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Publication numberCN104736583 B
Publication typeGrant
Application numberCN 201380052146
PCT numberPCT/EP2013/067151
Publication date15 Mar 2017
Filing date16 Aug 2013
Priority date4 Oct 2012
Also published asCN104736583A, EP2904026A1, US9574089, US20150240085, WO2014053268A1
Publication number201380052146.4, CN 104736583 B, CN 104736583B, CN 201380052146, CN-B-104736583, CN104736583 B, CN104736583B, CN201380052146, CN201380052146.4, PCT/2013/67151, PCT/EP/13/067151, PCT/EP/13/67151, PCT/EP/2013/067151, PCT/EP/2013/67151, PCT/EP13/067151, PCT/EP13/67151, PCT/EP13067151, PCT/EP1367151, PCT/EP2013/067151, PCT/EP2013/67151, PCT/EP2013067151, PCT/EP201367151
InventorsG·克莱恩, P·霍夫曼, A·费格尔, F·尼德尔迈尔, N·施泰德尔, B·瓦尔特
Applicant巴斯夫涂料有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
含氟非水性涂料组合物、涂覆方法和涂料组合物的用途 The use of non-fluorine-containing aqueous coating compositions, coating methods and coating compositions of translated from Chinese
CN 104736583 B
Abstract  translated from Chinese
本发明提供非水性涂料组合物,所述组合物包含30‑80重量%的至少一种聚(甲基)丙烯酸酯(A)、20‑70重量%的一种或多种含多异氰酸酯基团化合物(B),和一种或多种催化剂(D),其中重量百分数每种情况下分别基于(A)和(B)的基料含量,且(A)加(B)的重量含量之和每种情况下为100重量%,其中聚(甲基)丙烯酸酯(A)包含0.05‑15.0重量%的一种或多种如下组分的含氟反应产物:一种或多种具有两个具有不同反应性的异氰酸酯基团的二异氰酸酯(PI)、一种或多种(全)氟烷基单醇组分(FA),和任选一种或多种具有至少一个对异氰酸酯基团呈反应性的基团(G1)且任选具有不同于基团(G1)的其它官能团(G2)的化合物(V)。 The present invention provides a non-aqueous coating composition, said composition comprising 30-80% by weight of at least one poly (meth) acrylate (A), 20-70 weight percent of one or more polyisocyanates containing isocyanate groups weight content of compound (B), and one or more catalysts (D), wherein the percentages by weight are based in each case (a) and (B) the binder content, and (a) plus (B) and in each case 100% by weight, wherein the poly (meth) acrylate (a) comprises a fluorine-containing 0.05-15.0 weight percent of one or more of the following reaction products: of one or more having two diisocyanate the isocyanate groups of different reactivity (PI), one or more (per) fluoroalkyl monoalcohol component (FA), and optionally one or more compounds having at least one isocyanate-reactive groups of group (G1) and the compound (V) having other functional groups (G2) different from the group (G1) is optional. 本发明进一步提供多段涂覆方法以及涂料组合物的用途。 The present invention further provides the use of a coating method and a multi-stage coating composition.
Claims(27)  translated from Chinese
1. 非水性涂料组合物,其包含: (A) 30-80重量%的包含多羟基和(全)氟烷基的聚(甲基)丙烯酸酯组分(A), (B) 20-70重量种或多种含多异氰酸酯基团化合物(B),和(D)-种或多种催化剂(D), 其中组分(A)和(B)的重量百分数每种情况下分别基于组分(A)和(B)的基料含量,且组分(A)加(B)的重量含量之和每种情况下为100重量%, 其中聚(甲基)丙烯酸酯组分(A)包含每种情况下基于用于制备聚(甲基)丙烯酸酯组分(A)的所有化合物的量为0.05-15.0重量%的以下物质的一种或多种含全氟烷基反应产物(U)作为合成组分: (i) 一种或多种二异氰酸酯(PI),其带有两个具有不同反应性的异氰酸酯基团, (ii) 一种或多种(全)氟烷基单醇组分(FA),和(iii) 任选一种或多种化合物(V),其具有至少一个对异氰酸酯基团呈反应性的基团(G1)且任选具有不同于基团(G1)的其它官能团(G2)。 1. The non-aqueous coating composition, comprising: (A) 30-80% by weight and the polyhydroxy comprising (per) fluoroalkyl group of poly (meth) acrylate component (A), (B) 20-70 or more by weight of a polyisocyanate-containing group of the compound (B), and (D) - one or more catalysts (D), wherein the (a) component and the weight (B), respectively, in each case based on the percentage of the component and in each case the (a) and (B) the content of the binder and the components (a) plus (B) weight content of 100% by weight, wherein the poly (meth) acrylate component (a) comprises in each case based on the amount of all the compounds for the preparation of poly (meth) acrylate component (a) is one kind of 0.05-15.0% by weight or more of the following substances in the reaction product containing a perfluoroalkyl group (U) as synthesis components: (i) one or more diisocyanates (PI), which has two isocyanate groups having different reactivity, (ii) one or more (per) fluoroalkyl group monol min (FA), and (iii) optionally one or more compounds (V), having a group (G1) at least one which is reactive toward isocyanate groups and optionally having a different group (G1) of the other functional group (G2).
2. 根据权利要求1的涂料组合物,其中聚(甲基)丙烯酸酯组分(A)包含以下通式的全氟代醇作为(全)氟烷基醇组分(FA): 通式(I): CF3-(CF2)x-(CH2)y-〇-Az-H (I) 和/或通式(II): CR^- (CR22) x- (CH2) yO-Az-H (II) 其中R1和R2相互独立地为H、F或CF3,但R1和R 2必须不同时为H, x 为1-20,y为1-6 且z为0-100, A为CR ' R" -CR ' " R" " -0或(CR ' R")a-0或CO- (CR ' R")b-Ο, R'、R"、R'"和R""相互独立地为H、具有1-25个C原子的烷基、环烷基、芳基或任意有机基团, a和b各自为3_5, 且聚氧化烯结构单元Az包含任何所需氧化烯的均聚物、共聚物或嵌段聚合物,或者包含聚氧亚烷基二醇,或者包含聚内酯。 2. The coating composition of claim 1, wherein the poly (meth) acrylate component (A) comprises the general formula perfluoro alcohol as a (per) fluoroalkyl alcohol component (FA): Formula ( I): CF3- (CF2) x- (CH2) y-square-Az-H (I) and / or formula (II): CR ^ - (CR22) x- (CH2) yO-Az-H (II ) wherein R1 and R2 are each independently H, F or CF3, R1 and R 2 but need not simultaneously H, x is 1-20, y is 1-6 and z is 0-100, A is CR 'R " -CR ' "R" "-0 or (CR' R") a-0 or CO- (CR 'R ") b-Ο, R', R", R ' "and R" "each independently H , an alkyl group having 1-25 C atoms, a cycloalkyl group, an aryl group or any organic group, a and b are each 3_5, and a polyoxyalkylene unit Az comprise any desired structural alkylene oxide homopolymer, copolymer or block polymers, or a polyoxyalkylene glycol comprises, or includes polylactones.
3. 根据权利要求2的涂料组合物,其中聚(甲基)丙烯酸酯组分(A)包含以下物质作为(全)氟烷基醇组分(FA): F(CF2CF2)i-(CH2CH2〇)mH (III) 和/或CF3-(CF2)n-(CH2)〇-0-H (IV) 其中1 为l-8,m为1-15,11为1-12,且〇为1-10。 The coating composition according to claim 2, wherein the poly (meth) acrylate component (A) comprising, as (per) fluoroalkyl alcohol component (FA): F (CF2CF2) i- (CH2CH2〇 ) mH (III) and / or CF3- (CF2) n- (CH2) square-0-H (IV) wherein a is l-8, m is from 1 to 12 1-15,11, and the square is 1 10.
4. 根据权利要求1-3中任一项的涂料组合物,其中聚(甲基)丙烯酸酯组分(A)包含每种情况下基于用于制备聚(甲基)丙烯酸酯组分(A)的所有化合物的量为0.1-10.0重量%的一种或多种含氟反应产物(U)。 4. The coating composition according to any one of claims 1-3, wherein the poly (meth) acrylate component (A) comprises in each case based on a preparation of poly (meth) acrylate component (A ) in an amount of 0.1 to 10.0 All compounds% by weight of one or more fluorine-containing reaction product (U).
5. 根据权利要求1-3中任一项的涂料组合物,其中聚(甲基)丙烯酸酯组分(A)包含以下物质的反应产物(U)作为含氟合成组分: (i) 一种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团, (ii) 一种或多种(全)氟烷基单醇组分(FA),和(iii) 一种或多种化合物(V),其具有对异氰酸酯基团呈反应性的基团(G1),且具有烯属不饱和双键(G2)。 (I) a: The reaction product of (U) as a synthesis component according to claim 1-3 fluorine coating composition according to any one of claims, wherein the poly (meth) acrylate component (A) comprises one or more diisocyanates (PI), having two isocyanate groups having different reactivity, (ii) one or more (per) fluoroalkyl monoalcohol component (FA), and (iii) a one or more compounds (V), having isocyanate groups as a reactive group (G1), and having an ethylenically unsaturated double bond (G2).
6. 根据权利要求1-3中任一项的涂料组合物,其中聚(甲基)丙烯酸酯组分(A)包含以下物质的反应产物(U)作为含氟合成组分: (i) 一种或多种脂族和/或脂环族二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团, (ii) 一种或多种(全)氟烷基单醇组分(FA): CF3-(CF2)r-(CH2)P-〇-H (V) 其中r为1-8,且p为1-6, (iii) 一种或多种具有至少一个羧基和/或羟基(G1)且具有至少一个丙烯酸和/或甲基丙烯酸属不饱和双键(G2)的化合物(V)。 (I) a: 6. The reaction product of (U) as a synthesis component according to claim 1-3 fluorine coating composition according to any one of claims, wherein the poly (meth) acrylate component (A) comprises one or more aliphatic and / or cycloaliphatic diisocyanates (PI), having two isocyanate groups having different reactivity, (ii) one or more (per) fluoroalkyl monoalcohol component ( FA): CF3- (CF2) r- (CH2) P-square-H (V) wherein r is 1-8 and p is 1-6, (iii) one or more having at least one carboxyl group and / or a hydroxyl group (G1) and having at least one acrylic and / or methacrylic acid metal compound (V) an unsaturated double bond (G2) of.
7. 根据权利要求6的涂料组合物,其中r为1-6。 7. The coating composition according to claim 6, wherein r is 1-6.
8. 根据权利要求6的涂料组合物,其中p为1-2。 8. A coating composition according to claim 6, wherein p is 1-2.
9. 根据权利要求6的涂料组合物,其中化合物(V)选自丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯、与内酯反应的丙烯酸羟烷基酯、与内酯反应的甲基丙烯酸羟烷基酯及其混合物。 Methyl coating composition according to claim 6, wherein the compound (V) is selected from hydroxyalkyl acrylates, hydroxyalkyl esters of methacrylic acid, hydroxyalkyl acrylates react with the lactone, the lactone is reacted with hydroxyalkyl acrylates and mixtures thereof.
10. 根据权利要求1-3中任一项的涂料组合物,其中聚(甲基)丙烯酸酯组分(A)由一种或多种饱和含全氟烷基和多羟基聚丙烯酸酯或者由一种或多种饱和含全氟烷基和多羟基聚甲基丙烯酸酯,或者由一种或多种饱和含全氟烷基和多羟基聚丙烯酸酯和一种或多种饱和含全氟烷基和多羟基聚甲基丙烯酸酯的混合物组成,和/或饱和聚(甲基)丙烯酸酯组分(A)包含以下物质的反应产物(U)作为含全氟烷基合成组分:异佛尔酮二异氰酸酯、2-(全氟己基)乙醇,和丙烯酸羟基乙酯和/或甲基丙烯酸羟基乙酯和/或羟烷基己内酯丙烯酸酯和/ 或羟烷基己内酯甲基丙烯酸酯。 10. The coating composition according to any one of claims 1-3, wherein the poly (meth) acrylate component (A) consists of one or more saturated and containing a perfluoroalkyl group or a polyhydroxy polyacrylates one or more saturated perfluoroalkyl group and a polyhydroxy methacrylate, or from one or more saturated perfluoroalkyl group and a polyhydroxy polyacrylates, and one or more saturated perfluoroalkyl group, and a mixture of polyhydroxy polymethacrylate composition, and / or unsaturated polyester (meth) acrylate component (a) comprises the reaction product of (U) containing a perfluoroalkyl group as synthesis components: isoforskolin chalcone diisocyanate, 2- (perfluorohexyl) ethanol, and hydroxyethyl acrylate and / or hydroxyethyl methacrylate and / or hydroxyalkyl groups caprolactone acrylate and / or hydroxyalkyl methyl caprolactone Acrylate.
11. 根据权利要求1-3中任一项的涂料组合物,其中聚(甲基)丙烯酸酯组分(A)包含以下物质的反应产物(U)作为含氟合成组分: (i) l摩尔的一种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团, (ii) l摩尔的一种或多种(全)氟烷基单醇组分(FA),和(iii) l摩尔的一种或多种具有对异氰酸酯基团呈反应性的基团(G1)的烯属不饱和化合物(V)。 l (i): 11. The coating composition according to claim 1-3 in claim 1, wherein the poly (meth) acrylate component (A) comprises the reaction product of (U) as the fluorine-containing synthesis components one or more moles of diisocyanate (PI), having two isocyanate groups having different reactivity, (ii) l mole of one or more (per) fluoroalkyl monoalcohol component (FA) and (iii) l mole of one or more ethylenically groups (G1) of the isocyanate groups which are reactive unsaturated compound (V).
12. 根据权利要求1-3中任一项的涂料组合物,其中用作组分(A)的聚(甲基)丙烯酸酯或聚丙烯酸酯为饱和的并且由以下物质合成: (al )0.05-15.0重量%的一种或多种含氟烯属不饱和反应产物(U), (a2 )10-50重量%的一种或多种含羟基单体, (a3) 10-89.95重量%的一种或多种烯属不饱和羧酸的烷基和/或环烷基酯, (a4)0-50重量%的一种或多种乙烯基芳族化合物,和(a5)0-10重量%的其它烯属不饱和单体, 其中单体(al)至(a5)的重量含量之和每种情况下为100重量%。 12. The coating composition according to any one of claims 1-3, wherein the polyethylene used as component (A), (meth) acrylate or polyacrylate and is saturated by the substances synthesized: (al) 0.05 -15.0% by weight of one or more fluorine-containing ethylenically unsaturated reaction products (U), (a2) 10-50% by weight of one or more hydroxyl group-containing monomers, (a3) 10-89.95% by weight of one or more ethylenically unsaturated carboxylic acid alkyl and / or cycloalkyl esters, (a4) 0-50 wt% of one or more vinyl aromatic compounds, and (a5) 0-10 wt. % of other ethylenically unsaturated monomers, wherein the lower to (a5) of the sum of the contents by weight of each monomer (Al) case 100% by weight.
13. 根据权利要求1-3中任一项的涂料组合物,其中用作组分(A)的聚(甲基)丙烯酸酯具有60-300mg KOH/g的OH值。 1-3 13. The coating composition according to any of the claims, wherein the polyethylene used as component (A), (meth) acrylate having 60-300mg KOH / OH value of g.
14. 根据权利要求13的涂料组合物,其中用作组分(A)的聚(甲基)丙烯酸酯具有70-200mg KOH/g的0H值。 14. The coating composition according to claim 13, wherein the polyethylene used as component (A), (meth) acrylate having 70-200mg KOH / 0H g.
15. 根据权利要求1-3中任一项的涂料组合物,其中用作组分(A)的聚(甲基)丙烯酸酯具有-100°C至+100°C的玻璃化转变温度。 + 15. The glass transition temperature of 100 ° C The coating composition according to claim 1-3 in claim 1, wherein the polyethylene used as component (A), (meth) acrylates having to -100 ° C.
16. 根据权利要求15的涂料组合物,其中用作组分(A)的聚(甲基)丙烯酸酯具有-60°C 至+60 °C的玻璃化转变温度。 16. A coating composition according to claim 15, wherein the polyethylene used as component (A), (meth) acrylate having a -60 ° C to a glass transition temperature of +60 ° C.
17. 根据权利要求1-3中任一项的涂料组合物,其中涂料组合物包含每种情况下基于组分(A)加(B)之和的基料含量为0.2-15.0重量%的至少一种其羧基与π-电子体系共辄的单体芳族任选取代羧酸(S)。 17. The coating composition according to any one of claims 1-3, wherein the coating composition comprises in each case based on component (A) content of the matrix material plus (B) and the sum of at least 0.2-15.0 wt% one of its carboxyl groups with π- electron system of co noir optionally substituted aromatic carboxylic acid monomer (S).
18. 涂覆方法,其包括将根据权利要求1-17中任一项的涂料组合物的层施涂于任选预涂覆的基体上。 18. A coating method which comprises 1-17 layers according to any one of the requirements of the coating composition applied to optionally pre-coated on the substrate.
19. 根据权利要求18的涂覆方法,其中在施涂以后将根据权利要求1-17中任一项的涂料组合物在20-80 °C的温度下固化。 19. The coating method of claim 18, wherein after applying the coating composition according to claim any one of claims 1-17 cured at a temperature of 20-80 ° C.
20. 根据权利要求19的涂覆方法,其中在施涂以后将根据权利要求1-17中任一项的涂料组合物在20-60 °C的温度下固化。 20. The coating method according to claim 19, wherein after applying the coating composition according to claim any one of claims 1-17 cured at a temperature of 20-60 ° C.
21. 根据权利要求18或19的涂覆方法,其中任选预涂覆的基体为飞机或风能体系,或者其一个或多个部件。 21. The coating method according to claim 18 or claim 19, wherein the optionally pre-coated substrate is an aircraft or wind energy system, or one or more components.
22. 根据权利要求21的涂覆方法,其中任选预涂覆的基体为风能体系的动叶片。 22. The coating method according to claim 21, wherein the optionally pre-coated substrate is moving blades of the wind energy system.
23. 根据权利要求22的涂覆方法,其中将根据权利要求1-17中任一项的涂料组合物作为最外涂膜施涂于风能体系的动叶片上。 23. The coating method according to claim 22, wherein the coating composition according to any one of claims 1 to 17 as the outermost coating film applied to the moving blades of the wind energy system.
24. 根据权利要求1-17中任一项的涂料组合物作为透明涂料的用途,或者根据权利要求18-23中任一项的方法在永久防水和防污表面涂覆中的用途。 1-17 24. A coating composition according to any one of claims use as a clear coating, 18-23 or the method of any one of claims permanent use in water and soil in the surface coating.
25. 根据权利要求1-17中任一项的涂料组合物在飞机和风能体系或其部件的防冰涂层中的用途。 25. The use in aircraft anti-icing coating and wind systems or components thereof in the coating composition according to any one of claims 1-17.
26. 根据权利要求1-17中任一项的涂料组合物在涂覆飞机或风能体系的动叶片以减少由其移动产生的噪音中的用途。 26. The rotor blade 1-17 a coating composition in the coating system of the aircraft or wind claim to reduce the use of the noise generated by the movement.
27. 具有油漆体系,任选多涂层油漆体系的风能体系或者风能体系的一个或多个部件, 其中最顶层涂膜由根据权利要求1-17中任一项的涂料组合物产生。 27. paint systems having optionally one or more components of the wind energy system or a plurality of wind energy systems paint systems, wherein the topmost coating film produced according to claim 1-17 coating composition according to any one of claims.
Description  translated from Chinese

含氟非水性涂料组合物、涂覆方法和涂料组合物的用途 The use of non-fluorine-containing aqueous coating compositions, coating methods and coating compositions of

[0001] 本发明涉及非水性涂料组合物,所述组合物包含:至少一种含多羟基和(全)氟烷基聚(甲基)丙烯酸酯组分(A)、至少一种含多异氰酸酯基团化合物(B)和催化剂(D)。 [0001] The present invention relates to non-aqueous coating composition, said composition comprising: at least one polyhydroxy-containing and (per) fluoroalkyl group of poly (meth) acrylate component (A), containing at least one polyisocyanate group of the compound (B) and the catalyst (D).

