Self crosslinking polyurethanes and graft copolymers and based on polyurethane, for producing coating materials, adhesives and sealing masses

• US 6,602,972 B1
• Filed: 04/26/2002
• Issued: 08/05/2003
• Est. Priority Date: 11/06/1999
• Status: Expired due to Term

• Current Assignee: BASF Coatings AG (BASF SE)
• Original Assignee: BASF Coatings AG (BASF SE)
• Inventors: Angermüller, Harald, Wegner, Egon, Schwarte, Stephan
• Primary Examiner(s): GORR, RACHEL F
• Application Number:
  US10/111,730
• Time in Patent Office: 466 Days
• Field of Search: 528/45, 528/69, 528/71, 525/124, 525/63, 524/839, 524/840, 427/407.1
• US Class Current: 528/45
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/2865 Compounds having only one primary or secondary amino group; Ammonia
• CPC Class Codes: C08G 18/8077 Oximes
• CPC Class Codes: C08G 18/8108 having only one isocyanate or isothiocyanate group
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds

Abstract

Self crosslinking polyurethane comprising lateral or terminal ethenylarylene groups, produced by reacting a polyurethane pre-polymer with an adduct, obtained by reacting an ethenylarylene mono-isocyanate with a compound containing hydroxyl groups or amino groups such that at least one group that is reactive to isocyanate remains in the adduct. Also, a self crosslinking graft copolymer containing at least one (meth)acrylate copolymer and at least one polyurethane produced by dispersing at least one self crosslinking olefinically unsaturated polyurethane comprising lateral or terminal ethenylarylene groups and blocked isocyanate groups in an aqueous medium and by radical copolymerization of a mixture of a monomer comprising at least one functional group that is reactive to isocyanate with a monomer that can be copolymerised with the mixture.

Claims

1. A self-crosslinking polyurethane containing at least one ethenylarylene group, wherein the ethenylarylene group is at least one of pendant and terminal, comprising a reaction product of

(1) at least one polyurethane prepolymer containing at least one free and at least one blocked isocyanate group;

and

(2) at least one adduct comprising a reaction product of

(2.1) at least one ethenylarylene monoisocyanate, and

(2.2) at least one of i) a polyol, ii) a polyamine, and iii) a compound that contains at least one hydroxyl group and at least one amino group,

wherein at least one isocyanate-reactive group remains in the adduct.

2. The polyurethane of claim 1 wherein the ethenylarylene monoisocyanate has the general formula I:

3. The polyurethane of claim 1, wherein the polyurethane contains hydrophilic functional groups.

4. The polyurethane of claim 1, wherein the isocyanate groups still present are blocked.

5. The polyurethane of claim 1, wherein a blocking agent for the blocked polyisocyanate comprises at least one ketoxime.

13. A composition comprising the polyurethane of claim 1, wherein the composition is one of a sealing compound, an adhesive, and a coating material.

14. The coating material of claim 13, wherein the coating material is an aqueous basecoat material.

15. A multicoat paint system that is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, comprising a basecoat that is formed from the aqueous basecoat material of claim 14.

16. A process for producing a multicoat paint system, wherein the paint system is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, on a primed or unprimed substrate, comprising:

I) preparing a basecoat film by applying the aqueous basecoat material of claim 14 to the substrate,

(II) drying the basecoat film,

(III) preparing a clearcoat film by applying a clearcoat material to the basecoat film, and

(IV) jointly curing the basecoat film and the clearcoat film to give a basecoat and a clearcoat.

17. A process for producing a multicoat paint system, wherein the paint system is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, on a primed or unprimed substrate, comprising:

(I) preparing a surfacer film by applying a surfacer to the substrate,

(II) curing the surfacer film to give a surfacer coat,

(III) preparing a basecoat film by applying the aqueous basecoat material of claim 14 to the surfacer coat,

(IV) drying the basecoat film,

(V) preparing a clearcoat film by applying a clearcoat material to the basecoat film, and

(VI) jointly curing the basecoat film and the clearcoat film to give a basecoat and a clearcoat.

18. The process of claim 17, wherein the clearcoat material comprises a powder slurry clearcoat material.

19. A process for producing a multicoat paint system, wherein the paint system is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, on a primed or unprimed substrate, comprising:

(I) preparing a surfacer film by applying a surfacer to the substrate,

(II) drying the surfacer film,

(III) preparing a basecoat film by applying the aqueous basecoat material of claim 14 to the surfacer film,

(IV) drying the basecoat film,

(V) preparing a clearcoat film by applying a clearcoat material to the basecoat film, and

(VI) jointly curing the surfacer film, the basecoat film, and the clearcoat film to give a surfacer, a basecoat, and a clearcoat.

