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Publication numberCN104736583 A
Publication typeApplication
Application numberCN 201380052146
PCT numberPCT/EP2013/067151
Publication date24 Jun 2015
Filing date16 Aug 2013
Priority date4 Oct 2012
Also published asCN104736583B, EP2904026A1, US9574089, US20150240085, WO2014053268A1
Publication number201380052146.4, CN 104736583 A, CN 104736583A, CN 201380052146, CN-A-104736583, CN104736583 A, CN104736583A, 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
Fluorine-containing non-aqueous coating composition, coating process, and the use of the coating composition
CN 104736583 A
Abstract
The present invention relates to non-aqueous coating compositions containing from 30 to 80% by weight of at least one poly(meth)acrylate (A), from 20 to 70% by weight of at least one compound (B) containing polyisocyanate groups, and one or more catalysts (D), where the percentage by weight data are in each case based on the binder content of (A) and, respectively, (B), and where the sum of the proportions by weight of (A) plus (B) is in each case 100% by weight, characterized in that the poly(meth)acrylates (A) contain from 0.05 to 15.0% by weight of one or more fluorine-containing reaction products derived from one or more diisocyanates (PI) having two differently reactive isocyanate groups, from one or more (per)fluoroalkyl monoalcohol components (FA) and optionally from one or more compounds (V) having at least one group (G1) reactive towards isocyanate groups and optionally having another functional group (G2) differing from the group (G1). The present invention also relates to multistage coating processes, and to the use of the coating compositions.
Claims(20)  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(Gl)且任选具有不同于基团(Gl)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 poly (meth) acrylate component (A), (B) 20-70 wt% - or more polyisocyanate group-containing compound (B) containing, and (D) - one or more catalysts (D), which are based on the following components (A) and (B) weight percent of each case Under the component (A) and (B) the content of the binder, and the components (A) plus (B) and the weight content of in each case 100% by weight, wherein the poly (meth) acrylate component (A ) contains an amount in each case for the preparation of all the compounds of poly (meth) acrylate component (A) is based on a 0.05-15.0% by weight of one or more of the following substances containing a perfluoroalkyl group reaction product ( U) as a synthetic components: (i) one or more diisocyanate (PI), which has two isocyanate groups with different reactivity, (ii) one or more (per) fluoroalkyl single alcohol component (FA), and (iii) optionally one or more compounds (V), having at least one pair of isocyanate group reactive with a group (Gl) and optionally having a different group (Gl ) of other functional groups (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) yO-Az-H⑴ 和/或通式(II): CR13-(CR22)x-(CH 2)yO-Az-H (II) 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, A 为CR' R" -CR' " R"" -0 或(CR,R")a-0 或⑶-(CR,R")b-0, 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\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 following general formula perfluoro alcohol as a (per) fluoroalkyl alcohol component (FA): Formula ( I): CF3- (CF2) x- (CH2) yO-Az-H⑴ and / or the general formula (II): CR13- (CR22) x- (CH 2) yO-Az-H (II) wherein R1 and R2 each independently is H, F or CF3, but R 1 and R2 are not simultaneously be 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 ⑶- (CR, R") b-0, R ', R ", R'" and R "" are each independently H, having 1-25 alkyl C atoms, a cycloalkyl group, an aryl group or any organic group, a and b are each 3-5, and polyoxyalkylene structural units \ comprise any desired alkylene oxide homopolymers, copolymers or block stage polymer, or comprising a polyoxyalkylene glycol, or contains polylactone.
3. 根据权利要求1或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)1-(CH2CH 2O)mH (III) 和/或CF3-(CF2)n-(CH2) 0-OH (IV) 其中1 为l-8,m 为l-15,n 为1-12,且〇为1-10。 3. The coating composition as claimed in claim 1 or 2, wherein the poly (meth) acrylate component (A) contains the following substances as (per) fluoroalkyl alcohol component (FA): F (CF2CF2) 1- ( CH2CH 2O) mH (III) and / or CF3- (CF2) n- (CH2) 0-OH (IV) wherein a is l-8, m is l-15, n is 1-12, and the square of 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 for the preparation of poly (meth) acrylate component (A ) The amount of all compounds of 0. 1-10. 0 wt% of one or more fluorine-containing reaction product (U).
5. 根据权利要求1-4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(Gl),且具有烯属不饱和双键(G2)。 5. The coating composition according to claim any one of 1-4, wherein the poly (meth) acrylate component (A) comprises the reaction product of (U) as a fluorine-containing synthetic components: (i) a or more diisocyanate (PI), which has two isocyanate groups with different reactivity, (ii) one or more (per) fluoroalkyl single alcohol component (FA), and (iii) a or more compound (V), having an isocyanate group is in a reactive group (Gl), and having an ethylenically unsaturated double bond (G2).
6. 根据权利要求1-5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) pOH (V) 其中r为1-8,优选r为1-6,且p为1-6,优选p为1-2, (iii) 一种或多种具有至少一个羧基和/或羟基(Gl)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),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。 6. The coating composition according to claim any one of claims 1-5, wherein the poly (meth) acrylate component (A) comprises the reaction product of (U) as a fluorine-containing synthetic components: (i) a one or more aliphatic and / or cycloaliphatic diisocyanate (PI), which has two isocyanate groups with different reactivity, (ii) one or more (per) fluoroalkyl single alcohol component ( FA): CF3- (CF2) r- (CH2) pOH (V) wherein r is 1-8, preferably r is 1-6, and p is 1-6, p is preferably 1-2, (iii) one kind or more having at least one carboxyl group and / or hydroxyl (Gl) and having at least one acrylic and / or methacrylic unsaturated double bond (G2) of the compound (V), which is preferably selected from hydroxyalkyl acrylate, methyl hydroxyalkyl acrylate group, the reaction with the lactone hydroxyalkyl acrylate, the reaction with the lactone hydroxyalkyl esters of methacrylic acid, and mixtures thereof.
7. 根据权利要求1-6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。 7. The coating composition according to any one of claims 1-6, wherein the poly (meth) acrylate component (A) consists of one or more saturated and containing a perfluoroalkyl group or by a polyhydroxy polyacrylates one or more saturated perfluoroalkyl group and polyhydroxy polymethacrylate, or from one or more saturated perfluoroalkyl group and polyhydroxy polyacrylates and one or more saturated perfluoroalkyl a mixture of base and polyhydroxy polymethacrylate composition, and / or saturated poly (meth) acrylate component (A) comprises the reaction product of (U) as a perfluoroalkyl group-containing synthetic ingredients: iso Buddha Chalcone diisocyanate, 2_ (perfluorohexyl) ethanol, and hydroxyethyl acrylate and / or hydroxyethyl methacrylate and / or hydroxyalkyl caprolactone acrylate and / or hydroxyalkyl caprolactone methacrylate ester.
8. 根据权利要求1-7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) 1摩尔的一种或多种(全)氟烷基单醇组分(FA),和(iii) 1摩尔的一种或多种具有对异氰酸酯基团呈反应性的基团(Gl)的烯属不饱和化合物(V)。 8. A coating composition according to claim any one of 1-7, wherein the poly (meth) acrylate component (A) comprises the reaction product of (U) as a fluorine-containing synthetic components: (i) l A mole or more diisocyanate (PI), which has two isocyanate groups with different reactivity, one or more of (ii) 1 mole of the (per) fluoroalkyl single alcohol component (FA) and (iii) 1 mole of one or more ethylenically having an isocyanate group is in a reactive group (Gl) unsaturated compound (V).
9. 根据权利要求1-8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%。 9. The coating composition according to claim any one of 1-8, wherein as component (A) a poly (meth) acrylate or polyacrylate and is saturated by the following synthesis substances: (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 wt% of one or more ethylenically unsaturated carboxylic acid alkyl and / or cyclic alkyl ester, (a4) 0-50% by weight of one or more vinyl aromatic compounds, and ( a5) 0-10% by weight of other ethylenically unsaturated monomers, which is 100% by weight of a monomer (al) to (a5) and the weight content of the in each case.
10. 根据权利要求1-9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,优选70-200mg KOH/g 的OH 值。 10. A coating composition according to claim any one of 1-9, wherein as component (A) a poly (meth) acrylates having 60-300mg KOH / g, preferably 70-200mg KOH / OH g of value.
11. 根据权利要求1-10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-KKTC至+KKTC,优选-60°C至+60°C的玻璃化转变温度。 11. A coating composition according to claim any one of 1-10, wherein as component (A) a poly (meth) acrylates having -KKTC to + KKTC, preferably -60 ° C to + 60 ° C The glass transition temperature.
12. 根据权利要求1-11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. O重量%的至少一种其羧基与-电子体系共轭的单体芳族任选取代羧酸(S)。 12. The coating composition according to any one of claims 1 to 11, wherein the coating composition comprises in each case based on component (A) plus binder content of (B) is the sum of 0. 2-15. O % by weight of at least one carboxyl and - Electronic System conjugated aromatic monomer optionally substituted carboxylic acid (S).
13. 涂覆方法,其包括将根据权利要求1-12中任一项的涂料组合物的层施涂于任选预涂覆的基体上。 13. A coating method which comprises 1-12 layers according to claim any one of the coating composition is applied onto an optionally precoated substrate.
14. 根据权利要求13的涂覆方法,其中在施涂以后将根据权利要求1-12中任一项的涂料组合物在20-80°C,更特别是20-60°C的温度下固化。 14. The coating method according to claim 13, wherein after applying the coating composition according to claim any one of claims 1-12 at 20-80 ° C, more particularly at the curing temperature of 20-60 ° C .
15. 根据权利要求13或14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,优选风能体系的动叶片。 15. The coating method according to claim 13 or claim 14, wherein the optionally pre-coated substrate is plane or wind system, or one or more components of the moving blade, the wind energy system is preferred.
16. 根据权利要求13-15中任一项的涂覆方法,其中将根据权利要求1-12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。 16. A coating method according to any one of claims 13-15, wherein the coating composition according to claim any one of claims 1 to 12 as the outermost coating film applied to a rotor blade of the wind energy system.
17. 根据权利要求1-12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13-16中任一项的方法在永久防水和防污表面涂覆中的用途。 17. The coating composition of claim any one of claims 1 to 12 for use as a clear coating, or stain use in permanent waterproof surface coating and in a method according to any one of claims 13-16.
18. 根据权利要求1-12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。 18. The coating composition according to any one of claims 1 to 12 use in aircraft anti-icing coating and wind energy in the system or its components.
19. 根据权利要求1-12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。 19. A coating composition according to any one of claims 1 to 12 in the moving blade in a coating plane or wind energy systems to reduce noise Claim produced therefrom move in use.
20. 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1-12中任一项的涂料组合物产生。 20. with a paint system, optionally one or more components of wind energy systems or wind energy system multi-coat paint system, which is produced by most of topcoat coating composition according to claim any one of 1-12.
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 Use The fluorine-containing non-aqueous coating composition, coating method and the coating composition

[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 a non-aqueous coating composition, said composition comprising: at least one polyhydroxy and (per) fluoroalkyl poly (meth) acrylate component (A) containing at least one containing polyisocyanate group of compounds (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, and coating the coating composition as a clear coat and in the wind energy system or its components or aircraft, and more particularly the use as an anti-icing coating.

