MXPA06004400A - N-methylpyrrolidone-free polyurethane dispersions based on dimethylolpropionic acid - Google Patents

Abstract

The present invention relates to aqueous polyurethane dispersions that are free from N-methylpyrrolidone and other solvents and wherein the polyurethanes are the reaction products of A) a mixture of 25%to 90%by weight of 1-isocyanate-3,3,5,-trimethyl-5 - isocyanatomethylcyclohexane (IPDI) and 10%to 75%by weight of 4,4'- diisocyanatodicyclohexylmethane, wherein the preceding percentages are based on the weight of component A), with B) one or more polyols having average molarcular weights (Mn) of 500 to 6000, C) one or more compounds which have at least one OH- or NH-functional group and contain a carboxyl and/or carboxylate group, wherein at least 50 mol%of the acid groups, based on the total moles of acid incorporated into the polyurethane, are incorporated by dimethylolpropionic acid, D) one or more polyols and/or polyamines having average molecular weigh ts (Mn) of below 500, and E) optionally one or more monoalcohols and/or monoamines. The present invention also relates to a process for preparing the aqueous polyure- thane dispersions and to the use of the polyurethane dispersions for prepari ng coatings or adhesives.

Description

N-METHYLPROLROLONE-FREE POLYURETHANE DISPERSIONS BASED ON DIMETHYLOLOPROPIONIC ACID DESCRIPTION OF THE INVENTION The invention relates to aqueous polyurethane dispersions which contain as hydrophilizing agent dimethylolpropionic acid and are prepared without the use of N-methylpyrrolidone as well as their use as agents. coating with great resistance properties. In order to reduce the emissions of organic solvents, aqueous coating agents are increasingly used instead of systems containing solvents. An important class of aqueous paint binders are polyurethane dispersions. Polyurethane dispersions have the advantage that they combine important properties such as resistance to chemicals and mechanical load. Therefore, especially in the field of coating surfaces with strong mechanical stress, the use of polyurethane dispersions is advantageous. In dimethylolpropanoic acid (DMPS), a high-melting compound with poor solubility properties is frequently used as a hydrophilizing component in polyurethane dispersions (PUD). However, the acetone used mainly in the preparation of the PUD can not sufficiently dissolve the DMPS, so that the hydrophilizing agent is only insufficiently incorporated into the REF.:171508 polymeric skeleton. The dispersions thus prepared do not show sufficient storage stability. Therefore, DMPS is used in the state of the art in combination with N-methylpyrrolidone (NMP) as solvent for polyurethanes containing DMPS. New studies regarding the toxicology of the NMP show, however, that the NMP is classified as a toxic substance. It was therefore the object of the present invention to prepare polyurethane dispersions free of NMP and solvent containing DMPS as a hydrophilizing agent, which were stable for storage for more than 8 weeks at 40 ° C and, if necessary, provided with assistance of coalescence coadjuvants, transparent, bright coatings with good resistance to dyes. DE-A 4017525 discloses aqueous polyurethane preparations, in which a mixture of isocyanates of diisocyanates having no side alkyl groups and at least one diisocyanate having a side alkyl group is used. In the examples, a mixture of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4'-diisocyanato-dicyclohexylmethane is used for the preparation of the polyurethane. The ionic compound used in that document is N- (2-aminoethyl) -2-aminoethanic acid which is presented as an aqueous solution. This is added only after the preparation of the prepolymer with the dispersion water for the elongation of chains and final hydrophilization. However, a procedure like this with DMPS is not possible. DE-A 10221220 discloses polyurethane preparations containing from 10 to 60% by weight of a polyurethane and which lead to coatings with reduced gloss. The polyurethane is constituted by organic isocyanates that do not have side alkyl groups. If necessary, they can be used together with organic isocyanates having side alkyl groups. The dispersions used for the preparation of the polyurethane preparations are coarse particle and do not have the storage stability required. It has now been found that with the use of a particular mixture of isocyanates, composed of l-isocyanate-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) and 4,4'-diisocyanato-dicyclohexylmethane, which are used in a ratio determined with respect to one another in the synthesis of polyurethane, based on DMPS, products stable to storage with the previously mentioned properties are obtained. The subject of the present invention are aqueous dispersions of polyurethane free of N-methylpyrrolidone and solvent, containing A) a mixture of 25 to 90% by weight of l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) ) and from 10 to 75% by weight of 4,4 '-diisocyanato-dicylohexylmethane, B) one or more polyols with average molecular weights (Mn) from 500 to 3000, C) one or more compounds having at least one OH or NH functional group, containing a carboxyl and / or carboxylate group, in which at least 50 mol%, based on the amount of acid incorporated in the co-filled resin, is composed of dimethylolpropionic acid, as well as D) one or more polyols and / or polyamines with average molecular weights (Mn) below 500 as well as E) if appropriate, one or several onoalcohols and / or monoamines (E). In another embodiment of the present invention, the polyurethane dispersions according to the invention contain polyester (meth) acrylates (F) as well as one or more photoinitiators G). The polyurethane polymer particles of the polyurethane dispersions according to the invention have sizes = 120 nm, preferably = 100 nm and with particular preference = 80 nm. The polyurethane dispersion according to the invention contains from 5 to 60% by weight, preferably from 15 to 57% by weight and particularly preferably from 25 to 55% by weight in component (A), from 0.5 to 65% by weight, preferably from 2 to 55% by weight and particularly preferably from 5 to 50% by weight in component (B), from 0.5 to 15% by weight, preferably from 2 to 14% by weight, and with special preferably from 4 to 12% by weight in component (C), from 0.5 to 18% by weight, preferably from 2 to 12% by weight and particularly preferably from 4 to 10% by weight in component (D) as well as from 0 to 10% by weight, preferably from 0 to 7% by weight, and particularly preferably from 0 to 2% by weight in component (E), where the percentages refer to the weight of the solid particles of resin and add up to 100% by weight. Another polyurethane dispersion according to the invention contains from 5 to 60% by weight, preferably from 15 to 57% by weight and particularly preferably from 25 to 55% by weight in component (A), from 0.5 to 65% by weight, preferably from 2 to 55% by weight and particularly preferably from 5 to 50% by weight in component (B), from 0.5 to 15% by