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

Claim 2

A water-borne coating composition consisting essentially of liquid carrier and the reaction product of: (A) not less than 50% by weight, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 750-5000; (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 mono-protic 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 weight average molecular weight (determined by light scattering) of about 10000-160000 and an acid number of 100-500; (C) an aqueous solution of 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 R 1 R 2 R 3 N, pyridine, N-methylpyrrole, N-methyl piperidine, N-methyl pyrrolidine, N-methyl morpholine, and mixtures thereof and wherein R 1 and R 2 are substituted or unsubstituted monovalent alkyl groups containing one or two carbon atoms in the alkyl portion and R 3 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 Y is at least about 6+0.75(2 X ) wherein Y is the milliequivalent of carboxyl groups neutralized with primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide per 100 grams of acid polymer plus epoxy, and X is the epoxy equivalent weight divided by 1000; and 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.

Claim 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.

Claim 4

The composition of claim 2 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 mono-protic 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.

Claim 5

The composition of claim 2 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.

Claim 6

The composition of claim 2 wherein said epoxy resin has an epoxy equivalent weight of 1500-4000.

Claim 7

The composition of claim 2 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.

Claim 8

The composition of claim 6 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, R 1 and R 2 are hydrogen, an alkyl radical of 1-8 carbon atoms, halogen, cycloalkyl of 3-7 carbon atoms or phenyl, and R 3 is an alkylene radical of 1-6 carbon atoms; or half-esters thereof with alkanols of 1-8 carbon atoms.

Claim 9

The composition of claim 7 wherein said α,β-ethylenically unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.

Claim 10

The composition of claim 6 wherein said carboxyl-functional polymer has an acid number of 100-150.

Claim 11

The composition of claim 6 wherein said carboxyl-functional polymer has an acid number of 150-250.

Claim 12

The composition of claim 3 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.

Claim 13

The composition of claim 6 wherein said α,β-ethylenically unsaturated monomer is selected from the group consisting of ##STR10## where R, R 1 , R 2 and R 3 are hydrogen or an alkyl radical of 1-5 carbon atoms; ##STR11## where R and R 1 are hydrogen, an alkyl radical of 1-18 carbon atoms, tolyl, benzyl or phenyl, and R 2 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).

Claim 14

The composition of claim 12 wherein the α,β-ethylenically unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.

Claim 15

The composition of claim 13 wherein said carboxyl-functional polymer has the composition of styrene/acrylonitrile/α,β-ethylenically unsaturated acid//45-84/10-30/15-54.

Claim 16

The composition of claim 13 wherein said carboxyl-functional polymer has the composition of styrene/acrylonitrile/alkyl (meth)acrylate/α,β-ethylenically unsaturated acid//30-60/10-30/10-50/15-54.

Claim 17

The composition of claim 13 wherein said carboxyl-functional polymer has the composition of styrene/alkyl (meth)acrylate/α,β-ethylenically unsaturated acid//20-70/10-60/15-54.

Claim 18

The composition of claim 13 wherein said carboxyl-functional polymer has the composition of methyl methacrylate/alkyl (meth)acrylate/α,β-ethylenically unsaturated acid//20-40/30-74/15-54.

Claim 19

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

Claim 20

The composition of claim 2 wherein the tertiary amine of (C) R 1 R 2 R 3 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.

Claim 21

The composition of claim 13 wherein the tertiary amine of (C) is dimethyl ethanol amine.

Claim 22

The composition of claim 1 consisting essentially of liquid carrier and the reaction product of: (A) not less than 65% by weight, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of about 1500-4000; (B) a carboxyl-functional polymer in an amount sufficient to provide at least about 1.75 equivalents of carboxyl groups, when the source of the carboxyl group is a mono-protic 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 weight average molecular weight (determined by light scattering) of about 10000-80000 and an acid number of about 150-350; (C) an aqueous solution of at least about 1.75 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 R 1 R 2 R 3 N, pyridine, N-methylpyrrole, N-methyl piperidine, N-methyl pyrrolidine, N-methyl morpholine, and mixtures thereof and wherein R 1 and R 2 are substituted or unsubstituted monovalent alkyl groups containing one or two carbon atoms in the alkyl portion and R 3 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 Y is at least about 6+0.75(2 X ) wherein Y is the milliequivalent of carboxyl groups neutralized with primary, secondary or tertiary amines or monofunctional quaternary ammonium hydroxide per 100 grams of acid polymer plus epoxy, and X is the epoxy equivalent weight divided by 1000; and 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.