[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] The well established based on non-aqueous coating fluoropolymer for a large number of very different end applications.

[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 fluorine-containing polyacrylate binder containing multiple isocyanate cross-linking agents, non-aqueous transparent coatings, these coatings can be cured into anti-oil pollution and waterproof coating layer and used to coat vehicles such as underground railway vehicles, trains, buses, industrial systems, such as tanks, 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 easy to clean, as well as providing 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。 For the preparation of a fluorine-containing polyacrylate based material, a fluoroalkyl group having an ethylenically unsaturated compound, e.g., (meth) acrylate, a fluoroalkyl acrylate or methacrylate, 2- (N_-ethyl perfluoro octane sulfo 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 monomers must itself and the rest of the monomers is added separately, and this makes an expensive and inconvenient binder 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] In addition, as long as possible on how to obtain with high hydrophobicity, and also has a very high information surface mechanical and photochemical stability, e.g., wherein such a surface coating is required for the rotor blades of the wind energy system in this specification information than on how to ensure fast assembly adhesion strength and good repair more exist. 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 you can order as simple and inexpensive way to achieve these quality.

[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,其中〇. 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, the coating material in addition to the fluorine-containing polyacrylate based outside also contain more isocyanate crosslinking agent, wherein the square. 1-33 mol% of the isocyanate groups and perfluorinated 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迁移至膜表面,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。 In this paper, the fluorinated polyisocyanate preparation, in addition to the single fluorinated polyisocyanate, the expected high levels difluoride and three more fluorinated isocyanate, and two - and three more fluorinated isocyanate may migrate to the membrane surface, adversely affect the overall visual appearance of the resultant coating layer, hardness, chemical resistance and other mechanical technical performance.

[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 transparent coatings are also described in W005 / 030892, where these clearcoat binder is a fluorine-containing polyacrylates, polyacrylate further comprising the fluorine-containing organic silane monomer in copolymerized form. 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。 The fluorine-containing polyacrylates and fluoroalkyl for example, by an alkenyl group having unsaturated compounds such as (meth) acrylate, fluoroalkyl acrylate or (meth) acrylate, 2- (N- ethyl perfluoro octane sulfo amido ) obtained by copolymerizing an alkyl ester.

[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 a transparent coating having improved / clearcoat adhesion fluorinated clearcoat, based on these materials not only contain a fluoroalkyl group having a copolymerizable ethylenically unsaturated compounds such as (meth) acrylic acid fluoroalkyl yl ester or (meth) acrylate, 2- (N- ethyl perfluoro octane sulfo amido) alkyl ester of a fluorinated silane polymer, and contains a fluorinated urethane 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 does not contain any remaining free isocyanate groups by reacting a polyisocyanate with perfluorinated alcohol, and single and oligomeric and / or polymeric polyether polyols such as ethoxylated / propoxylated diol obtained by reacting, .

[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 paint the resulting anti-wear coating, and alkali, the addition curable outer coating binder systems and inorganic particles further comprise at least one fluorine-containing oligomer or polymer, The oligomer or polymer having at least one functional group of the binder system was reactive functional groups. 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 polymer or oligomer comprises such as fluorinated polyethers, fluorinated epoxide, the fluorinated polyurethane and the fluorine-containing polymer, wherein the fluorine-containing polymer is a fluorine-containing monomers such as the use of commercial tetrafluoroethylene, vinylidene fluoride ethylene and other preparation.

[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 curing two-component aqueous-based mechanisms of hybrid reactive resin system polyurethane, which is used in construction and industrial production is characterized by high mechanical strength and easy to clean coating layer. 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 amino - 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 a water having covalently bonded fluorinated side chains, optionally fluorinated polyurethane hybrid dispersions, polyurethane by means of the side chain group and / or by means of free-radically polymerizable containing fluorine monomer is 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。 Using these polyurethane hybrid dispersions, can take advantage of high crosslink density and high hardness, production has good mechanical properties and good chemical resistance, solvent resistance and antifouling coatings, these coatings suitable for a very large 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 a permanent anti-oil in the construction and industrial sectors, particularly for mineral and non-mineral matrix, waterproof and antifouling coating of fluorine-modified polyurethane coating.

[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] In addition, EP-A-2 085 442 discloses a water-based paint based on fluorinated silane component and for a variety of end applications of mineral and non-mineral base oil and water repellency, permanent 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 fluorine-containing inorganic polycondensate thereof and for coating glass, ceramics, metals, plastics and paper, and more particularly for coating the outer and inner mirrors and the windscreen of the motor vehicle The coating composition.

[0015] EP-AI 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-AI 844 863 also describes a coating liquid for producing a strong anti, in other words, showing the reference liquid, more particularly water, e.g., a very large contact angle of 120-180 ° paint coating . 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 is used comprising a polymer and a ceramic material or nanoparticles, and thus lead to 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 is not present.

[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 surface coating, used comb polymer having a fluorinated side chain of experiments were conducted. 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, it is known to achieve low surface energy and therefore good stain resistance and water resistance of the key factors include a very long chain fluorinated hydrocarbon form and with very short intervals based backbone. 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",Sa'idi,Salima ;Guittard,Fr6d6ric ;Guimon,Claude ; Geribaldi, Serge ;Journal of Polymer Science Part A :Polymer Chemistry,第43 卷, 条目17,第3737-3747 页)。 In contrast, longer intervals based cause results much worse (the "fluorinated comb type homopolymer: Impact spacer length on surface properties", Sa'idi, Salima; Guittard, Fr6d6ric; Guimon, Claude; Geribaldi, Serge ; Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, entry 17, pages 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, page 547-553 disclose by perfluorooctanol, isophorone diisocyanate and hydroxyethylacrylate ester reaction product with hydroxyethyl acrylate and octadecyl acrylate prepared by copolymerizing a fluorinated polyacrylate emulsion and the resulting emulsion was coated with a fluorinated polyacrylate use of cotton fibers.

[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 Chinese outstanding CN101020731 A specification describes a hydroxyl-containing acrylate copolymer and a diisocyanate reacted with a molar containing isocyanate groups and other perfluoroalkyl alcohol product prepared by reacting a 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 are a plurality of other specification, which discloses a process for the production of a hydrophobic waterproof coating paint. 因此,例如EP-BI 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1¾。 Thus, for example, EP-BI 210 396 describes a hydrophobic coating compositions for producing anti-icing coating, said coating by chemically attached to the gel particles, the silica-based gel is preferably produced, wherein the hydrophobic surface resistance by the surface roughness and physically mention 1¾.

[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 method for producing a self-cleaning surface hydrophobic coating, wherein the artificial surface texture produced by the projections and depressions formed, and projections of a hydrophobic material. 特氟隆例如用于该目的。 Teflon, for example used for this purpose.

[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 or its components, for example, especially the surface of the moving 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 the moving blade aerodynamics, wind energy system thus reducing efficiency. 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。 Recommended Teflon coatings include, for example, fluorine polyurethane, epoxy fluorinated components, silicide polyurea and the like. 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 for more detailed information on suitable coating composition does not exist.

[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 its components, in particular the movable blade surface highly hydrophobic coating, the coating based on fluorinated polyurethane or polyurethane mixed with a Teflon However, this description is not suitable for more detailed information about the composition of the material existence.

[0023] 此外,由EP-BI 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] In addition, the EP-BI 141 543 known rotor blades of wind energy systems can be coated with a coating liquid-proof, and therefore to reduce the noise emission of wind energy systems. 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 are given on suitable coatings include not only commercial micro-silicone paint, but also developed for marine polyurethane paint coating; however, this description is more detailed information on suitable coating composition does not exist.

[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 is to provide coating compositions, especially coating compositions used to coat the wind energy system or aircraft or parts thereof, to ensure that the composition on the respective substrate or already present in the matrix good adhesion of the coating, as well as a good portion of the resultant coating can be further coated with sex. 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。 Meanwhile, the paint should lead to durably waterproof and stain and especially continue to reduce ice, water and dirt in the wind energy system, aircraft or parts thereof, and more particularly on the rotor blades of wind energy systems adhering coating.

