United States Patent (19) 11 Patent Number: 6,071,994 Hummerich Et Al

US00607 1994A United States Patent (19) 11 Patent Number: 6,071,994 Hummerich et al. (45) Date of Patent: Jun. 6, 2000

54) FORMALDEHYDE-FREE AQUEOUS 5,427,587 6/1995 Arkens et al.. BNDERS 5,536,766 7/1996 Seyffer et al...... 524/100 5,661,213 8/1997 Arkens et al...... 524/555 (75) Inventors: Rainer Hummerich, Worms; Axel FOREIGN PATENT DOCUMENTS Kistenmacher, Ludwigshafen; Walter Denzinger, Speyer; Gunnar Schornick, O 116930 8/1984 European Pat. Off.. Neuleiningen; Bernd Reck, Grinstadt; O 445 578 9/1991 European Pat. Off.. Manfred Weber, Mannheim, all of O 583 086 2/1994 European Pat. Off.. German O 651 088 10/1994 European Pat. Off.. y 864. 151 1/1953 Germany. 73 ASSignee: BASF Aktiengesellschaft, 2217 2014450 712 10/19727/1971 Germany. Ludwigshafen, Germany 2357951 5/1975 Germany. 21 Appl. No.: 09/125,113 4408 688 9/1995 Germany. 22 PCT Filed: Feb. 19, 1997 OTHER PUBLICATIONS Patent Abstracts of Japan, vol. 014, No.220, May 10, 1990, 86 PCT No.: PCT/EP97/00770 JP Publ. No. 02 051531, Feb. 21, 1990, Appl. No.63200120, S371 Date: Aug. 18, 1998 Aug. 12, 1988, Koinuma Yasuyoshi, et al., Title: Water Soluble and Self-curing polymer and cured product thereof. S 102(e) Date: Aug. 18, 1998 Patent Abstracts of Japan, vol. 005, No. 180, Nov. 19, 1981, 87 PCT Pub. No.: WO97/31036 JPPubl. No. 56 104905, Aug. 21, 1981, Chino yasuyoshi, et y - - - al, Title: Production of Novel Modified Resin, Appl. No. PCT Pub. Date: Aug. 28, 1997 55008500, Jan. 28, 1980. 30 Foreign Application Priority Data Primary Examiner Edward J. Cain b Attorney, Agent, or Firm-Oblon, Spivak, McClelland, Feb. 21, 1996 DEI Germany ...... 196 06 394 Maier & Neustadt, P.C. 7 51) Int. Cl.' ...... C08K 3700 57 ABSTRACT 52 U.S. Cl...... 524/247; 524/249; 524/494 58 Field of Search ...... 324/247, 249, Formaldehyde-free aqueous binders comprise 324/494 A) a polymer containing from 5 to lacuna% by weight of units derived from an ethylenically unsaturated acid anhy 56) References Cited dride or from an ethylenically unsaturated dicarboxylic acid whose carboxyl groups can form an anhydride group, U.S. PATENT DOCUMENTS and 3,857.803 12/1974 Shenfeld et al.. B) an alkanolamine having at least two hydroxyl groups. 4,076.917 2/1978 Swift et al.. 5,340,868 8/1994 Strauss et al.. 29 Claims, No Drawings 6,071,994 1 2 FORMALDEHYDE-FREE AQUEOUS omittable only if a highly reactive polyol is used. BNDERS B-Hydroxyalkylamides are disclosed as highly reactive polyols. DESCRIPTION EP-A 651 088 describes formaldehyde-free aqueous bind The present invention relates to formaldehyde-free acque erS for cellulosic Substrates. The presence of phosphorus ous binders comprising containing reaction accelerant is mandatory in these binders. A) a free-radically polymerized polymer containing from DE 4 408 688 discloses formaldehyde-free binders for 5 to 100% by weight of units derived from an ethyl fibrous sheet materials, comprising a mixture of polycar enically unsaturated acid anhydride or from an ethyl boxylic acid and aromatic or cycloaliphatic polyols. Despite enically unsaturated dicarboxylic acid whose carboxyl a very high drying temperature (230° C), these binders groups can form an anhydride group, and provide only low wet breaking Strength on glass fiber WebS. B) an alkanolamine having at least two hydroxyl groups, In addition to existing formaldehyde-free binders, it is the aqueous binder including less than 1.5% by weight, always desirable to have further formaldehyde-free binders based on the Sum of A)+B), of a phosphorus-containing 15 available as alternatives. For economic reasons it is desirable reaction accelerant. to consolidate sheetlike fibrous Structures at low tempera The present invention further relates to the use of the tures within a short time while obtaining good mechanical binders as coatings, impregnants or binders for fiber WebS. properties. Suitable binders are Safe and do not emit toxic or The consolidation of sheetlike fibrous structures, or fiber environmentally harmful reaction products in use. WebS, is effected for example purely mechanically by nee Furthermore, Suitable binders ideally consist of readily dling or water jet consolidation of a wet- or air-laid web or obtainable, inexpensive components. by chemical consolidation of the webs with a polymeric It is an object of the present invention to provide Such binder. The binder is generally applied by impregnating, binders. Spraying or coating. To enhance the wet strength and heat We have found that this object is achieved by the above resistance of the WebS, use is frequently made of binders 25 described binders and their use as or in coatings, impreg comprising formaldehyde-eliminating crosslinkers. Alterna nants and also as binders for fiber webs, especially glass tives to existing binders are Sought to avoid formaldehyde fiber webs. emissions. The aqueous binder of this invention includes a polymer U.S. Pat. No. 4,076.917 discloses binders comprising A) containing from 5 to 100% by weight, preferably from 5 carboxylic acid or anhydride polymer S and to 50% by weight, particularly preferably from 10 to 40% by B-hydroxyalkylamides as crosslinkers. The molar ratio of weight, of units derived from an ethylenically unsaturated carboxyl groups to hydroxyl groups is preferably 1:1. The acid anhydride or an ethylenically unsaturated dicarboxylic disadvantage is the relatively complicated Synthesis of the acid whose carboxyl groups are capable of forming an B-hydroxyalkylamides. An appropriate binder is known 35 anhydride group (hereinafter referred to as monomer a)). from U.S. Pat. No. 5,340,868. The acid anhydrides are preferably dicarboxylic anhy EP 445 578 discloses rigid sheets of finely divided drides. Suitable ethylenically unsaturated dicarboxylic acids materials, for example glass fibers, in which mixtures of are generally those having carboxylic acid groups on vicinal