Composite with gloss reducing polymer composition

• US 20090191400A1
• Filed: 03/31/2009
• Published: 07/30/2009
• Est. Priority Date: 09/15/2004
• Status: Active Grant

• Current Assignee: Rohm and Haas Company (Dow, Inc.)
• Original Assignee: Rohm and Haas Company (Dow, Inc.)
• Inventors: Vanrheenen, Paul
• Granted Patent: US 7,989,082 B2
• Time in Patent Office: Days
• US Class Current: 428/319.7
• CPC Class Codes: B32B 2250/24 All layers being polymeric
• CPC Class Codes: B32B 2264/0242 Vinyl halide, e.g. PVC, PVDC, PVF or PVDF (co)polymers
• CPC Class Codes: B32B 2264/025 Acrylic resin particles, e.g. polymethyl methacrylate or ethylene-acrylate copolymers
• CPC Class Codes: B32B 2264/12 Mixture of at least two particles made of different materials
• CPC Class Codes: B32B 2307/408 Matt, dull surface
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/712 Weather resistant
• CPC Class Codes: B32B 2419/00 Buildings or parts thereof
• CPC Class Codes: B32B 25/042 of natural rubber or synthetic rubber
• CPC Class Codes: B32B 25/08 of synthetic resin
• CPC Class Codes: B32B 25/14 comprising synthetic rubber copolymers B32B25/18 and B32B25/20 take precedence
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/20 using fillers, pigments, thixotroping agents
• CPC Class Codes: B32B 27/26 using curing agents
• CPC Class Codes: B32B 27/304 comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: C08F 2/22 Emulsion polymerisation
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 265/06 Polymerisation of acrylate or methacrylate esters on to polymers thereof
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/24 : Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 33/06 : of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• CPC Class Codes: C08L 51/00 : Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds for ABS polymers C08L55/02; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 51/003 : grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 51/04 : grafted on to rubbers
• CPC Class Codes: C08L 61/24 : with urea or thiourea
• CPC Class Codes: C08L 61/28 : with melamine
• CPC Class Codes: 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
• CPC Class Codes: Y10T 428/249992 : Linear or thermoplastic
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/3158 : Halide monomer type [polyvinyl chloride, etc.]
• CPC Class Codes: Y10T 428/31583 : Nitrile monomer type [polyacrylonitrile, etc.]
• CPC Class Codes: Y10T 428/31587 : Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• CPC Class Codes: Y10T 428/3175 : Next to addition polymer from unsaturated monomer[s]
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 : Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/3192 : Next to vinyl or vinylidene chloride polymer
• CPC Class Codes: Y10T 428/31931 : Polyene monomer-containing
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer

Abstract

Thermoplastic polymer compositions are disclosed that can be processed into capstocks having a reduced gloss appearance, high impact strength and superior weatherability. The capstocks described herein are especially useful for extrusion into articles. They are also useful for application to various poor weathering structural plastic articles for preparing multi-layered composites having improved weatherability. Methods for manufacturing structural plastic capstocks and composites and articles produced therefrom having reduced gloss appearance are also described.

Claims

1. A synthetic composite comprising:

(a) an extrudable thermoplastic substrate layer and

(b) an extrudable thermoplastic capstock layer disposed thereon comprising

(i) a core/shell polymer wherein (i) the core comprises 45 to 99.9, parts by weight of units derived from at least one C1-C8 alkyl acrylate monomer, and from 0.1 to 5 parts by weight of units derived from at least one crosslinker, and

(ii) the shell comprises 80 to 99 parts by weight of units derived from at least one C1-C8 alkyl methacrylate monomer, and 1 to 20 by weight of units derived from at least one ethylenically unsaturated copolymerizable monomer different from the at least one C1-C8 alkyl methacrylate monomer and wherein the shell has a Tg above 20°

C.; and

(ii) at least 1% by weight of an acrylic polymer that contains 1-15%, by weight of the acrylic polymer, of one or more monomers selected from the

group consisting of (mono, di, tri alkoxysilyl) alkyl(meth)acrylate, methylol

acrylamide, methylol methacrylamide, methyl acrylamidoglycolate methyl

ether, and acrylamidoglycolic acid.

2. The synthetic composite of claim 1 wherein the capstock layer further comprises a curing agent capable of reacting with the curable gloss reducing acrylic polymer.

