Water-borne coating composition made from modified epoxy resin, polymeric acid and tertiary amine

• US 4,302,373 A
• Filed: 08/05/1980
• Issued: 11/24/1981
• Est. Priority Date: 08/05/1980
• Status: Expired due to Term

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Steinmetz, William H.
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): Lilling, Herbert J.
• Application Number:
  US06/175,397
• Time in Patent Office: 476 Days
• Field of Search: 260/29.4 UA, 260/29.4 R, 260/29.6 H, 260/29.3, 260/29.6 NR, 260/29.2 EP, 260/29.2 E, 260/29.6 B, 260/29.6 TA, 260/29.6 WA, 525/119, 525/531, 525/533
• US Class Current: 523/409
• CPC Class Codes: C08G 59/14 Polycondensates modified by chemical after-treatment
• CPC Class Codes: C08G 59/1433 with organic low-molecular-weight compounds
• CPC Class Codes: C08G 59/621 Phenols
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 5/4426 Esterified polyepoxides
• CPC Class Codes: Y10S 524/901 Electrodepositable compositions
• CPC Class Codes: Y10T 428/31522 Next to metal
• CPC Class Codes: Y10T 428/31529 Next to metal

Abstract

Water-borne reaction products of (a) carboxylfunctional polymers; (b) modified polyepoxides; and (c) tertiary amines are useful as film-forming components of coating compositions which can be spray-, flow-, dip-, roller-, or electro-coated. The coating compositions are useful as such or can be crosslinked with crosslinking agents such as a nitrogen resin and, when coated on metal and paper substrates, they provide coatings of improved properties, including a high degree of flexibility during machining and stamping of the coated articles, corrosion resistance, gloss, hydrolytic stability, and nonadulterating of foods and beverages in contact therewith.

Claims

1. A water-borne coating composition consisting essentially of liquid carrier and the product of the reaction in aqueous media of:

(A) not less than 50% by weight, based on the weight of (A) plus (B), of a modified polyepoxide in the form of an ester, an ether, or a phenolic hydroxyl which contained, prior to modification, on the average, two terminal 1,2-epoxy groups per molecule and had an epoxy equivalent weight of 750-5000, said modification being done by reacting at least about 25% of the epoxy groups with at least one of groups selected from monobasic acids to form esters, monohydric phenols to form ethers, or polyhydric phenols to form phenolic hydroxyl terminated polymers;

(B) a carboxyl-functional polymer in an amount sufficient to provide at least 1.25 equivalents of carboxyl groups, when the source of the carboxyl group is a monoprotic acid, and at least 2.0 equivalents of carboxyl groups, when the source of such groups is a diprotic acid, per equivalent of 1,2-epoxy groups in the epoxy resin, said polymer having a number average molecular weight (determined by gel permeation chromatography) of about 2,000-100,000 and an acid number of 100-500;

(C) at least 1.25 equivalents of a tertiary amine per equivalent of 1,2-epoxy groups in the epoxy resin, said tertiary amine being selected from the group consisting of R₁ R₂ R₃ N, pyridine, N-methylpyrrole, N-methyl piperidine, N-methyl pyrrolidine, N-methyl morpholine, and mixtures thereof and wherein R₁ and R₂ are substituted or unsubstituted monovalent alkyl groups containing one or two carbon atoms in the alkyl portion and R₃ is a substituted or unsubstituted monovalent alkyl group containing 1-4 carbon atoms; and

(D) optionally, 10-90% of the amount required for stoichiometric reaction with the carboxyl-functional polymer of (B) of at least one primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide;

wherein for increasing ratios of carboxyl groups to 1,2-epoxy groups, the amount of amine is increased to keep the carboxyl-functional polymer water dispersible,

in which reaction product at least about 50% of the epoxide groups on the modified polyepoxides are in the form of quaternary ammonium salts.

2. The composition of claim 1 wherein at least about 75% of the epoxide groups on the modified polyepoxides are in the form of quaternary ammonium salts.

3. The composition of claim 1 wherein components (A), (B) and (C) comprise about 0.1-50% by weight of the coating composition and the remainder is comprised of the liquid carrier which is water and, optionally, organic liquid in a volume ratio of from 70:

30 to all water.

4. The composition of claim 2 wherein the liquid carrier is water and organic liquid in a volume ratio of about 80:

20.

5. The composition of claim 1 wherein the group selected for the modification of the polyepoxide is at least one of pelargonic, stearic, para tertiary butyl benzoic, 2-ethyl hexoic, caprylic or benzoic acid.

