US4423165A — Water-borne coating composition made from epoxy r…

Claim 1

Independent Claim 382 words

A water-borne coating composition consisting essentially of liquid carrier and a second reaction product made by blending a second carboxyl-functional polymer with a first reaction product, wherein said first reaction product is the product of the reaction in an organic media of: (A) 50-90% by weight, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, about 11/2 to 2 terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 750-5000; (B) a first 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) 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; (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; (E) said second carboxyl-functional polymer being blended in an amount of 5 to 200 parts by weight per 100 parts by weight of (A) plus (B) and having a weight average molecular weight (determined by light scattering) of about 10,000-160,000 and an acid number of 50-500, said acid number being at least 50 units different than the acid number of said first carboxyl-functional polymer, said second reaction product containing not less than 30% by weight of epoxy resin (A) based on the total of (A), (B) and (E).

Claim 2

Dependent Claim 382 words

A water-borne coating composition consisting essentially of liquid carrier and a second reaction product made by blending a second carboxyl-functional polymer with a first reaction product, wherein said first reaction product is the product of the reaction in an organic media of: (A) 50-90% by weight, based on the weight of (A) plus (B), of an epoxy resin containing, on the average, about 11/2 to 2 terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 750-5000; (B) a first 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) 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; (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; (E) said second carboxyl-functional polymer being blended in an amount of 5 to 200 parts by weight per 100 parts by weight of (A) plus (B) and having a weight average molecular weight (determined by light scattering) of about 10,000-160,000 and an acid number of 50-500, said acid number being at least 50 units different than the acid number of said first carboxyl-functional polymer, said second reaction product containing not less than 30% by weight of epoxy resin (A) based on the total of (A), (B) and (E).

Claim 3

Dependent Claim 34 words

The composition of claim 1 wherein water is blended with the first reaction product in sufficient quantity in that the continuous phase is aqueous, and then (E) is blended with the first reaction product.

Claim 4

Dependent Claim 40 words

The composition of claim 1 wherein (E) is blended with the first reaction product to make the second reaction product and then water is blended with the second reaction product in sufficient quantity so that the continuous phase is aqueous.

Claim 5

Dependent Claim 25 words

The composition of claim 2 wherein the second carboxyl-functional polymer (E) is neutralized with an amine before (E) is blended with the first reaction product.

Claim 6

Dependent Claim 24 words

The composition of claim 3 wherein the second carboxyl-functional-polymer (E) is neutralized with an amine before (E) is blended with the first reaction product.

Claim 7

Dependent Claim 15 words

The composition of claim 1 wherein tertiary amine (C) is provided as an aqueous solution.

Claim 8

Dependent Claim 26 words

The composition of claim 1 wherein said first carboxyl-functional polymer has an acid number at least 100 units higher than that of said second carboxyl-functional polymer.

Claim 9

Dependent Claim 48 words

The composition of claim 1 wherein components (A), (B), (C), (D) and (E) 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 10

Dependent Claim 63 words

The composition of claim 1 wherein said first 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 groups 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 11

Dependent Claim 57 words

The composition of claim 9 wherein the source of said carboxyl groups is a mono-protic acid and said first-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 12

Dependent Claim 35 words

The composition of claim 1 wherein said first 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 13

Dependent Claim 16 words

The composition of claim 1 wherein said epoxy resin has an epoxy equivalent weight of 1500-4000.

Claim 14

Dependent Claim 35 words

The composition of claim 1 wherein said first and second carboxyl-functional polymers are polymers of the same monomers or different monomers, including at least one α,β-ethylenically unsaturated monomer and at least one α,β-ethylenically unsaturated acid.

Claim 15

Dependent Claim 70 words

The composition of claim 13 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 16

Dependent Claim 24 words

The composition of claim 14 wherein said α,β-ethylenically unsaturated acid is selected from the group consisting of acrylic cid, methacrylic acid, and itaconic acid.

