Production of coatings

• US 4,578,426 A
• Filed: 06/25/1984
• Issued: 03/25/1986
• Est. Priority Date: 06/24/1983
• Status: Expired due to Term

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Lenz, Werner, Moeller, Dieter, Sander, Hans
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): Carrillo, A. L.
• Application Number:
  US06/624,293
• Time in Patent Office: 638 Days
• Field of Search: 525/123, 525/124, 525/131
• US Class Current: 525/131
• CPC Class Codes: C08G 18/4063 Mixtures of compounds of group C08G18/62 with other macromolecular compounds
• CPC Class Codes: C08G 18/6283 Polymers of nitrogen containing compounds having carbon-to-carbon double bonds C08G18/6262, C08G18/6266 take precedence
• CPC Class Codes: C08G 18/721 Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C09D 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen

Abstract

A process for the production of coatings based on reaction products of

(A) mixtures of

(A1) polyhydroxypolyacrylate resins obtained from hydroxylalkyl esters of acrylic acid and/or methacrylic acid, alkyl esters of acrylic acid and/or methacrylic acid, and one or more polymerizable, olefinically unsaturated nitrogen-containing heterocyclic compounds, with or without vinylaromatics, (meth)acrylamides and other monomers, and

(A2) polyesterpolyols with

(B) isocyanurate-containing polyisocyanates which may or may not contain biuret groups, have a functionality of from 2.5 to 6 and possess predominantly cycloaliphatically bonded isocyanate groups, some of which may be replaced by aliphatically bonded isocyanate groups.

The process is particularly useful for coating metal components.

Claims

1. A process for the production of a coating based on a reaction product of

(A) a mixture of

(A1) a polyhydroxypolyacrylate resin obtained from an ester of acrylic acid or methacrylic acid with a monofunctional aliphatic alcohol, or a mixture of esters of acrylic acid and mehtacrylic acid with monofuctional aliphatic alcohols, a monoester of acrylic acid or methacrylic acid with a polyfunctional aliphatic alcohol, or a mixture of monoesters of acrylic acid and methacrylic acid woth polyfunctional aliphatic alcohols, and other compolymerizable olefinically unsaturated monomers, and

(A2) a polyesterpolyol whcih is soluble in organic solvents with

(B) a polyisocyanate which is unblocked or partially or completely blocked with CH-, NH- or OH-acidic blocking agents, contains isocyanurate groups and may or may not contain biuret groups and has a functionality of from 2.5 to 6,

wherein the polyhydroxypolyacrylate resin (A1) used comprises from 40 to 99% by weight of hydroxyl-containing copolymers consisting of

(a) from 6 to 70% by weight of one or more esters of the formula ##STR9## where R is hydrogen or methyl and R'"'"' is a straight-chain or branched alkylene radical of 2 to 18 carbon atoms or alkylene of 7 to 17 carbon atoms which contains one, two or three cycloaliphatic groups,

(b) from 0 to 50% by weight of one or more hydroxylalkyl esters of acrylic acid or methacrylic acid of the formula ##STR10## where R is hydrogen or methyl and R" is the alkyl radical of a branched aliphatic carboxylic acid of 4 to 26 carbon atoms,

(c) from 10 to 50% by weight of one or more alkyl esters of acrylic acid or methacrylic acid, which form homopolymers having a glass transition temperature of from +5°

to +120°

C.,

(d) from 0 to 10% by weight of a vinylaromatic,

(e) from 10 to 60% by weight of one or more alkyl esters or alkylglycol esters of acrylic acid or methacrylic acid, which form homopolymers which have a glass transition temperature of from -80°

to +4.5°

C., the alkylglycol esters containing not more than 2 ether oxygen bridges,

(f) from 0 to 10% by weight of an acrylamide or a methacrylamide which may or may not be substituted at the amide nitrogen atom by one or two alkyl radicals of 1 to 8 carbon atoms which may or may not contain a carbonyl group, or by one or two phenyl radicals,

(g) from 1 to 25% by weight of one or more polymerizable olefinically unsaturated heterocyclic compodnds of the formula ##STR11## where R¹, R² and R³ are each hydrogen, methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, or R² and R³ can form an aromatic six-membered ring which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, which ring is fused to the heterocyclic ring and