weight, preferably from 2 to 14% by weight and with special preference from 4 to 12% by weight in component (C), from 0.5 to 18% by weight, preferably from 2 to 12% by weight and particularly preferably from 4 to 10% by weight in component (D), from 0 at 10% by weight, preferably from 0 to 7% by weight and particularly preferably from 0 to 2% by weight in component (E), from 0.5 to 15% by weight, preferably from 2 to 12% by weight and particularly preferably from 4 to 10% by weight in component (F) as well as from 0.1 to 10% by weight, preferably from 0.5 to 7% by weight and particularly preferably from 0.8 to 5% by weight in component (G), where the percentage data refer to the weight of the solid particles of resin and add up to 100% by weight. As component (A), mixtures of 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate) and 4,4'-diisocyanatodicyclohexylmethane are used in a ratio of 25 to 90% by weight, preferably 35 to 80% by weight and particularly preferably from 45 to 70% by weight of IPDI at 10 to 75% by weight, preferably 65 to 20% by weight, and particularly preferably 55 to 30% by weight of 4,4'-diisocyanato-dicyclohexylmethane . It is possible to use proportionally up to 5% by weight, based on the polyurethane solid resin, of trifunctional and / or higher isocyanates, to thereby guarantee a certain degree of branching or crosslinking of the polyurethane. Isocyanates of this type are obtained, for example, by reacting difunctional isocyanates with one another, so that part of their isocyanate groups are derivatized to isocyanurate, biuret, allophanate, uretdione or carbodiimide groups. Also suitable are those polyisocyanates hydrophilized by ionic groups. Polyisocyanates of this type can have high functionalities, for example, of more than 3. Suitable polymer polyols (B) in the molecular weight range from 500 to 3000, preferably from 500 to 2500 and particularly preferably from 650 to 2000 are the polyols commonly used for the preparation of polyurethanes. These have an OH functionality of 1, 8 to 5, preferably 1, 9 to 3 and especially preferably 1, 9 to 2, 0. These are, for example, polyesters, polyethers, polycarbonates, polyester carbonates, polyacetals, polyolefins, polyacrylates and polysiloxanes. It is preferred to use polyesters, polyethers, polyestercarbonates and polycarbonates. Bifunctional polyestercarbonates and polycarbonates are especially preferred. Also particularly preferred are mixtures of polyesters and polycarbonates such as polymeric polyols (B). As component (C), at least 50 mole% is used, based on the amount of total acid incorporated in the dimethylolpropionic acid resin. In addition, compounds containing carboxyl groups can be used (Mn <; 300 g / mol) of low molecular weight with at least one to a maximum of 3 OH groups. These include, for example, dimethylolbutyric acid, hydroxypivalic acid, N- (2-aminoethyl) -2-aminoethanecarboxylic acid as well as reaction products of (meth) acrylic acid and polyamines (see, for example, DE-A- 19750186, page 2, lines 52 to 57). It is preferred to use dimethylolpropionic acid as a component (C) as a single hydrophilizing component. Suitable components (D) are polyols, aminopolyols or polyamines with a molecular weight of less than 500, which can be used as chain extenders such as, for example, ethanediol, 1,2- and 1,3-propanediol, 1,2- , 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2 -butylpropanediol, diols containing oxygen from ether with, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols, polypropylene glycols or polybutylene glycols, trimethylolpropane, glycerin as well as hydrazine, ethylenediamine, 1,4-diaminobutane, isophorone diamine, , 4'-diaminodicyclohexyl ethane, diethylenetriamine, triethylenetetramine and N-methyldiethanolamine. Preferred as component (D) are 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,4-cyclohexanediol and trimethylolpropane as well as ethylene diamine, 1,4-diaminobutane, isophorone diamine and diethylenetriamine. In addition to the use of polyfunctional compounds reactive with isocyanates, the termination of the polyurethane prepolymer with monofunctional alcohols or amines (E) is also considered. Suitable compounds (E) are monoalcohols and / or aliphatic monoamines with 1 to 18 carbon atoms, such as, for example, ethanol, 1-propanol, 2-propanol, primary butanol, secondary butanol, n-hexanol and its isomers, 2- alcohol ethylhexyl, ethylene glycol monomethyl ether, dietilenglicolmonsmetiléter, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropilenglícolmonometiléter, dipropilenglicolmonopropiléter, propilenglicolmonobutiléter, dipropilenglicolmonobutiléter, tripropilenglicolmonobutiléter, 1-octanol, 1-dodecanol, 1-hexadecanol, lauryl alcohol and stearyl alcohol and butylamine, propylamine, aminoethanol, aminopropanol , diethanolamine or dibutylamine. It is preferred to use ethanol, n-butanol, ethylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadec-nol, butylamine, propylamine, aminoethanol, dimethylethanolamine, aminopropanol, diethanolamine or dibutylamine. Especially preferred are n-butanol and ethylene glycol monobutyl ether. Binders F) with suitable (meth) acrylate functionality are those which include ester units of acrylic acid and / or methacrylic acid. If components F) are used as a constituent of the polyurethane dispersion according to the invention, these can then be used as a constituent that hardens by radiation in coatings. Suitable as binder F) with acrylate functionality are inert esters against NCO groups of acrylic acid or methacrylic acid, preferably of acrylic acid with mono- or multifunctional alcohols. Examples of suitable alcohols are butanols, pentanols, hexanols, heptanols, octanols, nonanols and isomeric decanes, in addition to cycloaliphatic alcohols such as isoborneol, cyclohexanol and alkylated cyclohexanols, dicyclopentanol, arylaliphatic alcohols such as phenoxyethanol and nonylphenylethanol, and tetrahydrofurfuryl alcohols. . In addition, alkoxylated derivatives of these alcohols can be used. Suitable dihydroxy alcohols are, for example, alcohols such as ethylene glycol, propanediol -1, 2, propanediol -1, 3, diethylene glycol, dipropylene glycol, isomeric butanediols, neopentyl glycol, hexanediol -1, 6, 2-ethylhexanediol and tripropylene glycol or alternatively alkoxylated derivatives of these alcohols. Preferred dihydroxy alcohols are hexanediol -1, 6, dipropylene glycol and tripropylene glycol. Suitable trihydric alcohols are glycerin or trimethylolpropane or their alkoxylated derivatives. They are tetrahydric alcohols pentaerythritol, ditrimethylolpropane or their alkoxylated derivatives. F) binders with inert acrylate functionality are preferred against preferred NCO groups, hexanediol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropanoethoxy triacrylate, dimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate. and ditrimethylolpropane tetraacrylate. Preferably used polyester (meth) acrylates containing hydroxyl groups with an OH content of 30 to 300 mg KOH / g, preferably 60 to 130 mg KOH / g.