[0002] 本发明进一步提供使用这些涂料组合物的涂覆方法,以及涂料组合物作为透明涂料以及在涂覆风能体系或飞机或其部件中,更特别是作为防冰涂层的用途。 [0002] The present invention further provides a coating method using these coating compositions, as well as the coating composition as a clear coating and in a coating or aircraft or wind power system components, and more particularly as an anti-icing coating purposes.

[0003] 很好地确立了基于含氟聚合物的非水性涂料用于大量非常不同的终端应用。 [0003] very well established in a lot of different applications on the terminal non-aqueous coating for fluoropolymers.

[0004] 因此,例如EP-B-856 020描述了基于含氟聚丙烯酸酯基料和含多异氰酸酯基团交联剂的非水性透明涂料,这些涂料可固化成防油、防污和防水涂层,且用于涂覆车辆,例如地下铁道车辆、火车、公共汽车等,工业体系,例如罐、建筑物和其它大厦。 [0004] Thus, for example, EP-B-856 020 describes a non-aqueous transparent coating based on fluorinated polyacrylate binder containing a polyisocyanate crosslinker groups, these coatings can be cured into oil, water and stain coating layer, and a coating vehicle, such as an underground railway vehicles, trains, buses, industrial systems, such as cans, buildings and other buildings. 透明涂料更特别地用于涂覆建筑物、公共汽车、火车和乱涂乱画是个问题的其它物体,因为所得涂层容易清洗,以及提供高抗污性。 More particularly clearcoat for coating buildings, buses, trains and other objects graffiti is a problem, because the resulting coating is easy to clean, and to provide high stain resistance. 为制备含氟聚丙烯酸酯基料,使用具有氟烷基的烯属不饱和化合物,例如(甲基)丙烯酸氟烷基乙酯或甲基丙烯酸2-(N-乙基全氟辛烷磺基酰氨基)乙酯。 Ethylenically unsaturated compounds such as (meth) acrylate, fluoroalkyl acrylate or methacrylate, 2- (N- ethyl-perfluorooctane sulfonic group to prepare a fluorine-containing polyacrylate based material, having a fluoroalkyl group amido) ethyl acrylate. 但是这些含氟单体必须自身并与其余单体分开地加入,且这使得基料必然昂贵且不方便地制备。 However, these fluorine-containing monomer must be added separately with itself and the rest of the monomers, and this makes it costly and inconvenient base necessarily prepared.

[0005] 此外,关于如何可得到具有尽可能长期的高疏水性且同时具有非常高的机械和光化学稳定性的表面的信息,其中这类表面例如是涂覆用于风能体系的动叶片所需的,在该说明书中不比关于如何确保极快组装强度和良好修补附着力的信息更多地存在。 [0005] Further, how to obtain a long-term high hydrophobicity information as possible while having a very high surface mechanical and photochemical stability, wherein such a surface coating, for example, the desired rotor blade for a wind energy system the information on how to ensure fast than the assembly adhesion strength and good repair more present in the specification. 也不存在关于如何可以以尽可能简单且便宜的方式实现这些质量的任何信息。 Nor is there any information on how these qualities can be achieved with as simple and inexpensive way.

[0006] 此外,EP-B-856 022公开了类似的涂料,所述涂料除含氟聚丙烯酸酯基料外还包含多异氰酸酯交联剂,其中0.1-33摩尔%的异氰酸酯基团与全氟代醇反应。 [0006] In addition, EP-B-856 022 discloses a similar coating, in addition to the fluorine-containing coating material further comprises a polyacrylate based polyisocyanate crosslinker, wherein 0.1 to 33 mol% of isocyanate groups and perfluoro Generation alcohol. 在本文所述氟化多异氰酸酯的制备中,除单氟化多异氰酸酯外,预期二氟化和三氟化多异氰酸酯的高含量,且二-和三氟化多异氰酸酯可迀移至膜表面,因此负面地影响所得涂层的总视觉外观、 硬度、耐化学品性和其它机械技术性能。 Herein the fluorinated polyisocyanates prepared ester in addition to more than one fluorinated polyisocyanate expected difluoride and trifluoride polyisocyanate high content, and the two - and three polyfluorinated polyisocyanates may Gan moved to the film surface, thus negatively affecting the overall visual appearance of the resultant coating layer, hardness, chemical resistance and other mechanical properties techniques.

[0007] 含氟透明涂料还描述于W005/030892中,其中这些透明涂料中的基料为含氟聚丙烯酸酯,所述含氟聚丙烯酸酯还包含共聚形式的有机硅烷单体。 [0007] The fluorine-containing clear coating is also described in W005 / 030892, where these transparent coatings binders are polyacrylates fluorine, the fluorine-containing polyacrylate copolymerized form further comprises an organic silane monomers. 含氟聚丙烯酸酯又例如通过具有氟烷基的烯属不饱和化合物如(甲基)丙烯酸氟烷基乙酯或(甲基)丙烯酸2-(N-乙基全氟辛烷磺基酰氨基)烷基酯共聚而得到。 Polyacrylates e.g. fluorine another unsaturated compound such as (meth) acrylate, fluoroalkyl acrylate or (meth) acrylate, 2- (N- ethyl-perfluorooctane sulfonate by amido alkenyl group having a fluoroalkyl ) alkyl ester copolymer obtained.

[0008] W005/030891公开了具有改进的透明涂层/透明涂层附着力的氟化透明涂料,这些材料不仅包含基于具有氟烷基的共聚烯属不饱和化合物如(甲基)丙烯酸氟烷基乙酯或(甲基)丙烯酸2-(N-乙基全氟辛烷磺基酰氨基)烷基酯的氟化硅烷聚合物,而且包含氟化聚氨酯树脂以促进附着力。 [0008] W005 / 030891 discloses an improved transparency coat / clear coat clear paint adhesion fluorinated, these materials not only comprising the (meth) acrylic acid-based fluoroalkyl fluoroalkyl group having a copolymerizable ethylenically unsaturated compound ethyl group or a (meth) acrylate, 2- (N- ethyl-perfluorooctane sulfo amido) alkyl esters fluorinated silane polymer, and contains a fluorinated polyurethane resin to promote adhesion. 该树脂可通过使多异氰酸酯与全氟化单醇以及与低聚和/或聚合聚醚多元醇如乙氧基化/丙氧基化二醇反应而得到,且不包含任何其余游离异氰酸酯基团。 This resin by reacting a polyisocyanate with perfluorinated alcohols and mono and oligomeric and / or polymeric polyether polyols such as ethoxylated / propoxylated diols obtained by the reaction and does not contain any remaining free isocyanate groups .

[0009] W005/080465描述了容易清洗并使用涂料得到的抗磨且抗碱涂层,所述涂料除可固化基料体系和无机颗粒外还包含至少一种含氟低聚物或聚合物,所述低聚物或聚合物具有至少一个对基料体系的官能团呈反应性的官能团。 [0009] W005 / 080465 describes the use is easy to clean and wear and alkali resistant coating material obtained in addition to the coating binder system curable outer and inorganic particles further comprise at least one fluorine-containing oligomer or polymer, the oligomer or polymer having at least one functional group which is reactive to the functional group of the binder system. 所用含氟聚合物或低聚物包括例如氟化聚醚、氟化环氧化物、氟化聚氨酯和含氟聚合物,其中含氟聚合物使用商业含氟单体如四氟乙烯、偏二氟乙烯等制备。 The fluorine-containing polymers or oligomers include, for example, a fluorinated polyether, fluorinated epoxy, fluorinated polyurethane and fluoropolymer, wherein the fluoropolymer commercial fluorinated monomer such as tetrafluoroethylene, vinylidene fluoride preparation of ethylene.

[0010] W007/115752描述了具有环氧化物/胺固化机制的基于聚氨酯的双组份含水性混杂反应性树脂体系,其用于建筑和工业领域中以生产特征是高机械强度的易清洗涂层。 [0010] W007 / 115752 describes a epoxide / amine based curing mechanism of the hybrid two-component aqueous polyurethane reactive resin systems for construction and industrial fields is characterized by the production of a high mechanical strength and easy to clean coating Floor. 这些涂料可任选包含氨基-和/或羟基-和/或巯基-官能、氟改性大单体或远螯物。 These coatings may optionally comprise an amino group - and / or hydroxyl - and / or mercapto - functional, fluorine-modified macromonomers or telechelic thereof.

[0011]此外,W005/007762描述了具有共价结合的氟化侧链的含水、任选氟化聚氨酯混杂物分散体,所述侧链可借助聚氨酯基和/或借助可自由基聚合的含氟单体引入。 [0011] In addition, W005 / 007762 describes aqueous fluorinated side chains covalently bound, optionally fluorinated polyurethane dispersion blend, the side chain by means of urethane groups and / or by means of free-radically polymerizable containing fluoromonomer introduced. 使用这些聚氨酯混杂物分散体,可借助高交联密度以及高硬度,生产具有良好机械性能和良好耐溶剂性和耐化学品性的防污涂层,这些涂层适于非常大量的不同最终用途。 The use of a polyurethane dispersion blend, can make use of a high crosslink density and high hardness, produced with good mechanical properties and good solvent resistance and chemical resistance of the antifouling coatings, these coatings are very suitable for a number of different end uses .

[0012] W008/040428还公开了在建筑和工业领域中尤其用于矿物和非矿物基体的永久性防油、防水和防污涂层的氟改性聚氨酯涂料。 [0012] W008 / 040428 also discloses oil in permanent construction and industrial fields, in particular for mineral and non-mineral matrix, fluorine-modified polyurethane coating waterproof and antifouling coatings.

[0013] 此外,EP-A-2 085 442公开了基于氟代硅烷组分且用于多种最终应用的矿物和非矿物基体的永久性防油和防水表面处理的水性涂料。 [0013] Further, EP-A-2 085 442 discloses aqueous coating based on fluorinated silane component and used for a variety of mineral and non-mineral matrix of the final application of the permanent oil and water repellent surface treatment.

[0014] EP-B-587 667公开了基于含氟无机缩聚物且用于涂覆玻璃、陶瓷、金属、塑料和纸,更特别是用于涂覆外部和内部镜子以及机动车辆的挡风玻璃的涂料组合物。 [0014] EP-B-587 667 discloses a windshield based on the fluorine-containing inorganic polycondensate thereof and for coating glass, ceramics, metals, plastics and paper, and more particularly for coating the exterior and interior mirrors of motor vehicles, and the coating composition.

[0015] EP-A-1 844 863也描述了用于生产强防液体的涂层,换言之,显示出与参比液体, 更特别地例如水的120-180°的非常大接触角的涂层的涂料。 [0015] EP-A-1 844 863 also describes a liquid-proof coating for the production of strong, in other words, showing than the liquid, and more particularly to a reference coating such as a very large contact angle of water of 120-180 ° paint. 这使用包含聚合物和陶瓷材料或纳米颗粒,并因此导致具有纹理表面的涂层的涂料。 This use comprises a polymer and a ceramic material or nanoparticles, and thus results in a coating having a textured surface coating. 然而,不存在关于聚合物的更确切组成的细节。 However, more details on the exact composition of the polymer does not exist.

[0016] 对于表面涂覆,已用具有氟化侧链的梳型聚合物进行了实验。 [0016] For the surface coating, it has been demonstrated using a comb polymer having pendant fluorinated. 就这点而言,已知实现低表面能以及因此良好防污性和防水性能的关键因素包括非常长的氟化链和烃基形式的与主链的非常短的间隔基。 In this regard, the known low surface energy and thus good antifouling property and water resistance of the key factors include very long chains and a fluorinated hydrocarbon group in the form of the very short intervals of the main chain. 相反,较长的间隔基导致差得多的结果("氟化梳型均聚物:间隔基长度对表面性能的影响",SaWi,Salima ;Guittard,Fr6d6ric ;Guimon,Claude ;G6 ribaldi,Serge; Journal of Polymer Science Part A:Polymer Chemistry,第43卷,条目17,第3737-3747页)。 Conversely, longer spacers cause much difference in the results ( "fluorinated comb-shaped homopolymer: Effect of spacer length on the surface properties", SaWi, Salima; Guittard, Fr6d6ric; Guimon, Claude; G6 ribaldi, Serge; Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, entry 17, pp. 3737-3747).

[0017] 此外,Journal of Donghua University (Natural Science),第35 卷,No · 5,2009 年10月,第547-553页公开了通过使全氟辛醇、异佛尔酮二异氰酸酯和丙烯酸羟基乙酯的反应产物与丙烯酸羟基乙酯和丙烯酸十八烷基酯共聚而制备氟化聚丙烯酸酯乳液,以及所得氟化聚丙烯酸酯乳液在涂覆棉纤维中的用途。 [0017] In addition, Journal of Donghua University (Natural Science), Vol. 35, No · 5,2009 October, pages 547-553 discloses a perfluoro octanol, isophorone diisocyanate and hydroxyethylacrylate ethyl reaction product of hydroxyethyl acrylate and octadecyl acrylate copolymer emulsions prepared fluorinated polyacrylate, fluorinated polyacrylate emulsion and the resultant use of cotton fiber in the coating.

[0018] 此外,中国未决说明书CN101020731 A描述了通过含羟基丙烯酸酯共聚物与二异氰酸酯与全氟烷基醇的含异氰酸酯基团的等摩尔反应产物反应而制备氟化丙烯酸酯共聚物。 [0018] In addition, the pending Chinese CN101020731 A specification describes a hydroxyl-containing acrylate copolymer and a reaction product of a diisocyanate with an equal molar reaction containing isocyanate groups and perfluoroalkyl alcohols fluorinated acrylate copolymer. 这些溶剂基氟化丙烯酸酯共聚物用于赋予皮革、织物产品等防水和防油性。 These solvent-based fluorinated acrylate copolymer for imparting leather, textile products, water and oil repellency.

[0019] 还存在多个其它说明书,其公开了用于生产防水涂层的疏水性涂料。 [0019] There is also a plurality of other specification, which discloses a waterproof coating for the production of hydrophobic coatings. 因此,例如EP-B-1 210 396描述了用于生产防冰涂层的疏水性涂料组合物,所述涂料通过颗粒化学附着于凝胶,优选二氧化硅基凝胶上而生产,其中表面的疏水性通过表面的粗糙度而物理地提尚。 Thus, for example, EP-B-1 210 396 describes a hydrophobic coating compositions for producing anti-icing coating, the coating particles by chemical attachment of the gel, preferably a silica-based gels produced, wherein the surface hydrophobic extract still physically by roughness of the surface.

[0020] W096/04123也描述了用于生产自清洁表面的疏水性涂料,其中产生由凸起和凹陷组成的人造表面纹理,且凸起由疏水化材料组成。 [0020] W096 / 04123 also describes a process for producing self-cleaning surfaces of the hydrophobic coating, wherein the artificial surface texture produced by the projections and recesses thereof, and the projection of a hydrophobic material. 特氟隆例如用于该目的。 For this purpose, for example, Teflon.

[0021] 此外,由W02011/147416中例如已知风能体系或其部件,尤其是动叶片的表面可具有强疏水性涂层,以减少冰、水和污垢的附着,因为后者可能具有例如负面地影响动叶片的重量和空气动力,因此降低风能体系的效率的作用。 [0021] In addition, the W02011 / 147416 are known in the wind energy system, for example, or parts thereof, in particular the surface of the rotor blade may have a strong hydrophobic coating to reduce ice, water and dirt adhesion, because the latter may have a negative e.g. affects the weight and aerodynamics of the rotor blades, thus reducing the efficiency of the action of the wind energy system. 推荐的涂料包括例如特氟隆、氟聚氨酯、环氧基氟化组分、硅化聚脲等。 Preferred coatings include, for example, Teflon, polyurethane fluorine, fluorinated epoxy component silicide polyurea. 该说明书也不存在关于合适涂料的组成的更详细信息。 The specification does not exist in more detail on suitable coating composition.

[0022]此外,还由W02011/020876中已知可赋予风能体系或其部件,尤其是动叶片的表面强疏水性涂层,所述涂层基于氟化聚氨酯或者基于与特氟隆混合的聚氨酯,然而,该说明书也不存在关于合适材料的组成的更详细信息。 [0022] In addition, the W02011 / 020876 are known to impart wind energy system or parts thereof, in particular the movable blade strongly hydrophobic surface a coating based on fluorinated polyurethane or polyurethane mixed with a Teflon However, the specification does not present more detailed information on the composition of a suitable material.

[0023]此外,由EP-B-1 141 543中已知风能体系的动叶片可涂有防液体的涂料,因此以降低风能体系的噪音发射。 [0023] Further, the movable blade is known from EP-B-1 141 543 in the wind energy system may be coated with a coating liquid-proof, wind energy systems and therefore to reduce noise emission. 关于合适涂料给出的实例不仅包括商业微硅氧烷油漆,而且包括开发用于船用涂层的聚氨酯油漆;然而,该说明书也不存在关于合适涂料的组成的更详细信息。 Examples of suitable coating on commercial micro analysis include not only silicone paints, urethane paints but also for the development of marine coatings; however, the description does not exist in more detail on suitable coating composition.

[0024] 问题 [0024] problem

[0025] 因此,本发明解决的问题是提供涂料组合物,尤其是用于涂覆风能体系或飞机或其部件的涂料组合物,所述组合物确保在各自的基体上或者在已存在于基体上的涂层上的良好附着力,以及在所得涂层部分上的良好可再涂覆性。 [0025] Accordingly, the present invention is to solve the problem of providing a coating composition, especially a coating composition for coating an aircraft or a wind power system or component, to ensure that the composition on the respective substrate or already present in the matrix good adhesion to the coating, and good coatability can be re-coated on the resultant portion. 同时,涂料应导致经久地防水和防污以及特别是持续降低冰、水和污垢在风能体系、飞机或其部件,更特别是在风能体系的动叶片上的附着的涂层。 At the same time, it should cause durable waterproof coating and continue to reduce pollution and in particular of ice, water and soil in the wind energy system, or a member of aircraft, and more particularly a coating adhered to the rotor blade of the wind energy system.

[0026] 另外,涂料组合物应产生同时还满足风能体系的动叶片的涂覆领域中的确切要求,尤其是在非常好的机械和光化学抗性方面的确切要求的涂层。 [0026] Further, the coating composition should yield the exact requirements while also meeting coating art rotor blade in the wind energy system, particularly in coating and very good mechanical resistance to photochemical aspect exact requirements.

[0027]此外,涂料组合物应在不大于80°C的低温下显示出良好且非常快的固化,换言之, 应在60°C下仅30分钟固化以后固化至这一程度使得可进行初始的组装操作或解掩模而不损害涂层。 [0027] In addition, the coating composition should show at a low temperature of not greater than to 80 ° C and very good fast cure, in other words, be only 30 minutes after the curing of the curable to this level at 60 ° C for that may be an initial Solutions or mask assembly operation without damaging the coating. 然而,同时应确保涂料组合物足够长的加工寿命("适用期")。 However, the coating composition while ensuring a sufficiently long processing life ( "potlife"). 适用期应当理解为涂料组合物达到两倍其初始粘度的时间间隔。 It should be understood that the pot life of the coating composition up to twice its initial viscosity interval.

[0028] 此外,所得涂层应具有非常好的总视觉外观、非常高的硬度、良好的耐化学品性以及在汽车修饰和塑料基体和/或商业车辆上漆中通常要求的其它机械-技术性能方面的良好得分。 [0028] Further, the resultant coating should have a very good overall visual appearance, very high hardness, and good chemical resistance in automotive finishing and the plastic matrix and / or commercial vehicle paint typically required in other machinery - Technology good scoring performance.

[0029] 最后,涂料组合物应当能够非常简单且便宜地制备。 [0029] Finally, the coating composition should be capable of very simply and inexpensively prepared.

