EP2089445A1 - Radiation-curable compounds - Google Patents

Abstract

The invention relates to radiation-curable compounds, to processes for their preparation, to their use and to coating materials with high scratch resistance which comprise them.

Description

 Radiation-curable compounds

description

The invention relates to radiation-curable compounds, processes for their preparation, their use and coating compositions containing them with high scratch resistance.

WO 00/39183 describes allophanate-containing polyisocyanates which carry free-radically polymerizable, activated C =C double bonds.

A disadvantage of these polyisocyanates is that they require a binder for curing in paints, which must contain isocyanate-reactive groups. Such additional components must be added in a precise stoichiometry, which can give rise to insufficient curing in misdosing.

EP-A1 544 465 describes radiation-curable, alkoxysilylated acrylates. Therein, acrylate groups are connected via spacers with alkoxysilyl groups. A disadvantage is the low structural variability of such compounds.

US 5,939,491 and US 6,187,863 describe thermally curable coating compositions with specific polysiloxanes.

These lack a mechanism for radiation curing.

US 6,635,341 and US 6,657,001 describe the same polysiloxanes in radiation and dual-cure coating compositions. For this purpose, half esters of polyols are silylated with 1,2-dianhydrides, which may contain polyisocyanates as optional synthesis components. Explicit examples are not disclosed. US Pat. No. 6,657,001 moreover describes 2K systems of polyacrylate polyol, melamine-formaldehyde resin and isocyanate, and also polysiloxanes. A disadvantage of such coating compositions is that they are two-component systems which are easily incorrectly metered. Furthermore, the polyisocyanates used have a relatively high viscosity.

US 5312943 and US 5523443 describe one-component alkoxysilyl acrylates. Initially, a urea derivative of isocyanate and a secondary amine carrying at least one trialkoxy group is formed. Such urea derivatives are generally poorly soluble. Another option is based on silyl group-bearing isocyanates. Such isocyanates are, however, not commercially available in technical quantities. US 5523443 additionally discloses the reaction with specific alcohols containing both a carbamate and an alkoxysilyl group. It is also a very special reaction component. WO 2006/058680 discloses organosilyl group-bearing urethane acrylates. For their construction, allophanate-containing polyisocyanates are listed only within extensive lists. Merely as a binder which does not carry any organic silyl groups, allophanate-containing polyisocyanates are listed as being preferred.

A disadvantage of all the above publications is that the only way to reduce the viscosity of coating compositions is the dilution with organic solvents. However, this should be avoided wherever possible to ensure the lowest possible content of volatile organic compounds (VOCs).

The object of the present invention was to provide stable water-dispersible radiation-curable compound which are curable by radiation and at least one other curing mechanism. These should be one-component coating compositions in order to rule out the possibility of incorrect metering in the case of two-component systems if optimum stoichiometry is not adhered to, which results in coatings with high hardness and scratch resistance and which can be produced from simple paint components.

The object was achieved by water-dispersible polyurethanes containing as structural components

(a) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate,

(b) at least one compound (b) having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,

(c) optionally at least one compound having exactly two isocyanate-reactive groups,

(d) optionally at least one compound having at least three isocyanate-reactive groups,

(e) optionally, at least one compound having exactly one isocyanate-reactive group, (f) at least one compound having at least one organosilicon group and at least one isocyanate-reactive group, and (g) at least one compound containing at least one isocyanate having reactive group and at least one dispersive group. The reaction mixtures obtained in the preparation of the polyurethanes of the invention generally have a number average molecular weight M _n of less than 10,000 g / mol, preferably less than 5000 g / mol, more preferably less than 4000 and most preferably less than 2000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

The component (a) may be monomers or oligomers of aromatic, aliphatic or cycloaliphatic diisocyanates, preferably of aliphatic or cycloaliphatic diisocyanates

The NCO functionality of such compounds is generally at least 1.8, and may be up to 8, preferably from 1.8 to 5 and more preferably from 2 to 4.

The content of isocyanate groups, calculated as NCO = 42 g / mol, is usually from 5 to 25% by weight.

The diisocyanates are preferably isocyanates having 4 to 20 carbon atoms. Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane ( Isophorone diisocyanate), 1, 3 or 1, 4

Bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and also 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ²⁶ ] decane Isomer mixtures, and aromatic diisocyanates such as 2,4- or 2,6-toluene diisocyanate and their isomer mixtures, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and isomer mixtures thereof, 1, 3 or 1, 4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4 , 4'-diisocyanate, tetramethylxylylene diisocyanate, 1, 4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

There may also be mixtures of said diisocyanates.

Particularly preferred are hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, completely Particularly preferred are isophorone diisocyanate and hexamethylene diisocyanate, particularly preferred is hexamethylene diisocyanate.

Isophorone diisocyanate is usually present as a mixture, namely the cis and trans isomers, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75 : 25 and most preferably in the ratio of about 75:25.

Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.

Aromatic isocyanates are those containing at least one aromatic ring system.

Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system.

Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie aeyclic compounds.

There are also higher isocyanates with an average of more than 2 isocyanate groups in consideration. For example, triisocyanates such as triisocyanatononane, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanato-diphenyl ether or the mixtures of di-, tri- and higher polyisocyanates which are suitable, for example, by phosgenation of corresponding aniline / Formaldehyde condensates are obtained and represent methylene bridges Polyphenylpolyiso- cyanate.

Suitable polyisocyanates are polyisocyanates containing isocyanurate, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates, carbodiimide, hyperbranched polyisocyanates, polyurethane-polyisocyanate prepolymers or polyurea-polyisocyanate prepolymers of rectilinear or branched C4-C20-alkylene diisocyanates, cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.

The usable di- and polyisocyanates preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42) of 10 to 60% by weight to the di- and polyisocyanate (mixture), preferably 15 to 60% by weight and more preferably 20 to 55% by weight.

Preference is given to aliphatic or cycloaliphatic, in the context of this document as (cyclo) aliphatically summarized, di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

For the present invention, both such di- and polyisocyanates can be used, which are obtained by phosgenation of the corresponding amines, as well as those which without the use of phosgene, d. H. after phosgene-free process, are produced. For example, EP-A-0 126 299 (USP 4 596 678), EP-A-126 300 (USP 4 596 679) and EP-A-355 443 (USP 5 087 739) may disclose (cyclo) aliphatic diisocyanates, e.g. such as 1, 6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and isocyanato-S-isocyanato-methyl-S ^^ - trimethylcyclohexane (isophorone diisocyanate or IPDI) are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to give (cycloaliphatic biscarbamic acid esters and their thermal cleavage into the corresponding diisocyanates and alcohols.) The synthesis is usually carried out continuously in a cyclic process and optionally in The presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products recycled from the reaction process Di- or polyisocyanates thus obtained generally have a very low or even inestimable amount of chlorinated compounds, resulting in favorable color numbers of the products.

In one embodiment of the present invention, the di- and polyisocyanates (a) have a total hydrolyzable chlorine content of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, most preferably less than 50 ppm, especially less than 15 ppm and especially less than 10 ppm. This can be measured, for example, by ASTM D4663-98. However, it is of course also possible to use diisocyanates and polyisocyanates (a) with a higher chlorine content.

The di- and polyisocyanates (a) may also be present at least partially in blocked form.

Further preferred

1) isocyanurate-containing polyisocyanates of aromatic, aliphatic see and / or cycloaliphatic diisocyanates. Particularly preferred in this case the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present in this case are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or

Mixtures with their higher, more than one isocyanurate homologs. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.

2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The uretdione diisocyanates can be used as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).

3) biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 4.5.

4) containing urethane and / or allophanate polyisocyanates having aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bound isocyanate groups, as for example by reaction of excess amounts of hexamethylene diisocyanate or

Isophorone diisocyanate with monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n Decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, n-pentanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, trimethylolpropane, Neopentyl glycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, pentaethylene glycol, glycerol, 1,2-dihydroxypropane, 2,2-dimethyl-1,2-ethanediol, 1,2-butanediol, 1,4-butanediol diol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, neopentyl glycol hydroxypivalate, ditrimethylolpropane, dipentaerythritol, 2,2-bis (4- hydroxycyclohexyl) propane, 1, 1, 1, 2-, 1, 3- and 1, 4-cyclohexanedimethanol, 1, 2, 1, 3 or 1, 4-cyclohexanediol or mixtures thereof can be obtained , These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 4.5.

5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.

6) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.

7) Uretonimine-modified polyisocyanates.

8) carbodiimide-modified polyisocyanates.

9) Hyperbranched polyisocyanates, as are known, for example, from DE-A1 10013186 or DE-A1 10013187.

10) polyurethane-polyisocyanate prepolymers, of di- and / or polyisocyanates with alcohols.

1 1) polyurea-polyisocyanate prepolymers.

The polyisocyanates 1) to 1 1) can be used in admixture, optionally also in admixture with diisocyanates.

In a preferred embodiment of the present invention, component (a) is a polyisocyanate and is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, particularly preferably from the group consisting of isocyanurates and allophanates. In a preferred embodiment, the polyurethanes contain allophanate groups, and the content of allophanate groups in such polyurethanes (calculated as C ₂ N ₂ HO ₃ = 101 g / mol) is preferably from 1 to 28% by weight, preferably from 3 to 25% by weight.

