MXPA97001566A - Aqueous polyurethane dispersions based on 1-methyl-2,4- and / or -2,6-diisiocianateciclohexane and their use as agglutinants for vit fiber apparators - Google Patents

Abstract

The present invention relates to: The present invention relates to aqueous polyurethane dispersions having a resin solids content of 20 to 60% by weight, a viscosity at 23øC of 10 to 20,000 mPa's and a pH of 5.5 to 8.5, wherein the polyurethane has a weight average molecular weight of 5,000 to 500,000 and a content of urethane groups (calculated as -NHCO-O- molecular weight = 59) of 2.5 to 15% by weight, and is based on one component of polyisocyanate containing 50 to 100% by weight of 1-methyl-2,4- and / or, 2,6-diisocyanatocyclohexane. The present invention also relates to aqueous binder compositions containing these aqueous polyurethane dispersions and known crosslinking resins, and to the use of aqueous polyurethane dispersions and aqueous binder compositions as binders for fiberglass encapsulations.

Description

AQUEOUS POLYURETHANE DISPERSIONS BASED ON 1- METHYL-2,4- AND / OR -2,6-DIISOCYANATECICLOHEXANE AND ITS USE AS AGGLUTINANTS FOR APRESTORS FOR FIBER GLASS BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to ionic and / or nonionic aqueous polyurethane dispersions based on l-methyl-2,4- and / or -2,6-diisocyanatocyclohexane, aqueous binder compositions containing these aqueous polyurethane dispersions and known crosslinking resins, and the use of dispersions and binder compositions as binders for fiber glass holders.

Description of the prior art Polyurethane dispersions are known and described, for example, in German Patents DE-A 1,495,745, 2,645,779, 3,903,538, 4,137,661 and 4,219,418, and in Kunststof fhandbuch Vol. 7, REF: 24109 3a. edition, 1993, pp. 30 and 31. These are also described in D. Dieterich, Angew. Makromol Chem. 98 (1981) 133 and H. Reiff, D. Dieterich, Angew, Makromol. Chem. 26 (1972) 85. The aqueous polyurethane dispersions described in these previous publications can be used to prepare paints or coatings with excellent properties, which can be used for various applications according to their composition. It has now been found that aqueous polyurethane dispersions containing as a major structural component l-methyl-2,4- and / or 2,6-diisocyanatocyclohexane incorporated through urethane groups and optionally through urea groups possess, in addition to excellent properties, very good viscosity stability during storage when compared to known systems. It has also been found that when these aqueous polyurethane dispersions are used as binders for glass fiber reamers, the glass fiber reinforced plastics have remarkable mechanical properties. Significantly improved processing capacity during the manufacture and use of fiberglass pretailers was also observed. An additional advantage of the fiberglass aprestadores according to the invention is their low apparent volume.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to aqueous polyurethane dispersions having a resin solids content of 20 to 60% by weight, a viscosity of 23 ° C of 10 to 20,000 mPa's and a pH of 5.5 to 8.5, wherein the polyurethane it has a weight average molecular weight of 5,000 to 500,000 and a content of urethane groups (calculated as -NHCO-O-, molecular weight = 59) of 2.5 to 15% by weight, and is the reaction product of a) from 50 to 91% by weight of a polyhydroxyl component containing one or more polyhydroxyl compounds having an OH number of from 15 to 350, b) from 7 to 45% by weight of a polyisocyanate component containing 50 to 100% by weight of l-methyl-2,4- and / or 2,6-diisocyanatocyclohexane and 0 to 50% by weight of one or more of other organic polyisocyanates having molecular weights of 140 to 1500, c) from 0 to 12% by weight of a component containing one or more compounds containing potential anionic or anionic groups, with the exception of the carboxylate groups, and one or more isocyanate-reactive groups. d) from 0 to 15% by weight of a nonionic hydrophilic component containing one or more compounds which are mono- to tetrafunctional in the isocyanate addition reactions and which contain at least one hydrophilic polyether chain and e) from 0 to 30% by weight of a component, which is different from components a), c) and d), which has a molecular weight of 62 to 2500 and contains isocyanate reactive groups, where the percentages from a) to e) add up to 100, with the proviso that c) and d) can not both be zero.

The present invention also relates to aqueous binder compositions containing these aqueous polyurethane dispersions and known crosslinking resins, and to the use of aqueous polyurethane dispersions and aqueous binder compositions as binders for glass fiber binders.

DETAILED DESCRIPTION OF THE INVENTION The present polyurethanes in the aqueous polyurethane dispersions are the reaction products of a) from 50 to 91, preferably from 65 to 90 and more preferably from 68 to 88% by weight of a polyhydroxyl component containing one or more polyhydroxy compounds having an OH number from 15 to 350, b) from 7 to 45, preferably from 10 to 30 and more preferably from 8 to 23% by weight of a polyisocyanate component containing from 50 to 100% by weight of l-methyl-2,4- and / or -2 , 6-diisocyanatocyclohexane and 0 to 50% by weight of other organic polyisocyanates having a molecular weight of 140 to 1,500, c) from 0 to 12, preferably from 3 to 9 and more preferably from 4 to 8% by weight of a component containing one or more components containing potential anionic or anionic groups, with the exception of the carboxylate groups, and one or more isocyanate-reactive groups, preferably sulfonate and phosphate groups, more preferably sulfonate groups, d) from 0 to 15, preferably from 0 to 8% by weight of a nonionic-hydrophilic structural component containing one or more compounds that are mono- to tetrafunctional in the isocyanate addition reactions, and which contain at least one chain of hydrophilic polyether, and e) from 0 to 30, preferably from 0 to 10 and more preferably from 0 to 7.5% by weight of a component. which is different from components a), c) and d), which has a molecular weight of 62 to 1200 and contains isocyanate-reactive groups, where the percentages from a) to e) add up to 100, with the proviso that c) or d) can not be zero. The aqueous binder compositions according to the invention contain A) an aqueous dispersion of polyurethane according to the invention and B) a hardener component selected from Bl) hydrophobic polyisocyanates having a viscosity at 23 ° C of 25 to 5000 mPa's and an NCO content of 5 to 26% by weight, B2) hydrophilic polyisocyanates containing chemically incorporated polyether * hydrophilic chains, and having an NCO content of 4 to 24% by weight.

