DE102005008932A1 - Radiation-hardenable aqueous polyurethane dispersion, useful as coating mass, comprises: compounds e.g. with free isocyanides-, reactive isocyanides- and acid groups; basic compounds; polyisocyanates; additives; water; and di-/polyamines - Google Patents

Abstract

Radiation-hardenable aqueous polyurethane dispersion (A) comprises: a compound with two free isocyanate-, allophanate (bonded) group, radical polymerized C=C double bond; compound with isocyanate reactive group and radical polymerized C=C double bond; optionally compound with at least two isocyanate reactive groups; compound with isocyanate reactive- and acid group; basic compound; optionally a different compound that has isocyanate reactive group; water; optionally: different polyisocyanate; additives and di- and/or polyamine (where (A) does not contain thermal initiators). Radiation-hardenable aqueous polyurethane dispersion (A) comprises: (a) at least one compound with at least two free isocyanate group, at least one (bound) allophanate group, and radical polymerized C=C double bond, which is directly bounded to double bond of a carbonyl group or oxygen atom in bound ether group; (b) at least one compound with at least one isocyanate reactive group and at least one radical polymerized C=C double bond; (c) optionally at least one compound with at least two isocyanate reactive group of hydroxyl-, mercapto-, primary- and/or secondary amino groups; (d) at least one compound with at least one isocyanate reactive group and at least one acid group; (e) at least one basic compound of partially neutralized acid groups of (d); (f) optionally compound of (b), (d) and/or (e) that has only one isocyanate reactive group; (g) optionally at least one different polyisocyanate of (a); (h) optionally further additives such as reactive solvents, photo initiators or lacquer additives; (i) water; and (j) optionally at least one di- and/or polyamine (where (A) does not contain thermal initiators). Independent claims are included for: (1) a coated substrate comprising (A); and (2) a method for coating substrates comprising applying (A) on the substrate, drying and radiation hardening.

Description

The The present invention relates to UV radiation curable polyurethane dispersions, a process for their preparation and their use.

Radiation-curable polyurethane dispersions are z. B. from DE-A-44 34 554 and are made of polyisocyanates, hydroxyl-containing polyesters, compounds with one towards isocyanates reactive group and an acid group and connections with one opposite Isocyanate-reactive group and C = C double bonds produced. However, the products still leave something to be desired with regard to their processability.

The WO 01/23453 describes with UV radiation and thermally curable polyurethane dispersions based on aliphatic polyisocyanates, which also include may be to polyisocyanates containing allophanate groups. These Dispersions necessarily contain an isocyanate blocking agent capped isocyanate groups and as a diol component with one Molecular weight of less than 500 g / mol.

The DE-A-198 60 041 describes reaction products of a) polyisocyanates and b) low molecular weight hydroxyl compounds having C = C double bonds such as hydroxyalkyl (meth) acrylates or hydroxyalkyl vinyl ethers, which mostly Allophanates of polyisocyanates with the unsaturated alcohols represent. The have low molecular weight and low viscosity reaction products in the molecule a high content of polymerizable C = C double bonds and can be used both with UV rays and with the participation of Isocyanate groups, e.g. B. by the action of water vapor, ammonia or amines, harden. An application in the form of aqueous Dispersions are not described.

The EP 392352 describes aqueous dispersions of crosslinkable by the action of high-energy radiation polyurethanes. They are composed of polyisocyanates, polyol, polyamine, aminoalcohol, polyetherol and hydroxyalkyl acrylate. They are used to coat leather. The coatings prepared from the described polyurethane acrylates have a very low hardness.

allophanate Polyisocyanates are used as starting compounds only in one broad list equivalent among other polyisocyanates listed.

Hardened by high-energy radiation, weather-resistant polyurethanes claimed EP 1118627 , The coatings are prepared by drying films of a polyurethane dispersion prepared from polyisocyanates, cycloaliphatic diols and / or diamines, NCO-reactive compounds having at least one unsaturated group and a dispersing-active group. The coatings produced in this way are weather-stable. The disadvantage was the relatively low scratch resistance.

allophanate Polyisocyanates are used as starting compounds only in one broad list equivalent among other polyisocyanates listed.

Among those in the examples of EP 1118627 Explicitly disclosed reaction conditions no allophanate groups are formed.

EP 574775 describes reactive, water-emulsifiable binders and their use for the production of paints. The binders are based on polyurethane dispersions consisting of an acrylate-containing prepolymer, z. Example, a polyester acrylate, one or more polyisocyanates and a water-emulsifiable polyester. The described coatings show only a low pendulum hardness of less than 100 s, which would lead to damage of the coating under mechanical stress.

allophanate Polyisocyanates are used as starting compounds only in one broad list equivalent among other polyisocyanates listed.

Among those in the examples of EP 574775 In the reaction conditions disclosed, no allophanate groups are formed.

Radiation curable, aqueous dispersions are also in EP 753531 described. They are prepared from a polyester acrylate having an OH number of 40 to 120 mg KOH / g, a polyester or poly etherol, an emulsifiable group, di- or polyisocyanates. Optionally, salt formation, dispersion and chain extension with diamines may be performed. The ethylenically unsaturated group is introduced exclusively via a hydroxyl-containing prepolymer. Thus, the possibilities are limited to increase the double bond density.

allophanate Polyisocyanates are used as starting compounds only in one broad list equivalent among other polyisocyanates listed.

Among those in the examples of EP 753531 also disclosed allophanate groups are not formed.

In DE 10031258 describes curable aqueous polyurethane dispersions consisting of a Hydroxyethylacrylatallophanat, hydroxyalkyl acrylate a polyol, polyamine or polythiol, at least one acid group and a basic compounds and a thermal initiator. Furthermore, the described polyurethanes still necessarily contain a thermal initiator. This reduces the thermal resistance. The described concentration of acid groups necessary for the dispersion in water is not sufficient to obtain storage-stable dispersions over several months. In addition, the hardness of the coatings obtained with these dispersions should be improved.

Of the present invention is based on the object with UV radiation curable aqueous Polyurethane dispersions available to deliver. These are coatings with good performance properties, especially with good chemical resistance and / or good mechanical properties Properties result, in particular a high hardness and at the same time high elasticity the coatings, a high scratch resistance and also a good storage stability exhibit.

• a) wenigstens einer Verbindung mit mindestens zwei freien Isocyanatgruppen, mindestens einer Allophanatgruppe und mindestens einer über die Allophanatgruppe gebundenen, radikalisch polymerisierbaren C=C-Doppelbindung, die direkt an die Doppelbindung eine Carbonylgruppe oder ein Sauerstoffatom in Etherfunktion gebunden ist,
• b) wenigstens einer Verbindung mit mindestens einer gegenüber Isocyanatgruppen reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren C=C-Doppelbindung,
• c) gegebenenfalls wenigstens einer Verbindung mit mindestens zwei gegenüber Isocyanatgruppen reaktiven Gruppen, die ausgewählt sind unter Hydroxyl-, Mercapto-, primären und/oder sekundären Aminogruppen,
• d) wenigstens einer Verbindung mit mindestens einer gegenüber Isocyanatgruppen reaktiven Gruppe und mindestens einer Säuregruppe,
• e) mindestens einer basischen Verbindung für eine Neutralisation oder Teilneutralisation der Säuregruppen der Verbindungen d),
• f) gegebenenfalls wenigstens einer von b), d) und e) verschiedenen Verbindung, die nur eine gegenüber Isocyanatgruppen reaktive Gruppe aufweist,
• g) gegebenenfalls wenigstens einem von a) verschiedenen Polyisocyanat,
• h) in Abwesenheit eines thermischen Initiators,
• i) gegebenenfalls weiteren Zusatzstoffen, die ausgewählt sind unter Reaktivverdünnern, Photoinitiatoren und üblichen Lackzusatzstoffen,
• k) Wasser sowie
• l) gegebenenfalls mindestens ein Di- und/oder Polyamin.

The object is achieved by radiation-curable aqueous polyurethane dispersions

• a) at least one compound having at least two free isocyanate groups, at least one allophanate group and at least one free-radically polymerizable C =C double bond bound via the allophanate group, which is bonded directly to the double bond to a carbonyl group or an oxygen atom in ether function,
• b) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable C =C double bond,
• c) optionally at least one compound having at least two isocyanate-reactive groups which are selected from hydroxyl, mercapto, primary and / or secondary amino groups,
• d) at least one compound having at least one isocyanate-reactive group and at least one acid group,
• e) at least one basic compound for a neutralization or partial neutralization of the acid groups of the compounds d),
• f) optionally at least one compound other than b), d) and e) which has only one isocyanate-reactive group,
• g) optionally at least one of a) different polyisocyanate,
• h) in the absence of a thermal initiator,
• i) optionally further additives which are selected from reactive diluents, photoinitiators and conventional paint additives,
• k) water as well
• l) optionally at least one di- and / or polyamine.