[0030] 解决方法 [0030] Solution

[0031] 鉴于上述问题陈述,发现非水性涂料组合物,所述组合物包含: [0031] In view of the problems Chen Shu above, find non-aqueous coating composition, said composition comprising:

[0032] (A)30-80重量%,优选50-70重量%的包含多羟基和(全)氟烷基的聚(甲基)丙烯酸酯组分(A), [0032] (A) 30-80% by weight, preferably 50-70% by weight comprising a poly (meth) acrylates and polyhydroxyl component (per) fluoroalkyl group (A),

[0033] (B)20-70重量%,优选30-50重量%的一种或多种含多异氰酸酯基团化合物(B), 和 [0033] (B) 20-70 wt%, preferably 30-50 wt% of one or more polyisocyanates containing group of the compound (B), and

[0034] (D)-种或多种催化剂(D), [0034] (D) - one or more catalysts (D),

[0035] 其中组分(A)和(B)的重量百分数每种情况下分别基于组分(A)和(B)的基料含量, 且组分(A)加(B)的重量含量之和每种情况下为100重量%, [0035] wherein the components (A) and the weight (B), respectively, in each case based on the percentage of components (A) (B) and the binder content group, and the components (A) plus (B) of the weight content of and in each case 100% by weight,

[0036] 其中聚(甲基)丙烯酸酯组分(A)包含每种情况下基于制备聚(甲基)丙烯酸酯组分(A)中所用所有组分的量为0.05-15.0重量%的以下物质的一种或多种含氟反应产物(U): [0036] wherein the poly (meth) acrylate component (A) comprises in each case based on the amount of the preparation of poly (meth) acrylate component (A) used in the all the components is 0.05-15.0 wt% or less the reaction product of one or more fluorine-containing substance (U):

[0037] (i) -种或多种二异氰酸酯(PI),其带有具有不同反应性的异氰酸酯基团, [0037] (i) - one or more diisocyanates (PI), which with isocyanate groups of different reactivity,

[0038] (ii) 一种或多种(全)氟烷基单醇组分(FA),和 [0038] (ii) one or more (per) fluoroalkyl monoalcohol component (FA), and

[0039] (iii)任选一种或多种化合物(V),其具有至少一个对异氰酸酯基团呈反应性的基团(G1)且任选具有不同于基团(G1)的其它官能团(G2)。 [0039] (iii) optionally one or more compounds (V), which have other functional groups different from group (G1) in the form of at least one reactive group (G1) of the isocyanate groups and optionally ( G2).

[0040] 本发明进一步提供使用这些涂料组合物的涂覆方法,以及涂料组合物作为透明涂料以及在涂覆风能体系或飞机或其部件中,更特别是作为防冰涂层的用途。 [0040] The present invention further provides a coating method using these coating compositions, as well as the coating composition as a clear coating and in a coating or aircraft or wind power system components, and more particularly as an anti-icing coating purposes.

[0041] 令人惊讶且不能预见的是本发明涂料组合物确保在各自的基体上或者在已存在于基体上的涂层上的良好附着力,以及在所得涂层部分上的良好可再涂覆性。 [0041] surprising and not foreseeable that the coating compositions of the present invention ensures that the substrate or on the respective good adhesion on the coating already on the substrate, and a good recoatability on the resulting coating portion Overturn. 同时,涂料导致经久地防水和防污以及特别是持续降低冰、水和污垢在风能体系、飞机或其部件,更特别是在风能体系的动叶片上的附着的涂层。 At the same time, resulting in durable waterproof coating and continue to reduce pollution and in particular of ice, water and soil in the wind energy system, or a member of aircraft, and more particularly a coating adhered to the rotor blade of the wind energy system.

[0042] 此外,涂料组合物导致同时还满足风能体系的动叶片的涂覆领域中的确切要求, 尤其是在非常好的机械和光化学抗性方面的确切要求的涂层。 [0042] In addition, the coating composition results in the coating while also meeting the exact requirements of the art rotor blade in the wind energy system, in particular the exact requirements photochemical resistance and very good mechanical aspects of coating.

[0043]此外,在不大于80°C的低温下,涂料组合物显示出良好且非常快的固化,换言之, 在60°C下仅30分钟固化以后固化至这一程度使得可进行初始的组装操作或解掩模而不损害涂层。 [0043] Further, at a low temperature of not greater than to 80 ° C, the coating compositions exhibit good and very fast cure, in other words, after curing to the extent that cure at 60 ° C for only 30 minutes for initial assembly Solutions or mask operation without damaging the coating. 然而,同时确保涂料组合物足够长的加工寿命("适用期")。 However, the coating composition while ensuring a sufficiently long processing life ( "potlife").

[0044] 此外,所得涂层值得注意的是良好的总视觉外观、非常高的硬度、良好的耐化学品性以及在汽车修饰和塑料基体和/或商业车辆上漆中通常要求的其它机械-技术性能方面的良好得分。 [0044] Further, the resultant coating is noteworthy that good overall visual appearance, very high hardness, and good chemical resistance in automotive finishing and the plastic matrix and / or commercial vehicle paint typically required in other machinery - good scoring performance technology.

[0045] 最后,涂料组合物可容易且便宜地制备。 [0045] Finally, the coating composition may be prepared easily and inexpensively.

[0046] 发明详述 [0046] DETAILED DESCRIPTION

[0047]聚(甲基)丙烯酸酯组分(A) [0047] Poly (meth) acrylate component (A)

[0048] 如从以下详细描述中获悉,聚(甲基)丙烯酸酯组分(A)更特别地包含饱和聚(甲基)丙烯酸酯共聚物。 [0048] As learned from the following detailed description, the poly (meth) acrylate component (A), more particularly a saturated poly (meth) acrylate copolymer.

[0049] 对本发明而言重要的是聚(甲基)丙烯酸酯组分(A)包含每种情况下基于用于制备聚(甲基)丙烯酸酯组分(A)的所有化合物的量为0.05-15.0重量%,优选0.1-10.0重量%的以下物质的一种或多种含氟反应产物(U)作为合成组分: [0049] Important for the present invention is a poly (meth) acrylate component (A) comprises in each case based on the amount of all the compounds for the preparation of poly (meth) acrylate component (A) is 0.05 -15.0% by weight of one or more of fluorine, preferably from 0.1 to 10.0% by weight or less of a reaction product (U) as synthesis components:

[0050] (i) -种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团, [0050] (i) - one or more diisocyanates (PI), having two isocyanate groups having different reactivity,

[0051] (ii)-种或多种(全)氟烷基单醇组分(FA),和 [0051] (ii) - one or more (per) fluoroalkyl monoalcohol component (FA), and

[0052] (iii)任选一种或多种化合物(V),其具有至少一个对异氰酸酯基团呈反应性的基团(G1)且任选具有不同于基团(G1)的其它官能团(G2)。 [0052] (iii) optionally one or more compounds (V), which have other functional groups different from group (G1) in the form of at least one reactive group (G1) of the isocyanate groups and optionally ( G2).

[0053] 含氟反应产物(U)在此处可以以各种方式引入聚(甲基)丙烯酸酯组分(A)中。 [0053] The fluorine-containing reaction product (U) can be introduced into the poly (meth) acrylate component (A) in a variety of ways here.

[0054] 例如,可首先制备含羟基聚(甲基)丙烯酸酯树脂,然后通过聚合物类似反应使聚(甲基)丙烯酸酯组分(A)的一些羟基与包含氟和异氰酸酯基团的反应产物(U)的其余游离异氰酸酯基团反应。 [0054] For example, hydroxy may be first prepared containing poly (meth) acrylate resin, and then by a polymer analogous reaction of poly (meth) acrylate component (A) comprising some of fluorine and hydroxy reactive isocyanate groups the remaining free isocyanate groups product (U) of the reaction.

[0055] 包含氟和异氰酸酯基团的反应产物(U)可由如下物质制备: [0055] comprising the reaction product of an isocyanate group and a fluoro group (U) can be prepared from the following materials:

[0056] (i) -种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团,和[0057] (ii) 一种或多种(全)氟烷基醇组分(FA)。 [0056] (i) - one or more diisocyanates (PI), having two isocyanate groups having different reactivity, and [0057] (ii) one or more (per) fluoroalkyl alcohol group points (FA).

[0058]另外,也可首先例如制备还具有其它官能团如羧基、酐基团、环氧基等的含羟基聚(甲基)丙烯酸酯树脂,然后使这些其它官能团与含氟反应产物(U)反应,所述含氟反应产物(U)还具有能够与聚(甲基)丙烯酸酯树脂的其它官能团反应的其它官能团。 [0058] Further, for example, may first be prepared also contain other functional groups, such as having a carboxyl group, anhydride group, epoxy group hydroxyl poly (meth) acrylate resin, and then these other functional groups with a fluorine-containing reaction product (U) the reaction of the fluorine-containing reaction product (U) is also capable of having a poly (meth) other functional groups of other functional groups reactive acrylate resin.

[0059] 这种包含氟基团的反应产物(U)在这种情况下可例如由以下物质制备: [0059] This reaction product contains a fluoro group (U) may be prepared from the following substances, for example, in this case:

[0060] (i) -种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团, [0061 ] (ii) 一种或多种(全)氟烷基醇组分(FA),和 [0060] (i) - one or more diisocyanates (PI), having two isocyanate groups having different reactivity, [0061] (ii) one or more (per) fluoroalkyl alcohol component (FA), and

[0062] (iii) -种或多种饱和化合物(V),其具有至少一个对异氰酸酯基团呈反应性的基团(G1),且任选具有不同于基团(G1)的其它官能团(G2)。 [0062] (iii) - one or more unsaturated compounds (V), having at least one group reactive properties (G1) toward isocyanate groups and optionally further functional groups having a different group (G1) of ( G2).

[0063] 合适化合物(V)的实例为例如具有至少两个羟基的聚合多元醇,例如聚酯多元醇、 聚亚烷基醚多元醇、聚碳酸酯多元醇、聚酯碳酸酯多元醇、聚缩醛多元醇、聚氨酯多元醇或聚硅氧烷多元醇。 Examples [0063] Suitable compounds (V) are, for example, polymeric polyol having at least two hydroxyl groups such as polyester polyols, polyalkylene ether polyols, polycarbonate polyols, polyester carbonate polyols, poly polyacetal polyols, polyurethane polyols, or polysiloxane polyols. 优选的聚合多元醇为聚酯、聚亚烷基醚、聚酯碳酸酯和聚碳酸酯。 The preferred polymeric polyols are polyesters, polyalkylene ether, polyester carbonates and polycarbonates.

[0064] 二异氰酸酯(PI)与化合物(V)以及与(全)氟烷基醇(FA)的这一反应可同时或者在多个阶段中,通过首先例如异氰酸酯组分与一种或多种化合物(V)反应,然后使所得中间体与(全)氟烷基醇组分(FA)反应而进行。 [0064] diisocyanate (PI) with the compound (V) and this is reacted with (per) fluoroalkyl alcohol (FA) may be simultaneously or in stages, for example, by first isocyanate component with one or more compound (V) and then reacting the resulting intermediate component fluoroalkyl alcohol (FA) is reacted with (per) is performed.

[0065] 然而,优选不通过聚合物类似反应,而是通过使包含(全)氟烷基的相应烯属不饱和反应产物(U)聚合而制备包含(全)氟烷基的聚(甲基)丙烯酸酯组分(A)。 [0065] However, the polymer is preferably not a similar reaction, but by containing the corresponding alkenyl (per) fluoroalkyl group is the reaction product of unsaturated (U) prepared by polymerizing comprising (per) fluoroalkyl poly (methyl ) acrylate component (A).

[0066] 因此,作为含氟合成组分,聚(甲基)丙烯酸酯组分(A)优选包含以下物质的反应产物(U): [0066] Thus, the synthesis of fluorine-containing component, poly (meth) acrylate component (A) preferably comprises the reaction product of (U):

[0067] (i) -种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团, [0067] (i) - one or more diisocyanates (PI), having two isocyanate groups having different reactivity,

[0068] (ii) 一种或多种(全)氟烷基单醇组分(FA),和 [0068] (ii) one or more (per) fluoroalkyl monoalcohol component (FA), and

[0069] (iii)-种或多种化合物(V),其具有对异氰酸酯基团呈反应性的基团(G1),且具有烯属不饱和双键(G2)。 [0069] (iii) - one or more compounds (V), having a group (G1) of the isocyanate groups is reactive, and having an ethylenically unsaturated double bond (G2).

[0070] 这些特殊烯属不饱和含氟反应产物(U)用作合成组分确保与用于制备聚(甲基)丙烯酸酯组分(A)的其它烯属不饱和化合物的高相容性。 [0070] These special fluorine-containing ethylenically unsaturated reaction products (U) used as synthesis components for the preparation of other ethylenically ensure a poly (meth) acrylate component (A) is a high compatibility with the unsaturated compound. 因此,在根据本发明使用的含全氟烷基烯属不饱和反应产物的情况下,通常不必以分开的进料提供它们一如用常规商业含氟单体所必需的;而是,它们可与其余单体一起使用。 Thus, in the case where the unsaturated reaction product of a perfluoroalkyl group-containing ethylenically according to the present invention is used in the case, is generally not necessary to provide a separate feed them with regular commercial fluorine-containing monomer as necessary; rather, they may be used with the remaining monomer.

[0071] 对于包含氟和异氰酸酯基团的上述反应产物(U)和优选使用的烯属不饱和含氟反应产物(U)的制备,对本发明而言必要的是使用具有两个具有不同反应性的异氰酸酯基团的二异氰酸酯(PI),例如异佛尔酮二异氰酸酯。 [0071] For the above reaction product containing fluorine and an isocyanate group (U) and alkenyl preferably used metal preparing unsaturated fluorine-containing reaction product (U) is, for the present invention, it is necessary to use two different reactivity diisocyanates isocyanate groups (PI), such as isophorone diisocyanate. 这确保得到选择性地单氟化的反应产物,因此一如果有的话一仅得到极小部分的二氟化反应产物。 This ensures that the resulting reaction product optionally mono- fluorinated, a so obtained only if a very small portion of the reaction product difluoride. 这又意指氟化反应产物(U)非常完全地并入聚(甲基)丙烯酸酯组分(A)中,因此在所得固化涂层中还并入网络中。 This in turn means that the fluorination reaction product (U) is completely incorporated into the poly (meth) acrylate component (A), the resultant cured coating and therefore also incorporated in the network.

[0072] 对于上述包含氟基团的反应产物(U)和优选使用的烯属不饱和含氟反应产物(U) 的制备,优选使用以下通式的全氟代醇作为(全)氟烷基单醇组分(FA): [0072] The reaction product of the above-described fluorine-containing group (U) Preparation of an unsaturated fluorine-containing reaction product (U) is preferably used and alkenyl genus, preferably the following general formula perfluoro alcohol as a (per) fluoroalkyl group monoalcohol component (FA):

[0073] 通式(I) [0073] Formula (I)

[0074] CF3- (CF2) X- (CH2) y-〇-Az-H (I) [0074] CF3- (CF2) X- (CH2) y-square-Az-H (I)

[0075] 和/或通式(II) [0075] and / or formula (II)

[0076] CR^- (CR22) x- (CH2) y-〇-Az-H (II) [0076] CR ^ - (CR22) x- (CH2) y-square-Az-H (II)

[0077] 其中R1和R2相互独立地为H、F或CF3,但R 1和R2必须不同时为H,x为1-20,y为1-6且z 为0-100, [0077] wherein R1 and R2 are each independently H, F or CF3, but R 1 and R2 must not simultaneously H, x is 1-20, y is 1-6 and z is 0-100,

[0078] A为CR,R" -CR,,,R",,-0或(CR,R")a-0或⑶-(CR,R")b-0, [0078] A is CR, R "-CR ,,, R" ,, - 0, or (CR, R ") a-0 or ⑶- (CR, R") b-0,

[0079] R'、R"、R'"和R""相互独立地为H、具有1-25个C原子的烷基、环烷基、芳基或任意有机基团, [0079] R ', R ", R'" and R "" independently of one another are H, alkyl having 1-25 C atoms, a cycloalkyl group, an aryl group or any organic radical,

[0080] a和b各自为3-5, [0080] a and b are each 3-5,

[0081] 且聚氧化烯结构单元Az包含任何所需氧化烯的均聚物、共聚物或嵌段聚合物,或者包含聚氧亚烷基二醇,或者包含聚内酯。 [0081] and a structural unit polyoxyalkylene Az comprise any desired alkylene oxide homopolymers, copolymers or block polymers, or a polyoxyalkylene glycol comprises, or includes polylactones.

[0082] 适用作全氟烷基醇(FA)的化合物的实例为例如W02008/040428,第33页第4行至第34页第3行所述的(全)氟烷基醇,以及EP-B-1 664 222B1,第9页第[0054]段至第10页第 [0082] Examples of compounds suitable as perfluoroalkyl alcohol (FA) are, for example, W02008 / 040428, page 33, line 4 to page 34, line 3 of said (per) fluoroalkyl alcohols, and EP- B-1 664 222B1, page 9, paragraph [0054] to page 10 of

[0057]段所述的(全)氟烷基醇。 [0057] (per) fluoroalkyl alcohol according to.

[0083]根据本发明更特别地使用下式的全氟烷基醇(FA): [0083] According to the present invention is more particularly the use of perfluoroalkyl alcohol of formula (FA):

[0084] 式(III) [0084] Formula (III)

[0085] F(CF2CF2)i-(CH2CH2〇)mH (III) [0085] F (CF2CF2) i- (CH2CH2〇) mH (III)

[0086] 和/ 或式(IV) [0086] and / or formula (IV)

[0087] CF3-(CF2)n-(CH2)〇-0-H (IV) [0087] CF3- (CF2) n- (CH2) square-0-H (IV)

[0088] 其中: [0088] wherein:

[0089] 1为1-8,优选1-6,更优选2-3, [0089] 1 is 1-8, preferably 1-6, more preferably 2-3,

[0090] m 为1-15,优选5-15, [0090] m is 1-15, preferably 5-15,

[0091] η 为1-12,优选1-6, [0091] η 1 to 12, preferably 1 to 6,

[0092] 〇为1-10,优选1-4。 [0092] The square is 1-10, preferably 1-4.

[0093] 合适全氟代醇的实例为^^^八八^卜十三氟辛-丨-醇、^^ 5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸-1-醇、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 11,11,12,12,12-二^-一氟十二-卜醇、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12, 12,13,13,14,14,14-二十五氟十四-1-醇、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11, 12,12,13,13,14,14,15,15,16,16,16-二十九氟十六-1-醇、3,3,4,4,5,5,6,6,7,7,8,8-十二氟庚-1-醇、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-十六氟壬-1-醇、3,3,4,4,5,5,6,6, 7,7,8,8,9,9,10,10,11,11,12,12-二十氟^-一-1-醇、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 10,11,11,12,12,13,13,14,14-二十四氟十三-1-醇和3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 10,11,11,12,12,13,13,14,14,15,15,16,16-二十八氟十五-1-醇。 [0093] Examples of suitable perfluorinated alcohols eighty-eight ^^^ oct-tridecafluoro ^ Bu - Shu - alcohol, ^^ 5,5,6,6,7,7,8,8,9,9,10 , 10,10-heptadecafluorodecyl-1-ol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 11, 11, 12,12,12- two ^ - a fluorine twelve - BU alcohol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11 , 11, 12, fourteen 12,13,13,14,14,14- twenty-five fluoro-1-ol, 3,3,4,4,5,5,6,6,7,7,8, 8,9,9,10,10,11,11, sixteen 12,12,13,13,14,14,15,15,16,16,16- twenty-nine fluoro-1-ol, 3,3 , 4,4,5,5,6,6,7,7,8,8- dodecafluoroheptyl 1-ol, 3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10- sixteen-fluoro-1-ol, 3,3,4,4,5,5,6,6, 7,7,8,8,9,9,10 , 10,11,11,12,12- twenty-fluoro ^ - a 1-ol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9, 10, 10,11,11,12,12,13,13,14,14- twenty thirteen tetrafluoro-1-ol 3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10, 10,11,11,12,12,13,13,14,14,15,15,16,16- twenty-eight fifteen fluoro-1-ol.

