Aqueous polyurethane dispersion which does not contain n-methylpyrrolidone and solvents, preparation method thereof and use

FIELD: chemistry.

SUBSTANCE: disclosed is an aqueous polyurethane dispersion which does not contain N-methylpyrrolidone and solvents and contains a product of reaction of a mixture of 1-isocyanate-3,3,5-trimethyl-5-isocyanatemethylcyclohexane and 4,4'-diisocyanatedicyclohexylmethane, one or more polyols with average molecular weight of 500-3000, one or more compounds with at least one OH- or NH- functional group, which contain a carboxyl and/or carboxylate group, where at least 50 mol % acid incorporated in the overall resin consists of dimethylol propionic acid, one or more polyols and/or polyamines with average molecular weight less than 500 and, if necessary, one or more monoalcohols and/or monoamines, as well as preparation method thereof and use thereof as an agent for coatings having good resistance characteristics.

EFFECT: obtaining a polyurethane dispersion which does not contain N-methylpyrrolidone and solvents, and contains a hydrophilization agent in form of dimethylol propionic acid, which can be stored for over 8 weeks and is suitable for making transparent shining coatings with high resistance to dyes.

8 cl, 2 tbl, 8 ex

The present invention relates to aqueous polyurethane dispersions, primarily waterborne polyurethane dispersions that do not contain N-methylpyrrolidone and solvents, to its preparation and its application.

With the aim of reducing emissions of organic solvents instead of solvent-containing systems are increasingly using tools for water based coatings. An important class of water lacquer binders are polyurethane dispersion. The advantage of polyurethane dispersions is that they combine such important qualities as resistance to chemicals and mechanical loads. In this regard, particularly preferred field of application of polyurethane dispersions is the manufacture of coatings subjected to strong mechanical impact on the surface.

As hydrophilizing component polyurethane dispersions are often used dimethylpropanoyl acid, representing insoluble high-melting compound. However, acetone, mainly used in the preparation of polyurethane dispersions, are not capable of sufficiently dissolving dimethylpropanoyl acid, and therefore it Hydrophilidae means partially embedded in the structure of the polymer chains. Therefore, the corresponding polyurethane var is these do not have sufficient storage stability. Therefore, according to the prior art dimethylpropanoyl acid used in combination with N in organic solvent containing dimethylpropanoyl acid polyurethanes.

However, the results of recent Toxicological studies of N-methyl-pyrrolidone show that it should be considered a toxic compound.

Given the above, the present invention was based on the task to offer you not containing N-methylpyrrolidone and solvent-free polyurethane dispersion, which as hydrophilizing tools contain dimethylolpropionic acid, remain stable for more than 8 weeks of storage at 40°C and under certain conditions form a transparent gloss coating with high resistance to impact dyes only when adding a coalescent AIDS.

In the German patent application DE-A 4017525 reported waterborne polyurethane compositions, in which a mixture of isocyanates, consisting of not containing alkyl side groups of the diisocyanates and diisocyanate containing at least one alkyl side group. In the example in the description of the examples to obtain a polyurethane, a mixture consisting of 1-isocyanato-3,3,5-trimethyl-5-isocyano-emailcollector and 4,4'-diisocyanatohexane. Used to indicated the data of the invention, the ionic compound is N-(2-amino-ethyl)-2-aminoethylamino acid in aqueous solution. It is added together with dispersing water for the final elongation of the polymer chains and hydrophilization only after obtaining the prepolymer. However, such technology is impossible in the case of dimethylolpropionic acid.

In the German patent application DE-A 10221220 described polyurethane compositions which contain from 10 to 60% wt. polyurethane and provide formation of coatings with low Shine. The polyurethane synthesized from organic isocyanates containing no alkyl side groups. Under certain conditions it is possible joint use of organic isocyanates containing alkyl side groups. Dispersion, intended for the production of polyurethane compositions are extremely coarse, and do not possess the necessary stability during storage.

It was found that the use of specific mixtures of isocyanates consisting of being in a certain relation to each other 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (isophoronediisocyanate) and 4,4'-diisocyanatohexane, for the synthesis of polyurethane on the basis of dimethylolpropionic acid allows to obtain stable when stored products, which have the above properties.

The object of the present invention is not containing N-methyl-Pierre is lidón and solvents aqueous polyurethane dispersion, which includes the product of the interaction:

A) a mixture containing from 25 to 90 wt.%. 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (isophoronediisocyanate) and from 10 to 75 wt.%. 4,4'-diisocyanatohexane,

B) one or more polyols with an average molecular mass (M_nfrom 500 to 3000,

C) one or more compounds with at least one IT - or NH-functional group, which contain carboxyl and/or carboxylate group, and at least 50 mol%. entered in the total resin acid consists of dimethylolpropionic acid, and

D) one or more polyols and/or polyamines with an average molecular mass (M_n) less than 500 and

E) optionally one or more monospitovo and/or monoamines.