In a preferred embodiment have the inventively prepared Polyurethanes, ie the reaction products of the synthesis components a) to d) and optionally f) and g) a double bond density of at least 1.3 mol / kg, preferably at least 1.8, more preferably at least 2.0.

The dispersions according to the invention do not use compounds containing isocyanate groups in which the isocyanate groups have been partially or completely reacted with so-called blocking agents. By blocking agents are meant compounds which convert isocyanate groups into blocked (capped or protected) isocyanate groups, which then do not exhibit the usual reactions of a free isocyanate group below the so-called deblocking temperature. Such compounds not used according to the invention with blocked isocyanate groups usually come in Dual-cure coating compositions that are finally cured via isocyanate group cure. After preparation, the polyurethane dispersions according to the invention preferably have substantially no free isocyanate groups, ie generally less than 1% by weight of NCO, preferably less than 0.75, more preferably less than 0.66, and most preferably less than 0 , 3 wt .-% NCO (calculated with a molecular weight of 42 g / mol).

Component a)

Component a) comprises at least one compound having at least two free isocyanate groups, at least one allophanate group and at least one free-radically polymerizable C =C double bond bound via the allophanate group, which bonds directly to the double bond a carbonyl group or an oxygen atom in ether function is
The component a) used according to the invention contains allophanate groups, the content of allophanate groups (calculated as C ₂ N ₂ HO ₃ = 101 g / mol) is preferably from 1 to 35% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 35% by weight. The polyurethanes of the invention of the synthesis components a) to d) and optionally f) and g) contain 1 to 30 wt .-%, preferably from 1 to 25 wt .-%, particularly preferably from 2 to 20 wt .-% allophanate. Furthermore, the component a) used according to the invention contains less than 5% by weight of uretdione.

The contained according to the invention Compounds of component a) are preferably substantially free of other isocyanate group-forming groups, especially Isocyanurate, biuret, uretdione, iminooxadiazinetrione and / or Carbodiimide.

steht, wobei R³ für einen von einem Alkohol A durch Abstraktion des H-Atoms von der alkoholischen Hydroxylgruppe abgeleiteten Rest steht, wobei der Alkohol A zusätzlich wenigstens eine radikalisch polymerisierbare C=C-Doppelbindung aufweist und wobei direkt an die Doppelbindung eine Carbonylgruppe oder ein Sauerstoffatom in Etherbindung gebunden ist, bevorzugt über eine Carbonylgruppe.Preferably, component a) is selected from compounds of general formula I. OCN-R ¹ ( R ² -C (O) -R ² -R ¹ ) NCO wherein
n is an integer from 1 to 10,
R ^{1 is} a divalent aliphatic or alicyclic C ₂ to C ₂₀ , preferably C ₄ to C ₁₂ , particularly preferably C ₆ to C ₁₀ hydrocarbon unit or an aromatic C ₆ to C ₂₀ , preferably C ₆ to C ₁₂ hydrocarbon unit,
R ² in each repeating unit for -NH- or for

wherein R ^{3 is} a radical derived from an alcohol A by abstraction of the H atom from the alcoholic hydroxyl group, wherein the alcohol A additionally has at least one free-radically polymerizable C = C double bond and wherein directly to the double bond, a carbonyl group or a Oxygen atom is bonded in ether bond, preferably via a carbonyl group.

The radicals R ¹ are preferably those which are derived by abstraction of the isocyanate group from customary aliphatic, cycloaliphatic or aromatic polyisocyanates. The diisocyanates are preferably aliphatic isocyanates having 4 to 20 carbon atoms. Examples of conventional diisocyanates are aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2-methyl-1,5-diisocyanato-pentane, 1,8-octamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, tetradecamethylene diisocyanate, 2,2,4- and 2,4,4-trimethylhexane diisocyanate, derivatives of lysine diisocyanate, tetramethylxylylene diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4 ' Di (isocyanatocyclohexyl) methane, isophorone diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, 2,4- and 2,6-diioscyanato-1-methylcyclohexane, and aromatic diisocyanates such as 2,4- or 2 , 6-tolylene diisocyanate, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 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 diisocyanate, 3-methyldiphenylmethane-4,4'-diisocyanate, and Diphenylether-4,4'-diisocyanate. There may be mixtures of said diisocyanates.

Prefers are 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Isophorone diisocyanate, tetramethylxylylene diisocyanate and di (isocyanatocyclohexyl) methane.

It can There are also mixtures of the diisocyanates mentioned.

2,2,4 and 2,4,4-trimethylhexane diisocyanate are, for example, as a mixture in proportion 1.5: 1 to 1: 1.5, preferably 1.2: 1-1: 1.2, more preferably 1.1: 1 to 1: 1.1 and most preferably 1: 1.

isophorone is present, for example, as a mixture, namely the cis and trans isomers, in which Usually in proportion from about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75:25 and more preferably in proportion from about 75:25.

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

aromatic Isocyanates are those containing at least one aromatic ring system contain.

cycloaliphatic Isocyanates are those which contain at least one cycloaliphatic ring system contain.

aliphatic Isocyanates are those that are exclusively straight or branched Contain chains, ie acyclic compounds.

For the alcohols A, from which the radical R ^{3 is} derived, it is z. Example, to esters of α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid (hereinafter "(meth) acrylic acid"), crotonic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid or vinylacetic acid, preferably acrylic acid and methacrylic acid and more preferably acrylic acid and polyols having preferably 2 to 20 C atoms and at least 2 hydroxyl groups, such as 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, hydroxypivalic acid neopentyl glycol ester, 1,2-, 1,3- or 1,4-butanediol, 1,6-hexanediol, 1,10 -Dekandiol, 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-cyclohexa diethanol, 1,2-, 1,3- or 1,4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (Lyxit ), Xylitol, dulcitol (galactitol), maltitol or isomalt, with the proviso that the ester has at least one isocyanate-reactive OH group. Furthermore, the radicals R ^{3 can} also from the amides of (meth) acrylic acid with amino alcohols z. B. 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol and the vinyl ethers of the aforementioned polyols derived, if they still have a free OH group.

Farther are also unsaturated Polyetherols, polyesterols or polyacrylate polyols having a mean OH functionality of 2 to 10 suitable as reactive components.

The radicals R ^{3 are} preferably derived from alcohols such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di ( meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol di- and tri (meth) acrylate. Most preferably, the alcohol A is selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl (meth) acrylate. Examples of amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, 5-hydroxy-3-oxo-pentyl (meth) acrylamide, N-hydroxyalkylcrotonamides such as N Hydroxymethylcrotonamide or N-hydroxyalkylmaleimides such as N-hydroxyethylmaleimide.

Component b)

component b) contains at least one compound having at least one opposite isocyanate groups reactive group and at least one free-radically polymerizable C = C double bond.

The Compounds of component b) have at least one radical polymerizable C = C double bond and at least one other across from Isocyanate groups reactive group.

preferred Compounds of components b) are z. As the esters two or polyhydric alcohols with α, β-ethylenic unsaturated Mono- and / or dicarboxylic acids and their anhydrides. As α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their anhydrides can z. For example, acrylic acid, Methacrylic acid, fumaric acid, maleic acid, maleic anhydride, crotonic, itaconic, etc. are used. Preference is given to acrylic acid and methacrylic acid, especially preferably acrylic acid used.

suitable Alcohols are z. Diols such as 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, hydroxypivalic 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, tricyclodecanedimethanol

suitable Triols and polyols have z. B. 3 to 25, preferably 3 to 18 carbon atoms on. These include z. B. trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, Glycerine, ditrimethylolpropane, dipentaerythritol, ditrimethylolpropane, Sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (Lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt.

Preferably the compounds of component b) are selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, Trimethylolpropane mono- or diacrylate, pentaerythritol di- or triacrylate and mixtures thereof.

If desired, can these compounds also by reaction with a suitable chain extender, such as As a polyfunctional isocyanate or a polyfunctional carboxylic acid chain extended be.