[0094] 为制备上述包含氟基团的反应产物(U)以及制备优选使用的烯属不饱和含氟反应产物(U),特别优选通式(V)的全氟代醇或不同式(V)全氟代醇的混合物作为(全)氟烷基醇组分(FA): [0094] To prepare the above-described fluorine-containing group is a reaction product of (U) and the preparation of ethylenically unsaturated preferably used the fluorine-containing reaction product (U), perfluoro alcohol and particularly preferably formula (V) or a different formula (V ) a mixture of alcohol as perfluoro (per) fluoroalkyl alcohol component (FA):

[0095] CF3-(CF2)r-(CH2)P-〇H (V) [0095] CF3- (CF2) r- (CH2) P-〇H (V)

[0096] 其中r为1 -8,优选1 -6,更特别是1 -4,且p为1 -6,更特别是1 -2。 [0096] wherein r is 1-8, preferably 1-6, more particularly 1-4, and p is 1-6, more particularly 1-2.

[0097]更特别地使用其中p = 2的式(V)全氟烷基乙醇,优选2_(全氟己基)乙醇和2_(全氟辛基)乙醇,和不同的式(V)全氟烷基乙醇的混合物,更特别是2-(全氟己基)乙醇和2-(全氟辛基)乙醇任选与其它(全)氟烷基乙醇的混合物。 [0097] More particularly used in which (V) perfluoroalkyl ethanol, preferably 2_ p = 2 in formula (perfluorohexyl) ethanol and 2_ (perfluorooctyl) ethanol, and a different formula (V) perfluoroalkyl a mixture of ethanol group, more particularly (perfluorooctyl) ethanol, optionally a mixture with other (per) fluoroalkyl ethanol, 2- (perfluorohexyl) ethanol and 2. 优选使用具有30-49.9重量%2-(全氟己基)乙醇和30-49.9重量%2-(全氟辛基)乙醇的全氟烷基乙醇混合物,例如商品JlnOWetŪ EA 612和FluowetŪEA 812;2-(全氟己基)乙醇,例如商品Daikin A-1620,或者2-(全氟辛基)乙醇,例如商品Daikin A-1820,其都来自Daikin Industries Ltd.,0saka,日本。 Preferably having 30-49.9 wt% 2-perfluoroalkyl% ethanol mixture of 2- (perfluorohexyl) ethanol and 30-49.9 wt (perfluorooctyl) ethanol, e.g. commodity JlnOWetŪ EA 612 and FluowetŪEA 812 ; 2- (perfluorohexyl) ethanol, for example, trade Daikin A-1620, or 2- (perfluorooctyl) ethanol, for example, trade Daikin A-1820, which are from Daikin Industries Ltd., 0saka, Japan. 尤其优选使用2_(全氟己基)乙醇。 2_ particularly preferably used (perfluorohexyl) ethanol.

[0098]预期作为具有对异氰酸酯基团呈反应性的基团(G1)且具有烯属不饱和双键(G2) 的化合物(V)的化合物的实例包括具有烯属不饱和双键且还包含羟基、氨基、巯基、羧基或酰胺基团的化合物。 [0098] contemplated as examples of having an isocyanate group as a reactive group of (G1) and a compound of the olefinic compound (V) an unsaturated double bond (G2) of having include those having an ethylenically unsaturated double bond and further comprising hydroxy, amino, mercapto, carboxy groups or amide compound. 更特别地预期作为化合物(V)的有具有丙烯酸和/或甲基丙烯酸属不饱和双键且还包含羟基、氨基、巯基、羧基或酰胺基团的化合物。 More specifically contemplated as compound (V) are acrylic acid and / or an unsaturated double bond and the compound further comprises a hydroxyl group, an amino group, a mercapto group, a carboxyl group or an amide group having or methacrylic species. 特别优选预期作为组分(V)的有具有丙烯酸和/或甲基丙烯酸属不饱和双键且还包含羟基的化合物。 Particularly preferred contemplated as component (V) are an acrylic and / or methacrylic acid metal compound further comprises an unsaturated double bond and a hydroxyl group.

[0099] 合适烯属不饱和化合物(V)的实例为烯属不饱和单羧酸和烯属不饱和二羧酸及其羟烷基酯,例如丙烯酸、甲基丙烯酸、乙基丙烯酸、巴豆酸、马来酸、富马酸、衣康酸、柠檬酸, 及其羟烷基酯,以及包含氨基的烷基酯,例如特别是甲基丙烯酸丁基氨基乙酯。 [0099] Examples of suitable ethylenically unsaturated compound (V) are ethylenically unsaturated monocarboxylic acids and ethylenically unsaturated dicarboxylic acids, hydroxyalkyl esters such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid , maleic acid, fumaric acid, itaconic acid, citric acid, and hydroxyalkyl esters, and alkyl esters containing an amino group, such as in particular methyl acrylate, butylaminoethyl methacrylate.

[0100] 特别优选化合物(V)选自丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯、丙烯酸羟基环烷基酯、甲基丙烯酸羟基环烷基酯及其混合物。 [0100] Particularly preferred compound (V) is selected from hydroxyalkyl acrylates, hydroxyalkyl esters of methacrylic acid, hydroxy cycloalkyl esters of acrylic acid, methacrylic acid, hydroxy cycloalkyl esters, and mixtures thereof.

[0101]优选使用的(甲基)丙烯酸羟烷基酯的实例为丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、丙烯酸2-羟基丙酯、甲基丙烯酸2-羟基丙酯、丙烯酸3-羟基丙酯、甲基丙烯酸3-羟基丙酯、丙烯酸3-羟基丁酯、甲基丙烯酸3-羟基丁酯、丙烯酸4-羟基丁酯、甲基丙烯酸4-羟基丁酯以及类似化合物。 [0101] (meth) acrylate, hydroxyalkyl esters preferably used are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methacrylate, 2-hydroxypropyl methacrylate, acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl acrylate, butyl methacrylate, 3-hydroxypropyl, 4-hydroxybutyl acrylate, methacrylate, 4-hydroxybutyl acrylate and similar compounds .

[0102] 作为具有对异氰酸酯基团呈反应性的基团(G1)的烯属不饱和化合物(V),也可特别地使用内酯与丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯及其混合物的反应产物。 [0102] As the alkenyl group having (G1) of the isocyanate groups which are reactive unsaturated compound (V), in particular can be used lactone with the hydroxyalkyl acrylate, hydroxyalkyl methacrylate and acrylate the reaction product mixtures thereof. 这些为内酯的均聚物或共聚物,优选内酯与合适二官能启动剂分子的加合物,所述加合物包含末端羟基。 These are homo- or copolymers of lactones, preferably adducts of lactones with suitable difunctional starter additive molecules, the adduct containing terminal hydroxyl groups. 合适内酯的实例为[ε]_己内酯、[β]_丙内酯、[γ ]_丁内酯和/或甲基_[ε]_己内酯及其混合物。 Examples of suitable lactones [[epsilon]] _-caprolactone, [β] _ propiolactone, [γ] _-butyrolactone and / or methyl _ [[epsilon]] _ caprolactone, and mixtures thereof. 代替内酯的聚合物,也可更特别优选使用对应于内酯的羟基羧酸的相应化学等价缩聚物。 Lactone in place of the corresponding, chemically equivalent polymer, may be particularly preferably used hydroxycarboxylic acids corresponding to the lactones polycondensates.

[0103] 此外,作为具有对异氰酸酯基团呈反应性的基团(G1)的烯属不饱和化合物(V),也可使用用聚合多元醇改性的丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯及其混合物,例如用聚酯多元醇、聚亚烷基醚多元醇、聚碳酸酯多元醇、聚酯碳酸酯多元醇、聚缩醛多元醇、聚氨酯多元醇或聚硅氧烷多元醇改性的丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯及其混合物。 [0103] Further, as the alkenyl group having (G1) of the isocyanate groups which are reactive unsaturated compound (V), it can also be used with a polymeric hydroxyalkyl acrylate-modified polyols, hydroxyethyl methacrylate alkyl esters and mixtures thereof, for example, polyester polyols, polyalkylene ether polyols, polycarbonate polyols, polyester carbonate polyols, polyacetal polyols, polyurethane polyols, or polysiloxane polyols, alcohol-modified hydroxyalkyl acrylates, hydroxyalkyl methacrylate and mixtures thereof. 优选的聚合多元醇为聚酯、聚亚烷基醚、聚酯碳酸酯和聚碳酸酯。 The preferred polymeric polyols are polyesters, polyalkylene ether, polyester carbonates and polycarbonates.

[0104] 特别优选,聚(甲基)丙烯酸酯组分(Α)包含以下物质的反应产物(U)作为含氟合成组分: [0104] Particularly preferably, the poly (meth) acrylate component ([alpha]) comprising the reaction product of (U) as the fluorine-containing synthesis components:

[0105] (i)-种或多种脂族和/或脂环族二异氰酸酯(ΡΙ),其具有两个具有不同反应性的异氰酸酯基团, [0105] (i) - one or more aliphatic and / or cycloaliphatic diisocyanates (ΡΙ), having two isocyanate groups having different reactivity,

[0106] (ii)-种或多种式(V)的(全)氟烷基醇组分(FA): [0106] (ii) - one or more compounds of formula (V), (per) fluoroalkyl alcohol component (FA):

[0107] CF3-(CF2)r-(CH2)P-〇H (V) [0107] CF3- (CF2) r- (CH2) P-〇H (V)

[0108] 其中r为1-8,优选r为1-6,更优选r为1-4,且p为1-6,优选p为1-2,和 [0108] wherein r is 1-8, r is preferably 1-6, more preferably r is 1-4, and p is 1-6, p is preferably 1-2, and

[0109] (iii)-种或多种具有羟基G1且具有丙烯酸和/或甲基丙烯酸属不饱和双键(G2) 的化合物(V),其优选选自丙烯酸羟烷基酯、甲基丙烯酸羟烷基酯、与内酯反应的丙烯酸羟烷基酯、与内酯反应的甲基丙烯酸羟烷基酯及其混合物。 [0109] (iii) - one or more G1 having a hydroxyl group and an acrylic and / or methacrylic acid metal compound (V) an unsaturated double bond (G2), which is preferably selected from hydroxyalkyl acrylates, methacrylates hydroxyalkyl acrylate, hydroxyalkyl acrylate is reacted with the lactone, the lactone is reacted with hydroxyalkyl esters of methacrylic acid, and mixtures thereof.

[0110] 非常特别优选聚(甲基)丙烯酸酯组分(A)包含以下物质的反应产物(U)作为含氟合成组分:异佛尔酮二异氰酸酯、2_(全氟己基)乙醇和丙烯酸羟基乙酯和/或甲基丙烯酸羟基乙酯和/或羟烷基己内酯丙烯酸酯和/或羟烷基己内酯甲基丙烯酸酯。 [0110] very particularly preferably poly (meth) acrylate component (A) comprises the reaction product of (U) as the fluorine-containing synthesis components: isophorone diisocyanate, 2_ (perfluorohexyl) ethanol and acrylic acid hydroxyethyl acrylate and / or hydroxyethyl methacrylate and / or hydroxyalkyl groups caprolactone acrylate and / or hydroxyalkyl methacrylate caprolactone.

[0111] 组分(PI)、(FA)和(V)的含量可改变。 [0111] Component (PI), (FA) and (V) content can be varied. 然而,对于全氟烷基的聚合物类似引入,优选的反应产物(U)为以下物质的那些: However, the polymer is similar to the introduction of a perfluoroalkyl group, preferably reaction products (U) are those of the following substances:

[0112] (i)l摩尔的一种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团,和 [0112] (i) l mole of one or more diisocyanates (PI), having two isocyanate groups having different reactivity, and

[0113] (ii)l摩尔的一种或多种(全)氟烷基单醇组分(FA)。 [0113] (ii) l mole of one or more (per) fluoroalkyl monoalcohol component (FA).

[0114] 特别优选使用包含以下物质的反应产物(U)作为含氟合成组分的聚(甲基)丙烯酸酯组分(A): [0114] particularly preferably used comprises the reaction product of (U) as a synthesis component in the fluorine-containing poly (meth) acrylate component (A):

[0115] (i)l摩尔的一种或多种二异氰酸酯(PI),其具有两个具有不同反应性的异氰酸酯基团, [0115] (i) l mole of one or more diisocyanates (PI), having two isocyanate groups having different reactivity,

[0116] (ii)l摩尔的一种或多种(全)氟烷基单醇组分(FA),和 [0116] (ii) l mole of one or more (per) fluoroalkyl monoalcohol component (FA), and

[0117] (iii)l摩尔的一种或多种烯属不饱和化合物(V),其具有至少一个对异氰酸酯基团呈反应性的基团(G1)。 [0117] (iii) l mole of one or more ethylenically unsaturated compounds (V), having at least one group reactive form (G1) to the isocyanate groups.

[0118] 根据本发明进一步优选聚(甲基)丙烯酸酯组分(A)由一种或多种饱和含全氟烷基和多羟基聚丙烯酸酯或者由一种或多种饱和含全氟烷基和多羟基聚甲基丙烯酸酯,或者由一种或多种饱和含全氟烷基和多羟基聚丙烯酸酯和一种或多种饱和含全氟烷基和多羟基聚甲基丙烯酸酯的混合物组成。 [0118] According to a further preferred poly (meth) acrylate of the present invention, component (A) consists of one or more saturated perfluoroalkyl group and a polyhydroxy polyacrylates of one or more saturated or perfluoroalkyl polyhydroxy groups and polymethacrylates, or from one or more saturated containing a perfluoroalkyl group and a polyhydroxy polyacrylates, and one or more saturated perfluoroalkyl group and a polyhydroxy methacrylate mixtures thereof. 然而,作为组分(A),当然也可使用一种或多种饱和含全氟烷基和任选饱和含多羟基聚(甲基)丙烯酸酯与不含氟基团的饱和含多羟基聚(甲基)丙烯酸酯的混合物。 However, as the component (A), of course, also possible to use one or more saturated, and optionally containing a perfluoroalkyl group-containing saturated polyhydroxy poly (meth) acrylates with unsaturated fluorine-containing group of polyhydroxy (meth) acrylate mixture. 在这种情况下,应仅确保混合物包含每种情况下基于用于制备聚(甲基)丙烯酸酯组分(A)的所有化合物的量为0.05-15重量%,优选0.1-10.0重量%的一种或多种含氟反应产物(U)。 In this case, it should ensure that only the mixture contains based on the amount of all the compounds for the preparation of poly (meth) acrylate component (A) is 0.05 to 15% by weight in each case, preferably 0.1 to 10.0% by weight one or more fluorine-containing reaction product (U).

[0119]特别优选,用作组分(A)的聚(甲基)丙烯酸酯是饱和的并由以下物质合成: [0119] Particularly preferably, the poly (meth) acrylate is used as component (A) is a saturated material by the following synthesis:

[0120] (al)0.05-15重量%,优选0.1-10重量%的一种或多种含氟烯属不饱和反应产物⑶, [0120] (al) 0.05-15% by weight, preferably 0.1 to 10% by weight of one or more fluorine-containing ethylenically unsaturated reaction product ⑶,

[0121] (a2)10_50重量%,优选15-45重量%的一种或多种含羟基单体, [0121] (a2) 10_50% by weight, preferably 15-45% by weight of one or more hydroxyl group-containing monomers,

[0122] (a3) 10-89.95重量%,优选30-84.9重量%的一种或多种烯属不饱和羧酸的烷基和/或环烷基酯, [0122] (a3) 10-89.95 wt%, preferably 30-84.9% by weight of one or more ethylenically unsaturated carboxylic acid alkyl and / or cycloalkyl esters,

[0123] (a4)0_50重量%,优选0-30重量%的一种或多种乙烯基芳族化合物,和 [0123] (a4) 0_50 wt%, preferably 0-30 wt% of one or more vinyl aromatic compounds, and

[0124] (a5)0_10重量%,优选0-5重量%的其它烯属不饱和单体, [0124] (a5) 0_10 wt%, preferably 0-5% by weight of other ethylenically unsaturated monomers,

[0125] 其中单体(al)至(a5)的重量含量之和每种情况下为100重量%。 [0125] wherein the weight content of the monomer (Al) to (a5) of the sum in each case 100% by weight.

[0126] 适用作单体(a2)的有(甲基)丙烯酸羟烷基酯和(甲基)丙烯酸羟基环烷基酯,以及烯属不饱和羧酸如富马酸、巴豆酸和马来酸的羟烷基酯和羟基环烷基酯,及其混合物,其在上文中已作为化合物(V)列出。 [0126] suitable as monomer (a2) are (meth) acrylic acid alkyl ester and hydroxyalkyl (meth) acrylate, hydroxy cycloalkyl esters, and unsaturated carboxylic acids such as fumaric acid, crotonic acid and maleic olefinic acid hydroxyalkyl esters and hydroxy cycloalkyl esters, and mixtures thereof as listed in the above compound (V).

[0127] 尤其适用作单体(a3)的有不具有活性氢的烯属不饱和羧酸的烷基酯,更优选不具有其它官能团的烷基酯,非常优选饱和单醇与烯属不饱和羧酸的烷基酯。 [0127] There are no particular alkenyl having active hydrogen metal alkyl esters of unsaturated carboxylic acids suitable for use as monomer (a3), more preferably an alkyl ester having no other functional groups, very preferably saturated mono alcohols with ethylenically unsaturated alkyl esters of carboxylic acids. 烯属不饱和羧酸的这类烷基酯(a3)的实例为丙烯酸、甲基丙烯酸、富马酸、巴豆酸和马来酸,优选丙烯酸和/ 或甲基丙烯酸的烷基酯和环烷基酯,优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸戊酯、甲基丙烯酸戊酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸乙基己酯、甲基丙烯酸乙基己酯、丙烯酸3,3,5_三甲基己酯、甲基丙烯酸3,3,5_三甲基己酯、丙烯酸硬脂基酯、甲基丙烯酸硬脂基酯、丙烯酸月桂基酯或甲基丙烯酸月桂基酯,丙烯酸环烷基酯和/或甲基丙烯酸环烷基酯,例如丙烯酸环戊酯、甲基丙烯酸环戊酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸 Such olefinic alkyl ester (a3) Examples of unsaturated carboxylic acid alkyl esters and cycloalkyl acrylic acid, methacrylic acid, fumaric acid, crotonic acid and maleic acid, preferably acrylic acid and / or methacrylic acid ester, preferably methyl acrylate, methyl methacrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, propyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, butyl acrylate, methyl methacrylate, butyl acrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, amyl acrylate, methacrylate, pentyl acrylate, hexyl acrylate, hexyl methacrylate, acrylate, ethyl hexyl methacrylate, ethyl hexyl acrylate, 3,3,5_ trimethyl hexyl methacrylate, 3,3,5_ trimethyl hexyl acrylate, stearyl acrylate, methyl stearyl acrylate, lauryl acrylate or methacrylate, lauryl acrylate, cycloalkyl esters and / or methacrylic acid cycloalkyl esters, for example acrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, isobornyl methacrylate, isobornyl acrylate, 环己酯和/或甲基丙烯酸环己酯。 Cyclohexyl acrylate and / or methacrylate, cyclohexyl acrylate.

[0128] 尤其适用作单体(a4)的有不具有活性氢的乙烯基芳族化合物。 [0128] In particular, the aromatic vinyl compound having no active hydrogen suitable for use as the monomer (a4) a. 合适乙烯基芳族化合物(a4)的实例为乙烯基芳族烃,例如乙烯基甲苯、α-甲基苯乙烯或者特别是苯乙烯。 Examples of suitable vinyl aromatic compounds (a4) are vinyl aromatic hydrocarbons such as vinyltoluene, alpha] -methylstyrene or particular styrene.

