Coating systems based on bismuth-containing catalysts with sterically bulky substituents
阅读说明：本技术 基于具有空间体积大的取代基的含铋催化剂的涂料体系 (Coating systems based on bismuth-containing catalysts with sterically bulky substituents ) 是由 W-A·荣 胡蔚秋 P·霍夫曼 C·科尔顿 许华君 B·施奈尔 黄正 张延路 于 2019-03-15 设计创作，主要内容包括：本发明涉及一种涂料体系,其包含组分(A)至(C)以及任选的其他组分,其中在第一种选择中,所有组分(A)至(C)以及存在的话其他任选组分彼此分开存在,换言之,各组分不是彼此原样混合,而是仅在使用前混合。相反,在本发明涂料体系的第二种选择中,上述组分也可以全部或至少部分地彼此混合。当组分至少部分地彼此混合时,这意味着例如组分(C)与组分(A)混合,而组分(B)与(A)和(C)的混合物分开存在。然而,任选地,组分(B)也可与一部分组分(C)混合。此外,(A)和(C)的混合物以及(B)和(C)的混合物可额外包含至少一种任选组分,例如溶剂。组分(A)包含至少一种含多羟基的化合物,组分(B)包含至少一种含多异氰酸酯基的化合物。相反,组分(C)为至少一种如下文所定义的通式(Ia)和/或通式(Ib)的含铋催化剂。可存在于本发明涂料体系中的其他组分包括例如含羟基的化合物(B)、涂料添加剂(F)、颜料(H)和/或溶剂(J)。(The invention relates to a coating system comprising components (A) to (C) and optionally further components, wherein in a first option all components (A) to (C) and, if present, further optional components are present separately from one another, in other words the components are not mixed with one another as such, but are mixed just before use. In a second alternative of the coating system according to the invention, on the contrary, the above-mentioned components can also be mixed with one another in whole or at least in part. When the components are at least partially mixed with each other, this means that, for example, component (C) is mixed with component (a), while component (B) is present separately from the mixture of (a) and (C). Optionally, however, component (B) may also be mixed with a portion of component (C). Furthermore, the mixture of (a) and (C) and the mixture of (B) and (C) may additionally comprise at least one optional component, for example a solvent. Component (A) comprises at least one polyhydroxy-containing compound and component (B) comprises at least one polyisocyanate-containing compound. In contrast, component (C) is at least one bismuth-containing catalyst of the general formula (Ia) and/or of the general formula (Ib) as defined below. Further components which may be present in the coating system of the present invention include, for example, hydroxyl-containing compounds (B), coating additives (F), pigments (H) and/or solvents (J).)
1. A coating system comprising components (a) to (C):
(A) at least one polyhydroxy-containing compound,
(B) at least one polyisocyanate group-containing compound, and
(C) at least one bismuth-containing catalyst of the general formula (Ia) and/or of the general formula (Ib),
wherein the bismuth-containing catalyst of the general formula (Ia) is defined as follows:
R1、R2and R3Each independently of the other being hydrogen or unsubstituted or at least monosubstituted C1-C30Alkyl radical, C6-C14Aryl or C7-C30An aralkyl group,
wherein the substituents are selected from the group consisting of hydroxy, halogen, carboxy, -CF3、-NH2、C1-C6Alkoxy radical, C1-C30Alkyl or C6-C14Aryl, the alkyl and aryl segments of these substituents being optionally substituted by hydroxy, halogen, -CF3、-NH2Or C1-C6The alkoxy group is at least mono-substituted,
and wherein the radical R1、R2Or R3At least one of which is unsubstituted or at least monosubstituted C6-C14An aryl group, a heteroaryl group,
R4and R5Each independently of the other being hydrogen or unsubstituted or at least monosubstituted C1-C30Alkyl or C7-C30An aralkyl group,
wherein the substituents are selected from the group consisting of hydroxy, halogen, carboxy, -CF3、-NH2、C1-C6Alkoxy radical, C1-C30Alkyl or C6-C14Aryl, the alkyl and aryl segments of these substituents being optionally substituted by hydroxy, halogen, -CF3、-NH2Or C1-C6The alkoxy group is at least mono-substituted,
and wherein the bismuth-containing catalyst of the general formula (Ib) is defined as follows:
R6is an unsubstituted or at least mono-substituted adamantyl radical, wherein the substituents are selected from C1-C10Alkyl, hydroxy, halogen or-CF3，
And wherein:
i) the components (A), (B) and (C) being present separately from one another, or
ii) are mixed with each other in whole or at least in part.