In the preparation of the hydroxy-functional polyester (meth) acrylates (F), a total of 7 groups of monomeric constituents can be used: 1. (cyclo) alkanediols (ie, dihydric alcohols with (cyclo) aliphatically bound hydroxyl groups) of molecular weight from 62 to 286, for example, ethanediol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6 hexane-diol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, diols containing oxygen from ether, such as, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol , tripropylene glycol, polyethylene glycols, polypropylene glycols or polybutylene glycols with a molecular weight of 200 to 4000, preferably 300 to 2000, particularly preferably 450 to 1200. Reaction products of the aforementioned diols with e-caprolactone can also be used as diols. other lactones. 2. Trihydric alcohols or higher alcohols of molecular weight range from 92 to 254, such as, for example, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol or polyethers initiated on these alcohols, such as, for example, the reaction product of 1 mol of trimethylolpropane with 4 moles of ethylene oxide. 3 . Monoalcohols such as, for example, ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol or benzyl alcohol. 4. Dicarboxylic acids of the molecular weight range from 10 4 to 600 and / or their anhydrides such as, for example, phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic acid anhydride , cyclohexanedicarboxylic acid,. anhydride of maleic acid, fumaric acid, malonic acid, succinic acid, succinic acid anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, decanedioic acid or hydrogenated dimeric fatty acids. 5. Higher functionality carboxylic acids or their anhydrides such as, for example, trimellitic acid and trimellitic acid anhydride. 6 Monocarboxylic acids such as, for example, benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, natural and synthetic fatty acids. 7 Acrylic acid, methacrylic acid or dimeric acrylic acid. polyester (meth) acrylates containing hydroxyl groups contain the reaction product of at least one constituent of group 1 and / or 2 with a constituent of group 4 and / or 5 and at least one constituent of group 7. It is also possible to react after the esterification of a part of the carboxyl groups, preferably those of (meth) acrylic acid, with mono-, di- or polyepoxides. Preferred epoxides are, for example, the epoxides (glycidyl ether) of bisphenol A, monomeric, oligomeric or polymeric bisphenol F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives. This reaction can be used in particular for increasing the OH number of the polyester (meth) acrylate, since an OH group is generated respectively in the epoxide-acid reaction. The acid number of the resulting product is between 0 and 20 mg of KOH / g, preferably between 0 and 10 mg of KOH / g and particularly preferably between 0 and 5 mg of KOH / g. Alternatively, epoxy (meth) acrylates containing hydroxyl groups, polyether (meth) acrylates containing hydroxyl groups or polyurethane (meth) acrylates containing hydroxyl groups with OH contents of from 20 to 300 mg KOH / g may also be used. as their mixtures with each other and mixtures with unsaturated polyesters containing hydroxyl groups as well as mixtures with polyester (meth) acrylates or mixtures of unsaturated polyesters containing hydroxyl groups with polyeste (meth) acrylates. Epoxy (meth) acrylates containing hydroxyl groups are preferably based on epoxides (glycidyl ether) of bisphenol A, monomeric, oligomeric or polymeric bisphenol F, hexanediol and / or butanediol or of the ethoxylated and / or propoxylated derivatives. Also suitable as component (F) are esters with monohydroxy functionality of acrylic and / or methacrylic acid. Examples of such compounds are the mono- (meth) acrylates of dihydric alcohols, such as ethanediol, oligoethylene glycol with Mn <.; 300 g / mol, the isomeric propanediols, oligopropylene glycol with Mn < 350 g / mol, oligoethylenepropylene glycols with Mn < 370 g / mol and butanediols or (meth) acrylates of polyhydric alcohols such as, for example, trimethylolpropane, glycerin and pentaerythritol, which contain on average a free hydroxyl group. Dispersions containing unsaturated (meth) acrylates are suitable for crosslinking by energy-rich radiation, preferably by UV radiation. Suitable photoinitiators (G) are, for example, aromatic ketone compounds such as benzophenones, alkylbenzophenones, 4,4'-bis- (dimethylamino) -benzophenone. (called Michler's ketone), anthrone and halogenated benzophenones. Also suitable are acylphosphine oxides, for example, 2,4,4-trimethylbenzoyldiphenylphosphine oxide, esters of phenylglyoxylic acid, anthraquinone and its derivatives, benzylcetals and hydroxyalkylphenones. G) photoinitiators are preferred for clear paints benzophenones and acylphosphine oxides for pigmented paints. Mixtures of these compounds can also be used. The present invention also relates to a process for the preparation of the aqueous polyurethane dispersions according to the invention, characterized in that the components (B), (C), (D) and optionally (E) are reacted separately and in discretionary sequence or as a mixture with component (s) (A), the component (C) is neutralized before, during or after the transformation of the prepolymer, which is present dissolved in the solvent preferably in 99 to 65% by weight , with particular preference in 95 to 70% by weight, with very special preference in 90 to 80% by weight, and the prepolymer is dispersed in water. The components are ideally reacted (E) aminofunctional only if the reactivity to isocyanates is moderate and thus the gelation of the reaction mixture is not reached. In this regard, both the component (A) and one or more of the components (B to E) can be arranged. It is preferred to arrange the component (A) and the components (B to E) are dosed and reacted with the component (A). As solvents, volatile components with boiling points below 100 ° C are used, which are subsequently separated by distillation from the dispersion. Suitable solvents are acetone, methyl ethyl ketone, tetrahydrofuran and tert-butyl methyl ether, acetone is preferred.

