben salts), tetrachloro-4-methyl-Sulphonylpyridine, pyrimetha Zothiazole, thiabendazole, benzoisothiazolinone, N-(2-hy nol, mepanipyrim, dipyrithion, 1-hydroxy-4-methyl-6-(2,4, droxypropyl)aminoethanol, benzyl alcohol (hemi)formal, 4-trimethylpentyl)-2(1H)-pyridine: N-methylolchloroacetamide, N-(2-hydroxypropyl) methoxyacrylates or similar such as: aminemethanol, glutaraldehyde, omadine, Zn-omadine, dim azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-me ethyl dicarbonate, 2-bromo-2-nitro-1,3-propanediol, 3-iodo thyl, metominostrobin, orysastrobin, picoxystrobin, pyra 2-propynyl n-butylcarbamate, bethoxazin, clostrobin, trifloxystrobin, 2,4-dihydro-5-methoxy-2-me o-phthaldialdehyde, 2,2-dibromo-3-nitrile-propionamide, thyl-4-2-1-3-(trifluoromethyl)phenylethylidene 1,2-dibromo-2,4-dicyanobutane, 1,3-bis(hydroxymethyl)-5, aminooxymethylphenyl-3H-1,2,4-triazol-3-one (CAS 25 5-dimethylimidazolidine-2,4-dione (DMDMH), tetramethy No. 185336-79-2); lolacetylenediurea (TMAD), ethyleneglycolhemiformal, metal Soaps such as: p-hydroxybenzoic acid, carbendazim, chlorophen, 3-methyl salts of the metals tin, copper and Zinc with higher fatty acids, 4-chlorophenol, o-phenylphenol. resin acids, naphthenoic acids and phosphoric acid, such as, Apart from with the abovementioned fungicides and bac 30 tericides, mixtures with a good efficacy are, moreover, also for example, tin naphthenate, tin octoate, tin 2-ethylhex prepared with other active compounds: anoate, tin oleate, tin phosphate, tin benzoate, copper naph insecticides/acaricides/nematicides: thenate, copper octoate, copper 2-ethylhexanoate, copper abamectin, acephate, acetamiprid, acetoprole, acrinathrin, oleate, copperphosphate, copper benzoate, Zinc naphthenate, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, alpha Zinc octoate, Zinc 2-ethylhexanoate, Zinc oleate, Zinc phos 35 cypermethrin, amidoflumet, amitraz, avermectin, azadirach phate, Zinc benzoate; tin, azinphos A, azinphos M. azocyclotin, metal salts such as: Bacillus thuringiensis, barthrin, 4-bromo-2(4-chlorophenyl)- salts of the metals tin, copper, Zinc, and also chromates and 1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbo dichromates, such as, for example, copper hydroxycarbonate, nitrile, bendiocarb, benfuracarb, bensultap, betacy fluthrin, Sodium dichromate, potassium dichromate, potassium chro 40 bifenthrin, bioresmethrin, bioallethrin, bistrilfluoron, bro mate, copper Sulphate, copper chloride, copper borate, Zinc mophos A, bromophos M, bufencarb, buprofezin, butathio fluorosilicate, copper fluorosilicate; phos, butocarboxim, butoxycarboxim, oxides such as: cadusafos, carbaryl, carbofuran, carbophenothion, carbosul oxides of the metals tin, copper and Zinc, Such as, for fan, cartap, quinomethionate, cloethocarb. 4-chloro-2-(2- example, tributyltin oxide, Cu2O, CuO, ZnO; 45 chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy-3 oxidizing agents Such as: (2H)-pyridazinone (CAS RN: 120955-77-3), chlordane, hydrogen peroxide, peracetic acid, potassium perSulphate; chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluaZu dithiocarbamates such as: ron, chlormephos, N-(6-chloro-3-pyridinyl)methyl-N'-cy cufraneb, ferban, potassium N-hydroxymethyl-N'-meth ano-N-methylethane-imidamide, chlorpicrin, chlorpyrifos A, yldithiocarbamate, Sodium dimethyl-dithiocarbamate, potas 50 chlorpyrifos M, cis-resmethin, clocythrin, clothiazoben, sium dimethyldithiocarbamate, mancoZeb, maneb, metam, cypophenothrin, clofentezin, coumaphos, cyanophos, cyclo metiram, thiram, Zineb, Ziram; prothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, nitriles such as: cyromazin, 2,4,5,6-tetrachloroisophthalonitrile, disodium cyanodithio decamethrin, deltamethrin, demeton M, demeton S, deme imidocarbamate; 55 ton-S-methyl, diafenthiuron, dialiphos, diazinon, 1.2-diben quinolines such as: Zoyl-1 (1,1-dimethyl)hydrazine, DNOC, dichlofenthion, 8-hydroxyquinoline and their copper salts; dichlorvos, dicliphos, dicrotophos, difethialone, diflubenzu