B3) mixtures of polyisocyanates Bl) and B2), B4) blocked polyisocyanates, optionally dispersed in water, prepared by blocking the polyisocyanates Bl) to B3) with blocking agents for the isocyanate groups, B5) amino crosslinker resins and B6) mixtures of crosslinking resins B4) and B5).

The aqueous polyurethane dispersions according to the invention preferably have a solids content of 30 to 60% by weight, a viscosity at 23 ° C of 30 to 5000 mPa's and a pH of 5 to 9. The pH is determined by the dilution of the aqueous polyurethane dispersions at a solids content of 10%. The polyurethanes present in the dispersion according to the invention have a weight-average molecular weight (MW / which can be determined by gel permeation chromatography using polystyrene as the calibration standard) of from 5,000 to 500,000, preferably 10,000 to 300,000; an OH number of < 20 mg KOH / g resin solids; a content of acid groups corresponding to an acid value of 7 to 70, preferably 10 to 45 mg of KOH / g of resin solids and a degree of neutralization of 20 to 100, preferably 50 to 100%, and a content of urethane groups (calculated as -NH-CO-O- molecular weight = 59) from 2.5 to 15, preferably from 5 to 12.5% by weight. The polyhydroxyl components a) include the polyester polyols described in Ullmanns Encyklopadie der technischen Chemie, 4a. edition, Vol. 19, pp. 62-65. Preferred polyester polyols are those obtained by the reaction of divalent alcohols a3) with divalent carboxylic acids. Instead of the polycarboxylic acids, polycarboxylic acid anhydrides or the corresponding esters of lower alcohols or their mixtures can also be used to make the polyester polyols. The polycarboxylic acids can be aliphatic polycarboxylic acids, cycloaliphatics or aromatics, saturated or unsaturated, which can optionally be substituted with inert substituents. The reaction to form the polyester polyols takes place by fusing or azeotropic condensation at a temperature of 140 to 240 ° C, optionally in the presence of conventional esterification catalysts. The polycarboxylic acid can be prepared from monocarboxylic acids al), as well as from dicarboxylic acids or polycarboxylic acids a2). The initial component a) is a component of monocarboxylic acid which consists of at least one monocarboxylic acid containing a molecular weight of from 112 to 340. Suitable monocarboxylic acids include benzoic acid, tert-butylbenzoic acid; hexahydro-benzoic acid; saturated fatty acids such as 2-ethylhexanoic acid, isononanoic acid and coconut oil fatty acid, hydrogenated industrial fatty acids, mixtures of fatty acids, decanoic acid, dodecanoic acid, tetradecanoic acid, stearic acid, docosanoic acid (behenic acid) and acid palmitic; unsaturated fatty acids such as soybean oil fatty acid, castor oil fatty acid, sorbic acid, peanut oil fatty acid, conjugated fatty acid, tallow oil fatty acid, sunflower fatty acid, and fatty acid oil of safflower; and mixtures of these and other monocarboxylic acids. The initial component a2) is selected from di-, tri- and / or tetracarboxylic acids or their anhydrides having a molecular weight of 98 to 840. Examples include phthalic acid (anhydride), isophthalic acid, terephthalic acid, tetrahydrophthalic acid (anhydride) ), hexahydrophthalic acid (anhydride), maleic acid (anhydride), succinic acid (anhydride), fumaric acid, adipic acid, sebacic acid, azelaic acid, dimeric fatty acid, trimeric fatty acid, trimellitic acid (anhydride), butan-tetra acid -carboxylic and mixtures of these or other acids. The initial component a3) is selected from diols, triols, tetraols and higher functional alcohols having a molecular weight of 62 to 1200, preferably 62 to 200. Examples include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-, 1,4- and 2,3-butanediol, 1,6-hexanediol, trimethyl-hexanediol, diethylene glycol, triethylene glycol, hydrogenated bisphenols, 1-cyclohexanediol, 1,4-clohexanedimethanol, neopentyl glycol, tricyclodecanediol, trimethylpropane, glycerol, pentaerythritol, trimethyl-pentanediol, dipentaerythritol, ditrimethylolpropane, castor oil and mixtures of these or other polyvalent alcohols. The polycarbonate diols are also suitable, such as those obtained by the reaction of phosgene with an excess of alcohols a3) of low molecular weight.