"Solvent-free" within the meaning of the present application means that the solvent amounts remain = 0.9% by weight, preferably = 0.5% by weight, with particular preference = 0.3% by weight in the dispersion. F) non-reactive components are added to isocyanates preferably after the reaction of components A) to E) to the prepolymer that is generated before or after neutralization of component C), but before dispersion of the prepolymer. Components F) containing OH groups are added together with components B) to E), so that incorporation into the polyurethane backbone is ensured. With the addition of component F), the polymerization inhibitors known to those skilled in the art, such as, for example, 2,6-di-tert-butyl-4-methylphenol, can be added to prevent premature polymerization of the units. unsaturated Suitable neutralizing agents are alkali metal and / or inorganic alkaline compounds. Further preferred are aqueous ammonia solution, ethylamine and dimethylamine, volatile primary, secondary and tertiary amines such as, for example, dimethylethanolamine, morpholine, N-methylmorpholine, piperidine, diethanolamine, triethanolamine, diisopropylamine, 2-amino-2-methylpropanol and -N, N-dimethylamino-2-methylpropanol or mixtures of these compounds. Especially preferred are tertiary amines non-reactive towards isocyanates, such as, for example, triethylamine, diisopropylethylamine and N-methylmorpholine, as well as mixtures of these tere-amines which are preferably added to the prepolymer before dispersion. According to each degree of neutralization the dispersion can be adjusted to very fine particles, so that it has almost the appearance of a solution. It is also possible to vary the solids content of the dispersion obtained after the distillation of the solvent within a wide range of, for example, 20 to 65% by weight. A more preferred solids range ranges from 30 to 50% by weight. A solid content of 33 to 45% by weight is especially preferred. The excess isocyanate groups are subsequently chain lengthened in the aqueous phase by reaction with compounds (D). The quantity of the components (D and / or E) reactive towards isocyanate containing nitrogen, preferably of a polyfunctional component (D) or a polyfunctional component mixture (D), is dimensioned so that 45 to 125% by weight, preferably 50 to 105% by weight, with particular preference of 55 to 125%, can be reacted. to 90% by weight of the isocyanate groups. The isocyanate groups that remain react with chain elongation with the water that is present. If necessary, crosslinking agents can be added before the application of the coating agent containing the polyurethane dispersion according to the invention. Hydrophilic and hydrophobic polyisocyanate crosslinkers are preferably suitable for this purpose. In two-component systems, the dispersions according to the invention are hardened preferably with the hydrophilic and / or hydrophobic paint polyisocyanates known to those skilled in the art. In the use of paint polyisocyanates it may be necessary to dilute these with other amounts of co-solvents, to achieve a good mixture of the polyisocyanates with the dispersion. The polyurethane dispersions according to the invention are preferably used as a binder in coatings and adhesives that are physically hardened and / or UV-irradiated. The coatings based on the polyurethane dispersions according to the invention can be applied on discrete substrates, for example, wood, metal, plastic, paper, leather, textiles, felt, glass or mineral substrates as well as on already coated substrates. A particularly preferred use is the coating of wooden and plastic floors, especially PVC. The polyurethane dispersions according to the invention can be used as such or in combination with the adjuvants and additives known in the technology of paints, such as fillers, pigments, solvents, leveling aids for the preparation of coatings. The application of the coating agent containing the polyurethane dispersion according to the invention can be carried out in a known manner, for example by painting, pouring, scraping, spraying, spraying (Vakumat), projection, rollers or immersion. Drying of the paint film can take place at room temperature or at elevated temperature. If the constituents which harden with UV radiation are present in the dispersions according to the invention, the drying process can also include irradiation with UV light. It is preferred to first separate water and optionally another solvent with known coating processes, then carry out the irradiation with UV light and optionally finally another drying or hardening.