other fungicides and bactericides such as: ron, dimethoate, 3,5-dimethylphenyl methylcarbamate, dim bethoxazin, 5-hydroxy-2(5H)-furanone, 4,5-benzodithiaz ethyl(phenyl)silylmethyl-3-phenoxybenzyl ether, dimethyl olinone, 4,5-trimethylenedithiazolinone, N-(2-p-chloroben 60 (4-ethoxyphenyl)silylmethyl-3-phenoxybenzyl ether, Zoylethyl)hexaminium chloride, 2-oxo-2-(4-hydroxyphenyl) dimethylvinphos, dioxathion, disulfaton, acetohydroxy-cinnamoyl chloride, tris-N- eflusilanate, emamectin, empenthrin, endosulfan, EPN, (cyclohexyldiazeniumdioxy)-aluminium, esfenvalerate, ethiofencarb, ethion, ethofenproX, etrimphos, N-(cyclohexyldiazenium-dioxy)-tributyltin or its potassium etoxazole, etobenzanid, salts, bis-N-(cyclohexyldiazeniumdioxy)-copper, iprovali 65 fenamiphos, fenaZaquin, fenbutatin oxide, fenflutbrin, feni carb, fenhexamide, Spiroxamine, carpropamid, diflumetorin, trothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropath quinoxyfen, famoxadone, polyoxorim, acilbenzolar S-me rin, fenpyrad, fenpyroximate, fensulfothion, fenthion, fenval US 7,943,644 B2 9 10 erate, fipronil, flonicamid, fluacrypyrim, fluaZuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, dicamba, dichlobenil, dimethamid, dithiopyr, dimetham flupyrazofos, flufenzine, flumethrin, flufenprox, fluvalinate, etryn, fonophos, formethanate, formothion, foSmethilan, fosthiaz eglinazine, endothal, EPTC, esprocarb, ethal fluralin, ethi ate, fubfenprox, furathiocarb, 5 dimuron, ethofumesate, ethobenzanid, ethoxyfen, ethamet halofenozide, HCH, (CAS RN; 58-89-9). heptenophos, Sulfuron, ethoxysulfuron, hexaflumuron, hexythiazox, hydramethylnon, hydroprene, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, imidacloprid, imiprothrin, indoxycarb, iodfenfos, iprinomec flazasulfuron, fluazifop, fluazifop-P, fuenachlor, fluchloralin, tin, iprobenfos, isaZophos, isoamidophos, isofenphos, isop flufenacet, flumeturon, fluorocglycofen, fluoronitrofen, flu 10 propanate, flurenol, fluridone, fluorochloridone, fluoroxypyr, rocarb, isoprothiolane, isoxathion, ivermectin, fomesafen, fosamine, foSametine, flamprop-isopropyl, flam kadedrin prop-isopropyl-L, flufenpyr, flumiclorac-pentyl, flumipro lambda-cyhalothrin, lufenuron, pyn, flumioXZim, flurtamone, flumioXZim, flupyrsulfuron malathion, mecarbam, mervinphos, mesulfenphos, metalde methyl, fluthiacet-methyl, hyde, methacrifos, methamidophos, methidathion, methio 15 glyphosate, glufosinate-ammonium carb, methomyl, metolcarb, milbemectin, monocrotophos, haloxyflop, hexaZinone, moxiectin, imazamethabenZ, isoproturon, isoxaben, isoxapyrifop, naled, NI 125, nicotine, nitenpyram, noviflumuron, imazapyr, imaZaquin, imazethapyr, ioxynil, isopropalin, ima omethoate, oxamyl, Oxydemethon M, Oxydeprofos, ZoSulfuron, imaZomox, isoxaflutole, imazapic, parathion A, parathion M, penfluron, permethrin, 2-(4-phe ketospiradox, noxyphenoxy)ethyl ethylcarbamate, phenthoate, phorate, lactofen, lenacil, linuron, phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pir MCPA, MCPA-hydrazide, MCPA-thioethyl, MCPB, meco imiphos M. pirimiphos A, prallethrin, profenophos, prome prop, mecoprop-P, mefenacet, mefluidide, mesosulfuron, carb, propaphos, propoXur, prothiophos, prothoate, metam, metamifop, metamitron, metaZachlor, methabenz pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, 25 thiazuron, methazole, methoroptryne, methyldymron, pyrethrum, pyridaben, pyridalyl pyrimidifen, pyriproxifen, methyl isothiocyanate, metobromuron, metoXuron, pyrithiobac-Sodium, metribuzin, metSulfuron, molinate, manolide, monolinuron, quinalphos, MSMA, metolachlor, metosulam, metobenzuron, resmethrin, rotenone, naproanilide, napropamide, naptalam, neburon, nicosulfu salithion, sebufos, silafluofen, spinosad, Spirodiclofen, 30 ron, norflurazon, Sodium chlorate, spiromesifen, Sulfotep, Sulprofos, oxadiazon, oxyfluorfen, oxysulfuron, orbencarb, oryzalin, tau-fluvalinate, taroils, tebufenozide, tebufenpyrad, tebupir oxadiargyl. imphos, teflubenzuron, tefluthrin, temephos, terbam, terbu