Lactone-based polyester diols are also suitable such as homo- or copolymers of lactones, preferably products of addition of lactones to difunctional initiator molecules. Examples of lactones include e-caprolactam, β-propiolactone, β-butyrolactone, methyl-e-caprolactone and mixtures thereof. Suitable initiator components include the low molecular weight divalent alcohols mentioned under a3). The corresponding polymers of e-caprolactone are particularly preferred. The polyester diols or low molecular weight polyether diols can also be used as initiators for the manufacture of the lactone polymers. Instead of the lactone polymers, the corresponding hydroxycarboxylic acids can also be used. The polyether polyols can also be used as polyhydroxy compounds a). These can be obtained by the polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, with each other, for example in the presence of BF3 or basic catalysts, or by the addition of these compounds , either as a mixture or sequentially, to the initiator components containing reactive hydrogen atoms such as alcohols or amines, for example water, ethylene glycol, 1,3-propanediol, 1,2-bis- (4-hydroxydiphenyl) -propane , glycerol, trimethylolpropane, pentaerythritol or aniline. The polyester diols and the polyether diols can also be used by mixtures in a weight ratio of 9: 1 to 1: 9. The hardness and modulus of elasticity of the polyurethanes can be increased if also low molecular weight diols having a molecular weight of 50 to 500, preferably 60 to 200 are used. Suitable alkane diols are those described as suitable for the preparation of polyester polyols, preferably unbranched diols having from 2 to 12 carbon atoms, more preferably those having an even number of carbon atoms. Component b) is selected from organic polyisocyanates having a weight average molecular weight of 140 to 1500, preferably 168 to 318, with the proviso that 50 to 100, preferably 75 to 100 and more preferably 100% by weight of the component b) consists of 1-methyl-2, -diisocyanatocyclohexane and / or 1-methyl-2,6-diisocyanatocyclohexane. This diisocyanate or mixture of diisocyanate is preferably the 2,4-isomer or a mixture thereof with up to 35% by weight, based on the weight of the mixture, of the 2,6-isomer. These diisocyanates are known and can be manufactured by the gas phase phosgenation described in German Patent DE-A-4, 412, 327.2. In addition to the essential diisocyanates described above for the invention, component b) may also contain other polyisocyanates such as hexamethylene diisocyanate (HDI), l-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), 2,4- and / or 2,6-diisocyanatotoluene (TDI), 4-4 '-diisocyanatodicyclohexylmethane (H? 2MDI) and 4-4' -diiso-cyanatodiphenylmethane (MDI), 1,4-butylene diisocyanate (BDI) , isomeric xylylene diisocyanates (XDI) and their hydrogenated products (H6-XDI). The polyisocyanate component b) can also contain lacquer polyisocyanates prepared from the preceding diisocyanates, preferably HDI, IPDI and / or TDI, and containing biuret, isocyanurate, urethane and / or allophonate groups.

