JP2018178006A - Thermoplastic elastomer composition, and application and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition less in deterioration of a polyacetal resin even when used in an application for contacting with the polyacetal resin.SOLUTION: There are provided a thermoplastic elastomer composition containing 90 to 10 pts.mass of ethylene α-olefin non-conjugated polyene copolymer (A), and 10 to 90 pts.mass of a crystalline olefin polymer (B) selected from homopolypropylene and/or a copolymer of propylene and α-olefin (excluding propylene), where propylene content is 40 mol% or more, where total amount of (A) and (B) is 100 pts.mass, and satisfying following requirements (i) to (iii): (i) percentage contents of a Sn element and a Pb element is 500 ppm or less as total, (ii) Shore A hardness according to JIS K6253 (instantaneous value):30 to 90, (iii) melt flow rate (ASTM D1238-65T;230°C, 10 kg load) of 1 to 150 g/10 min. or melt flow rate (ASTM D1238-65T;230°C, 2.16 kg load) of 0.1 to 10 g/10 min., a molded body in which a layer (I) containing the composition and a layer (II) containing a polyacetal resin are in contact, and a manufacturing method of the composition.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic elastomer composition, and a molded article and a method for producing the same.

  Thermoplastic elastomers are widely used in energy saving, resource saving type elastomers, especially as auto parts, industrial machine parts, electric / electronic parts, building materials etc. as substitutes for vulcanized rubber, because they are lightweight and easy to recycle. There is.

  Among them, olefin-based thermoplastic elastomers use ethylene / propylene / non-conjugated diene copolymer (EPDM) and crystalline polyolefins such as polypropylene as raw materials, so they have lower specific gravity and heat resistance than other thermoplastic elastomers. It is excellent in aging resistance, durability such as weather resistance, but depending on the application, further improvement is required.

  In addition, it is known that use of a phenol resin-based crosslinking agent and tin chloride as a crosslinking accelerator is effective for crosslinking of a general olefin-based thermoplastic elastomer (Patent Document 1).

International Publication No. 2016/204897 (Paragraph 0062)

  When the present inventors used a molded article of a thermoplastic elastomer composition using tin chloride or the like as a crosslinking accelerator for use in contact with a polyacetal resin, there arises a problem that the polyacetal resin is deteriorated with the passage of time. I understand.

  An object of the present invention is to provide a thermoplastic elastomer composition in which the polyacetal resin is less deteriorated even when used for application in contact with the polyacetal resin.

  As a result of examining in detail the relation between the content of Sn (tin) element and Pb (lead) element in the thermoplastic elastomer and the deterioration of the polyacetal resin in order to achieve the above-mentioned problems, the present inventors found out that Sn It has been found that the deterioration of the polyacetal resin is prevented by reducing the content of the element and the Pb element to 500 ppm or less in total.

That is, the gist of the present invention is as follows.
(1) 90. 10 parts by mass of ethylene / α-olefin / nonconjugated polyene copolymer (A), homopolypropylene, and / or copolymer of propylene and α-olefin (except for propylene) Thermoplastic elastomer composition containing 10 to 90 parts by mass of crystalline olefin polymer (B) selected from 40 mol% or more (provided that the total amount of (A) and (B) is 100 parts by mass) The object,
The following requirements (i) to (iii):
(I) The total content of Sn and Pb elements is 500 ppm or less in total,
(Ii) Shore A hardness (instantaneous value) according to JIS K6253: 30 to 90, and
(iii) Melt flow rate (ASTM D 1238-65 T; 230 ° C., 10 kg load) 1 to 150 g / 10 min or melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 0.1 to 10 g / 10 min Thermoplastic elastomer composition satisfying the requirements.
(2) At least one selected from the group consisting of a copolymer of an aromatic vinyl compound and a conjugated diene compound, a hydrogenated product of a copolymer of an aromatic vinyl compound and a conjugated diene compound, and a hydrogenated conjugated diene compound polymer The composition according to the above (1), wherein the polymer comprises 10 to 100 parts by mass of one polymer per 100 parts by mass of the ethylene / α-olefin / nonconjugated polyene copolymer (A).
(3) The composition according to (1) or (2), which is crosslinked with an organic peroxide.
(4) The composition according to (1) or (2), which is crosslinked with a halogenated phenolic resin crosslinking agent.
(5) A composition comprising 10 to 65% by mass of the composition according to any one of the above (1) to (4) and 35 to 90% by mass of a polyacetal resin.
(6) The molded object which layer (I) containing the composition in any one of said (1)-(4) and layer (II) containing polyacetal resin contact.
(7) The molded object as described in said (6) which is a motor vehicle component.
(8) The composition according to any one of the above (1) to (4), characterized in that the raw material composition is thermally treated without blending an additive containing a Sn element and / or a Pb element. Manufacturing method.

  The thermoplastic elastomer composition of the present invention causes less deterioration of the polyacetal resin even when used for applications in contact with the polyacetal resin.

<Ethylene · α-olefin · nonconjugated polyene copolymer (A)>
The ethylene / α-olefin / nonconjugated polyene copolymer (A) (also referred to as a copolymer (A) in the present invention) used in the present invention usually comprises (a) a unit derived from ethylene, and (b) α 50/50 to 95/5, preferably 60/40 to 80/20, more preferably 65/35 to 75/25 [(a) / (b)], with units derived from olefins Include in range.

  Further, the copolymer (A) comprises units (a) derived from ethylene, units (b) derived from α-olefins, and non-conjugated polyenes (c) derived from α-olefins. The total amount is preferably in the range of 50 to 90 mol%, more preferably 60 to 85 mol%, based on 100 mol%.

  The α-olefin constituting the ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention is usually an α-olefin having 3 to 20 carbon atoms, and specifically, propylene, 1 -Butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like. Among them, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. You may use these alpha-olefins individually or in combination of 2 or more types.

  Specific examples of the nonconjugated polyene constituting the ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4 -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1 Non-conjugated dienes such as 7, 7-nonadiene, 4-ethylidene-1, 7-undecadiene, etc .; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene , 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbo, Cyclic non-conjugated dienes such as nene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene and the like; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene And trienes such as 5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. These non-conjugated dienes may be used alone or in combination of two or more. be able to. Among these nonconjugated dienes, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are preferable.

  The ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention usually has an iodine value of 1 to 50, preferably 5 to 40, more preferably 10, which is an index of the amount of nonconjugated polyene component. It is in the range of -30.