Prefers the compounds (b) are different from those of Alcohol A described above.

worin
R⁷ und R⁸ unabhängig voneinander Wasserstoff oder gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C₁-C₁₈-Alkyl,
k, l, m, q unabhängig voneinander je für eine ganze Zahl von 1 bis 15, bevorzugt 1 bis 10 und besonders bevorzugt 1 bis 7 steht und
jedes X_i für i = 1 bis k, 1 bis l, 1 bis m und 1 bis q unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH₂-CH₂-O-, -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CHVin-O-, -CHVin-CH₂-O-, -CH₂-CHPh-O- und -CHPh-CH₂-O-, bevorzugt aus der Gruppe -CH₂-CH₂-O-, -CH₂-CH(CH₃)-O- und -CH(CH₃)-CH₂-O-, und besonders bevorzugt -CH₂-CH₂-O-,
worin Ph für Phenyl und Vin für Vinyl steht.Preferred compounds b) are esters of the abovementioned α, β-unsaturated acids, preferably (meth) acrylates, more preferably acrylates of compounds of the formulas (Ia) to (Ic),

wherein
R ⁷ and R ⁸ independently of one another denote hydrogen or C ₁ -C ₁₈ -alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
k, l, m, q independently of one another are each an integer from 1 to 15, preferably 1 to 10 and particularly preferably 1 to 7, and
each X _i for i = 1 to k, 1 to 1, 1 to m and 1 to q may independently be selected from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O -, -CH (CH ₃ ) -CH ₂ -O-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) 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 (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O-,
where Ph is phenyl and Vin is vinyl.

Therein C ₁ -C ₁₈ -alkyl 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-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl Methyl, ethyl or n-propyl, most preferably methyl or ethyl.

Prefers These are (meth) acrylates of one to thirty times and more preferably from three to twenty times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol.

suitable Compounds b) are furthermore the esters and amides of aminoalcohols with the aforementioned α, β-ethylenic unsaturated Mono- and / or dicarboxylic acids, Hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether, etc.

Further suitable compounds b) are at least one hydroxy group-bearing Epoxy (meth) acrylates, urethane (meth) acrylates, polyether (meth) acrylates, Polyester (meth) acrylates or polycarbonate (meth) acrylates

Urethane (meth) acrylates are z. B. available by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers and optionally chain extenders such as diols, Polyols, diamines, polyamines or dithiols or polythiols.

• (1) mindestens ein organisches aliphatisches, aromatisches oder cycloaliphatisches Di- oder Polyisocyanat, wie beispielsweise die oben unter a) aufgeführten
• (2) mindestens eine Verbindung mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren ungesättigten Gruppe, wie beispielsweise die oben angeführten Alkohole A oder die weiter oben unter b) aufgeführten, und
• (3) gegebenenfalls mindestens eine Verbindung mit mindestens zwei gegenüber Isocyanat reaktiven Gruppen wie beispielsweise die unten unter c) aufgeführten.

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

• (1) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate, such as those listed above under a)
• (2) at least one compound having at least one isocyanate-reactive group and at least one radically polymerizable unsaturated group, such as the above-mentioned alcohols A or those listed above under b), and
• (3) optionally at least one compound having at least two isocyanate-reactive groups such as those listed below under c).

The Components (1), (2) and (3) can be the same as above for the polyurethanes according to the invention described.

The urethane (meth) acrylates preferably have a number average molecular weight M _n of 500 to 20,000, in particular of 500 to 10,000, more preferably 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, more preferably from 2 to 4 moles of (meth) acrylic groups per 1000 g urethane (meth) acrylate.

Especially preferred urethane (meth) acrylates have an average OH functionality of 1.5 up to 4.5.

Epoxy (meth) acrylates are preferably available by reaction of epoxides with (meth) acrylic acid. As epoxides into consideration For example, epoxidized olefins, aromatic glycidyl ethers or aliphatic ones Glycidyl ethers, preferably those of aromatic or aliphatic Glycidyl ethers.

epoxidized Olefins can for example, be ethylene oxide, propylene oxide, iso-butylene oxide, 1-butene oxide, 2-butene oxide, vinyloxirane, styrene oxide or epichlorohydrin, preferred are ethylene oxide, propylene oxide, isobutylene oxide, vinyloxirane, Styrene oxide or epichlorohydrin, more preferably ethylene oxide, Propylene oxide or epichlorohydrin and most preferably ethylene oxide and epichlorohydrin.

aromatic Glycidyl ethers are z. Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, Bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, Alkylation products of phenol / dicyclopentadiene, e.g. B. 2,5-bis [(2,3-epoxypropoxy) 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 novolak (CAS no. [9003-35-4]) and cresol-based epoxy novolacs (CAS No. [37382-79-9]).

Prefers are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A diglycidyl ether is particularly preferred.

Examples of aliphatic glycidyl ethers are 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-epoxypropo xy) poly (oxypropylene) (CAS No. [16096-30-3]) and hydrogenated bisphenol A (2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. (13410 -58-7]).

Prefers are 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, Pentaerythritol tetraglycidyl ether and (2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane.

Especially preferred are the ones mentioned above aromatic glycidyl ether.

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).

preferred Epoxide (meth) acrylates have an OH number of 40 to 400 mg KOH / g on.

preferred Epoxide (meth) acrylates have an average OH functionality of 1.5 up to 4.5.

Especially preferred epoxide (meth) acrylates are those as known from processes can be obtained according to EP-A-54 105, DE-A 33 16 593, EP-A 680 985 and EP-A-279 303, in which in a first stage, a (meth) acrylic acid esters of (meth) acrylic acid and Hydroxy compounds is prepared and in a second stage with excess (meth) acrylic acid Epoxides is implemented.

Suitable hydroxy compounds are compounds having one or more hydroxyl groups. Mentioned are monoalcohols, z. B. C ₁ -C ₂₀ alkanols or alkoxylated alcohols having a remaining OH group, C ₂ -C ₈ alkylene diols, trimethylolpropane, glycerol or pentaerythritol, or z. B. with ethylene oxide and / or propylene oxide alkoxylated, hydroxy-containing compounds, for example, the above under a) or b) or the compounds mentioned under c) below.

preferred Hydroxy compounds are at least 2, in particular 2 to 6 free Containing hydroxy groups, saturated Polyesterols which optionally also contain ether groups can or polyetherols having at least 2, in particular 2 to 6 free Hydroxy groups.

The molecular weights M _{n of} the polyesterols or polyetherols are preferably between 100 and 4000 (M _n determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).

such hydroxy-containing polyesterols may, for. B. in the usual Manner by esterification of dicarboxylic acids or polycarboxylic acids with Diols or polyols are produced. The starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art.

Prefers can as dicarboxylic acids Succinic acid, glutaric, adipic acid, Sebacic acid, o-phthalic acid, whose Isomeric and hydrogenation products and esterifiable derivatives, such as Anhydrides, e.g. For example, maleic anhydride, or dialkyl esters of said acids are used. When polycarboxylic or their anhydrides are tri- or tetrasic acids such as trimellitic anhydride or benzene tetracarboxylic acid called.

When Diols are preferably ethylene glycol, 1,2-propylene glycol and -1.3, butanediol-1,4, hexanediol-1,6, neopentyl glycol, cyclohexanedimethanol and polyglycols of the ethylene glycol type with one molecular weight from 106 to 2000, propylene glycols having a molecular weight of 134 to 2000 or poly-THF with a molecular weight of 162 to 2000.

When Polyols are primarily trimethylolbutane, trimethylolpropane, Trimethylolethane, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, Pentaerythritol, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, glycerol, 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 sugar alcohols such. Sorbitol, mannitol, diglycerol, threitol, Erythritol, adonite (ribite), arabitol (lyxite), xylitol, dulcite (galactitol), To call maltitol or isomalt.

Also suitable as diols or polyols are oxalkylated (for example with ethylene oxide and / or propylene oxide) diols or polyols, in particular with an alkoxylation degree of 0 to 20, preferably 0-15 preferably 0-10 and most preferably 1-5, based on the respective hydroxy groups of the diol or polyol.

Under these are preferably each alkoxylated exclusively with ethylene oxide Products.

To include the usable polyesterols also polycaprolactone diols and triols, their preparation to the expert is also known.

When hydroxy-containing polyetherols come z. For example, such which by known methods by reaction of two and / or polyhydric alcohols with varying amounts of ethylene oxide and / or Propylene oxide can be obtained. Likewise are also polymerization of tetrahydrofuran or butylene oxide or iso-butylene oxide.

preferred hydroxyl-containing polyethers are alkoxylation products of above-mentioned diols or polyols, in particular having a degree of alkoxylation from 0 to 20, more preferably 1 to 15, most preferably 1-7 and especially 1-5, based on the respective hydroxyl groups of the diol or polyol, however, a total of at least 2 alkoxy groups present in the polyether are.

at the esterification of (meth) acrylic acid in the case of the hydroxyl-containing polyester, it is z. Belly possible, the (meth) acrylic acid together with starting materials of the hydroxyl-containing polyester, for. B. dicarboxylic acids or to submit their anhydrides and diols or polyols and the starting materials together with the (meth) acrylic acid to implement in one step.

to Esterification of (meth) acrylic acid with the hydroxy compound are the methods known in the art suitable.

at the esterification of (meth) acrylic acid with the hydroxy compound are preferably 0.1 to 1.5, especially preferably 0.5 to 1.4 and most preferably 0.7 to 1.3 equivalents (Meth) acrylic acid, based on 1 hydroxy equivalent the hydroxy compounds used. In the case mentioned above, that of the starting materials, z. As the hydroxy-containing polyester, in the esterification is assumed, the equivalents of (meth) acrylic acid on theoretically after reaction of the starting materials, for. B. Reaction of dicarboxylic acids with diols or polyols, remaining hydroxy equivalent.

