# US 4,889,765 A · Ink-receptive, water-based, coatings

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- Number: US 4,889,765 A
- Document ID: US4889765A
- Status: Granted
- Kind: A
- Application number: 07/136,264
- Filed: 1987-12-22
- Granted: 1989-12-26
- Earliest claimed: 1987-12-22
- Assignees: W. R. Grace & Co.
- Inventors: John L. Wallace
- Web page: https://patentgrep.com/patent/US4889765A

## CPC

- B41M 5/52: Macromolecular coatings
- C08L 77/12: Polyester-amides
- C09D 123/0869: {Acids or derivatives thereof}
- B41M 5/506: {Intermediate layers}
- B41M 5/508: {Supports}
- B41M 5/5218: {characterised by inorganic additives, e.g. pigments, clays}
- B41M 5/5227: {characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants}
- B41M 5/5254: {characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers}
- C08L 79/00: Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L 79/02: Polyamines
- Y10T 442/2098: At least two coatings or impregnations of different chemical composition
- Y10T 442/2107: At least one coating or impregnation contains particulate material
- B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Disclosed are coating compositions, coated articles made using said coating compositions and processes for preparing the same. More particularly disclosed are aqueous ink-receptive, water-based coatings which are smudgeproof and which will not wash off with water.

## Claims

### Claim 1

A coating composition comprising:
at least 5 weight percent of a polymer of a 2-oxazoline;
at least 50 weight percent of polyethylene acrylic acid copolymer; and
an aqueous liquid, said weight percents being based on the weight of the 2-oxazoline polymer and the polyethylene acrylic acid copolymer.

### Claim 2 (depends on 1)

The composition of claim 1 wherein the polymer of a 2-oxazoline comprises polyethyloxazoline.

### Claim 3 (depends on 1)

The composition of claim 1 further comprising filler in an amount of between 0-70 weight percent of the solids of the composition.

### Claim 4 (depends on 1)

The composition of claim 1 wherein the weight percent ratio of ethylene to acrylic acid comprises an 80/20 ratio.

### Claim 5 (depends on 1)

The composition of claim 1 further comprising a base capable of substantially neutralizing the acid groups of the polyethylene acrylic acid copolymer.

### Claim 6 (depends on 5)

The composition of claim 5 wherein said base will evaporate when said composition is dried.

### Claim 7 (depends on 6)

The composition of claim 6 wherein said base comprises ammonium hydroxide.

### Claim 8 (depends on 5)

The composition of claim 5 further comprising a carboxy functional acrylic ester polymer.

### Claim 9 (depends on 8)

The composition of claim 8 wherein the carboxy functional acrylic ester polymer comprises a polymer comprising acrylic acid, acrylonitrile and styrene.

### Claim 10 (depends on 8)

The composition of claim 8 further comprising a surfactant.

### Claim 11 (depends on 1)

The composition of claim 1 wherein said composition comprises between 2-35 weight percent solids.

### Claim 12 (depends on 3)

The composition of claim 3 wherein the filler is selected from the group consisting of fumed silica, clay, and silicates.

### Claim 13 (depends on 5)

The composition of claim 5 comprising between 5 to 30 weight percent of the 2-oxazoline polymer and between 70 to 95 weight percent of polyethylene acrylic acid copolymer, the pendant acid groups of which have been substantially neutralized by the base, said weight percents being based on the weight of the 2-oxazoline polymer and the polyethylene acrylic acid copolymer.

### Claim 14 (depends on 8)

The composition of claim 8 comprising between 10 to 20 weight percent of the 2-oxazoline polymer; between 60 to 80 weight percent of polyethylene acrylic acid copolymer, the pendant acid groups of which have been substantially neutralized by the base, and between 10 to 20 weight percent of the carboxy functional acrylic ester polymer, said weight percents being based on the weight of the 2-oxazoline polymer, the polyethylene acrylic acid copolymer and the carboxy functional acrylic ester polymer.

### Claim 15

A coating composition comprising:
at least 5 weight percent of a polymer of a 2-oxazoline;
at least 50 weight percent of an olefin copolymer containing substantially neutralized pendant acid groups;
a base capable of neutralizing acid groups;
a carboxy functional acrylic ester polymer;
a surfactant; and
an aqueous liquid, said weight percents being based on the weight of the 2-oxazoline polymer, the olefin copolymer and the carboxy functional acrylic ester polymer.