  In addition, the copolymer (A) is a unit (a) derived from ethylene, a unit (b) derived from α-olefin, and a nonconjugated polyene (c), the content of the unit (c) derived from the nonconjugated polyene The total of 100) is preferably in the range of 1 to 5 mol%, more preferably 1.5 to 3.5 mol%, based on 100 mol%.

  The ethylene / α-olefin / nonconjugated polyene copolymer (A) to be used in the present invention usually has an intrinsic viscosity [η] of 1 to 10 dl / g, preferably 1.5, as measured in a decalin solvent at 135 ° C. It is in the range of ̃8 dl / g.

  The ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention may be a so-called oil-extended rubber in which a softening agent, preferably a mineral oil-based softening agent, is blended in the production thereof. Examples of mineral oil-based softeners include conventionally known mineral oil-based softeners such as paraffinic process oil.

The Mooney viscosity [ML _{(1 + 4)} 100 ° C.] of the ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention is usually in the range of 10 to 250, preferably 30 to 150.

  The ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention may be used alone or in combination of two or more ethylene / α-olefin / nonconjugated polyene copolymers.

  The ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention can be produced by a conventionally known method.

<Crystalline Olefin-Based Polymer (B)>
The crystalline olefin polymer (B) (also referred to as the polymer (B) in the present invention) is a homopolypropylene and / or a copolymer of propylene and an α-olefin (except for propylene) (with a propylene content of 40 moles) No particular limitation is imposed on the crystalline polymer as long as it is a crystalline polymer selected from (1) and (2), but obtained by polymerizing propylene alone or propylene and one or more α-olefins other than propylene by high pressure method or low pressure method. It is preferred that the polymer comprises a crystalline high molecular weight solid product. Examples of such polymers include isotactic monoolefin polymers, syndiotactic monoolefin polymers and the like.

The polymer (B) may be obtained by synthesis according to a conventionally known method, or a commercially available product may be used.
As one or more types of alpha olefins other than propylene used as a raw material of a polymer (B), ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1- Propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like can be mentioned, with preference given to ethylene and 1-butene. These olefins may be used alone or in combination of two or more.

  Crystalline polymers selected from homopolypropylene and / or copolymers of propylene and α-olefin (excluding propylene) (provided that the propylene content is 40 mol% or more) are other crystalline olefin polymers It is preferable from the point of heat resistance and oil resistance compared with.

  From the viewpoint of heat resistance, the copolymer of propylene and an α-olefin (except for propylene) needs to have a content of 40 mol% or more of a structural unit derived from propylene, preferably 50 mol%. It is above.

  The polymerization mode may be random type or block type, and any polymerization mode may be adopted as long as a crystalline resin can be obtained.

  The crystalline olefin polymer (B) has a melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) is usually 0.01 to 100 (g / 10 min), preferably 0.05 to 0.05 It is 50 (g / 10 minutes).

  The melting point (Tm) obtained by differential scanning calorimetry (DSC) of the polymer (B) is usually 100 ° C. or more, preferably 105 ° C. or more. Differential scanning calorimetry is performed, for example, as follows. About 5 mg of the sample is packed in a dedicated aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min and kept at 200 ° C. for 5 minutes using DSCPyris 1 or DSC 7 manufactured by PerkinElmer Co., Ltd. The temperature is lowered from 10 ° C. to 30 ° C. at 10 ° C./min, held at 30 ° C. for further 5 minutes, and then the melting point is determined from the endothermic curve when raising the temperature at 10 ° C./min. In addition, when a several peak is detected at the time of DSC measurement, the peak temperature detected in the highest temperature side is defined as melting | fusing point (Tm).

  The polymer (B) plays a role of improving the flowability and heat resistance of the thermoplastic elastomer composition.

<Polymer (C)>
The thermoplastic elastomer composition of the present invention comprises (C-1) a copolymer of an aromatic vinyl compound and a conjugated diene compound, and (C-2) a hydrogenated copolymer of an aromatic vinyl compound and a conjugated diene compound. And at least one polymer (polymer (C)) selected from the group consisting of (C-3) hydrogenated conjugated diene compound polymers. The polymer (C) is used particularly for the purpose of improving the compression set characteristics in a high temperature range.

Polymer (C-1):
The polymer (C-1) is a random copolymer of a (C-1-1) aromatic vinyl compound and a conjugated diene compound, and a block of (C-1-2) an aromatic vinyl compound and a conjugated diene compound Including copolymers.

Polymer (C-1-1):
The polymer (C-1-1) is a random copolymer of an aromatic vinyl compound and a conjugated diene compound, and as the aromatic vinyl compound, for example, styrene, α-methylstyrene, vinyl toluene, p-third One or two or more species can be selected from butyl styrene and the like, and styrene is particularly preferable. Also, as the conjugated diene compound, for example, one or more selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, among which butadiene, isoprene and A combination of these is preferred.

  The polymer (C-1-1) contains 3 to 60% by mass, preferably 5 to 50% by mass, of an aromatic vinyl compound.

  The number average molecular weight of the polymer (C-1-1) is preferably in the range of 150,000 to 500,000, more preferably 170,000 to 400,000, still more preferably 200,000 to 350,000. There is a molecular weight distribution of 10 or less.

  As a specific example of a polymer (C-1-1), the copolymer (SBR) of styrene and butadiene is mentioned, for example.

Polymer (C-1-2):
The polymer (C-1-2) is a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and at least two polymer blocks A mainly composed of an aromatic vinyl compound and a conjugated diene compound And at least one polymer block B as a main component. For example, an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as A-B-A, B-A-B-A or A-B-A-B-A can be mentioned.

  The polymer (C-1-2) contains 5 to 60% by mass, preferably 20 to 50% by mass of an aromatic vinyl compound.

  The polymer block A mainly composed of an aromatic vinyl compound preferably comprises only an aromatic vinyl compound, or a copolymer of a conjugated diene compound and 50% by mass or more, preferably 70% by mass or more of an aromatic vinyl compound It is a united block.

  Preferably, the polymer block B mainly composed of a conjugated diene compound is composed only of a conjugated diene compound or 50 wt% or more of a conjugated diene compound, preferably 70 wt% or more of an aromatic vinyl compound and a copolymer It is a united block.

  The number average molecular weight of the polymer (C-1-2) is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000, still more preferably 100,000 to 400,000 The molecular weight distribution is 10 or less. The molecular structure of the block copolymer may be linear, branched, radial or any combination thereof.