Claim 23

The composition of claim 20 consisting essentially of liquid carrier and the reaction product of: (A) about 78%, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of about 3000; (B) a carboxyl-functional polymer in an amount sufficient to provide at least about 4.6 equivalents of carboxyl groups, when the source of the carboxyl group is a mono-protic 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 weight average molecular weight (determined by light scattering) of about 13000-18000 and an acid number of about 300; (C) an aqueous solution of at least about 3.0 equivalents of a dimethyl amino ethanol per equivalent of 1,2-epoxy groups in the epoxy resin; 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 Y is at least about 6+0.75(2 X ) wherein Y is the milliequivalent of carboxyl groups neutralized by primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide per 100 grams of acid polymer plus epoxy, and X is the epoxy equivalent weight divided by 1000; and 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.

Claim 24

The composition of claim 1, 2, 6, 8, 11, 12, 14, 15, 16, 17, 20, 21 or 22, additionally containing a crosslinking agent which is at least one of phenol formaldehyde and a nitrogen resin.

Claim 25

A water-borne coating composition consisting essentially of liquid carrier and the reaction product of: (A) 50-90%, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 875-2500; (B) a carboxyl-functional polymer in an amount sufficient to provide about 2.5 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin, wherein said polymer has a composition of styrene/acrylonitrile/itaconic acid//45-84/10-30/11.5-17.4, a weight average molecular weight (determined by light scattering) of 60,000-100,000 and an acid number of 100-150; and (C) an aqueous solution of about 2.5 equivalents of dimethyl ethanol amine per equivalent of 1,2-epoxy groups in the epoxy resin; wherein components (A), (B) and (C) comprise about 0.1-50% by weight of the coating composition and the remainder is comprised of water and organic liquid(s) in a volume ratio from 70:30 to 90:10.

Claim 26

A water-borne coating composition consisting essentially of liquid carrier and the reaction product of: (A) 50-90%, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 875-2500; (B) a carboxyl-functional polymer in an amount sufficient to provide about 2.5 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin, wherein said polymer has a composition of styrene/acrylonitrile/itaconic acid//45-84/10-30/11.5-17.4, a weight average molecular weight (determined by light scattering) of 60,000-100,000 and an acid number of 100-150; and (C) an aqueous solution of about 2.5 equivalents of dimethyl ethanol amine per equivalent of 1,2-epoxy groups in the epoxy resin; wherein components (A), (B) and (C) comprise about 0.1-50% by weight of the coating composition and the remainder is comprised of water and organic liquid(s) in a volume ratio from 70:30 to 90:10.

Claim 27

The composition of claim 24 wherein said polymer has a composition of styrene/acrylonitrile/itaconic acid//about 66/about 20/about 14.

Claim 28

The composition of claim 25 additionally containing diethoxytetramethoxymethylmelamine.

Claim 29

A water-borne coating composition consisting essentially of liquid carrier and the reaction product of: (A) 50-90%, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 875-2500; (B) a carboxyl-functional polymer in an amount sufficient to provide about 2.5 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin, wherein said polymer has a composition of styrene/ethyl acrylate/methacrylic acid//20-70/10-60/15.3-23, a weight average molecular weight (determined by light scattering) of 60,000-100,000 and an acid number of 100-150; and (C) an aqueous solution of about 2.5 equivalents of dimethyl ethanol amine per equivalent of 1,2-epoxy groups in the epoxy resin; wherein components (A), (B) and (C) comprise about 0.1-50% of the coating composition and the remainder is comprised of water and organic liquid(s) in a volume ratio from 70:30 to 90:10.

Claim 30

A water-borne coating composition consisting essentially of liquid carrier and the reaction product of: (A) 50-90%, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 875-2500; (B) a carboxyl-functional polymer in an amount sufficient to provide about 2.5 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin, wherein said polymer has a composition of styrene/ethyl acrylate/methacrylic acid//20-70/10-60/15.3-23, a weight average molecular weight (determined by light scattering) of 60,000-100,000 and an acid number of 100-150; and (C) an aqueous solution of about 2.5 equivalents of dimethyl ethanol amine per equivalent of 1,2-epoxy groups in the epoxy resin; wherein components (A), (B) and (C) comprise about 0.1-50% of the coating composition and the remainder is comprised of water and organic liquid(s) in a volume ratio from 70:30 to 90:10.