In a further preferred embodiment of the present invention, at least 20 mol%, preferably at least 25 mol%, particularly preferably at least 30 mol%, of the compound (b) having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group are very particularly preferred at least 35 mol%, in particular at least 40 mol%, and especially at least 50 mol%, of allophanate groups are incorporated in the polyurethane.

In order to reduce the content of oxadiazinetrione groups, as described, for example, in DE-A1 102 46 512, a complicated aftertreatment of polyisocyanates is necessary, for example heating for several hours in vacuo, optionally assisted by stripping with a gas stream. Therefore, it is preferred according to the invention to keep the content of oxadiazinetrione groups low from the outset by using oxadiazinetrione arms or free isocyanates, for example, in which the content of oxadiazinetrione groups in the isocyanates used (calculated as C ₃ N ₂ O ₄ = 128 g / mol) is less than 15% by weight, preferably less than 10, particularly preferably less than 8, very particularly preferably less than 5, in particular less than 2.5 and especially less than 1% by weight.

In a preferred embodiment, the polyurethanes according to the invention have the lowest possible content of oxadiazinetrione groups, for example less than 0.7% by weight (calculated as C ₃ N ₂ O ₄ = 128 g / mol), preferably less than 0.6, particularly preferably less than 0.5, more preferably less than 0.3, most preferably less than 0.2, more preferably less than 0.1, and especially less than 0.05 weight percent. This is of particular interest if, in addition to the polyurethanes according to the invention, binders which contain isocyanate-reactive groups are also present in the finished coating composition, since CO ₂ can be liberated from these by reaction of isocyanate-reactive groups with oxadiazine triones forms bubbles in the coating composition and can thus lead to paint defects.

In a further preferred embodiment, it is sufficient for the polyurethanes according to the invention if they have an oxadiazinetrione group content of between 0.2 and 0.6% by weight, preferably between 0.3 and 0.5, particularly preferably between 0.35 and 0.45 (calculated as C ₃ N ₂ O ₄ = 128 g / mol). This is of particular interest when, in addition to the finished coating composition polyurethanes according to the invention contain no further binders which have isocyanate-reactive groups. In this case, as a rule, there is no possibility of the above-described reaction in which CO2 could be released, so that such a content of oxadiazinetrione groups is generally tolerable.

The proportion of other isocyanate group-forming groups, especially isocyanurate, biuret, uretdione, iminooxadiazinetrione and / or carbodiimide groups, plays a minor role according to the invention.

In a further preferred embodiment, component (a) is isocyanurate-group-containing polyisocyanates. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.

In a preferred embodiment of the invention, the polyurethanes according to the invention have virtually no free isocyanate groups, i. the content of free isocyanate groups is less than 0.5% by weight, preferably less than 0.3, particularly preferably less than 0.2, very particularly preferably less than 0.1, in particular less than 0.05 and especially 0% by weight %.

As a result of the preparation, polyisocyanates (a) may still have a small proportion of the monomeric diisocyanate on which they are based, for example up to 5% by weight, more preferably up to 3% by weight, very preferably up to 2, in particular up to 1, especially up to 0.5 and even up to 0.25% by weight.

Suitable components (b) according to the invention are compounds which carry at least one isocyanate-reactive group and at least one free-radically polymerizable group.

In a preferred embodiment of the invention, the compound (b) is a compound having exactly one isocyanate-reactive group. The number of free-radically polymerizable unsaturated group is at least one, preferably one to five, more preferably one to four and most preferably one to three radically polymerizable unsaturated groups.

The components (b) preferably have a molecular weight of below 10,000 g / mol, more preferably below 5000 g / mol, very preferably below 4000 g / mol and in particular below 3000 g / mol. Specific compounds (b) have a molecular weight below 1000 or even below 600 g / mol. Isocyanate-reactive groups can be, for example, -OH, -SH, -NH 2 and -NHR ⁵ , wherein R ^{5 is} hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl iso-butyl, sec-butyl or tert-butyl.

Isocyanate-reactive groups may be preferred -OH, -NH 2 or -NHR ⁵ , more preferably -OH or -NH 2 and most preferably -OH.

Components (b) may e.g. Monoesters of α, β-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid or vinyl ethers with di- or polyols, which preferably have 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 2, 1, 3- or 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 1,4-dimethylolcyclohexane, 2 , 2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, erythritol, sorbitol, polyTHF having a molecular weight of between 162 and 2000, poly-1,3-propanediol of one molecular weight between 134 and 400 or polyethylene glycol mi t a molecular weight between 238 and 458. Furthermore, esters or amides of (meth) acrylic acid with amino alcohols z. B. 2-aminoethanol, 2- (methylamino) - ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or vinylacetic acid.

Furthermore, unsaturated polyether or polyesterols or polyacrylate polyols having an average OH functionality of 2 to 10 are also suitable, although less preferably.

Examples of amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxymethylmethacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N-hydroxyalkylcrotonamides such as N Hydroxymethyl crotonamide or N-hydroxyalkylmaleimides such as N-hydroxyethylmaleimide.

Preference is given to using 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1 , 6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate and 4-hydroxybutyl vinyl ether, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-thioethyl (meth) acrylate, 2-aminoethyl (meth) acrylamide, 2-aminopropyl (meth) acrylamide, 3 Aminopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide or 3-hydroxypropyl (meth) acrylamide. Particularly preferred are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1, 4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238.

In a preferred embodiment, at least two different compounds (b1) and (b2) can also be used as compound (b).

In this case, compound (b1) is a compound having just one isocyanate-reactive group and exactly one free-radically polymerizable unsaturated group and compound (b2) is a compound having just one isocyanate-reactive group and at least two , preferably two to five, more preferably two to four and most preferably two or three radically polymerizable unsaturated groups.

In a preferred embodiment, component (b1) is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate and 1,4-butanediol monoacrylate, preferably 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate and especially it is preferably 2-hydroxyethyl acrylate and component (b2) is selected from the group consisting of the 1, 2 or 1, 3-diacrylate of glycerol, trimethylolpropane diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate and dipentaerythritol pentaacrylate.

In a particularly preferred embodiment, component (b2) is a technical mixture of the acrylation of trimethylolpropane, pentaerythritol, ditrimethylolpropane or dipentaerythritol. These are mostly mixtures of complete and incomplete acrylated polyols. Very particular preference is given as compounds (b2) to technical mixtures of the acrylation of pentaerythritol, which generally have an OH number according to DIN 53240 of 99 to 15 mg KOH / g and consist predominantly of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and may contain minor amounts of pentaerythritol diacrylate , This has the advantage that pentaerythritol tetraacrylate is not incorporated into the polyurethane according to the invention, but at the same time acts as a reactive diluent. Suitable components (c) are compounds which have exactly two isocyanate-reactive groups, for example -OH, -SH, -NH 2 or -NHR ⁵ , in which R ⁵ is independently of one another hydrogen, methyl, ethyl, iso-propyl, n- Propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl may have.

Isocyanate-reactive groups may be preferred -OH, -NH 2 or -NHR ⁵ , more preferably -OH or -NH 2 and most preferably -OH.

These are preferably 2 to 20 carbon diols, e.g. Ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 1-dimethylethane-1, 2-diol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1, 3 Propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxypivic acid neopentyl glycol ester, 1, 2, 1, 3 or 1,4-butanediol, 1,6-hexanediol, 1, 10-decanediol, bis- (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalindiol, 2-ethyl-1, 3-hexanediol, 2,4-diethyl-octane -1, 3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, poly-THF having a molecular weight between 162 and 2000, poly-1, 2-propanediol or poly-1, 3-propanediol having a molecular weight between 134 and 1 178 or polyethylene glycol having a molecular weight between see 106 and 2000 and aliphatic diamines such as methylene, and isopropylidene-bis (cyclohexylamine), piperazine, 1, 2, 1, 3 or 1, 4-diaminocyclohexane, 1, 2-, 1, 3- or 1, 4-cyclohexane-bis (methylamine), etc., dithiols or polyhydric alcohols, secondary or primary amino alcohols such as ethanolamine, monopropanolamine etc. or thioalcohols, such as thioethylene glycol.

Particularly suitable here are the cycloaliphatic diols, e.g. Bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, 1, 1-, 1, 2-, 1, 3- and 1, 4- Cyclohexanedimethanol, cyclooctanediol or norbornanediol.

The optional component (d) is at least one compound having at least three isocyanate-reactive groups.

For example, components (d) may have 3 to 6, preferably 3 to 5, more preferably 3 to 4, and most preferably 3 isocyanate-reactive groups.

The molecular weight of components (d) is generally not more than 2000 g / mol, preferably not more than 1500 g / mol, more preferably not more than 1000 g / mol and most preferably not more than 500 g / mol. These are preferably polyols containing 2 to 20 carbon atoms, for example trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribite), arabitol (lyxite), xyNt , Dulcit (galactitol), maltitol, isomalt, particularly preferred are trimethylolpropane, pentaerythritol and glycerol, and most preferably trimethylolpropane.

Optional components (e) are those with optionally at least one compound with exactly one isocyanate-reactive group.

