# US 11,078,352 B2 · Thermoplastic elastomer composition, use thereof, method for producing same, ethylene/α-olefin/unconjugated polyene copolymer and use thereof

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- Number: US 11,078,352 B2
- Document ID: US11078352B2
- Status: Granted
- Kind: B2
- Application number: 15/559,366
- Filed: 2016-03-17
- Published: 2018-03-15
- Granted: 2021-08-03
- Earliest claimed: 2015-03-20
- Assignees: Mitsui Chemicals, Inc.
- Applicants: Mitsui Chemicals, Inc.
- Inventors: Kotaro Ichino; Tomohiro Yamaguchi; Yukio Aita; Yuji Noguchi
- Web page: https://patentgrep.com/patent/US11078352B2

## CPC

- C08L 23/083: {with aliphatic polyenes, i.e. containing two or more carbon-to-carbon double bonds}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08J 3/24: Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K)
- 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
- C08L 23/08: Copolymers of ethene (C08L23/16 takes precedence)
- C08L 61/06: of aldehydes with phenols
- C08F 2810/20: leading to a crosslinking, either explicitly or inherently
- C08J 2323/08: Copolymers of ethene (C08J2323/16 takes precedence)
- C08J 2423/12: Polypropene
- C08J 2461/06: of aldehydes with phenols
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2205/03: containing three or more polymers in a blend
- C08L 2207/04: Thermoplastic elastomer
- C08L 2312/04: with phenolic resin
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED 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

[Problem] The purpose of the invention is to provide: a thermoplastic elastomer composition capable of providing molded articles that are lightweight, have better oil resistance than those provided by conventional cross-linked thermoplastic elastomers, and have hardness and mechanical properties such as tensile strength and tensile elongation that are equal to or superior to those provided by conventional cross-linked thermoplastic elastomers; and an ethylene/α-olefin/unconjugated polyene copolymer having little compression set at low temperature as well as flexibility and an excellent balance of rubber elasticity at low temperature and tensile strength at normal temperature. [Solution] Produced are: a thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing a crystalline olefin polymer (A), an ethylene/α-olefin (having 4-20 carbon atoms)/unconjugated polyene copolymer (1B) that satisfies specific requirements, and a phenol resin-based crosslinking agent (C); and an ethylene-α-olefin/unconjugated polyene copolymer (2B) that satisfies specific requirements.

## Claims

### Claim 1

A thermoplastic elastomer composition obtained by dynamically cross-linking a mixture containing
a crystalline olefin polymer (A),
an ethylene.α-olefin (C4-C20).non-conjugated polyene copolymer (1B) satisfying the following requirements (1), (2), and (4), and
a phenol resin-based cross-linking agent (C);
wherein the crystalline olefin polymer (A) is a crystalline propylene polymer, and
wherein the α-olefin of the ethylene.α-olefin.non-conjugated polyene copolymer (1B) is 1-butene, and the non-conjugated polyene of the ethylene.α-olefin.non-conjugated polyene copolymer (1B) is at least one selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene;
(1) a B value represented by the following equation (i) is 1.20 to 1.80:
B value=([EX]+2[Y])/[2×[E]×([X]+[Y])] (i),
wherein [E], [X], and [Y] represent a mole fraction of structural units derived from the ethylene, a mole fraction of structural units derived from the C4-C20 α-olefin, and a mole fraction of structural units derived from the non-conjugated polyene respectively, and [EX] represents a diad chain fraction of the structural units derived from the ethylene—the structural units derived from the C4-C20 α-olefin; and
(2) in the copolymer (1B), a molar ratio of the structural units derived from the ethylene to the structural units derived from the α-olefin (C4-C20) is 40/60 to 70/30; and
(4) a content of the structural units derived from the non-conjugated polyene is 0.5 to 3.0 mol %, relative to a total of the structural units derived from the ethylene, the structural units derived from the α-olefin (C4-C20), and the structural units derived from the non-conjugated polyene as 100 mol %.

### Claim 2 (depends on 1)

The thermoplastic elastomer composition according to claim 1, wherein the mixture further comprises 2 to 100 parts by weight of a softener (D) relative to 100 parts by weight of a total of the crystalline olefin polymer (A) and the copolymer (1B).