The Reaction of (meth) acrylic acid with the hydroxy compounds may, for. In the presence of an acidic Esterification catalyst, such as. As sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic or acid ion exchangers, as well as in the presence of a hydrocarbon, which forms an azeotropic mixture with water, in particular up to a conversion of, for example, at least 80%, preferably at least 85, most preferably 90 to 98% and in particular 90-95%, the Hydroxy groups of the hydroxy compound, for example at 60 bis 140 ° C, to be performed. The reaction water formed is removed azeotropically. suitable Hydrocarbons are aliphatic and aromatic, z. B. alkanes and cycloalkanes such as pentane, n-hexane, n-heptane, methylcyclohexane and cyclohexane, aromatics such as benzene, toluene and the xylene isomers, and so-called special gasoline, which have boiling limits between 70 and 140 ° C.

to Prevention of premature polymerization is associated with the reaction (Meth) acrylic acid expediently in the presence of small amounts of inhibitors. there it is the usual Compounds used to prevent thermal polymerization z. B. of the type of hydroquinone, the hydroquinone monoalkyl ether, especially Hydroquinone monomethyl ether, 2,6-di-t-butylphenol, N-nitrosoamine of Phenothiazines, the phophoretic ester or hypophosphorous acid. They are generally used in amounts of 0.001 to 2.0%, preferably in amounts of 0.005 to 0.5%, based on the reaction in the first Step used.

To the esterification can be the solvent, z. As the hydrocarbon, from the reaction mixture by distillation, optionally under reduced pressure. The esterification catalyst can be neutralized in a suitable manner, for. B. by the addition of tertiary Amines or alkali hydroxides. Also, excess (meth) acrylic acid can partly z. B. be removed by distillation in vacuo.

The Reaction product of the first stage indicates the beginning of the reaction in the second stage generally one more acid number (SZ) above 20, preferably from 30 to 300, more preferably from 35 to 250 mg KOH / g substance (without solvent) on.

In the second stage becomes the reaction product obtained in the first stage reacted with one or more, preferably an epoxide compound. Epoxy compounds are those with at least one, preferably with at least two, preferably two or three epoxide groups in the molecule.

In consideration come z. Epoxidized olefins, glycidyl esters (e.g., glycidyl (meth) acrylate) of saturated or unsaturated carboxylic acids or glycidyl ethers of aliphatic or aromatic polyols. Such products are commercially available in large numbers. Particularly preferred are polyglycidyl compounds of the bisphenol A, F or B type and glycidyl ethers of polyfunctional alcohols, e.g. As the butanediol, 1,6-hexanediol, glycerol and pentaerythritol. Examples of such polyepoxide compounds are Epikote ^® 812 (epoxide value: about 0.67 mol / 100g) and Epikote ^® 828 (epoxide value: about 0.53 mol / 100g), Epikote ^® 1001, Epikote ^® 1007, and Epikote ^® 162 (epoxide : about 0.61 mol / 100 g) from resolution, Rütapox ^® 0162 (epoxide value: about 0.58 mol / 100g), Rütapox ^® 0164 (epoxide value: about 0.53 mol / 100g) and Rütapox ^® 0165 ( epoxide value: about 0.48 mol / 100g) Bakelite AG, Araldite ^® DY 0397 (epoxide value: about 0.83 mol / 100g) Huntsman.

The Epoxy compounds become the reaction product obtained in the first stage generally in amounts of more than 10% by weight, preferably 15 to 95 wt .-% and particularly preferably 15 to 70 wt .-%, based on the first stage reaction mixture (without solvent) was added. All most preferably, the epoxide compounds are approximately equimolar Quantities, based on the remaining acid equivalents in the reaction product the first stage, used.

at the reaction with epoxide compounds in the second stage is used excessively or unreacted acid, in particular (meth) acrylic acid, but also z. B. still present in the mixture as starting material Hydroxy compounds, dicarboxylic acid or resulting half esters of dicarboxylic acids with one remaining acid group bound as an epoxy ester.

The reaction with epoxide compounds can be accelerated by adding catalysts. Suitable catalysts are, for. Tertiary alkylamines, tertiary alkylaminoalcohols, tetraalkylammonium salts as described in U.S. Pat EP 686621 A1 , P. 4, lines 9-41.

Carbonate (meth) acrylates contain on average preferably 1 to 5, in particular 2 to 4, more preferably 2 to 3 (meth) acrylic groups, and more 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 easily obtainable by Transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, z. B. hexanediol) and subsequent esterification the free OH groups with (meth) acrylic acid or transesterification with (Meth) acrylic acid esters, such as it z. B. in EP-A 92 269 is described. They are also available through Implementation of phosgene, urea derivatives with polyvalent, z. B. dihydric alcohols.

In In an analogous manner, vinyl ether carbonates are also obtainable by reacting a hydroxyalkyl vinyl ether with Kohlensäureestern and optionally converts dihydric alcohols.

Conceivable are also (meth) acrylates or vinyl ethers of polycarbonate polyols, as the reaction product of one of said di- or polyols and a carbonic acid ester and a hydroxyl-containing (meth) acrylate or vinyl ether.

suitable carbonate ester are z. 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, Trimethylolpropane mono- and di (meth) acrylate as well as pentaerythritol mono-, di- and tri (meth) acrylate.

suitable hydroxyl-containing vinyl ethers are z. B. 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

worin R für N oder CH₃, X für eine C₂-C₁₈ Alkylengruppe und n für eine ganze Zahl von 1 bis 5, vorzugsweise 1 bis 3 steht.Particularly preferred carbonate (meth) acrylates are those of the formula:

wherein R is N or CH ₃ , X is a C ₂ -C ₁₈ alkylene group and n is an integer from 1 to 5, preferably 1 to 3.

R is preferably N and X is preferably C ₂ -C ₁₀ -alkylene, for example 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene or 1,6-hexylene, particularly preferred for C ₄ - to C ₈ -alkylene. Most preferably, X is C ₆ alkylene.

Preferably If the carbonate (meth) acrylates are aliphatic Carbonate (meth) acrylates.

To counting also usual, polycarbonates having terminal hydroxyl groups known to the person skilled in the art z. B. by reacting the aforementioned diols with phosgene or Carbonic acid diesters are available.

Polyether (meth) acrylates are, for example, mono- (meth) acrylates of poly-THF having a molecular weight between 162 and 2000, poly-1,3-propanediol of one molecular weight between 134 and 2000 or polyethylene glycol of one molecular weight between 238 and 2000.

Component c)

at the optional component c) is at least one Compound having at least two isocyanate-reactive Groups selected are hydroxyl, mercapto, primary and / or secondary amino groups.

suitable Compounds c) are both low molecular weight alcohols c1) and polymeric polyols c2), preferably compounds c2).

low molecular weight Alcohols c1) have a molecular weight of at most 500 g / mol. Especially preferred are alcohols having 2 to 20 carbon atoms and 2 to 6 hydroxyl groups such as. As the aforementioned glycols. Prefers are in particular hydrolysis-stable short-chain diols with 4 to 20, preferably 6 to 12 carbon atoms. These preferably include 1,1-, 1,2-, 1,3- or 1,4-di (hydroxymethyl) cyclohexane, bis (hydroxycyclohexyl) propane, Tetramethylcyclobutanediol, cyclooctanediol or norbornanediol. Especially preferred are aliphatic hydrocarbon diols, such as the isomers Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, Used decandiols, undecanediols and dodecanediols. Especially 1,2-, 1,3- or 1,4-butanediol, 1,4-pentanediol, 1,5-pentanediol are preferred, 1,6-hexanediol, 2,5-hexanediol, dihydroxymethylcyclohexane, bis-hydroxycyclohexyl-propane, Etc.