These are preferably monools, particularly preferably alkanols and very particularly preferably alkanols having 1 to 20, preferably 1 to 12, particularly preferably 1 to 6, very particularly preferably 1 to 4 and in particular 1 to 2 carbon atoms.

Examples thereof are methanol, ethanol, isopropanol, n-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n Dodecanol (lauryl alcohol), 2-ethylhexanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, 1,3-propanediol monomethyl ether, preferred are methanol, ethanol, isopropanol, n-propanol, n- Butanol, tert-butanol, n-hexanol, 2-ethylhexanol, cyclopentanol, cyclohexanol, and cyclododecanol, particularly preferred are methanol, ethanol, isopropanol, n-propanol, n-butanol and tert-butanol, most preferably methanol and Ethanol and especially methanol.

In a preferred embodiment, the monools may be the stated cycloaliphatic alcohols, preferably cyclopentanol or cyclohexanol, more preferably cyclohexanol.

In a further preferred embodiment, the monools can be the stated aliphatic alcohols having 6 to 20 carbon atoms, more preferably those having 8 to 20 carbon atoms, very particularly preferably those having 10 to 20 carbon atoms.

In a particularly preferred embodiment, the monools are the aliphatic alcohols mentioned, very particularly preferably those having 1 to 4 carbon atoms, in particular methanol. (f) Compounds (f) are at least one compound having at least one organosilicon group and at least one isocyanate-reactive group.

Isocyanate-reactive groups may be preferred -OH, -Nhb or -NHR ⁵ , more preferably -OH or -NH 2 and most preferably -OH.

The compounds (f) contain on average at least one, preferably at least one, particularly preferably one to 20, very particularly preferably one to 10, in particular one to 6, especially one to 4, often one to 3 and even exactly one isocyanate-reactive group.

Furthermore, the compounds (f) have at least one silicon-organic group, preferably 1 to 50, more preferably 1 to 40, most preferably 1 to 30, especially 1 to 20, especially 1 to 10, even 1 to 8 and often 1 to 7 silicon-organic groups.

In this context, silicon-organic groups are understood as meaning those atomic groups which consist of at least one silicon atom and which are substituted by any optionally substituted alkyl, aryl or cycloalkyl groups. This includes according to the ILJPAC rules D-6, such compounds in which the carbon is linked via oxygen, nitrogen or sulfur atoms to the silicon.

In the compounds (f), the organosilicon groups may preferably be present as siloxanes having at least one Si-O-C bond or likewise preferably in the form of poly-siloxanes, that is to say containing at least one Si-O-Si-OC-group the silicon atoms can then be substituted by any optionally substituted alkyl, aryl or cycloalkyl groups.

Preferably, the organosilicon compounds are those of the formula

_H χ ^{i _R iθ} - [- SiR ^H ₃ -v (OR ¹² ) v] w

wherein

X ^{1 is} oxygen (O), sulfur (S), imino (-NH-) or substituted imino (-NR ⁵ -), preferably oxygen or imino, particularly preferably oxygen, R ^{10 is} a (w + 1) -bindigen organic remainder, R ¹¹ and R ¹² independently of each other represent optionally substituted alkyl, Cycloalkyl or aryl, v is a positive integer from 1 to 3, preferably 2 or 3 and particularly preferably 3 and w is a positive integer from 1 to 5, preferably 1 to 4, particularly preferably 1 to 3, very particularly preferably 1 to 2 and in particular stands for 1.

R ¹⁰ may be C 1 -C 20 -alkylene, C 6 -C 12 -arylene, C 3 -C 12 -cycloalkylene.

Therein C 1 -C 4 -alkylene is linear or branched alkylene, e.g. Methylene, 1, 2-ethylene, 1, 2 or 1, 3-propylene, 1, 2, 1, 3 or 1, 4-butylene, 1, 1-dimethyl-1, 2-ethylene or 1, 2 Dimethyl 1, 2-ethylene, 1, 6-hexylene, 1, 8-octylene, 1, 10-decylene, or 1, 12-dodecylene. Preference is given to 1,2-ethylene, 1,2- or 1,3-propylene, 1,4-butylene and 1,6-hexylene, more preferably 1,2-ethylene.

C 3 -C 12 -cycloalkylene are, for example, cyclopropylene, cyclopentylene, cyclohexyl, cyclooctylene and cyclododecylene.

C 6 -C 12 -arylene is 1, 2-1, 3- or 1, 4-phenylene, 4,4'-biphenylene, 4,4'-bisphenylmethylene, 1, 3, 1, 4 or 1, 5 Naphthylene, 3,3'-dimethyl-4,4'-diphenylene, 3,3'-dichloro-4,4'-diphenylene, 2,4- or 2,6-pyridyl, 1,4-anthraquinonediyl, m- or p-toluylene, 4,6-dimethyl-1,3-phenylene, 4,6-dichloro-1,3-phenylene, 5-chloro-1, 3-phenylene, 5-hydroxy-1,3-phenylene, 5 Methoxy-1,3-phenylene, 2,3-dimethyl-1,4-phenylene, m- or p-xylylene, methylene-di-p-phenylene, isopropylidene-di-p-phenylene, thio-di-p-phenylene , Dithio-di-p-phenylene, sulfo-di-p-phenylene, carbonyl-di-p-phenylene, or 4,4'-bisphenyl ether.

Preferred radicals R ¹¹ and R ¹² are independently methyl, ethyl, n-propyl, n-butyl, tert-butyl, thexyl and phenyl.

Examples of compounds (f) are N-cyclohexylaminomethylmethyldiethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, N-trimethoxysilylmethyl-O-methyl-carbamate, 1- [3- (trimethoxysilyl) propyl] urea, 3- (diethoxymethylsilyl) propylamine, N- Dimethoxy (methyl) silylmethyl-O-methyl-carbamate, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl ) -3-aminopropyldimethoxysilane, (isocyanatomethyl) methyldimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydride, bis [3-trimethoxysilyl) propyl] amine or bis [(trimethoxysilyl) propyl] amine. Preferred compounds (f) are those which are obtainable by reacting at least one compound (f1) which has at least one silicon atom and at least one Si-H group with at least one compound (f2) which has at least one isocyanate-reactive group Group and at least one vinylic group bears.

Preferred compounds (f1) have 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, very particularly preferably 1 to 3, in particular 1 to 2 and especially 2 Si-H groups.

Preferred compounds (f1) have 1 to 50, preferably 2 to 40, particularly preferably 3 to 30, very particularly preferably 3 to 20, in particular 4 to 10, especially 4 to 8 and even 5 to 7 silicon atoms.

In a preferred embodiment, the compounds (f1) are at least one organic polysiloxane hydride of the formula (I)

has, in which

R ^{1 is} independently hydrogen, hydroxy (-OH), C 1 -C 6 -alkyl, C 6 -C 12 -aryl, C 1 -C 12 -cycloalkyl, C 1 -C -alkoxy or C 6 -C 12 -aryloxy and

n is an integer from 0 to 100

can mean

wherein at least one of the groups R ^{1 is} hydrogen.

In compounds of the formula (I), preference is given to the ratio of groups R ¹ which are hydrogen to groups R ¹ which are not hydrogen, from 0.1: 1 to 10: 1.

The compounds (f1) are particularly preferably at least one organic polysiloxane hydride of the formula (II) or formula (III)

wherein

R ² independently of one another hydroxy (-OH), Ci - Ciβ-alkyl, Cβ - Ci2-aryl, Cs - C12-cycloalkyl, Ci - Cis-Alkoky and Cβ - Ci2-aryloxy,

n is an integer from 0 to 50, m is an integer from 1 to 50, and p is an integer from 0 to 50

can mean.

In compounds of the formula (II) or (III), the ratio of hydrogen atoms bound to silicon atoms to groups R ² is preferably 0.1: 1 to 10: 1.

Mean in it

C 1 -C 18 -alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, Tetradecyl, hetadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl or 1, 1, 3,3-tetramethylbutyl.

C 1 -C 6 -alkoxy, for example methoxy, ethoxy, n-propyloxy, isopropoxy, n-butyloxy, isobutoxy, sec-butyloxy or tert-butyloxy.

Cβ - C 12 aryl, for example, phenyl, ToIyI, XyIyI, α-naphthyl, ß-naphthyl, 4-diphenylyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methylnaphthyl, isopropylnaphthyl, 6 - Dimethylphenyl or 2,4,6-trimethylphenyl. C 1 -C 12 -cycloalkyl, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl.

Cβ - Ci2-aryloxy, for example, phenyloxy, o-, m- or p-tolyloxy.

R ¹ and R ² are preferably, independently of one another, hydroxyl, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or C 6 -C 12 -aryl, particularly preferably C 1 -C ₄ -alkyl or phenyl, very particularly preferably C 1 -C ₄ -alkyl.

Ci to C ₄ -alkyl in the context of this document means methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, preferably methyl, ethyl, n-butyl or tert-butyl, particularly preferably methyl or Ethyl and most preferably methyl.

n is preferably an integer from 1 to 50, particularly preferably from 1 to 30, very particularly preferably from 2 to 20, in particular from 2 to 10 and especially from 3 to 5,

m is preferably an integer from 1 to 30, particularly preferably from 1 to 20, very particularly preferably from 1 to 10, in particular from 1 to 5 and especially m is 1 and

p is preferably an integer from 0 to 30, particularly preferably from 0 to 20, very particularly preferably from 0 to 10, in particular from 0 to 5 and especially p is 0.