Component c) is selected from the compounds containing potential anionic or anionic groups and one or more isocyanate-reactive groups. The carboxylate groups are excluded. These compounds are preferably sulfonic acids and phosphoric acids containing at least one, preferably one or two hydroxyl or amino groups or the corresponding salts of these amino- or hydroxy acids. The use of sulfonate diols optionally containing ether groups is preferred, such as those described in US Pat. No. 4,108,814 as the anionic structural component c). The free acid groups, in particular sulfonic acid groups, represent "potential anionic groups", while the saline groups obtained by the neutralization of the potential anionic groups with bases represent "anionic groups". Component d) is selected from nonionic hydrophilic compounds containing one to four, preferably one or two isocyanate-reactive groups, preferably hydroxyl or amino groups. The polyether chains present in these compounds contain at least 80% by weight, preferably 100%, by weight of ethylene oxide units. Other alkylene oxides include propylene oxide. Suitable nonionic hydrophilic structural components include polyethylene glycols having weight average molecular weights of 300 to 6000 (eg, Carbowax 300, 400, 1000, 1500, 2000 and 6000, available from Union Carbide); monofunctional polyethylene glycol monoalkyl ethers having weight average molecular weights of 350 to 5000 (for example Breox 350, '550 and 750, available from .BP Chemicals and Polyether LB 25, LB 30 and LB 40, available from Bayer AG); difunctional polyether amines (e.g. Jeffamine ED 6000, ED 900 and Ed 4000, available from Texaco Chemical Company); and monofunctional polyether amines (e.g. Jeffamine M 715, M 1000 and M 2070, available from Texaco). Component e) is selected from other mono-di- and / or trifunctional compounds having a molecular weight of 62 to 2500, preferably 62 to 1200, containing hydroxyl and / or amino groups, such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, diethanolamine, diethylenetriamine, cyclohexanol, dodecanol and monofunctional alcohols. unsaturated (for example Ocenol, available from Henkel). Higher molecular weight polyols, which are outside the scope of components a), c) or d), such as polycarbonate diols, are included within the scope of component e). The manufacture of the polyurethanes according to the invention takes place either in the absence of the solvent or as an organic solution at 40-99% by weight, wherein the components a), c), d) and e), optionally dissolved in solvent , are introduced and reacted with component b) at temperatures of 40 to 140 ° C in such a way that the OH or NH groups are for practical purposes no longer detectable after the reaction. Preferably, the components are used in sufficient amounts to provide an equivalent ratio of isocyanate groups to the isocyanate-reactive groups from 3: 1 to 0.9: 1. The free acid groups of component c) are not included in the calculation of this equivalent proportion. • The reaction optionally takes place in the presence of 0.01 to 1% by weight, based on the weight of the reaction mixture, of suitable catalysts. If the components containing saline groups are not used as component c), then at least partial neutralization of the chemically incorporated acid groups takes place during the reaction or before, during and / or after the dispersion or dissolution of the polyurethane. in water by adding a base. They are preferably neutralized from 20 to 100%, more preferably from 50 to 100%, of the chemically incorporated acid groups, in the particular carboxyl groups and the sulfonic acid groups. Any optionally used solvent may be partially or completely removed before, during or after the dispersion or dissolution step, by distillation, optionally azeotropically and / or under vacuum, and / or by the use of an inert gas stream. Suitable solvents include N-methylpyrrolidone, diethylene glycol dimethyl ether, ethyl ethyl ketone, methyl isobutyl ketone, acetone, toluene, xylene, butyl acetate, methoxypropyl acetate and mixtures of these or other solvents that do not react with the isocyanate groups. Suitable catalysts for the urethane-forming reaction include tertiary amines such as triethylamine, tin compounds such as tin octoate II, dibutyltin oxide and dibutyltin dilaurate; and other commonly used catalysts. Suitable bases include ammonia, N-methylmorpholine, dimethyl isopropanolamine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, morpholine, tripropylamine, ethanolamine, triisopropanolamine, 2-diethylamino-2-methyl-1-propanol and mixtures of these and other neutralizing agents. Also suitable, but less preferred as neutralizing agents, are sodium hydroxide, lithium hydroxide, and potassium hydroxide. Ammonia and dimethylethanolamine are preferred as neutralizing agents. After the urethanization reaction, small amounts of other organic solvents can be added to obtain particular properties. These solvents include ethanol, propanol, butanol, butyl glycol, hexanol, octanol, butyl diglycol, ethyldiglycol, methyldiglycol and methoxypropanol. The dispersion step can be carried out according to various modalities, for example, the water / neutralization agent mixture can be added to the resin; water can be added to the resin / neutralizing agent mixture, the resin can be added to the water / neutralizing agent mixture or the resin / neutralizing agent mixture can be added to the water. The dispersion capacity of the resin in water can be optionally enhanced through the additional use of external emulsifiers, such as ethoxylated nonylphenol. The dispersion step is preferably carried out at 40-120 ° C. In the binder compositions according to the invention, the aqueous polyurethane dispersions are present in combination with the crosslinking resins B) as previously described. The hydrophobic polyisocyanates Bl) which are suitable as crosslinking resins are selected from organic polyisocyanates having an NCO content of from 5 to 26%, containing isocyanate groups linked aliphatically, cycloaliphatically, araliphatically and / or aromatically, and are liquid at room temperature. The polyisocyanate component Bl) preferably has a viscosity of 50 to 5000 mPa's up to 23 ° C. The polyisocyanate component is preferably selected from polyisocyanates or polyisocyanate mixtures, which exclusively contain isocyanate groups linked aliphatically and / or cycloaliphatically, and have an average NCO functionality of between 1.8 and 5.0 and a preferred viscosity up to 23 ° C of 50 to 3000 mPa's. If necessary, the polyisocyanates can be used in admixture with small amounts of inert solvents to reduce the viscosity to a value within the ranges described. However, the amount of these solvents must be limited so that the resulting coating compositions do not contain more than 20% by weight of the solvent, based on the weight of the binder. Suitable solvents for the polyisocyanates include aromatic hydrocarbons such as "naphtha solvent" and the solvents previously described. The preferred hydrophobic polyisocyanates Bl) are the "lacquer polyisocyanates" prepared from hexamethylene diisocyanate (HDI), 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI) and / or bis (isocyanate -cyclohexyl) methane, in particular those based exclusively on HDI. It is understood that "lacquer polyisocyanates" mean the known derivatives of these diisocyanates containing biuret, urethane, uretdione, allophonate and / or isocyanurate groups, which after their manufacture have been released. in a known manner, preferably by distillation of the initial diisocyanate in excess to a residual content of less than 0.5% by weight. Preferred aliphatic polyisocyanates to be used according to the invention include polyisocyanates which are prepared from HDI and which contain biuret groups, such as those described in U.S. Patent Nos. 3,124,605, 3,358,010, 3,903,126, 3,903,127 and 3,976,622. These polyisocyanates contain mixtures of N, N ', N "-tris- (6-isocyanatohexyl) -biuret with minor amounts of their larger homolog. Other particularly preferred aliphatic polyisocyanates are the cyclic trimers of HDI such as those described in US Pat. -PS 4,324,879, which contain NN ', N "-tris- (6-isocyanatohexyl) isocyanurate in admixture with minor amounts of their higher homologs. Particularly preferred aliphatic polyisocyanates are polyisocyanates prepared from HDI and contain uretdione, allophonate and / or isocyanurate groups, which can be obtained by the catalytic oligomerization of hexamethylene diisocyanate with the use of trialkylphosphines. Particularly preferred are those having a viscosity at 23 ° C of 50 to 500 mPa's and an NCO functionality of 2.2 to 5.0.

Suitable aromatic polyisocyanates which can be used as hydrophobic polyisocyanate Ba) are lacquer polyisocyanates prepared from 2,4-diisocyanato toluene or mixtures thereof with 2,6-diisocyanato toluene or prepared from 4,4 ' -disocyanato-diphenylmethane or mixtures thereof with their isomers and / or higher homologs. These aromatic lacquer polyisocyanates include polyisocyanates containing urethane groups, which can be obtained by reacting excess amounts of 2,4-diisocyanatotoluene with polyvalent alcohols such as trimethylpropane and subsequently removing the excess diisocyanate without reacting by distillation. Other aromatic lacquer polyisocyanates include trimers of the monomeric diisocyanates, previously described, which have been freed from the excess of monomeric diisocyanates, preferably by distillation. The use of the unmodified polyisocyanates is also possible, with the proviso that it satisfies the viscosity requirements. This polyisocyanate component can also contain mixtures of the polyisocyanates mentioned as examples.