high molecular weight polycarboxylic acids and polyhydric 40 carbons. The carboxylic acid groups can also be present in alcohols, alkanolamines or polyacid amines act as binders. the form of their salts. The disclosed high molecular weight polycarboxylic acids Preferred monomers a) are maleic acid or maleic are polyacrylic acid, copolymers of methyl methacrylate/n- anhydride, itaconic acid, 1,2,3,6-tetrahydrophthalic acid, butyl acrylate/methacrylic acid and of methyl methacrylate/ 1,2,3,6-tetrahydrophthalic anhydride, their alkali metal and methacrylic acid. The polyhydric alcohols and alkanola 45 ammonium Salts or mixtures thereof. Maleic acid and maleic mines disclosed are 2-hydroxymethyl-1,4-butanediol, anhydride are particularly preferred. trimethylolpropane, glycerol, poly(methylmethacrylate-co As well as monomer a), the polymer may additionally hydroxypropyl acrylate), diethanolamine and triethanola contain monomer b). mine. Maleic acid is mentioned as a possible comonomer for Suitable monomers b) are for example: preparing the high molecular weight polycarboxylic acids. 50 Monoethylenically unsaturated C-Co-monocarboxylic EP583 086 discloses formaldehyde-free aqueous binders acids, (monomer b), for example acrylic acid, methacrylic for producing fiber webs, especially glass fiber webs. These acid, ethylacrylic acid, allylacetic acid, crotonic acid, Viny binders require a phosphorus-containing reaction accelerant lacetic acid, maleic monoesterS Such as methyl hydrogen to provide adequate glass fiber Web Strengths. The binders 55 maleate, their mixtures and their alkali metal and ammo comprise a polycarboxylic acid having at least 2 carboxyl nium Salts. groupS and optionally also anhydride groupS. Polyacrylic Linear 1-olefins, branched-chain 1-olefins or cyclic ole acid is used in particular, but copolymers of acrylic acid with fins (monomer ba), for example ethene, propene, butene, maleic anhydride are also disclosed. The binder further isobutene, pentene, cyclopentene, hexene, cyclohexene, comprises a polyol, for example glycerol, bisN,N-di(B- 60 octene, 2,4,4-trimethyl-1-pentene with or without 2,4,4- hydroxyethyl)adipamide sic, pentaerythritol, diethylene trimethyl-2-penten, Cs-Co-olefin, 1-dodecene, Ca-Ca glycol, ethylene glycol, gluconic acid, B-D-lactose, Sucrose, olefin, octadecene, 1-eicosene (C20), Co-C2a-olefin; polyvinyl alcohol, diisopropanolamine, 2-(2- metallocene-catalytically prepared oligoolefins having a ter aminoethylamino)ethanol, trie thanolamine, tris 65 minal double bond, for example oligopropene, oligohexene (hydroxymethylamino)methane and diethanolamine. The and oligooctadecene, cationically polymerized olefins hav phosphorus-containing reaction accelerant is Stated to be ing a high-olefin content, for example polyisobutene. 6,071,994 3 4 Vinyl and allyl alkyl ethers having from 1 to 40 carbon Preferred monomers are acrylic acid, methacrylic acid, atoms in the alkyl radical, which alkyl radical can carry ethene, propene, butene, isobutene, cyclopentene, methyl further Substituents Such as hydroxyl, amino or dialkylamino Vinyl ether, ethyl vinyl ether, acrylamide, 2-acrylamido-2- or one or more alkoxylate groups (monomer ba), for methylpropanesulfonic acid, Vinyl acetate, Styrene, example methyl vinyl ether, ethyl vinyl ether, propyl vinyl butadiene, acrylonitrile and mixtures thereof. ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl Particular preference is given to acrylic acid, methacrylic cyclohexyl ether, vinyl-4-hydroxybutyl ether, decyl vinyl acid, ethene, acrylamide, Styrene and acrylonitrile and mix ether, dodecyl vinyl ether, octadecyl vinyl ether, tures thereof. 2-(diethylamino)ethyl vinyl ether, 2-(di-n-butylamino)ethyl 1O Very particular preference is given to acrylic acid, meth Vinyl ether, methyldiglycol Vinyl ether and also the corre acrylic acid and acrylamide and mixtures thereof. sponding allyl ethers and mixtures thereof. The polymers can be prepared according to customary Acrylamides and alkyl-Substituted acrylamides polymerization processes, for example by mass, emulsion, (monomer ba), for example acrylamide, methacrylamide, 35 Suspension, dispersion, precipitation or Solution polymer N-tert-butyliacrylamide, N-methyl(meth)acrylamide. 15 ization. The polymerization processes mentioned are pref Sulfo-containing monomers (monomer b), for example erably carried out in the absence of oxygen, preferably in a allylsulfonic acid, methallylsulfonic acid, StyreneSulfonate, Stream of nitrogen. By whichever method the polymeriza Vinylsulfonic acid, allyloxybenzene Sulfonic acid, tion is carried out it is carried out in customary equipment, 2-acrylamido-2-methylpropanesulfonic acid and their corre for example Stirred tanks, Stirred tank cascades, autoclaves, sponding alkali metal or ammonium Salts or mixtures tubular reactors and kneaders. Preference is given to using thereof. the method of Solution, emulsion, precipitation or Suspen C-C-Alkyl or C-C-hydroxyalkyl esters of acrylic Sion polymerization. The methods of Solution and emulsion acid, methacrylic acid or maleic acid, or acrylic, methacrylic polymerization are particularly preferred. The polymeriza or maleic esters of C-C-alcohols alkoxylated with from 2 25 tion can be carried out in Solvents or diluents, for example to 50 mol of ethylene oxide, propylene oxide, butylene oxide toluene, O-Xylene, p-Xylene, cumene, chlorobenzene, or mixtures thereof (monomer b), for example methyl ethylbenzene, technical-grade mixtures of alkylaromatics, (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclohexane, technical-grade aliphatics mixtures, acetone, isopropyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth) cyclohexanone, tetrahydrofuran, dioxane, glycols and glycol acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth) derivatives, polyalkylene glycols and derivatives thereof, acrylate, hydroxypropyl (meth)acrylate, 1,4-butanediol diethyl ether, tert-butyl