Alkoxysilane-functionalized allophanates

Abstract

The present invention relates to alkoxysilane-functionalized allophanates, to methods for production thereof, and to the use thereof. In particular, the alkoxysilane-functionalized allophanate includes the reaction product of A) at least one alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1,
where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2, and B) at least one diisocyanate B), in a molar ratio of A) to B) of 3:1 to 1.5:1.

Claims

1. An alkoxysilane-functionalized allophanate comprising the reaction product of A) at least one alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1, where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2, and B) at least one diisocyanate B), in a molar ratio of A) to B) of 3:1 to 1.5:1.

2. The alkoxysilane-functionalized allophanate according to claim 1, wherein the molar ratio of A) to B) is from 2.5:1 to 1.8:1.

3. The alkoxysilane-functionalized allophanate according to claim 1, wherein R, R.sup.1, R.sup.2 and R.sup.3 are at the same time or each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

4. The alkoxysilane-functionalized allophanate according to claim 1, wherein n is 0, R.sup.1 and R.sup.3 are at the same time or each independently methyl or ethyl, and R.sup.2 is at the same time or mutually independently methyl or propyl.

5. The alkoxysilane-functionalized allophanate according to claim 1, wherein n is 0 and R.sup.2 is methyl or propyl, and R.sup.1 is methyl or ethyl and R.sup.3R.sup.1.

6. The alkoxysilane-functionalized allophanate according to claim 1, wherein n is 0, R.sup.1 and R.sup.3 are methyl and R.sup.2 is propyl.

7. The alkoxysilane-functionalized allophanate according to claim 1, wherein the diisocyanate B) is selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2-di cyclohexylmethane diisocyanate (2,2-H12MDI), 2,4-dicyclohexylmethane diisocyanate (2,4-H12MDI), 4,4-dicyclohexylmethane diisocyanate (4,4-H12MDI), 2-methylpentane diisocyanate (MPDI), pentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-TMDI), 2,4,4-trimethylhexamethylene diisocyanate (2,4,4-TMDI), norbornane diisocyanate (NBDI), methylenediphenyl diisocyanate (MDI), toluidine diisocyanate (TDI), tetramethylxylylene diisocyanate (TMXDI), xylylene diisocyanate (MXDI), individually or in a mixture.

8. The alkoxysilane-functionalized allophanate according to claim 1, wherein the diisocyanate B) is selected from IPDI, 4,4-H12MDI, HDI and mixtures of 2,2,4-TMDI and 2,4,4-TMDI, individually or in a mixture.

9. A composition, which may be coating compositions and paint compositions for metal, plastic, glass, wood, MDF (Middle Density Fibreboards) or leather substrates or other heat-resistant substrates, the composition comprising the alkoxysilane-functionalized allophanates according to claim 1.

10. An adhesive composition for bonding of metal, plastic, glass, wood, MDF or leather substrates or other heat-resistant substrates, the adhesive composition comprising the alkoxysilane-functionalized allophanates according to claim 1.

11. A coating composition, adhesives or sealant, comprising at least one alkoxysilane-functionalized allophanate according to claim 1.

12. An alkoxysilane-functionalized allophanate, obtained by reacting A) at least one alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1, where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2, and B) at least one diisocyanate B), in a molar ratio of A) to B) of from 3:1 to 1.5:1; C) optionally in the presence of at least one catalyst C), and D) optional reaction of the residual amount of NCO groups of B) with an alcohol D).

13. The alkoxysilane-functionalized allophanate according to claim 12, wherein the component c) is selected from the group consisting of metal carboxylates, tert-amines, amidine, guanidine, quaternary ammonium salts, tetraalkylammonium salts, quaternary phosphonium salts, metal acetylacetonates, quaternary ammonium acetylacetonates, quaternary phosphonium acetylacetonates, alone or in a mixture.

14. The alkoxysilane-functionalized allophanate according to claim 12, wherein the component c) is zinc acetylacetonate and/or zinc ethylhexanoate.

15. The alkoxysilane-functionalized allophanate according to claim 12, wherein the alcohol D) is selected from methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, pentanol, ethyl-2-hexanol, 1-hexanol.

16. A method for preparing alkoxysilane-functionalized allophanates according to claim 12, by reacting A) at least one alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1, where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2, and B) at least one diisocyanate B), in a molar ratio of A) to B) of from 3:1 to 1.5:1; C) optionally in the presence of at least one catalyst C), and D) optional reaction of the residual amount of NCO groups of B) with an alcohol D).