The polyisocyanate component B2) is selected from hydrophilically modified polyisocyanates, which include the above-described lacquer polyisocyanates, in particular HDI-based lacquer polyisocyanates containing isocyanurate groups, which have been made hydrophilic by reaction with monovalent polyether alcohols. and hydrophilic. These hydrophilic polyisocyanates preferably have an NCO content of 4 to 24% by weight and an ethylene oxide content of 4 to 30% by weight, accommodated within the polyether chains having from 6 to 60 members in the chain. The manufacture of these hydrophilic lacquer polyisocyanates, whose hydrophilic ether chains are almost exclusively based on ethylene oxide units, are described, for example, in US Pat. No. 4,663,337 or in European Patent EP-A-540, 985. The crosslinking component B3) is selected from mixtures of polyisocyanates Bl) and B2). In these mixtures the weight ratio of B1): B2) is preferably from 0.2: 1 to 5: 1. By "mixtures" is meant the non-hydrophilically modified polyisocyanate blends Bl) with separately manufactured hydrophilic polyisocyanates B2). The term "mixture" does not refer to the fact that during the manufacture of the hydrophilic polyisocyanates B2) only a portion of the polyisocyanates are hydrophilically modified since the component B2) itself represents a "mixture" of hydrophobic and hydrophilic polyisocyanates. The crosslinking component B4) is selected from the blocked polyisocyanates prepared by blocking isocyanate groups of polyisocyanate Bl) to B3) with reversible and monofunctional blocking agents for isocyanate groups. Suitable blocking agents include monovalent alcohols such as methanol, ethanol, n-butanol, cyclohexanol and benzyl alcohol; oximes such as acetone oxime and ethylethyl ketoxime; lactams such as e-caprolactam; active hydrogen compounds such as diethyl malonate or ethyl acetoacetate; phenols and heterocyclic blocking agents. The resins. of crosslinking B5) are selected from the condensation products of melamine- or urea-formaldehyde, diluted in water or dispersible in water, such as those described in DH. Solomon, The Chemistry of Organic Filmformers, p. 235 and subsequent, John Wiley & Sons, Inc., New York, 1967. Melamine resins can be totally or partially replaced by other aminoplast resins, such as those described in "Methoden der organischen Chemie" (Houben-Weyl), Vol. 14/2, Part 2 , 4a. edition, Georg Thieme Verlag Stuttgart 1963, p. 319 and subsequent. The crosslinking component B6) is selected from mixtures of blocked polyisocyanates B4) with melamine resins B5). Such mixtures are preferably used in a weight ratio of B4): B5) from 0.2: 1 to 5: 1. Polyisocyanates Bl), B2) and B3), which contain free isocyanate groups, are preferably used in the binder compositions according to the invention. A hydrophilic modification of the polyisocyanates is not always necessary, because the dissolved and dispersed polyurethane resin can also simultaneously function as an emulsifier for the polyisocyanate. This function can also be supported by the additional use of external emulsifiers. Preferably, the crosslinkers B) contain exclusively polyisocyanates Bl) and / or B2) containing free isocyanate groups. In this case, and also in the particularly preferred case of blocked polyisocyanates B4), the amounts of components A) and B) are selected to provide an equivalent ratio of NCO / OH, based on the isocyanate groups (optionally blocked) of the component B) and the alcoholic hydroxyl groups of component A), from 0.5: 1 to 5: 1, preferably 0.8: 1 to 2: 1. The manufacture of ready-to-use binder compositions occurs simply by mixing components A) and B) at room temperature, optionally with the use of appropriate mixing or dispersing units. During the manufacture of the aqueous binder compositions, the auxiliary solvents are used in such quantities, or after the manufacture of the aqueous polyurethane dispersions A) are removed by distillation to such an extent that the resulting binder compositions contain no more than 20% by weight, preferably no more than 10% by weight, of organic solvents. It is possible before, during or after the manufacture of the aqueous binder compositions by mixing individual components A) and B), and also during manufacture of the binder of a package, add known additives such as defoaming agents, thickening agents and agents for the flow control, auxiliary dispersion, catalysts, antidescostramiento agents, antisetting agents, emulsifiers and biocides additives . The preparation agents for glass fibers according to the invention contain as binders the polyurethanes according to the invention in the form of aqueous solutions or aqueous dispersions, and may also contain emulsifiers, other film-forming resins, coupling agents, lubricants and other additives such as wetting or antistatic agents. Coupling agents, lubricants and additives, the manufacturing method, the finishing method and the finishing of glass fibers are known and described for example in KL Loewenstein "The Manufacturing Technology of Continuous Glass Fibers", Elsevier Scientific Publishing Corp, Amsterdam, London, New York, 1983, The other film-forming resins which can be used in combination with the aqueous polyurethane dispersions according to the invention are polymers, which are dispersible, emulsifiable or water-soluble. Examples include polyester polymers or polyester polymers containing epoxy groups, polyurethanes, acrylic polymers, vinyl polymers, such as polyvinyl acetate, mixtures of such polymers and copolymers of the corresponding monomers. The concentration of the film-forming resins in the dressing agents according to the invention is preferably from 1 to 12% by weight, preferably from 2 to 8% by weight. The proportion of the polyurethanes according to the invention, based on the total weight of the film-forming resins, is preferably 10 to 100%, more preferably 50 to 100% by weight. The suitable coupling agents include silane coupling agents known, for example, 3-aminopropiltrimetoxi- or triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxy -propyltriethoxysilane. The silane coupling agents are present in the prepping agents according to the invention in an amount preferably of 0.05% to 2% by weight, more preferably 0.15 to 0.85% by weight, based on the total weight of the sizing agent.

