# US 9,751,284 B2 · Method for making skinned polyurethane composites

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- Number: US 9,751,284 B2
- Document ID: US9751284B2
- Status: Granted
- Kind: B2
- Application number: 14/410,091
- Filed: 2013-06-20
- Published: 2016-01-21
- Granted: 2017-09-05
- Earliest claimed: 2013-06-20
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Sara Cavalca; Sabrina Fregni
- Web page: https://patentgrep.com/patent/US9751284B2

## CPC

- B32B 27/065: {of foam}
- B32B 5/20: foamed in situ
- B32B 27/08: of synthetic resin
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/40: comprising polyurethanes
- B32B 37/14: characterised by the properties of the layers
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/3206: {aliphatic}
- C08G 18/4236: {containing only aliphatic groups}
- C08G 18/4816: {mixtures of two or more polyetherpolyols having at least three hydroxy groups}
- C08G 18/4837: {and other oxyalkylene units}
- C08G 18/4841: {containing oxyethylene end groups}
- C08G 18/6677: {having at least three hydroxy groups}
- C08G 18/725: {Combination of polyisocyanates of C08G18/78 with other polyisocyanates}
- C08G 18/7664: {containing alkylene polyphenyl groups}
- C08G 18/798: {containing urethdione groups}
- C08J 9/04: using blowing gases generated by a previously added blowing agent
- B32B 2266/0278: Polyurethane
- B32B 2305/72: Cured, e.g. vulcanised, cross-linked
- C08G 18/68: Unsaturated polyesters
- C08G 2110/0016: semi-rigid
- C08G 2110/0083: prepared using water as the sole blowing agent
- C08J 2375/04: Polyurethanes
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

Skinned composites contain a plasticized polymer skin layer adhered to a layer of a polyurethane. The polyurethane is made from a reaction mixture that contains specified amounts of a polyester polyol and an acidic material. The presence of both the polyester polyol and acid leads to significantly improved adhesion between the polyurethane and skin layer. The invention is particularly useful when the skin is highly plasticized.

## Claims

### Claim 1

A method for forming a skinned composite comprising forming a layer of a polyurethane-forming reaction mixture against a plasticized thermoplastic skin layer that contains 25 to 45% by weight of plasticizer, based on the combined weight of plasticizer and thermoplastic skin layer, and then curing the reaction mixture to form a polyurethane layer adhering to the skin, wherein the polyurethane-forming reaction mixture comprises
a) one or more polyols;
b) one or more organic polyisocyanates;
c) at least one blowing agent selected from water or a mixture of water and a hydrocarbon, hydrofluorocarbon, fluorocarbon, fluorochlorocarbon, hydrofluorochlorocarbon or dialkyl ether physical blowing agent in an amount sufficient to provide a foam density of 80 to 500 kg/m3;
d) at least one catalyst for the reaction of isocyanate groups towards hydroxyl groups;
wherein component a) includes at least one polyester polyol, and/or component b) includes at least one isocyanate-terminated prepolymer which is a reaction product of a polyester polyol with an excess of one or more polyisocyanates, and further wherein the at least one polyester polyol in component a) and/or provided in the preparation of the at least one isocyanate-terminated prepolymer included within component b) constitutes from 0.5 to 7% of the combined weight of components a) and b);
and further wherein the polyurethane-forming reaction mixture contains from 0.02 to 0.3% by weight of a Bronsted acid having a molecular weight of up to about 400 selected from one or more of formic acid, acetic acid, an alkanoic acid having three to eight carbon atoms, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, benzene sulfonic acid and an alkyl benzene sulfonic acid in which the alkyl group contains 1 to 20 carbon atoms, based on the combined weight of the a) one or more polyols and the Bronsted acid.

### Claim 2 (depends on 1)

The method of claim 1, wherein the Bronsted acid is formic acid or acetic acid.

### Claim 3 (depends on 2)

The method of claim 2 wherein the at least one polyester polyol included in component a) or provided in the preparation of the at least one isocyanate-terminated prepolymer in component b) has a hydroxyl functionality of at least 2.0 and an equivalent weight of 350 to 1500.

### Claim 4 (depends on 3)

The method of claim 3 wherein the at least one polyester polyol included in component a) or provided in the preparation of the at least one isocyanate-terminated prepolymer in component b) is an aliphatic polyester which is a reaction product of an aliphatic dicarboxylic acid or corresponding acid chloride or diester with at least one polyol having at least 2 hydroxyl groups and a hydroxyl equivalent weight of 150 or less.

### Claim 5 (depends on 4)

The method of claim 4, wherein the a) one or more polyols includes at least one tri- or higher functionality polyol and/or a diol having alkyl side groups.

### Claim 6 (depends on 1)

The method of claim 1 wherein the skin is a plasticized polymer of vinyl chloride.

### Claim 7 (depends on 1)

The method of claim 1, wherein the polyurethane-forming reaction mixture is formed into a layer between the skin and a substrate, and cured to form a polyurethane layer intermediate to the skin and the substrate and adhering to both.

### Claim 8 (depends on 1)

A skinned composite made in accordance with the method of claim 1.