[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] In addition, the coating composition is coated to be generated while meeting the field of wind energy system rotor blade in the exact requirements, particularly in the coating and a 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 exhibit at a low temperature of not more than 80 ° C are good and very fast cure, in other words, should only be 30 minutes after curing cured to the extent such that at 60 ° C can be an initial mask assembly operations or solution without compromising 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, at the same time should be long enough to ensure that the coating composition of the working life ("pot life"). 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。 Pot life should be understood as a coating composition up to twice its initial viscosity of the time 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] In addition, the resultant coating should have a very good overall visual appearance, very high hardness, good chemical resistance as well as in the automotive modified plastic matrix and / or commercial vehicles painted in typically require other mechanical - Technical 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 able to be prepared very simply and cheaply.

[0030] 解决方法 [0030] Workaround

[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 stated above, it found that the 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% by weight, preferably 30-50% by weight 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 lower component (A) and (B), respectively, the weight percentages in each case based on the component (A) and (B) the content of the binder, 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㈧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 comprising (viii) in each case based on the preparation of poly (meth) acrylate component (A) used in the amount of all components of 0.05-15.0% by weight of the following substances one or more fluorine-containing reaction product (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) - or more diisocyanate (PI), which have different reactivity with an isocyanate group,

[0038] (ii) 一种或多种(全)氟烷基单醇组分(FA),和 [0038] (ii) one or more (per) fluoroalkyl single alcohol 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(Gl)且任选具有不同于基团(Gl)的其它官能团(G2)。 [0039] (iii) optionally one or more compounds (V), having at least one isocyanate group is in a reactive group (Gl) and optionally other functional groups have a different group (Gl) of ( 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, and coating the coating composition as a clear coat and in the wind energy system or its components or aircraft, and more particularly the use as an anti-icing coating.

[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] The surprising and not foreseeable that the coating compositions of the present invention ensures that the respective substrate or on a substrate already present on the coating of good adhesion, as well as a good portion of the resultant coating can be recoat 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, lead paint durably waterproof and stain and especially continue to reduce ice, water and dirt in the wind energy system, aircraft or parts thereof, and more particularly on the rotor blades of wind energy systems adhering coating.

[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 resulting in coated areas while meeting the movable blade in the wind energy system exact requirements, especially in the very good mechanical resistance and photochemical aspect exact requirements of the 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] In addition, no more than 80 ° C under low temperature, the coating compositions exhibit good and very fast cure, in other words, cured to cured after only 30 minutes at 60 ° C at this level makes it possible to carry out the initial assembly operation or damage the coating solution without the mask. 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 ("pot life").

[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] In addition, the resultant coating is worth noting that a good overall visual appearance, very high hardness, good chemical resistance as well as in the automotive modified plastic matrix and / or commercial vehicles painted in typically require other mechanical - Good technical performance score.

[0045] 最后,涂料组合物可容易且便宜地制备。 [0045] Finally, the coating composition can 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 known 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 the amount of all the compounds for the preparation of poly (meth) acrylate component (A) is based on 0 ... 0 05-15 wt%, preferably 0 0. 1-10 wt% of one or more of the following fluorine-containing reaction product (U) as a synthetic component:

[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) - or more diisocyanate (PI), which has two isocyanate groups of different reactivity,

[0051] (ii) 一种或多种(全)氟烷基单醇组分(FA),和 [0051] (ii) one or more (per) fluoroalkyl single alcohol 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(Gl)且任选具有不同于基团(Gl)的其它官能团(G2)。 [0052] (iii) optionally one or more compounds (V), having at least one isocyanate group is in a reactive group (Gl) and optionally other functional groups have a different group (Gl) of ( 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) herein may be incorporated various poly (meth) acrylate component (A) is.

[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㈧的一些羟基与包含氟和异氰酸酯基团的反应产物⑶的其余游离异氰酸酯基团反应。 [0054] For example, first preparing a hydroxyl-containing poly (meth) acrylate resin, and then by a polymer analogous reaction of poly (meth) acrylate component of some hydroxy (viii) ⑶ with the reaction product containing fluorine and an isocyanate group The remaining free isocyanate groups reacted.

[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] contains fluorine and isocyanate groups of the reaction product of (U) may 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 [0056] (i) - or more diisocyanate (PI), which has two isocyanate groups with different reactivity, and

[0057] (ii) -种或多种(全)氟烷基醇组分(FA)。 [0057] (ii) - one or more (per) fluoroalkyl alcohol component (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, the first may be prepared, for example also have other functional group such as a carboxyl group, anhydride group, an epoxy group such as hydroxyl group-containing poly (meth) acrylate resin, and then these other functional groups with a fluorine-containing reaction product (U) reaction, the fluorine-containing reaction product (U) also have to work with poly (meth) other functional groups other functional acrylate resin reaction.

[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 fluorine-containing group of the reaction product of (U) in this case may for example be prepared from the following materials:

[0060] (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, [0060] (i) one or more diisocyanate (PI), which has two isocyanate groups of different reactivity,

[0061] (ii) 一种或多种(全)氟烷基醇组分(FA),和 [0061] (ii) one or more (per) fluoroalkyl alcohol component (FA), and

[0062] (iii) 一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(Gl),且任选具有不同于基团(Gl)的其它官能团(G2)。 [0062] (iii) one or more unsaturated compounds (V), having at least one isocyanate group is in a reactive group (Gl), and optionally other functional groups have a different group (Gl) 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, a polymeric polyol having at least two hydroxyl groups, e.g., polyester polyols, polyalkylene ether polyols, polycarbonate polyols, polyester carbonate polyols, poly polyacetal polyols, polyurethane polyols or silicone 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。 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), and the reaction with the compound (V) and (per) fluoroalkyl alcohol (FA) can be simultaneously or in stages by first example of the isocyanate component with one or more Compound (V) and then reacting the resulting intermediate with fluoroalkyl alcohol component (FA) reaction (All) 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, preferably not by a polymer analogous reaction, but by reacting the corresponding alkylene containing (per) fluoroalkyl unsaturated reaction products (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, as a synthesis of the 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) - or more diisocyanate (PI), which has two isocyanate groups of 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 single alcohol component (FA), and

[0069] (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(Gl),且具有烯属不饱和双键(G2)。 [0069] (iii) one or more compound (V), having an isocyanate group to form a reactive group (Gl), 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) for the synthesis of the component to ensure with other ethylenically for preparation of poly (meth) acrylate component (A) of the unsaturated compound high compatibility. 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 according to the present invention is a perfluoroalkyl group containing ethylenically genus, it is usually not necessary to provide a separate feed them as a conventional commercial fluoromonomer necessary; rather, they may be used in conjunction with the rest of the monomers.

[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] that contain fluorine and isocyanate groups of the above reaction product (U) and allyl preferably used in the preparation of the reaction product of a fluorine-containing unsaturated (U) in the case, is necessary for the purposes of the present invention is the use of having two different reactive isocyanate groups of the diisocyanate (PI), for example 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, and therefore if one is only a very small portion of the resulting 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) (meth) acrylate component (A) is completely incorporated in the polymer, and therefore also in the resulting cured coating is 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] For the above-described fluorine-containing groups of the reaction product of (U) Preparation of the reaction product of the fluorine-containing unsaturated (U) and alkenyl preferably used in the case, the following formula is preferably perfluoro alcohol as (per) fluoroalkyl single alcohol component (FA):

[0073]通式(I) [0073] formula (I)

[0074] CF3-(CF2)x-(CH2)yOA zH (I) [0074] CF3- (CF2) x- (CH2) yOA zH (I)

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

[0076] CR13-(CR22)x-(CH2)yOA zH (II) [0076] CR13- (CR22) x- (CH2) yOA zH (II)

[0077] 其中R1和R 2相互独立地为H、F或CF 3,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, [0077] wherein R1 and R 2 each independently is H, F or CF 3, but R1 and R 2 must not both 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CO- (CR,R")b-0, [0078] A is CR, R "-CR," R "" -0 or (CR, R ") a-0 or CO- (CR, R") b-0,

[0079] R'、R"、R'"和R""相互独立地为Η、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 "" are each independently Η, an alkyl group having 1-25 C atoms, a cycloalkyl group, an aryl group or any organic group,

[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\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 polyoxyalkylene structural units \ comprise any desired alkylene oxide homopolymers, copolymers or block polymers, or comprising a polyoxyalkylene glycol, or contains polylactone.

[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-BI 664 222B1,第9页第[0054]段至第10页第[0057]段所述的(全)氟烷基醇。 [0082] perfluoroalkyl alcohol (FA) Examples of compounds suitable for use as, for example, W02008 / 040428, page 33, line 4 to page 34, line 3 of said (per) fluoroalkyl alcohol, and EP- BI 664 222B1, (per) fluoroalkyl alcohol page page 9 [0054] paragraph to Article 10 of [0057] segment.

[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 more specifically using the following formula perfluoroalkyl alcohol (FA):

[0084] 式(III) [0084] Formula (III)

[0085] F(CF2CF2)1-(CH2CH2O) mH (III) [0085] F (CF2CF2) 1- (CH2CH2O) mH (III)

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

[0087] CF3-(CF2)n-(CH2)0-OH (IV) [0087] CF3- (CF2) n- (CH2) 0-OH (IV)

[0088] 其中: [0088] where:

[0089] 1 为1-8,优选1-6,更优选2-3, [0089] a 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 is 1-12, preferably 1-6,

[0092] 〇为1-10,优选1-4。 [0092] billion of 1-10, preferably 1-4.

[0093] 合适全氟代醇的实例为3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-十三氟辛-1-醇、3, 3, 4, 4, 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^-一氟十二-1-醇、3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11,11,12, 1 2, 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, 1 0, 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] Suitable examples of perfluorinated alcohol for 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8 tridecafluoro-oct-1-ol, 3, 3, 4, 4, 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 twelve-fluoro-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, 14 twenty-five fluorine fourteen 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, 16 twenty-nine fluorine sixteen-1-ol, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8-twelve fluoro-l-ol, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10 hexadecafluoro-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 tetrafluoro-1-ol and thirteen 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 groups of the reaction product of (U) and is preferably used in the preparation of ethylenically unsaturated fluorine-containing reaction product (U), particularly preferably the general formula (V) is perfluoro alcohols or different formula (V ) a mixture of perfluorinated alcohols as (per) fluoroalkyl alcohol component (FA):

[0095] CF3-(CF2)r-(CH2)p-OH (V) [0095] CF3- (CF2) r- (CH2) p-OH (V)

[0096] 其中:r为1_8,优选1_6,更特别是1_4,且ρ为1_6,更特别是1_2。 [0096] wherein: r is 1_8, 1_6 preferably, more particularly 1_4, 1_6 and ρ is, more particularly 1_2.

