JP5871924B2 - High functionality polyisocyanate with urethane groups - Google Patents

Description

  The present invention relates to novel urethane group-containing polyisocyanates based on aliphatic diisocyanates and / or cycloaliphatic diisocyanates and their use.

  European Patent (EP-B1) No. 1091991 describes a two-component polyurethane mixture having a high functionality, preferably at least tetrafunctional polyisocyanate as component A and a polyol as component B. ing. The component B may contain a low molecular diol or pentaol.

  Polyisocyanates and polyols are only used in an NCO: OH ratio of 0.6 to 1.4: 1, because the mixture is essentially free of all reactive groups after its curing. This is because it is a coating material for coating that should have finished reacting.

  European Patent (EP-B1) No. 1149951 describes the preparation of high-functional polyisocyanates by trimerization of mixtures containing aliphatic diisocyanates and uretdiones. There is no alcohol.

  EP-A 1061091 describes at least bifunctional polyisocyanates having allophanate groups by reaction of polyisocyanates with monoalcohols and optionally higher functionality diols or polyols. Is described.

  Disadvantageous to this is that no more than two polyisocyanates can be linked to each other by one allophanate bond, thereby limiting the functionality of the resulting product.

  EP-A2 620237 describes prepolymers from diisocyanates and polyols. Reactions with higher functionality polyisocyanates are not disclosed.

  A disadvantage to this is that the NCO functionality of the resulting product is not higher than the OH functionality of the polyol used.

  German Offenlegungsschrift DE-OS 2305695 describes prepolymers from diisocyanates and low molecular polyols having 2 to 4 hydroxy groups.

  Reactions with higher functionality polyisocyanates are not disclosed.

  The object of the present invention is to have a high hardness and / or scratch resistance, in particular accelerated and / or improved sulfuric acid resistance, even when already cured at low temperatures and / or in two-component polyurethane paints. It was to provide a novel polyisocyanate having a high functionality for paints, in particular for clearcoats.

The problem is
At least one tertiary dialkanolamine or trialkanolamine (A),
At least one kind having at least one functionality having at least one isocyanurate, biuret, uretdione and / or allophanate group and composed of an aliphatic isocyanate and / or a cycloaliphatic isocyanate Polyisocyanate (B) of
It can be obtained by reacting under the reaction conditions in which a urethane group is formed between (A) and (B), provided that
The molar ratio of NCO groups to OH groups between (B) and (A) is at least 3: 1;
This is solved by a highly functional polyisocyanate having a urethane group.

  Compound (A) may be a tertiary dialkanolamine or trialkanolamine.

  A trialkanolamine is understood within the scope of the present description to be the reaction product of ammonia and propylene oxide and / or ethylene oxide, preferably propylene oxide or ethylene oxide, particularly preferably ethylene oxide.

［式中、
ｎ、ｏ、ｐは、互いに独立してそれぞれ、１〜５、好ましくは１〜３、特に好ましくは１〜２の整数を表し、かつ極めて特に好ましくは１を表し、かつ
ｉ＝１〜ｎ、１〜ｏ及び１〜ｐについてのそれぞれＸ_iは、互いに独立して−ＣＨ₂−ＣＨ₂−Ｏ−、−ＣＨ₂−ＣＨ（ＣＨ₃）−Ｏ−及び−ＣＨ（ＣＨ₃）−ＣＨ₂−Ｏ−の群から選択されていてよく、好ましくは−ＣＨ₂−ＣＨ₂−Ｏ−を意味する］で示されるものである。 Preferred trialkanolamines (A) have the formula

[Where:
n, o and p each independently represent an integer of 1 to 5, preferably 1 to 3, particularly preferably 1 to 2, and very particularly preferably 1 and i = 1 to n, X _i for 1-o and 1-p are independently of each other —CH ₂ —CH ₂ —O—, —CH ₂ —CH (CH ₃ ) —O— and —CH (CH ₃ ) —CH _2. may have been selected from the group of -O-, in which preferably represented by 'means a -CH ₂ -CH ₂ -O-.

  In a preferred embodiment, the trialkanolamine (A) is 5- [bis (2′-hydroxyethyl) amino] -3-oxa-pentan-1-ol, triethanolamine or tripropanolamine, particularly preferably triethanolamine. It is.

  A tertiary dialkanolamine is understood within the scope of the present specification to be the reaction product of a primary amine with propylene oxide and / or ethylene oxide, preferably propylene oxide or ethylene oxide, particularly preferably ethylene oxide. The

［式中、
Ｒ¹は、直鎖状又は分枝鎖状のＣ₁〜Ｃ₂₀−アルキル基、場合により置換されたＣ₅〜Ｃ₁₂−シクロアルキル基、場合により置換されたＣ₇〜Ｃ₁₀−アラルキル基、又は場合により置換されたＣ₆〜Ｃ₁₂−アリール基であってよく、
ｑ及びｒは、互いに独立してそれぞれ、１〜５、好ましくは１〜３、特に好ましくは１〜２の整数を表し、かつ極めて特に好ましくは１を表し、かつ
ｉ＝１〜ｑ及び１〜ｒについてのそれぞれＸ_iは互いに独立して−ＣＨ₂−ＣＨ₂−Ｏ−、−ＣＨ₂−ＣＨ（ＣＨ₃）−Ｏ−及び−ＣＨ（ＣＨ₃）−ＣＨ₂−Ｏ−及び好ましくは−ＣＨ₂−ＣＨ₂−Ｏ−の群から選択されていてよい］である。 Preferred tertiary dialkanolamines are

[Where:
R ¹ is a linear or branched C ₁ -C ₂₀ -alkyl group, an optionally substituted C ₅ -C ₁₂ -cycloalkyl group, an optionally substituted C ₇ -C ₁₀ -aralkyl group. , or C ₆ -C ₁₂ optionally substituted - may be an aryl group,
q and r each independently represent an integer of 1 to 5, preferably 1 to 3, particularly preferably 1 to 2, and very particularly preferably 1 and i = 1 to q and 1 to each X _{i for} r is independently of each other —CH ₂ —CH ₂ —O—, —CH ₂ —CH (CH ₃ ) —O— and —CH (CH ₃ ) —CH ₂ —O— and preferably — It may be selected from the group of CH ₂ —CH ₂ —O—].

In these definitions:
Linear or branched C ₁ -C ₂₀ -alkyl groups are for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, Means 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl or 1,1,3,3-tetramethylbutyl;
If C ₅ -C ₁₂ substituted by - cycloalkyl groups are cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxy cyclohexyl, Means diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and saturated or unsaturated bicyclic systems such as norbornyl or norbornenyl;
Optionally substituted C ₇ -C ₁₀ -aralkyl groups are for example benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl)- Means ethyl, o-, m- or p-chlorobenzyl, 2,4-dichlorobenzyl, o-, m- or p-methoxybenzyl or o-, m- or p-ethoxybenzyl,
An optionally substituted C ₆ -C ₁₂ -aryl group means for example phenyl, 2-, 3- or 4-methylphenyl, α-naphthyl or β-naphthyl.

Among these groups, preferably R ¹ is C ₅ -C ₁₂ -cycloalkyl or C ₁ -C ₂₀ -alkyl, particularly preferably C ₅ -C ₆ -cycloalkyl or C ₁ -C ₁₀ -alkyl, very particularly preferably C ₁ -C ₈ - alkyl - alkyl and especially C ₁ -C _4.

Preferred for R ¹ are methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, phenyl, α- or β-naphthyl, Benzyl, cyclopentyl or cyclohexyl.

Particularly preferred radicals R ¹ are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, 2-ethylhexyl, cyclopentyl or cyclohexyl.

  Very particular preference is given to methyl, ethyl, n-propyl, isopropyl and n-butyl.

