Weldable coating compositions

• US 4,186,036 A
• Filed: 08/25/1978
• Issued: 01/29/1980
• Est. Priority Date: 08/25/1978
• Status: Expired due to Term

• Current Assignee: Hewitt-Robins Corp.
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Elms, William J., Weitzel, Steven A.
• Primary Examiner(s): Kendall, Ralph S.
• Application Number:
  US05/937,012
• Time in Patent Office: 522 Days
• Field of Search: 148/6.15 R, 148/6.2, 427/386, 427/388 A, 260/37 EP, 260/830 TW, 260/47 EP, 428/472, 428/416, 252/512
• US Class Current: 428/416
• CPC Class Codes: B05D 2701/40 withstanding welding
• CPC Class Codes: B05D 7/14 to metal, e.g. car bodies involving a chemical reaction between the metal and the coating C23
• CPC Class Codes: C09D 5/106 containing Zn
• CPC Class Codes: Y10T 428/31522 Next to metal
• CPC Class Codes: Y10T 428/31529 Next to metal

Abstract

An improvement in a weldable coating for metallic substrates containing a high molecular weight epoxy or phenoxy resin, an electroconductive pigment such as zinc and a diluent such as a glycol ether wherein the improvement resides in replacing at least about 70 weight percent of said resin with a composition containing a low molecular weight epoxy resin such as the diglycidyl ether of bisphenol A, a phenolic hydroxyl-containing compound such as a phenolic hydroxyl terminated adduct of a diglycidyl ether of a diphenolic compound such as bisphenol A and a catalyst for effecting the reaction between the epoxy resin and the adduct.

Claims

1. In a weldable coating composition for metallic substrates which comprises in admixture a high molecular weight epoxy or phenoxy resin, an electroconductive pigment and an diluent;

the improvement which comprises replacing at least about epoxy or phenoxy resin with a composition consisting essentially of;

(A) a low molecular weight epoxy resin or mixture of epoxy resins having an average of more than one vicinal epoxy group per molecule;

(B) a hydroxyl-containing or thiol-containing material or mixture of such materials which is (1) a polyhydric phenolic or thiophenolic compound or (2) the product of reacting (a) a low molecular weight epoxy resin having an average of more than one vicinal epoxy group per molecule with (b) a polyhydric phenolic or thiophenolic compound wherein the phenolic hydroxyl or thiol to epoxy equivalent ratio is from about 2;

1 to about 12;

1;

(C) a catalytic quantity of a catalyst for effecting the reaction between (A) and (B);

wherein (A) and (B) are present in quantities such that the hydroxyl or thiol to epoxy equivalent ratio is from about 0.5;

1 to about 1.1;

1.

2. The coating composition of claim 1 wherein Components (A) and (B-2a) are glycidyl ethers of a polyhydric aromatic compound and Component (B) is the reaction product of Component (B-2a) with Component (B-2b) and wherein the substrate is a ferrous metal.

3. The coating composition of claim 2 wherein at least about 75 percent by weight of the high molecular weight epoxy and phenoxy resin is replaced and Components (B-1) and (B-2b) are phenolic hydroxyl-containing compounds.

4. The coating composition of claim 3 wherein Components (A) and (B-2a) are represented by the formula ##STR10## wherein Z is represented by the formula ##STR11## having from about 1 to about 12 carbon atoms, ##STR12## independently hydrogen, chlorine or bromine;

n has a value of zero or one;

x has an average value of from about 0 to about 4;

the phenolic hydroxyl;

epoxy equivalent ratio in Component (B) is from about 3;

1 to about 8;

1 and Components (A) and (B) are present in quantities such that the phenolic hydroxyl to epoxy equivalent ratio is from about 0.75;

1 to about 1;

1 and the electroconductive pigment is zinc.

5. The coating composition of claim 4 wherein the low molecular weight epoxy resin of Components (A) and (B-2a) are that wherein X is hydrogen, n is 1, x has an average value of from about 0.02 to about 0.75, A is ##STR13## and the phenolic hydroxyl:

epoxy equivalent ratio in Component (B) is from about 5.5;

1 to about 6.5;

1.

6. The coating composition of claim 5 wherein the epoxy resin of Component A and Component (B-2a) are the same;

wherein Component (B-2b) is bisphenol A and Component (C) is 2-methylimidazole.