[0097] 更特别地使用其中ρ = 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, the use of the formula where ρ = (V) 2 perfluoroalkyl ethanol, preferably 2_ (perfluorohexyl) ethanol and 2_ (perfluorooctyl) ethanol, and a different formula (V) perfluoroalkyl -ethanol mixture, more in particular 2_ (perfluorohexyl) ethanol and 2_ (perfluorooctyl) ethanol, optionally with other (per) fluoroalkyl alcohol mixture. 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Flu〇Wet®EA 612和Flll〇wet®EA 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.,Osaka,日本。 Preferably having 30-49. 9% by weight of 2- (perfluorohexyl) ethanol, and 30-49. 9% by weight of 2- (perfluorooctyl) ethanol perfluoroalkyl ethanol mixture, e.g. commodity Flu〇Wet®EA Flll〇wet®EA 612 and 812; 2- (perfluorohexyl) ethanol, e.g., commodity Daikin A-1620, or 2_ (perfluorooctyl) ethanol, e.g., commodity Daikin A-1820, which are from Daikin Industries Ltd., Osaka, Japan. 尤其优选使用2-(全氟己基)乙醇。 Particularly preferred to use 2- (perfluorohexyl) ethanol.

[0098] 预期作为具有对异氰酸酯基团呈反应性的基团(Gl)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] expected as having an isocyanate group is in a reactive group (Gl) and having an unsaturated double bond (G2) of the compound (V) olefinic compounds include having an ethylenically unsaturated double bond and also contains hydroxy, amino, mercapto, carboxyl or amide group 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 particularly it expected as a compound (V) of acrylic and / or methacrylic acid metal compound having an unsaturated double bond and also contain a hydroxyl group, an amino group, a mercapto group, a carboxyl group or an amide group. 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。 Expected particularly preferred as component (V) has an acrylic and / or methacrylic unsaturated double bond and also contain hydroxyl compound.

[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) is an ethylenically unsaturated monocarboxylic acids and ethylenically unsaturated dicarboxylic acids and hydroxy alkyl esters, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid , maleic acid, fumaric acid, itaconic acid, citric acid, and hydroxyalkyl esters, and alkyl ester containing an amino group, such as in particular methyl methacrylate-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 an alkyl acrylate, hydroxyalkyl methacrylate, hydroxyalkyl acrylate, hydroxy cycloalkyl esters, hydroxy cycloalkyl esters of methacrylic acid, 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] Examples of hydroxyalkyl acrylate is preferably used (meth) acrylic acid 2-hydroxyethyl methacrylate, 2_ hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methacrylate, 2-hydroxypropyl acrylate, acrylate, 3-hydroxy propyl methacrylate, hydroxy propyl acrylate, hydroxy butyl methacrylate, 3- hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxy butyl methacrylate and the like compounds .

[0102] 作为具有对异氰酸酯基团呈反应性的基团(Gl)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 ene having an isocyanate group is in a reactive group (Gl) unsaturated compound (V), may be particularly lactone and hydroxyalkyl acrylates, methacrylates and hydroxy alkyl 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、[ Y]_ 丁内酯和/或甲基_[ε]_己内酯及其混合物。 Suitable examples of lactones [ε] _ caprolactone, [β] _ propiolactone, [Y] _-butyrolactone and / or methyl _ [ε] _-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 more particularly preferred to use hydroxy carboxylic acid corresponding to the lactone polycondensates.

[0103] 此外,作为具有对异氰酸酯基团呈反应性的基团(Gl)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 ene having an isocyanate group is in a reactive group (Gl) unsaturated compound (V), it can also be used with a polymeric polyol-modified hydroxyalkyl acrylate, methacrylate, hydroxyethyl alkyl esters and mixtures thereof, e.g., polyester polyols, polyalkylene ether polyols, polycarbonate polyols, polyester carbonate polyols, polyacetal polyols, polyurethane polyol or polysiloxane polyol alcohol-modified hydroxyalkyl acrylates, hydroxyalkyl methacrylates 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。 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(A)包含以下物质的反应产物(U)作为含氟合成组分: [0104] particularly preferably, poly (meth) acrylate component (A) comprises the reaction product of (U) as a fluorine-containing synthetic components:

[0105] (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, [0105] (i) one or more aliphatic and / or cycloaliphatic diisocyanate (PI), which has two isocyanate groups of different reactivity,

[0106] (ii) 一种或多种式(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-OH (V) [0107] CF3- (CF2) r- (CH2) p-OH (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Gl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) - or more and having a hydroxyl group Gl having acrylic and / or methacrylic unsaturated double bond (G2) of the compound (V), which is preferably selected from acrylic acid hydroxyalkyl methacrylate, hydroxyalkyl ester, the reaction with the lactone hydroxyalkyl acrylate, the reaction with the lactone 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 a fluorine-containing synthetic components: isophorone diisocyanate, 2_ (perfluorohexyl) ethanol and acrylic acid hydroxyethyl acrylate and / or hydroxyethyl methacrylate and / or hydroxyalkyl 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) of the content can be changed. 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, similar to the perfluoroalkyl polymer is introduced, the preferred reaction product (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 A [0112] (i) l or more moles of diisocyanate (PI), which has two isocyanate groups with different reactivity, and

[0113] (ii) 1摩尔的一种或多种(全)氟烷基单醇组分(FA)。 [0113] (ii) one or more 1 mole of (per) fluoroalkyl single alcohol 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) Synthesis of a fluorine-containing component as a 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] A (i) l or more moles of diisocyanate (PI), which has two isocyanate groups of different reactivity,

[0116] (ii) 1摩尔的一种或多种(全)氟烷基单醇组分(FA),和 [0116] (ii) one or more 1 mole of (per) fluoroalkyl single alcohol component (FA), and

[0117] (iii) 1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(Gl)。 [0117] (iii) 1 mole of one or more ethylenically unsaturated compounds (V), having at least one isocyanate group is in a reactive group (Gl).

[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 the present invention further preferably poly (meth) acrylate component (A) consists of one or more saturated perfluoroalkyl group-containing and polyhydroxy polyacrylates or of one or more saturated perfluoroalkyl containing group and polyhydroxy polymethacrylate, or a perfluoroalkyl group and a polyhydroxy polyacrylates and one or more saturated perfluoroalkyl group containing from one or more saturated and polyhydroxy-containing polymethacrylate ester 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, may be used one or more saturated, and optionally containing a perfluoroalkyl group-containing saturated polyhydroxy poly (meth) acrylate groups and non-fluorine-containing polyhydroxy saturated mixture of acrylates (meth). 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, to ensure that the mixture should contain only the amount of all the compounds in each case for the preparation of poly (meth) acrylate component (A) is based on 0. 05-15% by weight, preferably 0. 1- 10.0% by weight of 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 preferred for use as component (A) a poly (meth) acrylate is saturated by the following synthesis substances:

[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(U), [0120] (al) 0.05-15% by weight, preferably from 0.1 to 10% by weight of one or more fluorine-containing ethylenically unsaturated reaction products (U),

[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/或环烷基醋, [0122] (a3) 10-89. 95% by weight, preferably 30-84. 9% by weight of one or more ethylenically unsaturated carboxylic acid alkyl and / or cycloalkyl vinegar,

[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% by weight, preferably 0-30% by weight 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% by weight, 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] which is 100% by weight of a monomer (al) to (a5) and the weight content of each case.

[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 monomers (a2) are (meth) acrylic acid hydroxyalkyl esters and (meth) acrylic acid hydroxy cycloalkyl esters, and olefinically unsaturated carboxylic acids such as fumaric acid, crotonic acid and maleic hydroxy acid alkyl esters and hydroxy cycloalkyl esters, and mixtures thereof, which has been used as the compound (V) listed above.

[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] Especially suitable as monomer (a3) does not have an active hydrogen having an ethylenically unsaturated carboxylic acid alkyl ester, more preferably not having other alkyl ester functional group, very preferably alcohols with unsaturated monocarboxylic ethylenically unsaturated carboxylic acid alkyl ester. 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、丙烯酸环己酯和/或甲基丙烯酸环己酯。 Ethylenically unsaturated carboxylic acid alkyl ester such (a3) Examples of acrylic acid, methacrylic acid, fumaric acid, crotonic acid and maleic acid, preferably acrylic acid and / or methacrylic acid alkyl esters and naphthenic ester, preferably methyl acrylate, methyl acrylate, ethyl acrylate, methyl acrylate, ethyl acrylate, propyl methacrylate, propyl, isopropyl acrylate, methyl acrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, methacrylate, t-butyl acrylate, amyl acetate, methyl acrylate, hexyl acrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, methyl acrylate, 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 ester, e.g., cyclopentyl acrylate, methacrylate, cyclopentyl acrylate, isobornyl methacrylate, isobornyl methacrylate, 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] Especially suitable as monomers (a4) are vinyl aromatic compound having no active hydrogen. 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) is a vinyl aromatic hydrocarbon, e.g., vinyl toluene, α- methyl styrene or styrene in particular.