  Examples of tertiary dialkanolamines are N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N-cyclopentyldiethanolamine, N-cyclohexyldiethanolamine, N-ethyldipropanolamine, N-methyldipropanolamine and N -Butyldipropanolamine.

  N-ethyldiethanolamine, N-methyldiethanolamine and N-butyldiethanolamine are preferred, and N-ethyldiethanolamine and N-methyldiethanolamine are particularly preferred.

  Optionally, at least one diol (A1) and / or polyol (A2) may be added to compound (A), for example up to 70%, for example 10-70% of the total amount of hydroxy groups used. It is possible to use 15 to 55% and particularly preferably 20 to 40% in an amount derived from the diol (A1) and / or the polyol (A2).

  The polyol (A2) has a functionality of at least 3, for example 3-6, preferably 3-4, particularly preferably 3 or 4, and very particularly preferably 3.

  Examples of the polyol (A2) include trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerin, threitol, erythritol, adonitol (ribitol), Arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol and isomalt.

  Preference is given to polyols having a functionality of 3-4, particularly preferably those having a functionality of 3.

  Preferred polyols are trimethylolpropane, trimethylolethane, pentaerythritol, glycerin, ditrimethylolpropane and dipentaerythritol, particularly preferred are trimethylolpropane, pentaerythritol and glycerin, very particularly preferred are trimethylolpropane and Glycerin.

  Examples of the diol (A1) are aliphatic diols having 2 to 20, preferably 2 to 12 carbon atoms, particularly preferably 1,2-ethanediol, 2,2-dimethyl-1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2 -Ethyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methylpentane-1,5-diol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2-propyl-1,3-heptanediol, 1,8-octane Diol, 2,4-diethyloctane-1,3-diol, 1,10-decanediol, or a cycloaliphatic diol having 6 to 20 carbon atoms, preferably bis- (4-hydroxycyclohexane) isopropylidene, Tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2, -, 1,3- and 1,4-cyclohexanedimethanol.

  Among these, the aliphatic diols are preferable, and preferably 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1, 4-butanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol and 2-propyl-1,3-heptanediol, particularly preferably 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol and 2-propyl-1,3-heptanediol, very particularly preferably 1,4-butanediol and 1,6 -Hexanediol.

  A preferred embodiment of the present invention is to use the polyol (A2) in an alkoxylated form.

  Alkoxylated polyols are understood here to be polyols which have been reacted with one or more identical or different alkylene oxides formally on at least one hydroxy group.

  Suitable alkylene oxides for such alkoxylation are, for example, ethylene oxide, propylene oxide, n-butylene oxide, isobutylene oxide, vinyl oxirane and / or styrene oxide.

  The alkylene oxide chain may preferably be composed of ethylene oxide units, propylene oxide units and / or butylene oxide units. Such chains may consist of one type of alkylene oxide or a mixture of alkylene oxides. If a mixture is used, the different alkylene oxide units may be present randomly or as a block or blocks of the individual type. Preference is given to ethylene oxide, propylene oxide or mixtures thereof as alkylene oxide, particularly preferred is either ethylene oxide or propylene oxide and very particularly preferred is ethylene oxide.

  The number of alkylene oxide units in the chain is, for example, 1 to 10, preferably 1 to 5, particularly preferably 1 to 4 and especially 1 to 3, based on the respective hydroxy groups of the polyol.

［式中、
Ｒ²は水素又はＣ₁〜Ｃ₁₈−アルキルを表し、
ｋ、ｌ、ｍ、ｑは互いに独立してそれぞれ、１〜１０、好ましくは１〜５、特に好ましくは１〜４の整数を表し、かつ極めて特に好ましくは１〜３を表し、かつ
ｉ＝１〜ｋ、１〜ｌ、１〜ｍ及び１〜ｑについてのそれぞれＸ_iは互いに独立して−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−及び−ＣＨＰｈ−ＣＨ₂−Ｏ−の群から、好ましくは−ＣＨ₂−ＣＨ₂−Ｏ−、−ＣＨ₂−ＣＨ（ＣＨ₃）−Ｏ−及び−ＣＨ（ＣＨ₃）−ＣＨ₂−Ｏ−の群、及び特に好ましくは−ＣＨ₂−ＣＨ₂−Ｏ−から選択されていてよく、
ここに、Ｐｈはフェニルを表し、かつＶｉｎはビニルを表す］で示されるアルコキシル化ポリオールである。 Particularly preferred are the formulas (IIa) to (IIc)

[Where:
R ² represents hydrogen or C ₁ -C ₁₈ -alkyl,
k, l, m and q each independently represent an integer of 1 to 10, preferably 1 to 5, particularly preferably 1 to 4, and very particularly preferably 1 to 3 and i = 1. to k, 1 to L, 1 to m and each X _i for 1~q independently of one another are _{-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- From the group of CH ₂ —O—, —CH ₂ —CHPh—O— and —CHPh—CH ₂ —O—, preferably —CH ₂ —CH ₂ —O—, —CH ₂ —CH (CH ₃ ) —O. - and -CH (CH ₃₎ -CH ₂ -O- group, and particularly preferably may have been selected from -CH ₂ -CH ₂ -O-,
Here, Ph represents phenyl and Vin represents vinyl].

  Preferably they are 1 to 5 per hydroxy group, particularly preferably 1 to 4 and very particularly preferably 1 to 3, ethoxylated, propoxylated or mixed ethoxylated and propoxylated. And in particular glycerol, trimethylolpropane, trimethylolethane or pentaerythritol, which are exclusively ethoxylated or not specially alkoxylated.

  Preferably, the ratio of diol (A1) to polyol (A2) is 10:90 to 90:10 (based on the molar amount of diol and polyol), particularly preferably 20:80 to 80:20, very particularly preferably. 30:70 to 70:30 and in particular 40:60 to 60:40.

  The polyisocyanate (B) has a functionality of more than 2, preferably at least 2.2, particularly preferably at least 2.4, very particularly preferably at least 2.8 and in particular at least 3.

  The polyisocyanate (B) is composed of an aliphatic diisocyanate and / or a cycloaliphatic diisocyanate, preferably either an aliphatic diisocyanate or a cycloaliphatic diisocyanate.

The diisocyanate is preferably an isocyanate having 4 to 20 carbon atoms. Examples of conventional diisocyanates are aliphatic diisocyanates such as tetramethylene 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 3 (or 4), 8 (or 9) -bis (isocyanato) Methyl) -tricyclo [5.2.1.0 ^2.6 ] decane isomer mixture.

  Preferred diisocyanates are 1,6-hexamethylene diisocyanate, isophorone diisocyanate and / or 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, particularly preferred 1,6 Hexamethylene diisocyanate and / or isophorone diisocyanate and very particularly preferred is 1,6-hexamethylene diisocyanate.

  Mixtures of the aforementioned diisocyanates may also be present.

As the polyisocyanate, a urethane group from a polyisocyanate having an isocyanurate group, a uretdione diisocyanate, a polyisocyanate having a biuret group, a linear or branched C ₄ -C ₂₀ -alkylene diisocyanate And / or polyisocyanates having allophanate groups or cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or mixtures thereof are worth considering.

  The polyisocyanates which can be used are preferably 10 to 60% by weight, preferably 12 to 50% by weight and particularly preferably 12 to 40% by weight, based on the diisocyanates and polyisocyanates (mixtures). Content (NCO, calculated as molecular weight = 42 g / mol).

  Particularly preferred are hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane or their polyisocyanates, very particularly preferred Isophorone diisocyanate and hexamethylene diisocyanate or their polyisocyanates, particularly preferred are hexamethylene diisocyanate or its polyisocyanates.

