IP Library Granted Patent US 8,101,254
Granted Patent B2
US 8,101,254 · App. 12/314,155 · Granted Jan 24, 2012

Rubber composition, crosslinked product and foam thereof, molded product therefrom, and use thereof

Assignee: Mitsui Chemicals, Inc.
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Quick Facts
Patent No.
US 8,101,254
App. No.
12/314,155
Granted
Jan 24, 2012
Kind
B2
Abstract

The present invention provides a molded product exhibiting excellent various properties by improving compatibility of an ethylene/α-olefin/non-conjugated polyene copolymer with a polyolefin resin and a rubber composition for forming the molded product. The present invention further provides a molded product which comprises a rubber composition, is inhibited from fogging and tackiness and is excellent in mechanical strength and heat aging resistance. The rubber composition of the invention comprises an ethylene/α-olefin/non-conjugated polyene copolymer (A), and a polyolefin resin (B) having Mn of not less than 10,000 and/or an ethylene/α-olefin copolymer (C) having Mn of 2500 to 5000, and satisfies the following requirements: (1) a maximum value and a minimum value of an ethylene distribution parameter P of the component (A) have a relationship of Pmax/Pmin≦1.4, and (2) the B value of the component (C) ([EX]/(2[E]×[X])) ([E] and [X] are molar fractions of ethylene and the α-olefin of 3 to 20 carbon atoms, respectively, and [EX] is a fraction of dyad sequence of ethylene/α-olefin of 3 to 20 carbon atoms) is not more than 1.05.

Claims (35)

1. A rubber composition comprising an ethylene/α-olefin/non-conjugated polyene copolymer (A), and a polyolefin resin (B) and/or an ethylene/C3-C20 α-olefin copolymer (C), wherein

(1) a maximum value Pmax and a minimum value Pmin of an ethylene distribution parameter P of the ethylene/α-olefin/non-conjugated polyene copolymer (A), as determined by the following measuring method (X), have a relationship of Pmax/Pmin≦1.4,

measuring method (X): a test sample obtained by dissolving the ethylene/α-olefin/non-conjugated polyene copolymer (A) in cyclohexane is subjected to measurement with GPC-offline-FTIR using cyclohexane as an eluent under the conditions of a flow rate of 1.0 ml/min and a temperature of 60° C., and a peak intensity ratio (A721 cm −1 /A4320 cm −1 ) of a maximum peak (A721 cm −1 ) of the resulting spectrum in the range of 721±20 cm −1 to a maximum peak (A4320 cm −1 ) thereof in the range of 4320±20 cm −1 is regarded as an ethylene distribution parameter P,

and

(2) the B value of the ethylene/C3-C20 α-olefin copolymer (C), which is represented by the following formula (i), is not more than 1.05,

B value=[ EX ]/(2 [E]×[X ])  (i)

wherein [E] and [X] are molar fractions of ethylene and the α-olefin of 3 to 20 carbon atoms, respectively, and [EX] is a fraction of dyad sequence of ethylene/α-olefin of 3 to 20 carbon atoms.

2. The rubber composition as claimed in claim 1 , wherein the ethylene/α-olefin/non-conjugated polyene copolymer (A) satisfies the following requirements:

(1) the content of constituent units derived from ethylene is in the range of 50 to 90% by mol,

(2) the content of constituent units derived from the non-conjugated polyene is in the range of 0.1 to 5% by mol,

(3) the intrinsic viscosity [η] is in the range of 0.5 to 5.0 dl/g, and

(4) The B value represented by the following formula (ii) is not more than 1.05,

B value=([ EX]+ 2 [Y ])/{2 [E ]×([ X]+[Y ])}  (ii)

wherein [E], [X] and [Y] are molar fractions of ethylene, the α-olefin of 3 to 20 carbon atoms and the non-conjugated polyene, respectively, and [EX] is a fraction of dyad sequence of ethylene/α-olefin of 3 to 20 carbon atoms,

and

the content of constituent units derived from ethylene in the α-olefin copolymer (C) is in the range of 50 to 90% by mol.

3. The rubber composition as claimed in claim 1 or 2 , wherein the ethylene/α-olefin/non-conjugated polyene copolymer (A) and/or the α-olefin copolymer (C) is obtained by polymerization using a catalyst having a structure represented by the following formula (I):

4. The rubber composition as claimed in claim 1 or 2 , which contains the polyolefin resin (B) in an amount of 5 to 100 parts by weight and/or the α-olefin copolymer (C) in an amount of 1 to 50 parts by weight, based on 100 parts by weight of the ethylene/α-olefin/non-conjugated polyene copolymer (A).

