Thermoplastic elastomer composition, use thereof, method for producing same, ethylene/α-olefin/unconjugated polyene copolymer and use thereof

Patent metadata

Field	Value
Publication number	US-11078352-B2
Application number	US-201615559366-A
Country	US
Kind code	B2
Filing date	Mar 17, 2016
Priority date	Mar 20, 2015
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

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.

First claim

The invention claimed is:

1. A thermoplastic elastomer composition obtained by dynamically cross-linking a mixture containing
a crystalline olefin polymer (A),
an ethylene.α-olefin (C 4 -C 20 ).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 %.

2. 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).

3. 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.

4. 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).

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

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

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

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

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 C 4 -C 20 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.

10. 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).

11. 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.

12. 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).

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

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

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

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

Assignees

• Mitsui Chemicals Inc

Inventors

• Ichino Kotaro
• Yamaguchi Tomohiro
• Aita Yukio
• Noguchi Yuji

Classifications

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C08L61/06

  of aldehydes with phenols · CPC title

• C08L23/00

  Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title