Thermoplastic elastomeric resin composition and a process for the preparation thereof

• US 5,936,037 A
• Filed: 05/27/1997
• Issued: 08/10/1999
• Est. Priority Date: 05/28/1996
• Status: Expired due to Term

• Current Assignee: Riken Technos Corporation
• Original Assignee: Riken Vinyl Industry Co., Ltd.
• Inventors: Tasaka, Michihisa
• Primary Examiner(s): Short, Patricia A.
• Application Number:
  US08/864,061
• Time in Patent Office: 805 Days
• Field of Search: 525/92 F, 525/64, 525/66, 525/92 B, 525/92 C, 524/504, 524/505
• US Class Current: 525/92.00B
• CPC Class Codes: C08K 5/01 Hydrocarbons C08K5/0091 takes precedence
• CPC Class Codes: C08K 5/14 Peroxides
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2205/035 containing four or more polymers in a blend
• CPC Class Codes: C08L 23/00 Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 23/04 Homopolymers or copolymers of ethene
• CPC Class Codes: C08L 23/0884 Epoxide containing esters
• CPC Class Codes: C08L 23/10 Homopolymers or copolymers of propene
• CPC Class Codes: C08L 23/20 having four to nine carbon atoms
• CPC Class Codes: C08L 2312/00 Crosslinking
• 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 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; 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 51/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/02 of vinyl-aromatic monomers and conjugated dienes
• CPC Class Codes: C08L 53/025 modified
• CPC Class Codes: C08L 57/02 Copolymers of mineral oil hydrocarbons
• 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 75/04 : Polyurethanes
• 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: C08L 77/02 : Polyamides derived from omega-amino carboxylic acids or from lactams thereof C08L77/10 takes precedence
• CPC Class Codes: C08L 77/06 : Polyamides derived from polyamines and polycarboxylic acids C08L77/10 takes precedence
• CPC Class Codes: C08L 77/08 : from polyamines and polymerised unsaturated fatty acids
• CPC Class Codes: C08L 77/12 : Polyester-amides
• CPC Class Codes: C08L 9/00 : Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• CPC Class Codes: C08L 91/00 : Compositions of oils, fats or waxes; Compositions of derivatives thereof

Abstract

The invention provides a process for the preparation of a thermoplastic elastomeric resin composition comprising melt kneading

(a) 100 parts by weight of a block copolymer consisting of at least two polymeric blocks (A) composed mainly of a vinyl aromatic compound and at least one polymeric block (B) composed mainly of a conjugated diene compound, and/or a hydrogenated block copolymer obtained by hydrogenating said block copolymer,

(b) 20 to 300 parts by weight of a non-aromatic softening agent for rubber,

(c) 1 to 150 parts by weight of a peroxide-crosslinking type olefinic resin and/or a copolymeric rubber containing said resin, and

(d) 10 to 150 parts by weight of a peroxide-decomposing type olefinic resin and/or a copolymer containing said resin,

characterized in that the process comprises a step of heat-processing component (a), component (b), at least a part of component (c), at least a part of component (d) and at least a part of 1.0 to 1,200 parts by weight of component (e) in the presence of an organic peroxide to cause crosslinking, wherein component (e) is at least one thermoplastic polymer selected from the group consisting of polyester type (co)polymers, polyamide type (co)polymers and polyurethane type (co)polymers, and a subsequent step of blending these with the remaining part of component (c), and, the remaining part of component (d) and component (e), if any. The obtained composition is soft and excellent in heat deformation resistance and mechanical strength, moldability and processability, particularly in oil resistance and stain resistance.