[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烯属不饱和化合物。 [0129] Especially suitable as monomer (a5) are having at least two polymerizable ethylenically unsaturated compound having a unsaturated double bond and no active hydrogen olefinic. 合适的具有至少两个可聚合烯属不饱和双键的烯属不饱和单体(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 ethylenically unsaturated double bond ethylenically unsaturated monomer (a5) Examples of a saturated diol and an ethylenically unsaturated carboxylic acid diesters, more especially saturated diols with acrylic acid, 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, butylene glycol diacrylate, butylene glycol dimethacrylate, trimethylolpropane triacrylate and trimethylolpropane 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 a monomer (a5), it can also be used a polyisocyanate and an unsaturated alcohol or amine reaction products. 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 are given of the reaction product is the reaction product of 1 mole of hexamethylene diisocyanate and 2 moles of allyl alcohol, or isophorone diisocyanate and the 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、α -乙基丙烯酰胺、巴豆酰胺、富马酰胺和马来酰胺。 [0130] As different from the monomer (al) to (a4) other ethylenically unsaturated compound (a5), it can also be used without a silicon monomer having no active hydrogen, such as acrylic acid or methacrylic acid nitrile, vinyl ester or vinyl ether, an ethylenically unsaturated carboxylic acid amide, such as acrylamide, methacrylamide, itaconic acid amide, α - 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 generally, and preferably having 1000-20000 Daltons, more particularly 1500-10000 daltons mass average molecular weight of the in each case relative to polystyrene standard measured by gel permeation chromatography (GPC).

[0132] 共聚物的玻璃化转变温度通常为-100至KKTC,更特别是-60至<60°C (通过DSC 测量根据DIN-EN-ISO 11357-2 测量)。 [0132] The glass transition temperature of the copolymer is generally from -100 to KKTC, more particularly -60 to <60 ° C (measured by DSC in accordance with DIN-EN-ISO 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OH值。 [0133] poly (meth) acrylic acid esters of polyhydric alcohols having preferably 60-300mg KOH / g, more particularly 70-200mgK0H / g OH value.

[0134] 羟值(0H值)表示与在乙酰化中Ig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 number of mg and the amount of substance in the acetylation of Ig binding to the same acetic acid 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 measurement, the sample is treated with acetic anhydride - pyridine 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,OH值也可通过基于所用OH官能单体计算而以足够的准确度测定。 In the case of pure poly (meth) acrylate, OH value and can be measured with sufficient accuracy as used by the calculation is based on OH-functional monomers.

[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) acrylic acid esters of polyhydric alcohols preferably having 0_30mg KOH / g of acid value. 酸值在此处表示在中和Ig各化合物中消耗的氢氧化钾的mg数(DIN EN ISO 2114)。 Here, the acid value indicates the number of mg (DIN EN ISO 2114) and in each compound Ig consumed potassium hydroxide. 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(0。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。 [0136] Optionally, in addition to the polyhydroxy-containing poly (meth) acrylate component (A), the coating compositions of the present invention may further comprise one or more different from the component (A) containing more unsaturated monomers hydroxy compound, and / or saturated oligomeric and / or polymeric unsaturated polyester polyols, polyurethane polyols and polysiloxane polyols, more particularly saturated polyester polyol (0.5 These compounds (C) preferably accounts for 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EP-AO 994 117和EP-AI 273 640中。 [0137] Suitable polyester polyols described for example in EP-AO 994 117 EP-AI 273 640 and. 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-AI 273 640中。 Polyurethane polyols are preferably prepared by reacting polyester polyol prepolymers with suitable diisocyanates or isocyanate-reactive, and are described, for example, in EP-AI 273 640. 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 for example W0-A-01/09260 in.

[0138] 作为含羟基化合物(C),可使用低分子量多元醇。 [0138] As the hydroxyl-containing compound (C), you can use low molecular weight polyols. 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, for example diols such as 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-cyclohexane dimethanol, and polyhydric alcohols, e.g., preferably trimethylol ethane, trimethylol propane, trimethylol hexane, 1,2,4-butanetriol, pentaerythritol and di pentaerythritol. 这类低分子量多元醇优选以次要含量混入多元醇组分⑷中。 Such low molecular weight polyols preferably mixed with minor content ⑷ in the polyol component.

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

[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] According to an isocyanate group-containing compound used in the present invention (B) is preferably a conventional optionally substituted aromatic, aliphatic, cycloaliphatic and / or heterocyclic diisocyanate and / or polyisocyanate.

[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Desmodur15 W)、四甲基二甲苯二异氰酸酯(例如来自American Cyanamid的TMXDI& ),和上述多异氰酸酯的混合物。 [0141] Suitable diisocyanates the examples are as follows: 2, 4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane 4, 4 '- diisocyanate, diphenylmethane 2, 4' - diisocyanate, p-phenylene diisocyanate, diphenyl diisocyanate, 3, 3 '- dimethyl-4, 4' - diphenyl diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate , 2, 2, 4-trimethyl-hexane-1,6-diisocyanate, isophorone diisocyanate, ethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-bis diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, methylcyclohexyl diisocyanate, toluene-hexahydro-2,4-diisocyanate, toluene-hexahydro-2,6-diisocyanate, six hydrogen 1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-diphenyl methane 2, 4 '- diisocyanate, 4,4'-methylene-dicyclohexyl diisocyanate (for example, from Bayer AG's Desmodur15 W), tetramethyl xylene diisocyanate (such as from American Cyanamid of TMXDI &), and said polyisocyanate mixture.

[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] isocyanurate trimers and / or allophanate dimers and / or biuret two polymers and / or uretdione dimers Other preferred polyisocyanates for the above-mentioned diisocyanates of .

[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 present invention, the polyisocyanate is a polyisocyanate prepolymers having urethane structural units, and obtain it by reacting polyols with a stoichiometric excess of aforementioned polyisocyanates. 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 in.

[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] Particularly preferred polyisocyanate component (B) of hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-methylene-dicyclohexyl diisocyanate and / or isocyanurate trimers and / or allophanate dimers and / or biuret dimers 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) and the reaction product of (U) containing isocyanate groups except that in the preparation of the component (A), optionally using a particularly high isocyanate group content of esters, as component ( B) having an average of at least two isocyanate groups per molecule, and the reaction product of (U) containing isocyanate groups having 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 can 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 are Lewis acids (electron-deficient compounds), such as tin naphthenate, tin benzoate, tin octoate, tin butyrate, dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin octoate, lead, phosphate 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。 In the coating is preferably used for the catalyst reaction product also (U) of. 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 particularly to ensure that only one of those catalyst using an isocyanate group selectivity of the reaction in the preparation of the reaction product, for example, especially tin-containing catalysts.

[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] Preferably each case based on the use of components (A) plus (B) and the binder content of 0. 001-5% by weight, preferably from 0.1 01-2% by weight of one or more catalysts ( D).

[0149] 单体芳族羧酸(S) [0149] The aromatic carboxylic acid monomer (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η-电子体系共轭的单体芳族任选取代羧酸(S)。 [0150] In addition, to improve strength and mechanical properties of the assembly, preferably the coating composition comprises at least one carboxyl group and its conjugated electron system η- monomer optionally substituted aromatic carboxylic acid (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 in the number of carboxyl groups, preferably wherein the carboxylic acid having a carboxyl group. 单体芳族任选取代羧酸优选具有<500g/m 〇l,更优选<300g/m〇l的分子量。 Optionally substituted aromatic carboxylic acid monomer preferably has a <500g / m 〇l, molecular weight and more preferably <300g / m〇l of. 优选使用具有2-5的pKa的单体芳族任选取代羧酸。 It preferred to use an aromatic monomer having a pKa 2-5 optionally substituted carboxylic acid. pKa相当于半当量点下的pH,其中溶液介质优选为水。 pKa corresponds to a half equivalent point pH under which 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, can not be specified pKa in water, then the choice of medium is preferably DMSO or acid dissolved therein another suitable medium.

[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 with an aromatic mono- and poly-carboxylic acid, the corresponding alkyl - and aryl-substituted aromatic mono- and poly-carboxylic acid, and the corresponding hydroxyl-containing aromatic mono- and poly-carboxylic acids 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 isomers, polycyclic aromatic carboxylic acids such as naphthalene carboxylic acid isomers, 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-hydroxybenzoic 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], (B), a combination of components of the coating composition (A), optionally (C), (D) and optionally (S), 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, the polyisocyanate is selected group of compounds whose free isocyanate groups are sealed capping agent containing (B). 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, an isocyanate group may be substituted pyrazole, more particularly alkyl-substituted pyrazole such as 3-methylpyrazole, 3,5-dimethylpyrazole, 4-nitro-3,5-dicarboxylic -methylpyrazole, 4-bromo-3,5-dimethylpyrazole, etc. sealed. 特别优选组分(B)的异氰酸酯基团以非封闭形式使用。 Particularly preferred component (B) isocyanate groups to use in 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] 2-component (2K) coating compositions of the case, in applying the coating to shortly, will contain the polyhydroxy-containing compound (A) and the following other components of the coating composition comprising a polyisocyanate containing group of the compound (B) below, and optionally other components of the coating composition further mixing, wherein the mixing in a conventional manner, and usually contains the compound (A) of the coating composition 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] Multi-hydroxy component (A) 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(A)、(B)、(D)、(S)和任选(C)呈化学惰性,而且在涂料的固化过程中不与(A)、任选(C)、(B)、⑶和⑶反应的那些。 Suitable solvents (L) as many hydroxyl component content and fully dissolved in the coating of the compound (A), (B), (D), (S) and optionally (C) is chemically inert, and in coatings the curing process does not (A), optionally (C), (B), and those ⑶ ⑶ reactions. 更特别地,这些溶剂(L)为非质子溶剂。 More particularly, the solvent (L) is an aprotic solvent. 这类非质子溶剂(L)的实例稍后在下文中给出。 Examples of such aprotic solvents (L) 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。 [0157] The coating compositions of the invention by means of the component (A) and optionally (C) of the hydroxyl component (D) in the isocyanate group curing reaction.