The finishers agents according to the invention may contain one or more nonionic lubricants and / or nonionic surfactants such as ethers of polyalkylene glycerol fatty alcohols or fatty amines, polyalkylene glycol ethers and glycerol esters of fatty acids having from 12 to 18 carbon atoms, polyalkylene glycols, higher fatty acid amides having 12 to 18 carbon atoms of polyalkylene glycols and / or alkenyl amines, quaternary nitrogen compounds such as ethoxylated imidazolinium salts, mineral oils and waxes. The lubricant or lubricants are preferably used in a total concentration of 0.05 to 1.5% by weight, based on the total weight of the sizing agent. Furthermore, finishers agents according to the invention may contain one or more antistatic, such as lithium chloride, ammonium chloride, salts of Cr-III, organotitanium compounds, sulfates or sulfonates aryl sulfonates arilpoliglicólico ether and agents Quaternary nitrogen compounds. Antistatic agents are preferably used in concentrations of 0.01 to 0.8% by weight, based on the total weight of the sizing agent.The manufacture of fiberglass aprons according to the invention is not difficult. Approximately half of the total water required is introduced into a suitable mixing vessel, and then the polyurethane dispersion according to the invention, the lubricant and optionally other additives, are added successively with stirring. After this, the pH is adjusted to 5-7 and then a hydrolyzate, prepared according to the manufacturer's instructions (UCC, New York), of a trialkoxysilane is added. The dresser is ready to be used after an additional agitation time of 15 minutes; the pH is optionally adjusted again from 5 to 7. Suitable sized glass fibers include the known types of glass used for the manufacture of glass fiber, such as low alkali, high alkali, glass C and S, and also other Known products of fiberglass manufacturers. Among the types of glass mentioned for the manufacture of continuous glass fibers, high alkali glass fibers are the most important for the reinforcement of plastic materials due to their low alkali content, high tensile strength and high elasticity module. The preparing agents can be applied by various methods, for example, with the aid of appropriate devices such as spray or roller applicators. These are applied to the glass filaments drawn at high speed out of nozzles, to spin immediately after the latter have hardened, for example before winding. It is also possible, however, to prime the fibers in a dip coating bath after the spinning process. The prepared glass fibers can be processed for example into shredded strands either wet or dry. The drying of the intermediate or final product takes place at temperatures of 90 to 150 ° C. By drying is meant not only the removal of other volatile components, but also the solidification of the sizing ingredients. Dressing has become the finished coating only at the end of drying. The amount of the sizing agent, based on the weight of the prepared glass fibers, is preferably 0.1 to 2% by weight, more preferably 0.3 to 1.0% by weight.

A greater number of thermoplastic or thermosetting polymers can be used as matrix polymers. Examples of thermoplastic polymers include polyolefins such as polyethylene or polypropylene; polyvinyl chloride; polymers such as copolymers of styrene / acrylonitrile, ABS, polymethylmethacrylate or polyoxymethylene; aromatic and / or aliphatic polyamides such as polyamide-6 or polyamide-6, 6; polycondensates such as polycarbonate, polyethylene terephthalate, liquid crystalline polyaryl ester, polyarylene oxide, polysulfone, polyarylene sulfide, polyaryl sulphone, polyether sulfone, polyaryl ether or polyether ketone; and polyducts such as polyurethanes. Examples of thermosetting polymers include epoxy resins, unsaturated polyester resins, phenolic resins, aminated resins, polyurethane resins, polyisocyanurates, epoxy / isocyanurate combination resins, furan resins, cyanurate resins and bismaleimide resins. The dressing agents according to the invention are also suitable for all applications in which aqueous solvent and solvent-free or other solvent-containing coating and coating systems with an improved properties profile are used. Examples include the coating of virtually all surfaces of mineral material for construction (such as plasters or mortars bonded with limestone and / or cement, gypsum-containing surfaces, fibrous concrete building materials, and concrete), ordinary gray cardboard and paper; Painting and sealing of wood and wood-based materials such as particle board, cardboard and wood fiber roofing paper; painting and coating of metal surfaces; coating of bituminous surfaces for streets; and painting and sealing various surfaces of plastic material. The paint or coating compositions made with the binder compositions according to the invention are extremely varied in nature, such as primers, fillers, pigmented or transparent top coatings, for example, in industrial painting, manufacture of original automotive equipment (OEM ) and refinishing sectors. The coating compositions can be applied by a wide range of spray methods, such as air pressure, airless or electrostatic spraying methods, with the use of one spray equipment or optionally two components. The paints and coating compositions can also be applied by brush, roller application, or knife coating.

EXAMPLES In the following examples all percentages refer to percentages by weight, unless stated otherwise. All the examples were carried out under an inert gas (nitrogen) atmosphere. All figures referring to the hydroxyl and acid numbers refer to milligram of KOH / g resin solids.

Example 1 Manufacture of an aqueous anionic polyurethane dispersion containing sulfonate and polyoxyethylene oxide groups Quantities of the prepolymer batch: 2352.0 g (1.3835 mol) 1,6-hexanediol-neopentyl glycol-polyadipate (MW 1700, molar ratio of diols 0.65: 0.35) 89.3 g (0.0400 mol) polyoxyethylene-polyoxypropylene polyether initiated with butanol (MW 2250 , EO ratio: PO 83:17) 262.5 g (1.5625 mol) hexamethylene diisocyanate. 296.2 g (1.5625 mol) l-methyl-2,4- and -2,6-diisocyanatocyclohexane (80/20 isomeric mixture) 5690 ml acetone Quantities of the extension lot: (calculated on 4.7% of NCO Solution of 160.0 g (0.9410 mol) isophorone diamine 15.7 g (0.3137 mol) hydrazine hydrate 63.5 g (0.1620 mol) of a 50% aqueous solution of the sodium salt of 2-aminoethyl-β-aminoethanesulfonic acid in 478 ml of demineralised water 4093 ml of demineralised water Procedure: The dewatered polyols were introduced and mixed with the isocyanate mixture with stirring at room temperature. The reaction mixture was heated to 100 ° C. This was maintained at 100 ° C -105 ° C for 1: hour for 15 minutes and the NCO content was then determined. Target value: 4.4 ± 0.3%. The prepolymer was dissolved to form a 40% solution in acetone after reaching the NCO content. After cooling to 40 ° C, the solution was mixed with the extender solution with vigorous stirring and stirred once more for 15 minutes. The dispersion with water then takes place within about 3 minutes. After the distillation of the acetone, a homogeneous, finely distributed dispersion was obtained, which was then filtered and decanted.

