# US 9,434,849 B2 · Water based anionic polymers for ink, coating, and film applications

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- Number: US 9,434,849 B2
- Document ID: US9434849B2
- Status: Granted
- Kind: B2
- Application number: 14/056,783
- Filed: 2013-10-17
- Published: 2014-04-24
- Granted: 2016-09-06
- Earliest claimed: 2012-10-19
- Assignees: Penn Color, Inc.
- Applicants: Penn Color, Inc.
- Inventors: Michael D. Spiegel; Charles B. Rybny
- Web page: https://patentgrep.com/patent/US9434849B2

## CPC

- C09D 11/30: Inkjet printing inks
- C08F 255/00: Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F 259/02: on to polymers containing chlorine
- C08F 267/02: on to polymers of acids or salts
- C08F 283/12: on to polysiloxanes
- C08G 77/42: Block-or graft-polymers containing polysiloxane sequences (polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12)
- C08G 77/44: containing only polysiloxane sequences
- C09D 11/10: based on artificial resins
- C09D 11/106: containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08G 77/26: nitrogen-containing groups
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

The present invention provides a durable, external surfactant free, anionic, water based jet ink polymer which when formulated into an ink jet ink results in a printing that has an excellent adhesion to metal or plastic substrates. Such a jet ink polymer is suitable performance replacement of solvent soluble polymers currently in commercial use. The hybridized copolymer comprises a hydrophobic functional polymeric backbone comprised of a polysiloxane polymer, a polyolefin polymer, or a functional polyvinyl polymer. The hybridized copolymer also comprises a plurality of copolymeric side chains attached to the backbone, comprising a polymerizable acid-containing unsaturated monomer, and a polymerizable unsaturated monomer. The use of the inks of the present invention enhances performance criteria such as print-head open time, ink stability, and resistance to typical water based cleaners.

## Claims

### Claim 1

A hybridized polymer comprising:
(a) a hydrophobic functional polymeric backbone having an average molecular weight of from about 15,000 to about 200,000 g/mole, wherein the functional polymeric backbone comprises (i) a copolymer of a functional vinyl chloride-containing polymer and (ii) a hydroxy functional siloxane polymer having the structure [RR′SiO]n, wherein R and R′ are the same or different organic groups selected from hydrogen, alkyl, aryl, and alkylaryl, and terminated with an unsaturated isocyanate functional monomer; and
(b) a plurality of copolymeric side chains attached to the backbone, wherein one or more side chains comprises a free radically initiated reaction product involving the double bonds of at least one polymerizable unsaturated monomer and a polymerizable acid-containing unsaturated monomer.

### Claim 2 (depends on 1)

The hybridized polymer of claim 1, wherein the polymeric backbone comprises 10 to 60 weight percent of the functional vinyl chloride-containing polymer.

### Claim 3 (depends on 1)

The hybridized polymer of claim 1, wherein the polymerizable unsaturated monomer is selected from a group consisting of an acrylate monomer, an alkacrylate monomer, an aromatic vinyl monomer, an aliphatic vinyl monomer, a vinyl ester monomer, a vinyl cyanogen-containing monomer, a halogenoid monomer, an olefin monomer, and a diene monomer.

### Claim 4 (depends on 1)

The hybridized polymer of claim 1, wherein the polymerizable unsaturated monomer has the formula
CH2═C(R2)—X—Y—R1,
wherein
—R2 is H, halogen, or C1 to C3 alkyl group;
—X— is a bond, —CO—O—, or —O—CO—;
—Y— is a bond, or a C1 to C22 bridging alkyl group optionally substituted with one or more C1 to C6 alkyl groups; and
—R1 is
(1) H, halogen, —OH, or —CN;
(2) a C3 to C8 cycloalkyl group that is optionally substituted with one or more linear or branched C1 to C6 alkyl group;
(3) a C3 to C8 heterocycloalkyl group comprising one or more heteroatoms, wherein the heteroatom is a chalcogen;
(4) a C7 to C15 bicycloalkyl group that is optionally substituted with one or more halogens, or linear or branched C1 to C6 alkanes;
(5) a C6 to C14 aryl group that is optionally substituted with one or more groups selected from the group consisting of a halogen, a linear or branched C1 to C6 alkane, and C1 to C3 alkyloxy;
(6) SiR33, wherein R3 is C1 to C3 alkyl group;
(7) polyethylene glycol, polypropylene glycol, or a copolymer thereof, terminated with —OH or —OMe; or
(8) —CZ═CH2, wherein Z is H or halogen.

### Claim 5 (depends on 1)

The hybridized polymer of claim 1, wherein the polymerizable acid-containing unsaturated monomer is selected from the group consisting of an acid-containing acrylate, an acid-containing methacrylate, an acid-containing vinyl monomer, an acid-containing alkylallyl monomer, a monocarboxylic acid-containing alkene, and a dicarboxylic acid-containing alkene.

### Claim 6 (depends on 1)

The hybridized polymer of claim 1, wherein the polymerizable acid-containing unsaturated monomer has the formula
Ro4—CH═C(Ro2)—Xo—Yo—(Ro1)m,
wherein
Ro4— is H, C1 to C3 alkyl group, or an aryl group;
—Ro2 is H, halogen, or C1 to C3 alkyl group;
—Xo— is a bond, or —CO—O—;
—Yo— is a bond, or a C1 to C18 bridging alkyl, cycloalkyl, or heterocycloalkyl group optionally substituted with one or more C1 to C6 alkyl groups, aryl groups or alkoxyaryl groups;
—Ro1 is H, —COOH, —SO3H, or —OPO(OH)2; and
m=1 or 2.

### Claim 7 (depends on 1)

The hybridized polymer of claim 1, wherein the polymerizable acid-containing unsaturated monomer has the formula
wherein T1, T2, and T3, are each independently H, a C1 to C3 alkyl group, carboxylic group, or a C1 to C3 alkyl carboxylic group, provided that acid-containing unsaturated monomer comprises two —COOH groups.

### Claim 8 (depends on 1)

The hybridized polymer of claim 1 wherein the polymeric backbone comprises the functional vinyl chloride-containing polymer, the functional siloxane polymer and a functional olefin polymer.

### Claim 9 (depends on 1)

An aqueous mixture of hybridized polymer of claim 1, wherein the hybridized polymer is either partially or totally neutralized with a base.

### Claim 10 (depends on 9)

The aqueous mixture of claim 9, wherein the aqueous mixture comprises a colloidal dispersion suitable for use in preparation of a water based jet ink vehicle, wherein the particle size of more than 90% of particles in said dispersion is less than 500 nanometers.

### Claim 11 (depends on 10)

The aqueous mixture of claim 10, wherein the dispersion is prepared without the use of a surfactant.

### Claim 12 (depends on 9)

The aqueous mixture of claim 9, wherein the mixture further comprises an antimicrobial.

### Claim 13 (depends on 1)

A liquid ink comprising more than 50 weight percent of water, the hybridized polymer of claim 1, and a pigment or a dye.