17. The method according to claim 16, wherein the reaction is carried out at temperatures in the range from 15 to 40 C.

18. The method according to claim 16, wherein the reaction is carried out at temperatures in the range from 80 to 220 C.

19. The method according to claim 16, wherein the reaction of the residual amount of NCO groups of B) with an alcohol D) is carried out at temperatures in the range of 30-150 C.

20. The method according to claim 16, wherein the reaction is carried out in the presence of zinc acetylacetonate and/or zinc ethylhexanoate as catalyst C).

21. The method according to claim 16, wherein the residual amount of NCO groups of B) is reacted with an alcohol D) at the ratio of the NCO groups to OH groups of the alcohol D) of from 0.8:1 to 1.2:1.

Description

DETAILED DESCRIPTION

(1) The invention relates to alkoxysilane-functionalized allophanates comprising the reaction product of A) at least one, preferably one, alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1, where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2, and B) at least one diisocyanate B), in a molar ratio of A) to B) of from 3:1 to 1.5:1, preferably from 2.5:1 to 1.8:1, particularly preferably 2:1.

(2) Here, alkoxysilane-functionalized allophanates, which comprise the reaction product specified, are understood to mean in particular allophanates which consist of the reaction product of monourethane and diisocyanate itself or which were derivatized or further reacted based on unreacted isocyanate groups potentially in the reaction product. Preferably the reaction product specified is an allophanate which consists of the reaction product of monourethane and diisocyanate itself or which has been derivatized, i.e. reacted or capped, based on unreacted isocyanate groups potentially in the reaction product. Particularly preferably, the reaction product specified is an allophonate which consists of the reaction product of monourethane and diisocyanate itself or which has been reacted with at least one alcohol based on unreacted isocyanate groups potentially in the reaction product.

(3) The allophanates according to the invention, which can be considered as the reaction of at least one monourethane with at least one diisocyanate, are adducts having on average one or two allophanate units, since the diisocynate can react partially or completely with one or two monourethanes. However, the allophonate according to the invention preferably has two allophonate units.

(4) The reaction product is obtained by reacting at least one monourethane with at least one diisocyanate in the stoichiometry specified. Preferably, the reaction product is obtained by reacting one monourethane with at least one diisocyanate in the stoichiometry specified. More preferably, the reaction product is obtained by reacting one monourethane with one diisocyanate in the stoichiometry specified.

(5) One monourethane or one diisocyanate is understood to mean in this case the empirical formula of the respective monourethane or the respective diisocyanate in each case.

(6) The invention preferably relates to alkoxysilane-functionalized allophanates consisting of the reaction product of A) and B), as defined above, reacted in a molar ratio of A) to B) of 3:1 to 1.5:1, preferably from 2.5:1 to 1.8:1, particularly preferably 2:1.

(7) The invention also relates to alkoxysilane-functionalized allophanates, obtained by reacting A) at least one, preferably one, alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1, where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2, and B) at least one diisocyanate B), in a molar ratio of A) to B) of from 3:1 to 1.5:1, preferably from 2.5:1 to 1.8:1, particularly preferably 2:1; C) optionally in the presence of at least one catalyst C), and D) optional reaction of the residual amount of NCO groups of B) with an alcohol D).

(8) R, R.sup.1, R.sup.2 and R.sup.3 are preferably at the same time or each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

(9) Preferably, n=0.

(10) R.sup.1 and R.sup.3 are preferably at the same time or each independently methyl or ethyl.

(11) R.sup.2 is preferably methyl or propyl.

(12) Preference is given to compounds where n is 0, R.sup.1 and R.sup.3 are at the same time or each independently methyl or ethyl, and R.sup.2 is at the same time or mutually independently methyl or propyl.

(13) Preferably, R.sup.3R.sup.1.

(14) Preference is given to compounds where n is 0 and R.sup.2 is methyl or propyl, and R.sup.1 is methyl or ethyl and R.sup.3R.sup.1.

(15) Very particular preference is given to the compound where n is 0, R.sup.1 and R.sup.3 are methyl and R.sup.2 is propyl, N-trimethoxysilylpropylmethyl carbamate.

(16) After the reaction according to the invention of the alkoxysilane group-containing monourethane A) with the diisocyanate B), the NCO content in the end product is preferably <3% by weight, particularly preferably <1% by weight, especially preferably <0.2% by weight.

(17) The diisocyanate B) used in accordance with the invention may be any aliphatic, cycloaliphatic and/or (cyclo)aliphatic diisocyanate. In one preferred embodiment the term (cyclo)aliphatic diisocyanate as used herein means that in a molecule there are present simultaneously NCO groups bonded to a ring and NCO groups bonded to an aliphatic radical, as is the case, for example, for isophorone diisocyanate. In one preferred embodiment the term cycloaliphatic diisocyanate as used herein refers to a diisocyanate which only has NCO groups bonded directly on the cycloaliphatic ring,

(18) e.g. diisocyanatodicyclohexylmethane (H12MDI).