Claims

1. A process for the preparation of a thermoplastic elastomeric resin composition comprising melt kneading

(a) 100 parts by weight of a block copolymer consisting of at least two polystyrene blocks (A) and at least one hydrogenated polyisoprene block (B) wherein from 70 to 100% by weight of isoprene is in 1,4-microstructure and at least 90% of the aliphatic double bonds derived from isoprene are hydrogenated,

(b) from 20 to 300 parts by weight of a non-aromatic softening agent for rubber, in which from 0 to 30% of the whole carbon atoms are in aromatic rings,

(c) from 1 to 150 parts by weight of a peroxide-crosslinking olefinic resin selected from the group consisting of modified polyethylenes and modified copolymeric rubbers of ethylene, the modification being made with a group which is able to react with a hydroxyl, carboxyl or amino group, and

(d) from 10 to 150 parts by weight of a peroxide-decomposing olefinic resin selected from the group consisting of polypropylenes and copolymers of propylene with a smaller amount of another α

-olefine,

characterized in that the process comprises a step of heat-processing component (a), component (b), at least a part of component (c), at least a part of component (d) and at least a part of from 1.0 to 1,200 parts by weight of component (e) in the presence of an organic peroxide to cause crosslinking, wherein component (e) is at least one thermoplastic polymer selected from the group consisting of polyester (co)polymers, polyamide (co)polymers and polyurethane (co)polymers, and a subsequent step of blending these with the remaining part of component (c), and the remaining part of component (d) and component (e), if any.

2. The process as described in claim 1, wherein component (c) is one which is modified with a carboxyl, acid anhydride, epoxy or oxazolinyl group.

3. The process as described in claim 1, wherein (f) at most 100 parts by weight of a hydrogenated petroleum resin are further blended before said heat-processing.

4. The process as described in claim 1, wherein (g) at most 100 parts by weight of an inorganic filler are blended in any step.

5. The process as described in claim 1, wherein at least 3 parts by weight of component (d) are subjected to said heat-processing in the presence of an organic peroxide and at least 5 parts by weight of component (d) are blended after said heat-processing.

6. The process as described in claim 1, wherein at least 1 part by weight of component (c) is subjected to said heat-processing.

7. The process as described in claim 1, wherein at least 10 parts by weight of component (e) are subjected to said heat-processing.

8. The process as described in claim 1, wherein the crosslinking is carried out in the presence of a crosslinking aid which is a monomer having an ethylenically unsaturated group.

9. The process as described in claim 1, wherein the organic peroxide is used in an amount of 0.1 to 4.0 parts by weight.

10. A thermoplastic elastomeric resin composition comprising

(a) 100 parts by weight of a block copolymer consisting of at least two polystyrene blocks (A) and at least one hydrogenated polyisoprene block (B) wherein from 70 to 100% by weight of isoprene is in 1,4-microstructure and at least 90% of the aliphatic double bonds derived from isoprene are hydrogenated,

(b) from 20 to 300 parts by weight of a non-aromatic softening agent for rubber in which from 0 to 30% of the whole carbon atoms are in aromatic rings,

(c) from 1 to 150 parts by weight of a peroxide-crosslinking olefinic resin selected from the group consisting of modified polyethylenes and modified copolymeric rubbers of ethylene, the modification being made with a group which is able to react with a hydroxyl, carboxyl or amino group, and

(d) from 10 to 150 parts by weight of a peroxide-decomposing olefinic resin selected from the group consisting of polypropylenes and copolymers of propylene with a smaller amount of another α

-olefine, characterized in that said composition further comprises

(e) from 1.0 to 1,200 parts by weight of at least one polymer selected from the group consisting of polyester (co)polymers, polyamide (co)polymers and polyurethane (co)polymers, and component (c) is modified with a group which is able to react with a hydroxyl, carboxyl or amino group.

11. The thermoplastic elastomeric resin composition as described in claim 10, wherein component (c) is one which is modified with a carboxyl, acid anhydride, epoxy or oxazolinyl group.

12. The thermoplastic elastomeric resin composition as described in claim 10, wherein the composition further comprises (f) at most 100 parts by weight of a hydrogenated petroleum resin.

13. The thermoplastic elastomeric resin composition as described in claim 10, wherein the composition further comprises (g) at most 100 parts by weight of an inorganic filler.

14. The thermoplastic elastomeric resin composition as described in claim 10, wherein the composition further comprises 0.1 to 10 parts by weight of a crosslinking aid which is a monomer having an ethylenically unsaturated group.