methyl ether, methyl acetate, monoacrylate, dibutyl maleate, ethyldiglycol acrylate, meth isopropanol, ethanol, water or mixtures Such as, for ylpolyglycol acrylate (11 EO), (meth)acrylic esters of example, isopropanol/water mixtures. The preferred Solvent C-C-oxo alcohol reacted with 3,5,7,10 or 30 mol of 35 or diluent is water with or without proportions of up to 60% ethylene oxide, or mixtures thereof. by weight of alcohols or glycols. The use of water is Alkylaminoalkyl (meth)acrylates or alkylaminoalkyl particularly preferred. (meth)acrylamides or quaternization products thereof The polymerization can be carried out at temperatures (monomer b), for example 2-(N,N-dimethylamino)ethyl from 20 to 300, preferably from 60 to 200° C. Depending on (meth) acrylate, 3-(N,N-dimethylamino)propyl (meth) 40 the choice of polymerization conditions, it is possible to acrylate, 2-(N.N.N-trimethylammonio)ethyl (meth)acrylate obtain weight average molecular weights for example within chloride, 2-dimethylaminoethyl(meth) acrylamide, the range from 800 to 5,000,000, especially from 1,000 to 3 - dimethylamino propyl (meth) a crylamide, 1,000,000. The weight average molecular weights M are 3-trimethylammoniopropyl(meth)acrylamide chloride. 45 preferably above 15,000. Weight average molecular weights Vinyl and allyl esters of C1-Co-monocarboxylic acids from 15,000 to 600,000 are particular preferred. M is (monomer bs), for example vinyl formate, vinyl acetate, determined by gel permeation chromatography (detailed Vinyl propionate, Vinyl butyrate, Vinyl Valerate, Vinyl description in Examples). 2-ethylhexanoate, vinyl nonoate sic, vinyl decanoate, vinyl The polymerization is preferably carried out in the pres pivalate, Vinyl palmitate, Vinyl Stearate, Vinyl laurate. 50 ence of compounds forming free radicals. These compounds Examples of further monomers be are: are required in an amount of up to 30, preferably 0.05 to 15, N-vinyl formamide, N-vinyl-N-methylformamide, particularly preferably from 0.2 to 8.9% by weight, based on Styrene, -methylstyrene, 3-methylstyrene, butadiene, the monomers used in the polymerization. In the case of N-vinylpyrrollidone, N-vinylimidazole, 1-vinyl-2- 55 multicomponent initiator Systems (e.g. redox initiator methylimidazole, 1-vinyl-2-methylimidazoline, Systems), the foregoing weights are based on the Sum total N-Vinylcaprolactam, acrylonitrile, methacrylonitrile, allyl of the components. alcohol, 2-Vinylpyridine, 4-Vinylpyridine, diallyldimethy Examples of Suitable polymerization initiators are lammonium chloride, Vinylidene chloride, Vinyl chloride, peroxides, hydroperoxides, perOXOdisulfates, percarbonates, acrolein, methacrolein and Vinylcarbazole and mixtures 60 peroxyesters, hydrogen peroxide and azo compounds. thereof. Examples of initiators which can be water-soluble or else As well as monomer a), the polymer can additionally water-insoluble are hydrogen peroxide, dibenzoyl peroxide, contain from 0 to 95% by weight of monomere b. Preferably, dicyclohexyl peroxodicarbonate, dilauroyl peroxide, methyl as well as monomera), the polymer additionally contains 65 ethyl ketone peroxide, di-tert-butyl peroxide, acetylacetone monomerb in amounts from 50 to 95, particularly preferably peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, from 60 to 90% by weight. tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl 6,071,994 S 6 perpivalate, tert-butyl perneohexanoate, tert-butyl per-2- 10% by weight, based on the monomers. The average ethylhexanoate, tert-butyl perbenzoate, lithium, Sodium, molecular weight can also be influenced by the choice of potassium and ammonium per o Xo disulfate, Solvent. For instance, a polymerization in the presence of aZodiisobutyronitrile, 2,2'-azobis(2-amidinopropane) diluents having benzylic hydrogen atoms leads to a reduced dihydrochloride, 2-(carbamoylazo)isobutyronitrile and 4.4- average molecular weight due to chain transfer. aZobis(4-cyanovaleric acid). To prepare higher molecular weight copolymers it is The initiators can be used alone or mixed with each or one frequently advantageous to carry out the polymerization in another, for example mixtures of hydrogen peroxide and the presence of crosslinkers. Such crosslinkers are com Sodium perOXOdisulfate. The polymerization in aqueous pounds having two or more ethylenically unsaturated medium is preferably carried out using water-Soluble initia groups, for example diacrylates or dimethacrylates of at least torS. dihydric Saturated alcohols, e.g. ethylene glycol diacrylate, It is equally possible to use the known redox initiator ethylene glycol dimethacrylate, 1,2-propylene glycol Systems as polymerization initiators. Such redox initiator diacrylate, 1,2-propylene glycol dimethacrylate, 1,4- Systems include at least one peroxide-containing compound 15 butanediol diacrylate, 1,4-butanediol dimethacrylate, heX combined with a redox coinitiator, for example reducing anediol diacrylate, hexanediol dimethacrylate, neopentylg Sulfur compounds, for example bisulfites, Sulfites, lycol diacrylate, neopentylglycol dimethacrylate, thiosulfates, dithionites and tetrathionates of alkali metals 3-methylpentanediol diacrylate and 3-methylpentanediol and ammonium compounds. For instance, combinations of dimethacrylate. Similarly the acrylic and methacrylic esters peroxodisulfates with alkali metal or ammonium bisulfites of alcohols having more than 2 OH groups can be used as can be used, for example ammonium perOXOdisulfate and crosslinkers, e.g. trimethylolpropane triacrylate or trimethy ammonium disulfite. The ratio of peroxide-containing com lolpropane trimethacrylate. A further class of crosslinkers pound to redox coinitiator is within the range from 30:1 to are diacrylates or dimethacrylates of polyethylene glycols or O.05:1. 