propyZamide, prosulfocarb, pyrazolate, pyrazosulfuron, fos, tetrachlorvinphos, tetramethrin, tetramethacarb, thiaclo pyrazoxyfen, pyribenZoxim, pyributicarb, pyridate, paraquat, prid, thiafenox, thiamethoxam, thiapronil, thiodicarb, 35 pebulate, pendimethalin, pentachlorophenol, pentoxaZone, thiofanox, thiazophos, thiocyclam, thiomethon, thionazin, pentanochlor, petroleum oils, phenmedipham, picloram, pip thuringiensin, tralomethrin, transfluthrin, triarathen, triazo erophos, pretilachlor, primisulfuron, prodiamine, profoxy phos, triaZamate, triaZuron, trichlorfon, trifumuron, tri dim, prometryn, propachlor, propanil, propaquizafob, pro methacarb, pazine, propham, propisochlor, pyriminobac-methyl, vamidothion, Xylylcarb, Zetamethrin; 40 pelargonic acid, pyrithiobac, pyraflufen-ethyl, molluscicides: quinmerac, quinocloamine, quizalofop, quizalofop-P, fentin acetate, metaldehyde, methiocarb, niclosamide; quinchlorac, herbicides and algicides: rimsulfuron acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxy Sethoxydim, sifuron, Simazine, simetryn, Sulfosulfuron, Sul dim, ametryn, amidosulfuron, amitrole, ammonium Sulfa 45 fometuron, SulfentraZone, Sulcotrione, Sulfosate, mate, anilofos, asulam, atrazine, azafenidin, aZiptrotryne, tar oils, TCA, TCA-sodium, tebutam, tebuthiuron, terbacil, azimsulfuron, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifen benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, sulfuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, bentaZone, benzofencap, benzthiazuron, bifenox, bispyribac, triasulfuron, tribenuron, triclopyr, tridiphane, trietazine, trif bispyribac-sodium, borax, bromacil, bromobutide, bro 50 luoralin, tycor, thcliazimin, thiazopyr, trifluSulfuron, mofenoxim, bromoxynil, butachlor, butamifos, butralin, Vernolates. butylate, bialaphos, benzoyl-prop, bromobutide, butroxydim, The present invention further provides the use of azole carbetamide, carfentraZone-ethyl, carfenstrole, chlom compounds of the formula (I) for stabilizing iodine-contain ethoxyfen, chloramben, chlorbromuron, chlorflurenol, chlo ing biocides against chemical degradation reactions. The ridazon, chlorimuron, chlornitrofen, chloroacetic acid, chlo 55 materials to be protected from degradation may in principle ranSulam-methyl, cinidon-ethyl, chlorotoluron, chloroXuron, be any iodine-containing active compounds. chlorpropham, chlorSulfuron, chlorthal, chlorthiamid, cinm Preference is given to the inventive use for stabilizing the ethylin, cinosulfuron, clefoxydim, clethodim, clomaZone, iodine-containing biocides set out above as being preferred chlomeprop, clopyralid, cyanamide, cyanazine, cycloate, and particularly preferred. cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, 60 The present invention further provides the use of azole clometoxyfen, cyhalofop, cyhalofop-butyl, clopyrasuluron, compounds of the formula (I) as stabilizers in formulations cyclosulfamuron, comprising iodine-containing biocides and in technical prod diclosulam, dichlorprop, dichlorprop-P, diclofop, diethatyl, ucts to counter chemical degradation reactions and colour difenoXuron, difenZoquat, diflufenican, diflufenZopyr, dime changes. furon, dimepiperate, dimethachlor, dimethipin, dinitramine, 65 The azole compounds of the formula (I) can be used in dinoseb, dinoseb acetate, dinoterb, diphenarinid, dipropetryn, particular for Suppressing or at least retarding the chemical diquat, dithiopyr, diduron, DNOC, DSMA, 2,4-D, daimuron, degradation of iodine-containing biocides in active com US 7,943,644 B2 11 12 pound formulations, more particularly coating materials such desired drying characteristics of the paint. The amount of as paints, varnishes, primers, impregnating systems, stains dryers required can be determined by means of routine and other industrial materials. The azole compounds of the experiments. Generally speaking, 0.001% to 1%, preferably formula (I) which can be used in accordance with the inven 0.005% to 0.5% and very