  In the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds, the distribution of units derived from the conjugated diene compound or aromatic vinyl compound in the molecular chain is random, It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially blocked, or any combination thereof. When there are two or more polymer blocks A mainly composed of an aromatic vinyl compound or two or more polymer blocks B mainly composed of a conjugated diene compound, each polymer block may have the same structure but different structures. It may be.

  As an aromatic vinyl compound which comprises a polymer (C-1-2), 1 type, or 2 or more types can be selected from styrene, alpha-methylstyrene, vinyl toluene, p-tert-butyl styrene etc., for example Among these, styrene is preferred. Also, as the conjugated diene compound, for example, one or more selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, among which butadiene, isoprene and A combination of these is preferred.

  Specific examples of the polymer (C-1-2) include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS) and the like.

  A number of methods have been proposed as a method for producing the polymer (C-1-2), but as a representative method, for example, a lithium catalyst or Ziegler is disclosed by the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert medium using a type catalyst.

Polymer (C-2):
The polymer (C-2) is a hydrogenated product of a random copolymer of (C-2-1) aromatic vinyl compound and conjugated diene compound, and (C-2-2) aromatic vinyl compound and conjugated diene compound And hydrogenated products of block copolymers thereof.

Polymer (C-2-1):
The polymer (C-2-1) is a hydrogenated product of a random copolymer of an aromatic vinyl compound and a conjugated diene compound, and as the aromatic vinyl compound, for example, styrene, t-butylstyrene, α-methylstyrene And one or more selected from p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyl toluene, p-tert-butylstyrene, etc. Among these, styrene is preferred.

  As the conjugated diene compound, for example, one or more selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.

  The polymer (C-2-1) preferably has a melt flow rate (measured in accordance with ASTM D1238, 230 ° C., load 21.18 N) of 12 g / 10 min or less from the viewpoint of tensile properties and heat deformation resistance , 6 g / 10 minutes or less is more preferable.

  The content of the aromatic vinyl compound is preferably 50% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, for the purpose of obtaining a flexible resin composition. For the same purpose, it is also important to saturate the carbon-carbon double bond of the conjugated diene compound by hydrogenation.

  In the random structure of the aromatic vinyl compound and the conjugated diene compound, the aromatic vinyl compound is randomly bonded. Further, it is preferable that at least 90% of the aliphatic double bond based on the conjugated diene compound be hydrogenated.

  The number average molecular weight of the polymer (C-2-1) is preferably 5,000 to 1,000,000, more preferably 10,000 to 350,000, and the molecular weight distribution is 10 or less.

  As a specific example of a polymer (C-2-1), the hydrogenated substance (hydrogenated SBR or H-SBR) of a styrene butadiene random copolymer is mentioned, for example, As a commercial example, For example, Dynaron 1320P ( Trade name, manufactured by JESR Inc.).

Polymer (C-2-2):
The polymer (C-2-2) is a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and is conjugated with at least one polymer block A mainly composed of an aromatic vinyl compound It is obtained by hydrogenating a block copolymer consisting of at least one polymer block B mainly composed of a diene compound. For example, a block copolymer of an aromatic vinyl compound-conjugated diene compound having a structure such as A-B, A-B-A, B-A-B-A, A-B-A-B-A, etc. is hydrogenated It is obtained by

  The polymer block A mainly composed of an aromatic vinyl compound may be a polymer consisting only of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and a conjugated diene compound less than 50% by mass. The polymer block B mainly composed of a conjugated diene compound may be a polymer consisting only of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound of less than 50% by mass.

  As an aromatic vinyl compound which comprises a polymer (C-2-2), 1 type, or 2 or more types can be selected from styrene, alpha-methylstyrene, vinyl toluene, p-tert-butyl styrene etc., for example Among these, styrene is preferred. Also, as the conjugated diene compound, for example, one or more selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, among which butadiene, isoprene and A combination of these is preferred.

  The polymer (C-2-2) in the polymer block B mainly composed of a conjugated diene compound has an arbitrary hydrogenation rate, but is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more. In addition, the microstructure is optional. For example, when block B is composed of butadiene alone, in the polybutadiene block, the 1,2-microstructure is preferably 20 to 50% by mass, particularly preferably 25 to 45%. It is mass%. In addition, it may be one obtained by selectively hydrogenating 1,2-bond. When block B is composed of a mixture of isoprene and butadiene, the 1,2-microstructure is preferably less than 50%, more preferably less than 25%, still more preferably less than 15%.

  When the block B is composed of isoprene alone, preferably 70 to 100% by mass of the isoprene in the polyisoprene block has a 1,4-microstructure and preferably at least at least one aliphatic double bond derived from isoprene. It is preferred that 90% be hydrogenated.

  Moreover, it is preferable that the polymer block A exists in the ratio of 5-70 mass% of the whole component. Furthermore, as for the weight average molecular weight of the whole component, 150,000-500,000 are preferable, More preferably, they are 200,000-400,000. When the weight average molecular weight is less than 200,000, the compression set characteristics of the resulting composition are degraded. Within the above range, the larger the molecular weight, the better the compression set characteristics of the resulting composition.

  Specific examples of the polymer (C-2-2) include styrene-ethylene / butene copolymer (SEB), styrene-ethylene / propylene copolymer (SEP), styrene-ethylene / butene-styrene copolymer ( SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-butadiene-butylene-styrene copolymer (partially hydrogenated styrene-butadiene copolymer -Styrene copolymer, SBBS) etc. can be mentioned, and these can be used suitably according to a use.

  A number of methods have been proposed as a method for producing the polymer (C-2-2), but as a representative method, for example, a lithium catalyst or a lithium catalyst is disclosed by the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert medium using a Ziegler type catalyst. The hydrogenation treatment of such a block copolymer can be carried out by a known method in the presence of a hydrogenation catalyst in an inert solvent.

Polymer (C-3):
The polymer (C-3) is a hydrogenated product of a conjugated diene compound polymer, and has, for example, a crystalline ethylene block and an amorphous ethylene-butene block obtained by hydrogenating a block copolymer of butadiene A block copolymer (CEBC) etc. are mentioned. A polymer (C-3) may be used independently and may be used in mixture of 2 or more types.

  Moreover, the weight average molecular weight of a polymer (C-3) is 500,000 or less, Preferably it is 200,000-450,000. When the weight-average molecular weight exceeds 500,000, the extrusion / injection moldability deteriorates, and when the weight-average molecular weight is less than 200,000, the effect of improving the compression set property decreases.