In one of other embodiments of the present invention offer polyurethane dispersion further comprises a polyester(meth)acrylates (F), and one or more photoinitiators (G).

The size of the polymer particles is proposed in the invention of polyurethane dispersions is ≤120 nm, preferably ≤100 nm and particularly preferably ≤80 nm.

Proposed in the invention polyurethane dispersions contain from 5 to 60 wt.%, preferably from 15 to 57 wt.%. and particularly preferably from 25 to 55% by weight. component (A), from 0.5 to 65 wt.%, before occhialino from 2 to 55% by weight. and particularly preferably from 5 to 50% wt. component (B), from 0.5 to 15 wt.%, preferably from 2 to 14 wt.%. and particularly preferably from 4 to 12 wt.%. component (C), from 0.5 to 18 wt.%, preferably from 2 to 12 wt.%. and particularly preferably from 4 to 10% wt. component (D)and from 0 to 10 wt.%, preferably from 0 to 7 wt.%. and particularly preferably from 0 to 2% wt. component (E), moreover, these percentage data relate to the weight of solid polyurethane and sum up to 100% wt.

In one of other embodiments of the invention, the polyurethane dispersion contains from 5 to 60 wt.%, preferably from 15 to 57 wt.%. and particularly preferably from 25 to 55% by weight. component (A), from 0.5 to 65 wt.%, preferably from 2 to 55% by weight. and particularly preferably from 5 to 50% wt. component (B), from 0.5 to 15 wt.%, preferably from 2 to 14 wt.%. and particularly preferably from 4 to 12 wt.%. component (C), from 0.5 to 18 wt.%, preferably from 2 to 12 wt.%. and particularly preferably from 4 to 10% wt. component (D), from 0 to 10 wt.%, preferably from 0 to 7 wt.%. and particularly preferably from 0 to 2% wt. component (E)from 0.5 to 15 wt.%, preferably from 2 to 12 wt.%. and particularly preferably from 4 to 10% wt. component (F), and from 0.1 to 10 wt.%, preferably from 0.5 to 7 wt.%. and particularly preferably from 0.8 to 5% by weight. component (G), and the interest data concerning the are to the mass of solid polyurethane and sum up to 100 wt.%.

As component (A) use a mixture of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (isophoronediisocyanate) with 4,4'-diiso-cyanocobalaminitamin containing from 25 to 90 wt.%, preferably from 35 to 80 wt.%, particularly preferably from 45 to 70 wt.%. isophorondiisocyanate and from 10 to 75 wt.%, preferably from 65 to 20 wt.%, particularly preferably from 55 to 30% wt. diiso-cyanocobalaminitamin.

You can add up to 5% wt. (in terms of solid polyurethane) tri-functional isocyanates and/or isocyanates of higher functionality, and thus ensuring a certain degree of branching or structuring of polyurethane. Such isocyanates receive, for example, by reacting the bifunctional isocyanates with one another, ensuring the transformation of part of the isocyanate groups which is appropriate, biuret, allophanate, retentionof or carbodiimide groups. Suitable also polyisocyanates with increased functionality, hydro-filipovna through ionic groups. Such polyisocyanates may have high functionality, for example, making up more than three.

Suitable polyols (C) with molecular weight component from 500 to 3000, preferably 500 to 2500, and particularly preferably from 650 to 2000, are usually used for the controlled synthesis of polyurethane polyols. HE is the functionality ranges from 1.8 to 5, preferably from 1.9 to 3 and particularly preferably from 1.9 to 2.0. It is, for example, about complex polyesters, simple polyesters, polycarbonates, complex politicalmath, Polyacetals, polyolefins, polyacrylates and polysiloxanes. Preferred polyols are polyesters, polyethers, complex politicalparty and polycarbonates. Particularly preferred polyols are bifunctional complex politicalparty and polycarbonates. Especially preferred polyols (C) are also mixtures of polyesters with polycarbonates.

As component (C) used dimethylolpropionic acid, which amount is at least 50 mol%. from the total amount introduced into the polyurethane acid. In addition, there may be used low molecular weight compounds with carboxyl groups (M_n<300 g/mol)containing at least one, maximum three hydroxyl groups. Such compounds include, for example, dimethylaniline acid, hydroxypivalic acid, N-(2-amino-ethyl)-2-aminoethylamino acid, and the products of interaction of (meth)acrylic acid with polyamines (see, for example, German patent application DE-A-19750186, page 2, lines 52-57).

As component (C) suppose the equipment used dimethylolpropionic acid only hydrophilizing component.