preferably 0.01% to 0.1% by weight tion for stabilizing iodine-containing biocides have a good 5 of dryer is used, based in each case on the amount of binder. stabilizing activity especially in alkyd resin-based systems In the context of the inventive use, generally 1% to 150% Such as coating materials which comprise transition metal by weight of at least one compound of the formula (I), pref dryers. erably 2% to 100% by weight, more particularly 5% to 80% The present invention further provides the use of azole by weight, based on the iodine-containing biocide, is added. compounds of the formula (I) for stabilizing iodine-contain 10 ing biocides in alkyd resin-based coating materials which The iodine-containing biocides for stabilization in the con comprise transition metal dryers. text of the inventive use are the compounds set out specifically The coating materials used in accordance with the inven and generally above. The inventive use of azole compounds tion are especially paints, varnishes, primers, impregnating of the formula (I) is used in particular to stabilize IPBC in systems and stains which comprise binders based on alkyd 15 alkyd resin-based coating materials which comprise transi resins. tion metal dryers. The alkyd resins present in the coating materials are gen In the context of the inventive use it is preferred to employ erally polycondensation resins formed from polyols, polyba coating materials with the following composition: sic carboxylic acids and/or their anhydrides and fatty oils, or Colour pigments: generally 0% to 50%, preferably 0% to free natural and/or synthetic fatty acids. The alkyd resins may 45%, with particular preference 0% to 40% by weight. optionally have been chemically modified as well. Alkyd resin binder: generally 1% to 80%, preferably 2% to The stated polyols are preferably glycerol, pentaerythritol, 70%, with particular preference 3% to 60% by weight. trimethylolethane, trimethylolpropane and various diols such Iodine-containing biocide: generally 0.01% to 5%, preferably as ethane-?propanediol, diethylene glycol, neopentylglycol. 0.05% to 3%, with particular preference 0.1% to 2% by The stated polybasic carboxylic acids and/or their anhy 25 weight. drides are preferably phthalic acid, phthalic anhydride, Compound of formula (I): generally 0.001% to 5%, prefer maleic anhydride, isophthalic acid, terephthalic acid, trimel ably 0.05% to 3%, with particular preference 0.01% to 2% by litic anhydride, adipic acid, azelaic acid or sebacic acid. weight. The stated oils or fatty acids are generally linseed oil, The coating materials may further comprise fillers, anti oiticica oil, tung oil, soya oil, Sunflower oil, safflower oil, 30 skinning agents, rheological additives such as anti-settling ricinene oil, tall oil, castor oil, coconut oil, peanut oil, their agents and thixotropic agents, for example, further biocides fatty acids, and also synthetic monocarboxylic acids. Such as fungicides, bactericides, anti-fouling agents and algi The alkyd resins can optionally also be modified with cides, solvents, in-process additives, plasticizers, UV stabi natural resins, phenolic resins, acrylic resins, styrene, epoxy lizers and heat stabilizers, and corrosion inhibitors, in typical resins, silicone resins, isocyanates, polyamides or aluminium 35 amounts known to the person skilled in the art. alkoxides. Iodine-containing biocides are degraded in particular in the The alkyd resins generally have a molar mass of 500 to 100 presence of the dryers described in more detail above. 