# US 9,517,607 B2 · Skinned substrates with highly crosslinked polyurethane layer

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- Number: US 9,517,607 B2
- Document ID: US9517607B2
- Status: Granted
- Kind: B2
- Application number: 14/410,090
- Filed: 2013-06-20
- Published: 2016-01-21
- Granted: 2016-12-13
- Earliest claimed: 2012-06-27
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Sara Cavalca; Sabrina Fregni
- Web page: https://patentgrep.com/patent/US9517607B2

## CPC

- B32B 5/20: foamed in situ
- B29C 44/1233: {the preformed parts being supported during expanding}
- B32B 27/065: {of foam}
- B32B 27/20: using fillers, pigments, thixotroping agents
- B32B 27/22: using plasticisers
- B32B 27/302: {comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers}
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/306: {comprising vinyl acetate or vinyl alcohol (co)polymers}
- B32B 27/365: {comprising polycarbonates}
- C08G 18/4018: {Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48}
- C08G 18/4816: {mixtures of two or more polyetherpolyols having at least three hydroxy groups}
- C08G 18/482: {Mixtures of polyethers containing at least one polyether containing nitrogen}
- C08G 18/4833: {Polyethers containing oxyethylene units}
- C08G 18/4841: {containing oxyethylene end groups}
- C08G 18/5021: {having nitrogen}
- C08G 18/7664: {containing alkylene polyphenyl groups}
- C08J 9/35: Composite foams, i.e. continuous macromolecular foams containing discontinuous cellular particles or fragments
- B29K 2075/00: Use of {PU, i.e.} polyureas or polyurethanes {or derivatives thereof}, as moulding material
- B29K 2105/04: cellular or porous
- B29K 2627/06: PVC, i.e. polyvinylchloride
- B32B 2266/0278: Polyurethane
- B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers
- B32B 2307/71: Resistive to light or to UV
- B32B 2307/734: Dimensional stability
- B32B 2605/003: Interior finishings
- C08G 2110/0058: ≥50 and <150kg/m3
- C08J 2375/08: from polyethers
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- 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)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

PVC-skinned composites include a substrate, a skin and an intermediate polyurethane layer. The polyurethane layer is characterized in having a low molecular weight between crosslinks, i.e., is somewhat highly crosslinked. The high level of crosslinking in the polyurethane leads to improved performance of the skin layer. The skin layer retains its original color upon aging, is less prone to shrinking and other loss of physical properties, and adheres better to the polyurethane layer.

## Claims

### Claim 1

A skinned composite comprising
a) a substrate,
b) an exterior plasticized polymeric skin having a thickness of 0.5 to 2 mm covering at least a portion of the substrate, the exterior plasticized polymer skin comprising a thermoplastic polymer and 25 to 45% by weight of a plasticizer based on the combined weight of the plasticizer and the thermoplastic polymer and further having one or more score lines on an exposed and/or an inner surface; and
c) a polyurethane layer interposed between the substrate and the plasticized polymeric skin, wherein the polyurethane layer is the reaction product of a reaction mixture that contains one or more polyisocyanates and one or more isocyanate-reactive compounds that contain two or more isocyanate-reactive groups, wherein the polyurethane has a calculated molecular weight per crosslink of no greater than 1250 as calculated by the formula
MW
xl
=
A
+
B
A
⁡
(
C
-
2
)
CD
+
B
⁡
(
F
-
2
)
EFG
+
B
⁡
(
F
-
1
)
⁢
(
1
-
1
E
)
(
E
+
1
)
⁢
G
wherein
A is the combined weight, in grams, of all isocyanate-reactive materials that contain at least 2 isocyanate-reactive groups/molecule, including any water, provided to the reaction mixture;
B is the combined weight, in grams, of all isocyanate compounds provided to the reaction mixture;
C is average functionality of all isocyanate-reactive compounds provided to the reaction mixture that contain at least 2 isocyanate-reactive groups/molecule, including any water;
D is the average equivalent weight in grams per hydroxyl group of all isocyanate-reactive compounds provided to the reaction mixture that contain at least 2 isocyanate-reactive groups/molecule, including any water;
E is the isocyanate index, calculated as the number of equivalents of isocyanate groups provided to the reaction mixture divided by the number of equivalents of isocyanate-reactive groups provided to the reaction mixture;
F is the average functionality of all isocyanate compounds provided to the reaction mixture; and
G is the average equivalent weight in grams per isocyanate group of all isocyanate compounds provided to the reaction mixture.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 1)

The skinned composite of claim 1, wherein the density of the polyurethane layer is from 48 to 480 kg/m3.