20. The process of claim 19, wherein the clearcoat material comprises a powder slurry clearcoat material.

6. A graft copolymer comprising

A) at least one (meth)acrylate copolymer and

B) at least one polyurethane prepared by a process comprising:

1) dispersing at least one self-crosslinking olefinically unsaturated polyurethane containing at least one ethenylarylene group, wherein the ethenylarylene group is at least one of pendant and terminal, and at least one blocked isocyanate group in an aqueous medium; and

2) free-radical copolymerizing a mixture of at least one monomer containing at least one isocyanate-reactive functional group and at least one monomer copolymerizable therewith in an emulsion in the presence of the polyurethane.

7. The graft copolymer of claim 6, wherein the ethenylarylene group has the general formula II:

8. The graft copolymer of claim 7, wherein the ethenylarylene group is attached to the polyurethane main chain by way of a divalent or trivalent linking radical III that contains at least one of a urethane group and a urea group.

9. The graft copolymer of claim 8, wherein the linking radical III contains a group that is at least one of the general formulae IIIa to IIIc

10. The graft copolymer of claim 6, wherein at least one of the grafted-on (meth)acrylate copolymer and the grafted polyurethane contain at least one hydrophilic functional group.

11. The graft copolymer of claim 10, wherein the grafted polyurethane contains at least one of a carboxylic acid group and a carboxylate group.

12. The graft copolymer of claim 6, wherein the polyurethane comprises a self-crosslinking polyurethane containing at least one ethenylarylene group, wherein the ethenylarylene group is at least one of pendant and terminal, comprising a reaction product of

(1) at least one polyurethane prepolymer containing at least one free and at least one blocked isocyanate group;

and

(2) at least one adduct comprising a reaction product of

(2.1) at least one ethenylarylene monoisocyanate, and

(2.2) at least one of i) a polyol, ii) a polyamine, and iii) a compound that contains at least one hydroxyl group and at least one amino group,

wherein at least one isocyanate-reactive group remains in the adduct.

21. A composition comprising the graft copolymer of claim 6, wherein the composition is one of a sealing compound, an adhesive, and a coating material.

22. The coating material of claim 21, wherein the coating material is an aqueous basecoat material.

23. A multicoat paint system that is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, comprising a basecoat that is formed from the aqueous basecoat material of claim 22.

24. A process for producing a multicoat paint system, wherein the paint system is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, on a primed or unprimed substrate, comprising:

I) preparing a basecoat film by applying the aqueous basecoat material of claim 22 to the substrate,

(II) drying the basecoat film,

(III) preparing a clearcoat film by applying a clearcoat material to the basecoat film, and

(IV) jointly curing the basecoat film and the clearcoat film to give a basecoat and a clearcoat.

25. A process for producing a multicoat paint system, wherein the paint system is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, on a primed or unprimed substrate, comprising:

(I) preparing a surfacer film by applying a surfacer to the substrate,

(II) curing the surfacer film to give a surfacer coat,

(III) preparing a basecoat film by applying the aqueous basecoat material of claim 22 to the surfacer coat,

(IV) drying the basecoat film,

(V) preparing a clearcoat film by applying a clearcoat material to the basecoat film, and

(VI) jointly curing the basecoat film and the clearcoat film to give a basecoat and a clearcoat.

26. The process of claim 25, wherein the clearcoat material comprises a powder slurry clearcoat material.

27. A process for producing a multicoat paint system, wherein the paint system is one of i) a color paint system, ii) an effect paint system, and iii) a color and effect paint system, on a primed or unprimed substrate, comprising:

(I) preparing a surfacer film by applying a surfacer to the substrate,

(II) drying the surfacer film,

(III) preparing a basecoat film by applying the aqueous basecoat material of claim 22 to the surfacer film,

(IV) drying the basecoat film,

(V) preparing a clearcoat film by applying a clearcoat material to the basecoat film, and

(VI) jointly curing the surfacer film, the basecoat film, and the clearcoat film to give a surfacer, a basecoat, and a clearcoat.

28. The process of claim 27, wherein the clearcoat material comprises a powder slurry clearcoat material.