Examples of polysiloxane anhydrides are 1, 1, 3,3-tetramethyl disiloxane, polysiloxane anhydrides, in which n is 3 or 4, which are commercially available under the trade name Masilwax® BASE from PPG Industries Inc.

Formulas (I), (II) and (III) are schematic, and it is not intended to indicate that the parts in parentheses are necessarily blocks, although blocks may be used where desired. In many cases, the compound is more or less random, especially when more than a few siloxane units are used, and when mixtures are used. In those instances where more than a few siloxane units are used and it is desired to form blocks, oligomers are first formed and then these are joined to form the block compound. By judicious choice of reactants, compounds having an alternating structure or blocks of alternating structure can be used. The compounds of the formulas (I), (II) or (III) may therefore be alternating, random or block polymers, preferably random or block polymers and more preferably random polymers.

The compounds (f2) may preferably be those of the formula (IV)

Vin-R ⁴ -Y

wherein

Vin a vinyl group,

R ^{4 is} a single bond, an oxygen atom, a nitrogen atom, C 1 -C 20 -alkylene, C 6 -C 12 -arylene, C 3 -C 12 -cycloalkylene, or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Imino groups and / or by one or more - (CO) -, -O (CO) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O groups interrupted C ₂ -C ₂ o-alkylene and

Y is an isocyanate-reactive group

mean.

(g) the compulsory compounds (g) are those which contain at least one isocyanate-reactive group and at least one dispersive group.

Compounds preferred as component (g) have exactly one isocyanate-reactive group and exactly one dispersive-active group.

The dispersing groups may be

(g1) anionic groups or groups which can be converted into an anionic group, (g2) cationic groups which can be converted into a cationic group, or (g3) nonionic groups.

Of course, mixtures or mixed forms are conceivable.

Preferred dispersive groups are (gl) or (g3), more preferably either (gl) or alternatively (g3). Compounds (gl) contain exactly one isocyanate-reactive group and at least one anionic or anionic group-transferable hydrophilic group. These are, for example, those described in EP-A1 703 255, there especially of p. 3, Z. 54 to p. 4, Z. 38, in DE-A1 197 24 199, there especially of S 3, Z. 4 to Z. 30, in DE-A1 40 10 783, there especially of Sp. 3, Z. 3 to Z. 40, in DE-A1 41 13 160, there especially of Sp. 3 , Z. 63 to Sp. 4, Z. 4 and in EP-A2 548 669, where they are described in particular by S. 4, Z. 50 to S. 5, Z. 6. These documents are hereby incorporated by reference in the context of the present disclosure.

Preferred compounds (gl) are those having the general formula

RG-R ³ -DG

wherein

RG is at least one isocyanate-reactive group,

DG at least one dispersive group and

R ^{3 is} an aliphatic, cycloaliphatic or aromatic radical containing 1 to 20 carbon atoms.

Examples of isocyanate-reactive groups RG are -OH, -SH, -NH2 or -NHR ⁵ , wherein R ^{5 has} the abovementioned meaning, but may be different from the radical used there, preferred are -OH, -NH 2 or -NHR ⁵ , particularly preferred are -OH or -NH2, and most preferred is -OH.

Examples of DG are -COOH, -SO3H or -PO3H and their anionic forms to which any counterion may be associated, for example Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ or Ba ²⁺ . In addition, the ammonium ion or quaternary ammonium ions derived from ammonia or amines, especially tertiary amines, such as ammonium, methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, tributylammonium, di-iso-propyl-ethyl-ammonium, benzyldimethylammonium, Monoethanolammonium, diethanolammonium, triethanolammonium, hydroxyethyldimethylammonium, hydroxyethyldiethylammonium, monopropanolammonium, dipropanolammonium, tripropanolammonium, piperidinium, piperazinium, N, N'-dimethylpiperazinium, morpholinium, pyridinium, tetramethylammonium, triethylmethylammonium, 2-hydroxyethyl-trimethyl - mmonium, bis- (2-hydroxyethyl) -dimethylammonium, tris- (2-hydroxyethyl) -methyl- mmonium, be associated as a counterion. R ³ is preferably methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, 1,3-butylene, 1,6-hexylene, 1, 8-octylene, 1, 12-dodecylene, 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 1, 2-naphthylene, 1, 3-naphthylene, 1, 4-naphthylene, 1, 6 Naphthylene, 1, 2-cyclopentylene, 1, 3-cyclopentylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene or 1, 4-cyclohexylene.

Preferably component (gl) is e.g. hydroxyacetic, tartaric, lactic, 3-hydroxypropionic, hydroxypivalic, mercaptoacetic, mercaptopropionic, thiolactic, mercaptosuccinic, glycine, iminodiacetic, sarcosine, alanine, β-alanine, leucine, isoleucine, aminobutyric, hydroxysuccinic, hydroxydecanoic, ethylenediaminetriacetic, hydroxydodecanoic - Re, hydroxyhexadecanoic, 12-hydroxystearic, Aminonaphthalincarbonsäure, Hydroxethansulfonsäure, hydroxypropanesulfonic acid, Mercaptoethansulfonsäure, mercaptopropanesulfonic acid, Aminomethansulfonsäure, taurine, Aminopropansulfonsäure, N-alkylated or N-cycloalkylated Aminopropan- or -ethansulfonsäuren, for example N-Cyclohexylaminoethansulfonsäure or N-Cyclohexylaminopropansulfon- , as well as their alkali metal or alkaline earth ammonium salts and particularly preferably the monohydroxycarboxylic and -sulfonic acids as well as monoaminocarboxylic and -sulfonic acids.

To prepare the dispersion, the abovementioned acids, if they are not already salts, are partially or completely neutralized, preferably with alkali metal salts or amines, preferably tertiary amines.

Compounds (g2) contain exactly one isocyanate-reactive group and at least one cationic or cationic group convertible hydrophilic group and are, for example, those described in EP-A1 582 166, there especially from page 5, Z. 42 to S 8, Z. 22 and in particular from page 9, lines 19 to page 15, line 34, or in EP-A1 531 820, there in particular from page 3, lines 21 to page 4, Z 57 or in DE-A1 42 03 510, there especially from page 3, Z. 49 to page 5, Z. 35 are described. These documents are hereby incorporated by reference in the context of the present disclosure.

As potentially cationic compounds (g2), especially those having tertiary amino groups of particular practical importance, for example: N-hydroxyalkyl-dialkylamines, N-aminoalkyl-dialkylamines, where the alkyl radicals and alkanediyl units of these tertiary amines independently of one another from 2 to 6 carbon atoms. Furthermore, tertiary nitrogen atoms having polyether having a terminal hydroxyl group, as for example by alkoxylation of secondary amines into consideration. Such polyethers generally have between 500 and 6000 g / mol lying molecular weight.

These tertiary amines are reacted either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids, strong organic acids such as formic, acetic or lactic acid, or by reaction with suitable quaternizing agents such as C 1 to C 6 alkyl halides, e.g. Bromides or chlorides, or di-Cr to Cβ-alkyl sulfates or di-Cr to Ce alkylcarbonates converted into the ammonium salts.

Suitable compounds (g2) with isocyanate-reactive amino groups are aminocarboxylic acids such as lysine, β-alanine, the adducts of aliphatic diprimary diamines mentioned in DE-A2034479 to α, β-unsaturated carboxylic acids such as N- (2-aminoethyl) -2- aminoethanecarboxylic acid and the corresponding N-aminoalkylaminoalkylcarboxylic acids, wherein the alkanediyl units consist of 2 to 6 carbon atoms.

If monomers having potentially ionic groups are used, their conversion into the ionic form may take place before, during, but preferably after the isocyanate polyaddition, since the ionic monomers are often difficult to dissolve in the reaction mixture. The carboxylate groups are particularly preferably in the form of their salts with an alkali ion or an ammonium ion as the counterion.

Compounds (g3) are monofunctional polyalkylene oxide polyether alcohols obtainable by alkoxylation of suitable starter molecules.

Suitable starter molecules for preparing such polyalkylene oxide polyether alcohols are thiol compounds, monohydroxy compounds of the general formula

R ¹⁸ -OH

or secondary monoamines of the general formula

R ¹⁶ R ¹⁷ NH,

in which

R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently of one another independently C 1 -C 4 -alkyl, C 2 -C -alkyl which is optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 1 -C 12 -Aryl, C5 - Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle or R ¹⁶ and R ¹⁷ together form an unsaturated, saturated or aromatic ring optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, said radicals being in each case denoted by functional groups, aryl , Alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.

Preferably, R ¹⁶ , R ¹⁷ and R ^{18 are} independently Ci- to C ₄ -AlkVl, more preferably R ¹⁶ , R ¹⁷ and R ^{18 are} methyl.