### Claim 16 (depends on 1)

The composition of claim 1 formed by mixing a solution of the polymer of a 2-oxazoline in an aqueous liquid with a solution of the polyethylene acrylic acid copolymer in an aqueous liquid.

### Claim 17 (depends on 16)

The composition of claim 16 wherein the aqueous solution of the polyethylene acrylic acid copolymer further comprises a base which substantially neutralizes the acid groups of the polyethylene acrylic acid copolymer.

### Claim 18 (depends on 17)

The composition of claim 17 wherein said base will evaporate when said composition is dried.

### Claim 19 (depends on 18)

The composition of claim 18 wherein said base comprises ammonium hydroxide.

### Claim 20 (depends on 17)

The composition of claim 17 wherein the aqueous solution of the polyethylene acrylic acid copolymer and the base is formed by mixing the polyethylene acrylic acid copolymer and an aqueous liquid with an aqueous solution of ammonium hydroxide.

### Claim 21 (depends on 20)

The composition of claim 20 wherein the aqueous solution of ammonium hydroxide comprises between 25-30 weight percent ammonium hydroxide and 70-75 weight percent water.

### Claim 22 (depends on 17)

The composition of claim 17 wherein the polymer of a 2-oxazoline comprises polyethyloxazoline.

### Claim 23 (depends on 22)

The composition of claim 22 wherein the solution of polyethyloxazoline comprises between 10-30 weight percent polyethyloxazoline and between 70-90 weight percent water.

### Claim 24 (depends on 8)

The composition of claim 8 formed by mixing a solution of the polymer of a 2-oxazoline in an aqueous liquid, a solution of the base capable of substantially neutralizing the acid groups of the polyethylene acrylic acid copolymer and the polyethylene acrylic acid copolymer which pendant acid groups have been substantially neutralized by said base in an aqueous liquid; and a hydrophilic latex comprising a carboxy functional acrylic ester polymer, said solutions and latex being miscible with each other.

### Claim 25 (depends on 24)

The composition of claim 24 wherein the hydrophilic latex further comprises a surfactant.

### Claim 26 (depends on 25)

The composition of claim 25 wherein the hydrophilic latex comprises 45-50 weight percent of a polymer comprising acrylic acid, acrylonitrile and styrene; 1-5 weight percent surfactant and 45-50 weight percent water.

### Claim 27

A composition comprising:
at least 5 weight percent of a polymer of a 2-oxazoline;
at least 50 weight percent of an olefin copolymer containing pendant acid groups; and
a carboxy functional acrylic ester polymer, said weight percents being based on the weight of the 2-oxazoline polymer, the olefin copolymer and the carboxy functional acrylic ester polymer.

### Claim 28 (depends on 27)

The composition of claim 27 wherein the polymer of a 2-oxazoline comprises polyethyloxazoline and the olefin copolymer containing pendant acid groups comprises polyethylene acrylic acid copolymer.

### Claim 29

A process for producing a coated article having aqueous ink applied to it comprising the steps of:
(a) providing a substrate;
(b) coating at least one surface of said substrate with a coating composition formed by:
(1) mixing an olefin copolymer containing pendant acid groups with a base capable of substantially neutralizing said acid groups and an aqueous liquid to form an aqueous solution; and
(2) mixing said aqueous solution with an aqueous solution of a 2-oxazoline polymer;
said coating composition comprising at least 5 weight percent 2-oxazoline polymer and at least 50 weight percent olefin copolymer containing pendant acid groups, said weight percents being based on the weight of the 2-oxazoline polymer and the olefin copolymer;
(c) drying said coating; and
(d) applying an aqueous-based ink to the coated substrate.

### Claim 30 (depends on 29)

The process of claim 29 wherein the substrate comprises a sheetlike substrate selected from the group consisting of paper, plastic, spunbonded olefins, nonwovens and metal.

### Claim 31 (depends on 29)

The process of claim 29 wherein the olefin copolymer comprises polyethylene acrylic acid copolymer and the 2-oxazoline polymer comprises polyethyloxazoline.