6. The composition of claim 5 wherein the group selected for the modification of the polyepoxide is benzoic acid.

7. The composition of claim 1 wherein the group selected for the modification of the polyepoxide is at least one of monohydric phenols and hydrocarbon substituted monohydric phenols with 1-10 carbon atoms in the substituent.

8. The composition of claim 7 wherein the phenol selected is nonylphenol.

9. The composition of claim 1 wherein the group selected for the modification of the polyepoxide is at least one of polyhydric phenols.

10. The composition of claim 9 wherein the polyhydric phenol selected is bisphenol A.

11. The composition of claim 1 wherein the polyepoxide, before modification, has an epoxy equivalent weight of 1,500-4,000.

12. The composition of claim 1 wherein the carboxyl-functional polymer has an acid number of 150-350.

13. The composition of claim 1 wherein the carboxyl-functional polymer has a number average molecular weight of 3,000-40,000.

14. The composition of claim 1 wherein said carboxyl-functional polymer is present in an amount sufficient to provide at least 1.75 equivalents of carboxyl groups, when the source of the carboxyl group is a monoprotic acid, and at least 2.5 equivalents of carboxyl groups, when the source of such groups is a diprotic acid, per equivalent of 1,2-epoxy groups in the epoxy resin.

15. The composition of claim 14 wherein said carboxyl-functional polymer is present in an amount sufficient to provide 1.5-2.5 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups and said tertiary amine of (C) is present in the amount of 2.0-2.5 equivalents per equivalent of 1,2-epoxy groups.

16. The composition of claim 1 wherein said carboxyl-functional polymer is present in an amount sufficient to provide no more than 6.0 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin.

17. The composition of claim 1 wherein said carboxyl-functional polymer is a polymer of at least one α

,β

-ethylenically unsaturated monomer and at least one α

,β

-ethylenically unsaturated acid.

18. The composition of claim 17 wherein said α

,β

-ethylenically unsaturated acid is represented by the structures;

##STR9## wherein R is hydrogen or an alkyl radical of 1-6 carbon atoms, R₁ and R₂ are hydrogen, an alkyl radical of 1-8 carbon atoms, halogen, cycloalkyl of 3-7 carbon atoms or phenyl, and R₃ is an alkylene radical of 1-6 carbon atoms;

or

half-esters thereof with alkanols of 1-8 carbon atoms.

19. The composition of claim 18 wherein said α

,β

-ethylenically unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.

20. The composition of claim 17 wherein said α

,β

-ethylenically unsaturated monomer is selected from the group consisting of ##STR10## where R, R₁, R₂ and R₃ are hydrogen or an alkyl radical of 1-5 carbon atoms;

##STR11## where R and R₁ are hydrogen, an alkyl radical of 1-18 carbon atoms, tolyl, benzyl or phenyl, and R₂ is hydrogen or methyl;

(c) esters of acrylic acid, methacrylic acid or mixtures thereof with alkanols of 1-16 carbon atoms;

(d) a mixture of up to 20% of said polymer, of hydroxyalkyl (meth)acrylate with at least one of (a), (b) and (c); and

(e) a mixture of up to 20% of said polymer of (meth)acrylamide or N-alkoxymethyl (meth)acrylamide with at least one of (a), (b) and (c).

21. The composition of claim 20 wherein the α

,β

-ethylenically unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.

22. The composition of claim 1 wherein said epoxy resin is 50-90% by weight of (A) plus (B).

23. The composition of claim 1 wherein the tertiary amine of (C) R₁ R₂ R₃ N is selected from the group consisting of trimethyl amine, dimethyl ethanol amine, methyl diethanol amine, diethyl methyl amine, ethyl methyl ethanol amine, dimethyl benzyl amine, dimethyl propyl amine, dimethyl ethyl amine, dimethyl 3-hydroxy-1-propyl amine, dimethyl 2-hydroxy-1-propyl amine, dimethyl 1-hydroxy-2-propyl amine, and mixtures thereof.

24. The composition of claim 23 wherein the tertiary amine of (C) is dimethyl ethanol amine.

25. The composition of claim 1 additionally containing a crosslinking agent which is at least one of phenol formaldehyde and a nitrogen resin.

26. An article coated with a cured coating based on the composition of claim 1.

27. An article coated with a cured coating based on the composition of claim 1 additionally containing a crosslinking agent which is at least one of phenol formaldehyde and a nitrogen resin.

28. A coating composition of claim 1 wherein components (A), (B) and (C) are capable of forming a hydrogel structure.