More preferred is the following:
1) Polyisocyanates having isocyanurate groups from aliphatic diisocyanates and / or cycloaliphatic diisocyanates. Particularly preferred in this case are those based on the corresponding aliphatic isocyanatoisocyanurates and / or cycloaliphatic isocyanatoisocyanurates and in particular hexamethylene diisocyanate and / or isophorone diisocyanate. is there. The isocyanurate present is in particular a tris isocyanatoalkyl isocyanurate or tris isocyanatocycloalkyl isocyanurate which is a cyclic trimer of said diisocyanate, or more than one isocyanurate ring. And their higher homologues. The isocyanato isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight and an average NCO functionality of 2.6 to 4.5.

2) Uretodione diisocyanate having an isocyanate group bonded to aliphatic and / or cycloaliphatic, and particularly derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretodione diisocyanate is a cyclic dimerization product of diisocyanate.
The uretdione diisocyanate can be used as polyisocyanate (B) in a mixture with other polyisocyanates, especially those mentioned in 1).

  3) A polyisocyanate having a cyclic aliphatic group or an isocyanate group bonded to an aliphatic group and having a biuret group, particularly a tris (6-isocyanatohexyl) biuret or a mixture thereof and higher homologues thereof. These polyisocyanates with biuret groups generally have an NCO content of 18-22% by weight and an average NCO functionality of 2.8-4.5.

  4) Polyisocyanates having isocyanate groups bonded to aliphatic or cycloaliphatic and having urethane groups and / or allophanate groups, such as excess hexamethylene diisocyanate or isophorone diisocyanate; Mono- or polyhydric alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, s-butanol, t-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-propa Diol monomethyl ether, cyclopentanol, cyclohexanol, may be obtained by reaction with cyclooctanol, cyclododecanol, or mixtures thereof. These polyisocyanates having urethane groups 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.

  The polyisocyanate can be used as a mixture, and optionally a mixture with diisocyanate.

  In order to produce the urethane group-containing highly functional polyisocyanate, the polyisocyanate (B) and the compound (A) are reacted with each other under urethanization conditions with or without a solvent.

  “Urethanization conditions” means that the reaction conditions are selected so that urethane groups are at least partially generated by the reaction of the isocyanate group-containing component (B) and the hydroxy group-containing component (A). To do.

  The temperature is usually up to 150.degree. C., preferably up to 120.degree. C., particularly preferably less than 100.degree. C. and very particularly preferably less than 90.degree. In the presence of the catalyst. However, the reaction can also be carried out in the absence of a catalyst.

  As a rule, the temperature of the reaction should be at least 20 ° C., preferably at least 30 ° C., particularly preferably at least 40 ° C. and very particularly preferably at least 50 ° C.

  Catalysts in this case are compounds that, due to their presence in the starting material mixture, lead to a higher proportion of urethane group-containing reaction products than the same starting material mixture in the absence of them under the same reaction conditions It is.

  These are, for example, organic amines, in particular aliphatic, cycloaliphatic or aromatic tertiary amines and / or Lewis acidic organometallic compounds. Lewis acidic organometallic compounds include, for example, tin compounds such as tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctate, tin (II) bis (ethylhexanoate) and tin (II ) Dilaurate and dialkyltin (IV) salts of organic carboxylic acids such as dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, Dioctyltin dilaurate and dioctyltin diacetate are worth considering. In addition, zinc (II) salts such as zinc (II) dioctate can be used. Metal complexes such as acetylacetonate of iron, titanium, aluminum, zirconium, manganese, nickel, zinc and cobalt are also possible. Further metal catalysts are described in Blank et al., Progress in Organic Coatings, 1999, Vol. 35, pp. 19-29.

  Preferred Lewis acidic organometallic compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) dioctate, zirconium acetylacetonate And zirconium-2,2,6,6-tetramethyl-3,5-heptanedionate.

Bismuth and cobalt catalysts and cesium salts can also be used as catalysts. As cesium salts, compounds in which the following anions are used are worth considering: F ⁻ , Cl ⁻ , ClO ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , Br, I ⁻ , IO ₃ ⁻ , CN ⁻ , OCN _{^{-, NO 2 -, NO 3}} -, HCO 3 -, CO 3 2-, S 2-, SH -, HSO 3 -, SO 3 2-, HSO 4 -, SO 4 2-, S 2 O 2 2- , S ₂ O ₄ ²⁻ , S ₂ O ₅ ²⁻ , S ₂ O ₆ ²⁻ , S ₂ O ₇ ²⁻ , S ₂ O ₈ ²⁻ , H ₂ PO ₂ ⁻ , H ₂ PO ₄ ⁻ , HPO ₄ ^2- , PO ₄ ^3- , P ₂ O ₇ ^4- , (OC _n H _{2n + 1} ) ⁻ , (C _n H _2n-1 O ₂ ) ⁻ , (C _n H _2n-3 O ₂ ) ^{− and} ( C _{n + 1} H _2n-2 O ₄ ) ²⁻ , where n represents a number from 1 to 20.

Preference is given here to the fact that the anion has the formula (C _n H _2n-1 O ₂ ) ^{− and} (C _{n + 1} H _2n-2 O ₄ ) ²⁻ , where n is 1-20. Cesium carboxylate according to Particularly preferred cesium salts have a monocarboxylic acid ion of the general formula (C _n H _2n-1 O ₂ ) ⁻ as an anion, where n represents a number from 1 to 20. In this case, mention may be made in particular of formate ion, acetate ion, propionate ion, hexanoate ion and 2-ethylhexanoate ion.

の有機金属塩、ここに、次の意味を有する：
Ａは、ヒドロキシル基又は水素原子であり、
ｎは、１〜３の数であり、
Ｒは、線状又は分枝鎖状の、脂肪族又は芳香族の多官能性炭化水素基であり、かつ
Ｍ⁺は、カチオン、例えばアルカリ金属カチオン又は第四級アンモニウムカチオン、例えばテトラアルキルアンモニウムである、並びに
・触媒として独国特許出願公開(DE-A)第2631733号明細書（米国特許(US-A)第4040992号明細書）に記載の式

［式中、前記基については前記明細書に記載された定義を有する］の第四級ヒドロキシアルキルアンモニウム化合物。 In addition, the following can be used as catalysts:
・ Formula described in U.S. Pat.No. 3,817,939

Organometallic salts of which have the following meaning:
A is a hydroxyl group or a hydrogen atom,
n is a number from 1 to 3,
R is a linear or branched, aliphatic or aromatic polyfunctional hydrocarbon group, and M ⁺ is a cation such as an alkali metal cation or a quaternary ammonium cation such as tetraalkylammonium. And the formula described in DE-A 26163733 (US Pat. No. 4040992) as a catalyst.

A quaternary hydroxyalkylammonium compound, wherein the group has the definition described in the specification.

［式中、
Ｙ^-＝カルボン酸イオン（Ｒ¹³ＣＯＯ^-）、フッ化物イオン（Ｆ^-）、炭酸イオン（Ｒ¹³Ｏ（ＣＯ）Ｏ^-）又は水酸化物イオン（ＯＨ^-）］に相当する第四級アンモニウム塩であり、これらは例えばＹ^-＝ＯＨ^-については米国特許第4324879号明細書に及び独国特許出願公開第2806731号及び同第2901479号明細書に記載されている。 Particularly suitable as a catalyst for this process is the formula

[Where:
Y ⁻ = quaternary ammonium corresponding to carboxylate ion (R ¹³ COO ⁻ ), fluoride ion (F ⁻ ), carbonate ion (R ¹³ O (CO) O ⁻ ) or hydroxide ion (OH ⁻ )] a salt, it is, for example Y ^- = OH ^- are described in U.S. Pat. No. 4324879 and German Patent application Publication No. 2806731 and the specification No. 2901479 for.

Preferably, the group Y ⁻ is a carboxylate ion, carbonate ion or hydroxide ion, and particularly preferably a carboxylate ion or hydroxide ion.