  Among the polymers (C) described above, the polymer (C-2-2) is preferable in that it is excellent in the effect of imparting flexibility and excellent in improving the compression set, and among them, styrene-ethylene / ethylene / propylene-styrene Copolymers (SEEPS) and styrene-ethylene-butene-styrene copolymers (SEBS) are more preferred. Among them, Septon 4077 (manufactured by Kuraray Co., Ltd.) and KRATON MD6933 ES (manufactured by Kraton Polymer Japan Co., Ltd.) are most preferable because they are particularly excellent in the compression set improvement effect.

  The polymer (C) is used in an amount of usually 10 to 100 parts by mass, preferably 20 to 65 parts by mass, with respect to 100 parts by mass of the copolymer (A).

<Crosslinking agent>
Examples of the crosslinking agent used in the present invention include organic peroxides, sulfur, sulfur compounds, halogenated phenolic resin crosslinking agents, etc., among which organic peroxides and halogenated phenolic resin crosslinking agents are preferable. Used.

  Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5 -Di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl -4,4-Bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate DOO, diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.

  Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 in view of odor and scorch stability. 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (tert-butylperoxy) 2.) Valerate is preferred, among which 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

  These organic peroxides are generally 0.01 to 15 parts by mass with respect to 100 parts by mass of the total amount of the ethylene / α-olefin / nonconjugated polyene copolymer (A) and the crystalline olefin polymer (B), Preferably, it is used in a proportion of 0.03 to 12 parts by mass. When the organic peroxide is used in the above proportion, a thermoplastic elastomer composition in which at least a part of the ethylene / α-olefin / nonconjugated polyene copolymer (A) is crosslinked is obtained, and heat resistance, tensile properties and rubber elasticity are obtained. A sufficient molded product is obtained.

  In the case of using a phenol resin crosslinking agent as the crosslinking agent in the present invention, a halogenated phenol resin crosslinking agent is used.

  When a non-halogenated phenolic resin crosslinking agent is used as the crosslinking agent, a metal halide such as tin chloride or lead chloride is generally used as the crosslinking accelerator, but a thermoplastic elastomer composition using a certain amount or more of these is used. When the molded body of the present invention is used in contact with a polyacetal resin, there is a problem that the polyacetal resin is deteriorated with the passage of time.

  By using a halogenated phenolic resin-based crosslinking agent, the use of a metal halide such as tin chloride or lead chloride can be avoided, so that the above problem can be avoided.

  As a phenol resin type crosslinking agent which is halogenated, a halogenated alkyl phenol resin etc. are mentioned, for example, Preferably, what brominated the hydroxyl group of the terminal of a phenol resin is mentioned. An example of the phenolic resin-based cured resin whose end is brominated is shown in the following general formula (I).

（式中、ｎは０〜１０の整数、Ｒは炭素数１〜１５の飽和炭化水素基である。）

(Wherein, n is an integer of 0 to 10, and R is a saturated hydrocarbon group having 1 to 15 carbon atoms.)

  Further, as specific examples of the crosslinking of thermoplastic vulcanized rubber with a phenol resin, US Pat. No. 4,311,628, US Pat. No. 2,972,600 and US Pat. No. 3,287,440 can be used. As described in the specification, these techniques can also be used in the present invention.

U.S. Pat. No. 4,311,628 discloses a phenolic curative system comprising a phenolic curative resin and a cure activator. The basic component of the system is either the condensation of a substituted phenol (eg halogen substituted phenol, C ₁ -C ₂ alkyl substituted phenol) or unsubstituted phenol with an aldehyde, preferably formaldehyde, in an alkaline medium, or a difunctional phenol It is a phenol resin based crosslinking agent produced by condensation of dialcohols (preferably, dimethylol phenols substituted at the para position with a C ₅ -C ₁₀ alkyl group). Particularly suitable are halogenated alkyl-substituted phenolic resin-based crosslinking agents which are produced by halogenation of alkyl-substituted phenolic resin-based crosslinking agents. A phenolic resin based crosslinking agent consisting of a methylolphenol curable resin, a halogen donor and a metal compound is particularly recommended, the details of which are described in US Pat. Nos. 3,287,440 and 3,709,840. It is done. Non-halogenated phenolic resin based crosslinkers are used simultaneously with the halogen donor, preferably with a hydrogen halide scavenger. On the other hand, a halogenated phenolic resin based crosslinking agent, preferably a brominated phenolic resin based crosslinking agent containing preferably 2 to 10% by mass of bromine does not require a halogen donor, but iron oxide, for example And hydrogen halide scavengers such as titanium oxide, magnesium oxide, magnesium silicate, silicon dioxide and zinc oxide, preferably metal oxides such as zinc oxide. The hydrogen halide scavenger such as zinc oxide is usually used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the phenolic resin crosslinking agent. Although the presence of such a scavenger accelerates the crosslinking action of the phenolic resin crosslinking agent, in the case of a rubber which is not easily vulcanized by the phenolic resin crosslinking agent, it is desirable to share a halogen donor and zinc oxide. The preparation of halogenated phenolic curable resins and their use in vulcanizing agent systems using zinc oxide are described in US Pat. Nos. 2,972,600 and 3,093,613. , The disclosure of which is incorporated herein by reference along with the disclosures of the aforementioned U.S. Patent Nos. 3,287,440 and 3,709,840. Examples of suitable halogen donors include, for example, stannous chloride, ferric chloride or halogen donating heavy such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber) Coalescence is mentioned. As used herein, the term "vulcanization accelerator" refers to any material that substantially increases the crosslinking efficiency of the phenolic resin based crosslinking agent, and includes metal oxides and halogen donors, which are It is used alone or in combination. For more details on phenolic vulcanizing systems, see "Vulcanization and Vulcanizing Agents" (W. Hoffman, Palmerton Publishing Company). Suitable phenolic resin based crosslinking agents and brominated phenolic resin based crosslinking agents are commercially available, for example, as a product example of such a crosslinking agent, Tackilol® 250-I (4% bromination rate) Brominated alkylphenol-formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd., Takiroll (registered trademark) 250-III (brominated alkylphenol-formaldehyde resin manufactured by Taoka Chemical Industry Co., Ltd.), SP-1055F manufactured by Schenectady, etc. And brominated alkylphenol-formaldehyde resins.

  The amount of the halogenated phenol resin-based crosslinking agent is usually 0.1 to 20 parts by mass, preferably 1 to 12 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A) Used in various amounts.