Suitable compounds c2) are also polymeric polyols. Preferably, the number average molecular weight M _{n of} these polymers is in a range of about 500 to 100,000, more preferably 500 to 10,000. The OH numbers are preferably in a range of about 20 to 300 mg KOH / g polymer.

preferred Polymers c2) are z. B. copolymers containing at least one of aforementioned monoesters of dihydric or polyhydric alcohols with at least an α, β-ethylenic unsaturated Mono- and / or dicarboxylic acid and at least one further comonomer, preferably selected from Vinyl aromatics, such as. As styrene, esters of the aforementioned α, β-unsaturated Mono- and / or dicarboxylic acids with monoalcohols containing vinyl esters of up to 20 carbon atoms Carboxylic acids, Vinyl halides, non-aromatic hydrocarbons with 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated Contain nitriles, etc. and mixtures thereof in copolymerized form. These include furthermore (partially) hydrolyzed vinyl ester polymers, preferably polyvinyl acetates.

To counting Furthermore, polyesterols based on aliphatic, cycloaliphatic and / or aromatic di-, tri- and / or polycarboxylic acids Di-, tri- and / or polyols as well as lactone-based polyesterols.

Polyester polyols are z. B. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp 62 to 65 known. Preference is given to using polyesterpolyols 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, for. B. 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, suberic, azelaic, phthalic, tetrahydrophthalic, hexahydrophthalic, tetrachlorophthalic, endomethylenetetrahydrophthalic, 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 acids mentioned 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.

When Polyhydric alcohols are used to prepare the polyesterols Consider 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methylpentan-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, Poly-THF with a molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between 134 and 2000, poly-1,2-propanediol with a Molecular weight between 134 and 2000, polyethylene glycol with one molecular weight between 106 and 2000, neopentyl glycol, hydroxypivalic acid neopentylglycol 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), Xylitol, dulcitol (galactitol), maltitol or isomalt, optionally as described above may be alkoxylated.

Alcohols of the general formula HO- (CH ₂ ) _x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred. 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.

Further also come polycarbonate diols, as z. B. by implementation of Phosgene with a surplus of the as structural components for the polyester polyols mentioned low molecular weight alcohols can be into consideration.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH ₂ ) _z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also denoted 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 pivalolactone and mixtures thereof. Suitable starter components are for. As the above-mentioned as a structural component for the polyester polyols low molecular weight dihydric alcohols. 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.

To counting Furthermore, polyetherols obtained by polymerization of cyclic Ethern or by reaction of alkylene oxides with a starter molecule are available, and by reaction of polyetherols with ammonia available α, ω-diaminopolyether.

Examples of this are commonly known as Jeffamine ^® products from Huntsman.

In the mentioned here Jeffamines ^® is mono-, di- or triamines, the ethylene oxide on a polyether, polyethylene oxides, polypropylene oxides, or mixed poly / polypropylene oxide based, and up to about 5000 g / can comprise mol, a molar mass.

Examples of such monoamines are the so called Jeffamine ^® M series, the methylgekappte polyalkylene oxides having an amino function represented as M-600 (XTJ-505), with a propylene oxide (PO) / ethylene oxide (EO) ratio of about 9: 1 and a molecular weight of about 600, M-1000 (XTJ-506): PO / EO ratio 3:19, molecular weight about 1000, M-2005 (XTJ-507): PO / EO ratio 29: 6, molecular weight about 2000 or M-2070: PO / EO ratio 10:31, molecular weight about 2000.

Examples of such diamines are the so-called Jeffamine ^® D or ED series. The D series is amino-functionalized polypropylenediols from 3-4 1,2-propylene units (Jeffamine ^® D-230, mean molar mass 230), 6-7 1,2-propylene units (Jeffamine ^® D-400, mean molar mass 400), in section approximately 34 1,2-propylene units (Jeffamine ^® D-2000, mean molar mass 2000) or an average of about 69 1,2-propylene units (Jeffamine ^® XTJ-510 (D-4000), mean molar mass 4000). Some of these products may also be present as amino alcohols. The ED series is diamines based on polyethylene oxides which are idealiserterweise propoxylated on both sides, for example Jeffamine ^® HK-511 (XTJ-511) of 2 ethylene oxide and 2 propylene oxide units with a mean molar mass of 220, Jeffamine ^® XTJ-500 (ED 600) of 9 ethylene oxide and 3.6 propylene oxide units with a mean molar mass of 600 and Jeffamine ^® XTJ-502 (ED-2003) of 38.7 ethylene oxide and 6 propylene oxide units with a mean molar mass in 2000.

Examples of triamines are Jeffamine ^® T-403, a triamine based on a modified 5-6 1,2-propylene units trimethylolpropane, Jeffamine ^® T-5000, a triamine based on a modified with about 85 units of glycerol and 1,2-propylene Jeffamine ^® XTJ-509 (T-3000), a triamine based on a modified 50 with 1,2-propylene moieties glycerol.

The previously mentioned components c) used singly or as mixtures.

Component d)

component d) is at least one compound having at least one opposite isocyanate groups reactive group and at least one acid group.

Preferably are the acid groups the compounds of component d) selected from carboxylic acid groups, sulfonic acid groups, phosphonic and phosphoric acid groups. Preference is given to carboxylic acid and sulfonic acid groups, Particularly preferred are carboxylic acids.

When Compounds d) having at least one isocyanate-reactive group and at least one carboxylic acid or sulfonic acid group in particular aliphatic Monomercapto-, monohydroxy and Monoamino and iminocarboxylic acids and corresponding sulfonic acids in question, such as mercaptoacetic acid (Thioglycolic acid), mercaptopropionic mercaptosuccinic hydroxyacetic, hydroxypropionic (Lactic acid), Hydroybernsteinsäure, hydroxypivalic acid, dimethylolpropionic dimethylol, hydroxydecanoic, hydroxydodecanoic, 12-hydroxystearic acid, Hydroxyethansulfon acid, hydroxypropane, mercaptoethanesulfonic, mercaptopropanesulphonic, Aminoethanesulfonic acid, aminopropanesulfonic acid, glycine (Aminoacetic acid), N-Cyclohexylaminoethansulfonsäure, N-cyclohexylaminopropanesulphonic, or iminodiacetic acid.

Prefers are dimethylolpropionic acid and dimethylol butyric acid, dimethylolpropionic acid is particularly preferred.

Component e)

component e) is at least one basic compound for neutralization or Partial neutralization of acid groups the compounds d).

When basic compounds e) for a neutralization or partial neutralization of the acid groups the compounds d) are inorganic and organic bases such as Alkali and alkaline earth hydroxides, oxides, carbonates, bicarbonates and ammonia or primary, secondary or tert. Amines into consideration. Preference is given to neutralization or partial neutralization with amines such as ethanolamine or diethanolamine and in particular with tert. Amines, such as triethylamine, triethanolamine, dimethylethanolamine or diethylethanolamine. The amounts of introduced chemically bound acid groups and the extent of Neutralization of the acid groups (usually at 40 to 100% of the equivalence base is) should preferably be sufficient to a dispersion of the polyurethanes in an aqueous Medium to ensure what is familiar to the expert.

Component f)

In the dispersions of the invention can as component f) at least one further compound with a across from Isocyanate groups reactive group can be used. At this Group may be a hydroxyl, mercapto, or a primary or secondary Act amino group. Suitable compounds f) are the customary, known to those skilled compounds that as so-called stopper to reduce the number of reactive free isocyanate groups or for modifying the polyurethane properties usually in polyurethane production be used. These include z. B. monofunctional alcohols, such as methanol, ethanol, n-propanol, Isopropanol, n-butanol, etc. Suitable components f) are also amines with a primary or secondary Amino group, such as. Methylamine, ethylamine, n-propylamine, diisopropylamine, Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, etc.

Component g)

In the dispersions of the invention can as components g) at least one of the compounds of Components a) various polyisocyanate can be used. According to the invention as components g) no polyisocyanates are used in which the Isocyanate groups were reacted with a blocking agent.

preferred Compounds g) are polyisocyanates having an NCO functionality of 2 to 4.5, more preferably 2 to 3.5. Preferred are as a component g) aliphatic, cycloaliphatic and araliphatic diisocyanates used. This can for example, be the diisocyanates listed above under a) are but different from compound a). Preference is given to compounds g) which, in addition to 2 or more isocyanate groups, is still a group, selected from the group of urethane, urea, biuret, allophanate, carbodiimide, Urethonimine, urethdione and isocyanurate groups.

Prefers as component g) isophorone diisocyanate, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, their isocyanurates, biurets and mixtures thereof used.

Contain the dispersions of the invention in addition to the component a) nor a component g), the proportion is the compounds of component g) preferably 0.1 to 90% by weight, particularly preferably 1 to 50% by weight, in particular 5 to 30% by weight, based on the total amount of the compounds of the components a) and G).