R ¹³ is hydrogen, C ₁ -C ₂₀ -alkyl, C ₆ -C ₁₂ -aryl or C ₇ -C ₂₀ -arylalkyl, in which each said group may be optionally substituted.

Preferably R ¹³ is hydrogen or C ₁ -C ₈ - alkyl.

Preferred quaternary ammonium salts are those in which the radicals R ^{9 to} R ¹² are the same or different alkyl radicals having 1 to 20, preferably 1 to 4 carbon atoms, said radicals optionally being a hydroxyl group or a phenyl group. Is replaced by

Two of the groups R ^{9 to} R ¹² may be combined with the nitrogen atom and optionally another nitrogen atom or oxygen atom to form a 5-membered, 6-membered or 7-membered heterocycle. The groups R ^{9 to} R ¹¹ are in each case the group R ¹² is a hydroxyalkyl group having 2 to 4 carbon atoms, preferably a hydroxyl group located in the 2-position relative to the quaternary nitrogen atom. Under certain conditions, it may be an ethylene group that forms a bicyclic triethylenediamine structure together with a quaternary nitrogen atom and another tertiary nitrogen atom. One hydroxy-substituted group or a plurality of hydroxy-substituted groups may have other substituents, such as C ₁ -C ₄ -alkyloxy substituents.

  In this case, the ammonium ion is a part of a one-membered or multi-membered ring system derived from, for example, piperazine, morpholine, piperidine, pyrrolidine, quinuclidine or diaza-bicyclo- [2.2.2] -octane. May be.

Examples of groups R ^{9 to} R ¹² having 1 to 20 carbon atoms are, independently of one another, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl 2-ethylhexyl, 2,4,4-trimethylpentyl, nonyl, isononyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3- Tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichloro Benzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, Diethoxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3- Hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2 -Metoki Ethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, phenyl, tolyl , Xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, t-butylphenyl, dodecylphenyl , Methoxyphenyl, dimethoxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyph Nyl, 2,6-dichlorophenyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, norbornyl or norbornenyl .

［式中、Ｒ¹⁴及びＲ¹⁵は互いに独立して水素又はＣ₁〜Ｃ₄−アルキルであってよい］で示される基であってよい。 Preferably, independently of one another, the groups R ^{9 to} R ¹² are C _{1 to} C ₄ -alkyl. R ¹² is additionally benzyl or formula

[Wherein R ¹⁴ and R ¹⁵ may be independently of each other hydrogen or C ₁ -C ₄ -alkyl].

Particularly preferred groups R ^{9 to} R ¹² are, independently of one another, methyl, ethyl and n-butyl, and for R ¹² additionally benzyl, 2-hydroxyethyl and 2-hydroxypropyl.

の有機金属塩、ここに、次の意味を有する：Ａはヒドロキシル基又は水素原子であり、ｎは１〜３の数であり、Ｒは線状又は分枝鎖状の、脂肪族又は芳香族の多官能性炭化水素基であり、かつＭは強塩基のカチオン、例えばアルカリ金属カチオン又は第四級アンモニウムカチオン、例えばテトラアルキルアンモニウムである。 Preferably, the following catalysts can be used in the process according to the invention:
Quaternary ammonium hydroxides, preferably N, N, N-trimethyl-N-benzylammonium hydroxide and N, N, N—hydroxide as described in DE-A 3806276 Trimethyl-N- (2-hydroxypropyl) ammonium.
Hydroxyalkyl-substituted quaternary ammonium hydroxides described in European Patent Application (EP-A) No. 10589 (US Pat. No. 4,324,879).
Formulas described in U.S. Pat.No. 3,817,939

Having the following meaning: A is a hydroxyl group or a hydrogen atom, n is a number from 1 to 3, and R is linear or branched, aliphatic or aromatic And M is a strong base cation such as an alkali metal cation or a quaternary ammonium cation such as tetraalkylammonium.

  A preferred catalyst is a zinc (II) salt, especially zinc acetylacetonate.

  More preferred is dibutyltin dilaurate.

  Depending on the activity, the catalyst is usually from 0.001 to 10 mol%, preferably from 0.5 to 8 mol%, particularly preferably from 1 to 7 mol% and very particularly preferably, based on the isocyanate group used. Used in an amount of 2-5 mol%.

  The polyisocyanate (B) is an excess of at least 3 times, preferably at least 4 times, particularly preferably at least 5 times the excess of NCO groups, based on the hydroxy groups in compound (A) Particularly preferred is an excess of at least 6 times.

  The unreacted part of the polyisocyanate (B) may be separated or preferably left in the reaction mixture.

  The reaction is preferably carried out without a solvent, but can also be carried out in the presence of at least one solvent. Similarly, the resulting reaction mixture can be blended into the solvent after completion of the reaction.

  Usable as solvents are those which have no groups reactive with isocyanate groups and are at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight, very particularly preferably at least 75% by weight, in particular at least 90% by weight and especially at least 95% by weight of polyisocyanates are those which are soluble.

  Examples of such solvents are aromatic hydrocarbons (including alkylated benzenes and naphthalene) and / or (cyclic) aliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, esters, alkoxylations Alkanoic acid alkyl esters, ethers, and mixtures of the above solvents.

As the aromatic hydrocarbon mixture, those mainly containing aromatic C ₇ -C ₁₄ -hydrocarbons and capable of containing a boiling range of 110 to 300 ° C. are preferred, and toluene, o-, m- or p-xylene, trimethylbenzene isomer, tetramethylbenzene isomer, ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.

These examples are ExxonMobil Chemical's Solvesso® brand, in particular Solvesso® 100 (CAS-No. 64742-95-6, mainly C ₉ and C ₁₀ -aromatic compounds, boiling range about 154 ˜178 ° C.), 150 (boiling range approximately 182-207 ° C.) and 200 (CAS-No. 64742-94-5), Shellsol® brand from Shell, Caromax® from Petrochem Carless ( For example, Caromax® 18) and DHC's Hydrosol (eg as Hydrosol® A 170). Hydrocarbon mixtures of paraffins, cycloparaffins and aromatic compounds can be obtained from Kristalloel (eg Kristalloel 30, boiling range approx. 158-198 ° C. or Kristalloel 60: CAS-No. 64742-82-1), white spirit (eg CAS- No. 64742-82-1) or solvent naphtha (light: boiling range of about 155 to 180 ° C., heavy: boiling range of about 225 to 300 ° C.) is also commercially available. The aromatics content of this kind of hydrocarbon mixture is usually more than 90% by weight, preferably more than 95% by weight, particularly preferably more than 98% by weight and very particularly preferably more than 99% by weight. It may be meaningful to use a hydrocarbon mixture with a particularly low content of naphthalene.

  (Cyclic) aliphatic hydrocarbons are, for example, decalins, alkylated decalins and isomeric mixtures of linear or branched alkanes and / or cycloalkanes. The content of aliphatic hydrocarbons is generally less than 5% by weight, preferably less than 2.5% by weight and particularly preferably less than 1% by weight.

  Esters are for example n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.

  Ethers are, for example, tetrahydrofuran (THF), dioxane and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol dimethyl ether, diethyl ether or di-n-butyl ether.

  Ketones are, for example, acetone, diethyl ketone, ethyl methyl ketone, isobutyl methyl ketone, methyl amyl ketone and t-butyl methyl ketone.

  A preferred embodiment of the present invention is to combine a high functionality polyisocyanate according to the present invention with a solvent. A preferred solvent is n-butyl acetate.

  The concentration of the polyisocyanate according to the invention in the solution should be at least 50% by weight, preferably at least 60% by weight and particularly preferably at least 70% by weight.

  The urethane group-containing highly functional polyisocyanates according to the invention generally have an NCO functionality of more than 2, preferably at least 3, particularly preferably at least 4, very particularly preferably at least 5 and in particular more than 6. Has functionality.