  In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenyl guanidine, trimethylol in the crosslinking treatment with a crosslinking agent. Crosslinking assistants such as propane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc. A cross-linking coagent consisting of a polyfunctional methacrylate monomer of the following, or a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate may be added. By adding such a crosslinking coagent, a uniform and mild crosslinking reaction of the ethylene / α-olefin / nonconjugated polyene copolymer (A) can be expected. In the present invention, when divinylbenzene is used, it is easy to handle, and phase with the ethylene / α-olefin / nonconjugated polyene copolymer (A) and the crystalline olefin polymer (B) as the main components of the object to be treated. A thermoplastic elastomer composition having good solubility, having a solubilizing effect of the organic peroxide, and acting as a dispersion aid for the organic peroxide, so that the crosslinking effect by heat treatment is homogeneous, and the fluidity and physical properties are balanced. Is most preferable because

  The crosslinking aid used in the present invention is usually 0.01 to 15 parts by weight per 100 parts by weight of the total amount of the ethylene / α-olefin / nonconjugated polyene copolymer (A) and the crystalline olefin polymer (B). It is used in a proportion by mass, preferably 0.03 to 12 parts by mass.

<Other ingredients>
In the composition of the present invention, in addition to the copolymer (A), the polymer (B), the polymer (C) and the crosslinking agent, additives may be added as long as the effects of the present invention are not impaired. Good. Although it does not specifically limit as an additive, A softener, an inorganic filler, etc. are mentioned. Further, as the additive, rubber other than the copolymer (A) (for example, polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber, propylene / butene copolymer rubber, propylene / butene / ethylene copolymer rubber, etc.) Ethylene elastomers such as ethylene-propylene copolymer rubber); thermosetting resins, resins other than crystalline olefin polymers (B) such as thermoplastic resins such as polyolefins; UV absorbers; oxidized Antioxidants, heat stabilizers, anti-aging agents, light stabilizers, weather stabilizers, antistatic agents, metal soaps, metal amides, fatty amides, lubricants such as waxes, and the like known additives used in the field of polyolefins Be

  Each of these additives may be used alone or in combination of two or more.

  In addition, the blending amount of additives other than the additives specifically mentioned in the present specification is not particularly limited as long as the effects of the present invention are exhibited, but a total of 100 mass of the copolymer (A) and the polymer (B) The amount is usually about 0.0001 to 10 parts by mass, preferably about 0.01 to 5 parts by mass, per part.

  As the softener, softeners usually used for rubber can be used. As a softener, petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petrolatum and the like; coal tar-based softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil Fatty oil-based softeners such as soybean oil and coconut oil; tall oil; sub (factice); waxes such as beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, laurin Acid or fatty acid salt such as zinc acid; naphthenic acid; pine oil, rosin or derivative thereof; synthetic polymer substance such as terpene resin, petroleum resin, atactic polypropylene, coumarone indene resin; dioctyl phthalate, dioctyl adipate, dioctyl sebacate Ester softeners such as Black wax, liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils.

  These softeners are not particularly limited as long as the effects of the present invention are exhibited, but usually 2 to 400 parts by mass, preferably 50 to 350 parts by mass with respect to a total of 100 parts by mass of the copolymer (A) and the polymer (B). It is used in an amount of parts by mass, more preferably 70 to 250 parts by mass. When the softener is used in such an amount, the flowability at the time of preparation and molding of the composition is excellent, the dispersibility of carbon black and the like is improved, and the mechanical properties of the resulting molded article are difficult to be reduced. The resulting molded article is excellent in heat resistance and heat aging resistance.

  As an inorganic filler, calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite And carbon black, glass fibers, glass spheres, Shirasu balloon, basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers and the like.

  These inorganic fillers are usually used in an amount of 1 to 100 parts by mass, preferably 1 to 50 parts by mass, with respect to 100 parts by mass in total of the copolymer (A) and the polymer (B).

  Examples of anti-aging agents include aromatic secondary amine anti-aging agents such as phenylbutylamine and N, N-di-2-naphthyl-p-phenylenediamine; dibutyl hydroxytoluene, tetrakis [methylene (3,5-di) -T-Butyl-4-hydroxy) hydrocinnamate] phenolic anti-aging agent such as methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide etc Thioether antidegradants; dithiocarbamate antidegradants such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, zinc salts of 2-mercaptobenzimidazole, dilaurylthiodipropionate, distearylthiodipropionate, etc. There is a sulfur based antioxidant.

  When a rubber other than the copolymer (A) is used, the rubber is usually 2 to 200 parts by mass, preferably 5 parts by mass with respect to 100 parts by mass in total of the copolymer (A) and the polymer (B). Used in amounts of ̃150 parts by weight.

[Composition of the Present Invention, Method for Producing the Same, and Molded Article]
[Thermoplastic Elastomer Composition]
The thermoplastic elastomer composition of the present invention preferably comprises a mixture of copolymer (A), polymer (B), polymer (C) and a crosslinking agent, and additives optionally compounded. Heat treatment and crosslinking (dynamic crosslinking).

  The composition of the present invention is obtained by dynamically crosslinking the copolymer (A), the polymer (B) and the polymer (C) with a crosslinking agent.

  In the present invention, “dynamically heat-treating” refers to kneading the mixture in a molten state in the presence of a crosslinking agent. Also, "dynamic crosslinking" refers to crosslinking while applying shear force to the mixture.

  In the composition of the present invention, the mass ratio (A) / (B) of the copolymer (A) to the polymer (B) is 90/10 to 10/90, preferably 90/10 to 60/40, More preferably, it is 90/10 to 63/37. When the mass ratio (A) / (B) is in the above range, a molded article excellent in mechanical properties and moldability can be obtained.

The dynamic heat treatment is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide gas. The temperature of the heat treatment is usually in the range of 300 ° C. from the melting point of the polymer (B), preferably 150 to 280 ° C., more preferably 170 to 270 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is typically 10～100,000Sec ^-1 at the highest shear rate, preferably 100～50,000Sec ^-1, more preferably 1,000～10,000Sec ^-1, more preferably 2,000 It is in the range of ̃7,000 sec ⁻¹ .

  As a kneading apparatus at the time of kneading, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single screw extruder, a twin screw extruder, etc. may be mentioned. In addition, as these kneading apparatuses, a non-open type apparatus is preferable.

The composition of the present invention has a total content of Sn and Pb elements of 500 ppm or less.
Therefore, degradation of polyacetal resin is small even when used for applications in contact with polyacetal resin.

  In order to obtain a composition in which the total content of Sn and Pb elements is 500 ppm or less, an additive containing Sn and / or Pb elements may not be blended, or the blending amount may be limited to a certain amount or less.