Examples Table 1: Components used Name Designation Commercial manufacturer Desmodur® W 4, 4 '- Diisocyanatodiccycle Bayer MaterialScience hexylmethane, trans-trans content AG, Leverkusen, DE approximately 20% by weight Desmodur® I-Isocyanate-3, 3, 5-trimethyl-5-Bayer MaterialScience isocyanatomethylcyclohexane AG, Leverkusen, DE Desmophen® Polycarbonate (1,6-hexanediol) F * Bayer MaterialScience C 2200 2, molecular weight 2000 g / mol AG, Leverkusen, DE Desmophen® Polycarbonate (1, 6-hexanediol, Bayer MaterialScience C 1200 -caprolactone) F * 2, molecular weight AG, Leverkusen, DE 2000 g / mol Ebercryl® Cytec Surface Tetraacrylate 140 ditrimethylolpropane Specialties, Hamburg, DE Ebercryl® Bisphenol Diacrylate AF * = 2, Cytec Surface weight 140 molecular = 500 g / mol Specialties, Hamburg, DE Comperlan® Cogno fatty acid onoethanolamide, Dusseldorf, DE 100 F * = functionality against isocyanates Precursor of the polyester oligomer In a 5 1 reactor with distillation column are introduced weighing 3200 g of castor oil and 1600 g of soybean oil and 2.4 g of dibutyltin oxide. A stream of nitrogen (5 1 / h) is conducted through the reactants. It is heated in the period of 140 minutes to 240 ° C. After 7 hours at 240 ° C it cools. The OH number is 89 mg KOH / g, the acid number 2.5 mg KOH / g. Example 1 A mixture of 121.6 g of Desmophen® C 2200, 56.1 g of a polycarbonate diol (based on 1,6-hexanediol and 1,4-butanediol (25:75 parts by weight), molecular weight was heated. 1000 g / mol), 29.1 g of dimethylolpropionic acid, 39.0 g of neopentyl glycol, 1.4 g of butyl glycol and 160.6 g of acetone to 55 ° C and stirred. Then 117.9 g of Desmodur® W and 116.6 g of Desmodur® I were added and heated to 68 ° C. It was stirred at this temperature until an NCO content of 3.4% was achieved. It was then cooled to 60 ° C and 22.0 g of triethylamine were added. 550 g of this solution were dispersed with vigorous stirring in 546 g of water which was placed at a temperature of 35 ° C. After the dispersion it was stirred for 5 minutes. A solution of 5.0 g of hydrazine hydrate, 3.0 g of diethylenetriamine and 1.3 g of ethylenediamine in 60.7 g of water was then added over the period of 10 minutes. After the addition was complete, it was stirred for 20 minutes at 40 ° C before the acetone was distilled off under vacuum at this temperature. For the complete reaction of the isocyanate groups, it was stirred at 40 ° C until no more NCO was evidenced by IR spectroscopy. After cooling to < 30 ° C was filtered through a 240 μm fast filter from the company Erich Drehkopf. Characteristic data of the polyurethane dispersion: Average particle size: 29 nm (laser correlation spectroscopy, LCS) pH (humidity 10%, 20 ° C): 8.7 Solid content: 39.0% Weight ratio of IPDI at 4,4 '-diisocyanatodicyclohexylmethane: 50:50 Example 2 277.9 g of Desmophen® C 2200, 27.0 g of dimethylolpropionic acid, 37.9 g of neopentyl glycol, 1.2 g of butyl glycol and 185.3 g of acetone to 55 ° C and stirred. Then 37.5 g of Desmodur® W and 174.5 g of Desmodur® I were added and heated to 70 ° C. It was stirred at this temperature until an NCO content of 2.5% was achieved. It was then cooled to 68 ° C and 20.3 g of triethylamine were added. 600 g of this solution were dispersed with vigorous stirring in 726, 0 g of water, which was placed at a temperature of 35 ° C. After the dispersion it was stirred for 5 minutes. Then a solution of 4.0 g of hydrazine hydrate, 2.4 g of diethylenetriamine and 1.0 g of ethylenediamine in 80.7 g of water was added over the period of 10 minutes. After the addition was complete, it was stirred for 20 minutes at 40 ° C before the acetone was removed by vacuum distillation at this temperature. For the complete reaction of the isocyanate groups, it was stirred at 40 ° C until no more NCO was evidenced by IR spectroscopy. After cooling to <; 30 ° C was filtered through a 240 μm fast filter from the company Erich Drehkopf. Characteristic data of the polyurethane dispersion: Average particle size: 38 nm (laser correlation spectroscopy, LCS) pH (humidity of 10%, 20 ° C): 8.5 Solid content: 37.4% Weight ratio of IPDI at 4, 4 '-diisocyanatodicyclohexylmethane: 82:18 Example 3 152.1 g of Desmodur® W and 348.7 g of Desmodur® I up to 55 ° C and stirred. Then 62.2 g of dimethylolpropionic acid was added. After 5 minutes a solution of 470.4 g of Desmophen® C 1200, 96.3 g of neopentyl glycol, 2.8 g of butyl glycol and 377.5 g of acetone was added over the period of 20 minutes and heated to 68 minutes. C. It was stirred at this temperature until an NCO content of 2.8% was achieved. It was then cooled to 60 ° C and 46.9 g of triethylamine were added. 450 g of this solution were dispersed with vigorous stirring in 545.9 g of water, which was placed at a temperature of 35 ° C. After the dispersion it was stirred for 5 minutes. A solution of 2.0 g of diethylenetriamine, 1.1 g of butylamine and 3.5 g of ethylenediamine in 60.7 g of water was then added over the period of 10 minutes. After the addition was complete, it was stirred for 20 minutes at 40 ° C before the acetone was removed by vacuum distillation at this temperature. For the complete reaction of the isocyanate groups, it was stirred at 40 ° C until no more NCO was evidenced by IR spectroscopy. After cooling to < 30 ° C was filtered through a 240 μm fast filter from the company Erich Drehkopf. Characteristic data of the polyurethane dispersion: Average particle size (LCS): 25 nm pH (humidity of 10%, 20 ° C): 7,9 Solids content: 35.9% Weight ratio of IPDI to 4, 4 '-diisocyanatodicyclohexylmethane: 70:30 Example 4 (dispersion containing acryl groups) 71.7 g of Desmodur® W and 163.9 g of Desmodur® I were heated to 55 ° C and stirred. Then 29.2 g of dimethylolpropionic acid was added. After 5 minutes a solution of 226.0 g of Desmophen® C 1200, 45.2 g of neopentyl glycol, 1.3 g of butyl glycol and 177.3 g of acetone was added over the period of 20 minutes and heated to 68 minutes. C. It was stirred at this temperature until an NCO content of 2.8% was achieved. It was then cooled to 40 ° C and 22.1 g of triethylamine was added and stirred for 5 minutes. Then 26.9 g of Ebecryl® were added and stirred for another 5 minutes. 760 g of this solution were dispersed with vigorous stirring in 924 g of water, which was placed at a temperature of 35 ° C. After the dispersion it was stirred for 5 minutes. A solution of 4.7 g of diethylenetriamine, 1.7 g of n-butylamine and 4.4 g of ethylenediamine in 102.7 g of water was then added over the period of 10 minutes. After the addition was complete, it was stirred for 20 minutes at 40 ° C before the acetone was removed by vacuum distillation at this temperature. For the complete reaction of the isocyanate groups, it was stirred at 40 ° C until no more NCO was evidenced by IR spectroscopy. After cooling to < 30 ° C was filtered through a 240 μm fast filter from the company Erich Drehkopf.

