Multi-layer structure polymer composition

• US 4,508,875 A
• Filed: 08/26/1983
• Issued: 04/02/1985
• Est. Priority Date: 02/25/1981
• Status: Expired due to Term

• Current Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Original Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Inventors: Hasegawa, Akira, Kishida, Kazuo, Sugimori, Masahiro
• Primary Examiner(s): Michl, Paul R.
• Application Number:
  US06/526,546
• Time in Patent Office: 585 Days
• Field of Search: 525/308, 525/309, 525/310, 525/902
• US Class Current: 525/308
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 220/40 Esters of unsaturated alcohols , e.g. allyl (meth)acrylate
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 285/00 Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• CPC Class Codes: C08L 33/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C08L 51/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 69/00 Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: Y10S 525/902 Core-shell

Abstract

A multi-layer structure polymer composition having a gel content of at least 50% which is constituted of an innermost layer polymer (A) consisting mainly of alkyl acrylate and having a degree of swelling of 10 or lower, and having a glass transition temperature lower than 10° C., a crosslinked elastomer polymer (B) consisting mainly of alkyl acrylate and having a degree of swelling slightly higher than that of said polymer (A) and having a glass transition temperature not higher than 0° C., said innermost layer polymer (A) and said crosslinked elastomer polymer (B) constituting a double layer elastomer structure polymer, as well as an outermost layer polymer (C) consisting mainly of alkyl methacrylate and having a glass transition temperature not lower than 60° C., and at least one intermediate layer (D) existing between said polymer (B) layer and said polymer (C) layer, the amount of alkyl acrylate in said intermediate layer (D) linearly decreasing from said polymer (B) layer to said polymer (C) layer. Said polymer composition does not readily show the phenomenon of whitening even if dipped in hot water or boiling water and is excellent in weather resistance, solvent resistance, stress-whitening resistance, water-whitening resistance and transparency.

Claims

1. A multi-layer structure polymer composition having the following layers as fundamental structural units;

(a) an innermost layer polymer (A) comprising 50-100 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (A₁), 0-50 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (A₂), provided that the total of (A₁) and (A₂) is 80-100 parts by weight, 0-20 parts by weight of a monomer having a copolymerizable double bond (A₃), 0-10 parts by weight of a polyfunctional monomer (A₄), provided that the total of (A₁), (A₂), (A₃) and (A₄) is 100 parts by weight, and 0.1-5 parts by weight, per 100 parts by weight of the total of (A₁) to (A₄), of a graft linking agent (A₅) and having a glass transition temperature of lower than 10°

C., and a degree of swelling of from 2-10;

(b) a crosslinked elastic polymer (B) comprising 80-100 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (B₁), 0-20 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (B₂), 0-20 parts by weight of a monomer having a copolymerizable double bond (B₃), 0-10 parts by weight of a polyfunctional monomer (B₄), provided that the total of (B₁), (B₂) and (B₃) and (B₄) is 100 parts by weight, and 0.1-5 parts by weight, per 100 parts by weight of the total of (B₁) to (B₄), of a graft linking agent (B₅) and having a glass transition temperature of 0°

C. or lower and a degree of swelling of from 3-15, with the proviso that the degree of swelling of layer B is higher than that of said innermost layer polymer (A);

(c) an outermost layer polymer (C) comprising 51-100 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (C₂), 0-29 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (C₁) and 0-20 parts by weight of a monomer having a copolymerizable double bond (C₃), provided that the total of (C₁), (C₂) and (C₃) is 100 parts by weight, and having a glass transition temperature of 60°

C. or higher; and

(d) at least one intermediate layer (D) between said polymer (B) layer and said polymer (C) layer comprising 10-90 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (D₁), 90-10 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (D₂), 0-20 parts by weight of a monomer having a copolymerizable double bond (D₃), 0-10 parts by weight of a polyfunctional monomer (D₄), provided that the total of (D₁), (D₂), (D₃) and (D₄) is 100 parts by weight, and 0.15 parts by weight, based on a total of (D₁) to (D₄), of a graft linking agent (D₅), wherein the amount of alkyl acrylate in said intermediate layer (D) linearly decreases from the crosslinked elastic polymer (B) to the outermost layer polymer (C), and wherein the gel content of said multi-layer structural polymer composition is at least 50%.

2. The polymer composition according to claim 1, wherein the content of said polymer (A) is in the range of 5-35% by weight and is lower than the content of said polymer (B), the content of said polymer (B) is in the range of 10-45% by weight, the content of said polymer (C) is in the range of 10-80% by weight, and the content of each intermediate layer (D) is in the range of 5-35% by weight.

5. The polymer composition according to claim 1 which is produced by a successive multi-stage polymerization process by emulsion polymerization whereby the particle size of the emulsion in the final polymer composition is in the range of 800 Angstroms to 2000 Angstroms.

6. The polymer composition according to claim 1 which is produced by an emulsion-suspension polymerization process whereby an emulsion polymerization is initially carried out and thereafter a suspension polymerization is used for the polymerization of polymer (C).

7. The polymer composition according to claim 1, wherein said alkyl acrylate is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or n-octyl acrylate;

said alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate;

said monomer having copolymerizable double bond is lower alkyl (meth)acrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid or methacrylic acid;

said polyfunctional monomer is ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, divinylbenzene, trivinylbenzene or alkylene glycol diacrylate; and

said graft linking agent is allyl, methallyl or crotyl ester of α

,β

-unsaturated carboxylic or dicarboxylic acid or triallyl cyanurate or triallyl isocyannurate.