25 polypropylene glycols having molecular weights from 200 The initiators or redox initiator Systems can be combined to 9 000 in each case. Polyethylene glycols and polypropy with transition metal catalysts, for example Salts of iron, lene glycols used for preparing the diacrylates or cobalt, nickel, copper, Vanadium and manganese. Examples dimethacrylateS preferably have a molecular weight of from of suitable salts are iron(II) sulfate, cobalt(II) chloride, 400 to 2 000 in each case. As well as the homopolymers of nickel(II) sulfate, copper(I) chloride. Based on monomers, ethylene oxide and propylene oxide it is also possible to use the reducing transition metal Salt is used in a concentration block copolymers of ethylene oxide and propylene oxide or of from 0.1 ppm to 1,000 ppm. For instance, combinations copolymers of ethylene oxide and propylene oxide contain of hydrogen peroxide with iron(II) salts can be used, for ing the ethylene oxide and propylene oxide units in random example 0.5 to 30% of hydrogen peroxide with 0.1 to 500 35 distribution. The oligomers of ethylene oxide or propylene ppm of Mohr’s salt. oxide are also Suitable for preparing the crosslinkers, eg. Similarly, a polymerization in organic Solvents can be diethylene glycol diacrylate, diethylene glycol carried out using the abovementioned initiators combined dimethacrylate, triethylene glycol diacrylate, triethylene with redox coinitiators and/or transition metal catalysts, for glycol dimethacrylate, tetraethylene glycol diacrylate and/or example benzoin, dimethylaniline, ascorbic acid combined 40 tetraethylene glycol dimethacrylate. with Solvent-Soluble complexes of heavy metals, Such as Suitable crosslinkers further include vinyl acrylate, vinyl copper, cobalt, iron, manganese, nickel and chromium. The methacrylate, vinyl itaconate, divinyl adipate, butanediol amounts of redox coinitiators or transition metal catalysts divinyl ether, trimethylolpropane trivinyl ether, allyl customarily used here customarily range from about 0.1 to 45 acrylate, allyl methacrylate, pentaerythritol triallyl ether, 1,000 ppm, based on the amounts of the monomers used. triallylsucrose, pentaallylsucrose, pentaallylsaccharose, If the polymerization of the reaction mixture is Started at methylenebis(meth) acrylamide, divinylethyleneurea, the lower limit of a Suitable temperature range for the divinylpropyleneurea, divinylbenzene, divinyldioxane, trial polymerization and Subsequently completed at a higher lyl cyanurate, tetraallylsilane, tetravinylsilane and bis- or temperature, it is advantageous to use at least two different 50 polyacryloylsiloxanes (eg. TegomerSE) from Th. Gold initiators which decompose at different temperatures, So that schmidt AG). The crosslinkers are preferably used in a Sufficient concentration of free radicals is available within amounts from 10 ppm to 5% by weight, based on the every temperature interval. monomers to be polymerized. To prepare polymers having a low average molecular 55 If the method of emulsion, precipitation, Suspension or weight it is frequently advantageous to carry out the copo dispersion polymerization is used, it can be advantageous to lymerization in the presence of regulators. Customary regu Stabilize the polymer droplets or particles by means of lators can be used for this, for example organic interface-active auxiliaries. Typically these are emulsifiers SH-containing compounds, Such as 2-mercaptoethanol, or protective colloids. Emulsifiers used can be anionic, 2-mercaptopropanol, mercaptoacetic acid, tert-butyl 60 nonionic, cationic or amphoteric. Examples of anionic emul mercaptan, n-octyl mercaptan, n-dodecyl mercaptain and sifiers are alkylbenzeneSulfonic acids, Sulfonated fatty acids, tert-dodecyl mercaptan, C-C-aldehydes, Such as SulfoSuccinates, fatty alcohol Sulfates, alkylphenol Sulfates formaldehyde, acetaldehyde, propionaldehyde, hydroxy and fatty alcohol ether Sulfates. Examples of usable nonionic lammonium Salts. Such as hydroxylammonium Sulfate, for 65 emulsifiers are alkylphenol ethoxylates, primary alcohol mic acid, Sodium bisulfite or isopropanol. The polymeriza ethoxylates, fatty acid ethoxylates, alkanolamide tion regulators are generally used in amounts from 0.1 to ethoxylates, fatty amine ethoxylates, EO/PO block copoly 6,071,994 7 8 merS and alkylpolyglucosides. Examples of cationic and Solvent. If it is nonetheless desired to isolate the polymer, amphoteric emulsifiers used are quaternized amine this can be done by Spray drying, for example. alkoxylates, alkylbetaines, alkylamidobetaines and Sulfobe If the polymer is prepared by the method of solution, taines. precipitation or Suspension polymerization in a Solvent or Examples of typical protective colloids are cellulose Solvent mixture which is volatile in Steam, the Solvent can be derivatives, polyethylene glycol, polypropylene glycol, removed by introducing Steam into the reaction mixture in copolymers of ethylene glycol and propylene glycol, poly order that an aqueous Solution or dispersion may be obtained Vinyl acetate, polyvinyl alcohol, polyvinyl ether, Starch and in this way. The polymer can also be separated from the Starch derivatives, dextran, polyvinylpyrrollidone, organic diluent by a drying process. polyvinylpyridine, polyethyleneimine, polyvinylimidazole, Polymers A) are preferably present in the form of an polyvinylsuccinimide, polyvinyl-2-methylSuccinimide, aqueous dispersion or Solution having Solids contents from poly Vinyl-1,3-oxazolid-2- one, poly Vinyl-2- preferably 10 to 80%, in particular from 40 to 65%, by methylimidazoline and maleic acid or anhydride copolymers weight. as described for example in DE 2501 123. 