(19) Aliphatic diisocyanates preferably suitable for use as diisocyanate B) include a linear and/or branched alkylene radical having preferably 3 to 16 carbon atoms, more preferably 4 to 12 carbon atoms. Preferably suitable cycloaliphatic or (cyclo)aliphatic diisocyanates include a cycloalkylene radical having preferably 4 to 18 carbon atoms, more preferably 6 to 15 carbon atoms. Preferred examples of suitable diisocyanates include cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane di- and triisocyanate, undecane di- and triisocyanate, dodecane di- and triisocyanates. Likewise preferably suitable are 4-methylcyclohexane 1,3-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4-methylenebis(cyclohexyl) diisocyanate and/or 1,4-diisocyanato-4-methylpentane.

(20) Preferred diisocyanates B) are isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2-dicyclohexylmethane diisocyanate (2,2-H12MDI), 2,4-dicyclohexylmethane diisocyanate (2,4-H12MDI), 4,4-di cyclohexylmethane diisocyanate (4,4-H12MDI), 2-methylpentane diisocyanate (MPDI), pentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-TMDI), 2,4,4-trimethylhexamethylene diisocyanate (2,4,4-TMDI), norbornane diisocyanate (NBDI), methylenediphenyl diisocyanate (MDI), toluidine diisocyanate (TDI), tetramethylxylylene diisocyanate (TMXDI), xylylene diisocyanate (MXDI), individually or in a mixture.

(21) In a particularly preferred embodiment, the diisocyanate B) is IPDI and/or 4,4-H12MDI and/or HDI and/or a mixture of 2,2,4-TMDI and 2,4,4-TMDI.

(22) The invention also relates to a method for preparing alkoxysilane-functionalized allophanates, by reacting A) at least one, preferably one, alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1, where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2,

(23) and B) at least one diisocyanate B),

(24) in a molar ratio of A) to B) of from 3:1 to 1.5:1, preferably from 2.5:1 to 1.8:1, particularly preferably 2:1; C) optionally in the presence of at least one catalyst C),

(25) and D) optional reaction of the residual amount of NCO groups of B) with an alcohol D).

(26) The allophanates according to the invention are generally prepared solventlessly or using non-protic solvents, and the reaction may take place batchwise or continuously. The reaction is conducted in suitable equipment, for example stirred tanks, extruders, static mixers, kneading chambers. The reaction can be conducted at room temperature, i.e. at temperatures in the range of 15 to 40 C., especially in the range of 15 to 25 C. However, preference is given to using higher temperatures in the range from 80 to 220 C., especially in the range from 80 to 120 C. The reaction is conducted with exclusion of water. Preference is given to conducting the reaction solventlessly.

(27) To accelerate the reaction, it is advantageously possible to use catalysts C) known in urethane chemistry, for example organometallic compounds such as tin or zinc compounds, salts, for example Zn(II) chloride, and/or bases. Suitable examples are carboxylates of Sn, Bi, Zn and other metals, for example dibutyltin dilaurate, tin octoate, zinc ethylhexanoate, bismuth neodecanoate, tert-amines, for example 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), triethylamine, amidine, guanidine, and quaternary ammonium salts, preferably tetraalkylammonium salts, and/or quaternary phosphonium salts.

(28) Useful catalysts C) also include metal acetylacetonates. Examples thereof are zinc acetylacetonate, lithium acetylacetonate, iron acetylacetonate and tin acetylacetonate, alone or in mixtures. Preference is given to using zinc acetylacetonate or zinc ethylhexanoate. Useful catalysts are also quaternary ammonium acetylacetonates or quaternary phosphonium acetylacetonates.

(29) After the reaction according to the invention of the alkoxysilane group-containing monourethane A) with the diisocyanate B), the NCO content is preferably <3% by weight, particularly preferably <1% by weight, especially preferably <0.2% by weight. In the case that the NCO content is between 3% by weight and 0.2% by weight, the residual amounts of NCO groups of B) are reacted with an alcohol D) at the ratio of NCO groups to OH groups of the alcohol D) of from 0.8:1 to 1.2:1, preferably from 0.9:1 to 1.1:1, the stoichiometric reaction i.e. at the ratio of 1:1, being especially preferred. The reaction of the residual amount of NCO groups of B) with an alcohol D) is preferably carried out at temperatures in the range of 30-150 C., in particular in the range of 50-150 C. The reaction is carried out with exclusion of water. Preference is given to conducting the reaction solventlessly.