5. The rubber composition as claimed in claim 1 or 2 , wherein the polyolefin resin (B) contains at least one resin selected from the group consisting of a polyethylene resin, a crystalline ethylene/α-olefin copolymer of ethylene and an α-olefin and a polypropylene resin.

6. The rubber composition as claimed in claim 1 or 2 , wherein the constituent units derived from the non-conjugated polyene of the component (A) are constituent units derived from at least one non-conjugated polyene selected from the group consisting of 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB).

7. The rubber composition as claimed in claim 1 or 2 , further comprising a reinforcing agent.

8. The rubber composition as claimed in claim 7 , wherein the reinforcing agent is carbon black.

9. The rubber composition as claimed in claim 8 , wherein the carbon black is contained in an amount of 20 to 200 parts by weight based on 100 parts by weight of the ethylene/α-olefin/non-conjugated polyene copolymer (A).

10. The rubber composition as claimed in claim 1 or 2 , which is obtained by alloying the ethylene/α-olefin/non-conjugated polyene copolymer (A) with the polyolefin resin (B) and/or the ethylene/C3-C20 α-olefin copolymer (C) by means of an extruder in the presence of a solvent.

11. The rubber composition as claimed in claim 1 or 2 , which is obtained by alloying an ethylene/α-olefin/non-conjugated polyene copolymer composition (A′) that is obtained by mixing the ethylene/α-olefin/non-conjugated polyene copolymer (A) with a softener (X), with the polyolefin-resin (B) by means of an extruder.

12. The rubber composition as claimed in claim 11 , wherein the softener (X) is at least one softener selected from the group consisting of mineral oil and an ethylene/C3-C20 α-olefin copolymer having a number-average molecular weight in terms of polystyrene, as measured by gel permeation chromatography (GPC), of 2500 to 5000.

13. The rubber composition as claimed in claim 11 , wherein the softener (X) is contained in an amount of 0.1 to 120 parts by weight based on 100 parts by weight of the ethylene/α-olefin/non-conjugated polyene copolymer (A).

14. The rubber composition as claimed in claim 1 or 2 , further comprising paraffinic oil (D), wherein the paraffinic oil (D) is contained in an amount of 1 to 200 parts by weight based on 100 parts by weight of the ethylene/α-olefin/non-conjugated polyene copolymer (A).

15. An olefin-based thermoplastic elastomer obtained by treating the rubber composition of claim 1 or 2 and a polypropylene-based resin through dynamic crosslinking in the presence of a crosslinking agent.

16. A crosslinked product obtained by crosslinking the rubber composition of claim 1 or 2 .

17. A foamed product obtained by crosslinking and foaming the rubber composition of claim 1 or 2 .

18. A glass run channel, a weatherstrip sponge, door opening trim or an automobile seal part comprising the crosslinked product of claim 16 or the foamed product of claim 17 .

19. A part for automobiles, a part for ships, a part for civil engineering and construction, a medical part, a part for electric/electronic components, a seal article, a sheet, a shoe, a tire sidewall, a tire tube, a covered electric wire, an electrically insulating part, a household rubber article, a part for leisure, a coating material or an adhesive obtained by the use of the rubber composition of claim 1 or 2 .

20. A hose which is the hose of claim 19 and has a tensile creep value (change of elongation in heating of the hose from 25° C. to 80° C. at a rate of 2° C./min under a constant load of 0.6 MPa using a viscoelasticity tester) of not more than 2.5%.

21. A hose which is the hose of claim 19 and has a shrinkage ratio (change of length in crosslinking of an unvulcanized hose) of not more than 4.0%.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 29, 2009
From: NOGUCHI, YUJI; HAKUTA, TAKASHI; EBATA, HIROKI; ICHINO, KOTARO; NONAKA, SHUICHI; HASE, SATOSHI; KANEKO, KAZUYOSHI; TAKEHARA, AKINORI
To: MITSUI CHEMICALS, INC.
Reel/Frame 022754/0446 →
Priority Claims (5)
JP 2007-314885 · Dec 5, 2007 · national
JP 2007-314887 · Dec 5, 2007 · national
JP 2008-028670 · Feb 8, 2008 · national
JP 2008-192846 · Jul 25, 2008 · national
JP 2008-194056 · Jul 28, 2008 · national
Continuity (3)
Provisional Application 60996822 · Dec 6, 2007
Provisional Application 60996824 · Dec 6, 2007
Related Publication 20090239014A1 · Sep 24, 2009