2. The coating system of claim 1, wherein the bismuth-containing catalyst of component (C) is at least one bismuth-containing catalyst of the general formula (Ia), wherein
i)R1Is unsubstituted or at least monosubstituted C6-C14Aryl, wherein the substituents are selected from the group consisting of hydroxy, chloro, -CF3Or C1-C6An alkyl group, a carboxyl group,
preferably R1Is unsubstituted or at least mono-substituted phenyl, wherein the substituents are selected from the group consisting of hydroxy, -CF3Methyl or ethyl; more preferably R1Is unsubstituted or monosubstituted phenyl, wherein the substituent is in the para-position and is selected from-CF3Or a hydroxyl group; most preferred is R1Is phenyl, and/or
ii)R2And R3Each independently of the other being hydrogen or unsubstituted or at least monosubstituted C6-C14Aryl radical, wherein
The substituents being selected from hydroxy, chloro, -CF3Or C1-C6An alkyl group, a carboxyl group,
preferably R2And R3Independently of one another, are each hydrogen or phenyl; most preferred is R2And R3Are all hydrogen, and/or
iii)R4Is hydrogen or unsubstituted or at least monosubstituted C7-C30Aralkyl or C1-C10Alkyl, wherein the substituents are selected from the group consisting of hydroxy, chloro, -CF3Or C1-C6An alkyl group, a carboxyl group,
preferably R4Is hydrogen or unsubstituted or at least monosubstituted-CH2-aryl or C1-C6Alkyl, wherein the substituents are selected from the group consisting of hydroxy, chloro, -CF3Or C1-C6An alkyl group; more preferably R4Is hydrogen or unsubstituted or at least monosubstituted-CH2-phenyl or C1-C3Alkyl, wherein the substituents are selected from the group consisting of hydroxy, -CF3Methyl or ethyl; even more preferably R4Is hydrogen, C1-C3Alkyl or unsubstituted or monosubstituted-CH2-a phenyl group,wherein the substituents are in the para position and are selected from the group consisting of-CF3Or a hydroxyl group; most preferred is R4is-CH2-phenyl or ethyl, and/or
iv)R5Is unsubstituted or at least monosubstituted C1-C30Alkyl, wherein the substituents are selected from hydroxy, chloro or-CF3，
Preferably R5Is C1-C18An alkyl group; more preferably R5Is C3-C10An alkyl group; most preferred is R5Is C6-C8An alkyl group.
3. A coating system as claimed in claim 1 or 2, wherein in the coating system:
i) the polyol-containing compounds of component (A) are selected from polyacrylate polyols, polymethacrylate polyols, polyester polyols, polyurethane polyols and/or polysiloxane polyols, more particularly from polyacrylate polyols and/or polymethacrylate polyols, and/or
ii) the polyisocyanate group-containing compound of component (B) is selected from the group consisting of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylenedicyclohexyl diisocyanate, biuret dimer of the above diisocyanates, imino group of the above diisocyanatesDiazinediones and/or asymmetric trimers of the aforementioned diisocyanates.
4. A coating system as claimed in any one of claims 1 to 3, wherein the acid value of the polyol-containing compound of component (a) is not more than 9mg KOH/g of the corresponding polyol-containing compound, preferably not more than 7mg KOH/g of the corresponding polyol-containing compound, more particularly 0.5 to 5mg KOH/g of the corresponding polyol-containing compound.
5. A coating system as claimed in any of claims 1 to 4, comprising at least one further component (D) to (J) selected from hydroxyl-containing compounds (D), aminoplast resins and/or tris (alkoxycarbonylamino) triazines (E), coating additives (F), pigments (H), further fillers (I) and/or solvents (J),
wherein:
i) the components (D) to (J) being present separately from one another, or
ii) mixed in whole or at least in part with each other and/or with components (A) to (C),
the coating system preferably comprises at least one further component selected from hydroxyl-containing compounds (D), coating additives (F), pigments (H) and/or solvents (J).
6. The coating system of any one of claims 1-5, wherein:
i) the coating system is not aqueous, and/or
ii) components (A) and/or (B) each form a mixture with at least one solvent (J), but components (A) and (B) are present separately from one another, and/or
iii) the catalyst of component (C) is present in whole or at least in part in at least one of components (A) or (B) which are present separately from one another, preferably in component (A).
7. The coating system of any of claims 1 to 6, wherein the bismuth-containing catalyst of component (C) is at least one bismuth-containing catalyst of the general formula (Ib), wherein R6Is an unsubstituted or at least mono-substituted adamantyl radical, wherein the substituents are selected from C1-C6Alkyl or hydroxy; preferably R6Is unsubstituted or monosubstituted adamantyl, wherein the substituent is methyl or hydroxy; most preferred is R6Is adamantyl.
8. The coating system as claimed in any of claims 1 to 7, wherein the coating system is present as a complete mixture of components (A), (B) and (C) and optionally components (D) to (J).
9. A process for preparing the coating system as claimed in claim 8, wherein components (A), (B) and (C) and optionally components (D) to (J) are provided separately from one another and are subsequently mixed with one another,
wherein the mixing is preferably carried out at room temperature, wherein components (A) and (C) are mixed with one another beforehand and/or component (B) is added to component (A) or to the mixture comprising component (A).