[0129] 尤其适用作单体(a5)的有具有至少两个可聚合烯属不饱和双键且不具有活性氢的稀属不饱和化合物。 [0129] Especially suitable as monomer (a5) is having at least two polymerizable ethylenically unsaturated double bonds and does not dilute the active hydrogen-having unsaturated compound. 合适的具有至少两个可聚合稀属不饱和双键的稀属不饱和单体(a5) 的实例为饱和二醇与烯属不饱和羧酸的二酯,更特别是饱和二醇与丙烯酸、甲基丙烯酸、富马酸、巴豆酸和马来酸,优选丙烯酸和/或甲基丙烯酸的二酯,例如己二醇二丙烯酸酯、己二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、丁二醇二丙烯酸酯、丁二醇二甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯和三羟甲基丙烷三甲基丙烯酸酯。 Suitable having at least two polymerizable unsaturated double bonds dilute dilute genus genus Examples of the unsaturated monomer (a5) genus diesters of unsaturated carboxylic acids and ethylenically unsaturated diols are, more particularly acrylic acid and a saturated diol, methacrylic acid, fumaric acid, crotonic acid and maleic acid, preferably acrylic acid and / or methacrylic acid diesters, such as hexanediol diacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate , ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylol propane triacrylate and trimethylol propane trimethacrylate. 最后,作为单体(a5),也可使用多异氰酸酯和不饱和醇或胺的反应产物。 Finally, as the monomer (A5), the polyisocyanate may be the reaction product of an unsaturated alcohol or amine used. 给出的该反应产物的实例为1 摩尔六亚甲基二异氰酸酯和2摩尔烯丙醇的反应产物,或者异佛尔酮二异氰酸酯和丙烯酸羟基乙酯的反应产物。 Examples of the reaction product is the reaction product of a given mole of hexamethylene diisocyanate and 2 moles of allyl alcohol, or isophorone diisocyanate and a reaction product of hydroxy ethyl acrylate.

[0130] 作为不同于单体(al)至(a4)的其它烯属不饱和化合物(a5),也可使用不具有活性氢的无硅单体,例如丙烯酸或甲基丙烯酸的腈、乙烯基酯或乙烯基醚、烯属不饱和羧酰胺, 例如丙烯酰胺、甲基丙烯酰胺、衣康酰胺、乙基丙烯酰胺、巴豆酰胺、富马酰胺和马来酰胺。 [0130] As different from the monomers (Al) other ethylenically to (a4) unsaturated compound (A5), can also be used a silicon-free monomer having no active hydrogen, such as acrylic acid or methacrylic acid nitrile, vinyl or vinyl ethers, ethylenically unsaturated carboxamides such as acrylamide, methacrylamide, itaconic acid amide, ethyl acrylamide, crotonic acid amide, fumaric acid amide and maleic acid amide.

[0131] 根据本发明尤其优选的聚(甲基)丙烯酸酯多元醇通常为共聚物,且优选具有1000-20 000道尔顿,更特别是1500-10 000道尔顿的质量平均分子量,其每种情况下通过凝胶渗透色谱法(GPC)相对于聚苯乙烯标准测量。 [0131] According to the present invention is particularly preferred poly (meth) acrylate copolymer polyols are typically, and preferably has 1000-20000 daltons, and more especially 1500-10000 daltons weight average molecular weight, which by gel permeation chromatography (GPC) relative to polystyrene standards measured in each case.

[0132] 共聚物的玻璃化转变温度通常为-100至100°C,更特别是-60至<60°C (通过DSC测量根据DIN-EN-IS0 11357-2 测量)。 The glass [0132] transition temperature of the copolymer is usually -100 to 100 ° C, more particularly -60 to <60 ° C (measured by DSC in accordance with DIN-EN-IS0 11357-2 measurement).

[0133] 聚(甲基)丙烯酸酯多元醇优选具有60-300mg KOH/g,更特别是70-200mgK0H/g的0H值。 [0133] Poly (meth) acrylate esters of polyols having preferably 60-300mg KOH / g, more particularly 70-200mgK0H / 0H g.

[0134] 羟值(0H值)表示与在乙酰化中lg物质结合的乙酸的量相同的氢氧化钾的mg数。 [0134] hydroxyl value (0H) indicates the amount of lg mg of acetic acid in the substance bound in the same acetylation of potassium hydroxide. 对于测定,将试样用乙酸酐-吡啶煮沸,并将形成的酸用氢氧化钾溶液滴定(DIN 53240-2)。 For the assay, the sample with acetic anhydride - pyridine to boil, and the resulting acid titrated with potassium hydroxide solution (DIN 53240-2). 在纯聚(甲基)丙烯酸酯的情况下,0H值也可通过基于所用0H官能单体计算而以足够的准确度测定。 In the case of pure poly (meth) acrylate, 0H 0H functional monomers is also based on the value calculated with sufficient accuracy and can be determined by.

[0135] 聚(甲基)丙烯酸酯多元醇优选具有0_30mg KOH/g的酸值。 [0135] Poly (meth) acrylate polyols preferably have 0_30mg KOH / g acid number. 酸值在此处表示在中和lg各化合物中消耗的氢氧化钾的mg数(DIN EN ISO 2114)。 Herein represents the acid value mg consumed in each of the compound and lg of potassium hydroxide (DIN EN ISO 2114). 含多羟基化合物(C) Polyhydroxy-containing compound (C)

[0136] 任选,除含多羟基聚(甲基)丙烯酸酯组分(A)外,本发明涂料组合物可进一步包含一种或多种不同于组分(A)的单体饱和含多羟基化合物,和/或饱和低聚和/或饱和聚合聚酯多元醇、聚氨酯多元醇和聚硅氧烷多元醇,更特别是饱和聚酯多元醇(C)。 [0136] Optionally, in addition to the polyhydroxy-containing poly (meth) acrylate component (A), the coating compositions of the invention may further comprise one or more unsaturated monomers different from components containing (A) a plurality hydroxy compound, and / or unsaturated oligomeric and / or polymeric unsaturated polyester polyols, polyurethane polyols and polysiloxane polyols, and more particularly a saturated polyester polyol (C). 这些化合物(C) 优选占0-20重量%,更优选0-10重量%,非常优选1-5重量%的含量,每种情况下基于涂料组合物的基料含量。 These compounds (C) preferably comprises 0-20% by weight, more preferably 0-10 wt%, 1-5 wt% of the content is preferably, in each case based on the binder content of the coating composition.

[0137] 合适的聚酯多元醇描述于例如ΕΡ-Α-0 994 117和EP-A-1 273 640中。 [0137] Suitable polyester polyols are described in, for example ΕΡ-Α-0 994 117 and EP-A-1 273 640 in. 聚氨酯多元醇优选通过使聚酯多元醇预聚物与合适的二异氰酸酯或多异氰酸酯反应而制备,且描述于例如EP-A-1 273 640中。 Polyurethane polyols preferably prepared by reacting the polyester polyol prepolymers with suitable diisocyanates or isocyanate-reactive, and are described for example in EP-A-1 273 640 in. 合适的聚硅氧烷多元醇描述于例如W0-A-01/09260中。 Suitable polysiloxane polyols are described in W0-A-01/09260, for example.

[0138] 作为含羟基化合物(C),可使用低分子量多元醇。 [0138] As the hydroxyl group-containing compound (C), low molecular weight polyols may be used. 所用低分子量多元醇为例如二醇,例如优选乙二醇、新戊二醇、1,2-丙二醇、2,2-二甲基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,5-戊二醇、2,2,4-三甲基-1,3-戊二醇、1,6-己二醇、1,4-环己烷二甲醇和1,2-环己烷二甲醇,以及多元醇,例如优选三羟甲基乙烷、三羟甲基丙烷、三羟甲基己烷、1,2,4_ 丁三醇、季戊四醇和二季戊四醇。 The low molecular weight polyols such as glycols, e.g. ethylene glycol, neopentyl glycol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1 1,3-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and 1,2-cyclohexanedimethanol, and polyhydric alcohols, e.g. preferably trimethylolethane, trimethylol propane, trimethylol hexane, 1,2,4_ butanetriol, pentaerythritol and dipentaerythritol . 这类低分子量多元醇优选以次要含量混入多元醇组分(A)中。 Such low molecular weight polyol is preferably mixed with a minor content of the polyol component (A) is.

[0139] 含多异氰酸酯基团的组分(B) [0139] Component (B) polyisocyanate containing isocyanate groups of

[0140] 根据本发明使用的含异氰酸酯基团化合物(B)优选为常用的取代或未取代芳族、 脂族、脂环族和/或杂环二异氰酸酯和/或多异氰酸酯。 [0140] The isocyanate group-containing compound used in the present invention (B) is preferably a substituted or unsubstituted aryl conventional aromatic, aliphatic, cycloaliphatic and / or heterocyclic diisocyanates and / or polyisocyanates.

[0141] 合适二异氰酸酯的实例如下:2,4_甲苯二异氰酸酯、2,6_甲苯二异氰酸酯、二苯基甲烷4,4 二异氰酸酯、二苯基甲烷2,4 二异氰酸酯、对苯二异氰酸酯、联苯二异氰酸酯、 3,3'_二甲基_4,4'_二苯二异氰酸酯、四亚甲基1,4_二异氰酸酯、六亚甲基1,6_二异氰酸酯、2,2,4_三甲基己烷1,6_二异氰酸酯、异佛尔酮二异氰酸酯、亚乙基二异氰酸酯、1,12-十二烷二异氰酸酯、环丁烷1,3_二异氰酸酯、环己烷1,3_二异氰酸酯、环己烷1,4_二异氰酸酯、甲基环己基二异氰酸酯、六氢甲苯2,4_二异氰酸酯、六氢甲苯2,6_二异氰酸酯、六氢亚苯1,3-二异氰酸酯、六氢亚苯1,4-二异氰酸酯、全氢二苯基甲烷2,4 二异氰酸酯、4,4 亚甲基二环己基二异氰酸酯(例如来自Bayer AG的Desm〇d_Ury<)_O、四甲基二甲苯二异氰酸酯(例如来自American Cyanamid的TMXDIŪP,和上述多异氰酸酯的混合物 [0141] Suitable diisocyanates of the examples are as follows: 2,4_ tolylene diisocyanate, 2,6_ toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4-diisocyanate, p-phenylene diisocyanate , biphenyl diisocyanate, dimethyl _4,4'_ 3,3'_ diphenyl diisocyanate, tetramethylene diisocyanate 1,4_, 1,6_ hexamethylene diisocyanate, 2,2 , 4_ 1,6_ trimethyl hexane diisocyanate, isophorone diisocyanate, ethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3_ diisocyanate, cyclohexyl alkoxy diisocyanate 1,3_, 1,4_-cyclohexane diisocyanate, methylcyclohexyl diisocyanate, hexahydro-toluene diisocyanate 2,4_, 2,6_-hexahydro-toluene diisocyanate, phenylene-hexahydro-1 , 3-diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4-diphenylmethane diisocyanate, 4,4'-methylene dicyclohexyl diisocyanate (e.g. Desm〇d_Ury from Bayer AG < ) _O, tetramethyl xylene diisocyanate (TMXDIŪP from American Cyanamid, a mixture of the above-described example, and the polyisocyanate

[0142] 其它优选的多异氰酸酯为上述二异氰酸酯的异氰尿酸酯三聚物和/或脲基甲酸酯二聚物和/或缩二脲二聚合物和/或脲二酮二聚物。 [0142] Other preferred polyisocyanates for the above-described diisocyanates of isocyanurate trimers and / or dimers allophanate and / or biuret two polymers and / or uretdione dimer .

[0143] 在本发明另一实施方案中,多异氰酸酯为具有氨基甲酸酯结构单元的多异氰酸酯预聚物,其通过使多元醇与化学计量过量的上述多异氰酸酯反应而得到。 [0143] In another embodiment of the invention, the polyisocyanate is a polyisocyanate prepolymer having a urethane structure unit, which is obtained by reacting a polyol with a stoichiometric excess of the polyisocyanate reaction. 这类多异氰酸酯预聚物描述于例如US-A-4,598,131中。 Such polyisocyanate prepolymers described, for example in US-A-4,598,131.

[0144] 特别优选的多异氰酸酯组分(B)为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和4,4 亚甲基二环己基二异氰酸酯和/或其异氰尿酸酯三聚物和/或脲基甲酸酯二聚物和/ 或缩二脲二聚物和/或脲二酮二聚物。 [0144] A particularly preferred polyisocyanate component (B) is hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-methylene dicyclohexyl diisocyanate and / or isocyanurate trimers and / or allophanate dimers and / or dimer, biuret and / or uretdione dimer.

[0145] 因此,多异氰酸酯组分(B)与含异氰酸酯基团的反应产物(U)不同的是在制备组分(A)中任选使用特别具有较高异氰酸酯基团含量,因为组分(B)具有平均至少两个异氰酸酯基团每分子,而含异氰酸酯基团的反应产物(U)具有平均小于两个,优选一个异氰酸酯基团每分子。 [0145] Thus, the polyisocyanate component (B) the reaction product containing isocyanate groups, (U) except that in the preparation of component (A) is optionally used particularly group content of higher polyisocyanates, as component ( B) having an average of at least two isocyanate groups per molecule, the reaction product containing isocyanate groups, (U) has an average of less than two, preferably one isocyanate group per molecule.

[0146] 催化剂(D) [0146] Catalyst (D)

[0147] 作为催化剂(D),可使用常规化合物。 [0147] As the catalyst (D), conventional compounds may be used. 实例为路易斯酸(贫电子化合物),例如环烷酸锡、苯甲酸锡、辛酸锡、丁酸锡、二月桂酸二丁锡、二乙酸二丁锡、氧化二丁锡、辛酸铅、磷酸或磺酸的胺加合物(例如来自King Industries的Nacure产品)。 Examples of a Lewis acid (electron-deficient compounds), such as tin naphthenate, tin benzoate, tin octoate, tin butyrate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, lead octoate, phosphoric acid, or sulfonic acid amine adduct (e.g. Nacure from King Industries of product). 在涂料中,优选使用还用于制备反应产物(U)的催化剂。 The coating is preferably used also for the preparation of a catalyst the reaction product (U) is. 因此,更特别地使用确保在反应产物的制备中仅一个异氰酸酯基团选择性反应的那些催化剂,例如特别是含锡催化剂。 Thus, more specifically those catalysts used to ensure that only one isocyanate reactive group selectively in the preparation of the reaction product, such as in particular a tin-containing catalyst.

[0148] 优选使用每种情况下基于组分(A)加(B)的和的基料含量为0.001-5重量%,优选0.01-2重量%的一种或多种催化剂(D)。 [0148] Based on the content of binder component (A) plus (B) is 0.001 to 5 wt%, preferably used in each case preferably 0.01 to 2% by weight of one or more catalysts (D).

[0149] 单体芳族羧酸(S) [0149] monomeric aromatic carboxylic acid (S)

[0150]此外,为改进组装强度和机械性能,优选涂料组合物包含至少一种其羧基与π-电子体系共辄的单体芳族任选取代羧酸(S)。 [0150] Further, to improve the assembling strength and mechanical properties, the coating composition preferably comprises at least one of its carboxyl groups with π- electron system of co noir optionally substituted aromatic carboxylic acid monomer (S). 此处,羧基的数目该改变,其中羧酸优选具有1个羧基。 Here, the change of the number of carboxyl groups, preferably wherein the carboxylic acid having one carboxyl group. 单体芳族任选取代羧酸优选具有<500g/mol,更优选<300g/mol的分子量。 Optionally substituted aromatic carboxylic acid monomers preferably have <500g / mol, and more preferably a molecular weight <300g / mol of. 优选使用具有2-5的pKa的单体芳族任选取代羧酸。 Preferably an aromatic-substituted carboxylic acid monomer having a pKa 2-5 optional. pKa相当于半当量点下的pH,其中溶液介质优选为水。 at pH pKa corresponding to the half equivalent point, wherein the solution medium is preferably water. 如果对于酸,不能规定在水中的pKa,则所选择的介质优选为DMSO或者酸可溶于其中的另一合适介质。 If the acid, pKa in water of not specified, then the selected medium is preferably an acid soluble in DMSO or another suitable medium therein.

[0151]合适的有单体芳族单羧酸和聚羧酸、相应的烷基-和芳基取代芳族单羧酸和聚羧酸,以及相应的含羟基芳族单羧酸和聚羧酸,例如邻苯二甲酸和对苯二甲酸、烷基-和/或芳基取代的邻苯二甲酸和对苯二甲酸、苯甲酸和烷基-和/或芳基取代的苯甲酸、具有其它官能团的芳族羧酸如水杨酸和乙酰水杨酸、烷基-和/或芳基取代的水杨酸或其异构体、多环芳族羧酸如萘羧酸的异构体,及其衍生物。 [0151] Suitable monomers are aromatic monocarboxylic acids and polycarboxylic acids, the corresponding alkyl - aryl group and a substituted aromatic monocarboxylic acids and polycarboxylic acids, and the corresponding hydroxyl group-containing aromatic monocarboxylic acids and polycarboxylates acids, such as phthalic acid and terephthalic acid, alkyl - and / or aryl-substituted phthalic acid and terephthalic acid, benzoic acid and alkyl - and / or aryl-substituted benzoic acid, having aromatic carboxylic acids with other functional groups such as salicylic acid and acetyl salicylic acid, alkyl - and / or aryl-substituted salicylic acid or an isomer thereof, a polycyclic aromatic carboxylic acids such as isomers of naphthalene carboxylic acid, and derivatives thereof.

[0152] 作为单体芳族羧酸(S),涂料组合物优选包含苯甲酸、叔丁基苯甲酸、3,4_二羟基苯甲酸、水杨酸和/或乙酰水杨酸,更优选苯甲酸。 [0152] As the aromatic carboxylic acid monomer (S), the coating composition preferably comprises benzoic acid, tert-butylbenzoic acid, 3,4_-dihydroxy benzoic acid, salicylic acid and / or acetylsalicylic acid, more preferably benzoic acid.

[0153] 涂料组合物的组分(A)、(B)、任选(C)、(D)和任选(S)以及其它组分的组合 [0153], optionally (C), (D) and optionally (S) in combination Component (A) of the coating composition (B) and other components

[0154] 如果涂料组合物为单组分组合物,则选择其游离异氰酸酯基团被封端剂封住的含多异氰酸酯基团化合物(B)。 [0154] If the coating composition is a one-component composition containing the select group of polyisocyanate compound (B) whose free isocyanate groups are capping agent is sealed. 例如,异氰酸酯基团可被取代的吡唑,更特别是被烷基取代的吡唑如3-甲基吡唑、3,5-二甲基吡唑、4-硝基-3,5-二甲基吡唑、4-溴-3,5-二甲基吡唑等封住。 For example, the isocyanate groups may be substituted pyrazoles, and more particularly a substituted alkyl group such as pyrazol-3-methylpyrazole, 3,5-dimethylpyrazole, 4-nitro-3,5- methyl pyrazole, 4-bromo-3,5-dimethyl pyrazole and the like is sealed. 特别优选组分(B)的异氰酸酯基团以非封闭形式使用。 Isocyanate groups are particularly preferred component (B) is used in a non-closed form.

[0155] 在2-组分(2K)涂料组合物的情况下,在施涂涂料以前不久,将包含含多羟基化合物(A)以及下文所述其它组分的涂料组分与包含含多异氰酸酯基团化合物(B)以及任选下文所述其它组分的另一涂料组分混合,其中混合以常规方式进行,并且通常包含化合物(A) 的涂料组分还包含催化剂(D)和一部分溶剂。 [0155] In the 2-component (2K) coating composition in the case, shortly before the application of the coating, comprising a polyhydroxy compound containing (A) and the following other components of the coating composition comprising a polyisocyanate containing compound group (B) below, and optionally other components of the coating component further mixing, wherein the mixing is carried out in a conventional manner, and generally contain the compound coating component (a) further comprises a catalyst (D) and a portion of the solvent .