Claim 31

The composition of claim 27 wherein said polymer has a composition of styrene/ethyl acrylate/methacrylic acid//about 42/about 40/about 18.

Claim 32

The composition of claim 28 additionally containing diethoxytetramethoxymethylmelamine.

Claim 33

A water-borne coating composition consisting essentially of liquid carrier and the reaction product of: (A) 50-90%, based on the weight of (A) and (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 875-2500; (B) a carboxyl-functional polymer in an amount sufficient to provide about 2.0 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin, wherein said polymer has a composition of methyl methacrylate/ethyl acrylate/acrylic acid/N-isobutoxymethyl (meth)acrylamide//20-40/30-74/12.8-19.3/0-20, a weight average molecular weight (determined by light scattering) of 60,000-100,000 and an acid number of 100-150; and (C) an aqueous solution of about 2.0 equivalents of dimethyl ethanol amine per equivalent of 1,2-epoxy groups in the epoxy resin; wherein components (A), (B) and (C) comprise about 0.1-50% of the coating composition and the remainder is comprised of water and an organic liquid(s) in a volume ratio from 70:30 to 90:10.

Claim 34

A water-borne coating composition consisting essentially of liquid carrier and the reaction product of: (A) 50-90%, based on the weight of (A) and (B), of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 875-2500; (B) a carboxyl-functional polymer in an amount sufficient to provide about 2.0 equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin, wherein said polymer has a composition of methyl methacrylate/ethyl acrylate/acrylic acid/N-isobutoxymethyl (meth)acrylamide//20-40/30-74/12.8-19.3/0-20, a weight average molecular weight (determined by light scattering) of 60,000-100,000 and an acid number of 100-150; and (C) an aqueous solution of about 2.0 equivalents of dimethyl ethanol amine per equivalent of 1,2-epoxy groups in the epoxy resin; wherein components (A), (B) and (C) comprise about 0.1-50% of the coating composition and the remainder is comprised of water and an organic liquid(s) in a volume ratio from 70:30 to 90:10.

Claim 35

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

Claim 36

An article coated with a cured coating based on the composition of claim 1 additionally containing a nitrogen resin crosslinking agent.

Claim 37

A coating compression of claim 1, 20, 21, 24, 27 or 30 wherein components (A), (B) and (C) are capable of forming a hydrogel structure.

Claim 38

A method of making the composition of claim 1 wherein a first solution is made by dissolving the epoxy resin of (A) and the carboxyl-functional polymer of (B) in an organic liquid, then the tertiary amine of (C) is added to the first solution, to make a second solution, then water is mixed with the second solution, if needed, to achieve a volume ratio of water to organic liquid between 70:30 and 90:10.

Claim 39

A method of making the composition of claim 1 wherein a first solution is made by dissolving the epoxy resin of (A) in an organic liquid, then the tertiary amine of (C) is added to the first solution to form a polymeric quaternary ammonium hydroxide in an organic liquid, then the carboxyl-functional polymer of (B), dissolved in an organic liquid, is mixed with the polymeric quaternary ammonium hydroxide with agitation to form a second solution, then water is mixed with the second solution, if needed, to achieve a weight ratio of water to organic liquid between 70:30 and 90:10.

Claim 40

The method of claim 35 wherein the carboxyl-functional polymer of (B) is pre-reacted to 10-90% of stoichiometry with at least one primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide (D) before being mixed with the polymeric quaternary ammonium hydroxide.

Claim 41

A method of making the composition of claim 1 wherein a first solution is made by dissolving the carboxyl-functional polymer of (B) in an organic liquid, then an aqueous solution of a tertiary amine of (C) is mixed with the first solution to form a second solution, then the epoxy resin of (A) is mixed with the second solution to form a third solution, then water is mixed with the third solution, if needed, to achieve a volume ratio of water to organic liquid between 70:30 and 90:10.

Claim 42

The method of claim 34, 35, 36 or 37 wherein the resulting mixture of (A), (B) and (C) is heated between 50° and 95° C. to react (A), (B) and (C).

Claim 43

The method of claim 34, 35, 36 or 37 wherein the resulting mixture of (A), (B) and (C) is heated between 70° and 80° C. to react (A), (B) and (C).

Claim 44

The method of claim 34, 35 or 37 wherein the mixed ingredients of said claim are allowed to react to produce a reaction product and then at least one primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide of (D) is mixed with the reaction product.

Claim 45

The composition of claim 1 wherein the liquid carrier is water and organic liquid in a volume ratio of about 80:20.