10. A process for preparing polyurethanes by at least partial or complete curing, preferably by complete curing, of the coating system as claimed in claim 8.
11. The method of claim 10, wherein the polyurethane forms, or is at least a part of, a layer or coating, preferably a paint film.
12. The method according to claim 10 or 11, wherein the polyurethane comprises at least one pigment (H) and/or wherein the polyurethane is applied in the form of a layer to an undercolor paint film, optionally comprising at least one pigment (H), or to an optionally precoated substrate.
13. A process according to any one of claims 10 to 12, wherein the curing of the polyurethane is carried out at a temperature of from 20 to 80 ℃, preferably from 20 to 60 ℃, wherein the optional base paint film is optionally previously dried at a temperature of from 20 to 80 ℃.
14. Use of the coating system according to any one of claims 1 to 8 or the polyurethane prepared according to the process of any one of claims 10 to 13 as a coating, preferably a clear coating or a pigmented paint, in automotive finishing, for refinishing of coatings, for automotive refinishing, and/or for coating parts mounted in or on automobiles, plastic substrates, or commercial vehicles.
15. A process for producing coatings, wherein at least one coating system as claimed in any of claims 1 to 8 is applied to an optionally precoated substrate or base paint film.
16. The method according to claim 15, wherein the coating comprises a polyurethane obtained by at least partial or complete curing, preferably by complete curing, of the coating system.
17. Use of a bismuth-containing catalyst of the general formula (Ia) wherein:
R1、R2and R3Each independently of the other being hydrogen or unsubstituted or at least monosubstituted C1-C30Alkyl radical, C6-C14Aryl or C7-C30An aralkyl group,
wherein the substituents are selected from the group consisting of hydroxy, halogen, carboxy, -CF3、-NH2、C1-C6Alkoxy radical, C1-C30Alkyl or C6-C14Aryl, the alkyl and aryl segments of these substituents being optionally substituted by hydroxy, halogen, -CF3、-NH2Or C1-C6The alkoxy group is at least mono-substituted,
and wherein the radical R1、R2Or R3At least one of which is unsubstituted or at least monosubstituted C6-C14An aryl group, a heteroaryl group,
R4and R5Each independently of the other being hydrogen or unsubstituted or at least monosubstituted C1-C30Alkyl or C7-C30An aralkyl group,
wherein the substituents are selected from the group consisting of hydroxy, halogen, carboxy, -CF3、-NH2、C1-C6Alkoxy radical, C1-C30Alkyl or C6-C14Aryl, the alkyl and aryl segments of these substituents being optionally substituted by hydroxy, halogen, -CF3、-NH2Or C1-C6The alkoxy group is at least mono-substituted,
for use in a coating system according to any one of claims 1 to 8, for catalyzing a urethane reaction in a coating system, for preparing a polyurethane according to any one of claims 10 to 13, for preparing a paint, for repairing a paint finish, for automotive refinishing and/or for coating parts mounted in or on an automobile, plastic substrates or commercial vehicles.
18. A bismuth-containing catalyst of the general formula (Ia) wherein:
R1、R2and R3Each independently of the other being hydrogen or unsubstituted or at least monosubstituted C1-C30Alkyl radical, C6-C14Aryl or C7-C30An aralkyl group,
wherein the substituents are selected from the group consisting of hydroxy, halogen, carboxy, -CF3、-NH2、C1-C6Alkoxy radical, C1-C30Alkyl or C6-C14Aryl, the alkyl and aryl segments of these substituents being optionally substituted by hydroxy, halogen, -CF3、-NH2Or C1-C6The alkoxy group is at least mono-substituted,
and wherein the radical R1、R2Or R3At least one of which is unsubstituted or at least monosubstituted C6-C14An aryl group, a heteroaryl group,
R4and R5Each independently of the other being hydrogen or unsubstituted or at least monosubstituted C1-C30Alkyl or C7-C30An aralkyl group,
wherein the substituents are selected from the group consisting of hydroxy, halogen, carboxy, -CF3、-NH2、C1-C6Alkoxy radical, C1-C30Alkyl or C6-C14Aryl, the alkyl and aryl segments of these substituents being optionally substituted by hydroxy, halogen, -CF3、-NH2Or C1-C6The alkoxy group is at least monosubstituted.
19. Use of a bismuth-containing catalyst of the general formula (Ib) wherein:
R6is an unsubstituted or at least mono-substituted adamantyl radical, wherein the substituents are selected from C1-C10Alkyl, hydroxy, halogen or-CF3，
For use in a coating system according to any one of claims 1 to 8, for catalyzing a urethane reaction in a coating system, for preparing a polyurethane according to any one of claims 10 to 13, for preparing a paint, for repairing a paint finish, for automotive refinishing and/or for coating parts mounted in or on an automobile, plastic substrates or commercial vehicles.