Characteristic data of the polyurethane dispersion: Average particle size (LCS): 30 nm pH (humidity of 10%, 20 ° C): 8.3 Solid content: 36.4% Weight ratio of IPDI to 4, 4 '-diisocyanatodicyclohexylmethane: 70:30 Example 5 (dispersion containing acryl groups) 71.7 g of Desmodur® W and 163.9 g of Desmodur® I were heated to 55 ° C and stirred. Then 29.2 g of dimethylolpropionic acid was added. After 5 minutes a solution of 226.0 g of Desmophen® C 1200, 39.8 g of neopentyl glycol, 1.3 g of butyl glycol, 26.7 g of Ebecryl® 600, 0.6 g of 2.6 was added. -di-tert-butyl-4-methylphenol and 177.3 g of acetone over the period of 20 minutes and warmed to 60 ° C. It was stirred at this temperature until an NCO content of 2.7% was achieved. . It was then cooled to 40 ° C and 22.1 g of triethylamine was added and stirred for 5 minutes. 760 g of this solution were dispersed with vigorous stirring in 924 g of water, which was placed at a temperature of 35 ° C. After the dispersion it was stirred for 5 minutes. A solution of 4.7 g of diethylenetriamine, 1.7 g of n-butylamine and 4.4 g of ethylenediamine in 102.7 g of water was then added over the period of 10 minutes. After the addition was complete, it was stirred for 20 minutes at 40 ° C before the acetone was removed by vacuum distillation at this temperature. For the complete reaction of the isocyanate groups, it was stirred at 40 ° C until no more NCO was evidenced by IR spectroscopy. After cooling to <; 30 ° C was filtered through a 240 μm fast filter from the company Erich Drehkopf. Characteristic data of the polyurethane dispersion: Average particle size (LCS): 42 nm pH (humidity of 10%, 20 ° C): 8.0 Solid content: 35.5% Weight ratio of IPDI to 4, 4 '-diisocyanatodicyclohexylmethane: 70:30 Comparative Example 6 208.6 g of Desmophen® C 1200, 35.1 g of dimethylolpropionic acid, 28.6 g of neopentyl glycol, 2.3 g of Comperlan® 100 and 171 were heated. 9 g of acetone to 55 ° C and stirred. Then 206.1 g of Desmodur® W and 35.1 g of Desmodur® I were added and heated to 68 ° C. It was stirred at this temperature until an NCO content of 3.6% was achieved. It was then cooled to 60 ° C and 22.0 g of ethyldisopropylamine were added. 600 g of this solution were dispersed with vigorous stirring in 793.4 g of water, which was placed at a temperature of 35 ° C. After the dispersion it was stirred for 5 minutes. A solution of 4.4 g of hydrazine hydrate, 3.9 g of diethylenetriamine and 3.7 g of ethylenediamine in 88.2 g of water was then added over the period of 10 minutes. After the addition was complete, it was stirred for 20 minutes at 40 ° C before the acetone was removed by vacuum distillation at this temperature. For the complete reaction of the isocyanate groups, it was stirred at 40 ° C until no more NCO was evidenced by IR spectroscopy. After cooling to < 30 ° C was filtered. by a 240 μm fast filter from the company Erich Drehkopf. The dispersion was not stable and settled after a short time. Solid content: 34.0% Weight ratio of IPDI to 4,4 '-diisocyanatodicyclohexylmethane: 15:85 Comparative example 7 (analogous to the example of DE 4017525) 216.7 g of an adipic acid polyester were heated , 1,6-hexanediol and neopentyl glycol (OH value 56 mg KOH / g), 49.5 g 1,4-butanediol and 150.0 g acetone to 55 ° C and stirred. Then 142.0 g of Desmodur® W and 39.9 g of Desmodur® I were added and stirred for 30 minutes at 55 ° C. Then 0.1 g of dibutyltin dilaurate was added and heated to 70 ° C. It was stirred at this temperature for 1 hour until another 200.0 g of acetone was added. It was then stirred for 2 hours at 63 ° C until an NCO content of 0.7% was achieved. It was then cooled to 50 ° C and 200.0 g of acetone were added.