[0156] 多羟基组分(A)可在合适的溶剂中。 [0156] polyhydroxyl component (A) may in a suitable solvent. 合适的溶剂(L)为容许多羟基组分的充分溶解且在涂料中对化合物以)、0)、(〇)、(5)和任选(〇呈化学惰性,而且在涂料的固化过程中不与(A)、任选(C)、(B)、(D)和(S)反应的那些。更特别地,这些溶剂(L)为非质子溶剂。这类非质子溶剂(L)的实例稍后在下文中给出。 Suitable solvent (L) to house a number of the hydroxyl component of the compound and is sufficiently soluble), 0), (square), (5), and optionally in the coating (square chemically inert, and during curing of the coating does not (a), optionally (C), those of (B), (D) and (S) of the reaction. more specifically, the solvent (L) is an aprotic solvent. such aprotic solvent (L), examples are given later below.

[0157] 本发明涂料组合物借助组分(A)和任选(C)中的羟基与组分(D)中的异氰酸酯基团反应而固化。 A hydroxyl group with the components (D) [0157] The coating composition of the present invention by means of components (A) and optionally (C) in the reaction of the isocyanate groups is cured.

[0158]优选选择多元醇(A)和任选(C)以及多异氰酸酯(B)的重量含量,使得含多羟基化合物(A)加任选(C)的羟基与组分(B)的异氰酸酯基团的摩尔当量比为1:0.9-1:1.5,优选1: 0 · 9-1:1 · 1,更优选1:0 · 95-1:1 · 05。 Weight content of [0158] preferably selected polyol (A) and optionally (C) and the polyisocyanate (B) so that the hydroxyl group of component (B) containing a polyhydroxy compound (A) plus optionally (C) an isocyanate group molar equivalent ratio is 1: 0.9 to 1: 1.5, preferably 1: 9-1 0.5: 1.1, more preferably from 1: 0 · 95-1: 1. 05.

[0159] 根据本发明使用的涂料组合物包含每种情况下基于组分(A)的基料含量为30-80 重量%,优选50-70重量%的含多羟基和含(全)氟烷基聚(甲基)丙烯酸酯组分(A),和每种情况下基于组分(B)的基料含量为20-70重量%,优选30-50重量%的含多异氰酸酯基团化合物(B),其中组分(A)加(B)的重量含量之和总是为100重量%。 [0159] According to the present invention comprises a coating composition in each case on the binder content of the component (A) 30 to 80 wt%, preferably 50-70% by weight and containing polyhydroxyl-containing (per) fluoroalkyl poly (meth) acrylate component (a), and in each case based on the content of the base material component (B) is 20 to 70 wt%, preferably 30-50% by weight of a polyisocyanate-containing compound groups ( B), wherein component (a) plus weight content of (B), and always 100% by weight.

[0160] 本发明涂料组合物进一步包含每种情况下基于组分(A)加(B)之和的基料含量优选0.001-5重量%,更优选0.01-2重量%的一种或多种催化剂(D)。 [0160] The present invention is a coating composition further comprises, based on component (A) was added 0.001 weight (B) of the sum of the content of the binder is preferably in each case%, more preferably from 0.01 to 2 wt% of one or more The catalyst (D).

[0161 ]本发明涂料组合物优选进一步优选包含0.2-15.0重量%,优选0.5-8.0重量%,更优选0.5-5.0重量%的至少一种芳族羧酸(S),其中重量百分数每种情况下基于组分(A)加(B)之和的基料含量。 [0161] The coating composition of the present invention preferably further comprises preferably 0.2-15.0 wt%, preferably 0.5-8.0% by weight, more preferably from 0.5 to 5.0% by weight of at least one aromatic carboxylic acid (S), wherein the weight percentages in each case based on the component (a) plus binder content (B) of the sum.

[0162]基料含量每种情况下意指在交联以前可溶于四氢呋喃(THF)中的涂料组合物部分。 [0162] binder content in each case mean a crosslinked coating composition can be dissolved before the portion (THF) is tetrahydrofuran. 它如下测定:称出小试样(P),将它溶于50-100倍量的THF中,通过过滤除去不溶性组分, 将THF蒸发掉,然后通过在130°C下干燥60分钟,在干燥器中冷却,然后重复称重而确定先前溶于THF中的组分的固体。 It is measured as follows: Weigh out a small sample (P), which was dissolved in 50 to 100 times the amount of THF, insoluble components were removed by filtration, the THF was evaporated, and then dried at 130 ° C 60 minutes, cool in a desiccator, and then weighed to determine repeat previously dissolved solid component of THF. 残余物相当于试样(P)的基料含量。 The residue was equivalent to the binder content in the sample (P) is.

[0163] 组分(A)加(B)的重量含量之和(单每种情况下仅考虑基料含量,而不是可能存在的任何溶剂含量)因此每种情况下产生100重量%,且组分(D)和(S)的量基于组分(A)加(B) 的这一重量含量之和。 [0163] Component (A) plus (B) the sum of the weight content (in each case to consider only the single binder content, rather than the content of any solvent that may be present) thus produced in each case 100% by weight, and the group amount of fraction (D) and (S), based on the weight of the content of the component (a) plus (B) is.

[0164] 本发明涂料组合物优选为非水性涂料并可包含溶剂或者可配制成无溶剂体系。 [0164] The coating composition of the present invention may preferably comprise a non-aqueous coating can be formulated as a solvent or solvent-free systems.

[0165] 尤其适于本发明涂料组合物中的溶剂(L)为在涂料组合物中对化合物(A)和(B)呈化学惰性,而且在涂料的固化过程中不与(A)和(B)反应的那些。 [0165] In particular, the coating compositions of the present invention is suitable for the solvent (L) for the compound (A) is chemically inert in the coating composition, and (B), but during curing of the coating does not (A) and ( B) those reactions. 这类溶剂(L)的实例为脂族和/或芳族经,例如甲苯、二甲苯、溶剂石脑油、So 1 vesso 100或Hydrosoi# (来自ARAL), 酮,例如丙酮、甲乙酮或甲基戊基酮,酯,例如乙酸乙酯、乙酸丁酯、乙酸戊酯或乙氧基丙酸乙酯,醚,或者上述溶剂的混合物。 Examples of such solvent (L) is an aliphatic and / or by aromatic, such as toluene, xylene, solvent naphtha, So 1 vesso 100 or Hydrosoi # (from the ARAL), ketones such as acetone, methyl ethyl ketone or methyl amyl ketone, esters such as ethyl acetate, butyl acetate, amyl acetate or ethyl ethoxypropionate, ether, or mixtures of the solvents. 非质子溶剂或溶剂混合物优选具有基于溶剂不大于1重量%,更优选不大于0.5重量%的水含量。 Aprotic solvent or solvent mixture having a water content of preferably not more than 1 based on the solvent weight percent, and more preferably not more than 0.5% by weight.

[0166] 溶剂(L)优选以一定量用于本发明涂料组合物中,使得涂料组合物的固体含量为至少50重量%,更优选至少60重量%。 [0166] solvent (L) is preferably in an amount used in the coating compositions of the present invention, so that the solids content of the coating composition is at least 50 wt%, more preferably at least 60 wt%.

[0167] 本发明涂料组合物可进一步包含每种情况下基于涂料组合物的基料含量为0-30 重量%,优选0-15重量%的一种或多种氨基树脂和/或一种或多种三(烷氧基羰基氨基)三嗪(E) 〇 [0167] Coating compositions of the present invention may further comprise in each case on the binder content of the coating composition is 0-30 wt%, preferably 0-15 wt% of one or more amino resins and / or one or various (alkoxy carbonylamino) triazine (E) square

[0168] 合适三(烷氧基羰基氨基)三嗪的实例在US-A-4 939 213、US-A-5 084541和EP-A-0 624 577中给出。 [0168] Suitable (alkoxy carbonyl amino) triazine examples are given in US-A-4 939 213, US-A-5 084541 and EP-A-0 624 577.

[0169] 合适氨基树脂(E)的实例为油漆工业中常用的所有氨基树脂,所得涂料的性能可借助氨基树脂的反应性控制。 [0169] Examples of suitable amino resin (E) for all amino resin commonly used in the paint industry, the performance of the resulting coating can be controlled by means of a reactive amino resin. 所述树脂为醛,更特别是甲醛,和例如脲、三聚氰胺、胍胺和苯并胍胺的缩合产物。 The resin is an aldehyde, more especially formaldehyde, and condensation products of urea, melamine, guanamine, and benzoguanamine. 氨基树脂包含醇基团,优选羟甲基,其通常用醇部分或者优选完全醚化。 Amino resins containing alcohol groups, preferably methylol groups, typically with an alcohol partially or preferably fully etherified. 更特别地使用用较低级醇醚化的氨基树脂。 More particularly using amino resin etherified with a lower level. 优选使用用甲醇和/或乙醇和/或丁醇醚化的氨基树脂,实例为可以以名称Cymel% Resimene*、MaprenalŪ:和LuwipalŪ 市售的产品。 Preferably using methanol and / or ethanol and / or butanol-etherified amino resins, examples being under the name Cymel% Resimene *, MaprenalŪ: LuwipalŪ and commercially available products.

[0170] 氨基树脂(e)是很好地确立的化合物并且详细地描述于例如美国专利申请us 2005/0182189 A1,第1页第[0014]段至第4页第[0028]段中。 [0170] an amino resin compound (e) are well established and are described in detail in U.S. Patent Application e.g. us 2005/0182189 A1, page 1, paragraph [0014] to page 4 [0028] section.

[0171] 本发明基料混合物或本发明涂料组合物可进一步包含有效量,即每种情况下基于涂料组合物的基料含量优选至多20重量%,更优选至多15重量%,更特别是至多10重量% 的量的至少一种常用且已知的涂料添加剂(F)。 [0171] invention BenQ feed mixture or coating compositions of the invention may further comprise an effective amount, i.e. in each case on the binder content of the coating composition is preferably at most 20 wt%, more preferably at most 15 wt%, more in particular at most an amount of 10% by weight of at least one known and commonly used coating additives (F).

[0172] 合适涂料添加剂(F)的实例如下: [0172] Examples of suitable coating additives (F) are as follows:

[0173]-特别是UV吸收剂; [0173] - in particular UV absorbers;

[0174]-特别是光稳定剂,例如HALS化合物、苯并三唑或草酰替苯胺; [0174] - especially light stabilizers, e.g. HALS compounds, benzotriazole, or oxanilide;

[0175] -自由基清除剂; [0175] - free radical scavengers;

[0176] -滑爽添加剂; [0176] - slip additives;

[0177] -聚合抑制剂; [0177] - a polymerization inhibitor;

[0178] -消泡剂; [0178] - antifoaming agents;

[0179] -不同于组分(A)和(C)的活性稀释剂,更特别是仅通过与其它组分和/或与水反应而变成反应性的活性稀释剂,例如或天冬氨酸酯; [0179] - other than the component (A) and (C) a reactive diluent, more particularly the other components only by a reactive diluent and / or react with water and become reactive, for example aspartic or esters;

[0180] -不同于组分(A)和(C)的润湿剂,例如硅氧烷、含氟化合物、羧酸单酯、磷酸酯、聚丙烯酸及其共聚物,或聚氨酯; [0180] - other than the component (A) and (C) wetting agents, such as silicone, fluorine compounds, carboxylic monoesters, phosphates, polyacrylic acids and their copolymers, or polyurethanes;

[0181] -附着力促进剂; [0181] - an adhesion promoter;

[0182]-流动控制剂; [0182] - flow control agents;

[0183] -成膜助剂,例如纤维素衍生物; [0183] - coalescent, such as cellulose derivatives;

[0184] -填料,例如基于二氧化硅、氧化铝或氧化锆的纳米颗粒;关于其它细节,参考RomppLexikon uLacke und Druckfarben",Georg Thieme Verlag,Stuttgart,1998,第250-252 页; [0184] - fillers, for example based on silica, alumina or zirconia nanoparticles; For further details, reference RomppLexikon uLacke und Druckfarben ", Georg Thieme Verlag, Stuttgart, 1998, pp. 250-252;

[0185] -不同于组分(A)和(C)的流变控制添加剂,例如由专利WO 94/22968、EP-A-0 276 501、EP-A-0 249 201或WO 97/12945中已知的添加剂;交联聚合物微粒,例如ΕΡ-Α-0 008 127中所公开类型的;无机页硅酸盐,例如铝镁硅酸页、钠镁页硅酸盐和蒙脱石类型的钠镁氟锂页硅酸盐;二氧化硅如▲ei'osilsŪ;或者具有离子和/或缔合基团的合成聚合物,例如聚(甲基)丙烯酰胺、聚(甲基)丙烯酸、聚乙烯吡咯烷酮、苯乙烯-马来酸酐共聚物或乙烯-马来酸酐共聚物及其衍生物,或者疏水改性的乙氧基化氨基甲酸酯,或聚丙烯酸酯; [0185] - other than the component (A) and (C), rheology control additives, for example, from patent WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or in WO 97/12945 known additives; crosslinked polymer particles, e.g. ΕΡ-Α-0 008 127 of the type disclosed; inorganic phyllosilicates such as aluminum magnesium silicate page, sodium and magnesium phyllosilicate of the smectite type sodium lithium magnesium fluoro phyllosilicate; silica such as ▲ ei'osilsŪ; or having ionic and / or associative groups synthetic polymers such as poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene - maleic anhydride copolymer or ethylene - maleic anhydride copolymer and its derivatives, or hydrophobically modified ethoxylated urethanes, or polyacrylates;

[0186] -阻燃剂。 [0186] - a flame retardant.

[0187] 特别优选包含如下组分的涂料组合物: [0187] Particularly preferred coating compositions comprising the following components:

[0188] 基于组分(A)的基料含量为50-70重量%的至少一种含多羟基聚丙烯酸酯(A)和/ 或至少一种含多羟基聚甲基丙烯酸酯(A), [0188] Based on the content of the base material component (A) is 50-70% by weight of at least one polyhydroxy-containing polyacrylate (A) and / or at least one polyhydroxy-containing polymethacrylate (A),

[0189] 基于组分(B)的基料含量为30-50重量%的含多异氰酸酯基团化合物(B), [0189] Based on the content of binder component (B) is 30-50% by weight of a polyisocyanate-containing group of the compound (B),

[0190] 基于涂料组合物的基料含量为0-10重量%的含羟基组分(C), [0190] Based on the binder content of the coating composition is 0-10 wt% of hydroxyl group-containing component (C),

[0191] 基于组分(A)加(B)之和的基料含量为0.5-8.0重量%的至少一种芳族羧酸(S), [0191], based on component (A) plus binder (B) content is 0.5-8.0 and the sum of the wt% of at least one aromatic carboxylic acid (S),

[0192] 基于涂料组合物的基料含量为0-15重量%的一种或多种氨基树脂和/或一种或多种三(烷氧基羰基氨基)三嗪(E), [0192] Based on the binder content of the coating composition is 0-15 wt% of one or more amino resins and / or one or more of tris (alkoxy carbonylamino) triazine (E),

[0193] 基于涂料组合物的基料含量为0-10重量%的至少一种常用且已知的涂料添加剂(F),和 [0193] Based on the binder content of the coating composition is 0-10% by weight of at least one known and commonly used coating additives (F), and

[0194] 基于组分(A)加(B)之和的基料含量为0.01-2重量%的至少一种催化剂(D),其中组分(A)加(B)的重量含量之和每种情况下为100重量%,且其中聚(甲基)丙烯酸酯组分(A) 每种情况下基于用于制备聚(甲基)丙烯酸酯组分(A)的所有化合物的量为0.1-10.0重量% 的以下物质的一种或多种含氟反应产物(U): Binder content [0194], based on component (A) plus (B) the sum of 0.01 to 2% by weight of at least one catalyst (D), wherein component (A) plus (B) the sum of the contents by weight of each the case of 100% by weight, and wherein the poly (meth) acrylate component (a) in each case based on the amount of all the compounds for the preparation of poly (meth) acrylate component (a) is 0.1 10.0% by weight of one or more of the following fluorine-containing reaction product of (U):

[0195] (i) -种或多种脂族和/或脂环族二异氰酸酯(PI ),其具有两个具有不同反应性的异氰酸酯基团, [0195] (i) - one or more aliphatic and / or cycloaliphatic diisocyanates (PI), having two isocyanate groups having different reactivity,

[0196] (ii)-种或多种(全)氟烷基醇组分(FA), [0196] (ii) - one or more (per) fluoroalkyl alcohol component (FA),

[0197] CF3-(CF2)n-CH2-CH2〇-H [0197] CF3- (CF2) n-CH2-CH2〇-H

[0198] 其中η为1-6,以及 [0198] wherein η is 1-6, and

[0199] (iii)-种或多种具有羟基(G1)且具有丙烯酸和/或甲基丙烯酸属不饱和双键(G2)的化合物(V),其优选选自(甲基)丙烯酸羟烷基酯、与内酯反应的(甲基)丙烯酸羟烷基酯及其混合物。 [0199] (iii) - having one or more hydroxyl group (G1) and an acrylic and / or methacrylic acid metal compound (V) an unsaturated double bond (G2), which is preferably selected from (meth) acrylate, hydroxyalkyl ester, and (meth) acrylic acid hydroxyalkyl esters and lactones reaction mixture.

[0200] 在本发明另一实施方案中,本发明基料混合物或本发明涂料组合物还可进一步包含颜料和/或填料,并可用于生产着色顶涂层或着色底涂层或者头二道混合底漆层,更特别是着色顶涂层。 [0200] In another embodiment of the present invention, the present invention BenQ feed mixture or coating compositions of the invention may further comprise a pigment and / or filler, it can be used for the production of colored pigmented basecoat or topcoat or two heads mixed primer layer, more particularly a pigmented top coat. 用于这些目的的颜料和/或填料是技术人员已知的。 For purposes of these pigments and / or fillers are known to the skilled person. 颜料通常以一定量使用,使得颜料:基料比每种情况下基于涂料组合物的基料含量为0.05:1-1.5:1。 Pigments are generally used in an amount such that the pigment: binder ratio in each case on the binder content of the coating composition is 0.05: 1 to 1.5: 1.

[0201] 由于由本发明涂料产生的本发明涂层甚至显著地附着于已固化的电涂层、头二道混合底涂层、底涂层或常规且已知的透明涂层上,除了它们在汽车OEM涂饰中的用途外,它们显著地适用于汽车修饰和/或安装在机动车中或安装在机动车上的部件的涂层,和/或用于多用型车辆的涂层。 [0201] Since the present invention the coating produced from the coating of the present invention, even significantly, attached to the cured electrocoat layer, the first two mixing undercoat, primer or clearcoat customary and known, In addition to their use outer automotive OEM finishing, which is significantly suitable for coating automotive finishing and / or in the mounting member mounted on the motor vehicle or motor vehicle, and / or coatings for multi-type vehicle.

[0202] 本发明涂料组合物可通过任何常规施涂技术施涂,例如喷涂、刀涂、涂布、倾注、浸浴、浸渍、滴流或辊涂。 [0202] Coating compositions of the present invention may be applied by any conventional application techniques, such as spraying, knife coating, coating, pouring, bathing, impregnating, trickling or rolling. 关于这类施涂,待涂覆的基体本身可以是静止的,其中施涂装置或设备是移动的。 Respect to such application, the substrate to be coated itself may be stationary, wherein the application means or device is mobile. 作为选择,待涂覆基体,更特别是盘卷可以是移动的,其中施涂装置相对于基体是静止的或者适当地移动。 Alternatively, the substrate to be coated, more particularly a coil may be mobile, in which the applicator means is stationary relative to the base or suitably moved.

[0203] 优选单独或者与热喷涂如热空气喷涂联合使用喷涂技术,例如压缩空气喷涂、无空气喷涂、高速旋转、静电喷涂(ESTA)。 [0203] Preferred thermal spraying alone or in combination, such as spraying of hot air spray techniques, such as compressed air spraying, airless spray, high-speed rotation, electrostatic spray (ESTA).