15 Polymer A) can also be obtained by grafting maleic acid The emulsifiers or protective colloids are customarily or maleic anhydride or a monomer mixture comprising used in concentrations from 0.05 to 20% by weight, based on maleic acid or maleic anhydride onto a grafting base. the monomers. Examples of Suitable grafting bases are monosaccharides, If the polymerization is carried out in aqueous Solution or oligosaccharides, modified polysaccharides and alkylpolyg dilution, the monomers can be wholly or partly neutralized lycol ethers. Such graft polymers are described for example with bases before or during the polymerization. Examples of in DE 4 003 172 and EP 116 930. Suitable bases are alkali metal and alkaline earth metal Component B) comprises alkanolamines having at least compounds Such as Sodium hydroxide, potassium two OH groups. Preference is given to alkanolamines of the formula hydroxide, calcium hydroxide, magnesium oxide, Sodium 25 carbonate, ammonia; primary, Secondary and tertiary a mine S, Such as ethylamine, propylamine, monoisopropylamine, monobutylamine, he Xylamine, R2 ethanolamine, dimethylamine, diethylamine, di-n- R-N-R, propylamine, tributylamine, trie thanolamine, dimethoxyethyla mine, 2-ethoxyethylamine, where R is hydrogen, C1-Co-alkyl or C1-Co 3-ethoxypropylamine, dimethylethanolamine, diisopro hydroxyalkyl and R and Rare each C-Co-hydroxyalkyl. panolamine and morpholine. It is particularly preferable for R and R to be indepen Polybasic Sicamines can also be used for neutralization, 35 dently of each other C-Cs-hydroxyalkyl and R' to be for example ethylenediamine, 2-diethylaminoethylamine, hydrogen, C-C-alkyl or C-C-hydroxyalkyl. 2,3-dia mino propane, 1,2-propylene diamine, Examples of Suitable compounds of the formula I are dimethylaminopropylamine, neopentane diamine, diethanolamine, triethanolamine, diisopropanolamine, hexamethylenediamine, 4,9-dioxadodecane-1,12-diamine, triisopropanolamine, methyldiethanolamine, butyldiethano polyethyleneimine or polyvinylamine. 40 lamine and methyldiisopropanolamine. Triethanolamine is Ammonia, triethanolamine and diethanolamine are pre particularly preferred. ferred for partially or completely neutralizing the ethyleni The formaldehyde-free binders of this invention are pref cally unsaturated carboxylic acids before or during the erably prepared by using polymer A) and alkanolamine B) in polymerization. 45 Such a relative ratio that the molar ratio of carboxyl groups The ethylenically unsaturated carboxylic acids are par of component A) to the hydroxyl groups of component B) is ticularly preferably not neutralized before and during the within the range from 20:1 to 1:1, preferably within the polymerization. It is similarly preferred not to add a neu range from 8:1 to 5:1, particularly preferably within the tralizing agent after the polymerization either, apart from range from 5:1 to 1.7:1 (anhydride groups are here calcu alkanolamine B). The polymerization can be carried out 50 lated as 2 carboxyl groups). continuously or batchwise according to a multiplicity of The formaldehyde-free aqueous binders of this invention variants. It is customary to introduce part of the monomers are prepared for example simply by adding the alkanolamine as initial charge, if necessary in a Suitable diluent or Solvent to the aqueous dispersion or Solution of polymer A). and in the absence or presence of an emulsifier, a protective 55 The binders of this invention preferably include less than colloid or further assistants, to provide a blanket of an inert 1.0% by weight, particularly preferably less than 0.5% by gas, and to raise the temperature until the desired polymer weight, very particularly preferably less than 0.3% by ization temperature is achieved. However, the initial charge weight, especially less than 0.1% by weight, based on the may also be a Suitable diluent alone. The free-radical Sum of A)+B), of a phosphorus-containing reaction acceler initiator, further monomers and other assistants, for example 60 ant. Phosphorus-containing reaction accelerants are men regulators or crosslinkers, each in a diluent, if necessary, are tioned in U.S. Pat. No. 651 088 and U.S. Pat. No. 583 086. metered in over a defined period. The addition times may They are in particular alkali metal hypophosphites, differ in length. For example, the initiator may be added over phosphites, polyphosphates, dihydrogenphosphates, poly a longer period than the monomer. 65 phosphoric acid, hypophosphoric acid, phosphoric acid, If the polymer is obtained in water following a solution alkylphosphinic acid and oligomers and polymers of these polymerization, there is usually no need to Separate off the Salts and acids. 6,071,994 9 10 The binders of this invention preferably include no for wallpaperS or as inliners or loadbearing materials for phosphorus-containing reaction accelerants, or amounts of a floor coverings, for example PVC floor coverings. PVC floor phosphorus-containing compound effective for reaction coverings manufactured using glass fiber webs consolidated acceleration. The binders of this invention may include an using the binders of this invention and PVC plastisols have esterification catalyst, for example Sulfuric acid or little if any tendency to yellow. p-toluenesulfonic acid. The binders of this invention can be When used as roofing membranes, the bonded fiber webs used as impregnants or coatings. The binders of this inven are generally coated with bitumen. tion can be the Sole constituent of Said impregnants or The binders of this invention can also be used in admix coatings. However, the impregnants or coatings may addi ture with further binders, for example formaldehyde tionally include further additives suitable for the particular containing binderS Such as urea-formaldehyde resins, intended use. Examples of Suitable additives are dyes, melamine-formaldehyde resins or phenol-formaldehyde res pigments, biocides, plasticizers, thickeners, adhesion ins. improvers, reductants and transesterification catalysts. The binders of this invention can further be used as The binders of this invention dry at 50° C. in 72 hours to 15 a film from 0.3 to 1 mm in thickness and following a binders for insulating materials composed of the abovemen Subsequent 15 minutes cure at 130° C. in air preferably tioned