Suitable components (D) are polyols, AMINOPHENYL or polyamine with molecular weight less than 500, which can be used as an extension of polymer chains, such as, for example, ethanediol, 1,2-propandiol, 1,3-propandiol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, cyclohexane-1,4-dimethanol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2-ethyl-2-buypropecia, diols containing oxygen simple ether, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropyleneglycol, glycols, polypropylenglycol or polietilenglikoli, trimethylolpropane, glycerin, as well as hydrazine, Ethylenediamine, 1,4-diaminobutane, ISOPHORONEDIAMINE, 4,4'-diaminodicyclohexylmethane, Diethylenetriamine, Triethylenetetramine and N-methyldiethanolamine. Preferred components (D) are 1,4-butanediol, 1,6-hexanediol, neopentylglycol, cyclohexane-1,4-dimethanol, 1,4-tikaexception and trimethylolpropane, as well as Ethylenediamine, 1,4-diaminobutane, ISOPHORONEDIAMINE and Diethylenetriamine.

Along with the use of polyfunctional compounds reactive toward isocyanates, it is also envisaged the formation of end groups of the polyurethane prepolymer through the use of monofunctional alcohols or amines (E) Suitable compounds (E) are aliphatic monosperma and/or monoamines with 1-18 carbon atoms, such as, for example, ethanol, 1-propanol, 2-propanol, primary butanol, secondary butanol, n-hexanol and its isomers, 2-ethylhexyloxy alcohol, onomatology ether of ethylene glycol, onomatology ether of diethylene glycol, monobutyl ether of ethylene glycol, monobutyl ether of diethylene glycol, onomatology ether of propylene glycol, onomatology broadcast dipropyleneglycol, onomatology ether three-propylene glycol, monopropylene broadcast dipropyleneglycol, monobutyl ether of propylene glycol, monobutyl broadcast dipropyleneglycol, monobutyl broadcast tripropyleneglycol, 1-octanol, 1-dodecanol, 1-hexadecanol, lauric alcohol and stearyl alcohol, as well as butylamine, Propylamine, aminoethanol, aminopropanol, diethanolamine or dibutil-Amin. As component (E) preferably using ethanol, n-butanol, monobutyl ether of ethylene glycol, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol, butylamine, Propylamine, aminoethanol, dimethylethanolamine, aminopropanol, diethanolamine or di-butylamine. Especially preferred are n-butanol and monobutyl ether of ethylene glycol.

Suitable binders (F) with (meth)acrylate functional groups contain monomer units of acrylic esters and/or methacrylic acid, If proposed in the invention, the polyurethane dispersion as an integral part contains com is ananti (F), further, they can be used as the curing under the action of radiation integral part of the coating.

For use as a binder (F) acrylate functional groups suitable inert to NCO-groups of the esters of acrylic or methacrylic acid (compound polyester-(meth)acrylates), preferably the esters formed acrylic acid and monosperma or polyhydric alcohols. As alcohols are suitable, for example, isomers of butanol, pentanol, hasanali, heptanol, octanol, nonanol and decanol, in addition, cycloaliphatic alcohols, such as isoborneol, cyclohexanol and apriliawan cyclohexanol, dicyclopentane, arylaliphatic alcohols such as Phenoxyethanol and nonylphenylether and tetrahydrofurfuryl alcohols. In addition, can be used alkoxysilane derivatives of these alcohols. Suitable diatomic alcohols are, for example, alcohols such as ethylene glycol, propandiol-1,2, propandiol-1,3, dietilen glycol, dipropyleneglycol, isomers of butanediol, neopentylglycol, hexanediol-1,6, 2-ethylhexanediol and tripropyleneglycol and alkoxysilane derivatives of these alcohols. Preferred diatomic alcohols are hexanediol-1,6, dipropyleneglycol and dipropyleneglycol. Suitable trivalent alcohols aplaydevices, trimethylolpropane or alkoxysilane derivatives. Chetyrekhtomnym alcohols are pentaerythritol, ditrimethylol or paxilonline derivatives.

The preferred binder (F) acrylate functional groups inert to NCO-groups are hexaniacinate, Tetraethylenepentamine, dipropylenetriamine, tripropyleneglycol, trimethylolpropane, trimethylolpropantriacrylated, dimethylpropanediamine, pentaerythritoltetranitrate, dipentaerythritol and diameteroperating.

As component (F) preferably use complex hydroxycobalamin polyester(meth)acrylates with a content of hydroxyl groups from 30 to 300 mg KOH/g, preferably from 60 to 130 mg KOH/g

To obtain a challenging hydroxyl-containing polyester(meth)acrylates (F) can be used monomer components selected from the following seven groups.

1. (Cyclo)arcangioli (i.e. diatomic alcohols with United through (cyclo)aliphatic bridge hydroxyl groups), with molecular weights from 62 to 286, such as, for example, ethanediol, 1,2-propandiol, 1,3-propandiol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, cyclohexane-1,4-dimethanol, 1,2-cyclohex ndia, 1,4-cyclohexanediol, 2-ethyl-2-buypropecia, diols containing oxygen simple ester, such as, for example, diethylene glycol, tri-ethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropyleneglycol, polyethylene glycol, polypropyleneglycol or poliatilenglikol with a molecular mass of from 200 to 4000, preferably from 300 to 2000, particularly preferably from 450 to 1200. Suitable for use as diols can also be products of the interaction of the above mentioned diols with ε-caprolactone or other lactones.