[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。 [0158] Preferably select the polyol (A) and optionally (C) and the polyisocyanate (B), the weight content of such hydroxyl component containing polyol (A) plus optionally (C), (B) an isocyanate group molar ratio of 1: 0 9-1: 1.5, preferably 1: 0 9-1: 1.1, more preferably from 1: 95-1 0: 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] The coating compositions of the present invention comprises in each case based on component (A) of the binder content of 30-80 wt.%, Preferably 50-70% by weight and containing a polyhydroxy-containing (per) fluoroalkyl poly (meth) acrylate component (A), and in each case based on the component (B) of the binder content of 20 to 70 wt%, more isocyanate groups preferably 30-50% by weight of the compound containing ( B), wherein the component (A) plus (B) is always the sum of the weight content of 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 based on the coating composition further comprises a component (A) plus (B) the sum of the content of the binder is preferably 0.1% by weight in each case 001-5, and more preferably 0.1% by weight of a 01-2 one or more catalysts (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⑶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 0.5-5. 0 wt% of at least one aromatic carboxylic acid (S), wherein the binder content and the addition of lower ⑶ weight percent each case based on the component (A).

[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 is meant in each case can be cross-linked before coating composition portion was dissolved in tetrahydrofuran (THF) in. 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 50-100 times the amount of THF insoluble component was removed by filtration, the THF was evaporated off, and then dried at 130 ° C for 60 minutes, in dryer to cool, then repeat the weighing determined previously dissolved in THF in a solid component. 残余物相当于试样(P)的基料含量。 The residue was equivalent to sample (P) the content of the binder.

[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) and the weight content of the (in each case considering only single binder content, rather than the content of any solvent that may be present) and therefore produce 100% by weight in each case, and the group the amount of points (D) and (S) based on the component (A) plus (B), and the weight of the contents of.

[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 preferably comprises a solvent and a non-aqueous coating or may be formulated as 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 suitable solvent (L) of the coating composition to the compound (A) and (B) is chemically inert, and during curing of the coating does not (A) and ( B) the reaction of those. 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、Solvesso 100或Hydrosol_®i (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 a solvent (L) is an aliphatic and / or aromatic by, e.g., toluene, xylene, solvent naphtha, Solvesso 100 or Hydrosol_®i (from 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 a mixture of the above 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, 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] The solvent (L) is preferably used in an amount to the coating composition of the present invention, so that the solid content of the coating composition is at least 50% by weight, more preferably at least 60% by weight.

[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)。 [0167] The coating composition of the present invention may further comprise in each case based 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 a variety of tris (alkoxy carbonylamino) triazine (E).

[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-AO 624 577 中给出。 [0168] Suitable tris (alkoxy carbonylamino) triazine instance in US-A-4 939 213, US-A-5 084541 and EP-AO 624 577 is given.

[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) is commonly used in the paint industry all amino resin, the resultant properties of the 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。 Said 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, which is usually the alcohol moiety or preferably fully etherified. 更特别地使用用较低级醇醚化的氨基树脂。 More particularly, the use of alcohol with the lower level of the amino resins. 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' Maprenal®:和Luwipal®_ 市售的产品。 Preferred to use methanol and / or ethanol and / or butylated amino resins, examples can name Cymel®, Resimene 'Maprenal®: and Luwipal®_ 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] The compound amino resin (E) is a well established and are described in detail in, for example U.S. Patent Application US 2005/0182189 A1, page 1, [0014] to page 4, paragraph [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] The present BenQ feed mixture or coating compositions of the present invention may further comprise an effective amount, i.e., in each case based on the coating composition of the binder content is preferably at most 20 wt%, more preferably at most 15% by weight, more in particular at most 10 wt% of at least one of an amount commonly used and known 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] _ particularly 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] - in particular light stabilizers, such as HALS compounds, benzotriazole or oxanilides;

[0175] _自由基清除剂; [0175] _ 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] - defoamers;

[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Ineozoi®或天冬氨酸酯; [0179] - other than the component (A) and (C) a reactive diluent, more particularly only by other components and / or react with water and become reactive with the reactive diluent, e.g. Ineozoi® or days aspartic acid ester;

[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] - adhesion promoters;

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

[0183] -成膜助剂,例如纤维素衍生物; [0183] - a film-forming aids 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Rompp Lexikon iiLacke und DruckfarbenGeorg Thieme Verlag, Stuttgart, 1998, 第250-252 页; [0184] - fillers, e.g., based on silica, alumina or zirconia nanoparticles; reference Rompp Lexikon iiLacke und DruckfarbenGeorg Thieme Verlag, Stuttgart, 1998, p. 250-252 with respect to other details;

[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-AO 276 50UEP-A-0 249 201或WO 97/12945中已知的添加剂;交联聚合物微粒,例如EP-AO 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Aei*osils® ;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) a rheology control additives, for example by the patent WO 94/22968, EP-AO 276 50UEP-A-0 249 201 or WO 97/12945 known additives ; crosslinked polymer microparticles, e.g., in EP-AO 008 127 of the type disclosed; inorganic phyllosilicates, e.g., aluminum magnesium silicate pages, sodium magnesium phyllosilicate and smectite type sodium lithium magnesium fluoro-p Si salt; silica as Aei * osils®; or having ionic and / or synthetic polymer associative groups, such as poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene - maleic anhydride copolymers or ethylene - maleic anhydride copolymer and its derivatives, or hydrophobically modified ethoxylated urethanes, or polyacrylates;

[0186] -阻燃剂。 [0186] - flame retardants.

[0187] 特别优选包含如下组分的涂料组合物: [0187] Particularly preferred coating composition 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 component (A) of the binder content of 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 component (B) of the binder content of 30-50% by weight of an ester group-containing multi-compound (B) isocyanate,

[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 binder content of the coating composition is 0-10% by weight of the hydroxyl-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 the component (A) plus binder content of (B) to the sum of 0.5 to 8. 0 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 binder content of the coating composition is 0-15% by weight 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 binder content of the coating composition is 0-10 wt% of at least one conventional and known coating additives (F), and

[0194] 基于组分㈧加⑶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): [0194] (viii) The content of the component based on the binder plus ⑶ sum is 0.01% by weight of at least one catalyst (D), wherein the lower component (A) plus (B) and the weight content of each case 100 wt%, and wherein the poly (meth) acrylate component at (A) the amount of all the compounds in each case for the preparation of poly (meth) acrylate component (A) based on 0.1 to 10. 0 wt. % of one or more fluorine-containing reaction product of (U):

[0195] (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, [0195] (i) one or more aliphatic and / or cycloaliphatic diisocyanate (PI), which has two isocyanate groups of different reactivity,

[0196] (ii) 一种或多种(全)氟烷基醇组分(FA), [0196] (ii) one or more (per) fluoroalkyl alcohol component (FA),

[0197] CF3- (CF2)n-CH2-CH2O-H [0197] CF3- (CF2) n-CH2-CH2O-H

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

[0199] (iii) 一种或多种具有羟基(Gl)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)丙烯酸羟烷基醋及其混合物。 [0199] (iii) having one or more hydroxyl group (Gl) and having an acrylic and / or methacrylic unsaturated double bond (G2) of the compound (V), which is preferably selected from (meth) acrylate, hydroxyalkyl ester, reacted with a lactone (meth) acrylate, hydroxyalkyl vinegar and mixtures thereof.

[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 invention, the invention BenQ feed mixture or coating compositions of the present invention may further contain pigments and / or fillers can be used to produce colored top coat or pigmented basecoat or head Erdao mixing the primer layer, more particularly colored 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 skilled artisans. 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〇. 05:1-1. 5:1。 In certain pigments are generally used in an amount such that the pigment: binder ratio in each case based on the binder content of the coating composition is square 05: 1-1 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 by the present invention, the coating significantly even attached to the electrical cured coating, the first two channel mix undercoat, basecoat or clearcoat conventional and known, in addition to their automotive OEM finishing the uses, they significantly suited for coating automotive modification and / or installed in a vehicle or on a motor vehicle components, and / or used to coat multi-use vehicles.

[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] The coating composition of the present invention may be applied by any conventional application techniques, such as spraying, knife coating, coating, pouring, bath, dipping, trickle or roll coating. 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。 Applied on such, the substrate to be coated itself may be stationary, wherein the applicator device or apparatus is movable. 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 disk volumes can be moved, which is applied with respect to the substrate means is stationary or moving properly.

[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] Preferably alone or in combination with thermal spraying thermal spray techniques in combination with air spray, such as compressed air spraying, airless spray, high-speed rotation, electrostatic spraying (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] The present invention is applied cured coating can be carried out after a specific still time. 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。 Still time, for example leveling and degassing of volatile components or for coating such as evaporation of 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。 Rest time can be applied at an elevated temperature and / or by a reduced atmospheric humidity assisted and / or shortened, with the proviso that it does not make the film experience any damage or 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] heat-curable coatings in the absence of the special nature of the technical aspects, but in accordance with conventional and known techniques, such as heating or irradiation with IR lamps carried out in a forced air oven. 该热固化也可分阶段进行。 The thermal curing can also 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 with 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 at temperatures 20_200 ° C for 1 minute up to 10 hours, can be used at low temperatures or longer curing time. 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, as well as multi-use vehicle painting automobiles modification and plastic components, usually and 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,更特别是⑶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。 [0207] The coating composition of the present invention is remarkably useful as a means of transport (and more particularly a motor vehicle, such as bicycles, motorcycles, buses, trucks or automobiles) or parts of the body decorative, protective and / or effect coatings and finishes; particularly 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, hood, tailgate, buffer, 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, vessels, aircraft, and agricultural equipment such as tractors and combine harvesters and their components, as well as furniture, windows and doors; plastic products, more particularly ⑶ and windows; small industrial parts, coils, containers, and packaging; appliances; film; optical, electronic and mechanical components ; and hollow glass products and household decorative, protective and / or effect coating and finishing.