  The composition of the present invention has a Shore A hardness (instantaneous value) of 30 to 90 in accordance with JIS K6253.

  Therefore, when made to contact with polyacetal resin, rubber elasticity, anti-vibration property, and sealability can be provided.

  In order to obtain a composition having a Shore A hardness (instantaneous value) of 30 to 90 according to JIS K6253, 90 to 10 parts by mass of an ethylene / α-olefin / nonconjugated polyene copolymer (A) and a crystalline olefin system The compounding amount of the softener may be adjusted to a predetermined hardness with respect to 10 to 90 parts by mass of the polymer (B) (provided that the total amount of (A) and (B) is 100 parts by mass).

  Furthermore, the composition of the present invention has a melt flow rate (ASTM D 1238-65 T; 230 ° C., 10 kg load) is 1 to 150 g / 10 min, or a melt flow rate (ASTM D 1238-65 T; 230 ° C., 16 kg load) is 0.1 to 10 g / 10 min.

  By setting the melt flow rate to the above range, a thermoplastic elastomer excellent in moldability can be provided.

  In order to obtain a composition having a melt flow rate in the above range, the crystalline olefin polymer (B) generally has a melt flow rate (ASTM D1238-65T; 230 ° C., 2.16 kg load) of 0. The blending amount of the softener may be adjusted to that of 01 to 100 (g / 10 min) to obtain a predetermined melt flow rate.

  When the composition of the present invention is used in combination with a polyacetal resin, from the viewpoint of heat resistance, abrasion resistance and mechanical strength, the ratio of both is 10 to 65% by mass of the composition of the present invention, polyacetal resin 35 to 90 It is preferable to set it as mass%.

  Since the composition of the present invention is excellent in moldability, it can be molded by various molding methods. Examples of the molding include extrusion molding, injection molding, compression molding, calendar molding, vacuum molding, press molding, stamping molding, blow molding and the like. In addition, as blow molding, breath blow molding, direct blow molding, injection blow molding and the like can be mentioned.

[Molded body of the present invention]
In the molded article of the present invention, the layer (I) containing the composition of the present invention is in contact with the layer (II) containing polyacetal resin.

  The polyacetal resin used in the present invention can be produced by a known production method. As polyacetal resin, any of polyacetal homopolymer and polyacetal copolymer may be used. Moreover, as base resin of polyacetal resin, what carried out the bridge | crosslinking or graft copolymerization and modified | denatured by the well-known method of polyacetal can be used. The degree of polymerization of the polyacetal resin and the structure of the end groups are not limited to particular ones.

  The molded article of the present invention contains no component that degrades the polyacetal resin such as tin chloride or lead chloride in the layer (I) or is limited to a certain amount or less. Deterioration can be prevented.

  Therefore, by using a formed body in which the layer (I) containing the composition of the present invention and the layer (II) containing polyacetal resin are in contact, a product free from the problem of deterioration of the polyacetal resin can be produced. .

  As a molded article in which the layer (I) containing the composition of the present invention and the layer (II) containing polyacetal resin are in contact, for example, a clamp for fixing a hose (pipe) to a vehicle Clips, grommets and hooks.

  The molded article in which the layer (I) containing the composition of the present invention and the layer (II) containing polyacetal resin are in contact with each other is, for example, the layer (I) containing the composition of the present invention It is obtained by fitting, laminating, insert molding, multilayer blow molding of each part injection molded product of II).

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

[Measuring method]
[Ethylene-α-olefin-nonconjugated polyene copolymer]
[Molecular weight and mass of each structural unit]
The molar amount and the mass of the structural unit derived from ethylene [A], the structural unit derived from α-olefin [B] and the structural unit derived from non-conjugated polyene [C] are measured by intensity measurement with ¹ H-NMR spectrometer. I asked.

[Mooney viscosity]
The Mooney viscosity ML _{(1 + 4)} 100 ° C. was measured according to JIS K 6300 (1994) using a Mooney viscometer (Model SMV 202 manufactured by Shimadzu Corporation).

[Physical Properties of Thermoplastic Resin Composition and Molded Body]
The evaluation method of the physical property of the thermoplastic-elastomer composition in a following example and a comparative example and a molded object is as follows.

[Shore A hardness (instant value)]
The pellets of the obtained thermoplastic elastomer composition are press molded for 6 minutes at 230 ° C. using a 100 t electrothermal automatic press (manufactured by Shoji), and then cold pressed for 5 minutes at room temperature to obtain a 3 mm-thick press sheet Made. Using the sheet, a scale was read immediately after contact with a needle using an A-type measuring device in accordance with JIS K6253.

[Melt flow rate (MFR) (g / 10 min)]
According to JIS K 6721, it measured at a load of 10 kg at 230 ° C.
Moreover, it measured at 230 degreeC and the load of 2.16 kg according to ISO1133 (or ASTM D1238).

[Sn content]
The Sn content was determined by fluorescent X-ray analysis using a wavelength dispersive fluorescent X-ray apparatus LAB CENTER XRF-1700 (Shimadzu Corporation). The analysis conditions are as follows.
Analysis conditions: X-ray tube Rh 40kV 95mA aperture φ 20 mm, measurement atmosphere: vacuum

[POM surface appearance observation]
The press temperature was set to 220 ° C. and a sheet was formed at a pressure of 10 MPa using a hydraulic 100-ton electrothermal automatic press manufactured by Shoji Co., Ltd. After preheating was pressurized for 6 minutes at 10 MPa for 4 minutes, it was compressed at 10 MPa using a cooling press set at 25 ° C. and cooled for 5 minutes (chiller cooling temperature set at 25 ° C.) to prepare a measurement sample.

  The molded thermoplastic elastomer sheet and polyacetal resin (POM) (trade name "Duracon M90-44", manufactured by Polyplastics Co., Ltd.) are overlapped, and the contact surface after heating for 168 hours at 120 ° C in an oven is visually observed. I observed it.

Synthesis Example 1 Synthesis of Ethylene / Propylene • 5-Ethylidene-2-Norbornene Copolymer (EPDM) Ethylene, propylene as α-olefin, non-continuously using a 300 L volume polymerizer equipped with a stirring blade The polymerization reaction of a terpolymer consisting of 5-ethylidene-2-norbornene (ENB) as a conjugated polyene was carried out at 90.degree.