8. The polymer composition according to claim 1, wherein the content of residual metal in the multi-layer structure polymer composition is 500 ppm or less.

9. A film-formed or sheet-formed composition having a thickness of 1 mm or less which is obtained by molding the resin composition according to claim 1.

10. A resin composition comprising a mixture consisting of 99-1 parts by weight of a multi-layer structure polymer composition according to claim 1 and 1-99 parts by weight of a thermoplastic resin which is at least one polymer selected from the following group (a) or group (b) or a mixture of at least one polymer selected from group (a) and at least one polymer selected from group (b):

(a) homopolymers of vinyl monomers having the formula CH₂ ═

CHX, homopolymers of vinylidene monomers having the formula CH₂ ═

CXY and copolymers constituted of two or more members of these monomers, provided that X and Y in the above-mentioned formulas represent H, Cl, F, Br, CH₃, COOH, COOCH₃, CN, OCOCH₃, C₆ H₅, alkoxy, OCCH₃ or SO₃ H;

(b) polycarbonates, thermoplastic polyesters and polyamides.

11. The resin composition according to claim 10, wherein said thermoplastic resin selected from group (a) is a methyl methacrylate polymer.

12. The resin composition according to claim 10, wherein said thermoplastic resin selected from group (a) is polyvinyl chloride.

13. The resin composition according to claim 10, wherein said thermoplastic resin selected from group (a) is polyvinylidene fluoride.

14. The polymer composition according to claim 1, wherein said grafting agent (A₅) is present in the amount of 0.5-2.0 parts by weight per 100 parts by weight of (A₁)-(A₄).

15. The polymer composition according to claim 1, wherein said innermost layer polymer (A) is 5 to 35% by weight of the total weight.

16. The polymer composition according to claim 15, wherein said innermost layer polymer (A) is 5-15% by weight of the total weight, and is present in a lesser amount than said elastic polymer (B).

17. The polymer composition according to claim 1, wherein said elastic polymer (B) is present in the amount of 10-45 weight percent based on the total weight.

18. The polymer composition according to claim 1, wherein the degree of swelling of combined double layer (A) and (B) is 3-13.

19. The polymer composition according to claim 1, wherein the gel content of each of the polymer layers (A) and (B) is at least 60%.

20. The polymer composition according to claim 19, wherein said gel content of each layer is at least 85%.

3. A multi-layer structure polymer composition having the following layers as fundamental structure units:

(a) an innermost layer polymer (A) comprising 50-90 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (A₁), 1-50 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (A₂) provided that the total of (A₁) and (A₂) is 80-100 parts by weight, 0-19 parts by weight of a monomer having a copolymerizable double bond (A₃), 1-10 parts by weight of a polyfunctional monomer (A₄), provided that the total of (A₁), (A₂), (A₃) and (A₄) is 100 parts by weight, and 0.1-5 parts by weight, per 100 parts by weight of the total of (A₁) to (A₄), of a graph linking agent (A₅) and having a glass transition temperature of lower than 10°

C., a gel content of 80% by weight or higher, and a degree of swelling of from 2-10;

(b) a crosslinked elastic polymer (B) comprising 90-100 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (B₁), 0-10 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (B₂), 0-20 parts by weight of a monomer having a copolymerizable double bond (B₃), 0-10 parts by weight of a polyfunctional monomer (B₄), provided that the total of (B₁), (B₂), (B₃) and (B₄) is 100 parts by weight, and 0.1-5 parts by weight, per 100 parts by weight of the total of (B₁) to (B₄), of the graft linking agent (B₅) and having a glass transition temperature of 0°

C. or lower and a degree of swelling of from 3-15, with the proviso that the degree of swelling of layer (B) is a higher than that of said innermost layer polymer (A);

(c) an outermost layer polymer (C) comprising 75-100 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (C₂), 0-25 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (C₁) and 0-20 parts by weight of a monomer having a copolymerizable double bond (C₃), provided that the total of (C₁), (C₂) and (C₃) is 100 parts by weight, and having a glass transition temperature of 60°

C. or higher; and

(d) at least one intermediate layer (D) between said polymer (B) layer and said polymer (C) layer comprising 30-70 parts by weight of an alkyl acrylate having a C₁ -C₈ alkyl group (D₁), 70-30 parts by weight of an alkyl methacrylate having a C₁ -C₄ alkyl group (D₂), 0-20 parts by weight of a monomer having a copolymerizable double bond (D₃), 0-10 parts by weight of a polyfunctional monomer (D₄), provided that the total of (D₁), (D₂), (D₃) and (D₄) is 100 parts by weight, and 0.1-5 parts by weight, based on the total of (D₁) to (D₄) of a graft linking agent (D₅), wherein the amount of alkyl acrylate in said intermediate layer (D) linearly decreases from the crosslinked elastic polymer (B) to the outermost layer polymer (C), and wherein the gel content of said multi-layer structural polymer composition is at least 50%.

4. The polymer composition according to claim 3, wherein the content of said polymer (A) is in the range of 5-15% by weight and is lower than the content of said polymer (B), the content of said polymer (B) is in the range of 10-45% by weight, the content of said polymer (C) is in the range of 40-60% by weight, and the content of said intermediate layer (D) is 5-35% by weight.