[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 composition of the present invention may be applied to the example uncoated or pre-coated substrate, and the invention of colored paint or stain. 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 clearcoat. 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。 Because with good mechanical and photochemical resistance combined hydrophobic properties, they are also used for very many non-coated or pre-coated substrate in any kind of permanent water 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 present invention is used in the coating process, wherein the film is applied with the coating composition of the present invention to 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 rotor blades of wind energy systems.

[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 present invention are also useful in which the optionally pre-coated first substrate with a colored base coating film, followed by the present invention is a coating composition comprising a film coating method. 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 is also provided by the at least one multi-colored base coating film and a coating disposed effects and / or color paint system at least one transparent coating film formed thereon, these systems are characterized by a clear coating of the present invention, the coating composition 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] can be diluted with water of a primer and a primer based on organic solvents. 合适的底涂料描述于例如EP-AO 692 007和其中在第3栏第50行及随后列举的文件中。 Suitable primer described for example in EP-AO 692 007 which in column 3, line 50 and the file is then enumerated and. 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 applied primer was dried first, which means at least some of the organic solvent and / or water in the coating film is removed from the bottom of the evaporation stage. 干燥优选在从室温至80°C的温度下进行。 Dried preferably at from room temperature to 80 ° C temperature. 在进行干燥以后,施涂本发明涂料组合物。 After carrying out drying, the coating compositions of the present invention is applied. 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 calcined, preferably in the condition range used in automotive OEM finishing two-coat paint system, at a temperature of 20-200 ° C for 1-10 minutes baking time, but at a temperature for a modified car, 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 present invention, the coating compositions of the present invention is used as a clear coating for coating a plastic substrate, and more particularly mounted on the inside or outside of the plastic parts. 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 the optionally precoated or pretreated for better adhesion of the subsequent coating (e.g. substrate by flame treatment, corona treatment or plasma treatment) The first substrate is coated with a colored base coating film, followed by coating with a layer comprising the coating composition of 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MO %,更特别是>50 %的聚碳酸酯含量使用。 [0213] plastic member is usually composed of a mixture ASA, polycarbonate, ASA and polycarbonate, polypropylene, polymethyl methacrylate or impact-modified polymethyl methacrylate, polycarbonate and more particularly ASA mixture composition, it is preferably MO%, more particularly> 50% of the polycarbonate content use.

[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 on polyacrylic acid, acrylonitrile-alkyl acrylate rubber The graft copolymer is 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 preferred coating composition of the present invention is used in aircraft and wind energy system or its components, and more particularly in the field of wind dynamic coating method leaves a very demanding, particularly as the rotor blades of wind energy systems 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 present invention in aircraft anti-icing coating and wind energy system or components thereof, and more particularly the wind energy system rotor blade deicing coating purposes.

[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 also provides a coating composition of the present invention, the movable blade in the coating system of the aircraft or wind to reduce noise generated by the use of the mobile.

[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, the wind energy system or a multi-coat paint system, a characteristic feature of these wind energy systems or their components is the topmost coating film by the coating of the present invention generating composition.

[0219] 实施例1-3 [0219] Example 1-3

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

[0221] 将83g异佛尔酮二异氰酸酯与0.1 g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IL三颈烧瓶中。 [0221] The 83g of isophorone diisocyanate and 0.1 g dibutyl tin introduced together equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel IL 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, and then by means of a dropping funnel was slowly added based on 2- (perfluoro-hexyl) commercial fluoroalcohol ethanol (from Daikin Industries Ltd, Osaka, Japan, commodity Daikin 40. 7g of A- 1620). 保持6. 85%的NCO含量,其通过下文所述用二丁胺滴定而测定。 Maintaining an NCO content of 6.85%, which by following the determination with dibutylamine titration. 其后,同样在55°C下,逐滴加入14. 5g甲基丙烯酸羟基乙酯。 Thereafter, at 55 ° C under the same, 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NCO含量时,将体系冷却。 When it reaches the NCO content of 0.01% or less, the system was cooled. 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 93.3% by weight of a fluorine-containing monomer content.

[0222] 本发明含氟单体2的制备 [0222] The present invention is the preparation of a fluorine-containing monomer 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 was added at 50ppm as dibutyltin 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。 Thereafter, the reaction product was 55 ° C was added dropwise 1 mol of the reaction product of 1 mole of fluoroalcohol with the IPDI.

[0224] 本发明含氟单体3的制备 [0224] Preparation of a fluorine-containing monomers of the present invention 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 was added at 50ppm as dibutyltin 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。 At 55 ° C and then the reaction product was added dropwise to the reaction product of 1 mole of fluoroalcohol with 1 mole of IPDI.

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

[0227] 未反应NCO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 amount of unreacted NCO by following with 0. 5N hydrochloric acid titration using dibutylamine relative to BPB determination:

[0228] 在实际滴定以前,进行关于空白值的测定。 [0228] In practice, before titration, were determined on a blank value. 对于空白值测定,使用溴酚蓝作为指示剂,用〇.5摩尔/升含水盐酸以蓝色至黄色(pH = 4.6 (蓝色)一pH = 3.0(黄色))滴定以指定方式加入的一定量的二丁胺。 For a blank value measurement, using bromophenol blue as an indicator, with 〇.5 mol / liter aqueous hydrochloric acid to blue to yellow (pH = 4.6 (blue) a pH = 3.0 (yellow)) titrated to specify joins certain amount of dibutylamine. 该消耗量视为"空白试验中的消耗量"。 The consumption as a "blank test in 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, sample by reaction with dibutylamine and completely consumed. 在该反应中,NC双键打开,并将二丁胺加在其上。 In this reaction, NC double open, and dibutylamine added thereto. 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 from blue to yellow back titration. 颜色变化必须持续约30秒。 Color changes must be continued for about 30 seconds. 该消耗量视为"主试验中的消耗量"。 The consumption is regarded as "the main test of consumption."

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

[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. Ig乙酸丁酯。 [0231] 911. Ig charged butyl acetate in the use of oil is hot stainless steel jacket to adjust the temperature and fitted with an anchor stirrer, reflux condenser and 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 2.5 bar overpressure reactor was heated to 160 ° C. 然后使用隔膜泵经4小时计量加入1200g各单体混合物。 Then use the diaphragm pump after four hours of each monomer mixture metered 1200g. 并行地,也使用隔膜泵以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, the diaphragm pump is also used to run 10 minutes preparation time, and 4.75 hours total feeding time, measuring the amount of monomer added to the base amount of 7.0% by weight of di-t-butyl peroxide concentration of 50% ( 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。 At 160 ° C at 60 minutes after the addition, the batch was stopped and the reactor was cooled.

[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IOOym四通棒式涂布器刮涂在玻璃板上。 [0232] The polymer solution obtained by the above method was diluted with butyl acetate to a solids content of about 60%, and use the four-way IOOym bar coater blade coating on the glass. 在130°C下干燥30分钟以后测量这些膜上的接触角。 At 130 ° C measured contact angles of these film 30 minutes after drying.

[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, the drop of water applied to the upper surface. 然后通过使用来自Kriiss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。 Then by using Mobiledrop mobile contact angle measuring system measured from Kriiss tangent point of contact between the droplet and the surface of the coating while contact angle (H) is measured under a microscope. 类似地测定相对于二碘代甲烷的接触角。 Similarly, with respect to the contact angle measuring two methyl iodide. 对于该测量,将测量头放在试样上。 For this measurement, the measuring head on the sample. 计量控制杆降低计量导管并计量加入液滴。 Metering lever to reduce measurement catheter and 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 the integration of the camera prism configuration contour image liquid introduced a notebook PC connection. 在那里借助KRtJSS SW23软件(DSA2)分析液滴视频并测定接触角。 Where aid KRtJSS SW23 software (DSA2) analysis and measuring the contact angle of droplets video.

[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 containing perfluoroalkyl alkyl poly (meth) acrylate composition, expressed in weight%, and critical data

[0235] [0235]

Figure CN104736583AD00211

[0236] 表1的要点 Highlights [0236] Table 1

[0237] Mw =重均分子量,其通过凝胶渗透色谱法(GPC)相对于聚苯乙烯标准测量 [0237] Mw = weight average molecular weight, relative to polystyrene standard measured by gel permeation chromatography (GPC)

[0238] Mn =数均分子量,其通过凝胶渗透色谱法(GPC)相对于聚苯乙烯标准测量 [0238] Mn = number average molecular weight relative to polystyrene standards as measured by gel permeation chromatography (GPC)

[0239] SC AP =(聚合反应结束以后的固体含量) [0239] SC AP = (after completion of the polymerization reaction solids content)

[0240] 将Ig测量物质与Ig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 Ig Ig butyl acetate measurement substance in a carrier (metal cover) on the mixed and in a forced air oven dried at 130 ° C 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 333s4测量 [0242] Viscosity: Brookfield CAP 2000+ models using a rotary viscosity at 23 ° C under counter to the spindle 3, RPM1000 or shear rate measured 13 333s4

[0243] 接触角H2O :测量的相对于水的接触角 [0243] The contact angle H2O: measured with respect to the contact angle of 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 two of the contact angle of iodomethane

[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 fluorine-containing monomer is incorporated in the same manner as the polymer, and having a surface tension equivalent effect. 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 the fluorine-containing monomer 1 may be the least labor-intensive and complex chemical preparation, other experiments carried out using the monomer 1.

[0246] 实施例4-20 [0246] Example 4-20

[0247] 为测定在Tg、OH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] The best formulated in Tg, OH value and the fluorine-containing monomer content areas measured, using the following basic formula with the aid of a high-throughput system for polymerization. 用于所有合成的批料尺寸为约200ml。 For all synthetic batch size of about 200ml.