000. The molar mass is preferably 1000 to 50 000 and more Although the strongest effects are observed in the presence of preferably 1500 to 20 000. these dryers, a series of other paint components also have a The alkyd resins are generally present at 1% to 80%, pref 40 destabilizing effect on iodine-containing biocides. These erably at 2% to 70% and with particular preference at 3% to include organic and inorganic pigments, fillers, anti-skinning 60% by weight in the coating materials, preferably paints, agents, rheological additives Such as anti-settling agents and varnishes, primers, impregnating systems or stains. thixotropic agents, for example, further biocides Such as fun The transition metal dryers are used in order to accelerate gicides, bactericides, anti-fouling agents and algicides, Sol the drying and the curing of oxidatively drying alkyd resin 45 vents, in-process additives, plasticizers, UV stabilizers and paints. Used here in accordance with the invention preferably heat stabilizers, corrosion inhibitors, etc. Here as well the are the salts of transition metals of groups Vb, VIb, VIIb, VIII imidazoles, triazoles or tetrazoles of the formula (I) display a and Ib of the chemical periodic system. Preferably they are strongly stabilizing effect. the salts of cobalt, manganese, Vanadium, nickel, copper and The stabilizing effect in accordance with the invention of iron, more particularly cobalt, manganese, iron and Vana 50 azole compounds of the formula (I) is, however, not restricted dium. In this context they are not necessarily used only alone, solely to active compound formulations, paints, varnishes and but in some cases also in combination with non-transition stains, but also includes the stabilization of iodine-containing metal salts, such as lead, calcium or Zirconium, for example. biocides in other media, Such as, for example, plastics, seal The transition metal salts are generally composed of the ants, adhesives, sizes, cooling lubricants, active compound salts of the stated transition metals that are soluble in organic 55 concentrates and formulations. solvents. In principle they may be the salts of all carboxylic The stabilizing effect of the azole compounds of the for acids that have good compatibility with the alkyd resin bind mula (I) is independent of the way in which they are added. ers and that ensure sufficient solubility of the metal salt. For example, the stabilizer can be added directly or as a Preference is given to using the transition metal salts of fatty Solution, Suspension or emulsion to the medium containing acids, Such as oleates or linoleates, of resin acids, such as 60 the iodine-containing biocide. Alternatively the stabilizer can resinates, or salts of 2-ethylhexanoic acid (octoates). Pre be added to the biocide formulation or to the biocide concen ferred transition metal dryers are cobalt octoate and cobalt trate, which additionally has the advantage that the iodine naphthenate. containing biocide is protected against degradation not only The amounts of dryers in the coating materials based on in the eventual medium but also in the active compound alkyd resins can be varied within a wide range and are guided, 65 formulation itself. for example, by the nature and concentration of the alkyd In addition it is also possible, in the use of the invention, to resin binder and the other paint constituents and also the add further stabilizers as well, such as, for example, the

US 7,943,644 B2 17 18 2-mercaptopyridine, 2-dimethylaminopyridine, 1.2-bis(dim azole compounds of the formula (I) specified as a stabilizer in ethyl-phosphino)ethane, 1.2-bis(diphenylphosphino)ethane, Table 1. The mixture was stored at 40° C. The amount of 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphos IPBC was determined by means of HPLC at the beginning phino)butane, polyaspartic acid, iminodisuccinate, and after two weeks. or else further imidazoles, triazoles or tetrazoles of the for mula (I). The azole compounds of the formula (I), where appropriate in a mixture with one or more of the stabilizers mentioned Amount above, protect the iodine-containing biocides from decompo Amount of IPBC sition not only in the liquid paint, but also, additionally, have 10 a stabilizing activity on the iodine-containing biocides in the Example of IPBC (2 weeks, dry paint film and an activity against decomposing effects No. Stabilizer (start) 40° C.) Remark induced by light. The