fibers, especially inorganic fiberS Such as mineral have a gel content of above 50% by weight, particularly fibers and glass fibers. preferably of above 60% by weight, very particularly pref The hitherto customary binders based on phenol erably above 70% by weight, in particular above 75% by formaldehyde condensation resins have the disadvantage weight. that significant amounts of phenol, formaldehyde and low After curing, the cured films are stored at 23° C. in water molecular weight condensation products thereof are emitted for 48 hours. Solubles remain in the water. The film is then in vapor form during the manufacture of insulating materi dried at 50 C. to constant weight and weighed. The weight als. Costly measures have to be taken to prevent their escape corresponds to the gel content, the gel content is calculated 25 to the environment. Furthermore, the finished insulating in 96 by weight, based on the weight before the solubles are products can emit formaldehyde, which is particularly unde Separated off. Constant weight is achieved when the weight Sirable when the insulating products are used in residential decrease over 3 hours is less than 0.5, in particular less than buildings. 0.1% by weight. Fibers for insulating materials are widely produced in The binders of this invention are particularly useful as industry by Spinning melts of the corresponding mineral raw binders for fiber webs. Examples of fiber webs are webs of materials (see for example EP 567 480). cellulose, cellulose acetate, esters and ethers of cellulose, In the manufacture of insulating materials, the aqueous cotton, hemp, animal fibers, Such as wool or hairs and binder Solution is preferably Sprayed onto the freshly pre especially WebS of Synthetic or inorganic fibers, e.g. aramid, 35 pared fibers while they are still hot. Most of the water carbon, acrylic, polyester, mineral, PVC or glass fibers. evaporates, leaving the resin as a Viscous high-Solids mate If used as binders for fiber webs, the binders of this rial adhering to the fibers in an essentially uncured State. The invention can include the following additives for example: fibers are then used to produce binder-containing fiber mats Silicates, Silicones, boron-containing compounds, lubricants, and these are further transported by suitable conveyor belts Wetting agents. 40 through a curing oven. There the resin cures at oven tem Glass fiber webs are preferred. The binder of this inven peratures of from about 150 to 350° C. to form a stiff, tion has the effect of converting unbonded fiber webs, thermoset matrix. After curing, the mats of insulating mate especially of glass fibers, into consolidated or bonded WebS. rial are Suitably finished, ie. cut into a shape Suitable for the For this the binder of this invention is applied to the 45 end-user. unbonded web, for example by coating, impregnating, The binders used in the manufacture of insulating mate Saturating, preferably in a weight ratio of fiber/polymer A rials may include customary auxiliary and additive Sub (solid) of from 10:1 to 1:1, particularly preferably from 6:1 stances. Examples thereof are hydrophobicizing agents, for to 3:1. example Silicone oils, alkoxy Silane S Such as The binder of this invention is preferably used for this in 50 3-aminopropyltriethoxysilane as coupling agent, Soluble or the form of an aqueous dilute preparation having a water emulsifiable oils as lubricants and dustproofing agents and content of from 95 to 40% by weight. also wetting aids. After the binder of this invention has been applied to the The predominant proportion of the mineral or glass fibers web, it is generally dried preferably at from 100 to 400, 55 used in the insulating materials have a diameter within the especially at from 130 to 280 C., very particularly prefer range from 0.5 to 20 um and a length within the range from ably at from 130 to 230 C., for a period of preferably from 0.5 to 10 cm. 10 Seconds to 10 minutes, especially from a period within Customary use-forms for insulating materials are rectan the range from 10 Seconds to 3 minutes. gular or triangular sheets and rolled-up webs. The thickness The resulting bonded fiber web has high strength dry and 60 and density of the insulating materials can be varied within wet. After drying, the bonded fiber web does not show any wide limits, making it possible to produce products having Significant yellowing, if any. The binders of this invention the desired insulating effect. Customary thicknesses range provide in particular short drying times and also low drying from 1 to 20 cm, customary densities from 20 to 300 kg/m. temperatures. 65 The insulating effect is characterized by the thermal con The bonded fiber webs, especially glass fiber webs, are ductivity lambda (in mw/mK). The insulating sheets have useful as or in roofing membranes, as loadbearing materials dry and wet strength. 6,071,994 11 The binders of this invention are also useful for manu facturing Saucepan cleaners or Scourers based on bonded TABLE 1-continued fiber webs. Fibers can be natural fibers and synthetic fibers, Solids especially on sic mineral fibers or glass fibers. Fiber webs CO- Visco for Saucepan cleaners or Scourers are preferably consoli Polymer TEA tent sity dated using the Spraying process. Binder g g % pH mPas EXAMPLES 11: Mw: 1000,000, SC; 23.5, pH: 5.1 '': Preparation similar to copolymer 5, SC: 40.7%, pH: 2.5, Mw: 80,000 Preparation of aqueous binders ": Preparation similar to copolymer 5, SC: 40.7%, pH: 2.5, Mw: 80,000 The polymer solutions were mixed with triethanolamine '': Preparation similar to copolymer 5, SC: 40.7%, pH: 2.5, Mw: 80,000 ": Polyacrylic acid, Mw: 100,000, SC: 35.0%, pH: 1.0, for comparison (TEA) in the respective amounts indicated in Table 1, which ": Copolymer of acrylic acid/methacrylic acid 30:70% by weight, Mw: also shows the solids content of the binder, the pH and the 22,000, SC: 25.8%, pH: 1.4, for comparison. Viscosity. Determination of average molecular weight: TABLE 1. 