Curing agent composition

Patent metadata

Field	Value
Publication number	US-10155841-B2
Application number	US-201315037200-A
Country	US
Kind code	B2
Filing date	Nov 26, 2013
Priority date	Nov 26, 2013
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

A curing agent composition for curing an epoxy compound comprising a mixture of: (a) at least one natural oil phenol compound, (b) at least one phenolic resin compound, and (c) at least one amine curing agent; in particular, wherein the curing agent composition is adapted for providing a curable epoxy resin composition with a Shore D hardness build-up greater than 0 after within 2 hours at 23±2° C. and having an anti-blushing property such that 30 minutes after scratching a film cured on a glass panel, the film is at least 50 percent transparent; a curable composition including (I) at least one epoxy compound; and (II) the above curing agent composition, and a thermoset prepared from the above curable composition.

First claim

The invention claimed is:

1. A curing agent composition for curing an epoxy compound comprising, based on the total weight of the curing agent composition, a mixture of:
(a) about 0.1 to about 50 wt % of at least one natural oil phenol compound,
(b) about 0.1 to about 50 wt % of at least one phenolic resin compound, and
(c) about 40 to about 99 wt % of at least one amine crosslinking agent comprising an aliphatic amine, a polyether amine, an aromatic amine, a cycloaliphatic amine, a piperazine, or a mixture thereof;
wherein epoxy resin compounds are excluded from the curing agent composition.

2. The curing agent composition of claim 1 , wherein the at least one natural oil phenol compound is a natural oil phenol compound comprising three different functional groups including an aromatic ring, at least one hydroxyl group attached to at least one position on the aromatic ring and an alkyl chain from C 9 -C 20 attached to at least one position on the aromatic ring.

3. The curing agent composition of claim 1 , wherein the natural oil phenol compound is selected from the group consisting of a phenolic lipid, urushiol, cardol, cardanol, or mixtures thereof.

4. The curing agent composition of claim 1 , wherein the at least one natural oil phenol compound is at least one cardanol or cardol from cashew nutshell oil; and the cardanol or cardol is one or more of the compounds illustrated by Structures (I) and (I) as follows:

where n, in Structures (I) and (II) above, is 0, 2, 4 or 6, which depends upon whether the side chain is saturated or unsaturated.

5. The curing agent composition of claim 1 , wherein the at least one phenolic resin compound is a phenol formaldehyde resin obtained by reacting a phenol or a substituted phenol with formaldehyde.

6. The curing agent composition of claim 1 , wherein the at least one phenolic resin compound is a resol novolac, phenol novolac, cresol novolac, bisphenol-A novolac, a multi-functional novolac, or a mixture thereof.

7. The curing agent composition of claim 1 , wherein the at least one phenolic resin compound is a phenol novolac illustrated by Structure (III) as follows:

where, in Structure (III), R is hydrogen or a C 1 -C 3 alkyl; and n is in the range of 1<n≤2.

8. The curing agent composition of claim 1 , wherein a curable epoxy resin composition comprising the curing agent composition has a Shore D hardness build-up greater than 0 after within 2 hours at 23±2° C. and has an anti-blushing property such that 30 minutes after scratching a film comprising the curable epoxy resin composition cured on a glass panel, the film is at least 50 percent transparent.

9. A two-component curable composition comprising:
as component (I), about 30 to about 95 wt %, based on the total weight of the curable composition, of at least one epoxy compound; and
as component (II), about 5 to about 70 wt % based on the total weight of the curable composition, of at least one curing agent composition, wherein the curing agent composition comprises, based on the total weight of the curing agent composition, a mixture of:
(a) about 0.1 to about 50 wt % of at least one natural oil phenol compound,
(b) about 0.1 to about 50 wt % of at least one phenolic resin compound, and
(c) about 40 to about 99 wt % of at least one amine crosslinking agent comprising an aliphatic amine, a polyether amine, an aromatic amine, a cycloaliphatic amine, a piperazine, or a mixture thereof,
wherein epoxy resin compounds are excluded from component (II).