(30) Preferred alcohols D) used are linear or branched alcohols wherein the hydroxyl function is attached to a primary, secondary or tertiary carbon atom. It is also possible to use diols or polyols. Particular preference is given to methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, pentanol, ethyl-2-hexanol, 1-hexanol. Very particular preference is given to ethanol, propanol and 1-butanol.

(31) The invention also relates to coating compositions and adhesives, comprising or consisting of: alkoxysilane-functionalized allophanates comprising the reaction product of A) at least one, preferably one, alkoxysilane group-containing monourethane A) of the formula 1
R.sub.n(OR.sup.1).sub.3-nSiR.sup.2NH(CO)OR.sup.3formula 1, where R, R.sup.1, R.sup.2 and R.sup.3 are each independently hydrocarbyl radicals having 1-8 carbon atoms, which may be linear, branched or cyclic, or else may be integrated together to form a cyclic system, and n is 0-2, and B) at least one diisocyanate B), in a molar ratio of A) to B) of from 3:1 to 1.5:1.

(32) Also provided by the invention is the use of the alkoxysilane-functionalized allophanates according to the invention in coating compositions and paint compositions for metal, plastic, glass, wood, MDF (Middle Density Fiberboards) or leather substrates or other heat-resistant substrates.

(33) The invention also provides the use of the alkoxysilane-functionalized allophanates in adhesive compositions for bonding of metal, plastic, glass, wood, MDF or leather substrates or other heat-resistant substrates.

(34) The present invention is more particularly illustrated by the following non-limiting examples from which further features, embodiments, aspects and advantages of the present invention may be discerned.

EXAMPLES

(35) Feedstocks:

(36) Vestanat EP-UPMS: Trimethoxysilylpropyl methyl carbamate (Evonik Resource Efficiency GmbH)

(37) Vestanat IPDI: Isophorone diisocyanate (Evonik Resource Efficiency GmbH)

(38) Vestanat TMDI: Mixture of 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-TMDI) and 2,4,4-trimethylhexamethylene diisocyanate (Evonik Resource Efficiency GmbH)

(39) Vestanat HT 2500/100: Hexamethylene-1,6-diisocyanate, homopolymer (isocyanurate type) (Evonik Resource Efficiency GmbH)

(40) Vestanat EP Cat 11 B: Tetraethylammonium benzoate in butanol (Evonik Resource Efficiency GmbH)

(41) Tegoglide 410: Glide and antiblocking additive based on a polyether siloxane copolymer (Evonik Resource Efficiency GmbH)

(42) 1. Preparation

Example 1

Alkoxysilane-Functionalized Allophanate 1

(43) A three-necked flask with reflux condenser was initially charged with 340.2 g of Vestanat EP-UPMS, 0.3 g of zinc(II) ethylhexanoate and 159.7 g of Vestanat IPDI, flushed with nitrogen and heated to 100 C. with stirring. After heating for 20 hours, an NCO content of 1.4% by weight NCO was obtained. 10.84 g of butanol were then added and the mixture was heated at 100 C. for 1 h, until an NCO content of <0.1% by weight NCO was reached. After cooling to room temperature, the alkoxysilane-functionalized allophanate 1 according to the invention is obtained as a clear liquid with a viscosity of 14.3 Pas (at 23 C.).

Example 2

Alkoxysilane-Functionalized Allophanate 2

(44) A three-necked flask with reflux condenser was initially charged with 474.6 g of Vestanat EP-UPMS, 0.22 g of zinc(II) ethylhexanoate and 211.8 g of Vestanat TMDI, flushed with nitrogen and heated to 100 C. with stirring. After heating for 24 hours, an NCO content of 0.8% by weight NCO was obtained. 10.35 g of butanol were then added and the mixture was heated at 65 C. for 3 h until an NCO content of <0.1% by weight NCO was reached. After cooling to room temperature, the alkoxysilane-functionalized allophanate 2 according to the invention is obtained as a clear liquid with a viscosity of 1170 mPas (at 23 C.).

Comparative Example 3A

Alkoxysilane-Functionalized Allophanate 3A (Comparative Example)

(45) A three-necked flask with reflux condenser was initially charged with 44.3 g of Vestanat EP-UPMS, 0.01 g of zinc(II) ethylhexanoate and 35.7 g of Vestanat HT 2500/100, flushed with nitrogen and heated to 100 C. with stirring until the NCO content of <0.1% by weight was achieved. With continued heating for the purpose of lowering viscosity, 20 g of butyl acetate were then added. The alkoxysilane-functionalized allophanate 3 thus obtained is a clear liquid with a viscosity of 750 mPas (at 23 C.).