amount of azole compounds of the formula (I) needed Ole 10.3% 2.2% comparison in order to stabilize the iodine-containing biocide in a tech 15 without nical medium can be determined by means of routine experi stabilizer ments and is guided both by the nature and concentration of the iodine-containing biocide and by the nature and amount 1 N-N 10.2% 9.0% of additives in the technical medium, Such as the paint or formulation. > In the case of alkyd resin-based systems such as coating H materials, the amount of azole compounds of the formula (I) which must be used in order to stabilize is dependent on the nature and amount of the dryer employed, of the alkyd resins, 2 N-N 9.9% 8.9% and of further constituents in the paint formulation. 25 In the case of alkyd resin paints the amount must be set Such --> that, while the iodine-containing biocides do not undergo H degradation, the actual effect of the dryer is not suppressed either. In other media, the application amount must be set so 3 N-N 9.7% 9.5% that, although stabilization is observed, the properties of the 30 medium are not altered. -> In the industrial media the azole compounds of the formula H (I) are used generally in concentrations of 0.001% by weight to 5% by weight, based on the total amount of the paint. 4 N-N 9.7% 9.7% Preferably the imidazoles, triazoles or tetrazoles of the for 35 mula (I) are used in concentrations of 0.005% to 3% and with - - particular preference between 0.01% and 2% by weight. H In active compound formulations and concentrates, the azole compounds of the formula (I) are used in larger amounts. Use is made in general of 0.5% to 50%, preferably 40 1% to 40% and with particular preference 2% to 30% by EXAMPLEB weight of azole compounds of the formula (I), based on the amount of formulation or amount of concentrate. Incorporated by vigorous stirring (using, for example, a EXAMPLEA 45 dissolver) into a woodstain whose composition was as speci fied below was 1% of IPBC and the amount specified in the A solution was prepared in Dowanol TPM (tripropylene table of azole compound of the formula (I) as a stabilizer. The glycol methyl ether), containing 10% by weight of iodopro composition was stored at 40°C. The amount of IPBC was pargylbutylcarbamate, 5% by weight of Octasoligen-Cobalt determined by means of HPLC at the beginning and after one 8 (Borchers, Langenfeld, Germany) and 5% by weight of the month.

Amount Amount Amount of IPBC Example of of IPBC (1 month, No. Stabilizer stabilizer (start) 40° C.) Remark

Ole O.98% 0.25% comparison without stabilizer (N-N ) O.2% O.99% O.90% US 7,943,644 B2 20 -continued

Amount Amount Amount of IPBC Example of of IPBC (1 month, No. Stabilizer stabilizer (start) 40° C.) Remark 6 ->N-N O.S90 1.01% 0.81% H 7 N-N> O.05% 1.05% 0.98% H

8 N-N O.1% 1.02% 0.80%

-->H NH2

Composition of the preservative woodstain used: 2. The mixture according to claim 1 wherein R" is hydrogen, hydroxyl, mercapto, amino, C-C-alky lamino. 25 Alkydal F 681, 75% strength in white spirit 28% 3. The mixture according to claim 1 or 2, wherein the 2-Phenoxyethanol 3% iodine-containing biocide is one or more iodoalkynyl com Dowano DPM 3% pounds. SolveSSO 150 10% BHT, 1% in Kristalloel K 60 296 4. The mixture according to claim 1 or 2, characterized in Octa Soligen Co 8% O.19% 30 that it contains 0.01%-70% by weight of the iodine-contain Octa Soligen Zr 18% 1.4% ing biocide and 0.001%-50% by weight of the at least one Kristalloel 60 52.41% azole of the formula (I). 