2. Trivalent or higher alcohols with a molecular weight of 92 to 254, such as, for example, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol, or polyethers on the basis of these alcohols, such as, for example, the product of the interaction of one mole of trimethylolpropane with four moles of ethylene oxide.

3. Monosperma, such as, for example, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol or benzyl alcohol.

4. Dibasic carboxylic acid with a molecular weight of from 104 to 600, and/or their anhydrides, such as phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophtalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanecarbonyl acid, malinowy the anhydride, fumaric acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, Emelyanova acid, cork acid, sabotinova acid, dodekanision acid or hydrogenated dimer fatty acid.

5. Carboxylic acids of higher functionality, respectively, their anhydrides, such as, for example, trimellitate acid and trimellitic anhydride.

6. Monocarboxylic acids, such as, for example, benzoic acid, cyclohexanecarbonyl acid, 2-ethylhexanoate acid, hexanoic acid, Caprylic acid, capric acid, lauric acid, natural and synthetic fatty acids.

7. Acrylic acid, methacrylic acid, respectively dimeric acrylic acid.

Complex hydroxycobalamin polyester(meth)acrylates contain the product of the interaction of at least one component from group 1 and/or 2 with at least one component from group 4 and/or 5 and at least one component from group 7.

In addition, after the esterification part of carboxyl groups, preferably carboxyl groups, (meth)acrylic acid can be carried out interaction with mono-, di - or polyepoxide. Preferred are, for. example, epoxides (simple glycidyloxy esters) of Monomeric, oligomeric or polymer the th biphenol, bisphenol-F, hexanediol and/or butanediol or their ethoxylated and/or propoxycarbonyl derivatives. This interaction can be used primarily to improve the content of hydroxyl groups in a complex polyester(meth)acrylate, since the reaction between the epoxide and acid proceeds with the formation of the corresponding hydroxyl group. Acid number of the resulting product is in the range from 0 to 20 mg KOH/g, preferably from 0 to 10 mg KOH/g and particularly preferably from 0 to 5 mg KOH/g

In another embodiment, can also be used in themselves known, hydroxycobalamin epoxy(meth)acrylates, hydroxycobalamin simple polyester(meth)acrylates or hydroxycobalamin polyurethane(meth)acrylates with a content of hydroxyl groups from 20 to 300 mg KOH/g, and mixtures thereof with each other, with hydroxyl-containing unsaturated complex polyesters and complex polyester(meth)acrylates, or mixtures of hydroxyl-containing unsaturated polyesters with a complex of the polyester(meth)acrylates. Hydroxycobalamin epoxy(meth)acrylates preferably based on epoxides (simple glycidyloxy esters) of Monomeric, oligomeric or polymeric biphenol-A, bisphenol-F, hexanediol and/or butanediol, respectively, their ethoxylated and/or propoxycarbonyl derivatives.

As the component (F) is also suitable esters of acrylic and/or methacrylic acid, containing one hydroxyl functional group. Examples of such compounds are mono(meth)acrylates of diatomic alcohols, such as, for example, ethanediol, oligoethyleneglycols with a molecular mass (M_n) less than 300 g/mol, isomers of propane diol, algorithmical with M_nless than 350 g/mol, oligotetramethyleneglycol with M_nless than 370 g/mol and butandiol, or (meth)acrylates of polyols, such as, for example, trimethylolpropane, glycerol and pentaerythritol, which in the middle of the molecules contain a hydroxyl group. A dispersion containing unsaturated (meth)acrylates suitable for crosslinking under the action of high-energy radiation, preferably UV radiation.

As photoinitiator (G) is suitable, for example, aromatic ketones such as benzophenone, alkylbenzene, 4,4'-bis(dimethyl-amino)benzophenone (so-called michler ketone), Andron and halogenated benzophenone. Also suitable are allfashion-oxides, for example 2,4,6-trimethylbenzaldehyde-phosphine oxide, esters phenylglyoxylic acid, anthraquinone and its derivatives, benzylacetone and hydroxyacetone. The preferred photoinitiator (G) for transparent varnishes are benzophenone, and for pigmented varnishes acylphosphatase. Can also be used mixtures of these compounds.

the moreover, an additional object of the present invention is a method of obtaining the proposed aqueous polyurethane dispersion, which is that components (B), (C), (D), a solvent, and optionally component (E), separately and in random order or in a mixture subjected to interaction with the component (components) (A), neutralize the component (C) before, during or after the conversion of the prepolymer, which is in the form of a solution in the solvent concentration is preferably from 99 to 65 wt.%, particularly preferably from 95 to 70 wt.%, even more preferably from 90 to 80 wt.%, the prepolymer is dispersed in water and the solvent is distilled off. In the ideal case containing the amino groups of component (E) is added only if they have moderate reactivity toward isocyanates and, therefore, their addition will not result in the structuring of the composition. You can enter as component (a)and one or more components (b-E). Preferably introduced component (A), and to it add and mix with it the components (b-E).