In addition, 26.4 g of a 40% strength by weight aqueous solution of the N- (2-aminoethyl) -2-aminoethanecarboxylic acid Na salt were then added to the thermally conditioned prepolymer at 50 ° C over the period of 5 minutes and 56.2 g of water. After 15 minutes, 615.0 g of water were added with vigorous stirring in the period of 5 minutes. After the addition was complete, it was stirred for 20 minutes before the acetone was distilled off under vacuum at 40 ° C. The dispersion was not stable and settled after one day of storage at room temperature. Characteristic data of the polyurethane dispersion Average particle size: 756 nm Solid content: 40% Weight ratio of IPDI to 4,4 '-diisocyanatodicyclohexylmethane: 22:78 Comparative example 8 216.7 g of a polyester were heated of adipic acid, 1,6-hexanediol and neopentyl glycol (OH number 56 mg KOH / g), 41.7 g of 1,4-butanediol, 8.8 g of dimethylolpropionic acid and 150.0 g of acetone up to 55 ° C and stirred. Then 142.0 g of Desmodur® W and 39.9 g of Desmodur® I were added and stirred for 30 minutes at 55 ° C. Then 0.1 g of dibutyltin dilaurate was added and heated to 63 to 68 ° C. C. It was stirred at this temperature until an NCO content of 2.2% was achieved. It was then cooled to 50 ° C and 401.2 g of acetone were added. In addition, a solution of 8.7 g of 2-methyl-1,5-pentanediamine and 68.0 g of water was then added to the thermally conditioned prepolymer at 50 ° C over the period of 5 minutes. After 15 minutes, 6.7 g of triethylamine were added and stirred for 10 minutes. Subsequently, 612.0 g of water were added with vigorous stirring in the period of 5 minutes. After the addition was complete, it was stirred for 20 minutes before the acetone was distilled off under vacuum at 40 ° C. For the complete reaction of the isocyanate groups, it was stirred at 40 ° C until no more NCO was evidenced by IR spectroscopy. . The obtained dispersion could not be filtered after cooling down to < 30 ° C by a 1000 μm rapid filter from the company Erich Drehkopf. Characteristic data of the polyurethane dispersion Average particle size: 453 nm (laser correlation spectroscopy, LCS) pH (humidity of 10%, 20 ° C): 9.7 Solids content: 40.6% Weight ratio of IPDI a 4, 4 '-diisocyanatodicyclohexylmethane: 22:78 Coatings resistance tests Felt pieces are soaked with coffee solution according to DIN 68861, red wine (alcohol content: minimum 12% by volume, maximum 13% in volume) or ethanol (48%) and placed for 24 hours on the coating and covered with a cover. After the loading time of 24 hours, the felt piece is removed, the surface is buffered and evaluated. The surfaces loaded with red wine or coffee are then cleaned with a solution (15 ml of cleaning concentrate / 1 1 of water (for example: wash and cleaning concentrate Falterol, from the company Falter Chemie Krefeld)). Flexibility with cold break is determined by storing a coated, flexible substrate for one hour at -18 ° C and immediately after storage by bending it on a table edge at 90 °. The assessment is made according to the following scale: 100% no visible change 75% not broken, only 50% broken cracks, some cracks (broom type) 25% broken, several cracks 0% smooth break With enough shear force is added to the dispersion of Example 4 2.5% by weight (based on the solid binder) of Irgacure® 500 (photoinitiator, company Ciba-Geigy, Lampertheim, DE) and 0.8% by weight (based on the solid binder) of BYK® 346 (company Byk, Wesel, DE) and dispersed approximately for 5 minutes. The applied and dry coating (1 hour at room temperature) is reticulated in the UV radiation tunnel (mercury vapor lamp, 5 m / min). Table 2: Resistance properties of the coating after drying the paint for 24 hours at 20 ° C; thickness of the wet film layer 180 μm.