Component h)

thermal Initiators h) in the context of the present invention are those the one half-life at 60 ° C of at least one hour. The half-life of a thermal Initiator, is the time after the initial amount of the initiator in half has fallen into free radicals.

thermal Initiators are mandatory according to the invention absent, so are present in amounts of less than 0.1 wt .-%.

Component i)

The Dispersion according to the invention may contain at least one other compound, as it usually does as a reactive diluent is used. These include z. B. the reactive diluents, as described in P.K.T. Oldring (Editor), Chemistry & Technology of UV & EB formulations for Coatings, Inks & Paints, Vol. II, Chapter III: Reactive Diluents for UV & EB Curable Formulations, Wiley and SITA Technology, London 1997.

preferred reactive are of the component b) different compounds, at least have a free-radically polymerizable C = C double bonds.

Reactive diluents are, for example, esters of (meth) acrylic acid with alcohols having 1 to 20 carbon atoms, eg. Methyl (meth) acrylate, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, dihydrodicyclopentadienyl acrylate, vinyl aromatic compounds, e.g. Styrene, divinylbenzene, α, β-unsaturated nitriles, e.g. For example, acrylonitrile, methacrylonitrile, α, β-unsaturated aldehydes, z. Acrolein, methacrolein, vinyl esters, e.g. For example, vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds, eg. As vinyl chloride, vinylidene chloride, conjugated un saturated compounds, e.g. As butadiene, isoprene, chloroprene, monounsaturated compounds, eg. Ethylene, propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds, e.g. B. 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, such as. As N-vinylcaprolactam, N-vinyl-N-alkyl-carboxylic acid amides or N-vinyl-carboxylic acid amides, such as. N-vinylacetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers, e.g. 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-hydroxybutyl vinyl ether, and mixtures thereof.

links with at least two free-radically polymerizable C =C double bonds: These include in particular the diesters and polyesters of the aforementioned α, β-ethylenically unsaturated Mono- and / or dicarboxylic acids with diols or polyols. Particularly preferred are hexanediol diacrylate, Hexanediol dimethacrylate, octanedioldiacrylate, octanediol dimethacrylate, Nonandioldiacrylate, nonandioldimethacrylate, decanediol diacrylate, Decandioldimethacrylate, pentaerythritol diacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol triacrylate, pentaerythritol tetraacrylate, etc. Preferred are also the esters of alkoxylated polyols, with α, β-ethylenically unsaturated Mono- and / or dicarboxylic acids such as As the polyacrylates or methacrylates of alkoxylated Trimethylolpropane, glycerol or pentaerythritol. Suitable are still the esters of alicyclic diols, such as cyclohexanediol di (meth) acrylate and bis (hydroxymethylethyl) cyclohexanedi (meth) acrylate. Other suitable reactive are trimethylolpropane monoformal acrylate, glycerol formal acrylate, 4-tetrahydropyranyl acrylate, 2-tetrahydropyranyl methacrylate and tetrahydrofurfuryl acrylate.

Provided the curing the dispersions of the invention not with electron beams, but with UV radiation, contain the preparations according to the invention preferably at least one photoinitiator which initiates the polymerization ethylenically unsaturated Can initiate double bonds.

photoinitiators can for example, be known in the art photoinitiators, z. B. those in "Advances in Polymer Science ", Volume 14, Springer Berlin 1974 or K. K. Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London, mentioned.

In consideration come z. B. mono- or Bisacylphosphinoxide as z. For example, in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980 are described, for example, 2,4,6-Trimethylbenzoyldiphenylphosphinoxid (Lucirin ^® TPO BASF AG), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin ^® TPO L from BASF AG), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure ^® 819 from Ciba specialty Chemicals), benzophenones, hydroxyacetophenones, phenylglyoxylic 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-butyl anthraquinone, 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, thioxanthene 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 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, trio-tolylphosphine, benz [a] anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzil ketals 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.

Suitable are also non- or slightly yellowing phenylglyoxalic ester type photoinitiators, such as in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.

Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2-hydro xy-2-methyl-1-phenylpropan-1-one, benzophenone and 1-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone , 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4,6-trimethylbenzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Prefers 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.

The dispersions according to the invention preferably contain the photoinitiators in an amount of 0.05 to 10 wt .-%, particularly preferably 0.1 to 8 wt .-%, in particular 0.2 to 5 wt .-%, based on the total amount of the components a) to i).

The dispersions according to the invention can more paint usual Additives, such as leveling agents, defoamers, UV absorbers, dyes, Pigments and / or fillers contain.

suitable fillers include silicates, e.g. B. by hydrolysis of silicon tetrachloride available Silicates such as Aerosil R from Degussa, silica, talc, aluminum silicates, Magnesium silicates, calcium carbonates, etc. Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin R brands of Ciba Specialty Chemicals) and benzophenones. these can 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 their derivatives, eg. Bis- (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate, be used. Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-% based on the "solid" components contained in the preparation used.

Component I)

polyamines with 2 or more primary and / or secondary Amino groups can especially used when the chain extension or crosslinking in the presence of water, since amines usually faster than alcohols or water with isocyanates react. That's common then required if aqueous dispersions of crosslinked polyurethanes or high molecular weight polyurethanes. In such cases one proceeds in such a way that one prepolymers with isocyanate groups, these are dispersed rapidly in water and subsequently by adding compounds with several isocyanate-reactive amino groups chain extended or networked.

For this Suitable amines are generally polyfunctional amines of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which at least two primary, two secondary or a primary one and a secondary one Contain amino group. Examples include diamines such as diaminoethane, diaminopropane, Diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (Isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane or higher Amines such as triethylenetetramine, tetraethylenepentamine or polymers Amines such as polyethyleneamines, hydrogenated poly-acrylonitriles or at least partially hydrolyzed poly-N-vinylformamide each with a Molar weight up to 2000, preferably up to 1000 g / mol.

The Amines can also in blocked form, z. B. in the form of the corresponding ketimines (See, for example, CA-1 129 128), ketazines (see, for example, US-A 4,269 748) or amine salts (see US-A 4,292,226). Also Oxazolidines, as used for example in US-A 4,192,937 are blocked polyamines used for the production of polyurethanes for chain extension the prepolymer can be used. When using such capped polyamines they become in general with the prepolymers mixed in the absence of water and then this mixture with the dispersion water or a part of the dispersion water, so that hydrolytic the corresponding polyamines are released.

Prefers For example, mixtures of di- and triamines are used, more preferred Mixtures of isophoronediamine and diethylenetriamine.

The proportion of polyamines can be up to 10, preferably up to 8 mol% and particularly preferably up to 5 mol%, based on the total amount of C = C double bonds.

Of the Solids content of the aqueous dispersions of the invention is preferably in a range of about 5 to 70, especially 20 to 50% by weight.

• – 5 bis 80 Mol-%, bevorzugt 10 bis 80 Mol-%, besonders bevorzugt 15–75 Mol% mit gegenüber Isocyanatgruppen reaktiven Gruppen wenigstens einer Verbindung der Komponente b),
• – 0 bis 70 Mol-% bevorzugt 0,2 bis 60 Mol-%, besonders bevorzugt 0,5–30 Mol% mit gegenüber Isocyanatgruppen reaktiven Gruppen wenigstens einer Verbindung der Komponente c),
• – 0,1 bis 40 Mol-%, bevorzugt 2 bis 35 Mol-%, besonders bevorzugt 5 bis 30 Mol% mit gegenüber Isoocyanatgruppen wenigstens einer Verbindung der Komponente d),

umgesetzt sind. Die Angaben beziehen sich auf molare Äquivalente einer funktionellen Gruppe.Preference is given to dispersions, the isocyanate groups of the compounds of component a) and, if present, g) to

• From 5 to 80 mol%, preferably from 10 to 80 mol%, particularly preferably from 15 to 75 mol%, of isocyanate-reactive groups of at least one compound of component b),
• From 0 to 70 mol%, preferably from 0.2 to 60 mol%, particularly preferably from 0.5 to 30 mol%, of isocyanate-reactive groups of at least one compound of component c),
• From 0.1 to 40 mol%, preferably from 2 to 35 mol%, particularly preferably from 5 to 30 mol%, with isococyanate groups of at least one compound of component d),

are implemented. The data refer to molar equivalents of a functional group.

The dispersions according to the invention are particularly suitable for coating substrates such as wood, paper, Textile, leather, nonwoven, plastic surfaces, glass, ceramics, mineral Building materials, such as cement blocks and fiber cement boards, and in particular of metals or coated metals.

advantageously, form the dispersions of the invention after curing by high-energy radiation films with good application technology Properties such as a good scratch resistance, good chemical resistance, good weather stability and / or good mechanical properties.