As solvents used volatile compounds with boiling point below 100°C, which are further removed from the dispersion by distillation. Suitable solvents are acetone, methyl ethylketone, tetrahedr the furan and tert-butyl methyl ether, preferably use acetone.

In accordance with the present invention, the term "solvent-free dispersion" means that the amount remaining in the dispersion solvent is ≤0,9% wt., preferably ≤0,5% wt., particularly preferably ≤0,3% wt.

Inert towards isocyanate component (F) is added to the prepolymer resulting from the interaction of the components (a-E), preferably before or after the neutralization component (S), but the pepper dispersion of the prepolymer.

Containing the hydroxyl group of component (F) is added together with the components (b-E)to ensure their incorporation into the polyurethane chain. Simultaneously with the dispensing of the component (F) in order to avoid premature polymerization of the unsaturated monomer unit if necessary add well-known specialists polymerization inhibitors, such as, for example, 2,6-decret-butyl-4-METHYLPHENOL.

Suitable means for neutralization are organic alkaline and/or alkaline inorganic compounds. Along with an aqueous solution of ammonia, ethylamine and dimethylamine are preferred volatile primary, secondary and tertiary amines, such as, for example, dimethylethanolamine, morpholine, N-methylmorpholine, piperidine, diethanolamine, triethanolamine, Diisopropylamine, 2-amino-methylpropanol and 2-N,N-dimethylamino-2-methylpropanol or mixtures of these compounds. Especially preferred are inert towards isocyanates tertiary amines, such as, for example, triethylamine, diisopropylethylamine and N-methylmorpholine, as well as mixtures of these tertiary amines, which are added to the prepolymer preferably before dispersing.

Depending on the degree of neutralization can be obtained dispersion with such a high dispersion that outwardly, it looks almost like the solution. In addition, the solid content obtained after removal of the solvent dispersion can be varied within wide limits, for example, in the range from 20 to 65% by weight. The preferred spacing of the solids content is from 30 to 50% wt. Particularly preferred interval of contents solids ranges from 33 to 45% wt.

Excess isocyanate groups then react in the aqueous phase with the compounds (D), which provides the elongation of the polymer chains.

The number of reactive towards isocyanates nitrogen-containing components (D and/or E), preferably the amount of the polyfunctional component (D) or a mixture of polyfunctional component (D), calculated so that might react from 45 to 125% wt., preferably from 50 to 105% wt., particularly preferably from 55 to 90 wt.%. isocyanate groups. The unreacted ISOC analnye groups interact with the existing moisture which leads to the elongation of the polymer chains.

Before applying the coating composition containing the proposed in the invention polyurethane dispersion, if necessary, you can add a structuring agent. For this purpose, preferably suitable hydrophilic and hydrophobic polyisocyanate structuring agents. If we are talking about both supplied in two packages of systems, the curing is proposed in the invention of polyurethane dispersions is preferably carried out by means known in the art hydrophilic and/or hydrophobic lacquer polyisocyanates. When applying lacquer polyisocyanates may be necessary dilution with additional co-solvents in order to ensure good mixing polyisocyanates with dispersion.

Proposed in the invention polyurethane dispersions are used preferably as a binder for coatings and adhesives, curable physically and/or under the action of UV radiation. Coatings on the basis proposed in the invention polyurethane dispersions can be applied to any substrates, such as wood, metal, polymer, paper, leather, textiles, fur, glass or mineral substrate, and the substrate has been inflicted on them by the floor. A particularly preferred field of application of the invention in polyurethane the dispersions is the coating on the flooring of wood or polymers, primarily from polyvinyl chloride.

Proposed in the invention, the polyurethane dispersion may be applied to the coating as such or in combination with known from the technology of lacquer auxiliary substances or additives, such as fillers, pigments, solvents and means to improve the wetting of the surface.

The application of a coating medium containing proposed in the invention, the polyurethane dispersion can be carried out with known methods, for example by spreading, pouring, using a doctor blade, by spraying, irrigation (in vacuum), centrifugation, rolling method or dipping. The drying of the varnish film can be performed at room or elevated temperatures. If the composition of the proposed invention the polyurethane dispersions include UV-curable components, the drying process can additionally include exposure to UV light. Preferably the first coating known methods remove the water and, if necessary, another solvent, followed by exposure of the coating to UV light and possible additional final drying or curing.