Suitable monovalent starter molecules, for example, may be saturated monoalkanols, that is, they have no C-C or C-heteroatom double or triple bonds, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols , Hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, cyclopentanol, the imideren methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxy-methyloxetane, or tetrahydrofurfuryl; aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisalcohol or cinnamyl alcohol; secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, diisobutylamine,

Bis (2-ethylhexyl) amine, N-methyl and N-ethylcyclohexylamine or dicyclohexylamine, heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole, and amino alcohols such as 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-diisopropylaminoethanol , 2-dibutylaminoethanol, 3- (dimethylamino) -1-propanol or 1- (dimethylamino) -2-propanol.

Preferred starter molecules are alcohols having not more than 6 carbon atoms, more preferably not more than 4 carbon atoms, most preferably not more than 2 carbon atoms, and especially methanol.

Suitable for the alkoxylation reaction alkylene oxides are ethylene oxide, propylene oxide, iso-butylene oxide, vinyloxirane and / or styrene oxide, which can be used in any order (for the preparation of block copolymers) or in admixture (for the preparation of random copolymers) in the alkoxylation reaction.

Preferred alkylene oxides are ethylene oxide, propylene oxide and mixtures thereof, particularly preferred is ethylene oxide.

Preferred polyether alcohols are those based on polyalkylene oxide polyether alcohols, in the preparation of which saturated aliphatic or cycloaliphatic alcohols of the above type were used as starter molecules. Very particularly preferred are those based on polyalkylene oxide polyether alcohols which have been prepared using saturated aliphatic alcohols having 1 to 4 carbon atoms in the alkyl radical. Particular preference is given to methanol-initiated polyalkylene noxidpolyetheralkohole.

The monohydric polyalkylene oxide polyether alcohols generally have on average at least 2 alkylene oxide units, preferably 5 ethylene oxide units, in copolymerized form per molecule, more preferably at least 7 and most preferably at least 10.

The monohydric polyalkylene oxide polyether alcohols generally have on statistical average up to 90 alkylene oxide units, preferably ethylene oxide units, in copolymerized form per molecule, preferably up to 45, more preferably up to 40 and very particularly preferably up to 30.

The molecular weight of the monohydric polyalkylene oxide polyether alcohols is preferably up to 4000, particularly preferably not more than 2000 g / mol, very particularly preferably not less than 500 and in particular 1000 ± 500 g / mol.

Preferred polyether alcohols are thus compounds of the formula

wherein

R ^{18 has} the abovementioned meanings, s is an integer from 2 to 90, preferably 5 to 45, particularly preferably 7 to 40 and very particularly preferably 10 to 30, and each X, for i = 1 to s, can be selected independently of one another may be selected from the group consisting of -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CHs) -O-, -CH (CHs) -CH ₂ -O-, -CH ₂ -C (CHs) ₂ - O-,

-C (CHs) ₂ -CH ₂ -O-, -CH ₂ -CHVin-O-, -CHVin-CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, are preferred from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CHs) -O- and -CH (CHs) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O- wherein Ph stands for phenyl and Vin stands for vinyl.

In a particular embodiment of the present invention, compound (g) may also be an alkoxylated (meth) acrylate, for example one of the formula

or

H ₂ C = C (CH 3) -CO-CK-Xr] SH

wherein

X, and s can assume the meanings given above.

Examples of these are polyethylene oxide mono (meth) acrylate (PEA6 / PEM6, Laporte Performance Chemicals Ltd.), polypropylene oxide mono (meth) acrylate (PPA6 / PPM5S, Laporte Performance Chemicals Ltd.) or polyalkylene oxide mono (meth) acrylate (PEM63P, La Porte Performance Chemicals Ltd.).

Such alkoxylated (meth) acrylates are preferably bound at least partially via urethane groups, but not via allophanate groups.

However, preference is given to the abovementioned saturated polyalkylene oxide polyether alcohols.

In order to achieve a good dispersing activity, the polyurethanes according to the invention preferably have a density of the dispersing cationic, nonionic and / or anionic group-carrying molecules of 1 to 25 mol% based on a functional group and isocyanate groups, preferably at least 3 mol%, and particularly preferably from 5 to 15 mol% on.

The polyurethanes which can be used according to the invention are obtained by reacting the components (a), (b), (f) and (g) and optionally (c) and / or (d) and / or (e) with one another.

The molar composition (a) :( b) :( f) :( c) :( d) :( e) :( g) per 1 mol of reactive isocyanate groups in (a) is generally as follows:

(b) 1-50, preferably 5-40, particularly preferably 10-37.5 and in particular 15-33 mol% of isocyanate-reactive groups,

(c) 0-50, preferably 0-30, particularly preferably 0-25 and in particular 0-20 mol% of isocyanate-reactive groups, (d) 0-10, preferably 0-5, particularly preferably 0-3 and in particular 0-2 mol% of isocyanate-reactive groups,

(e) 0-5, preferably 0-4, particularly preferably 0-3 and in particular 0-2 mol% of isocyanate-reactive groups, (f) 1-40, preferably 2-35, particularly preferably 5-30 and in particular

10 to 25 mol% of isocyanate-reactive groups, (g) 1 to 25, preferably 2 to 20, particularly preferably 3 to 15 and in particular 5 to 15 mol% of isocyanate-reactive groups,

with the proviso that the sum of the isocyanate-reactive groups corresponds to the number of isocyanate groups in (a).

The formation of the adduct of isocyanate group-containing compound and the compound containing isocyanate-reactive groups is generally carried out by mixing the components in any order, optionally at elevated temperature.

In this case, the compound containing isocyanate-reactive groups is preferably added to the compound containing isocyanate groups, preferably in several steps.

The isocyanate group-containing compound is more preferably initially introduced, and the compounds containing isocyanate-reactive groups are added. In particular, the isocyanate group-containing compound (a) is initially charged and then (b) and / or (f) and / or (g) are added. Subsequently, if desired, further desired components can be added.

In general, the reaction at temperatures between 5 and 100 ⁰ C, preferably between 20 to 90 ⁰ C and more preferably between 40 and 80 ⁰ C and in particular between 60 and 80 ⁰ C performed.

Preference is given to working under anhydrous conditions during the preparation of the polyurethane.

Anhydrous here means that the water content in the reaction system is not more than 5% by weight, preferably not more than 3% by weight and more preferably not more than 1% by weight, most preferably not more than 0.75 and in particular not more than 0.5% by weight %.

Preferably, the reaction is carried out in the presence of at least one oxygen-containing gas, for example air or air-nitrogen mixtures or mixtures of oxygen or an oxygen-containing gas with an inert under the reaction conditions Gas having an oxygen content below 15, preferably below 12, more preferably below 10, most preferably below 8 and in particular below 6% by volume.

The reaction may also be carried out in the presence of an inert solvent, e.g. Acetone, iso-butyl methyl ketone, toluene, xylene, butyl acetate, methoxypropyl acetate or ethoxyethyl acetate. Preferably, however, the reaction is carried out in the absence of a solvent.

In a preferred embodiment, the reaction of (a) can be carried out with (b) under Al lophanatisierungsbedingungen.

Typical catalysts for such a reaction are organozinc compounds, such as zinc acetylacetonate or zinc 2-ethylcaproate, or a tetraalkylammonium compound, such as N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide or N, N, N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, or organotin compounds such as dibutyltin dilaurate.

In a further preferred embodiment, such compounds are used as described in WO 00/39183, p. 4, Z. 3 to p. 10, Z. 19, the disclosure of which is herewith part of the present document. Particularly preferred among these are those compounds which have as structural components at least one (cyclo) aliphatic isocyanate containing allophanate groups and at least one hydroxyalkyl (meth) acrylate, very particularly preferably the product Nos. 1 to 9 in Table 1 to S 24 of WO 00/39183.

The polyurethanes according to the invention can be used for coating various substrates, such as. As wood, wood veneer, paper, cardboard, cardboard, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, metals or coated metals.

When used in coating compositions, the polyurethanes according to the invention can be used in particular in primers, fillers, pigmented topcoats and clearcoats in the field of car repair or large vehicle painting. Particularly suitable are those coating compositions for applications in which a particularly high application security, outdoor weathering resistance, optics, solvent, chemical and water resistance are required, such as in the car repair and large vehicle painting. The coating compositions according to the invention are suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as cement molded bricks and fiber cement boards, or metals or coated metals, preferably of plastics or metals, in particular in the form of films, more preferably metals.

Thus, a further subject of the present invention are these substrates coated with a coating composition according to the invention.

The coating compositions according to the invention are suitable as or in exterior coatings, ie those applications which are exposed to daylight, preferably of building parts, interior coatings, coatings on vehicles and aircraft. In particular, the coating compositions of the invention are used as or in automotive clearcoat and topcoat (s). Further preferred fields of application are can coating and coil coating.

Thus, vehicles and aircraft coated with a coating composition according to the invention are also part of the present invention.

They are particularly suitable as primers, fillers, pigmented topcoats and clearcoats in the field of industrial, wood, automotive, in particular OEM paintwork, or decorative lacquering. The coating compositions are particularly suitable for applications in which particularly high application safety, outdoor weathering resistance, appearance, scratch resistance, solvent and / or chemical resistance are required.

Another object of the present invention are radiation-curable coating compositions comprising at least one polyurethane according to the invention, - optionally at least one compound having one or more than one free-radically polymerizable double bond, optionally at least one photoinitiator optionally further typical water additives.