(h) from 0 to 20% by weight of monomers which are not included under (a) to (g) and whose copolymerized radicals are inert to isocyanate groups, with the proviso that the sum of the percentages stated under (a) and (b) is from 6 to 70, the sum of the percentages stated under (c), (d) and (g) is from 11 to 60, and the sum of the percentages of the components stated under (a) to (h) is 100, the polyesterpolyol (A2) used comprises from 1 to 60% by weight of a hydroxyl-containing polyester which has a hydroxyl number of from 30 to 500 and an acid number of from 0 to 30 and is soluble in conventional surface coating solvents or solvent mixtures which are inert to isocyanates and essentially contain one or more aromatic, halogen, ether, ester or keto groups, or several different groups from amongst these, and this polyesterpolyol (A2) can also contain as much as 10% by weight of a polyfunctional alcohol having a molecular 1 weight of from 62 to 300, with the proviso that the sum of the percentages stated under (A1) and (A2) is 100, and the polyisocyanate (B) used, which contains isocyanurate groups, may or may not contain biuret groups and has a functionality of from 2.5 to 6 comprises (B1) from 60 to 100% by weight of an isocyanurate-containing polyisocyanate which possesses predominantly cycloaliphatically bonded isocyanate groups, and (B2) from 0 to 40% by weight of a polyisocyanate which contains biuret or isocyanurate groups or both biuret and isocyanurate groups and possesses predominantly aliphatically bonded isocyanate groups, with the proviso that the sum of the percentages stated under (B1) and (B2) is 100.

2. The process of claim 1, wherein the cycloaliphatic isocyanurate-containing polyisocyanate (B1) used is a product obtained from 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) as the diisocyanate monomer.

3. The process of claim 1, wherein a product which contains, as copolymerized units, from 60 to 99% by weight of isophorone diisocyanate and from 1 to 40% by weight of hexamethylene diisocyanate is used as the isocyanurate-containing polyisocyanate (B1) possessing predominantly cycloaliphatically bonded isocyanate groups.

4. The process of claim 3, wherein the polyisocyanate (B1) used contains, is copolymerized units, from 70 to 98% by weight of isophorone diisocyanate and from 2 to 30% by weight of hexamethylene diisocyanate.

5. The process as of claim 1, wherein a product obtained from hexamethylene diisocyanate, as the diisocyanate monomer, is used as the polyisocyanate (B2) which contains biuret groups and possesses predominantly aliphatically bonded isocyanate groups.

6. The process of claim 1, wherein a product obtained from hexamethylene diisocyanate, as the diisocyanate monomer, is used as the isocyanurate-containing polyisocyanate (B2) possessing predominantly aliphatically bonded cyanate groups.

7. The process of claim 1, wherein the hydroxyl number of the hydroxyl-containing copolymer (A1) is from 30to 250.

8. The process of claim 1, wherein the hydroxyl number of the hydroxyl-containing copolymer (A1) is from 50 to 150.

9. The process of claim 1, wherein hydroxyethyl acrylate or methacrylate, or a mixture of hydroxyethyl acrylate and hydroxyethyl methacrylate, is used as component (a) of the hydroxyl-containing copolymer.

10. The process of claim 1, wherein one or more compounds from the group consisting of butane-1,4-diol monacrylate, butane-1, 4-diol monomethacrylate, hexane-1, 6-diol monoacrylate and hexane-1, 6-diol monomethacrylate are used as component (a) of the hydroxyl-containing copolymer.

11. The process of claim 1, wherein from 2 to 20% by weight of component (g) is used for the hydroxyl-containing copolymer.

12. The process of claim 1, wherein the hydroxyl number of the soluble polyesterpolyol (A2) is from 50 to 400.

13. The process of claim 1, wherein the acid number of the soluble polyesterpolyol (A2) is from 0 to 15.

14. The process of claim 1, wherein the soluble polyesterpolyol (A2) is used in an amount of from 5 to 55% by weight, based on the total amount of the polyol (A).

15. The process of claim 1, wherein a branched polyesterol is used as component (A2).

16. The process of claim 1, wherein the hydroxyl number of the polyol mixture (A) is from 30 to 250.

17. The process of claim 1, wherein the hydroxyl number of the polyol mixture (A) is from 50 to 170.

18. The process of claim 1, wherein the ratio of the reactants (A) and (B) is cohsen so that the ratio of the number of equivalents of isocyanate groups which are unblocked or partially or completely blocked with CH-, NH- or OH-acidic blocking agents to the number of equivalents of reactive hydroxyl groups is from 0.25:

1 to 4;

1.

19. The process of claim 1, wherein a monofunctional ketoxime is used as the blocking agent for the partially or completely blocked polyisocyanate.

20. The process of claim 19, wherein dimethyl ketoxime or methyl ethyl ketoxime is used as the blocking agent for the polyisocyanate.