  The urethane group-containing highly functional polyisocyanates according to the invention usually have a number average molecular weight Mn of 1000 to 20000, preferably 1200 to 10,000 and particularly preferably 1500 to 5000 g / mol and a mass of 1000 to 50000 and preferably 1500 to 30000. It has an average molecular weight Mw. These molecular weights can be determined by gel permeation chromatography using a suitable polymer standard and tetrahydrofuran or dimethylformamide as the eluent.

  The urethane group-containing highly functional polyisocyanate according to the present invention is used, for example, in a two-component polyurethane paint containing at least one component (binder) having at least two groups reactive to isocyanate. The For this purpose, the urethane group-containing highly functional polyisocyanate according to the invention can be used alone or in a mixture with other polyisocyanates (C) as a crosslinker component.

  Other polyisocyanates (C) of this kind can be obtained by oligomerization of isocyanate monomers.

  The isocyanate monomer used for this purpose may be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, abbreviated herein as (cyclo) aliphatic. Particularly preferred are aliphatic isocyanates.

  Aromatic isocyanates are those having at least one aromatic ring system, ie pure aromatic compounds as well as araliphatic compounds.

  Cycloaliphatic isocyanates are those having at least one cycloaliphatic ring system.

  Aliphatic isocyanates are exclusively linear or branched, ie acyclic compounds.

  The isocyanate monomer is preferably a diisocyanate having exactly two isocyanate groups. However, in principle, it may also be a monoisocyanate having one isocyanate group.

  In principle, higher order isocyanates having on average more than 2 isocyanate groups are also worth considering. For this purpose, for example, triisocyanates such as triisocyanatononane, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4′-triisocyanatodiphenyl ether or diisocyanate, triisocyanate Mixtures of isocyanates and higher order polyisocyanates are suitable, for example polyphenyl polyisocyanates obtained by phosgenation of the corresponding aniline / formaldehyde condensates and having methylene bridges.

  These isocyanate monomers are essentially free of reaction products of their isocyanate groups with themselves.

The isocyanate monomer is preferably an isocyanate having 4 to 20 carbon atoms. Examples of conventional 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 diisocyanate 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5- Trimethyl-5- (isocyanatomethyl) cycl Hexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4-, or 2,6-diisocyanato-1-methylcyclohexane and 3 (or 4), 8 ( Or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ^2.6 ] decane isomer mixture, and aromatic diisocyanates such as 2,4- or 2,6-toluylene diisocyanates and the like 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, diphenylene-4, 4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldi-phenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-di Isocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

  Particularly preferred are 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane. Very particularly preferred are isophorone diisocyanate and 1,6-hexamethylene diisocyanate, particularly preferred is 1,6-hexamethylene diisocyanate.

  Mixtures of the aforementioned isocyanates may also be present.

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

  Dicyclohexylmethane-4,4'-diisocyanate may also exist as a mixture of various cis and trans isomers.

  It is possible to use diisocyanates obtained by phosgenation of the corresponding amines, as well as diisocyanates prepared without phosgene, i.e. by a phosgene-free process. For example, European Patent Application Publication (EP-A) No. 0126299 (U.S. Pat. No. 4,596,678), European Patent Application Publication (EP-A) No. 126300 (U.S. Pat. No. 4596679). ) And European Patent Application Publication (EP-A) No. 355443 (US Pat. No. 5087739), (cyclic) aliphatic diisocyanates such as 1, 6-hexamethylene diisocyanate (HDI), aliphatic diisocyanate isomers having 6 carbon atoms in the alkylene group, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1- Isocyanato-3-isocyanato-methyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI) is obtained by reacting (cyclic) aliphatic diamines with, for example, urea and alcohols (cyclic) aliphatic biscarbamines Acid ester And pyrolyzing them to the corresponding diisocyanates and alcohols. The synthesis is usually carried out continuously in the circulation and optionally in the presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products returned from the reaction process. The diisocyanates thus obtained usually have a very small proportion or even a non-measurable proportion of chlorinated compounds, which is advantageous, for example, for use in the electronics industry.

  In one embodiment, the isocyanate used is less than 200 ppm, preferably less than 120 ppm, particularly preferably less than 80 ppm, very particularly preferably less than 50 ppm, especially less than 15 ppm and especially less than 10 ppm hydrolyzable chlorine. Have a rate. This can be measured, for example, according to ASTM standard D4663-98. Of course, however, isocyanate monomers having a higher chlorine content, for example up to 500 ppm, can also be used.

  Of course, the isocyanate monomers obtained by reaction of the (cyclo) aliphatic diamines with, for example, urea and alcohols and the decomposition of the (cyclo) aliphatic biscarbamic esters obtained, and the phosgenation of the corresponding amines. It is also possible to use mixtures with diisocyanates obtained by

The polyisocyanate (C) that can be obtained by oligomerization of the isocyanate monomer is typically characterized as follows:
The average NCO functionality of such compounds is typically at least 1.8 and may be up to 8, preferably 2 to 5 and particularly preferably 2.4 to 4.

  The isocyanate group content after the oligomerization, calculated as NCO = 42 g / mol, is typically 5-25% by weight unless otherwise indicated.

Preferably, the polyisocyanate (C) is the following compound:
1) Polyisocyanates having isocyanurate groups from aromatic diisocyanates, aliphatic diisocyanates and / or cycloaliphatic diisocyanates. Particular preference is given in this case to the corresponding aliphatic isocyanatoisocyanurates and / or cycloaliphatic isocyanatoisocyanurates and in particular hexamethylene diisocyanate and isophorone diisocyanate. . The isocyanurate present is in particular a tris isocyanatoalkyl isocyanurate or tris isocyanatocycloalkyl isocyanurate which is a cyclic trimer of said diisocyanate, or more than one isocyanurate ring. And their higher homologues. The isocyanato isocyanurates generally have an NCO content of 10-30% by weight, in particular 15-25% by weight and an average NCO functionality of 2.6-8.

2) A polyisocyanate having an isocyanate group bonded to an aromatic, aliphatic and / or cycloaliphatic, preferably bonded to an aliphatic and / or cycloaliphatic and having a uretdione group, and in particular hexamethylene Those derived from diisocyanate or isophorone diisocyanate. Uretodione diisocyanate is a cyclic dimerization product of diisocyanate.
The polyisocyanates having uretdione groups are obtained within the scope of the invention in a mixture with other polyisocyanates, in particular those mentioned under 1). To that end, the diisocyanate is subjected to reaction conditions under which uretdione groups as well as other polyisocyanates are formed, or first the uretdione groups are formed and these are subsequently converted to other polyisocyanates. The reaction can be carried out under reaction conditions or under reaction conditions in which the diisocyanate is first converted to other polyisocyanates and these are subsequently converted to uretdione group-containing products.

  3) Polyisocyanates having aromatic, cycloaliphatic or aliphatically bonded, preferably cycloaliphatic or aliphatically bonded isocyanate groups and biuret groups, especially tris- (6-isocyanate) Nathexyl) -biuret or its higher homologues and mixtures. These polyisocyanates with biuret groups generally have an NCO content of 18-22% by weight and an average NCO functionality of 2.8-6.

  4) Polyisocyanates having isocyanate groups bonded to aromatic, aliphatic or cycloaliphatic, preferably bonded to aliphatic or cycloaliphatic, urethane groups and / or allophanate groups, For example, by reaction of an excess of diisocyanate, such as hexamethylene diisocyanate or isophorone diisocyanate, with a mono- or polyhydric alcohol. These polyisocyanates having urethane and / or allophanate groups generally have an NCO content of 12 to 24% by weight and an average NCO functionality of 2.5 to 4.5. Such polyisocyanates having urethane groups and / or allophanate groups can be used without catalysis or preferably in the presence of a catalyst, for example ammonium carboxylate or hydroxide, or an allophanate catalyst, for example a Zn (II) compound. Can be produced in the presence of monovalent, divalent or polyvalent, preferably monovalent alcohols, respectively.