10. The two-component curable composition of claim 9 , wherein the epoxide compound comprises a liquid epoxy resin.

11. The two-component curable composition of claim 9 , including at least one curing catalyst.

12. The two-component curable composition of claim 9 , including a second curing agent separate and different from the curing agent composition (II), a filler, a reactive diluent, a flexibilizing agent, a processing aide, a toughening agent, or a mixture thereof.

13. The two-component curable composition of claim 9 comprising:
as component (I), about 60 to about 80 wt %, based on the total weight of the curable composition, of the at least one epoxy compound; and
as component (II), about 20 to about 40 wt %, based on the total weight of the curable composition, of the at least one curing agent composition, wherein the curing agent composition comprises, based on the total weight of the curing agent composition, a mixture of:
(a) about 5 to about 30 wt % of the at least one natural oil phenol compound,
(b) about 5 to about 35 wt % of the at least one phenolic resin compound, and
(c) about 55 to about 85 wt % of the at least one amine crosslinking agent;
wherein epoxy resin compounds are excluded from component (II).

14. A process for preparing a curing agent composition comprising admixing, based on the total weight of the curing agent composition:
(a) about 0.1 to about 50 wt % of at least one natural oil phenol compound,
(b) about 0.1 to about 50 wt % of at least one phenolic resin compound, and
(c) about 40 to about 99 wt % of at least one amine crosslinking agent comprising an aliphatic amine, a polyether amine, an aromatic amine, a cycloaliphatic amine, a piperazine, or a mixture thereof;
wherein epoxy resin compounds are excluded from the curing agent composition.

15. The process of claim 14 , wherein a curable epoxy resin composition comprising the curing agent composition has a Shore D hardness build-up greater than 0 after within 2 hours at 23±2° C. and has an anti-blushing property such that 30 minutes after scratching a film cured on a glass panel, the film is at least 50 percent transparent.

16. A process for preparing a curable composition comprising admixing:
(I) at least one epoxy compound; and
(II) at least one curing agent composition, wherein the curing agent composition comprises, based on the total weight of the curing agent composition, a mixture of:
(IIa) about 0.1 to about 50 wt % of at least one natural oil phenol compound,
(IIb) about 0.1 to about 50 wt % of at least one phenolic resin compound, and
(IIc) about 40 to about 99 wt % of at least one amine curing agent comprising an aliphatic amine, a polyether amine, an aromatic amine, a cycloaliphatic amine, a piperazine, or a mixture thereof;
wherein epoxy resin compounds are excluded from the curing agent composition.

17. A process for preparing a thermoset comprising:
(i) admixing:
(I) at least one epoxy compound; and
(II) at least one curing agent composition, wherein the curing agent composition comprises, based on the total weight of the curing agent composition, a mixture of:
(IIa) about 0.1 to about 50 wt % of at least one natural oil phenol compound,
(IIb) about 0.1 to about 50 wt % of at least one phenolic resin compound, and
(IIc) about 40 to about 99 wt % of at least one amine crosslinking agent comprising an aliphatic amine, a polyether amine, an aromatic amine, a cycloaliphatic amine, a piperazine, or a mixture thereof;

wherein epoxy resin compounds are excluded from the curing agent composition; and

(ii) curing the mixture of (I) and (II) of step (i).

18. The process of claim 17 , wherein the curing step (ii) is carried out at a temperature of from about 10° C. to about 200° C.

19. A cured thermoset article prepared by the process of claim

Assignees

• Dow Global Technologies Llc
• Dow Chemical China Investment Company Ltd

Inventors

• Chen Cuiping
• Zhang Yi

Classifications

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08G59/50

  Amines · CPC title

• C08G59/621 Primary

  Phenols · CPC title

• C08G59/56

  together with other curing agents · CPC title