[0204]施涂的本发明涂料的固化可在特定静止时间以后进行。 [0204] curing the applied coating of the present invention may be carried out after a certain rest period. 静止时间例如用于涂膜的均涂和除气或者挥发性组分如溶剂的蒸发。 And a rest time are coated, for example, gas or other volatile components such as a coating film for evaporating the solvent. 静止时间可通过在升高的温度下施涂和/或通过降低的大气湿度辅助和/或缩短,条件是这不会使涂膜经受任何损害或变化的情形,例如过早的完全交联。 By applying a dead time and / or by a reduced atmospheric humidity of the auxiliary and / or shortened at elevated temperatures, provided that it does not damage the coating or subjected to any change in circumstances, such as premature complete crosslinking.

[0205] 涂料的热固化在技术方面不存在特殊性,而是根据常规且已知的技术,例如在强制通风烘箱中加热或者用IR灯照射而进行。 [0205] absence of thermosetting coatings technology particularity, but in accordance with conventional and known techniques, such as heating in a forced air oven or irradiation with IR lamps for. 该热固化也可分阶段进行。 The thermal curing may be carried out in stages. 另一优选的固化技术是用近红外线(NIR辐射)固化。 Another preferred curing technique is cured by near infrared (NIR radiation).

[0206] 热固化有利地在20-200 °C的温度下进行1分钟至多10小时的时间,在低温下可使用甚至更长的固化时间。 [0206] Advantageously, thermal curing for 1 minute up to 10 hours at a temperature of 20-200 ° C, can be used at low temperatures or longer curing times. 对于汽车修饰和塑料部件的上漆,以及多用型车辆的上漆,通常使用优选为20-80 °C,更特别是20-60 °C的较低温度。 For painting, painting and multi-type vehicle and automotive finishing plastic parts, usually preferably 20-80 ° C, more in particular a relatively low temperature of 20-60 ° C.

[0207] 本发明涂料组合物显著地适用作运输工具(更特别是机动车辆,例如自行车、摩托车、公共汽车、卡车或汽车)的车体或其部件的装饰性、保护性和/或效果涂层和涂饰层;尤其是用于涂覆安装在汽车车体中或安装在汽车车体上的塑料部件,例如用于生产车顶、舱口盖、引擎罩、后挡板、缓冲器、阻流片、基石、保护条、边饰片等,以及用于涂饰多用型车辆, 例如卡车、链传动工程车辆如吊车、推土机和混凝土混合机、公共汽车、铁路车辆、船只、飞机,以及农用设备如拖拉机和联合收割机及其部件,以及家具、窗户和门;塑料模制品,更特另IJ是CD和窗户;小工业部件、线圈、容器和包装;家用电器;膜;光学、电子和机械组件;以及空心玻璃制品和日用品的装饰性、保护性和/或效果涂层和涂饰。 Decorative [0207] Coating compositions of the present invention is remarkably suitable as the vehicle (more particularly a motor vehicle, such as a bicycle, a motorcycle, a bus, a truck or a car) or a vehicle body member, protective and / or effect and finishing the coating layer; especially for coating an automobile body or mounted in a plastic member mounted on an automobile body, for example for the production of a roof, hatches, hoods, tailgates, buffers, spoilers, the cornerstone of protection strips, trim pieces, as well as multi-use vehicle for finishing, such as trucks, chain drive construction vehicles such as cranes, bulldozers and concrete mixers, buses, rail vehicles, ships, aircraft, and agricultural equipment such as tractors and combine harvesters and their components, and furniture, windows and doors; plastic article more particularly windows and the other is a CD IJ; small industrial parts, coils, containers and packaging; household appliances; film; optical, electronic and mechanical assembly; and a decorative hollow glass articles and commodities, protective and / or effect coatings and finishes.

[0208] 因此,本发明涂料组合物可施涂于例如未涂覆或预涂覆的基体上,且本发明涂料为着色或未染色的。 [0208] Thus, the coating compositions of the invention may be applied to a substrate, for example, pre-coated or uncoated, and the coating of the present invention is colored or dyed. 本发明涂料组合物优选用作透明涂料。 The coating composition of the present invention is preferably used as a clear coating. 由于与良好机械和光化学抗性联合的疏水性能,它们还用于非常多种未涂覆或预涂覆基体中任一种的永久防水和防污表面涂层。 Due to good mechanical resistance combined photochemical and hydrophobic properties, it is more They are also used uncoated or precoated substrate according to any one permanent waterproof and stain the surface coating.

[0209]特别优选,本发明涂料组合物用于涂覆方法中,其中将具有本发明涂料组合物的膜施涂于任选预涂覆基体上。 [0209] Particularly preferred, the coating compositions of the invention for coating methods, wherein a film coating composition is applied to the present invention is optionally pre-coated substrate. 该任选预涂覆基体更特别是飞机和风能体系或其一个或多个部件,更特别是风能体系动叶片。 The optionally pre-coated substrate and more particularly aircraft and wind energy system or one or more components, more particularly wind energy system rotor blade.

[0210]此外,本发明涂料组合物还用于其中首先将任选预涂覆基体用着色底涂膜,随后用包含本发明涂料组合物的膜涂覆的方法中。 [0210] In addition, the coating compositions of the invention, optionally also be used in which first substrate precoated with a pigmented base coating film, followed by a film coating method comprising coating the composition of the invention. 因此,本发明还提供由至少一个着色底涂膜和置于其上的至少一个透明涂膜构成的多涂层效果和/或彩色油漆体系,这些体系的特征是透明涂膜由本发明涂料组合物产生。 Accordingly, the present invention also provides a multi-effect coating and / or color paint system on which the at least one transparent coating film composed of at least one colored base coating film and disposed, features of these systems are clear coating film from the coating composition of the invention produce.

[0211] 可使用水稀释性底涂料以及基于有机溶剂的底涂料。 [0211] allows the water reducible primer and a primer based on an organic solvent. 合适的底涂料描述于例如ΕΡ-Α-0 692 007和其中在第3栏第50行及随后列举的文件中。 Suitable coatings are described, for example, the bottom ΕΡ-Α-0 and wherein column 3, line 50 and subsequent documents cited in 692,007. 优选,施涂的底涂料首先干燥,意指至少一些有机溶剂和/或水在蒸发阶段中从底涂膜中除去。 Preferably, the primer is first applied and dried, means that some organic solvent and / or water is removed from the base coating film in the evaporation stage at least. 干燥优选在从室温至80 °C的温度下进行。 Drying is preferably carried out at from room temperature to the temperature to 80 ° C. 在进行干燥以后,施涂本发明涂料组合物。 After carrying out drying, the coating composition is applied to the present invention. 然后将双涂层油漆体系焙烧, 优选在汽车OEM涂饰范围内使用的条件下,在20-200 °C的温度下焙烧1分钟至10小时的时间,但在用于汽车修饰的温度,通常20-80°C,更特别是20-60°C下,也可使用较长的固化时间。 Then dual paint system firing conditions are preferably used in automotive OEM finishing range, at a temperature of 20-200 ° C of from 1 to 10 minutes baking time, but for the automotive finishing temperature, usually 20 -80 ° C, more particularly at 20-60 ° C, may also be used a longer cure time.

[0212] 在本发明另一优选实施方案中,本发明涂料组合物作为透明涂料用于涂覆塑料基体,更特别是安装在内部或外部的塑料部件。 [0212] In another preferred embodiment of the invention, the coating compositions of the present invention as a clear coating composition for coating a plastic substrate, and more particularly is mounted inside or outside of the plastic member. 这些塑料部件优选也在多段涂覆方法中涂覆, 其中将任选预涂覆或者已预处理以便随后涂层的更好附着力(例如通过基体的火焰处理、 电晕处理或等离子体处理)的基体首先用着色底涂膜涂覆,其后用包含本发明涂料组合物的层涂覆。 These plastic parts are preferably coated multistage coating process, wherein, optionally pre-coated or pre-treated in order to subsequently better adhesion of the coating (e.g. substrate by flame treatment, corona treatment or plasma treatment) the substrate is first coated with a colored base coating film, followed by applying a coating composition layer comprising the present invention.

[0213]塑料部件通常由ASA、聚碳酸酯、ASA与聚碳酸酯的混合物、聚丙烯、聚甲基丙烯酸甲酯或抗冲改性聚甲基丙烯酸甲酯,更特别是ASA与聚碳酸酯的混合物组成,其优选以〉 40%,更特别是>50 %的聚碳酸酯含量使用。 [0213] Plastic parts are typically a mixture of ASA, polycarbonate, ASA and polycarbonate, polypropylene, polymethyl methacrylate or impact-modified polymethyl methacrylate, polycarbonates and more particularly ASA the mixtures, it is preferably> 40%, more particularly> 50% of the content of the polycarbonate used.

[0214] ASA通常意指抗冲改性苯乙烯-丙烯腈聚合物,其中乙烯基芳族化合物,更特别是苯乙烯和乙烯基氰化物,更特别是丙烯腈在聚丙烯酸烷基酯橡胶上的接枝共聚物存在于特别是苯乙烯和丙烯腈的共聚物基体中。 [0214] ASA generally means an impact modified styrene - acrylonitrile polymer, wherein the vinyl aromatic compounds, more particularly styrene and vinyl cyanides, and more particularly the polyacrylic acid, acrylonitrile-alkyl acrylate rubbers a graft copolymer present in particular styrene and acrylonitrile matrix.

[0215] 非常特别优选,本发明涂料组合物用于飞机和风能体系或其部件,更特别是风能动叶片的极苛求的涂覆方法领域中,尤其是作为在风能体系的动叶片上的顶涂层(即最外涂膜)。 [0215] Very particularly preferably, the coating compositions of the invention for an aircraft and a wind power system or components thereof, and more particularly the field of wind blade electrode active demanding coating methods, in particular as wind energy system rotor blade top coating (i.e., the outermost coating film).

[0216] 因此,本发明还提供本发明涂料组合物在飞机和风能体系或其部件的防冰涂层, 更特别是风能体系的动叶片的防冰涂层中的用途。 [0216] Accordingly, the present invention also provides a coating composition of the invention in aircraft anti-icing coating and the wind energy system or parts thereof, more particularly the use of an anti-icing coating blade of a wind energy system.

[0217] 此外,本发明还提供本发明涂料组合物在涂覆飞机或风能体系的动叶片以减少由其移动产生的噪音中的用途。 [0217] Further, the present invention provides a coating blade in a coating composition of the invention an aircraft or wind energy systems to reduce the noise by use of the mobile generated.

[0218] 因此,本发明还提供具有油漆体系,任选多涂层油漆体系的风能体系或者风能体系的一个或多个部件,这些风能体系或其部件的特性特征是最顶层涂膜由本发明涂料组合物产生。 [0218] Accordingly, the present invention also provide a paint system, optionally one or more components of the wind energy system or wind energy system of multi-coat paint systems, wind characteristic features of these systems or parts thereof is the topcoat coating by the present invention generating composition.

[0219] 实施例卜3 [0219] Example 3 Bu

[0220] 本发明含氟单体1的制备 Preparation [0220] The fluorine-containing monomer of the present invention 1

[0221] 将83g异佛尔酮二异氰酸酯与O.lg二月桂酸二丁锡一起引入装配有搅拌器、回流冷凝器、温度计和滴液漏斗的1L三颈烧瓶中。 [0221] The 83g of isophorone diisocyanate and dibutyl tin dilaurate O.lg introduced together fitted with a stirrer, a reflux condenser, a thermometer and a dropping funnel was 1L three-necked flask. 将三颈烧瓶加热至55°C,然后借助滴液漏斗缓慢地加入40.7g的基于2-(全氟己基)乙醇的商业氟代醇(来自Daikin Industries Ltd, Osaka,日本的商品Daikin A-1620)。 The three-necked flask was heated to 55 ° C, then slowly via a dropping funnel was added 40.7g based on 2- (perfluorohexyl) ethanol commercial fluoroalcohol (from Daikin Industries Ltd, Osaka, Japan that Daikin A-1620 ). 保持6.85 %的NC0含量,其通过下文所述用二丁胺滴定而测定。 Holding NC0 content of 6.85%, which is determined by the dibutylamine titration below. 其后,同样在55°C下,逐滴加入14.5g甲基丙烯酸羟基乙酯。 Thereafter, likewise at 55 ° C, was added dropwise 14.5g hydroxyethyl methacrylate. 另外,加入5.2g乙酸丁酯。 Further, 5.2g of butyl acetate was added. 当达到0.01 %以下的NC0含量时,将体系冷却。 When reaching NC0 content of 0.01% or less of the cooling system. 所得清澈无色溶液具有93.3重量%的含氟单体含量。 The resulting clear, colorless solution having a fluorine-containing monomer content of 93.3% by weight.

[0222] 本发明含氟单体2的制备 [0222] Preparation of fluorine-containing monomers of the invention 2

[0223] 在120°C下随着加入50ppm二月桂酸二丁锡而将1摩尔甲基丙烯酸羟基乙酯与2摩尔ε-己内酯一起搅拌2小时。 [0223] at 120 ° C for addition of 50ppm as dibutyl tin dilaurate and 1 mole of hydroxyethyl methacrylate and 2 moles of ε- caprolactone was stirred for 2 h. 然后将反应产物在55°C下逐滴加入1摩尔氟代醇与1摩尔IPDI 的反应产物中。 The reaction product was then at 55 ° C for by dropwise addition of the reaction product of 1 mole of fluoroalcohol with one mole of IPDI.

[0224] 本发明含氟单体3的制备 [0224] The fluorine-containing monomer of the present invention is prepared 3

[0225] 在120°C下随着加入50ppm二月桂酸二丁锡而将1摩尔甲基丙烯酸羟基乙酯与4摩尔ε-己内酯一起搅拌2小时。 [0225] at 120 ° C for addition of 50ppm as dibutyl tin dilaurate and 1 mole of hydroxyethyl methacrylate and 4 moles of ε- caprolactone was stirred for 2 h. 然后在55°C下将反应产物逐滴加入1摩尔氟代醇与1摩尔IPDI 的反应产物中。 Then at 55 ° C for the reaction product was added dropwise to the reaction product of 1 mole of fluoroalcohol with one mole of IPDI.

[0226] 含氟单体NC0含量的测定: [0226] Determination of content of the fluorine-containing monomer NC0:

[0227] 未反应NC0的量通过如下用0.5N盐酸滴定使用二丁胺相对于溴酚蓝测定: [0227] The use amount of unreacted dibutylamine NC0 relative to bromophenol blue was measured by titration with 0.5N hydrochloric acid:

[0228] 在实际滴定以前,进行关于空白值的测定。 [0228] In practice before the titration was measured on blank value. 对于空白值测定,使用溴酚蓝作为指示剂,用0.5摩尔/升含水盐酸以蓝色至黄色(pH=4.6(蓝色)-pH=3.0(黄色))滴定以指定方式加入的一定量的二丁胺。 For the assay blank value, using bromophenol blue as an indicator, a 0.5 mol / liter aqueous hydrochloric acid blue to yellow (pH = 4.6 (blue) -pH = 3.0 (yellow)) targeting titrated amount of added dibutylamine. 该消耗量视为"空白试验中的消耗量"。 The consumption as a "blank test of consumption."

[0229] 对于主滴定,试样通过与二丁胺反应而完全消耗。 [0229] For the main titration, the sample is completely consumed by reaction with dibutylamine. 在该反应中,NC双键打开,并将二丁胺加在其上。 In this reaction, NC opened double bond, and dibutylamine applied thereon. 这产生脲衍生物。 This produces urea derivatives. 使用溴酚蓝作为指示剂,将未反应的二丁胺用0.5摩尔/ 升含水盐酸从蓝色至黄色反滴定。 Using bromophenol blue as an indicator, the unreacted dibutylamine with 0.5 mol / liter aqueous hydrochloric acid was back titrated from blue to yellow. 颜色变化必须持续约30秒。 Color change must continue for about 30 seconds. 该消耗量视为"主试验中的消耗量"。 The consumption as a "real test of consumption."

[0230]用不同的含氟单体制备本发明聚合物溶液 [0230] The polymer solution prepared by the present invention is a fluorine-containing monomer different

[0231] 在借助油热不锈钢夹套调整温度且装配有锚式搅拌器、回流冷凝器和稳定剂的4L 不锈钢压力反应器中装入911. lg乙酸丁酯。 [0231] 911. lg of butyl acetate was charged in a stainless steel jacketed hot oil by adjusting the temperature and fitted with an anchor stirrer, a reflux condenser and a stabilizer 4L stainless steel pressure reactor. 将设备用氮气冲洗,然后在2.5巴的过压下将反应器加热至160°C。 The apparatus was flushed with nitrogen, and then the reactor was heated to 160 ° C at 2.5 bar overpressure. 然后使用隔膜栗经4小时计量加入1200g各单体混合物。 Li separator then metered in over 4 hours each monomer mixture was 1200g. 并行地,也使用隔膜栗以10分钟的预备运行时间以及4.75小时的总进料时间,计量加入基单体量7.0重量%的量的50 %浓度二叔丁基过氧化物(DTBP)溶液。 In parallel, also using the separator Li to 10 minutes and a run time of 4.75 hours preliminary total feed time, added to the base amount of monomers metered in an amount of 7.0% by weight concentration of 50% butyl peroxide (DTBP) solution. 在160 °C下另外60分钟以后,将批料冷却并将反应器停下。 After a further 60 minutes, the batch was cooled and the reactor was stopped at 160 ° C.

[0232] 将通过以上方法得到的聚合物溶液用乙酸丁酯稀释至约60%的固体含量,并使用100μπι四通棒式涂布器刮涂在玻璃板上。 [0232] The polymer obtained by the above method was diluted with butyl acetate to a solids content of about 60%, and use the four-way 100μπι knife bar coater on a glass plate. 在130°C下干燥30分钟以后测量这些膜上的接触角。 After drying for 30 minutes measuring the contact angle of these films at 130 ° C.

[0233] 为测定涂层的疏水性,在对固化涂层的研究下,将一滴水应用于表面上。 [0233] To determine the hydrophobicity of the coating, in the study of the cured coating, it is applied on the surface of the drop of water. 然后通过使用来自KrUs s的Mobi 1 edrop移动式接触角测量体系测定水滴与涂层表面之间的接触点处的切线而在显微镜下进行接触角(H)的测量。 The contact angle is then measured (H) is measured under a microscope by a tangent at the contact point between the water droplets and the coating surface using Mobi 1 edrop movable contact angle measurement system from the KrUs s. 类似地测定相对于二碘代甲烷的接触角。 Similarly, the contact angle measured with respect to diiodomethane. 对于该测量,将测量头放在试样上。 For this measurement, the measuring head on the specimen. 计量控制杆降低计量导管并计量加入液滴。 Metering lever lowered and the metering conduit metered droplets. 棱镜配置借助一体化相机将液体的轮廓图像引入连接的笔记本PC中。 With an integrated camera prism configuration profile image liquid is introduced into the notebook PC connection. 在那里借助KR0 SW 2 3软件(DSA2)分析液滴视频并测定接触角。 Analysis by droplets where video KR0 SW 2 3 Software (DSA2) and the contact angle was measured.

[0234] 表1:实施例1-3的含全氟烷基烷基聚(甲基)丙烯酸酯的组成,以重量%表示,和关键数据 [0234] Table 1: Examples 1-3 perfluoroalkyl group containing an alkyl poly (meth) acrylate composition, in% by weight, and key data

Figure CN104736583BD00201

[0236] ~表1的要点 Points [0236] Table 1 -

Figure CN104736583BD00211

[0237] Mw =重均分子量,其通过凝胶渗透色谱法(GPC)相对于聚苯乙稀标准测量[0238] Mn =数均分子量,其通过凝胶渗透色谱法(GPC)相对于聚苯乙稀标准测量[0239] SC AP=(聚合反应结束以后的固体含量) [0237] Mw = weight average molecular weight, measured relative [0238] determined by gel permeation chromatography (GPC) for standard polystyrene Mn = number average molecular weight, relative to polystyrene by gel permeation chromatography (GPC) ethylene standard measurement [0239] SC AP = (polymeric solid content after the completion of the reaction)

[0240] 将lg测量物质与lg乙酸丁酯在载体(金属盖)上混合并在强制通风烘箱中在130°C 下干燥60分钟。 [0240] The measurement substance lg lg of butyl acetate in a carrier (metal cover) on the mixed and dried at 130 ° C in a forced air oven for 60 minutes.