Notes: 5 corresponds to no change of the film or complete coloration of the substrate It is noted that in relation to this date the best method known by the applicant to bring the invention into practice, is that which is clear from the present description of the invention.

Claims (9)

CLAIMS Having described the invention as above, the content of the following claims is declared as property:

1. Aqueous polyurethane dispersions free of N-methylpyrrolidone and solvent, characterized in that they contain A) a mixture of 25 to 90% by weight of l-isocyanate-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) and 10 to 75% by weight of 4,4 '-diisocyanato-dicylohexylmethane, B) one or more polyols with average molecular weights (Mn) from 500 to 3000, C) one or more compounds having at least one OH or NH functional group, containing a carboxyl and / or carboxylate group, in which at least 50 mol%, based on the amount of acid incorporated in the complete resin, is composed of dimethylolpropionic acid, as well as D) one or more polyols and / or polyamines with average molecular weights (Mn) below 500 as well as E ) optionally one or more monoalcohols and / or monoamines (E).

2. Aqueous polyurethane dispersions free of N-methylpyrrolidone and solvent according to claim 1, characterized in that they contain polyester (meth) acrylates F) as well as one or more photoinitiators G).

3. Aqueous polyurethane dispersions free of N-methylpyrrolidone and solvent according to claim 1, characterized in that the polyurethane polymer particles have a size = 120 nm.

4. Aqueous polyurethane dispersions free of N-methylpyrrolidone and solvent according to claim 1, characterized in that component B) are polyesters, polyethers, polyestercarbonates and polycarbonates.

5. Aqueous polyurethane dispersions free of N-methylpyrrolidone and solvent according to claim 1, characterized in that the component B) are mixtures of polyesters and polycarbonates.

6. Aqueous polyurethane dispersions free of N-methylpyrrolidone and solvent according to claim 1, characterized in that component C) is exclusively dimethylolpropionic acid.

7. Process for the preparation of the aqueous polyurethane dispersion according to claim 1, characterized in that the components (B), (C), (D) as well as the case (E) are reacted separately and in sequence optionally or as a mixture with component (s) (A), the component (C) is neutralized in water before, during or after the transformation of the prepolymer, which is present in 99 to 65% by weight dissolved in the solvent, and dispersed the prepolymer in water.

8. Use of the aqueous polyurethane dispersion according to claim 1 as a binder for the preparation of coatings and adhesives that harden physically and / or with UV radiation.

9. Use of the aqueous polyurethane dispersion according to claim 1 for the coating of wood and plastic floors.