The substrates are coated by customary methods known to the person skilled in the art, at least one dispersion of the invention being applied to the substrate to be coated in the desired thickness and the volatile constituents of the dispersions being removed. If desired, this process can be repeated one or more times. The application to the substrate can in a known manner, for. B. by spraying, filling, doctoring, brushing, rolling, rolling or pouring done. The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

Possibly can if several layers of the coating agent on top of each other are applied, followed by radiation curing after each coating process.

The radiation curing is effected by the action of high-energy radiation, ie UV radiation or daylight, preferably light of wavelength 250 to 600 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 radiators. The radiation dose for UV curing, which is usually sufficient for crosslinking, is in the range from 80 to 3000 mJ / cm ² .

The Irradiation may also be possible with the exclusion of oxygen, z. B. under inert gas atmosphere, carried out become. As inert gases are preferably nitrogen, noble gases, Carbon dioxide or combustion gases. Furthermore, the irradiation done by adding the coating mass with transparent media is covered. Transparent media are z. B. plastic films, Glass or liquids, z. B. water. Particular preference is given to irradiation in the manner as described in DE-A1 199 57 900.

In In a preferred method, the curing is carried out continuously by the same with the preparation according to the invention treated substrate at a constant speed past a radiation source. This is it required that the cure speed the preparation according to the invention is sufficiently high.

this Different temporal course of the hardening one can in particular then take advantage of the coating of the object followed by a processing step in which the film surface in direct Contact with another object occurs or works mechanically becomes.

Of the Advantage of the dispersions of the invention is that the coated objects immediately after the radiation can process further, because the surface no longer sticks. on the other hand the dried film is still so flexible and stretchable that the Subject can still be deformed without the film flakes off or rips.

One Another object of the invention is the use of a dispersion, as previously described, for coating substrates of metal, Wood, paper, ceramics, glass, plastic, textile, leather, fleece or mineral Building materials.

The the polyurethane dispersions of the invention can especially as primers, fillers, pigmented topcoats and clearcoats in the field of industrial, in particular aircraft or Transportation coatings, Wood, car, especially OEM or Car refinish, or decorative paint can be used. Particularly suitable are the coating compositions for applications, in which a particularly high application safety, outdoor weather resistance, Optics, solvent and / or chemical resistance are required.

The Invention will be apparent from the following non-limiting Examples closer explained.

So far Unless otherwise indicated, parts and percentages are by weight on the weight.

Component A: Allophanate from hexamethylene diisocyanate and hydroxyethyl acrylate described in WO 00/39183, page 24, Table 1, 14.9% NCO content, 2 mol / kg content of acrylate groups.
Polyesterol C: polyester of adipic acid and 1,4-butanediol, molar mass 1000 g / mol

Preparation of the polyester acrylate D:

In of an apparatus with water separator were ethoxylated 258.1 g Trimethylpropane (OH number about 610 mg KOH / g), 206.1 g phthalic anhydride, 125.3 g of 1,4-butanediol, 210.5 g of acrylic acid and 16 g of p-toluenesulfonic acid (65 % in water), 310 g of methylcyclohexane in the presence of 0.8 g 2,6-di (t-butyl) -4-methylphenol, 0.8 g triphenyl phosphite, 0.8 g hypophosphorous Acid (50 % in water), 2.83 g of 4-methoxyphenol and 0.055 g of phenothiazine. After a reaction time of 10 hours, about 83 g of water were removed from the system. The solvent was subsequently in vacuo (20 mbar) at 102 ° C distilled off 18 g of aqueous Tetra (n-butyl) ammonium bromide (75%) added. The acid number after distillation was about 55 mg KOH / g. The excess acrylic acid was with 115.6 g of bisphenol A diglycidyl ether (epoxide content about 5.4 mol / kg) at a temperature of 105-110 ° C 6 hours implemented. The acid number of the obtained acrylate was 4 mg KOH / g. The viscosity of the resin was 18 Pas according to DIN 53019. Content of acrylate groups: 3.0 mol / kg

Example 1: Preparation a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 149.4 g of polycaprolactone diol ( ^Capa® 212 from Solvay, molecular weight = 1000 g / mol, OH number = 113 mg KOH / g), 21.7 g of 1,2-ethanediol, 69.66 g of hydroxyethyl acrylate, 26.8 g of dimethylolpropionic acid, 0.08 g of 2,6-di-t-butyl-4-methylphenol and 0.04 g of hydroquinone monomethyl ether and at a bath temperature of 75 ° C stirred. Within 60 minutes, 149.86 g of isophorone diisocyanate, 59.1 g of tris (hexamethylene-isocyanato) isocyanurate and 82.5 g of component A were added dropwise in parallel. After completion of the feed 115.4 g of acetone were added. Subsequently, 0.125 g of dibutyltin dilaurate were added dropwise after 90 minutes and 4 hours. At an NCO content of 0.50% was diluted with 186.2 g of acetone and neutralized with 76 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 782.1 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 157.5 g of water.
Solids content: 36%, pH value: 8.10, viscosity: 91.7 mPas, average particle diameter: 152 nm.

Example 2: Preparation a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 74.7 g of polycaprolactone (Capa 212 from Solvay, molecular weight = 1000 g / mol, OH number = 113 mg KOH / g), 26 , 35 g of 1,2-ethanediol, 69.66 g of hydroxyethyl acrylate, 26.8 g of dimethylolpropionic acid, 0.088 g of 2,6-di-t-butyl-4-methylphenol and 0.047 g of hydroquinone monomethyl ether stirred at a bath temperature of 75 ° C. Within 60 minutes, 261.25 g of component A and 131 g of bis (4,4'-isocyanatocyclohexyl) methane were added dropwise. When the feed had ended, 130 g of acetone were metered in. Subsequently, 0.145 g of dibutyltin dilaurate were added dropwise after 90 minutes and 4 hours. At an NCO content of 0.60% was diluted with 187.6 g of acetone and neutralized with 76 g of a 10% aqueous sodium hydroxide solution. Within 20 693.96 g of water were added dropwise with stirring into the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 136.13 g of water.
Solids content: 36%, pH value: 8.03, viscosity: 38.4 mPas, average particle diameter: 83 nm.

Example 3: Production a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 74.7 g of polycaprolactone (Capa 212 from Solvay, molecular weight = 1000 g / mol, OH number = 113 mg KOH / g), 26 , 35 1,2-ethanediol, 69.66 g of hydroxyethyl acrylate, 26.8 g of dimethylolpropionic acid, 0.08 g of 2,6-di-t-butyl-4-methylphenol and 0.04 g of hydroquinone monomethyl ether at a bath temperature of 75 ° C stirred. Within 60 minutes, 261.25 g of component A were added dropwise. When the feed had ended, 130 g of acetone were metered in. Subsequently, 0.14 g of dibutyltin dilaurate were added dropwise after 90 minutes and 4 hours. At an NCO content of 0.50% was diluted with 187 g of acetone and neutralized with 76 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 666.93 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 131.3 g of water.
Solids content: 34%, pH value: 8.06, viscosity: 147.2 mPas, average particle diameter: 106 nm.

Example 4: Preparation a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 485.76 g of polyester acrylate D, 36.6 g of polyesterol C, 31.09 g of dimethylolpropionic acid, 0.055 g of 4-hydroxy-2,2,6, 6-tetramethylpiperidine N-oxide in 156.1 g of acetone and stirred at a bath temperature of 75 ° C. Within 40 minutes 302.5 g of component A were added dropwise. After 90 minutes, 0.54 g of dibutyltin dilaurate was added dropwise. At an NCO content of 0.72% was diluted with 305.12 g of acetone and neutralized with 83.6 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 1222.13 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 81.5 g of water.
Solids content: 36%, pH value: 7.51, viscosity: 96 mPas, average particle diameter: 153 nm.

Example 5: Preparation a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, were added 364.8 g of polyester acrylate D, 36.6 g of polyesterol C, 9 g of 1,4-butanediol, 26.13 g of dimethylolpropionic acid, 0.046 g of Submitted to hydroxy-2,2,6,6-tetramethylpiperidine N-oxide in 130.49 g of acetone and stirred at a bath temperature of 75 ° C. Within 40 minutes, 275 g of component A were added dropwise. After completion of feed, 0.46 g of dibutyltin dilaurate was added. At an NCO content of 0.55% was diluted with 266.98 g of acetone and neutralized with 70 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 1015.55 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 84.5 g of water.
Solids content: 35%, pH value: 7.82, viscosity: 299 mPas, average particle diameter: 181 nm.

