# US 6,723,820 B1 · Solvent soluble poly(urethane/urea) resins

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- Number: US 6,723,820 B1
- Document ID: US6723820B1
- Status: Granted
- Kind: B1
- Application number: 09/710,941
- Filed: 2000-11-13
- Granted: 2004-04-20
- Earliest claimed: 2000-11-13
- Assignees: Sun Chemical Corporation
- Inventors: Ralph Arcurio; Mark Rocco; David J. Slavinski; Mark Schneider
- Web page: https://patentgrep.com/patent/US6723820B1

## CPC

- C08G 18/6607: {with compounds of group C08G18/3203}
- C08G 18/12: using two or more compounds having active hydrogen in the first polymerisation step
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)

## Abstract

Solvent based poly(urethane/urea) resins suitable for formulating flexographic and gravure laminating printing ink and coating compositions formed from a poly(urethane) prepolymer solution made from a blend of polymeric diols and diols reacted with diisocyanates and then with diamine in an organic solvent. The resin is prepared by adding the poly(urethane) prepolymer solution at a controlled rate to the diamine in a organic solvent which allows a resin solution to be formed, which may be used in the formulation of laminating printing ink and coating compositions without the need for adjuvants, grinding in polyvinyl butyral or blending with nitrocellulose base.

## Claims

### Claim 1

A solvent-soluble poly(urethane/urea) resin derived from a polyurethane prepolymer being the reaction product of:
(a) a diisocyanate component and a diol component having:
(i) a first diol having a molecular weight below 2000 and
(ii) a polymeric diol having a molecular weight below 3000; wherein the —NCO/—OH ratio is less than 2 and containing 1.3 to 6.0 wt. % of unreacted —NCO groups and
(b) diamine; wherein the amount of diamine is 100% to 120% based on the equivalents of unreacted —NCO groups and the polyurethane prepolymer is added to the diamine, in the absence of monoamine chain terminators, at a controlled rate of between about 3.33 to about 10 weight percent per minute of polyurethane prepolymer.

### Claim 2 (depends on 1)

The resin of claim 1 wherein the first diol has a lower molecular weight than the polymeric diol.

### Claim 3 (depends on 1)

The resin of claim 1 wherein the nitrogen content of the resin derived from the unreacted —NCO groups of the diisocyanate component is from 1.3 to 6.0 wt. %.

### Claim 4 (depends on 1)

The resin of claim 1 wherein the polymeric diol comprises 30 to 80% of the equivalents of the diol component.

### Claim 5 (depends on 1)

The resin of claim 1 wherein the —NCO/—OH ratio is between 1 and 2.

### Claim 6 (depends on 1)

The resin of claim 1 having a molecular weight between about 10,000 and about 80,000.

### Claim 7 (depends on 1)

The resin of claim 1 wherein the diisocyanate component comprises two or more diisocyanate compounds.

### Claim 8 (depends on 1)

The resin of claim 1 wherein the diisocyanate component is an aromatic diisocyanate compound, an aliphatic diisocyanate compound, or a mixture thereof.

### Claim 9 (depends on 8)

The resin of claim 8 wherein the diisocyanate component is 4,4′-diphenylmethane diisocyanate; 4,4′-dicyclohexyl diisocyanate; hexamethylene diisocyanate; meta-tetramethylene-xylenediisocyanate; isophorone diisocyanate; toluene diisocyanate; or a mixture thereof.

### Claim 10 (depends on 1)

The resin of claim 1 wherein the diisocyanate component comprises isophorone diisocyanate.

### Claim 11 (depends on 1)

The resin of claim 1 wherein the first diol is selected from the group consisting of aliphatic diols, polyether diols and polycaprolactone diols, and mixtures thereof.

### Claim 12 (depends on 11)

The resin of claim 11 wherein the first diol is selected from the group consisting of 1,4 butanediol, 1,5 pentanediol, and alpha-hydro-omega-hydroxy-poly(oxy 1,4 butyldiyl) having a molecular weight of 1000.

### Claim 13 (depends on 11)

The resin of claim 11 wherein the first diol is an aliphatic diol.

### Claim 14 (depends on 11)

The resin of claim 11 wherein the aliphatic diol is 1,4-butanediol.

### Claim 15 (depends on 1)

The resin of claim 1 wherein the polymeric diol has a molecular weight between 425 and 3000.

### Claim 16 (depends on 1)

The resin of claim 1 wherein the polymeric diol is a polyether diol or a polycaprolactone diol.

### Claim 17 (depends on 1)

The resin of claim 1 wherein the polymeric diol is selected from the group consisting of alpha-hydro-omega-hydroxy-poly(oxy-1,4-butyldiyl), and polypropylene glycol.

### Claim 18 (depends on 17)

The resin of claim 17 wherein the polymeric diol is a polycaprolactone.

### Claim 19 (depends on 18)

The resin of claim 18 wherein the polycaprolactone has a molecular weight of 2500 or less.

### Claim 20 (depends on 1)

The resin of claim 1 wherein the diamine is hydrazine, methylene diamine, ethylene diamine, diamino cyclohexane, hexamethylene diamine, piperazine, or isophorone diamine or mixtures thereof.

### Claim 21 (depends on 20)

The resin of claim 20 wherein the diamine is ethylene diamine, isophorone diamine, or a mixture thereof.

### Claim 22 (depends on 1)

The resin of claim 1 wherein the organic solvent is an ester or an alcohol/ester mixture.

### Claim 23 (depends on 22)

The resin of claim 22 wherein the ester is ethyl acetate or n-propyl acetate; and the alcohol is methanol, ethanol, n-propanol, isopropanol, or butanol.