  5) Polyisocyanates having an oxadiazine trione group, preferably those derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates having oxadiazine trione groups are available from diisocyanates and carbon dioxide.

  6) Polyisocyanates having iminooxadiazinedione groups, preferably those derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates having iminooxadiazinedione groups can be produced from diisocyanates using special catalysts.

  7) Uretonimine modified polyisocyanate.

  8) Carbodiimide-modified polyisocyanate.

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

  10) Polyurethane-polyisocyanate prepolymers from diisocyanates and / or polyisocyanates and alcohols.

  11) Polyurea-polyisocyanate prepolymer.

  12) Polyisocyanates 1) to 11), preferably 1), 3), 4) and 6) are bonded to aromatics, cycloaliphatics or aliphatics after their preparation, preferably (cyclic ) It can be converted to a polyisocyanate having an isocyanate group bonded to an aliphatic group and having a biuret group or a urethane group / allophanate group. Biuret groups are formed, for example, by adding water or reacting with an amine. Said formation of urethane groups and / or allophanate groups is effected by reaction with monovalent, divalent or polyvalent, preferably monovalent alcohols, optionally in the presence of a suitable catalyst. These polyisocyanates having biuret groups or urethane groups / allophanate groups generally have an NCO content of 18-22% by weight and an average NCO functionality of 2.8-6.

  13) A hydrophilically modified polyisocyanate, that is, a form obtained by adding a molecule having an NCO-reactive group and a hydrophilic group to the isocyanate group of the molecule in addition to the groups described in 1 to 12 above. A polyisocyanate having a group which occurs spontaneously. The latter are nonionic groups such as alkyl-polyethylene oxide and / or ionic groups derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, or salts thereof.

  14) Polyisocyanate modified for use in dual cure, ie, in addition to the groups described in 1-12, the isocyanate groups of the molecule can be cross-linked with NCO-reactive groups and UV or actinic radiation. A polyisocyanate having a group formally formed by the addition of a molecule having These molecules are, for example, hydroxyalkyl (meth) acrylates and other hydroxyvinyl compounds.

  Said diisocyanate or polyisocyanate may be present in at least partially blocked form.

  The types of compounds used to block are listed in DA Wicks, ZW Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001). Have been described.

  Examples of the types of compounds used to block are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoates, secondary amines, lactams, CH-acidic cyclics. Ketone, malonate or alkyl acetoacetate.

  In a preferred embodiment of the invention, the polyisocyanate (C) is from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, particularly preferably isocyanurates. And isocyanatolate-containing polyisocyanates, in particular selected from the group consisting of allophanates.

  In a particularly preferred embodiment, the polyisocyanate (C) is a polyisocyanate having an isocyanurate group from 1,6-hexamethylene diisocyanate.

  In a further particularly preferred embodiment, the polyisocyanate is a mixture of polyisocyanates having isocyanurate groups from 1,6-hexamethylene diisocyanate and isophorone diisocyanate.

  In a particularly preferred embodiment, the polyisocyanate (C) is a low-viscosity polyisocyanate, preferably a polyisocyanate having an isocyanurate group having a viscosity of less than 600 to 1500 mPa · s, in particular less than 1200 mPa · s, 200 to 1600 mPa A mixture containing low viscosity urethanes and / or allophanates having a viscosity of s, particularly 600-1500 mPa · s, and / or polyisocyanates having iminooxadiazinedione groups.

In this specification, unless otherwise noted, viscosities are described at 23 ° C. according to DIN EN ISO 3219 / A.3 in a cone-plate system with a velocity gradient of 1000 s ⁻¹ .

  The urethane group-containing highly functional polyisocyanate according to the invention can optionally be used in polyurethane paints with at least one binder in a mixture with other polyisocyanates (C) as crosslinker component.

Typically, for the polyisocyanate composition, i.e. the sum of the isocyanate group-containing compounds,
50 to 100% by weight, preferably 50 to 90% by weight and particularly preferably 60 to 80% by weight, and other polyisocyanates (C) 0 to 50% by weight, of urethane group-containing highly functional polyisocyanates according to the invention, Preferably 10-50% by weight, particularly preferably 20-40% by weight are used,
However, the total is always 100% by mass.

  Examples of the binder include polyacrylate polyol, polyester polyol, polyether polyol, polyurethane polyol; polyurea polyol; polyester polyacrylate polyol; polyester polyurethane polyol; polyurethane polyacrylate polyol, polyurethane-modified alkyd resin; fatty acid-modified polyester polyurethane polyol. , Copolymers with allyl ethers, for example graft polymers from said group of substances having different glass transition temperatures, as well as mixtures of said binders. Preference is given to polyacrylate polyols, polyester polyols and polyether polyols.

  Preferred OH numbers measured according to DIN 53240-2 are 40 to 350 mg KOH / g solid resin for polyester, preferably 80 to 180 mg KOH / g solid resin, and 15 to 250 mg KOH / g solid resin for polyacrylateol, preferably Is 80-160 mg KOH / g.

  In addition, the binder may have an acid number according to DIN EN ISO 3682 of up to 200 mg KOH / g, preferably up to 150 mg KOH / g and particularly preferably up to 100 mg KOH / g.

The polyacrylate polyol preferably has a molecular weight _Mn of at least 1000 g / mol, particularly preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol. The molecular weight M _n may in principle have no upper limit, but is preferably up to 200000 g / mol, particularly preferably up to 100000 g / mol, very particularly preferably up to 80000 g / mol and in particular up to 50000 g / mol.

  The latter includes, for example, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid (abbreviated herein as “(meth) acrylic acid”), preferably at least 2-20 carbon atoms and at least a hydroxy group Diols or polyols having two, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, tripropylene Ethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3- propane All, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl- 1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-octane-1,3-diol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2-, 1,3- and 1,4-bis (hydroxymethyl) -cyclohexane, 1,2-, 1,3- or 1,4-cyclohexanediol, glycerin, trimethylolethane, trimethylolpropane, tri Methylolbutane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerin, Reytol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomalt, 162-500, preferably poly-THF having a molar mass of 250-2000, poly-1,3 It may be a monoester with propanediol or polypropylene glycol having a molar mass of 134-2000 or polyethylene glycol having a molar mass of 238-2000.

  Preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate or 3- (acryloyloxy) -2-hydroxypropyl acrylate. Rates and particularly preferably 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate.

The monomer having a hydroxy group, other polymerizable, preferably radically polymerizable monomer, preferably, 50 mass percent is C ₁ -C ₂₀ -, preferably C ₁ -C ₄ - alkyl (meth) acrylate , (Meth) acrylic acid, vinyl aromatic compounds having up to 20 carbon atoms, vinyl esters of carboxylic acids having up to 20 carbon atoms, vinyl halides, 4-8 carbon atoms and 1 or 2 double bonds A mixture of monomers comprising non-aromatic hydrocarbons having unsaturated nitriles, unsaturated nitriles and mixtures thereof is charged to the copolymerization. Particularly preferred are 60 mass percent is C ₁ -C ₁₀ - alkyl (meth) acrylates, styrene and its derivatives, a polymer consisting of vinyl imidazole or mixtures thereof.

  Furthermore, the polymer may be a hydroxy-functional monomer corresponding to the hydroxy group content and optionally another monomer such as (meth) acrylic acid glycidyl epoxy ester, an ethylenically unsaturated acid, in particular a carboxylic acid, an acid anhydride. Or it may contain an acid amide.

  Further polymers are, for example, polyesterols, for example, which can be obtained by condensation of polycarboxylic acids, in particular dicarboxylic acids, with polyols, in particular diols. In order to ensure the functionality suitable for the polymerization of the polyester polyol, triols, tetraols, etc. as well as triacids, etc. are also used.