Furthermore, acids or capped acids can be added as catalysts for the curing of the organosilyl groups. Preference is given to organic sulfonic acid, for example methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid. Further examples are capped sulfonic acids, such as, for example, as Nacure® types of the company King Industries. Acid catalysts are generally added in amounts of up to 2% by weight, based on the coating composition, preferably up to 1.5% by weight.

The polyurethanes according to the invention can be used as the sole binder or in combination with another free-radically polymerizable compound.

Compounds having one or more than one free-radically polymerizable double bond are, for example, those compounds which have 1 to 6, preferably 1 to 4 and particularly preferably 1 to 3 free-radically polymerizable groups.

Free-radically polymerizable groups are, for example, vinyl ether or (meth) acrylate groups, preferably (meth) acrylate groups and particularly preferably acrylate groups.

Radical polymerizable compounds are often subdivided into monofunctional (compound having a radically polymerizable double bond) and multifunctional (compound having more than one radically polymerizable double bond), polymerizable compounds.

Monofunctional, polymerizable compounds are those having exactly one free-radically polymerizable group; multifunctional, polymerizable compounds are those having more than one, preferably having at least two free-radically polymerizable groups.

Monofunctional, polymerizable compounds are, for example, esters of (meth) acrylic acid with alcohols having 1 to 20 C atoms, for example (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2 ethylhexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dihydrodicyclopentadienyl acrylate, vinylaromatic compounds, eg styrene, divinylbenzene, α, β-unsaturated nitriles, eg acrylonitrile, methacrylonitrile , α, β-unsaturated aldehydes, for example acrolein, methacrolein, vinyl esters, for example vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds, for example vinyl chloride, vinylidene chloride, conjugated unsaturated compounds, for example butadiene, isoprene, chloroprene, monounsaturated compounds, for example ethylene, Propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds, for example cyclopentene, cyclohexene, cyclododecene, N-vinylformamide, allylacetic acid , Vinylacetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their water-soluble alkali metal, alkaline earth metal or ammonium salts such as: Acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, maleic acid, N-vinylpyrrolidone, N-vinyllactams, for example N-vinylcaprolactam, N-vinyl-N-alkyl- carboxylic acid amides or N-vinylcarboxamides, such as. As N-vinyl acetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso Butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxy-butyl vinyl ether, and mixtures thereof.

Preferred among these are the esters of (meth) acrylic acid, particular preference is given to (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate, completely Particularly preferred are (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate and especially 2-hydroxyethyl acrylate.

(Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.

Multifunctional, polymerizable compounds are preferably multifunctional (meth) acrylates which carry more than 1, preferably 2-10, more preferably 2-6, most preferably 2-4 and especially 2-3 (meth) acrylate groups, preferably acrylate groups.

These may be, for example, esters of (meth) acrylic acid with correspondingly at least dihydric polyhydric alcohols.

Such polyalcohols are, for example, at least divalent polyols, polyether or polyesterols or polyacrylate polyols having an average OH functionality of at least 2, preferably 3 to 10, suitable.

Examples of polyfunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,8 Octanediol diacrylate, neopentyl glycol diacrylate, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol diacrylate, 1, 2, 1, 3 or 1, 4-cyclohexanediol diacrylate, trimethylolpropane triacrylate, ditri methylolpropane penta- or hexaacrylate, pentaerythritol tri- or tetraacrylate, glycerol di- or triacrylate, and di- and polyacrylates of sugar alcohols, such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, Dulcitol (galactitol), maltitol or isomalt, or of polyester polyols, polyetherols, polyTHF with a molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between see, 134 and 1178, polyethylene glycol having a molecular weight between 106 and 898, and epoxy (meth) acrylates, urethane (meth) acrylates or polycarbonate (meth) acrylates.

Further examples are (meth) acrylates of compounds of the formula (Villa) to (VIIIc),

> ° ^H "I ^x ₁ , ⁰ Vl ^H

(Villa) (VIIIb) (VIIIc)

wherein

R ⁷ and R ⁸ independently of one another denote hydrogen or C 1 -C 6 -alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,

k, I, m, q independently of one another are each an integer from 1 to 10, preferably 1 to 5 and particularly preferably 1 to 3, and

each X, for i = 1 to k, 1 to I, 1 to m and 1 to q can be independently selected from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CHs) -O- , -CH (CHs) -CH ₂ -O-, -CH ₂ - C (CH) ₂ -O-, -C (CHs) ₂ -CH ₂ -O-, -CH ₂ -CHVin-O-, -CHVin -CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, preferably from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CHs) -O- and -CH (CHs) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O-,

where Ph is phenyl and Vin is vinyl.

Therein Cis-alkyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethyl-propyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl , preferably methyl, ethyl or n-propyl, very particularly preferably methyl or ethyl.

Preference is given to (meth) acrylates of one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol. Preferred multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyester polyol acrylates, polyetherol acrylates and triacrylate of one to twenty times alkoxylated, particularly preferably ethoxylated trimethylolpropane.

Very particularly preferred multifunctional, polymerizable compounds are 1, 4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and triacrylate of one to twenty times ethoxylated trimethylolpropane.

Polyester polyols are e.g. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp. 62-65. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:

Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products, and esterifiable derivatives such as anhydrides or dialkyl esters, for example C 1 -C 4 -alkyl esters, preferably methyl, ethyl or n-butyl esters, of the abovementioned Acids are used. Preference is given to dicarboxylic acids of the general formula HOOC- (CH 2) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable polyhydric alcohols for preparing the polyesterols are 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1, 3-diol, 2,4-diethyloctane-1, 3-diol, 1, 6-hexanediol, poly-THF with one molecular weight between 162 and 2000, poly-1, 3-propanediol having a molecular weight between 134 and 1 178, poly-1, 2-propanediol having a molecular weight between 134 and 898, polyethylene glycol with a Molar mass between 106 and 458, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1 , 1, 2-, 1, 3- and 1, 4-cyclohexanedimethanol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol , Sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol or isomalt, which may optionally be alkoxylated as described above.

Alcohols of the general formula HO- (CH 2) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20. Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.

Also included are polycarbonate diols, e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably hydroxyl-terminated addition products of lactones to suitable difunctional starter molecules. Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) Σ-COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a C 1 to C 4 alkyl radical may be substituted. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivolactone, and mixtures thereof. Suitable starter components are e.g. the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones. Furthermore, the multifunctional, polymerizable compound may be urethane (meth) acrylates, epoxy (meth) acrylates or carbonate (meth) acrylates.

Urethane (meth) acrylates are obtainable, for example, by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols. In water without the addition of emulsifiers dispersible urethane (meth) acrylates additionally contain ionic and / or nonionic hydrophilic groups which For example, be introduced by structural components such as hydroxycarboxylic acids in the urethane.

Such urethane (meth) acrylates contain as structural components essentially:

(a) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate,

(B) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated

Group and

(C) optionally at least one compound having at least two isocyanate-reactive groups.

Components (a), (b) and (c) may be the same as described above for the polyurethanes of the invention.

The urethane (meth) acrylates preferably have a number average molecular weight M _{n of} from 500 to 20,000, in particular from 500 to 10,000, more preferably from 600 to

3000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

The urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4 moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate.

Epoxide (meth) acrylates are obtainable by reacting epoxides with (meth) acrylic acid. Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.

Epoxidized olefins may be, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1-butoxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin. Preferred are ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide , Propylene oxide or epichlorohydrin and most preferably ethylene oxide and epichlorohydrin.

Aromatic glycidyl ethers are, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, for example 2,5-bis [(2, 3-D poxypropoxy) phenyl] octahydro-4,7-methano-5H-indene (CAS No. [13446-85-0]), tris [4- (2,3-epoxypropoxy) phenyl] methane isomers) CAS-No. [66072-39-7]), phenol based epoxy novolacs (CAS # [9003-35-4]) and cresol based epoxy novolacs (CAS # [37382-79-9]).

Aliphatic glycidyl ethers are, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane (CAS No. [ 27043-37-4]), diglycidyl ethers of polypropylene glycol (α, ω-bis (2,3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and of hydrogenated bisphenol A (2 , 2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. [13410-58-7]).

The epoxy (meth) acrylates and vinyl ethers preferably have a number average molecular weight M _{n of} from 200 to 20,000, particularly preferably from 200 to 10,000 g / mol and very particularly preferably from 250 to 3,000 g / mol; the content of (meth) acrylic or vinyl ether groups is preferably 1 to 5, more preferably 2 to 4 per 1000 g of epoxy (meth) acrylate or vinyl ether epoxide (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).

On average, carbonate (meth) acrylates preferably contain 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.

The number average molecular weight M _{n of} the carbonate (meth) acrylates is preferably less than 3000 g / mol, more preferably less than 1500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).

The carbonate (meth) acrylates are readily obtainable by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or transesterification with (meth) acrylic esters, as it eg in EP-A 92,269. They are also available by reacting phosgene, urea derivatives with polyvalent, e.g. dihydric alcohols.