### Claim 24 (depends on 1)

The resin of claim 1 wherein the polyurethane prepolymer has the structure:
OCN—(—A—NH—CO—O—R2—0—CO—NH—)n—A—NH—CO—O—R2—O—CO—NH—A—NCO
wherein —A— is an aryl or alkyl group; and R2 comprises R3 and R4; wherein R3 is an alkyl or a polymeric group having a molecular weight below 2000; wherein R4 is a polymeric group having a molecular weight below 3000; wherein n is 1 or 2.

### Claim 25 (depends on 24)

The resin of claim 24 wherein the molecular weight of R3 is less than the molecular weight of R4.

### Claim 26 (depends on 24)

The resin of claim 24 wherein R2 comprises from about 30 to about 80 equivalent % of R4.

### Claim 27 (depends on 24)

The resin of claim 24 wherein the ratio of R4 to R3 ranges between about 90:10 and about 10:90.

### Claim 28 (depends on 1)

The resin of claim 1 wherein the poly(urethane/urea) resin has the structure:
NH2—R1—NH—CO—NH—(—U—NH—CO—NH—R1—NH—CO—NH—)m—U—NH—CO—NH—R1—NH2
wherein R1 is a covalent bond or a C1-10 alkyl group; —U— has the structure; and m is an integer:
OCN—(—A—NH—CO—O—R2—0—CO—NH—)n—A—NH—CO—O—R2—O—CO—NH—A—NCO
wherein —A— is an aryl or alkyl group; and R2 comprises R3 and R4; wherein R3 is an alkyl or a polymeric group having a molecular weight below 2000; wherein R4 is a polymeric group having a molecular weight below 3000; wherein n is 1 or 2.

### Claim 29

A solvent-based flexographic and gravure compatible laminating printing ink comprising:
(A) a solvent-soluble poly(urethane/urea) resin derived from a polyurethane prepolymer being the reaction product of:
(a) a diisocyanate component and a diol component having:
(i) a first diol having a molecular weight below 2000 and
(ii) a polymeric diol having a molecular weight below 3000; wherein the —NCO/—OH ratio is less than 2 and containing 1.3 to 6.0% by weight of unreacted —NCO groups, and
(b) diamine; wherein the amount of diamine is 100% to 120% based on the equivalents of unreacted —NCO groups and the polyurethane prepolymer is added to the diamine, in the absence of monoamine chain terminators, at a controlled rate of between about 3.3 to about 10 weight percent per minute of polyurethane prepolymer,
(B) a colorant; and
(C) an organic solvent.

### Claim 30 (depends on 29)

The ink of claim 29 wherein the colorant is a pigment, dye or a mixture thereof.

### Claim 31 (depends on 29)

The ink of claim 29 wherein the organic solvent is an ester or an alcohol/ester mixture.

### Claim 32 (depends on 31)

The ink of claim 31 wherein the ester is ethyl acetate or n-propyl acetate; and the alcohol is methanol, ethanol, n-propanol, isopropanol, or butanol.

### Claim 33 (depends on 29)

The ink of claim 29 further comprising a polymeric dispersant.

### Claim 34 (depends on 33)

The ink of claim 33 wherein the polymeric dispersant is a nitrocellulose.

### Claim 35 (depends on 33)

The ink of claim 33 wherein the polymeric dispersant is a polyvinyl butyral.

### Claim 36 (depends on 29)

The gravure compatible laminating printing ink of claim 29 comprising:
about 8 to about 60 wt. % solvent-soluble poly(urethane/urea) resin;
about 3 to about 30 wt. % colorant; and
about 15 to about 60 wt. % organic solvent.

### Claim 37 (depends on 29)

The flexographic compatible laminating printing ink of claim 29 comprising:
about 8 to about 60 wt. % solvent-soluble poly(urethane/urea) resin;
about 3 to about 30 wt. % colorant; and
about 15 to about 60 wt. % organic solvent.

### Claim 38 (depends on 29)

The ink of claim 29 further comprising an ink viscosity between 15 and 30 seconds as measured using a #2 efflux cup.

### Claim 39 (depends on 29)

A method for printing on a polymeric substrate comprising the steps:
applying the laminating ink of claim 29 onto the surface of the polymeric substrate to form an image; and
drying the image to form a polymeric substrate having a tack-free, firmly adherent laminating ink which is un-blocked when contacted under pressure at ambient temperatures with a second surface of the substrate.

### Claim 40 (depends on 39)

The method of claim 39 wherein the ink is applied to the polymeric substrate with a flexographic printing press.

### Claim 41 (depends on 39)

The method of claim 39 wherein the ink is applied to the polymeric substrate with a gravure printing press.

### Claim 42 (depends on 39)

The method of claim 39 further comprising applying a second substrate surface to the image to form a laminate.

### Claim 43 (depends on 42)

The method of claim 42 wherein the second substrate surface is formed by melt extrusion.

### Claim 44 (depends on 42)

The method of claim 42 wherein the second substrate surface has an adhesive surface.

### Claim 45 (depends on 42)

The method of claim 42 further comprising subjecting the laminate to retort conditions, thereby forming a retorted laminate wherein the image remains substantially unchanged and is free of delamination defects.

### Claim 46 (depends on 39)

The method of claim 39 wherein the polymeric substrate is polyethylene, polypropylene, polyethylene terephthalate, cellulose acetate, cellulose acetate butyrate, polycarbonate, polyamide, polyvinyldichloride coated polyethylene terephthalate, polyvinyldichloride coated polypropylene, metallized polyethylene terephthalate, and metallized polypropylene.

### Claim 47 (depends on 39)

The method of claim 39 wherein the polymeric substrate is a polypropylene or a polyester film or sheet.

### Claim 48 (depends on 42)

The method of claim 42 wherein the second substrate is a polymeric substrate.

### Claim 49 (depends on 42)

The method of claim 42 wherein the second substrate is a polyethylene.