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

[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] describe the following general polymerization conditions: polymerization temperature 110 ° C, feeding time 3 hours monomer mixture, initiator solution 3 for 5 hours, one hour after the polymerization initiator based on the monomer is 7%, the methyl isobutyl. initiator solution of butyl ketone (respectively 25% and a concentration of 17.4%).

[0255] [0255]

Figure CN104736583AD00231

[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 of Example 4-20 containing embodiment of perfluoroalkyl alkyl poly (meth) acrylate

[0257] [0257]

Figure CN104736583AD00232
Figure CN104736583AD00241

[0258] SC =固体含量:将Ig测量物质与Ig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 Ig Ig butyl acetate substance in a carrier (metal cover) on the mixed and 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)相对于聚苯乙烯标准测量 [0259] Mw = weight average molecular weight, relative to polystyrene standard measured by gel permeation chromatography (GPC)

[0260] Mn =数均分子量,其通过凝胶渗透色谱法(GPC)相对于聚苯乙烯标准测量 [0260] Mn = number average molecular weight relative to polystyrene standards as measured by gel permeation chromatography (GPC)

[0261] 实施例4-20的涂料的制备 Paint Preparation Example 4-20 [0261] Example

[0262] 随后由如上得到的聚丙烯酸酯溶液配制透明涂料。 [0262] Subsequently polyacrylate solution consisting of the above obtained clear coating formulation. 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 is accomplished by first 1.762 parts acid was dissolved with stirring in Table 4 of the acrylate resin solution in an amount performed. 随后随着搅拌将表4所述量的甲基异丁基酮、〇. 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(I: 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。 As in Table 4 followed by stirring of the amount of methyl isobutyl ketone, square. 132 parts of a 10% concentration dilaurate in butyl acetate solution of tributyl tin, 0.881 parts by UV and HALS light stabilizers (I: 1) commercial light stabilizer mixture composition and flow control agents based on fluorine-containing acrylate mixed 0.0655 parts. 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Desmodur® N3600)使得OH/NCO化学计量为I: I. I 以后,将膜刮涂在玻璃板上(约100 μ m的湿膜厚度)。 In adding a certain amount (Table 4 of the amount) is based contains isocyanurate group trimer hexamethylene diisocyanate (HDI), with a 23.4% based on solvent-free trimeric hexamethylene diisocyanate low viscosity isocyanate content of the polyisocyanate curing agent (from BAYER of Desmodur® N3600) so that OH / NCO stoichiometry is I: I. I then, the film is drawn down on a glass plate (approximately 100 μ m wet film thickness) . 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 after the evaporation, and then the film was dried at 60 ° C for 30 minutes. 在130°C下干燥30分钟以后测量这些膜上的接触角。 At 130 ° C measured contact angles of these film 30 minutes after drying.

[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 acrylate containing coating composition perfluoroalkyl alkyl poly (meth), expressed in parts by weight

[0264] [0264]

Figure CN104736583AD00251

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

[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's

[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: Coating Example 4-20 on the measurement results of the implementation of water contact angle

[0269] [0269]

Figure CN104736583AD00252
Figure CN104736583AD00261

[0270] [0270]

[0271] 此外,确定实施例4-20的涂层的Fischer Scope硬度。 [0271] In addition, to determine the cases of Fischer Scope 4-20 coating hardness implemented. 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)。 According to Vickers Hardness HV test method using HP100VP X-Prog instruments from Helmut Fischer GmbH will be (on the hardness test DIN 50133 penetration method, hardness measurement methods). 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, in order to specify the type of force to improve the pyramid diamond indenter into the sample. 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] 15 seconds of wait (creep)

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

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

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

[0277] HU在最大试验力下的万用硬度,N/mm2。 [0277] HU In the biggest test of universal hardness, N / mm2. 不考虑进行的形状校准。 Does not consider the shape of the calibration performed. 为考虑形状校准,打开控制场校准。 To consider the shape of the calibration, open the Control field calibration.

[0278] Y弹性渗透模数,GPa (MPa)。 [0278] Y elastic modulus penetration, GPa (MPa). 在所有情况下考虑形状校准。 Consider 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。 Elastic deformation energy (We) and the total deformation energy ratio.

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

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

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

[0283] hmax压针在最大试验力下的渗透深度,μ m(nm)。 [0283] hmax indenter at the maximum test force of penetration depth, μ m (nm). 不考虑进行的形状校准。 Does not consider the shape of the calibration performed. 为考虑形状校准,打开控制场校准。 To consider the shape of the calibration, open the Control field calibration.

[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 you open the control field, the HU, HU (h), HU (F), HU Cr, h (F) and hmax parameters of the true shape of the indenter calibration. 每种情况下考虑进行的形状校准。 Consider 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「02861 [0285] Table 6: Fischer Scope paint surface hardness measurements Example 4-20 embodiment of "02861

Figure CN104736583AD00271

[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] the test results obtained by the statistical test program in the recipe selection scale capacity. 为此(对应于表7),以中试规模制备以下聚丙烯酸酯。 To this end (corresponding to Table 7), was prepared in the following pilot scale polyacrylate. 此处用以下条件测试配方: Here the test formulation with the following conditions:

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

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

[0292] -高氟含量以及高Tg和较高OH值(实施例23)。 [0292] - a high fluorine content and a high Tg and a higher OH values (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 clearcoat to test their adhesion.

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

[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] The means of regulating the temperature of the oil is hot stainless steel jacket and fitted with an anchor stirrer, reflux condenser and thermometer 4L stainless steel reactor was charged as the amount shown in Table 7 methyl isobutyl ketone (MIBK). 在氮气覆盖下,将反应器加热至IKTC。 Under a blanket of nitrogen, the reactor was heated to IKTC. 然后使用隔膜泵经4小时计量加入1200g各单体混合物。 Then use the diaphragm pump after four hours of each monomer mixture metered 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,再次使用隔膜泵计量加入50%浓度的过-2-乙基己酸叔丁酯(TBPEH)的甲基异丁基酮(MIBK)溶液。 In parallel, with 10 minutes of preparation time and 4.75 hours run total feed time, again using the diaphragm metering concentration of 50% was added over 2-ethyl tert-butyl (TBPEH) of methyl isobutyl yl ketone (MIBK) was added. 在IKTC下另外60分钟以后,将批料冷却。 In IKTC under another 60 minutes, the batch was cooled.

[0296] [0296]

Figure CN104736583AD00291

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

[0298] 随后由如上得到的聚丙烯酸酯溶液配制透明涂料。 [0298] Subsequently polyacrylate solution consisting of the above obtained clear coating formulation. 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(I: I) 组成的商业光稳定剂混合物、〇. 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。 To this end, in each case with stirring a solution of 50 parts of an acrylate resin and 0.03 parts of dibutyltin dilaurate, 2 parts by UV and HALS light stabilizers: commercial light stabilizer (I I) composed of mixture, square. 15 parts of fluorine-based flow control agents acrylate and 1 part of benzoic acid and mixed. 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Desmodur® N3600)使得OH/NCO化学计量为1:1. 1以后,将膜刮涂在玻璃板上(约100 μ m的湿膜厚度)。 In adding a certain amount based on inclusion isocyanurate group trimer hexamethylene diisocyanate (HDI), having based on low-viscosity solvent-free trimeric hexamethylene diisocyanate 23.4% of the isocyanate content of more isocyanate curing agent (from BAYER of Desmodur® N3600) so that OH / NCO stoichiometry of 1: 1.1 after the film drawn down on a glass plate (approximately 100 μ m wet film thickness). 将膜保持蒸发约30分钟,然后在60°C下干燥30分钟。 The film holding evaporated for about 30 minutes, and then dried at 60 ° C for 30 minutes.

[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, the drop of water applied to the upper surface. 然后如上所述通过借助来自Kriiss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。 Then determined as described above tangent point of contact between water droplets and the coating surface by means of contact angle measurements Mobiledrop mobile system from Kriiss while contact angle (H) is measured 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 embodiments are described in Table 8. 该接触角越小,表面的润湿越好。 The smaller the contact angle, surface wetting as possible. 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 contact angle of water measured over at least 65 °, more particularly at least 90 °.

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

[0303] [0303]

Figure CN104736583AD00301

[0304] 可再涂覆性的测定: [0304] recoatable Determination:

[0305] 为此,将阴极电涂覆金属板(约50 X 50cm)用来自Glasurit Reihe 90 [90 系列]的水性纯黑色修饰底涂料以l〇-15ym的膜厚度涂覆,并将施涂的底涂层根据关于来自Glasurit的Glasurit® ratIO Aqua,可选Glasurit®头二道混合底漆层285-700/-730/790的技术信息公告闪蒸。 [0305] To this end, the cathode coated metal plate (approximately 50 X 50cm) with an aqueous pure black from Glasurit Reihe 90 [90 series] modified primer to the film thickness of the coating l〇-15ym, and will be applied Based on its undercoating from Glasurit's Glasurit® ratIO Aqua, optional Glasurit® first two channel mix technical information bulletin flashed primer layer 285-700 / -730 / 790. 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, and then sprayed with a pneumatic film thickness 40-60μ embodiment of the present invention is applied clearcoat 23. 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 clearcoat in a laboratory oven dried at room temperature at 60 ° C for 30 minutes.

[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20 μ m至0 μ m的涂层厚度施涂。 [0306] After the plates were stored at room temperature for 7 days, then they are not polished clearcoat from Glasurit 90 series with a black waterborne basecoat modification, but now with a tapered wedge to 20 μ m to 0 μ m of coating thickness applied. 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°。 Repeated flash, clearcoat Example 23 above embodiment will be thereafter applied to the wedge, but with respect to the clearcoat wedge undercoat wedge rotated 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。 Baked in an oven at 60 ° C for 30 minutes later and after cooling, through 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 implementation of a transparent coating, very good adhesion was found in 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 unmodified on the transparent coating of the present invention, an undercoat layer is concerned, but also on its own in terms of transparent paint are significant.

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