Vinyl ether carbonates are also obtainable in an analogous manner by reacting a hydroxyalkyl vinyl ether with carbonic esters and optionally dihydric alcohols. Also conceivable are (meth) acrylates or vinyl ethers of polycarbonate polyols, such as the reaction product of one of said diols or polyols and a carbonic acid ester and a hydroxyl-containing (meth) acrylate or vinyl ether.

Suitable carbonic acid esters are e.g. Ethylene, 1, 2 or 1, 3-propylene carbonate, carbonic acid dimethyl, diethyl or dibutyl ester.

Suitable hydroxyl-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth ) acrylate, trimethylol propane mono- and di (meth) acrylate and pentaerythritol mono-, di- and tri (meth) acrylate.

Suitable hydroxyl-containing vinyl ethers are e.g. 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

Particularly preferred carbonate (meth) acrylates are those of the formula:

wherein R is H or CH3, X is a C2-C18 alkylene group and n is an integer from 1 to 5, preferably 1 to 3.

R is preferably H and X is preferably C 2 - to C 10 -alkylene, for example 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 4-butylene or 1, 6-hexylene, more preferably for C ₄ - to Cs-alkylene. Most preferably, X is Ce-alkylene.

The carbonate (meth) acrylates are preferably aliphatic carbonate (meth) acrylates.

Among the multifunctional polymerizable compound, urethane (meth) acrylates are particularly preferred.

Photoinitiators may be, for example, photoinitiators known to the person skilled in the art, for example those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London.

Consider, for example, Mono or bisacyl phosphine oxides, as described e.g. EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO from BASF AG) , Ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin® TPO L from BASF AG), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure® 819 from Ciba Spezialitätenchemie), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and their Derivatives or mixtures of these photoinitiators. Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, β-methylanthraquinone, tert-butylanthraquinone, anthraquinone-carboxylic acid ester, benzaldehyde, α-tetralone, 9-acetylphenanthrene,

2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1, 3,4-triacetylbenzene, thioxanthen-9-one, xanthen-9-one, 2,4- Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyltrioxanthone, 2,4-dichlorothioxanthone, benzoin, benzoin isobutyl ether, chloroxanthenone, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, Benzoin iso-propyl ether, 7-H-benzoin methyl ether, benz [de] anthracen-7-one, 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone Michler's ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1, 1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone dimethyl ketal, o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz [a] anthracen-7,12-dione, 2,2-diethoxyacetophenone, benzilke- tals, such as benzil dimethyl ketal, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2,3- butanedione.

Also suitable are non-yellowing or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.

Preferred among these photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol , 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone. As further paint typical additives, for example, antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.

It is also possible to add one or more thermally activatable initiators, for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl propar- mate, tert-butyl peroctoate or benzopinacol, and for example, those thermally activatable initiators having a half life of 80 ⁰ C of more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated Pinacol, the z. B. commercially available under the trade name ADDID 600 from Wacker or hydroxyl-containing amine-N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6- Tetramethylpiperidine-N-oxyl etc.

Further examples of suitable initiators are described in "Polymer Handbook" 2nd ed., Wiley & Sons, New York.

Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.

As chelating agents, e.g. Ethylenediaminetic acid and its salts and ß-di-ketones are used.

Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.

Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin® grades from Ciba Specialty Chemicals) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. For example, bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used. Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation. It is an advantage of the present invention that the coating compositions need not necessarily contain a solvent such as butyl acetate, ethyl acetate, methoxypropyl acetate, toluene, xylene, fluorinated aromatics, aliphatic and aromatic hydrocarbon mixtures.

According to the invention, therefore, preference is given to those coating compositions which are free from organic solvents.

In the so-called "prepolymer mixing process", first a prepolymer is prepared from components (a) to (g). This may, if necessary, be carried out in a water-miscible and at normal pressure below 100 ⁰ C boiling solvent, preferably acetone, ethyl methyl ketone or diethyl ketone. The prepolymer is first dispersed in water and optionally simultaneously and / or subsequently by reaction of the isocyanate groups crosslinked with amines carrying more than 2 isocyanate-reactive amino groups, or chain-extended with amines carrying the 2 isocyanate-reactive amino groups. Chain extension also occurs when no amine is added. In this case, excess isocyanate groups are hydrolyzed to amine groups, which react with remaining isocyanate groups of the prepolymers with chain extension.

The average particle size (z average), measured by dynamic light scattering with the Malvern® Autosizer 2 C, the dispersions according to the invention is not essential to the invention and is generally <1000 nm, preferably <500 nm, more preferably <200 nm and most preferably between 20 and under 200 nm.

The dispersions generally have a solids content of 10 to 75, preferably from 20 to 65 wt .-% and a viscosity of 10 to 500 m Pas (measured at a temperature of 20 ⁰ C and a shear rate of 250 S " ¹ .

For some applications it may be useful to adjust the dispersions to another, preferably a lower, solids content, for example by dilution.

The coating of the substrates with the coating compositions of the invention is carried out by customary methods known to the person skilled in the art. coating composition according to the invention or a paint formulation containing this, applied to the substrate to be coated in the desired thickness and optionally dried. If desired, this process can be repeated one or more times. The application to the substrate can in a known manner, for. Example by spraying, filling, doctoring, brushing, rolling, rolling, pouring, lamination, injection molding or coextrusion. The application of the coating composition can also be carried out electrostatically in the form of powder (powder coatings). The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

In addition, a process for coating substrates is disclosed, in which the coating composition according to the invention or a coating formulation containing it, optionally mixed with further typical coatings additives and thermally, chemically or radiation-curable resins, applied to the substrate and optionally dried, with electron beams or UV exposure under oxygen-containing atmosphere or preferably under inert gas hardens, optionally at temperatures up to the height of the drying temperature and then at temperatures up to 160 ⁰ C, preferably between 60 and 160 ⁰ C, more preferably between 100 and 160 ⁰ C, thermally treated.

The radiation curing is carried out with high-energy light, for example UV light or electron beams. The radiation curing can be carried out at higher temperatures. Preference is given to a temperature above the T _{9 of} the radiation-curable binder.

Radiation curing here means the free radical polymerization of polymerizable compounds due to electromagnetic and / or corpuscular radiation, preferably UV light in the wavelength range of λ = 200 to 700 nm and / or electron radiation in the range of 150 to 300 keV and more preferably with a radiation dose of at least 80, preferably 80 to 3000 mJ / cm ² .

In addition to radiation curing, other curing mechanisms may be involved, for example thermal, moisture, chemical and / or oxidative curing.

The coating compositions can be prepared by a variety of spraying methods, such as air pressure, airless or electrostatic spraying using single- or two-component spray systems, but also by spraying, filling, doctoring, brushing, rolling, rolling, casting, lamination, back molding or Coextrusion be applied once or several times. The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

The drying and curing of the coatings is generally carried out under normal temperature conditions, ie without heating the coating. However, the mixtures according to the invention can also be used to produce coatings which, after application at elevated temperature, eg at 40-250 ⁰ C, preferably 40-150 ⁰ C and in particular at 40 to 100 ⁰ C dried and cured. This is limited by the thermal stability of the substrate.

Furthermore, a process for coating substrates is disclosed, in which the inventive Beschichutngsmasse or coating formulations containing, optionally applied with thermally curable resins, applied to the substrate, dried, and then cured with electron beams or UV exposure under an oxygen-containing atmosphere or preferably under inert gas , optionally at temperatures up to the level of the drying temperature.

The process for coating substrates can also be carried out so that after application of the coating composition according to the invention or paint formulations is first irradiated with electron beams or UV exposure under oxygen or preferably under inert gas to achieve a pre-cure, then at temperatures up to 160 ⁰ C, preferably between 60 and 160 ⁰ C, thermally treated and then cured by electron beam or UV exposure under oxygen or preferably under inert gas.

Optionally, if several layers of the coating composition are applied one above the other, drying and / or radiation curing may take place after each coating operation.

Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulse emitters, metal halide lamps, electronic flash devices, whereby a radiation curing without photoinitiator is possible, or Excimerstrahler. The radiation is cured by exposure to high-energy radiation, ie UV radiation or daylight, preferably light in the wavelength range of λ = 200 to 700 nm, particularly preferably from λ = 200 to 500 nm and most preferably λ = 250 to 400 nm, or by Irradiation with high-energy electrons (electron radiation, 150 to 300 keV). The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or Excimer lamps. The radiation dose for UV curing, which is usually sufficient for crosslinking, is in the range from 80 to 3000 mJ / cm ² .

Of course, several radiation sources can be used for the curing, e.g. two to four.

These can also radiate in different wavelength ranges.

The drying and / or thermal treatment can also be carried out in addition to or instead of the thermal treatment by NIR radiation, where NIR radiation here denotes electromagnetic radiation in the wavelength range from 760 nm to 2.5 μm, preferably from 900 to 1500 nm is.

The irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, are performed. As inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases. Furthermore, the irradiation can be carried out by covering the coating mass with transparent media. Transparent media are z. As plastic films, glass or liquids, eg. B. water. Particular preference is given to irradiation in the manner described in DE-A1 199 57 900.

The polyurethanes of the invention have a high scratch resistance, which is also expressed in a high gloss after mechanical stress. If lower demands are placed on the scratch resistance, alternatively or additionally, the flexibility can be set by selecting the component (c) to the desired value.