  Using ethylene (feed rate 74 L / h) as the polymerization solvent, the ethylene feed rate is 6.6 kg / h, the propylene feed rate is 3.2 kg / h, the ENB feed rate is 0.56 kg / h Each component was continuously supplied to the polymerization vessel such that the hydrogen feed amount was 10.9 NL / h.

While maintaining the polymerization pressure at 1.8 MPa and the polymerization temperature at 90 ° C., [N- (1,1-dimethylethyl) -1,1-dimethyl-1-[(1,2,3,3A, 8A-η) -1,5,6,7-Tetrahydro-2-methyl-S-indacen-1-yl] silane aminate (2-)-κN] [(1,2,3,4-η)- Using 1,3-pentadiene] -titanium, the main catalyst was continuously fed at a feed rate of 0.015 mmol / h. In addition, the feed amount of (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ as a co-catalyst is 0.075 mmol / h, and the feed amount of triisobutylaluminum (TIBA) as an organic aluminum compound is 10 mmol / h, Each was supplied continuously.

  In this way, an ethylene / α-olefin / nonconjugated polyene copolymer consisting of ethylene, propylene and ENB was obtained in a solution state of 9.1% by mass. A small amount of methanol is added to the polymerization reaction solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the ethylene • α-olefin • nonconjugated polyene copolymer is separated from the solvent by steam stripping, and then 80 It was dried under reduced pressure overnight.

  By the above operation, an ethylene / α-olefin / nonconjugated polyene copolymer formed from ethylene, propylene and ENB was obtained at a rate of 5.3 kg / h.

Example 1 Thermoplastic Elastomer Composition and Molded Article Ethylene-propylene-5 having an ethylene content of 63 mol%, an iodine value of 13 and a Mooney viscosity [ML _{(1 + 4)} 100 ° C.] of 75 obtained in Synthesis Example 1 100 parts by mass of ethylidene-2-norbornene copolymer rubber (EPDM), propylene having a melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 1 g / 10 min, density 0.91 g / cm ³ Propylene homopolymer (PP: 30 parts by mass of homopolymer (PP-1), melt flow rate (ASTM D1238-65T; 230 ° C, 2.16 kg load): 12 g / 10 min, density: 0.91 g / cm ³ -2) 16 parts by mass, softener (Diana Process PW-100, paraffin oil, manufactured by Idemitsu Kosan Co., Ltd.) 110 parts by mass, pheno 6 parts by mass of brominated alkylphenol-formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) as an epoxy resin-based crosslinking agent, 0.3 parts by mass of zinc oxide (2 kinds of zinc oxide, manufactured by Haxeitec), and carbon black master Batch (trade name: PEONY BLACK F32387MM, manufactured by DIC Corporation) 4 parts by mass of an extruder (Product No. KTX-30, manufactured by Kobe Steel, Ltd., cylinder temperature: C1: 50 ° C., C2: 90 ° C., C3: 100) C4: 120 ° C., C5: 180 ° C., C6: 200 ° C., C7 to C14: 200 ° C., die temperature: 200 ° C., screw rotation number: 500 rpm, extrusion amount: 40 kg / h) Dynamic crosslinking to obtain pellets of the thermoplastic elastomer composition. The formulation and evaluation results are shown in Table 1.

Example 2 Thermoplastic Elastomer Composition and Molded Article Ethylene / Propylene • 5 having an ethylene content of 63 mol%, an iodine value of 13 and a Mooney viscosity [ML _{(1 + 4)} 100 ° C.] of 75 obtained in Synthesis Example 1 100 parts by mass of ethylidene-2-norbornene copolymer rubber (EPDM), propylene having a melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 1 g / 10 min, density 0.91 g / cm ³ Propylene homopolymer (PP: 30 parts by mass of homopolymer (PP-1), melt flow rate (ASTM D1238-65T; 230 ° C, 2.16 kg load): 12 g / 10 min, density: 0.91 g / cm ³ -2) 16 parts by mass, softener (Diana Process PW-100, paraffin oil, Idemitsu Kosan Co., Ltd.) 110 parts by mass, 1, 3 -0.1 parts by mass of bis (tert-butylperoxyisopropyl) benzene (Pox), 0.2 parts by mass of divinylbenzene (DVB) and 4 parts by mass of carbon black master batch (trade name: PEONY BLACK F 32387 MM, manufactured by DIC Corporation) The part is an extruder (Product No. KTX-30, manufactured by Kobe Steel, Ltd., cylinder temperature: C1: 50 ° C, C2: 90 ° C, C3: 100 ° C, C4: 120 ° C, C5: 180 ° C, C6: 200 ° C, Dynamic crosslinking of the obtained mixture was performed at C7 to C14: 200 ° C., die temperature: 200 ° C., screw rotation number: 500 rpm, extrusion amount: 40 kg / h) to obtain pellets of a thermoplastic elastomer composition . The formulation and evaluation results are shown in Table 1.

Example 3 Thermoplastic Elastomer Composition and Molded Article Ethylene / Propylene • 5 having an ethylene content of 63 mol%, an iodine value of 13 and a Mooney viscosity [ML _{(1 + 4)} 100 ° C.] of 75 obtained in Synthesis Example 1 100 parts by mass of ethylidene-2-norbornene copolymer rubber (EPDM), propylene having a melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 1 g / 10 min, density 0.91 g / cm ³ Propylene homopolymer (PP (PP-1): 38 parts by mass, melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load): 12 g / 10 min, density: 0.91 g / cm ³ -2) 25 parts by mass, hydrogenated styrene thermoplastic elastomer (SEBS) (hydrogenated styrene-ethylene-butadiene-styrene) Block copolymer, styrene content 30% by mass, weight average molecular weight 230,000, hydrogenation rate 95% or more, melt flow rate (ISO 1133; 230 ° C., 2.16 kg load) No Flow, oil spread = 56 (PHR) 60 parts by mass, softener (Diana Process PW-100, paraffin oil, Idemitsu Kosan Co., Ltd.) 110 parts by mass, brominated alkylphenol formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) as a phenol resin crosslinking agent 6 parts by mass, 0.3 parts by mass of zinc oxide (2 kinds of zinc oxide, manufactured by HAXI TEC Co., Ltd.), and 4 parts by mass of carbon black master batch (trade name: PEONY BLACK F 32387 MM, manufactured by DIC Corporation) 30, manufactured by Kobe Steel, Ltd., cylinder temperature: C 1: 50 ° C., C 2: 90 ° C. C3: 100 ° C., C4: 120 ° C., C5: 180 ° C., C6: 200 ° C., C7 to C14: 200 ° C., die temperature: 200 ° C., screw rotation speed: 500 rpm, extrusion amount: 40 kg / h) The resulting mixture was subjected to dynamic crosslinking to obtain pellets of a thermoplastic elastomer composition. The formulation and evaluation results are shown in Table 1.