15 The weight average molecular weight was determined by gel permeation chromatography (GPC) using aqueous elu Solids CO- Visco ents. The system was calibrated with a broadly distributed Polymer TEA tent sity Sodium polyacrylate mixture, whose cumulative molecular Binder g g % pH mPas weight distribution curve had been determined by coupled A. 882.O 17.2 49.4 2.9 7,100 GPC laser light Scattering, according to the calibration Cop. AA/MA' 80:20 B 875.O 25.0 46.8 3.2 5,400 method of M. J. R. Cantow et al. (J. Polym. Sci., A-1.5 Cop. AA/MA 85:15 (1967) 1391-1394), albeit without the concentration correc C 882.O 18.0 49.4 2.9 3,700 tion Suggested there. The eluent used was an aqueous Cop. AA/MA 75:25 25 D 891.9 O8.1 45.1 3.3 4,900 tris(hydroxymethyl)aminomethane (TRIS) buffer solution Cop. AA/MA 90:10 (0.08 molar). The chromatography columns were loaded E 894.8 O5.2 44.0 2.8 2,800 Cop. AA/MA 70:30 with TSK PW-XL 3000 and TSK PW-XL 5000 (from F 884.3 15.7 48.5 2.3 8OO ToSoHaas) as Stationary phase. A differential refractometer Cop. AA/MA 60:40 was used for detection. G 881.5 18.5 SO.8 3.0 2,400 Cop. AA/MA 80:20 Determination of the Solids content: H 88O1 19.9 50.2 2.9 900 A defined amount of the Sample is weighed (starting Cop. AA/MA 70:30 weight) into an aluminum dish. The sample is dried in a I 886.7 13.3 46.4 2.5 440 drying cabinet at 50° C. for 72 hours. The sample is then Cop. AA/MA 60:40 35 K 928.2 71.8 29.9 3.3 10,800 reweighed (final weight). The percentage Solids content SC EMA10 L 925.3 74.7 30.8 3.2 14,200 is calculated as follows: SC=final weightx100/starting MA anhydride/V1 11 weight 9%). M 924.7 75.3 43.7 3.7 2,700 Cop. AA/MA 70:30 Determination of the viscosity: N 891.2 108.8 45.4 2.9 2,400 40 The solution viscosity was determined using an LVF Cop. AA/MA' 70:30 O 860.3 139.7 47.5 2.4 2,300 viscometer from Brookfield. The samples were conditioned Cop. AA/MA 70:30 to 23° C. beforehand. P 905.O 95.0 40.4 3.5 2,100 Poly-AA' Application tests O 928.2 71.8 29.9 3.0 28O 45 Glass fiber webs Cop. MAA/AA' Binder Solutions. A to Q were diluted with water to a total Abbreviations solids content of 15% by weight and introduced into an AA: Acrylic acid impregnating trough. The web used was a glass fiber web EMA: Ethylene/maleic acid copolymer 26.5x32.5 cm in size which had been lightly prebonded with SC: Solids content 50 MAA: Methacrylic acid melamine-formaldehyde resins (about 7% of binder add-on, MA: Maleic acid Mw: weight average molecular weight basis weight about 50 g/mi). After 2x20 sec dips into the TEA: Triethanolamine impregnating liquor, the exceSS binder was Sucked off to V1: Methyl vinyl ether achieve a binder content of 20% (based on the total weight) ": Copolymer of acrylic acid/maleic acid 80:20% by weight, Mw 160, 000, polymerized at 110° C. with hydrogen peroxide as free-radical 55 and the impregnated glass web was dried in a Mathis oven initiator, as per EP 75 820. SC: 44.5%, pH: 0.8 for a predetermined time (t) at the temperature Setting (T) *: Preparation similar to copolymer 1, SC: 40.5%, pH: 1.1, M.: 240,000 : Preparation similar to copolymer 1, SC: 44.6%, pH: 0.7, Mw: 90,000 (see Table 2). The glass fiber sheet was cut into strips 50 mm : Preparation similar to copolymer 1, SC: 40.4%, pH: 1.1, Mw: 205,000 in width which were stretched in a tensile tester at 50 : Preparation similar to copolymer 1, SC: 39.2%, pH: 2.7, Mw: 84,000 mm/min to the point of rupture (dry breaking strength BS). : Preparation similar to copolymer 1, Mw: SC: 43.6%, pH: 1.0, Mw: 60 5,000 The temperature of the fiber web is reported in Table 2. To : polymerized at 130° C. with hydrogen peroxide as free-radical initiator measure the wet strength, corresponding test-Strips were as per EP 75 820. SC:44.8%, pH: 0.8, Mw: 80,000 : polymerized at 130° C. with hydrogen peroxide as free-radical initiator placed in water at 25 or 80 C. for 15 min and then stretched as per EP 75 820. SC: 45.4%, pH: 1.4, M.: 27,000 to rupture in the moist State at the Stated temperature (wet '': polymerized at 130° C. with hydrogen peroxide as free-radical initiator as per EP 75 820. SC: 42.6%, pH: 0.7, Mw: 15,000 65 BS). The results of the measurements (averages of 5 10: Mw: 820,000, SC: 21.6, pH: 4.6 Specimens) are reported in newtons (N) and are based on a test-strip width of 50 mm. 6,071,994 13 14 To determine the boil-off loss (BOL) the decrease in the A Fischer bar thus prepared is tested in the dry state at 23 web weight after 15 min of boiling in distilled water was C. in a three-point bending test. In this bending test, the test determined. Specimen rests on 2 points and is Subjected to a force in the Yellowing was assessed qualitatively. middle until it breaks (bending strength = breaking force The results are shown in Table 2. divided by cross-sectional area).

TABLE 2 Exam- Drying Drying Dry BS at Wet BS at Wet BS at Dry BS at ple temp. time 25° C. 25° C. 80° C. 180° C. BOL No. Binder I. C. sec. N N N N % Yellowing 17 A. 8O 25 88 78 45 43 3.9 Ole 18 A. 8O 3O 84 88 46 39 2.5 Ole 19 A. 8O 60 2O7 65 89 59 .4 Ole 2O A. 8O 90 210 76 14 3O .1 Ole 21 A. 8O 2O 2O2 86 3O 54 0.5 Ole 22 B 8O 2O 97 87 19 53 .1 Ole 23 C 8O 2O 89 8O 25 57 O.8 Ole 24 D 8O 2O 2O2 68 22 52 O.9 Ole 25 E 8O 2O 205 85 35 49 5 Ole 26 F 8O 2O 88 84 27 39 .9 Ole 27 G 8O 2O 2O7 68 16 60 .2 Ole 28 G 2OO 2O 81 81 40 46 O6 yes 29 H 8O 2O 97 65 28 31 2.7 Ole 3O H 2OO 2O 98 75 45 29 O.8 yes 31 I 8O 2O 88 55 O1 32 8 Ole 32 K 8O 2O 22O 86 3O 50 0.5 Ole 33 L 8O 2O 223 94 74 42 3 yes 34 M 8O 2O 96 87 89 52 .2 Ole 35 N 8O 2O 95 94 32 46 .4 Ole 36 O 8O 2O 99 74 14 41 5 Ole 37 P 8O 2O 91 O8 62 27 2.6 Ole 38 O 8O 2O 47 61 48 58 16.O Ole 39 O 8O 3O 45 63 46 66 17.0 Ole 40 O 8O 60 62 88 61 62 2.8 Ole 41 O 8O 90 70 05 74 61 1.5 Ole 42 O 8O 12O 76 26 8O 56 2.O Ole 43 O 2OO 12O 87 67 144 58 1.3 yes Examples 37 to 43 are comparative