Ppm and percentages used in this specification, unless otherwise indicated, are by weight percent and ppm.

The following examples are intended to illustrate but not to limit the invention.

Examples

example 1

200 parts of an isocyanurate of hexamethylene isocyanate (Basonat® HMOO, commercial product of BASF AG, Ludwigshafen), 15 parts of 1, 4-cyclohexanedimethanol, 40 parts of hydroxyethyl acrylate, 0.03 part of dibutyltin dilaurate, 0.35 part of hydroquinone mono- Methyl ether, 0.35 parts of o, o-di-t-butyl-cresol and 100 parts of methyl ethyl ketone were combined at room temperature and stirred. Within 30 minutes, the temperature rose to 60 ⁰ C. It was allowed to react with addition of a second portion of dibutyltin dilaurate for a further 3 hours at 60 ⁰ C, 8 parts of hydroxyacetic added and stirred again at 60 ⁰ C for 2 hours. Thereafter, it was treated with 1 1 parts of triethylamine and 75 parts of aminopropyltriethoxysilane was added dropwise and allowed to react at 60 ° C for an additional hour.

The reaction solution was dispersed with 700 parts of water and then distilled off within about 3 hours under vacuum, the solvent. The result is a stable dispersion with 40% solids content.

Example 2:

The procedure is as in Example 1, but instead of the Basonat HMOO Laromer® 9000 (commercial product of BASF AG, Ludwigshafen) is used, which is an allophanate-containing polyisocyanate from 1, 6-hexamethylene diisocyanate and 2-hydroxyethyl acrylate having an NCO content of 15.1 wt% (residual monomer content <0.5 wt%), a viscosity of 940 mPas at 23 ⁰ C, an average molecular weight of about 800 g / mol and a via ¹ H-NMR certain double bond density of 2 mol / kg.

Example 3:

The procedure was as in Example 1, but instead of the cyclohexanedimethanol now polytetrahydrofuran having an average molecular weight of 1000 was used.

Example 4:

300 parts of Laromer® 9000 (commercial product from BASF AG, Ludwigshafen as described in Example 2), 30 parts of 1,4-cyclohexanedimethanol, 0.03 part of dibutyltin dilaurate, 0.35 part of hydroquinone monomethyl ether, 0.35 part of o, o-di-t butyl-cresol and 100 parts of methyl ethyl ketone were combined at room temperature and stirred. Within 30 minutes, the temperature rose to 60 ⁰ C. It was allowed to react with addition of a second portion of dibutyltin dilaurate for a further 3 hours at 60 ⁰ C, 8 parts of hydroxyacetic added and stirred again at 60 ⁰ C for 2 hours. Thereafter, 11 parts of triethylamine were added and 145 parts of bis (trimethoxysilylpropyl) an-added dropwise and allowed to react at 60 ⁰ C for a further hour. The reaction solution was dispersed with 1000 parts of water and then distilled off within about 3 hours under vacuum, the solvent. The result is a stable dispersion with 34% solids content. The particle size is 200 nm.

example

The dispersion of Example 1 was admixed with 4% by weight Irgacure® 500 photoinitiator (50:50 mixture of (I-hydroxycyclohexyl) phenyl ketone and benzophenone from Ciba Spezialitatenchemie) and layer thicknesses of about 40 μm were applied to various substrates overnight flashed off at room temperature, then annealed at 60 ⁰ C for 15 min and irradiated on a conveyor belt at 10 m / min with 2 UV lamps (80W / cm).

Making movies

The dispersions were mixed with 4% by weight Irgacure® 500 (50:50 mixture of (I-hydroxycyclohexyl) phenyl ketone and benzophenone from Ciba Specialty Chemicals) and 1% Nacure® 2500 (King Industries) photoinitiator Irgacure® 500 and films were applied to various substrates overnight Ventilated room temperature, then annealed at 60 ⁰ C for 15 min and a) irradiated on a conveyor belt at 10 m / min with 2 UV lamps (80W / cm) or b) baked in a drying oven at 100 ⁰ C for 30 minutes. c) exposed as in a) and then baked as in b)

Both films are physically dry and through-hardened (fingernail test)

Application assessment:

The pendulum damping was determined in accordance with DIN 53157. High values mean high hardness.

The Erichsen depression was determined in accordance with DIN 53156. High values mean high flexibility.

Scratch resistance was evaluated in a scrub test using 10 scoops of Scotch Brite fabric weighing 750 g. The degree of scratching was determined by determining the gloss drop (before and after corresponding stress at an angle of 60 °).

It can be seen that with a combination of the different hardening mechanisms an improved hardness is achieved, while still satisfying flexibility.

Claims

claims

1. Water-dispersible polyurethanes containing as structural components

(a) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate,

(b) at least one compound (b) having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group, (c) optionally at least one compound having exactly two groups which are reactive toward isocyanate,

(d) optionally at least one compound having at least three isocyanate-reactive groups, (e) optionally at least one compound having exactly one isocyanate-reactive group,

(f) at least one compound containing at least one organosilicon

Group and at least one isocyanate-reactive group, and

(g) at least one compound having at least one isocyanate-reactive group and at least one dispersive-active group.

2. Water-dispersible polyurethanes according to claim 1, characterized in that it is the component (a) is a polyisocyanate which is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates.

3. Water-dispersible polyurethanes according to one of the preceding claims, characterized in that of the compound (b) with at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group at least 20 mol% of allophanate natgruppen are incorporated in the polyurethane according to the invention.

4. Water-dispersible polyurethanes according to one of the preceding claims, characterized in that it is in the compound (a) monomers or oligomers of aliphatic or cycloaliphatic diisocyanates.

5. Water-dispersible polyurethanes according to one of the preceding claims, characterized in that compound (b) has exactly one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group.

6. Water-dispersible polyurethanes according to one of the preceding claims, characterized in that compound (b) is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1, 6

Hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate and 4-hydroxybutyl vinyl ether, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, A-aminobutyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-

Thioethyl (meth) acrylate, 2-aminoethyl (meth) acrylamide, 2-aminopropyl (meth) acrylamide, 3-aminopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide and 3-hydroxypropyl ( meth) acrylamide.

7. Water-dispersible polyurethanes according to one of claims 1 to 4, characterized in that compound (b) is a mixture of at least two different compounds (b1) and (b2), wherein the compound (b1) is a Compound with exactly one isocyanate-reactive group and exactly one free-radically polymerizable unsaturated group and compound (b2) is a compound having exactly one isocyanate-reactive group and at least two radically polymerizable unsaturated groups.

8. water-dispersible polyurethanes according to any one of the preceding claims, characterized in that the organosilicon group is selected from the group consisting of siloxanes having at least one Si-O-C bond or poly-siloxanes having at least one Si-O-Si OC grouping, wherein the silicon atoms may be substituted with any optionally substituted alkyl, aryl or cycloalkyl groups.

9. Water-dispersible polyurethanes according to one of the preceding claims, characterized in that the organosilicon compound (f) is one of the formula

_H χ ⁱ _ -R ⁱ o _ [- SiR ⁱⁱ _{3 -v} (OR ¹² ) _v ] _w

is in which

X ^{1 is} oxygen (O), sulfur (S), imino (-NH-) or substituted

Imino (-NR ⁵ -) stands, R ^{10 is} a (w + 1) -binding organic radical,

R ¹¹ and R ^{12 are} independently of each other optionally substituted alkyl,

Cycloalkyl or aryl, v is a positive integer from 1 to 3 and w is a positive integer from 1 to 5

stands.

10. Water-dispersible polyurethanes according to one of the preceding claims, characterized in that compound (f) is selected from among

A group consisting of N-cyclohexylaminomethylmethyldiethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, N-trimethoxysilylmethyl-O-methyl-carbamate, 1- [3- (trimethoxysilyl) propyl] urea, 3- (diethoxymethylsilyl) propylamine, N-dimethoxy (methyl) silylmethyl O-methyl carbamate, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-

Cyclohexyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, (1-socyanatomethyl) methyldimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Triethoxysilyl) propyl succinic anhydride, bis [3-trimethoxysilyl) propyl] amine and bis [(trimethoxysilyl) propyl] amine.

1 1. Water-dispersible polyurethanes according to one of the preceding claims, characterized in that it is the compound (g) is a compound (gI) with anionic or in an anionic group convertible

Groups acts.

12. Water-dispersible polyurethanes according to one of claims 1 to 10, characterized in that the compound (g) is a compound fertil with nonionic groups (g3).

13. Coating composition containing

at least one water-dispersible polyurethane according to any one of claims 1 to 12, optionally at least one compound having one or more than one free-radically polymerizable double bond,

optionally at least one photoinitiator,

- optionally further paint typical additives and

- Water.

14. Use of coating compositions according to claim 13 for coating substrates selected from the group consisting of wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramic, mineral Building materials, cement blocks, fiber cement boards, metals and coated metals.

15. Use of coating compositions according to claim 13 as primer, fillers, pigmented topcoats and clearcoats in the field of industrial,

Wood, car, OEM paintwork or decoration.

16. A substrate according to claim 14 coated with a coating composition according to claim 13.

17. A vehicle or aircraft coated with a coating composition according to claim 13.