Example 4 Thermoplastic Elastomer Composition and Molded Article Ethylene / Propylene • 5 having an ethylene content of 63 mol%, an iodine value of 13 and a Mooney viscosity [ML _{(1 + 4)} 100 ° C.] of 75 obtained in Synthesis Example 1 100 parts by mass of ethylidene-2-norbornene copolymer rubber (EPDM), propylene having a melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 1 g / 10 min, density 0.91 g / cm ³ Propylene homopolymer (PP: 30 parts by mass of homopolymer (PP-1), melt flow rate (ASTM D1238-65T; 230 ° C, 2.16 kg load): 12 g / 10 min, density: 0.91 g / cm ³ -2) 16 parts by mass, softener (Diana Process PW-100, paraffin oil, manufactured by Idemitsu Kosan Co., Ltd.) 110 parts by mass, pheno 6 parts by mass of brominated alkylphenol-formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) as an epoxy resin-based crosslinking agent, 0.3 parts by mass of zinc oxide (2 kinds of zinc oxide, manufactured by Haxeitec), anhydrous chloride Extruder (No. KTX-30, Kobe Steel Co., Ltd.) with 0.1 part by weight of monotin (Showa Kako Co., Ltd.) and 4 parts by mass of carbon black masterbatch (trade name: PEONY BLACK F 32387 MM, DIC Corporation) , Cylinder temperature: C1: 50 ° C, C2: 90 ° C, C3: 100 ° C, C4: 120 ° C, C5: 180 ° C, C6: 200 ° C, C7 to C14: 200 ° C, die temperature: 200 ° C, screw rotation speed The obtained mixture was subjected to dynamic crosslinking at 500 rpm and an extrusion rate of 40 kg / h), and the thermoplastic elastomer composition was It was obtained Tsu door. The formulation and evaluation results are shown in Table 1.

Comparative Example 1
Ethylene / propylene • 5-ethylidene-2-norbornene copolymer rubber (EPDM) having an ethylene content of 63 mol%, an iodine value of 13 and a Mooney viscosity [ML _{(1 + 4)} 100 ° C.] of 75 obtained in Synthesis Example 1 100 parts by mass, 30 parts by mass of a propylene homopolymer (PP-1) having a melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) of 1 g / 10 min and a density of 0.91 g / cm ³ , a melt 16 parts by mass of a propylene homopolymer (PP-2) having a flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) of 12 g / 10 min and a density of 0.91 g / cm ³ , a softener (Diana Process PW -100, paraffin oil, 110 parts by mass of Idemitsu Kosan Co., Ltd., non-halogenated phenolic resin as a phenolic resin-based crosslinking agent Cross-linking agent (Brand name: SP-1045, manufactured by Schenectady) 6 parts by mass, zinc oxide (Zinc oxide 2 type, manufactured by Haxeitec) 0.3 parts by mass, anhydrous stannous chloride (manufactured by Showa Kako) 1 part And carbon black masterbatch (trade name: PEONY BLACK F32387MM, manufactured by DIC Corporation) 4 parts by mass of an extruder (Product No. KTX-30, manufactured by Kobe Steel, Ltd., cylinder temperature: C1: 50 ° C., C2: 90 ° C. C3: 100 ° C., C4: 120 ° C., C5: 180 ° C., C6: 200 ° C., C7 to C14: 200 ° C., die temperature: 200 ° C., screw rotation speed: 500 rpm, extrusion amount: 40 kg / h) The resulting mixture was subjected to dynamic crosslinking to obtain pellets of a thermoplastic elastomer composition. The formulation and evaluation results are shown in Table 1.

[Comparative Examples 2 and 3]
Pellets of a thermoplastic elastomer composition were produced in the same manner as in Comparative Example 1 except that the blending amount of anhydrous stannous chloride (manufactured by Showa Kako Co., Ltd.) was changed as described in Table 1 in Comparative Example 1.
Physical properties were evaluated using the obtained pellets. The results are shown in Table 1.

[Comparative Examples 4 and 5]
Dynamically cross-linked polyolefin elastomer made of ethylene / propylene copolymer and polypropylene component, manufactured by E. E. S. Inc., Santoprene 101-64 (Comparative Example 4) or Santoprene 101-55 (Comparative Example 5) The same evaluation as in Examples 1 to 4 and Comparative Examples 1 to 3 was performed using The results are shown in Table 1.

Claims (8)

90 to 10 parts by mass of ethylene / α-olefin / nonconjugated polyene copolymer (A), homopolypropylene, and / or copolymer of propylene and α-olefin (except for propylene) (with propylene content of 40% by mole) A thermoplastic elastomer composition comprising 10 to 90 parts by mass of the crystalline olefin polymer (B) selected from the above (provided that the total amount of (A) and (B) is 100 parts by mass). ,
The following requirements (i) to (iii):
(I) The total content of Sn and Pb elements is 500 ppm or less in total,
(Ii) Shore A hardness (instantaneous value) according to JIS K6253: 30 to 90, and
(iii) Melt flow rate (ASTM D 1238-65 T; 230 ° C., 10 kg load) 1 to 150 g / 10 min or melt flow rate (ASTM D 1238-65 T; 230 ° C., 2.16 kg load) 0.1 to 10 g / 10 min Thermoplastic elastomer composition satisfying the requirements.   At least one polymer selected from the group consisting of a copolymer of an aromatic vinyl compound and a conjugated diene compound, a hydrogenated product of a copolymer of an aromatic vinyl compound and a conjugated diene compound, and a hydrogenated conjugated diene compound polymer The composition according to claim 1, which contains 10 to 100 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / nonconjugated polyene copolymer (A).   The composition according to claim 1 or 2, which is crosslinked with an organic peroxide.   The composition according to claim 1 or 2, which is crosslinked with a halogenated phenolic resin crosslinking agent.   The composition containing 10-65 mass% of compositions of any one of Claims 1-4, and 35-90 mass% of polyacetal resin.   The molded object in which layer (I) containing the composition of any one of Claims 1-4, and layer (II) containing polyacetal resin are in contact.   The molded article according to claim 6, which is an automobile part.   The method for producing a composition according to any one of claims 1 to 4, wherein the raw material composition is thermally treated without blending an additive containing a Sn element and / or a Pb element.