Polyester polyols are known, for example, from Ullmanns Encyklopaedie der technischen Chemie, 4th edition, volume 19, pp. 62-65. Preferably, a polyester polyol obtained by a reaction between a dihydric alcohol and a divalent carboxylic acid is used. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or the corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used for the preparation of the polyester polyols. The polycarboxylic acid may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may be optionally substituted and / or unsaturated, for example by halogen atoms. Examples of these include the following:
Oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid or Tetrahydrophthalic acid, suberic acid, azelaic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride , dimer fatty acid, esterifiable derivatives thereof isomers and hydrogenation products and said acid is used, such as anhydrides or dialkyl esters, for example C ₁ -C ₄ - alkyl ester, preferably methyl ester, ethyl Esters or n-butyl esters. Preference is given to dicarboxylic acids of the general formula HOOC— (CH ₂ ) _y —COOH in which y is an even number from 1 to 20, preferably from 2 to 20, particularly preferably succinic acid, adipic acid, Sebacic acid and dodecanedicarboxylic acid.

  As polyhydric alcohols, the following may be considered for the production of the polyesterol: 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, 162-4500, preferably poly-THF having a molar mass of 250-2000, poly-1,3-propanediol having a molar mass of 134-1178, 134 Poly-1,2-propanediol having a molar mass of ˜898, polyethylene glycol having a molar mass of 106 to 458 Coal, 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, trimethylol Ethane, neopentyl glycol, pentaerythritol, glycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerin, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (Galactitol), maltitol or isomalt, which may be alkoxylated as described above optionally.

Preference is given to alcohols of the general formula HO— (CH ₂ ) _x —OH, wherein x is a number from 1 to 20, preferably an even number from 2 to 20. Preference is given to ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. More preferred is neopentyl glycol.

  In addition, polycarbonate diols deserve consideration, which can be obtained, for example, by reaction of phosgene with an excess of low molecular alcohols listed as constituents of polyester polyols.

Also suitable are lactone based polyester diols, which are homopolymers or mixed polymers of lactones, preferably addition products having terminal hydroxyl groups of the lactone to a suitable bifunctional initiator molecule. It is worth considering that the lactone is preferably derived from a compound of the general formula HO— (CH ₂ ) _z —COOH, where z is a number from 1 to 20 and the hydrogen atom of the methylene unit is C ₁ -C ₄ - it may be substituted by an alkyl group. Examples are ε-caprolactone, β-propiolactone, γ-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthalene acid or pivalolactone and mixtures thereof. Suitable initiator components are, for example, the low molecular dihydric alcohols mentioned above as constituents of the polyester polyol. The corresponding polymer of ε-caprolactone is particularly preferred. Low order polyester diols or polyether diols may also be used as initiators in the production of the lactone polymer. Instead of the polymer of lactones, the corresponding polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used.

  Also suitable as polymers are polyetherols prepared by addition of ethylene oxide, propylene oxide or butylene oxide to the H-active ingredient. Similarly, polycondensates from butanediol are suitable.

  In addition, hydroxy-functional carboxylic acids such as dimethylolpropionic acid or dimethylolbutanoic acid can be used.

  Of course, the polymer may be a compound having a primary amino group or a secondary amino group.

  To produce the polyurethane paint, the polyisocyanate composition and the binder are 0.1: 1 to 10: 1, preferably 0.2: 1 to 5: 1, particularly preferably 0.3: 1 to 3. : 1, very particularly preferably 0.5: 1 to 2: 1, in particular 0.8: 1 to 1.2: 1 and especially 0.9: 1 to 1.1: 1 They are mixed with one another in a molar ratio of groups reactive to nalts, in which case further further components typical of paints can be incorporated and applied onto the substrate.

  Subsequently, the paint mixture is cured under suitable conditions. Depending on the application, this can be done for example at 100-140 ° C., for example in the case of paints in OEM applications, or at a lower temperature range, for example 20-80 ° C.

  This usually requires up to 12 hours, preferably up to 8 hours, particularly preferably up to 6 hours, very particularly preferably up to 4 hours and in particular up to 3 hours, depending on the temperature.

  Furthermore, the coating material may contain 0 to 10% by weight of at least one UV stabilizer.

  Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazoles (the latter available as Tinuvin® brand from Ciba-Spezialitaetenchemie) and benzophenones.

  These are additionally suitable radical scavengers such as steric hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof such as bis- (2,2 , 6,6-tetra-methyl-4-piperidyl) sebacate may be contained in an amount of 0 to 5% by mass.

  Furthermore, the coating material may further contain 0 to 10% by weight of further additives typical of paints.

  Additional additives typical of paints include, for example, antioxidants, activators (accelerators), fillers, pigments, dyes, antistatic agents, flameproofing agents, thickeners, thixotropic agents, surface active agents, Viscosity modifiers, plasticizers or chelating agents can be used.

  As thickeners, in addition to radical (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite deserve consideration.

  As chelating agents, for example, ethylenediamineacetic acid and their salts and β-diketones can be used.

  Suitable fillers are silicates, such as those obtained by hydrolysis of silicon tetrachloride, such as Aerosil® from Degussa, silica, talc, aluminum silicates, magnesium silicates, carbonates. Including calcium.

  The coating of the substrate is carried out by conventional methods known to those skilled in the art, in which at least one coating material is applied to the substrate to be coated in the desired thickness and is optionally included in the coating material. The volatile components present are removed, optionally with heating. This process can be repeated once or many times if desired. Application to the substrate in known ways, e.g. spray, trowel, spatula, brush, roll (Rollen), roll coating (Walzen), flow coating, lamination, back molding (Hinterspritzen) Or it can carry out by coextrusion.

  The thickness of such a layer to be cured may be from 0.1 μm to several mm, preferably from 1 to 2000 μm, particularly preferably from 5 to 200 μm, very particularly preferably from 5 to 60 μm (the solvent is from the paint). (Based on the paint being removed).

  Furthermore, a base coated with a paint containing a urethane group-containing polyisocyanate according to the present invention is also an object of the present invention.

  Such polyurethane paints are particularly suitable for applications requiring particularly high application reliability, outdoor weather resistance, optical quality, solvent resistance, chemical resistance and water resistance.

  The resulting two-component coating materials and paint formulations are in principle substrates, such as wood, veneer veneer, paper, paperboard, cardboard, textiles, film, leather, non-woven fabric, plastic surfaces, glass, ceramics, mineral building materials Suitable for example for cement-forming blocks and fiber cement boards or metal coatings, each of which may optionally be pre-coated or pre-treated. Particularly preferably, however, they are suitable for coating plastic surfaces and metal substrates.

  Preferably, these coating materials are used as clearcoats, basecoats and topcoats, primers and surfacers, in particular due to their high scratch resistance, as topcoats, preferably as clearcoats, in particular (large) vehicles and Suitable for coating on aircraft and in automotive paints for OEM and repair applications.

  The advantage of the urethane group-containing polyisocyanates according to the invention is that they produce high scratch resistance as well as good elasticity in the clearcoat. Moreover, the products according to the invention usually give lower viscosities.

Example:
Polyisocyanate A:
BASF SE's Basonat® HI 100, HDI isocyanurate having an NCO content of 22.2% and a viscosity of 3500 mPa · s at 23 ° C., a functionality of about 3.4.

Hazen color number:
Method for measuring the yellow color of industrial liquids according to DIN ISO 6271. An acidic solution of potassium hexachloroplatinate is used as a standard.

Comparative Example 1:
BASF SE's Basonat® HI 100: HDI isocyanurate having an NCO content of 22.2% and a viscosity of 2800 mPa · s at 23 ° C.

Comparative Example 2:
Bayer AG Desmodur® N3790: HDI isocyanurate (90% in butyl acetate) with an NCO content of 17.8% and a viscosity of 2150 mPa · s at 23 ° C.