Claim 17

Dependent Claim 27 words

The composition of claim 13 wherein said first carboxyl-functional polymer has an acid number of 150-350 and said second carboxyl-functional polymer has an acid number of 50-150.

Claim 18

Dependent Claim 130 words

The composition of claim 13 wherein said α,β-ethylenically unsaturated monomer is at least one selected from the group consisting of ##STR10## where R, R 1 , R 2 and R 3 are hydrogen or an akyl 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 19

Dependent Claim 24 words

The composition of claim 17 wherein the α,β-ethylenically unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.

Claim 20

Dependent Claim 61 words

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

Dependent Claim 15 words

The composition of claim 19 wherein the tertiary amine of (C) is dimethyl ethanol amine.

Claim 22

Dependent Claim 359 words

The composition of claim 1 consisting essentially of liquid carrier and the reaction product of: (A) 65-90% 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 grups, 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; (D) optionally, 10-90% of the amount required for stiochiometric 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; (E) said second carboxyl-functional polymer being blended in an amount of 5 to 200 parts by weight per 100 parts by weight of (A) plus (B) and having a weight average molecular weight (determined by light scattering) of about 10,000-160,000 and an acid number of 50-500, said acid number being at least 50 units different than the acid number of said first carboxyl-functional polymer, said second reaction product containing not less than 30% by weight of epoxy resin (A) based on the total of (A), (B), and (E).

Claim 23

Dependent Claim 48 words

The composition of claim 21 wherein components (A), (B), (C), (D) and (E) 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 24

Dependent Claim 21 words

The composition of claim 22 wherein the liquid carrier is water and organic liquid in a volume ratio of about 80:20.

Claim 25

Dependent Claim 26 words

The composition of claim 1 or 21 additionally containing a crosslinking agent which is at least one of a phenol formaldehyde resin and a nitrogen resin.

Claim 26

Dependent Claim 10 words

The composition of claim 1 or 21 additionally containing diethoxytetramethoxymethylmelamine.

Claim 27

Dependent Claim 14 words

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

Claim 28

Dependent Claim 21 words

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

Claim 29

Dependent Claim 22 words

A coating composition of claim 1 or 21 wherein components (A), (B), (C) and (E) are capable of forming a hydrogel structure.

Claim 30

Dependent Claim 97 words

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

Claim 31

Dependent Claim 106 words

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

Claim 32

Dependent Claim 119 words

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 a third reaction mixture is made by adding a second carboxyl-functional polymer of (E) to said second reaction mixture, 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 33

Dependent Claim 128 words

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 reaction mixture, then a third reaction mixture is made by adding a second carboxyl-functional polymer of (E) to said second reaction mixture, 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 34

Dependent Claim 41 words

The method of claim 31 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 35

Dependent Claim 41 words

The method of claim 32 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 36

Dependent Claim 108 words

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, the the epoxy resin of (A) is mixed with the second solution to form a third solution, then a third reaction mixture is made by adding a second carboxyl-functional polymer of (E) to said second reaction mixture, 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 37

Dependent Claim 117 words

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 second reaction mixture, then a third reaction mixture is made by adding a second carboxyl-functional polymer of (E) to said second reaction mixture, 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 38

Dependent Claim 35 words

The method of claim 29, 30, 31, 32, 33, 34, 35 or 36 wherein the resulting mixture of (A), (B) and (C) is heated between 50° and 95° C., to react (A), (B) and (C).

Claim 39

Dependent Claim 35 words

The method of claim 29, 30, 31, 32, 33, 34, 35 or 36 wherein the resulting mixture of (A), (B) and (C) is heated between 70° and 80° C., to react (A), (B) and (C).

Claim 40

Dependent Claim 50 words

The method of claim 20, 30, 31, 32, 35 or 36 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.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1986-12-26	1987-06-27	1987-12-27	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1990-12-26	1991-06-27	1991-12-27	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1994-12-26	1995-06-27	1995-12-27	$7700.00	Window Closed / Lapsed

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

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