Heat-curing sealant compositions having fast skin formation and high tensile strength

Patent metadata

Field	Value
Publication number	US-9512341-B2
Application number	US-201113997294-A
Country	US
Kind code	B2
Filing date	Dec 19, 2011
Priority date	Dec 23, 2010
Publication date	Dec 6, 2016
Grant date	Dec 6, 2016

Abstract

The present invention relates to heat-curing sealant compositions including at least epoxy resin, dicyanodiamide or an amine complex of a Lewis acid, polyurethane polymer (PUP) containing isocyanate groups and polyaldimine. These single component sealant compositions are characterized by a rapid skin formation and high tensile strength. Because of the short skin formation time, said compositions are optimally suitable for use as sealants in autobody work because they can be excellently layered on top of same.

First claim

The invention claimed is:

1. A heat-curing sealant composition, comprising:
at least one epoxy resin (A) with an average of more than one epoxy group per molecule;
at least one heat-activatable curing agent or accelerator (B) selected from the group consisting of dicyanodiamide and an amine complex of a Lewis acid;
at least one polyurethane polymer (PUP) containing isocyanate groups; and
at least one polyaldimine (PA);
wherein:
a weight ratio of the epoxy resin (A) to the polyurethane polymer (PUP) containing isocyanate groups is in a range between 0.1:1 and 0.5:1;
the polyurethane polymer (PUP) is obtained from a reaction between at least one polyol and at least one polyisocyanate; and
the polyol has an average molecular weight of 250 to 30,000 g/mol.

2. The heat-curing sealant composition according to claim 1 , wherein the weight ratio of the epoxy resin (A) to the polyurethane polymer (PUP) containing isocyanate groups is in a range between 0.15:1 and 0.4:1.

3. The heat-curing sealant composition according to claim 1 , wherein the polyaldimine (PA) is present in the sealant composition in an amount such that a ratio of a number of aldimino groups to a number of isocyanate groups has a value in a range of from 0.2:1 to 0.8:1.

4. The heat-curing sealant composition according to claim 1 , wherein the polyaldimine (PA) does not have a hydrogen atom on the carbon atom in α-position to the carbon of the aldimino group.

5. The heat-curing sealant composition according to claim 1 , wherein the polyaldimine (PA) has formula (I)

wherein:
A represents a radical of an amine after removal of n primary aliphatic amino groups and does not contain any active hydrogen atoms,
n represents 2 or 3,
R 1 and R 2 either,
independently of one another, each represents a monovalent hydrocarbon radical, each having 1 to 12 carbon atoms, or
together represent a divalent hydrocarbon radical having 4 to 12 carbon atoms, which is part of an optionally substituted carbocyclic ring having 5 to 8 carbon atoms,

R 3 represents a hydrogen atom, an alkyl group, an aralkyl group, or an alkoxycarbonyl group;
R 4 and R 5 either,
independently of one another, each represents a monovalent aliphatic, cycloaliphatic, or araliphatic radical having 1 to 20 carbon atoms, optionally containing heteroatoms in a form of an ether oxygen or a tertiary amine nitrogen, or
together represent a divalent aliphatic radical having 3 to 20 carbon atoms, which is part of an optionally substituted heterocyclic ring having 5 to 8 ring atoms, the heterocyclic ring optionally containing, in addition to the nitrogen atom, further heteroatoms in a form of ether oxygen or tertiary amine nitrogen.

6. The heat-curing sealant composition according to claim 1 , wherein the dicyanodiamide has an average particle size of less than 12 μm.

7. The heat-curing sealant composition according to claim 1 , further comprising at least one catalyst (KA) that accelerates hydrolysis of aldimino groups.

8. The heat-curing sealant composition according to claim 1 , further comprising at least one heat-activatable curing agent or accelerator (B′) that is selected from the group consisting of guanamines, guanidines, aminoguanidines, derivatives thereof, substituted ureas, imidazoles, imidazole salts, imidazolines, amidoamines, and iminoamines.

9. The heat-curing sealant composition according to claim 8 , wherein the curing agent or accelerator (B′) is an amidoamine with a primary amino group, which can be obtained by reacting phthalic anhydride and a polyamine with primary amino groups.

10. A coated substrate obtained by applying the heat-curing sealant composition according to claim 1 to a surface of a substrate.

11. A method for sealing, comprising:
i) applying the heat-curing sealant composition according to claim 1 to a substrate so that a portion of a surface of the sealant composition is in contact with air;
ii) forming a skin on the surface of the sealant composition that is in contact with the air;
iii) heating the sealant composition to a temperature of from 160 to 220° C. to form a fully cured sealant composition.

12. The method for sealing according to claim 11 , further comprising a step iia) between steps ii) and iii):
iia) applying a paint to the sealant composition.

13. The method according to claim 11 , wherein step iii) is performed in a CDC oven.

14. The method according to claim 11 , wherein the heat-curing sealant composition in step i) is applied to or into a gap, which is bordered by a surface of the substrate and a surface of a second substrate.

15. A sealed article obtained by the method according to claim 11 .

16. The heat-curing sealant composition according to claim 1 , wherein the weight ratio of the epoxy resin (A) to the polyurethane polymer (PUP) containing isocyanate groups is in a range between 0.2:1 and 0.3:1.

17. The heat-curing sealant composition according to claim 1 , wherein the polyaldimine (PA) is present in the sealant composition in an amount such that a ratio of a number of aldimino groups to a number of isocyanate groups has a value in a range of from 0.3:1 to 0.7:1.

18. The heat-curing sealant composition according to claim 1 , wherein the poly has an average molecular weight of 400 to 20,000 g/mol.

19. A heat-curing sealant composition, comprising:
at least one epoxy resin (A) with an average of more than one epoxy group per molecule;
at least one heat-activatable curing agent or accelerator (B) selected from the group consisting of dicyanodiamide and an amine complex of a Lewis acid;
at least one polyurethane polymer (PUP) containing isocyanate groups; and
at least one polyaldimine (PA);
wherein:
a weight ratio of the epoxy resin (A) to the polyurethane polymer (PUP) containing isocyanate groups is in a range between 0.1:1 and 0.5:1;
the polyurethane polymer (PUP) is obtained from a reaction of at least one polyhydrocarbon polyol and at least one polyisocyanate; and
the polyhydrocarbon polyol is selected from the group consisting of polyhydroxy functional polyolefins and polyhydroxy functional polymers of dienes.

20. The heat-curing sealant composition according to claim 19 , wherein the polyhydrocarbon polyol has an average molecular weight of 250 to 30,000 g/mol.

Assignees

• Voci Antonio
• Kramer Andreas
• Schulenburg Jan Olaf
• Gutgsell Michael
• Burckhardt Urs
• Sika Tech Ag

Inventors

• Voci Antonio
• Kramer Andreas
• Schulenburg Jan Olaf
• Gutgsell Michael
• Burckhardt Urs

Classifications

• C09J163/00 Primary

  Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins · CPC title

• C09D175/08

  from polyethers · CPC title

• C25D13/20

  Pretreatment · CPC title

• C09J175/04 Primary

  Polyurethanes · CPC title

• B05D3/02

  by baking {(B05D3/04 takes precedence)} · CPC title