### Claim 4 (depends on 1)

The skinned composite of claim 1 wherein the polyisocyanate(s) have an average functionality of at least 2.0 and an isocyanate equivalent weight of 85-200.

### Claim 5 (depends on 1)

The skinned composite of claim 1 which exhibits a discoloration, after heating for 8 days at 120° C., characterized by a ΔE* value of 3 or less.

### Claim 6 (depends on 1)

A method for preparing the skinned composite of claim 1, comprising positioning the skin and the substrate within a mold to form a gap between the skin and the substrate, introducing the reaction mixture into the mold between the skin and the substrate and curing the reaction mixture in the mold between the skin and substrate.

### Claim 7

A skinned composite comprising
a) a substrate,
b) an exterior plasticized polymeric skin having a thickness of 0.5 to 2 mm covering at least a portion of the substrate, the exterior plasticized polymer skin comprising a thermoplastic polymer and 25 to 45% by weight of a plasticizer based on the combined weight of the plasticizer and the thermoplastic polymer, and further having one or more score lines on an exposed and/or an inner surface; and
c) a polyurethane layer interposed between the substrate and the plasticized polymeric skin, wherein the polyurethane layer is the reaction product of a reaction mixture that contains one or more polyisocyanates and one or more isocyanate-reactive compounds that contain two or more isocyanate-reactive groups, wherein the reaction mixture has an isocyanate index of from 0.9 to 1.25 and the isocyanate-reactive compounds that contain two or more isocyanate-reactive groups are selected from the group consisting of:
1) a blend of a high functionality polyol having a hydroxyl functionality of at least 4, and a hydroxyl equivalent weight of 80 to 250 with at least one low equivalent weight polyol, aminoalcohol or polyamine that has an equivalent weight per isocyanate group of up to about 125, and a functionality of 3 to 4;
2) a blend of a high functionality polyol having a hydroxyl functionality of at least 4, and a hydroxyl equivalent weight of 80 to 250 with one or more high equivalent weight polyether polyols or polyether amines, the high equivalent weight polyol or polyether amine having a functionality of 2 to 3 and an equivalent weight of at least 350 to 2200;
3) a blend of a high functionality polyol having a hydroxyl functionality of at least 4, and a hydroxyl equivalent weight of 80 to 250 with at least one low equivalent weight polyol, aminoalcohol or polyamine that has an equivalent weight per isocyanate group of up to about 125and a functionality of 3 to 4 and one or more high equivalent weight polyols or polyether amines having a functionality of 2 to 3 and an equivalent weight of at least 350 to 2200;
4) a blend as in any of 1)-3), further including water; and
5) a blend as in any of 1)-4), further including one or more aliphatic polyesters having a hydroxyl functionality of at least 2 and a hydroxyl equivalent weight of about 350 to 1500 and which are 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, or a mixture of such a polyol with one or more diols having a hydroxyl equivalent weight of 150 or less.

### Claim 8 (depends on 7)

The skinned composite of claim 7 wherein the skin is a plasticized polymer of vinyl chloride.

### Claim 9 (depends on 7)

The skinned composite of claim 7, wherein the density of the polyurethane layer is from 48 to 480 kg/m3.

### Claim 10 (depends on 7)

The skinned composite of claim 7 wherein the polyisocyanate(s) have an average functionality of at least 2.0 and an isocyanate equivalent weight of 85-200.

### Claim 11 (depends on 7)

The skinned composite of claim 7 which exhibits a discoloration, after heating for 8 days at 120° C., characterized by a ΔE* value of 3 or less.

### Claim 12 (depends on 7)

A method for preparing the skinned composite of claim 7, comprising positioning the skin and the substrate within a mold to form a gap between the the skin and the substrate, introducing the reaction mixture into the mold between the skin and the substrate and curing the reaction mixture in the mold between the skin and the substrate.