Examples

Complex oligoether as the original product

In equipped with a reflux condenser reactor with a volume of 5 l was downloaded 3200 g of castor oil and 1600 g of soybean oil, and 2.4 g of oxide dibutylamine. Through the reaction mixture at a speed of 5 l/h was passed gaseous nitrogen. The reactor within 140 min was heated to a temperature of 240°C. After 7 h of heating at 240°C and the mixture was cooled. The content of hydroxyl groups was 89 mg KOH/g, an acid number of 2.5 mg KOH/g

Example 1

A mixture consisting of to 121.6 g of Desmophen^®With 2200, 56,1 g polycarbonatediol (based on 1,6-hexandiol and 1.4 g of butanediol, 25:75 parts by weight, molecular weight 1000 g/mol), 29,1 g dimethylolpropionic acid, 39,0 g neopentyl glycol, 1,4 g butylglycol and 160,6 g of acetone was heated to a temperature of 55°C and stirred. Then added to 117.9 g of Desmodur^®W and 116,6 g Desmodur^®I, and the mixture was heated to a temperature of 68°C. was Continued stirring at this temperature until the content of the PSO-groups was reduced to 3.4%. After that, the mixture was cooled to a temperature of 60°C and added to 22.0 g of triethylamine. 550 g of the resulting solution with vigorous stirring was dispersible in 546 g of water, and eUSA temperature of 35°C. After the dispersion was kept stirring for another 5 minutes and Then for 10 min was added a solution of 5.0 g of hydrazine hydrate, 3.0 g of Diethylenetriamine and 1.3 g of ethylene diamine in a total of 60.7 g of water. Upon completion of the addition the mixture was stirred for 20 min at 40°C, prior to the distillation of the acetone under vacuum at the same temperature. For complete conversion of isocyanate groups, the stirring was continued at 40°C up until according to the IR spectroscopy did not show complete absence of NCO-groups. After cooling to a temperature below 30°C. the dispersion was passed through a fast filter company Erich Drehkopf hole size 240 microns.

Features polyurethane dispersion

Note the R 2

277,9 g Desmophen^®With 2200, 27,0 g dimethylolpropionic acid, of 37.9 g Neopan-tipicos, 1.2 g of butylglycol and 185,3 g of acetone was heated to a temperature of 55°C and stirred. Then added to 37.5 g of Desmodur^®W and of 174.5 g of Desmodur^®I, and the mixture was heated to a temperature of 70°C. was Continued stirring at this temperature until the content of NCO-groups is not reduced to 2.5%. After that, the mixture was cooled to a temperature of 68°C was added a 20.3 g of triethylamine. 600 g of the resulting solution with vigorous stirring was dispersible in 726,0 g of water having a temperature of 35°C. After the dispersion was kept stirring for another 5 minutes and Then for 10 min, the solution was added 4.0 g of hydrazine hydrate, 2.4 g of Diethylenetriamine and 1.0 g of Ethylenediamine in 80,7 g of water. Upon completion of the addition the mixture was stirred for 20 min at 40°C, prior to the distillation of the acetone under vacuum at the same temperature. For complete conversion of isocyanate groups, the stirring was continued at 40°C up until according to the IR spectroscopy did not show complete absence of NCO-groups. After cooling to a temperature below 30°C. the dispersion was passed through a fast filter company Erich Drehkopf hole size 240 microns.

Features polyurethane dispersion

Example 3

152,1 g Desmodur^®W and Russia for USD 348.7 g Desmodur^®I was heated to a temperature of 55°C and stirred. Then added to 62.2 g dimethylolpropionic acid. After 5 min for 20 min was added to the solution 470,4 g Desmophen^®With 1200, the 96.3 g of neopentyl glycol, 2.8 g of butylglycol and 377,5 g of acetone, and the mixture was heated to 68°C. was Stirred at this temperature until the content of NCO-groups is not reduced to 2.8%. After that, the mixture was cooled to a temperature of 60°C and added 46,9 g of triethylamine. 450 g of the resulting solution with vigorous stirring was dispersible in 545,9 g of water having a temperature of 35°C. After the dispersion was kept stirring for another 5 minutes and Then for 10 min, the solution was added 2.0 g of Diethylenetriamine, 1.1 g of n-butylamine and 3.5 g of ethylene diamine in a total of 60.7 g of water. Upon completion of the addition the mixture was stirred for 20 min at 40°C,prior to the distillation of the acetone under vacuum at the same temperature. For complete conversion of isocyanate groups, the stirring was continued at 40°C up until according to the IR spectroscopy did not show complete absence of NCO-groups. After cooling to a temperature below 30°C. the dispersion was passed through a fast filter company Erich Drehkopf hole size 240 microns.