5. A microbicidal composition comprising an active com The present invention has been described with reference to pound mixture according to claim 1 or 2, further comprising specific details and examples of particular embodiments 35 at least one solvent or diluent. thereof. It is not intended that such details and examples be 6. A process for protecting an industrial material from regarded as limitations upon the scope of the invention except infestation and/or destruction by microorganisms, compris insofar as and to the extent that they are included in the ing: accompanying claims. contacting the industrial material with the active com As used in this specification and the appended claims, the 40 pound mixture according to claim 1 or 2. singular forms “a” “an.” and “the include plural referents 7. A process for stabilizing an iodine-containing biocide unless the content clearly dictates otherwise. against chemical degradation reactions, comprising: a) mixing an iodine-containing biocide selected from the What is claimed is: group consisting of iodoalkynyl compounds, com 1. An active compound mixture comprising at least one 45 pounds in which one or more iodine atoms are bonded to iodine-containing biocide selected from the group consisting double bound systems and compounds in which one or of iodoalkynyl compounds, compounds in which one or more more iodine atoms are bonded to singly bonded atoms iodine atoms are bonded to double bound systems and com and an at least one azole compound of the formula (I) or pounds in which one or more iodine atoms are bonded to tautomers thereof, singly bonded atoms; and at least one azole compound of the 50 formula (I) or tautomer thereof, (I) X-Y (I) X-Y RI -K)N1 Z 55 H R1 -K)N1 Z H in which R" is hydrogen, hydroxyl, mercapto or optionally substi in which 60 tuted amino R" is hydrogen, hydroxyl, mercapto or optionally substi and tuted amino X, Y and Z independently of one another are N or C R. and in which X, Y and Z independently of one another are N or C R. R is hydrogen, hydroxyl, mercapto or optionally substi in which 65 tuted amino. R is hydrogen, hydroxyl, mercapto or optionally substi 8. The process according to claim 7, wherein the iodine tuted amino. containing biocide is stabilized in an industrial material. US 7,943,644 B2 21 22 9. The process according to claim 8, wherein the industrial 12. The microbicidal composition according to claim 11 material is a paints based on alkyd resin binders comprising further comprising further antimicrobial compounds. transition metal dryers. 13. The mixture according to claim 3, wherein the 10. An industrial material comprising at least one iodine iodoalkynyl compounds are selected from the group consist containing biocide selected from the group consisting of 5 ing of 3-iodo-2-propynylpropyl carbamate, 3-iodo-2-propy iodoalkynyl compounds, compounds in which one or more nylbutyl carbamate (IPBC), 3-iodo-2-propynyl-m-chlo iodine atoms are bonded to double bound systems and com rophenyl carbamate, 3-iodo-2-propynylphenyl carbamate, pounds in which one or more iodine atoms are bonded to 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-pro singly bonded atoms; pynyl 4-chlorophenyl formal (IPCF), di(3-iodo-2-propynyl) and at least one azole of the formula (I) or tautomerthereof, 10 hexyl dicarbamate, 3-iodo-2-propynyloxyethanol ethylcar bamate, 3-iodo-2-propynyloxyethanol phenyl carbamate, 3-iodo-2-propynylthioxothioethyl carbamate, 3-iodo-2-pro (I) pynylcarbamic ester (IPC), N-iodpropargyloxycarbonylala } W nine, N-iodoproparayloxycarbonylalanine ethyl ester, 343 R1 -KyN1 15 iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargyl)-6- H chlorobenzoxazol-2-one, diiodomethyl p-tolyl Sulphone, diiodomethyl p-chlorophenyl Sulphone, 3-iodo-2-propynyl in which R" is hydrogen, hydroxyl, mercapto or optionally substi alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2, tuted amino 3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alco and hol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-pro X, Y and Z independently of one another are N or C R. pynyl n-hexylcarbamate, and 3-iodo-2-propynyl in which cyclohexylcarbamate. R is hydrogen, hydroxyl, mercapto or optionally substi 14. The mixture according to claim 5, further comprising tuted amino. further antimicrobial compounds. 11. A microbicidal composition comprising an active com 25 pound mixture according to claim 1 or 2, further comprising at least one solvent or diluent and processing assistants.