7. A weldable coating composition comprising:

(A) a low molecular weight epoxy resin or mixtures of thereof having an average of more than one vicinal epoxy group per molecule;

(B) a hydroxyl-containing or thiol-containing material or mixture of such materials which is (1) a polyhydric phenolic or thiophenolic compound or (2) the product of reacting (a) a low molecular weight epoxy resin having an average of more than one vicinal epoxy group per molecule with (b) a polyhydric phenolic or thiophenolic compound wherein the phenolic hydroxyl or thiol to epoxy equivalent ratio is from about 2;

1 to about 12;

1;

(C) a catalytic quantity of a catalyst for effecting the reaction between (A) and (B);

(D) an electroconductive pigment and;

wherein the equivalent ratio of phenolic hydroxyl or thiol groups in (B) to epoxy groups in (A) is from about 0.5;

1 to about 1.1;

1; and

(E) a diluent or solvent in an amount of from about 2% to about 40% by weight of the total composition.

8. The coating composition of claim 7 wherein Component (A), Component (B-2a) are glycidyl ethers of polyhydric aromatic compounds and Components (B-1) and (B-26) are phenolic hydroxyl-containing compounds.

9. The coating composition of claim 8 wherein Components (A) and (B-2a) are represented by the formula ##STR14## wherein Z is represented by the formula ##STR15## from about 1 to about 12 carbon atoms, ##STR16## independently hydrogen, chlorine or bromine;

n has a value of zero or one;

x has an average value of from about 0 to about 4;

the phenolic hydroxyl;

epoxy equivalent ratio in Component (B) is from about 3;

1 to about 8;

1 and electroconductive pigment is zinc.

10. The coating composition of claim 9 wherein the phenolic hydroxyl:

epoxy equivalent ratio in Component (B) is from about 5.5;

1 to about 6.5;

1 and Components (A) and (B) are present in quantities such that the phenolic hydroxyl to epoxy equivalent ratio is from about 0.75;

1 to about 1;

1, the electroconductive pigment is zinc and Component (B) is present in quantities of from about 5% to about 20%.

11. The coating composition of claim 10 wherein the low molecular weight epoxy resin of Components (A) and (B-2a) are that wherein X is hydrogen, n is 1, x has an average value of from about 0.02 to about 0.75 and A is ##STR17##

12. The coating composition of claim 11 wherein the epoxy resin of Component A and Component (B-2a) are the same;

Component (B-2b) is bisphenol A and Component (C) is 2-methylimidazole.

13. The coating compositions of claims 7, 8, 9, 10, 11, or 12 which contain additionally up to about 25 weight percent based upon the weight of Components (A) and (B) of an epoxy resin or a phenoxy resin having a weight average molecular weight of at least about 15,000.

14. The coating composition of claim 13 wherein said epoxy or phenoxy resin has a weight average molecular weight of at least about 30,000.

15. A method for preparing a coated article which comprises applying to a metallic substrate a weldable coating, which process comprises:

(1) cleaning a non-precoated metallic substrate so as to remove grease, oil dirt and the like;

(2) applying to the resultant cleaned metal from step 1, a coating composition as described in claims 7, 8, 9, 10, 11 or 12 and optionally, additionally up to about 25 weight percent based upon the weight of Components (A) and (B) of an epoxy or phenoxy resin having a weight average molecular weight of at least about 15,000; and

(3) heating the coated metallic substrate from step 2 at a sufficient temperature for a sufficient time to cure the coating.

16. The method of claim 15 wherein said substrate is a ferrous metal and wherein said epoxy of phenoxy resin has a weight average molecular weight of at least about 30,000.

17. The method of claim 16 wherein said substrate is steel.

18. The method of claim 17 wherein in step (1) the substrate is also etched with an inorganic etching agent after said cleaning.

19. The method of claim 18 wherein an electroconductive pigment-free coating containing chromate and/or phosphate ions is applied between steps (1) and (2).

20. The method of claim 17 wherein an electroconductive pigment-free coating containing chromate and/or phosphate ions is applied between steps (1) and (2).

21. The method of claim 16 wherein in step (1) the substrate is also etched with an inorganic etching agent after said cleaning.

22. The method of claim 21 wherein an electroconductive pigment-free coating containing chromate and/or phosphate ions is applied between steps (1) and (2).

23. The method of claim 16 wherein an electroconductive pigment-free coating containing chromate and/or phosphate ions is applied between steps (1) and (2).

24. An article coated by the method of claim 15.

25. An article coated by the method of claim 17.

26. An article coated by the method of claim 19.

27. An article coated by the method of claim 23.