Features polyurethane dispersion

Example 4 (containing acrylic groups variance)

71,7 g Desmodur^®W and 163,9 g Desmodur^®I was heated to a temperature of 55°C and stirred. Then added 29,2 g dimethylolpropionic acid. After 5 min for 20 min was added to the solution 226,0 g Desmophen^®With 1200, of 45.2 g of neopentyl glycol, 1,3 g butylglycol and 177,3 g of acetone, and a mixture of n is gravely to 68°C. Was stirred at this temperature until the content of NCO-groups is not reduced to 2.8%. After that, the mixture was cooled to a temperature of 40°C, was added 22.1 g of triethylamine and stirred for 5 minutes Then added to 26.9 g Ebercryl^®140 and continued stirring for another 5 minutes 760 g of the resulting solution with vigorous stirring was dispersible in 924 g of water having a temperature of 35°C. After the dispersion was kept stirring for another 5 minutes and Then for 10 min was added 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. Upon completion of the addition the mixture was stirred for 20 min at 40°C, prior to the distillation of the acetone under vacuum at the same temperature. For complete conversion of isocyanate groups, the stirring was continued at 40°C up until according to the IR spectroscopy did not show complete absence of NCO-groups. After cooling to a temperature below 30°C. the reaction dispersion was passed through a fast filter company Erich Drehkopf hole size 240 microns.

Features polyurethane dispersion

Example 5 (containing acrylic groups variance)

71,7 g Desmodur^®W and 163,9 g Desmodur^®I was heated to a temperature of 55°C and stirred. Then added 29,2 dimethylolpropionic acid. After 5 min for 20 min was added to the solution 226,0 g Desmophen^®C 1200, 39,8 g of neopentyl glycol, 1,3 g butylglycol, 26.7 g Ebercryl^®600, 0.6 g of 2,6-decret-butyl-4-METHYLPHENOL and 177,3 g of acetone, and the mixture was heated to 60°C. was Stirred at this temperature until the content of NCO-groups is not reduced to 2.7%. After that, the mixture was cooled to a temperature of 40°C, was added 22.1 g of triethylamine and stirred for 5 minutes 760 g of the resulting solution with vigorous stirring was dispersible in 924 g of water having a temperature of 35°C. After the dispersion was kept stirring for another 5 minutes and Then for 10 min was added 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. Upon completion of the addition the mixture was stirred for 20 min at 40°C, before producing the distillation of acetone under what Aquum at the same temperature. For complete conversion of isocyanate groups, the stirring was continued at 40°C up until according to the IR spectroscopy did not show complete absence of NCO-groups. After cooling to a temperature below 30°C. the reaction dispersion was passed through a fast filter company Erich Drehkopf hole size 240 microns.

Features polyurethane dispersion

Comparative example 6

208,6 g Desmophen^®C 1200, 35,1 g dimethylolpropionic acid, 28.6 g of neopentyl glycol, 2,3 g Comperlan^®100 and 171,9 g of acetone was heated to a temperature of 55°C and stirred. Then added 206,1 g Desmodur^®W and 35.1 g of Desmodur^®I, and the mixture was heated to a temperature of 68°C. was Continued stirring PR is the temperature, until the content of NCO-groups is not reduced to 3.6%. After that, the mixture was cooled to a temperature of 60°C and added to 22.0 g of ethyldiethanolamine. 600 g of the resulting solution with vigorous stirring was dispersible in 793,4 g of water having a temperature of 35°C. After the dispersion was kept stirring for another 5 minutes and Then for 10 min was added a solution of 4.4 g of hydrazine hydrate, 3,9 g Diethylenetriamine and 3.7 g of Ethylenediamine in 88,2 g of water. Upon completion of the addition the mixture was stirred for 20 min at 40°C, prior to the distillation of the acetone under vacuum at the same temperature. For complete conversion of isocyanate groups, the stirring was continued at 40°C up until according to the IR spectroscopy did not show complete absence of NCO-groups. After cooling to a temperature below 30°C. the dispersion was passed through a fast filter company Erich Drehkopf hole size of 240 μm. The dispersion was unstable and after some time was sedimentable.

Comparative examples the 7 (a similar example from German patent DE 4017525)

216,7 g complex polyester obtained from adipic acid, 1,6-hexanediol and neopentyl glycol (the content of hydroxyl groups of 56 mg KOH/g), 49.5 g of 1,4-butanediol and 150,0 g of acetone was heated to a temperature of 55°C and stirred. Then added 142,0 g Desmodur^®W and 39.9 g of Desmodur^®I, and the mixture was stirred for 30 min at 55°C. Then was added 0.1 g of dilaurate dibutylamine, and the mixture was heated to a temperature of 70°C. was Continued stirring at this temperature for 1 h, then was added to 200.0 g of acetone. Then the mixture for 2 h and was stirred at 63°C until the content of NCO-groups is not reduced to 0.7%. After that, the mixture was cooled to 50°C and added to 200.0 g of acetone. Then thermostated at 50°C. the prepolymer for 5 min was added to 26.4 g of an aqueous solution of sodium salt of N-(2-amino-ethyl)-2-aminoethanethiol acid concentration of 40 wt.%. and of 56.2 g of water. After 15 min with vigorous stirring for 5 min was added 615,0 g of water. After adding water, the mixture was stirred for 20 min before to produce a distillation of the acetone under vacuum at 40°C. the Dispersion was unstable and was sedimentable after storage for one day.