[0241] AN=测量的酸值,mg KOH/g [0241] AN = acid value measurement, mg KOH / g

[0242] 粘度:在23°C下使用型号CAP 2000+的布氏旋转式粘度计以心轴3,RPM1000或剪切速率13 333s-1测量 [0242] Viscosity: Brookfield CAP 2000+ type rotary viscosity meter at 23 ° C for 3, RPM1000 or 13 333s-1 shear rate measured in the mandrel

[0243] 接触角H20:测量的相对于水的接触角 [0243] The contact angle H20: measured with respect to the contact angle with water

[0244] 接触角CH2I2:测量的相对于二碘代甲烷的接触角 [0244] The contact angle CH2I2: measured with respect to diiodomethane contact angle

[0245] 发现研究的所有含氟单体以相同的方式并入聚合物中,以及具有在表面张力方面相当的效果。 [0245] Study found that all the fluorine-containing monomer is incorporated in the same polymer, and a considerable effect on surface tension. 由于含氟单体1可以以最少的化学耗力和复杂性制备,其它实验使用所述单体1进行。 Since a fluorine-containing monomer may be, other experiments using the monomer 1 with a minimum of complexity and labor-intensive chemical preparation.

[0246] 实施例4-20 [0246] Example 4-20

[0247] 为测定在Tg、0H值和含氟单体含量方面的最佳配制,使用以下基础配方以借助高吞吐量体系进行聚合。 [0247] To determine the optimal formulation in terms of Tg, 0H value and the fluorine-containing monomer content, by using the following base formulation at a high throughput system for the polymerization. 用于所有合成的批料尺寸为约200ml。 All batches used for the synthesis of a size of about 200ml.

[0248] 所用可变组分为以下单体: [0248] The following monomers are divided into groups with a variable:

[0249] 甲基丙烯酸羟基乙酯(HEMA) [0249] Hydroxyethyl methacrylate (HEMA)

[0250] 丙烯酸正丁酯(nBA) [0250] n-butyl acrylate (nBA)

[0251] 苯乙烯(Sty) [0251] Styrene (Sty)

[0252] 甲基丙烯酸甲酯(mma) [0252] Methyl methacrylate (MMA)

[0253] 含氟单体(1) [0253] The fluorine-containing monomer (1)

[0254] 描述以下一般聚合条件:聚合温度110°C,进料时间3小时单体混合物,3.5小时引发剂溶液,1小时后聚合,引发剂基于单体为7%,在甲基异丁基酮中的引发剂溶液(分别25% 和浓度17.4%)。 [0254] General polymerization conditions described in the following: the polymerization temperature of 110 ° C, the feed time of 3 hours a monomer mixture, an initiator solution of 3.5 hours, After 1 hour the polymerization initiator based on the monomer is 7% in methyl isobutyl initiator solution of ketone (respectively 25% and a concentration of 17.4%).

Figure CN104736583BD00221

[0256]表3:实施例4-20的含全氟烷基烷基聚(甲基)丙烯酸酯的特征 [0256] Table 3: Characteristics Example embodiments containing 4-20 perfluoroalkyl alkyl poly (meth) acrylate

Figure CN104736583BD00231

[0258] SC=固体含量:将lg测量物质与lg乙酸丁酯在载体(金属盖)上混合并在强制通风烘箱中在130°C下干燥60分钟。 [0258] SC = Solid content: The measurement substance lg lg of butyl acetate in a carrier (metal cover) on and mixed in a forced air oven dried at 130 ° C for 60 minutes.

[0259] Mw =重均分子量,其通过凝胶渗透色谱法(GPC)相对于聚苯乙稀标准测量[0260] Mn =数均分子量,其通过凝胶渗透色谱法(GPC)相对于聚苯乙稀标准测量 [0259] Mw = weight average molecular weight, measured relative [0260] determined by gel permeation chromatography (GPC) for standard polystyrene Mn = number average molecular weight, relative to polystyrene by gel permeation chromatography (GPC) Yixi standard measurement

[0261] 实施例4-20的涂料的制备 Example 4-20 Preparation of Coating [0261] Embodiment

[0262] 随后由如上得到的聚丙烯酸酯溶液配制透明涂料。 [0262] obtained as described above followed by a polyacrylate solution prepared clear coating. 这通过首先将1.762份苯甲酸随着搅拌溶于表4所述量的丙烯酸酯树脂溶液中而进行。 This first stirred with 1.762 parts of benzoic acid were dissolved in Table 4 the amount of acrylate resin solution is carried out by. 随后随着搅拌将表4所述量的甲基异丁基酮、0.132份的10%浓度二月桂酸二丁锡的乙酸丁酯溶液、0.881份的由UV和HALS光稳定剂(1:1)组成的商业光稳定剂混合物和0.0655份的基于含氟丙烯酸酯的流动控制剂混合。 Then with stirring in Table 4 the amount of methyl isobutyl ketone, 0.132 parts of a 10% strength dibutyltin dilaurate in butyl acetate, 0.881 parts of a UV light stabilizer and HALS (1: 1 ) commercial light stabilizer mixture consisting of 0.0655 parts of a mixing and flow control agents based on fluorine-containing acrylate. 在加入一定量(表4所述量)的基于包含异氰尿酸酯基团的三聚六亚甲基二异氰酸酯(HDI),具有基于无溶剂三聚六亚甲基二异氰酸酯23.4%的异氰酸酯含量的低粘度多异氰酸酯固化剂(来自BAYER的Ι)68ΙΙΜΜ!ΐ1Ι^Ν3600)使得0H/NC0化学计量为1:1.1以后,将膜刮涂在玻璃板上(约100μπι的湿膜厚度)。 In certain amount (Table amount of 4) based on trimerized hexamethylene diisocyanate (HDI) containing isocyanurate groups, having an isocyanate 23.4% based on the solvent-free trimerized hexamethylene diisocyanate content of a low viscosity polyisocyanate curing agent (from BAYER the Ι) 68ΙΙΜΜ ΐ1Ι ^ Ν3600) such 0H / NC0 stoichiometry of 1:! after 1.1, the film is drawn down on a glass plate (wet film thickness of about 100μπι). 在保持蒸发约30分钟以后,然后将膜在60 °C下干燥30 分钟。 Maintained for about 30 minutes was evaporated, and then the film was dried at 60 ° C 30 min. 在130°C下干燥30分钟以后测量这些膜上的接触角。 After drying for 30 minutes measuring the contact angle of these films at 130 ° C.

[0263] 表4:基于实施例4-20的含全氟烷基烷基聚(甲基)丙烯酸酯的涂料的组成,以重量份表示 [0263] Table 4: Examples 4-20 Based embodiment containing acrylate coating composition perfluoroalkyl alkyl poly (meth), expressed in parts by weight

Figure CN104736583BD00241

[0265] 苯甲酸溶液=在MIBK中25% [0265] The benzoic acid solution in MIBK = 25%

[0266] *1 =来自BASF SE的商业光稳定剂混合物 [0266] * 1 = commercial light stabilizer mixture from BASF SE

[0267] *2 =来自Byk Chemie GmbH的基于聚醚改性的甲基烷基聚硅氧烷的商业流动控制剂 [0267] * 2 = from Byk Chemie GmbH based polyether-modified methyl alkyl polysiloxane commercial flow control agent

[0268] 表5:关于实施例4-20的涂层的水接触角测定结果 [0268] Table 5: Measurement results for Examples 4-20 the coating embodiment of the water contact angle

Figure CN104736583BD00242

[0271 ] 此外,确定实施例4-20的涂层的Fischer Scope硬度。 [0271] In addition, hardness of the coating is determined according to Fischer Scope of the embodiment 4-20. 试验根据Vickers Hardness HV方法,使用来自Helmut Fischer GmbH的HP100VP X-Prog仪器进行(关于硬度试验DIN 50133的渗透方法,硬度测量方法)。 The Vickers Hardness HV test method using HP100VP X-Prog instrument from Helmut Fischer GmbH performed (permeation test method on hardness DIN 50133, the hardness measurement method). 在该试验中,以指定力提高将棱锥型金刚石压入试样中。 In this test, a specified force to increase a pyramid diamond indenter into the specimen. 所用参数如下: The parameters used are as follows:

[0272] 试验力提高lmN/s [0272] Test force increase lmN / s

[0273] 15秒的等待(蠕变) [0273] Wait 15 seconds (creep)

[0274] 试验力降低lmN/s [0274] Test force reduction lmN / s

[0275] 在OmN下15秒的等待 [0275] In the waiting OmN 15 seconds

[0276]力提高时间:力提高至20mN 20秒。 [0276] Force time increase: force increased to 20mN 20 seconds. 测量整个时间期间的位移。 Measuring the displacement of the entire period of time. 包括硬度在内的参数可由力/位移曲线计算: Including hardness, including parameters may force / displacement curve calculation:

[0277] HU在最大试验力下的万用硬度,N/mm2。 [0277] HU universal hardness at the maximum test force, N / mm2. 不考虑进行的形状校准。 Without considering the shape of the calibration performed. 为考虑形状校准, 打开控制场校准。 To take into account the shape of the calibration, field calibration opening control.

[0278] Y弹性渗透模数,GPa(MPa)。 [0278] Y permeable elastic modulus, GPa (MPa). 在所有情况下考虑形状校准。 Considering the shape of the calibration in all cases.

[0279] We/Wtot弹性变形成分(hHU),%。 [0279] We / Wtot elastically deformable component (hHU),%. 弹性变形能(We)与总变形能的比。 The elastic deformation energy (We) and the ratio of the total deformation energy.

[0280] Wtot渗透能的塑性和弹性成分。 [0280] Wtot permeable plastic and elastic components of energy. 在所有情况下考虑形状校准。 Considering the shape of the calibration in all cases.

[0281] Cr 1负荷下的蠕变,%。 [0281] Creep,% under a load of 1 Cr. 材料在最大试验力下的行为。 Behavior of the material at the maximum test force. 在所有情况下考虑形状校准。 Considering the shape of the calibration in all cases.

[0282] Cr 2负荷下的蠕变,%。 [0282] Creep,% under a load of Cr. 材料在力减小以后的恒定(预定)最小试验力下的行为。 In the future behavior of the material is reduced the force constant (predetermined) minimum test force. 在所有情况下考虑形状校准。 Considering the shape of the calibration in all cases.

[0283] hmax压针在最大试验力下的渗透深度,μπι(ηπι)。 [0283] hmax penetration depth of the indenter at the maximum test force, μπι (ηπι). 不考虑进行的形状校准。 Without considering the shape of the calibration performed. 为考虑形状校准,打开控制场校准。 To take into account the shape of the calibration, field calibration opening control.

[0284] corr.当打开控制场时,将HU、HU(h)、HU(F)、HU Cr、h(F)和hmax参数对压针的真实形状校准。 [0284] corr. When the control field is opened, a HU, HU (h), HU (F), HU Cr, h (F) and the calibration of the actual shape parameters hmax indenter. 每种情况下考虑进行的形状校准。 Considering the shape of the calibration performed in each case.

[0285] 表6:实施例4-20的涂料的Fischer Scope表面硬度测量结果 [0285] Table 6: Fischer Scope Hardness measurements of surface coatings according to the embodiment 4-20

Figure CN104736583BD00251
Figure CN104736583BD00261

[0288] 实施例21-23 [0288] Examples 21-23

[0289] 测试通过统计试验计划得到的结果在配方选择中的规模化能力。 [0289] Test results obtained by statistical test planning large-scale capacity in the recipe selection. 为此(对应于表7),以中试规模制备以下聚丙烯酸酯。 For this purpose (corresponding to Table 7), the following pilot scale preparation of polyacrylates. 此处用以下条件测试配方: Here tested formula with the following conditions:

[0290] -低含氟单体含量和低总Tg(实施例21); [0290] - low fluorine content and a low total monomer Tg (Example 21);

[0291] -高氟含量以及低Tg(实施例22);和 [0291] - a high fluorine content and a low Tg (Example 22); and

[0292] -高氟含量以及高Tg和较高0H值(实施例23)。 [0292] - a high fluorine content and a high Tg and a high value 0H (Example 23).

[0293] 所有树脂是透明且不显示凝胶颗粒。 [0293] All the resin is transparent and does not show gel particles. 然后将实施例23的配方配制成透明涂料以测试它们的附着力。 Formulation Example 23 was then formulated into a clear coating to test their adhesion.

[0294] 实施例21-23的聚丙烯酸酯树脂 [0294] Example embodiments 21-23 polyacrylate resin

[0295] 将借助油热不锈钢夹套调节温度且装配有锚式搅拌器、回流冷凝器和温度计的4L 不锈钢反应器中装入如表7所列量的甲基异丁基酮(MIBK)。 [0295] A stainless steel jacketed by adjusting the temperature of the hot oil and fitted with an anchor stirrer, a reflux condenser, a thermometer and 4L stainless steel reactor was charged with the amount listed in Table 7 as methyl isobutyl ketone (MIBK). 在氮气覆盖下,将反应器加热至110°C。 Under a nitrogen blanket, the reactor was heated to 110 ° C. 然后使用隔膜栗经4小时计量加入1200g各单体混合物。 Li separator then metered in over 4 hours each monomer mixture was 1200g. 并行地,以10分钟的预备运行时间和4.75小时的总进料时间,再次使用隔膜栗计量加入50 %浓度的过-2-乙基己酸叔丁酯(TBPH1)的甲基异丁基酮(MIBK)溶液。 In parallel, in a preliminary run time of 10 minutes and 4.75 hours total feed time, again using a diaphragm metering Li addition of 50% strength per-2-ethylhexanoate, tert-butyl (TBPH1) in methyl isobutyl ketone (MIBK) was added. 在110°C下另外60分钟以后,将批料冷却。 At 110 ° C for an additional 60 minutes, the batch was cooled.

Figure CN104736583BD00271

[0297] 实施例21-23的透明涂料的制备和所得涂层的制备: [0297] Preparation and coating the resulting clearcoat Example 21-23: Preparation of

[0298] 随后由如上得到的聚丙烯酸酯溶液配制透明涂料。 [0298] obtained as described above followed by a polyacrylate solution prepared clear coating. 为此,随着搅拌将每种情况下50份的丙烯酸酯树脂溶液与0.03份二月桂酸二丁锡、2份的由UV和HALS光稳定剂(1:1)组成的商业光稳定剂混合物、0.15份的基于含氟丙烯酸酯的流动控制剂和1份苯甲酸混合。 For this purpose, in each case with stirring 50 parts of the acrylate resin solution and 0.03 parts of dibutyltin dilaurate, 2 parts of a UV light stabilizer and HALS: Commercial light (11) consisting of a stabilizer mixture of , 0.15 parts of a mixed flow control agents based on fluorine-containing acrylate and 1 part of benzoic acid. 在加入一定量的基于包含异氰尿酸酯基团的三聚六亚甲基二异氰酸酯(HDI),具有基于无溶剂三聚六亚甲基二异氰酸酯23.4%的异氰酸酯含量的低粘度多异氰酸酯固化剂(来自BAYER 的Desm〇dUTŪN3600)使得OH/NCO化学计量为1:1.1以后,将膜刮涂在玻璃板上(约100μπι 的湿膜厚度)。 In a certain amount based on trimerized hexamethylene diisocyanate containing isocyanurate groups (HDI), having a low viscosity based on the solvent trimer 23.4% isocyanate content of hexamethylene diisocyanate polyisocyanate curing agent (Desm〇dUTŪN3600 from BAYER) is such that the OH / NCO stoichiometry of 1: 1.1 after the film is drawn down on a glass plate (wet film thickness of about 100μπι). 将膜保持蒸发约30分钟,然后在60°C下干燥30分钟。 Film evaporator maintained for about 30 minutes and then dried at 60 ° C 30 min.

[0299] 接触角测量: [0299] Contact angle measurements:

[0300] 为测定涂层的疏水性,在对固化涂层的研究下,将一滴水应用于表面上。 [0300] To determine the hydrophobicity of the coating, in the study of the cured coating, it is applied on the surface of the drop of water. 然后如上所述通过借助来自KrUss的Mobiledrop移动式接触角测量体系测定水滴与涂层表面之间的接触点处的切线而在显微镜下进行接触角(H)的测量。 Is then determined as described above tangential line at the contact point between the water droplets and the coating surface by means of contact angle measurements Mobiledrop mobile system KrUss from the contact angle measurement is performed (H) under a microscope.

[0301] 实施例21-23的涂层的结果描述于表8中。 [0301] The results of Examples 21-23 Coating embodiment are described in Table 8. 该接触角越小,表面的润湿越好。 The smaller the contact angle, the better the wetting of the surface. 对于本发明涂层,相对于水测量的理想的接触角为至少65°,更特别是至少90°。 For the coating of the present invention, with respect to the desired contact angle of water was measured to be at least 65 °, more particularly at least 90 °.

[0302] 表8:接触角测量结果 [0302] Table 8: Contact angle measurements

Figure CN104736583BD00281

[0304]可再涂覆性的测定: [0304] Determination of re-coatability:

[0305] 为此,将阴极电涂覆金属板(约50X50cm)用来自Glasurit Reihe 90[90系列]的水性纯黑色修饰底涂料以1〇-15μπι的膜厚度涂覆,并将施涂的底涂层根据关于来自Glasurit的GlaSUritŪRATI0 Aqua,可选GlasuritŪ头二道混合底漆层285-700/-730/ 790的技术信息公告闪蒸。 [0305] For this purpose, the cathode coated metal plate (approximately 50x50cm) using an aqueous primer modified from pure black Glasurit Reihe 90 [90 series] The film thickness of the coating 1〇-15μπι, and applied the bottom technical information bulletin coating flash 285-700 / -730 / 790 based on GlaSUritŪRATI0 Aqua from Glasurit, optionally GlasuritŪ first primer surfacer layer. 因此,然后通过气动喷涂以40-60μ的膜厚度施涂实施例23的本发明透明涂料。 Accordingly, the present invention is then clear coating 23 by spraying a pneumatic embodiment is applied to a film thickness of 40-60μ. 在室温下闪蒸约15分钟以后,将透明涂料在实验室干燥箱中在60 °C下干燥30 分钟。 Flash for about 15 minutes, the clear coating was dried at 60 ° C 30 minutes at room temperature in a laboratory drying oven.

[0306]在将板储存在室温下7天以后,然后将未打磨的透明涂层又用来自Glasurit 90系列的水性黑色修饰底涂料,但现在以渐缩楔形以20μπι至Ομπι的涂层厚度施涂。 [0306] The plates were stored in clear coating at room temperature after 7 days, and then with unpolished Glasurit 90 series from black aqueous basecoat modification, a tapered wedge but a coating thickness 20μπι applied to Ομπι Tu. 重复闪蒸,其后还将实施例23的以上透明涂料以楔形施涂,但该透明涂层楔形相对于底涂层楔形旋转90°。 Repeat flash, followed by a clear coating of Example 23 above embodiment will be applied in a wedge, the wedge relative to the clearcoat basecoat wedge rotating 90 °. 在烘箱中在60°C下焙烧30分钟以后并在冷却以后,通过十字划格法测试附着力。 After calcination in an oven at 60 ° C for 30 minutes and after cooling, the cross cut adhesion test.

[0307]对于实施例23的透明涂料,在整个区域中发现非常好的附着力。 [0307] For Example 23 the clearcoat embodiment, found to be very good adhesion over the entire region. 这显示附着力不仅对于在本发明透明涂层上的未改性底涂层而言,而且对在其本身上的透明涂料而言都是显著的。 This shows not only for adhesion to the unmodified on the transparent coating of the present invention, the undercoat layer, and that for a clear coating on their own are significant.

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