### Claim 32 (depends on 29)

The process of claim 29 wherein said base will evaporate when said coating is dried in step (c).

### Claim 33 (depends on 32)

The process of claim 32 wherein said base comprises ammonium hydroxide.

### Claim 34 (depends on 29)

The process of claim 29 wherein the coating composition comprises between 5 to 30 weight percent of the 2-oxazoline polymer and between 70 to 95 weight percent of the olefin copolymer containing substantially neutralized pendant acid groups, said weight percents being based on the weight of the 2-oxazoline polymer and the olefin copolymer.

### Claim 35 (depends on 29)

The process of claim 29 wherein in step (b), the coating composition is formed by mixing the aqueous solution of the olefin copolymer with the aqueous solution of the 2-oxazoline polymer and with a hydrophilic latex comprising a carboxy functional acrylic ester polymer, said solutions and latex being miscible with each other.

### Claim 36 (depends on 35)

The process of claim 35 wherein the coating composition comprises between 10 to 20 weight percent of the 2-oxazoline polymer, between 60 to 80 weight percent of the olefin copolymer, and between 10 to 20 weight percent of the carboxy functional acrylic ester polymer, said weight percents being based on the weight of the 2-oxazoline polymer, the olefin copolymer and the carboxy functional acrylic ester polymer.

### Claim 37 (depends on 35)

The process of claim 35 wherein the hydrophilic latex further comprises a surfactant.

### Claim 38 (depends on 37)

The process of claim 37 wherein the hydrophilic latex comprises a polymer comprising acrylic acid, acrylonitrile and styrene; a surfactant; and water.

### Claim 39 (depends on 29)

The process of claim 29 wherein in step b, filler is added to the mixture of the aqueous solution of the olefin copolymer and the aqueous solution of the 2-oxazoline polymer in an amount of between 0-70 weight percent of the solids of the composition.

### Claim 40 (depends on 29)

The process of claim 29 wherein prior to coating at least one surface of the substrate in step (b), said surface of said substrate is coated with a- pigment base coating.

### Claim 41

A coated article having aqueous ink applied to it prepared by a process comprising the steps of:
(a) providing a substrate;
(b) coating at least one surface of said substrate with a coating composition formed by:
(1) mixing an olefin copolymer containing pendant acid groups with a base capable of substantially neutralizing said acid groups and an aqueous liquid to form an aqueous solution; and
(2) mixing said aqueous solution with an aqueous solution of a 2-oxazoline polymer;
said coating composition comprising at least 5 weight percent 2-oxazoline polymer and at least 50 weight percent olefin copolymer containing pendant acid groups, said weight percents being based on the weight of the 2-oxazoline polymer and the olefin copolymer;
(c) drying said coating; and
(d) applying an aqueous-based ink to the coated substrate.

### Claim 42 (depends on 41)

The coated article of claim 41 wherein the coating composition comprises between 5 to 30 weight percent of the 2-oxazoline polymer and between 70 to 95 weight percent of the olefin copolymer containing substantially neutralized pendant acid groups, said weight percents being based on the weight of the 2-oxazoline polymer and the olefin polymer.

### Claim 43 (depends on 41)

The coated article of claim 41 wherein in step (b), the coating composition is formed by mixing the aqueous solution of the olefin copolymer with the aqueous solution of the 2-oxazoline polymer and with a hydrophilic latex comprising a carboxy functional acrylic ester polymer, said solutions and latex being miscible with each other.

### Claim 44 (depends on 43)

The coated article of claim 43 wherein the coating composition comprises between 10 to 20 weight percent of the 2-oxazoline polymer, between 60 to 80 weight percent of the olefin copolymer, and between 10 to 20 weight percent of the carboxy functional acrylic ester polymer, said weight percents being based on the weight of the 2-oxazoline polymer, the olefin copolymer and the carboxy functional acrylic ester polymer.

### Claim 45 (depends on 41)

The coated article of claim 41 wherein said coating comprises an aqueous ink-receptive coating.

### Claim 46 (depends on 45)

The coated article of claim 45 wherein prior to coating at least one surface of the substrate in step (b), said surface of said substrate is coated with a pigment base coating.