Example 6: Preparation a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 522.24 g of polyester acrylate D, 19.62 g of polyesterol C, 29.48 g of dimethylolpropionic acid, 0.057 g of 4-hydroxy-2,2,6, 6-tetramethylpiperidine N-oxide in 161.11 g of acetone and stirred at a bath temperature of 75 ° C. Within 40 minutes, 151.25 g of component A and 72.05 g of bis (4,4'-isocyanatocyclohexyl) methane were added dropwise. After completion of feed 0.58 g of dibutyltin dilaurate were added. At an NCO content of 0.72% was diluted with 267.05 g of acetone and neutralized with 79.2 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 1133.35 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 113.3 g of water.
Solids content: 34%, pH value: 7.51, viscosity: 36 mPas, average particle diameter: 197 nm.

Example 7: Preparation a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 441.6 g of polyester acrylate D, 36.6 g of polyesterol C, 29.48 g of dimethylolpropionic acid, 0.05 g of 4-hydroxy-2,2, 6,6-tetramethylpiperidine N-oxide in 143.19 g of acetone and stirred at a bath temperature of 75 ° C. Within 40 minutes, 275 g of component A were added dropwise. After completion of feed 0.5 g of dibutyltin dilaurate was added. At an NCO content of 0.80 was diluted with 278.5 g of acetone. Subsequently, 2.1 g of 1,2-ethanediamine dissolved in 20 g of acetone were added at a temperature of 30 ° C and neutralized with 79.2 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 1118.59 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 93.2 g of water.
Solids content: 35%, pH value: 7.70, viscosity: 324 mPas, average particle diameter: 152 nm.

Example 8: Preparation a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 412.8 g of polyester acrylate D, 36.6 g of polyesterol C, 28.14 g of dimethylolpropionic acid, 0.048 g of 4-hydroxy-2,2,6, 6-tetramethylpiperidine N-oxide in 134.69 g of acetone and stirred at a bath temperature of 75 ° C. Within 40 minutes, 275 g of component A were added dropwise. After completion of the feed, 0.48 g of dibutyltin dilaurate was added. At an NCO content of 1.06, it was diluted with 270.8 g of acetone. Subsequently, at a temperature of 30 ° C., 3.6 g of 1,2-ethanediamine dissolved in 20 g of acetone were metered in and neutralized with 75.6 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 1078.3 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 71.9 g of water.
Solids content: 36%, pH value: 7.63, viscosity: 307 mPas, average particle diameter: 159 nm.

Comparative Example 1 Preparation of a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 74.7 g of polycaprolactone (Capa 212 from Solvay, molecular weight = 1000 g / mol, OH number = 113 mg KOH / g), 26 , 35 g of 1,2-ethanediol, 69.66 g of hydroxyethyl acrylate, 26.8 g of dimethylolpropionic acid, 0.088 g of 2,6-di-t-butyl-4-methylphenol and 0.047 g of hydroquinone monomethyl ether stirred at a bath temperature of 75 ° C. Within 60 minutes, 231.8 g allophanatmodifiziertes polyisocyanate of 1,6-hexamethylene diisocyanate and 2-ethylhexanol (NCO content = 17.2%, viscosity about 300 mPas) and 131 g of bis (4,4'-isocyanatocyclohexyl) methane dropwise. After completion of feed 100 g of acetone were added. After 90 minutes, 0.29 g of dibutyltin dilaurate was added dropwise. At an NCO content of 1.21% was diluted with 201.97 g of acetone and neutralized with 76 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 784.24 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 157.89 g of water.
Solids content: 36%, pH value: 8.16, viscosity: 36 mPas, average particle diameter: 249 nm.

Comparative Example 2: Preparation of a polyurethane and a polyurethane dispersion

In a 4 l reaction vessel equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 74.7 g of polycaprolactone (Capa 212 from Solvay, molecular weight = 1000 g / mol, OH number = 113 mg KOH / g), 26 , 35 g of 1,2-ethanediol, 69.66 g of hydroxyethyl acrylate, 26.8 g of dimethylolpropionic acid, 0.072 g of 2,6-di-t-butyl-4-methylphenol and 0.039 g of hydroquinone monomethyl ether stirred at a bath temperature of 75 ° C. Within the course of 60 minutes, 189.95 g of bis (4,4'-isocyanatocyclohexyl) methane and 98.5 g of tris (hexamethylenediisocyanato) isocyanurate were added dropwise. After completion of the feed, 95 g of acetone were added. After 90 minutes, 0.21 g of dibutyltin dilaurate was added dropwise. At an NCO content of 0.50% was diluted with 130.13 g of acetone and neutralized with 76 g of a 10% aqueous sodium hydroxide solution. Within 20 minutes 473.41 g of water were added dropwise with stirring in the polymer solution. Subsequently, the acetone was distilled off in vacuo and diluted with 96.75 g of water.
Solids content: 36%, pH value: 8.04, viscosity:> 500 mPas, average particle diameter: 955 nm.

It no stable dispersion could be obtained.

movie tests

The coating compositions were (based on the solids content of the dispersions) with 4% by weight of photoinitiator Irgacure 500 mixed ^® (mixture of 50 wt .-% of benzophenone and 1-hydroxycyclohexyl phenyl ketone) from Ciba Specialty Chemicals, to the respective substrate with a layer thickness of 150 microns (wet), dried for 20 minutes at 60 ° C in a drying oven to remove water and under an undoped high pressure mercury lamp (power 120 W / cm) with a lamp distance to the substrate of 12 cm and a belt speed of 10 m / min twice exposed so that fingernail scratch resistant coatings were obtained.

The Erichsenhärte was determined according to DIN 53156 and is a measure of flexibility and elasticity. The indication takes place in millimeters (mm). High values mean high flexibility. The movies to determine the Erichsentiefung were using a spiral squeegee applied to metal. The layer thickness after exposure was approx. 50 μm.

• * Filmprüfung war nicht möglich, da die Dispersion nicht zur Herstellung von Filmen geeignet ist

The pendulum hardness was determined according to DIN 53157 and is a measure of the hardness of the coating. The information is given in seconds until the pendulum stops. High values mean high hardness. The pendulum hardness films were applied to glass using a box wiper. The layer thickness after exposure was about 50 μm.

• * Film testing was not possible because the dispersion is not suitable for making films

Claims (10)

A radiation aqueous Polyurethane dispersions, composed of a) at least one Compound with at least two free isocyanate groups, at least an allophanate group and at least one bound via the allophanate group, radically polymerizable C = C double bond, which directly to the Double bond a carbonyl group or an oxygen atom in ether function is bound b) at least one compound having at least one opposite Isocyanate groups reactive group and at least one radical polymerisable C = C double bond, c) optionally at least a compound having at least two isocyanate-reactive groups, the selected are hydroxyl, mercapto, primary and / or secondary amino groups, d) at least one compound having at least one opposite isocyanate groups reactive group and at least one acid group, e) at least a basic compound for an at least partial neutralization of the acid groups of the compounds d) f) optionally at least one of b), d) and e) different Connection, only one opposite Has isocyanate-reactive group, g) if necessary at least one of a) different polyisocyanate, h) in Absence of a thermal initiator, i) if appropriate other additives that are selected from reactive thinners, photoinitiators and usual Paint additives k) water as well l) optionally at least a di- and / or polyamine. Polyurethane dispersion according to claim 1, characterized in that that at least a component c) is present. Polyurethane dispersion according to claim 2, characterized in that that the Component c) has a molecular weight of more than 500 g / mol. Polyurethane dispersion according to one of the preceding claims, characterized characterized in that the reaction product from the structural components a) to d) and optionally f) and g) has a double bond density of at least 1.4 mol / kg. Polyurethane dispersion according to one of the preceding claims, characterized characterized in that the component a) at least one synthesis component contains selected from the group consisting from 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Isophorone diisocyanate, tetramethylxylylene diisocyanate and di (isocyanatocyclohexyl) methane. Polyurethane dispersion according to one of the preceding claims, characterized characterized in that the component a) at least one synthesis component contains selected from the group consisting from 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, Neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, Trimethylolpropane mono- and di (meth) acrylate, pentaerythritol di- and tri (meth) acrylate. Polyurethane dispersion according to one of the preceding claims, characterized characterized in that the component d) selected is selected from the group consisting of dimethylolpropionic acid and Dimethylol. Substrate coated with a polyurethane dispersion according to one the claims 1 to 7. Process for coating substrates, characterized characterized in that a polyurethane dispersion according to a the claims 1 to 7 applied to a substrate, then dried and radiation-cured. Use of polyurethane dispersions according to one the claims 1 to 7 as a coating composition.