Data equivalent proportion of NCO / OH: 2.23: 1% NCO (calculated): 4.8% NCO (found): 4.7% extension: 8.5% ethylene oxide (EOx): 2.3% resin solids: 40% of sulfonate: 0.4 pH value: 6.1 Example 2 (comparative example) The procedure was exactly the same as in Example 1, except that an equi-olar mixture of hexamethylene diisocyanate and isophorone diisocyanate was used as the polyisocyanate mixture.

Data: NCO / OH equivalent ratio: 2.22: 1% NCO (calculated): 4.8% NCO (found): 4.7% extension: 85% Eox: 2.3% resin solids: 40% sulfonate: 0.4 pH value: 6.1 Example 4: Manufacture of a non-ionic aqueous polyurethane dispersion containing polyoxyethylene oxide Prepolymer batch quantities: 2241.0 g (0.2668 mol) hexanediol polyadipate (PM 840) 71.4 g (0.0320 mol) polyoxyethylene-polyoxypropylene polyether initiated with n-butanol (PM 2250) 8.3 g (0.1334 mol) ethylene glycol 87.9 g (0.4638) mol) l-methyl-2,4- and 2,6-diisocyanatocyclohexane (80/20 isomeric mixture) 1 drop tin octoate 759 ml acetone 11.0 g (0.1058 mol) diethanolamine 767 ml demineralised water Process: The waterless polyols were introduced and mixed with the isocyanate with stirring at 45 ° C. The reaction mixture was heated to 100 ° C. This was maintained at 100 ° C -105 ° C for 3 hours (the catalysis was carried out at after 2 hours) and the NCO content was then determined. Target value: 1.0 ± 0.1% The prepolymer was dissolved to form a 40% solution in acetone after reaching the NCO content. After cooling to 30 ° C, the solution was mixed with the diethanolamine with vigorous stirring, and stirred again for 10 minutes. Dispersion then takes place with water within about 3 minutes. After the distillation of the acetone, a finely distributed homogeneous dispersion was obtained, which was then filtered and decanted.

Data: NCO / OH equivalent ratio: 1.11: 1% NCO (calculated): 1.02% NCO (found): 1-.05 diethanolamine based on the NCO content found: 100% mol% of Eox: 14.9% humidity: 35 pH value: 8 OH group content: 0.9% Example 5 Manufacture of an aqueous, anionic, polyurethane dispersion containing sulfonate and polyoxyethylene oxide groups. 244.8 parts of a polyester prepared from adipic acid, 1,6-hexanediol and neopentyl glycol (molar ratio of the diols 0.65: 0.35) and having an OH number of 66, with 18.0 parts of polyether alcohol were mixed. monofunctional having an OH number of 26 (manufactured by alkoxylation of n-butanol with the use of a mixture of 83% ethylene oxide and 17% propylene oxide) and 25.8 parts of a sulfonate diol (propoxylated adduct of 2-butan-1,4-diol and NaHS03 PM 430) and mixed at 50 ° C with 35.8 parts of a mixture of 80% l-methyl-2,4-diisocyanatocyclohexane and 20% l-methyl-2,6 -diisocyanatocyclohexane - ("H6TDI") and 33.6 parts of 1,6-diisocyanatohexane (HDI) and reacted at 75 ° C until the NCO content of the resulting prepolymer had dropped to 4.2%. The mixture was cooled to 70 ° C and mixed with 33.4 parts of a bis-ketimine manufactured from methyl isobutyl ketone and 3-aminomethyl-3,5,5-trimethylcyclohexylamine (diamine of isophorone). A mixture of 605.9 parts of demineralized water preheated to 50 ° C, and 1.5 parts of hydrazine hydrate was then added with vigorous stirring, and stirred again for 3 hours at 70 ° C. The obtained bluish dispersion had a solids content of 39% and a viscosity of 100 mPa's (23 ° C).

Example 6 Manufacture of an aqueous, anionic, polyurethane dispersion containing sulfonate and polyoxyethylene oxide groups. '246.5 parts of a polyester prepared from adipic acid, 1,6-hexanediol and neopentyl glycol (molar ratio of diols 0.65: 0.35) were mixed and having an OH number of 66, with 17.1 parts of monofunctional polyether alcohol having an OH number of 26 (manufactured by alkoxylation of n-butanol with the use of a mixture of 83% ethylene oxide and 17% propylene oxide) and 32.3 parts of a sulfonate diol (2-propoxylated adduct) -butan-1,4-diol and NaHS03 PM 430) and mixed at 50 ° C with 51.9 parts of a mixture of 80% l-methyl-2,4-diisocyanatocyclohexane and 20% l-methyl-2,6- diisocyanatocyclohexane ("H6TDI") and 21.0 parts of 1,6-diisocyanatohexane (HDI) and reacted at 75 ° C until the NCO content of the resulting prepolymer had dropped to 4.2%. The mixture was then dispersed by the addition of the hot prepolymer at 80 ° C with vigorous stirring to 500 parts of demineralized water which had a temperature of 50 ° C. A mixture of 1.8 parts of hydrazine hydrate was then added dropwise, 12.9 parts of 2-methyl-pentamethylenediamine and 89.7 parts of demineralized water, and the mixture was stirred for 2 hours at 70 ° C. The resulting bluish dispersion had a solids content of 40% and a viscosity of 60 mPa's (23 ° C). ).