3. The synthetic composite of claim 2 wherein the curable gloss reducing acrylic polymer comprises, as polymerized units, one or more carboxylic acid functional monomers and the curing agent comprises one or more compositions selected from the group consisting of polyfunctional amines, polyfunctional epoxides, polyfunctional carbodiimides, polyols, polyisocyantes, activated polyamides, melamine-formaldehyde resins, urea-formaldehyde and polyaziridines.

4. The synthetic composite of claim 1 wherein the thermoplastic polymer of the capstock layer further comprises a non-core/shell polymer.

5. The synthetic composite of claim 1 wherein the thermoplastic substrate layer comprises one or more polymers selected from the group consisting of poly(vinyl chloride), chlorinated poly(vinyl chloride), high impact polystyrene, polypropylene, acrylonitrile-butadiene-styrene, and combinations thereof.

6. The synthetic composite of claim 1 wherein the thermoplastic substrate layer is a foamed material.

7. The synthetic composite of claim 1 wherein the capstock layer has an average gloss measured at a 75 degree incident angle geometry of less than 35.

8. The synthetic composite of claim 1 wherein the capstock layer has a drop dart impact strength of greater than 25 in-lbs per 40 mils thickness at 23°

C. according to ASTM D4226.

9. The synthetic composite of claim 7 wherein the capstock layer has a drop dart impact strength of greater than 25 in-lbs per 40 mils thickness at 23°

C. according to ASTM D4226.

10. The synthetic composite of claim 1 wherein the core of the core/shell polymer comprises 80 to 99.5 parts by weight of units derived from at least one C1-C8 alkyl acrylate monomer;

0.5 to 2 parts by weight of units derived from at least one crosslinker, and the shell of the core/shell polymer comprises 85 to 97 by weight of units derived from at least one C1-C8 alkyl methacrylate monomer and 10 to 20 parts by weight of units derived from at least one ethylenically unsaturated copolymerizable monomer different from the at least one C1-C8 alkyl methacrylate monomer; and

wherein the acrylic polymer comprises at least 5% by weight of an acrylic polymer that itself contains 1-15% by weight of one or more monomers selected from the group consisting of (mono, di, tri alkoxysilyl) alkyl(meth)acrylate, methylol acrylamide, methylol methacrylamide, methyl acrylamidoglycolate methyl ether, and acrylamidoglycolic acid.

11. The synthetic composite of claim 1 wherein the core of the core/shell polymer comprises 94 to 99.5 by weight of units derived from at least one C1-C8 alkyl acrylate monomer and 0.5 to 1.5 parts by weight of units derived from at least one crosslinker, and the shell of the core/shell polymer comprises 92 to 96 by weight of units derived from at least one C1-C8 alkyl methacrylate monomer and 10 to 20 parts by weight of units derived from at least one ethylenically unsaturated copolymerizable monomer different from the at least one C1-C8 alkyl methacrylate monomer.

12. The synthetic composite of claim 1 wherein the extrudable thermoplastic capstock layer comprises:

(a) a core/shell polymer wherein (i) the core comprises 45 to 99.9, parts by weight of units derived from at least one C1-C8 alkyl acrylate monomer, and 0.1 to 5 parts by weight of units derived from at least one crosslinker, and (ii) the shell comprises 80 to 99 parts by weight of units derived from at least one C1-C8 alkyl methacrylate monomer, and 1 to 20 by weight of units derived from at least one ethylenically unsaturated copolymerizable monomer different from the at least one C1-C8 alkyl methacrylate monomer and wherein the shell has a Tg above 20°

C.;

(b) at least 1% by weight of an acrylic polymer that itself contains 1-15% by weight of one or more monomers selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, maleic anhydride, itaconic anhydride, dimethyl amino ethyl(meth)acrylic, dimethyl amino propylmethacrylamide, vinyl pyridine, t-butylaminoethyl methacrylate, hydroxylpropyl(meth)acrylate, hydroxylethyl(meth)acrylate, acetoacetoxyethyl(meth)acrylate, glycidyl(meth)acrylate, allyl glycidyl ether, vinyl isocyanate, and allyl isocyanate; and

(c) 0.1 to 10% by weight based on the weight of polymer (b) of a curing agent for polymer (b).