Example 1:
300.00 g (0.524 mol) of polyisocyanate A and 13.00 g (0.087 mol) of triethanolamine were mixed in 134.1 g of butyl acetate. This solution was biphasic at room temperature and had an NCO content of 15.0%. The solution became homogeneous after raising its temperature from room temperature to 60 ° C. This mixture was reacted with the addition of dibutyltin dilaurate catalyst. After 1 hour at 60 ° C., the NCO content was 12.1%. The batch was then cooled and filtered off through a Zeit type filter T5500. The corresponding product had a viscosity of 440 mPa · s at 23 ° C. and a Hazen color number of 21.

Example 2:
360.99 g (0.630 mol) of polyisocyanate A and 10.43 g (0.070 mol) of triethanolamine were mixed in 159.2 g of butyl acetate. This solution was biphasic at room temperature and had an NCO content of 14.5%. This solution was homogeneous after raising its temperature from room temperature to 60 ° C. This mixture was reacted with the addition of dibutyltin dilaurate catalyst. After 1.5 hours at 60 ° C., the NCO content was 12.2%. The batch was then cooled and filtered off through a Zeit type filter T5500. The corresponding product had a viscosity of 320 mPa · s at 23 ° C. and a Hazen color number of 23.

Example 3:
343.80 g (0.600 mol) of polyisocyanate A and 7.45 g (0.050 mol) of triethanolamine were mixed in 150.54 g of butyl acetate. This solution was biphasic at room temperature and had an NCO content of 15.5%. This solution became homogeneous when the temperature was increased from room temperature to 60 ° C. This mixture was reacted with the addition of dibutyltin dilaurate catalyst. After 3 hours at 60 ° C., the NCO content was 13.5%. The batch was then cooled and filtered off through a Zeit type filter T5500. The corresponding product had a viscosity of 120 mPa · s at 23 ° C. and a Hazen color number of 21.

Example 4:
343.80 g (0.600 mol) of polyisocyanate A is mixed in 153.5 g of butyl acetate, and 5.40 g (0.060 mol) of 1,4-butanediol and 8.94 g (0.060 mol) of triethanolamine are mixed. Mol) was added. This solution was cloudy at room temperature and had an NCO content of 14.8%. This solution became clear after raising its temperature from room temperature to 60 ° C. This mixture was reacted with the addition of dibutyltin dilaurate catalyst. After 2.5 hours at 60 ° C., the NCO content was 11.8%. The batch was then cooled and filtered off through a Zeit type filter T5500. The corresponding product had a viscosity of 370 mPa · s at 23 ° C. and a Hazen color number of 28.

Applied technical test:
The polyisocyanates according to the invention as well as the comparative polyisocyanates are free of acrylic acid, hydroxy-functional polyacrylate polyols (Joncryl® 922, BASF; solid content = 80% in butyl acetate; OH number = 143 mg KOH / G, corresponding to a 1: 1 NCO / OH stoichiometric ratio) and adjusted with butyl acetate to an application viscosity of 20 s (DIN 53 211, cup 4 mm spout). Using an applicator frame, a coating having a wet film thickness of 200 μm was applied on a metal plate. The clearcoat thus obtained was cured after 10 minutes of flash-off time at room temperature or for a period of 30 minutes at 60 ° C. for measurement of scratch and acid resistance. Prior to the test, the coatings were stored for 24 h at 23 ± 2 ° C. and 50 ± 10% air humidity.

Test method:
The period between paint formulation and complete gelation of the paint is considered the gel time.
In order to determine the drying speed of the paint surface, the applied paint was touched with cotton balls at regular intervals. The test is terminated as soon as cotton fibers no longer adhere on the paint surface.

  The shaking hardness was measured by Koenig (EN ISO 1522).

  Cross cut measurements were made according to EN ISO 2409. In that case, the score is from 0 (very good adhesion) to 5 (very poor adhesion).

  In order to measure the scratch resistance of the paint, the surface is scratched with a corundum particle-containing abrasive nonwoven fabric weighing 500 g. The damage is determined by the gloss value of the paint. The reflow is determined by performing a heat treatment at the temperature shown in the table for the period shown in the table after scratching by 50 reciprocations.

A sulfuric acid resistance test (etching test) was carried out in a temperature range of 35-75 ° C. according to EN ISO 2812-1 (method 3):
Using a pipette, a 25 μm drop of 1% sulfuric acid is added onto the paint cured at a given temperature (80 or 130 ° C. for 30 minutes) on a gradient oven plate, and this is added at 35-75 ° C. in a gradient oven. Heated for 30 minutes. The plate was then rinsed with water and dried. Shown is the lowest temperature at which the initial etching of the paint could be confirmed by visual inspection.

  In the table, 80 ° C. or 130 ° C. indicates the curing temperature of the paint.

  n.b. represents an unmeasured measurement value.

Claims (12)

A highly functional polyisocyanate having a urethane group,
At least one tertiary dialkanolamine or trialkanolamine (A),
At least one kind having at least one functionality having at least one isocyanurate, biuret, uretdione and / or allophanate group and composed of an aliphatic isocyanate and / or a cycloaliphatic isocyanate Polyisocyanate (B) of
Obtained by reacting under the reaction conditions in which a urethane group is formed between (A) and (B), provided that
The molar ratio of NCO groups to OH groups between (B) and (A) is at least 3: 1;
A highly functional polyisocyanate having a urethane group.   The urethane group according to claim 1, wherein the polyisocyanate (B) is a polyisocyanate having an isocyanurate group based on 1,6-hexamethylene diisocyanate having a viscosity of 600 to 3000 mPa · s. High functionality polyisocyanate having. Tertiary dialkanolamine or trialkanolamine (A) is 5- [bis (2'-hydroxyethyl) amino] -3-oxa-pentan-1-ol, triethanolamine, tripropanolamine, N-ethyl The highly functional polyisocyanate having a urethane group according to claim 1, which is selected from the group consisting of diethanolamine, N-methyldiethanolamine and N-butyldiethanolamine.   The highly functional polyisocyanate having a urethane group according to claim 3, wherein the trialkanolamine (A) is triethanolamine.   The high functionality having a urethane group according to claim 1, wherein 10 to 70% of the total amount of hydroxy groups used in addition to the compound (A) is derived from the diol (A1) and / or the polyol (A2). Polyisocyanate.   Use of a highly functional polyisocyanate having a urethane group according to any one of claims 1 to 5 in a two-component coating material. -At least one highly functional polyisocyanate having a urethane group according to any one of claims 1 to 5 ;
At least one compound having at least two groups reactive with isocyanate groups,
-Two-component coating materials optionally containing solvents, pigments, additives and / or thickeners. A polyurethane coating material, characterized in that the high-functional polyisocyanate having a urethane group according to any one of claims 1 to 5 is reacted with at least one binder having a group reactive with isocyanate. Manufacturing method. A highly functional polyisocyanate having a urethane group according to any one of claims 1 to 5 , a polyacrylate polyol, a polyester polyol, a polyether polyol, a polyurethane polyol, a polyurea polyol, a polyetherol, a polycarbonate, Selected from the group consisting of polyester polyacrylate polyols, polyester polyurethane polyols, polyurethane polyacrylate polyols, polyurethane-modified alkyd resins, fatty acid-modified polyester polyurethane polyols, copolymers with allyl ethers and copolymers or graft polymers from the aforementioned substance groups A method for producing a polyurethane paint, characterized by reacting with at least one binder. Use of a highly functional polyisocyanate having a urethane group according to any one of claims 1 to 5 as a curing agent in a polyurethane coating. Use of the highly functional polyisocyanate having a urethane group according to any one of claims 1 to 5 as a curing agent in repair coating, wood coating or large vehicle coating. Use of a highly functional polyisocyanate having a urethane group according to any one of claims 1 to 5 as a curing agent in paints, adhesives or sealants.