Determination of gel content Dry bending strength: 740 N/mm Binder R: A further Fischer bar is stored in distilled water at 23° C. for one hour. The water taken up by the test Specimen and 40 its bending strength in the wet state at 23° C. are determined. Water uptake: 21.7% by weight 150 g of an 80AA/20 MA copolymer (copolymer 1) and Wet bending strength: 620 N/mm. 30 g of triethanolamine were added together. Example 45 45 (for comparison) The mixture is poured into a Silicone mold and dried at Example 44 was repeated using a commercial phenol 50° C. in a through-circulation oven. The thickness of the formaldehyde resin (Kauresin(R) 259 liquid) instead of binder R. resulting film is within the range from 0.5 to 1 mm. Dry bending strength:850 N/mm About 1 g of the film thus prepared is cured at 130 C. for 50 Water uptake: 22% by weight 15 min. The cured film is stored in distilled water at 23° C. Wet bending strength: 690 N/mm. for 48 h. We claim: The gel content is the ratio of the weight of the water 1. A proceSS for producing fiber webs, which comprises Stored film after drying back to constant weight to the using formaldehyde-free acqueous binders comprising: original weight of the film. 55 A) a free-radically polymerized polymer containing from 5 to 100% by weight of units derived from an ethyl Gel content: 83% enically unsaturated acid anhydride or from an ethyl Insulating materials enically unsaturated dicarboxylic acid whose carboxyl groups can form an anhydride group, and Example 44 60 B) an alkanolamine having at least two hydroxyl groups, wherein the aqueous binder comprises less than 0.5% by Preparation of a test Specimen from fused basalt beads using weight, based on the Sum of A)+B), of a phosphorus binder R containing reaction accelerant, 300 g of fused basalt powder beads are mixed with 30.6 as binders for the fiber webs. g of binder R. The mixture is molded into a test Specimen 65 2. A process as claimed in claim 1, wherein the binder (Fischer bar) having the dimensions of 17x2.3x2.3 cm and comprises less than 0.3% by weight of a phosphorus cured at 200° C. for 2 h. containing reaction accelerant. 6,071,994 15 16 3. A process as claimed in claim 1, wherein the binder has 19. A formaldehyde-free aqueous binder, comprising: a gel content greater than 50% by weight following 15 A) a free-radically polymerized polymer which contains minutes drying at 130 C. from 5 to 100% by weight of units derived from an 4. A process as claimed in claim 1, wherein the polymer ethylenically unsaturated acid anhydride or from an contains from 5 to 100% by weight of units derived from ethylenically unsaturated dicarboxylic acid whose car maleic acid or maleic anhydride. boxyl groups can form an anhydride group, and 5. A proceSS as claimed in claim 1, wherein the alkano lamine is a compound represented by formula (I): B) an alkanolamine having at least two hydroxyl groups, wherein the aqueous binder comprises less than 0.5% by 1O I weight, based on the Sum of A)+B), of a phosphorus R2 containing reaction accelerant, and wherein the binder dries at 50 C. in 72 hours to a film R-N-R, from 0.3 to 1 mm in thickness and, following a sub 15 Sequent 15 minutes cure at 130 C. in air, has a gel wherein content of above 50% by weight. R" is hydrogen, C1-Co-alkyl or C1-Co-hydroxyalkyl, 20. A proceSS as claimed in claim 1, wherein the aqueous and binder comprises less than 0.3% by weight, based on the R and R are each C-Co-hydroxyalkyl. Sum of A)+B), of a phosphorus-containing reason acceler 6. A proceSS as claimed in claim 1, wherein the alkano ant. lamine is triethanolamine. 21. A proceSS as claimed in claim 1, wherein the aqueous 7. A proceSS as claimed in claim 1, wherein the molar ratio binder comprises less than 0.1% by weight, based on the of the carboxyl groups and anhydride groups (1 anhydride Sum of A)+B), of a phosphorus-containing reaction acceler group calculated as 2 carboxyl groups) of A) to the hydroxyl ant. groups of B) is within the range from 20:1 to 1:1. 25 8. A process for producing bonded fiber webs, which 22. A formaldehyde-free acqueous binder as claimed in comprises coating or impregnating fiber webs with an aque claim 19, comprising less than 0.3% by weight, based on the ous binder as claimed in claim 1 and drying. Sum of A)+B), of a phosphorus-containing reaction acceler 9. A proceSS as claimed in claim 1 for producing bonded ant. glass fiber webs. 23. A formaldehyde-free acqueous binder as claimed in 10. Bonded fiber webs obtained by using a formaldehyde claim 19, comprising less than 0.1% by weight, based on the free aqueous binder as claimed in claim 1. Sum of A)+B), of a phosphorus-containing reaction acceler 11. Bonded glass fiber webs obtained by using a ant. formaldehyde-free acqueous binder as claimed in claim 1. 24. A proceSS as claimed in claim 1, wherein the alkano 12. Roofing membranes comprising bonded fiber webs as 35 lamine is a tri-(hydroxy-Co-alkyl)amine. claimed in claim 10. 25. A formaldehyde-free acqueous binder as claimed in 13. Roofing membranes comprising bonded glass fiber claim 19, wherein the alkanolamine is a tri-(hydroxy-Co WebS as claimed in claim 11. alkyl)amine. 14. Insulating materials comprising bonded fiber WebS as 40 26. Bonded fiber webs bonded by using a formaldehyde claimed in claim 10. free aqueous binder as obtained by the process of claim 20. 15. Insulating materials comprising bonded glass fiber 27. Bonded fiber webs bonded by using a formaldehyde WebS as claimed in claim 11. free aqueous binder obtained by the process of claim 21. 16. Floor coverings comprising bonded fiber webs as 28. Bonded fiber webs obtained by using the claimed in claim 10. 45 formaldehyde-free aqueous binder as claimed in claim 19. 17. Floor coverings comprising bonded glass fiber webs 29. Bonded fiber webs obtained by using the as claimed in claim 11. formaldehyde-free aqueous binder as claimed in claim 25. 18. Saucepan cleaners comprising bonded fiber WebS as claimed in claim 10. k k k k k