Comparative Example 3B

Alkoxysilane-Functionalized Allophonate 3B (Comparative Example)

(46) A three-necked flask with reflux condenser was initially charged with 335.7 g of Vestanat EP-UPMS, 0.076 g of zinc(II) ethylhexanoate, 237.8 g of Vestanat HT 2500/100 and 152 g of xylene, blanketed with nitrogen and heated to 100 C. with stirring until the NCO content of 1% by weight was reached. 13.58 g of butanol were then added and the mixture heated at 100 C. for 0.5 h until an NCO content of <0.1% by weight NCO was reached. The alkoxysilane-functionalized allophanate 3b thus obtained is a clear liquid with a viscosity of 542 mPas (at 23 C.).

(47) 2. Preparation of Clearcoats from the Alkoxysilane-Functionalized Allophanates as Coating Compositions

(48) For the formulation of the clearcoats according to the invention and the comparative examples, the components of the compositions shown in Table 1 and 2 were mixed directly before processing.

(49) The viscosity of the formulations, determined as the flow time in the DIN 4 cup at 23 C., was approximately 60 seconds.

(50) TABLE-US-00001 TABLE 1 Composition of the inventive clearcoats and comparative example of systems curing at room temperature (RT) Data in % by weight IIIa IIIb (com- (com- para- para- Item I II tive) tive) 1 Allophanate 1 91.24 2 Allophanate 2 99.00 3 Comparative example: 98.5 Allophanate 3a (comparative) 4 Comparative example: 98.5 Allophanate 3b (comparative) 5 1,8-Diazabicyclo[5.4.0]undec- 0.92 1.0 1.0 1.0 7-ene (DBU) 6 Xylene 7.79 0.45 0.45 7 Tegoglide 410 0.05 0.45 0.05

(51) Based on the resin, the content of catalyst DBU is 1.0% in examples I and II and 1.25% DBU in example IIIa and b.

(52) TABLE-US-00002 TABLE 2 Composition of the inventive clearcoats and comparative example of hot-curing systems Data in % by weight Va Vb Item IV (comparative) (comparative) 1 Allophanate 1 84.00 2 Allophanate 2 3 Comparative example: 88.53 Allophanate 3a (comparative) 4 Comparative example: 88.53 Allophanate 3b (comparative) 5 Vestanat Cat 11 B 1.71 1.45 1.45 6 Xylene 14.29 10.02 10.02

(53) Based on the resin, the content of catalyst Vestanat Cat 11 B is 1.0% in all examples.

(54) The mechanical characteristics were determined by applying all of the coating materials to phosphatized steel plates (Chemetall Gardobond 26S/60/OC) using a 100 m doctor blade and curing them at room temperature (23 C.), Table 3, or at 140 C., Table 4.

(55) TABLE-US-00003 TABLE 3 Coating properties of the compositions I-III after curing at 23 C. (7 days) IIIa IIIb Composition I II (comparative) (comparative) Pendulum hardness 189 168 158 140 (Knig) [s] n 7 d MEK test >150 >150 >150 >150 [ASTM D 4752] (Double rubs, 1 kg applied weight) Appearance of the glossy glossy glossy glossy coating

(56) The coating properties of coatings I and II, comprising the inventive alkoxysilane-functionalized allophanate 1 or 2, show significantly higher pendulum hardness than comparative examples IIIa and b. In particular, in the three-fold functionalized product in coating material IIIa and b, a greater hardness would have been expected due to the higher degree of crosslinking.

(57) TABLE-US-00004 TABLE 4 Coating properties of the compositions IV-V after curing at 140 C. (22 min) Va Vb Composition IV (comparative) (comparative) Pendulum hardness 178 118 59 (Knig) [s] n 1 d MEK test >150 >150 >150 [ASTM D 4752] (Double rubs, 1 kg applied weight) Appearance of the glossy matt glossy coating

(58) The coating properties of coating IV comprising the inventive alkoxysilane-functionalized allophanate 1 shows a significantly higher pendulum hardness than comparative examples V a and b. In particular, in the three-fold functionalized product in coating material V a and b, a greater hardness would have been expected due to the higher degree of crosslinking. In addition, coating IV, with its glossy surface, exhibits a better appearance than the matt coating Va.

(59) The results from Table 3 and 4 show that the inventive alkoxysilane-functionalized allophanates may be used for the development of highly crosslinked, particularly rigid coatings and only these can be used in this case as sole binder both in cold and hot curing, even solvent-free if required.