### Claim 3 (depends on 1)

The thermoplastic elastomer composition according to claim 1, wherein the phenol resin-based cross-linking agent (C) is a halogenated phenol resin-based cross-linking agent.

### Claim 4 (depends on 1)

The thermoplastic elastomer composition according to claim 1, comprising the crystalline olefin polymer (A) and the ethylene.α-olefin.non-conjugated polyene copolymer (1B) at a weight ratio of (A)/(1B)=90/10 to 10/90, and comprising 0.1 to 20 parts by weight of the phenol resin-based cross-linking agent (C) relative to 100 parts by weight of the ethylene.α-olefin.non-conjugated polyene copolymer (1B).

### Claim 5 (depends on 1)

A molded article comprising the thermoplastic elastomer composition according to claim 1.

### Claim 6 (depends on 1)

An automobile part comprising the thermoplastic elastomer composition according to claim 1.

### Claim 7 (depends on 1)

An automobile hose comprising the thermoplastic elastomer composition according to claim 1.

### Claim 8 (depends on 1)

An automobile boot comprising the thermoplastic elastomer composition according to claim 1.

### Claim 9

A thermoplastic elastomer composition obtained by dynamically cross-linking a mixture containing
a crystalline olefin polymer (A),
an ethylene.α-olefin.non-conjugated polyene copolymer (2B), and
a phenol resin-based cross-linking agent (C),
wherein the crystalline olefin polymer (A) is a crystalline propylene polymer, and
wherein the ethylene.α-olefin.non-conjugated polyene copolymer (2B) is the ethylene.α-olefin.non-conjugated polyene copolymer (2B) comprising a structural unit derived from ethylene [A], a structural unit derived from a C4-C20 α-olefin [B], and a structural unit derived from a non-conjugated polyene [C], and satisfying the following (1) to (4), wherein the C4-C20 α-olefin [B] is 1-butene, and the non-conjugated polyene [C] is at least one selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene:
(1) a molar ratio ([A]/[B]) of the structural units derived from the ethylene [A] to the structural units derived from the α-olefin [B] is 40/60 to 70/30;
(2) a content of the structural units derived from the non-conjugated polyene [C] is 0.5 to 3.0 mol % based on a total of the structural units [A], [B], and [C] as 100 mol %;
(3) a Mooney viscosity ML(1+4)125° C. at 125° C. is more than 100 and not more than 200; and
(4) a B value represented by the following equation (i) is 1.20 to 1.80:
B value=([EX]+2[Y])/[2×[E]×([X]+[Y])] (i),
wherein [E], [X], and [Y] represent a mole fraction of the ethylene [A], the C4-C20 α-olefin [B], and the non-conjugated polyene [C] respectively, and [EX] represents an ethylene [A]- C4-C20 α-olefin [B] diad chain fraction.

### Claim 10 (depends on 9)

The thermoplastic elastomer composition according to claim 9, wherein the mixture further comprises 2 to 100 parts by weight of a softener (D) relative to 100 parts by weight of a total of the crystalline olefin polymer (A) and the copolymer (2B).

### Claim 11 (depends on 9)

The thermoplastic elastomer composition according to claim 9, wherein the phenol resin-based cross-linking agent (C) is a halogenated phenol resin-based cross-linking agent.

### Claim 12 (depends on 9)

The thermoplastic elastomer composition according to claim 9, comprising the crystalline olefin polymer (A) and the ethylene.α-olefin.non-conjugated polyene copolymer (2B) at a mass ratio of (A)/(2B)=90/10 to 10/90, and
comprising 0.1 to 20 parts by weight of the phenol resin-based cross-linking agent (C) relative to 100 parts by weight of the ethylene.α-olefin.non-conjugated polyene copolymer (2B).

### Claim 13 (depends on 9)

A molded article comprising the thermoplastic elastomer composition according to claim 9.

### Claim 14 (depends on 9)

An automobile part comprising the thermoplastic elastomer composition according to claim 9.

### Claim 15 (depends on 9)

An automobile hose comprising the thermoplastic elastomer composition according to claim 9.

### Claim 16 (depends on 9)

An automobile boot comprising the thermoplastic elastomer composition according to claim 9.