Features polyurethane dispersion

Comparative example 8

216,7 g complex polyester obtained from adipic acid, 1,6-hexanediol and neopentyl glycol (the content of hydroxyl groups of 56 mg KOH/g), and 41.7 g of 1,4-butanediol, 8.8 g dimethylolpropionic acid and of 150.0 g of acetone was heated to a temperature of 55°C and stirred. Then added 142,0 g Desmodur^®W and 39.9 g of Desmodur^®I, and the mixture was stirred for 30 min at 55°C. Then was added 0.1 g of dilaurate dibutylamine, and the mixture was heated to a temperature 63-68°C. was Continued stirring at this temperature until the content of NCO-groups is not reduced to 2.2%. After that, the mixture was cooled to 50°C and added 401,2 g of acetone. Then thermostated at 50°C. the prepolymer for 5 min was added a solution of 8.7 g of 2-methyl-1,5-pentanediamine and to 68.0 g of water. After 15 minutes under stirring was added 6.7 g of triethylamine. Then with vigorous stirring for 5 min was added 612,0 g of water. After adding water, the mixture was stirred for 20 min before to produce a distillation of the acetone under vacuum at 40°C. For complete conversion of isocyanate groups p is remesiana continued at 40°C until while according to the IR spectroscopy did not show complete absence of NCO-groups. Cooled to a temperature below 30°C. the dispersion was passed through a fast filter company Erich Drehkopf hole size 1000 microns.

Features polyurethane dispersion

Test resistance of coatings

Pieces of felt impregnated with coffee solution in accordance with DIN 68861, red wine (the minimum alcohol content of 12% vol., the maximum content of 13% by vol.) or ethanol (concentration 48%), 24 h laid on the floor and cover. After a 24-hour load impacts are removing a piece of felt, get wet the surface with cotton wool and assess her condition.

Then on top of the spine, exposed to red wine or coffee, purified by solution of 15 ml of concentrated cleaner (for example, concentrate detergent and cleaning products Falterol company FalterChemie Krefeld) in one liter of water.

Low-temperature elasticity of the flexible substrate coated with destruction determined after exposure for one hour at a temperature of -18°C and carried out immediately after the bending of the sample at the edge of the table at a right angle. Assessment is made in accordance with the following scale:

The dispersion from example 4 with sufficient shear mixed with 2.5% wt. (calculated on the solid binder) photoinitiator Irgacure^®500 (firm Ciba-Geigy, Lampertheim, Germany) and 0.8% wt. (calculated on the solid binder) product BYK^®346, Byk, Wesel, GE is mania) and subjected to further dispersion. Applied and dried for 1 h at room temperature the coating is subjected to structuring in the UV tunnel (mercury lamp, the moving speed of the sample 5 m/min).

1. Aqueous polyurethane dispersion containing no N-methylpyrrolidone and solvents, including product interaction
A) a mixture containing from 25 to 90 wt.% 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (isophoronediisocyanate) and from 10 to 75 wt.% 4,4'-diisocyanatohexane,
B) one or more polyols with an average molecular mass (M_nfrom 500 to 3000,
C) one or more compounds with at least one IT - or NH-functional group, which contain carboxyl and/or carboxylate group, and at least 50 mol.% entered in the total resin acid consists of dimethylolpropionic acid, and
D) one or more polyols and/or polyamines with an average molecular mass (M_n) less than 500 and
E) optionally one or more monospitovo and/or monoamines.

2. Water that does not contain N-methylpyrrolidone and solvent-free polyurethane dispersion according to claim 1, characterized in that it further comprises a complex of the polyester(meth)acrylates (F), and one or more photoinitiators (G).

3. Water that does not contain N-methylpyrrolidone and solvent-free polyurethane dispersion according to claim 1, characterized in that the polyurethane particles have a size of ≤120 nm.

4. Water, not containing the th N-methylpyrrolidone and solvent-free polyurethane dispersion according to claim 1, characterized in that component (B) are polyesters, polyethers, politicalparty and polycarbonates.

5. Water that does not contain N-methylpyrrolidone and solvent-free polyurethane dispersion according to claim 1, characterized in that component (C) is a mixture consisting of polyesters and polycarbonates.

6. Water that does not contain N-methylpyrrolidone and solvent-free polyurethane dispersion according to claim 1, characterized in that component (C) is solely dimethylolpropionic acid.

7. The method of obtaining the aqueous polyurethane dispersion according to claim 1, characterized in that components (B), (C), (D), a solvent, and optionally component (E), separately and in random order or in a mixture subjected to interaction with the component (components) (A), neutralize the component (C) before, during or after the conversion of the prepolymer, which is in the form of a solution in a solvent concentration of from 99 to 65 wt.%, and the prepolymer is dispersed in water and produce a distillation of solvent.

8. The use of aqueous polyurethane dispersion according to claim 1 as a binder for the manufacture of physically and/or UV-curable coatings and adhesives or as a means for coating of flooring from wood and polymers.