Fabrication of glass fiber embankments according to the invention Approximately half of the total amount of water required was introduced into an appropriate mixing vessel (47 Kg) and then 5 kg of the polyurethane dispersion according to the invention, 0.5 kg of a lubricant (Breox 50-A140, available from BP Chemicals) and optionally other additives were added successively with stirring. The pH value was adjusted to 5-7 and then a hydrolyzate (0.5 kg of 3-amino-propyl-triethoxysilane in 47 kg of water, manufactured according to the manufacturer's instructions, UCC New York) was added. After an additional agitation time of 15 minutes, the sizing agent was ready to be used; if necessary, the pH value was adjusted once again to 5-7. Glass fibers that have a diameter of 9 to 11 μm, they were manufactured using a roller applicator, they were shredded and dried with the previously described prepping agents. This is known in the art and is described in numerous patents, one of which is DBP-2, 553, 839. The standard test specimens were manufactured from 70 parts of polyamide 6 (BKV, Bayer AG) and 30 parts of these shredded fibers (shredded strands having a length of 4.5 mm) in an extruder at 250 ° C and the mechanical data were measured. The following table contains the data on the particle size, medium, the particle size distribution (PSD, given here as the so-called DV-0.9 values) of the prepared glass fibers, the amount of prescribing agent used, the apparent volume of the glass fibers, and the measured values for the tensile strength, the flexural strength and the impact resistance. The table also provides information on the improvements in the properties for the glass fibers prepared according to the invention, when compared to those of Comparison Example 2. Examples 1, 4, 5 and 6 are according to the invention. These show equal or better flexural strength and impact resistance with less primer coating (0.50 - 0.54% compared to 0.60%). This is unexpected, since normally the greater the percentage of coating, the greater the resistance to bending and impact.

Test results PUR dispersions / fiberglass / GF-reinforced plastic material Product »(%) PS | nm solids | PSD ÜV Coating Volume R Reessiisstteenncciiaa u Resistance to the Resistance of (09) * apprestador apparent traction fle? Ion21 impact [μM | % (I? G) (MPa) (MPa) (JJ // m2) Ex empl o 1 of 40 207 0.51 0.53 1.95 185 283 66.1 according to the agreement Example 2 40 228 0.54 0.60 1.87 180 272 64.3 (Com. ..) Example 4 of 35 208 0.76 0.51 1.90 189 287 67.0 according to the invention Example 5 of 39 111 0.49 0.50 1.65 182 273 58. 1 according to the invention 'Example 6 of 40 173 0.51 0.54 1.75 181 274 59.0 according to the invention An OV-0.9 value of 10 μm means that 90% of all particles in volume were smaller than 10 μm. The numerical value by itself provides information on the accumulated size by volume distribution. See Handbuch astersizer E, Fa. Malvern, D-71083 Herrenberg Germany. 1) According to DIN 53 4SS 2) according to DIN 53 457 3) according to DIN ISO 180 Although the invention has been described in detail in the foregoing for purposes of illustration, it should be understood that such details are solely for that purpose, and that variations may be made therein by those skilled in the art without departing from the spirit and scope of the invention, except as may be limited by the claims. l It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention Having described the invention as above, property is claimed as contained in the following:

Claims (3)

1. An aqueous polyurethane dispersion having a resin solids content of 20 to 60% by weight, a viscosity at 23 ° C of 10 to 20,000 mPa's and a pH of 5.5 to 8.5 characterized in that the polyurethane has a weight average molecular weight from 5,000 to 500,000 and a content of urethane groups (calculated as -NHCO-O-, molecular weight-59) of 2.5 to 15% by weight, and is the reaction product of: a) from 50 to 91% by weight of a polyhydroxyl component containing one or more polyhydroxyl compounds having an OH number of 15 to 350, b) of 7 to 45% by weight of a polyisocyanate component containing 50 to 100% by weight of 1- 'methyl -2,4- and / or 2, 6-diisocyanatocyclohexane and 0 to 50% by weight of one or more other organic polyisocyanates having molecular weights of 140 to 1500, c) from 0 to 12% by weight of a component that contains one or more compounds containing potential anionic or anionic groups, with the exception of carboxylate groups, and one or more group s reactive with isocyanate. d) from 0 to 15% by weight of a nonionic hydrophilic component containing one or more compounds which are mono- to tetrafunctional in the isocyanate addition reactions and which contain at least one hydrophilic polyether chain and e) from 0 to 30 % by weight of a component, which is different from components a), c) and d), which has a molecular weight of 62 to 2500 and contains groups reactive with isocyanate, wherein the percentages of a) to e) add up to 100, with the proviso that c) and d) can not both be zero.

2. The aqueous polyurethane dispersion according to claim 1, characterized in that the polyurethane is the reaction product of 65% to 90% by weight of polyhydroxyl component a), 10 to 30% by weight of polyisocyanate component b), at 8% by weight of component c), 0 to 15% by weight of the nonionic hydrophilic component d), and 0 to 30% by weight of component e), which has a molecular weight of 62 to 1200.

3. An aqueous binder composition, characterized in that it comprises: A) the aqueous polyurethane dispersion according to claim 1 and B) a hardening component comprising a member selected from the group consisting of Bl) hydrophobic polyisocyanates having a viscosity at 23 ° C of 25 to 5000 mPa's and a content of NCO from 5 to 26% by weight, B2) hydrophilic polyisocyanates containing hydrophilic polyether chains chemically incorporated, and having an NCO content of 4 to 24% by weight, B3) mixtures of polyisocyanates Bl) and B2), B4) polyisocyanates blocked, optionally dispersed in water, prepared by blocking the polyisocyanates Bl) to B3) with blocking agents for the isocyanate groups, B5) amino crosslinking resins and B6) crosslinking resin mixtures B4) and B5).