JP2019098677A - Laminate and seal material using thermoplastic elastomer composition suitable for co-extrusion foam molding - Google Patents

Abstract

To provide a laminate consisting of a thermoplastic elastomer excellent in both of high foaming and surface skin.SOLUTION: There are provided a laminate having a layer (I) consisting of a resin foam body containing an ethylene α-olefin with 3 to 20 carbon atoms non-conjugated polyene (A) of 10 to 35 pts.mass, a propylene polymer having intrinsic viscosity [η] measured in decalin at 135°C of 0.1 dl/g or more and less than 5 dl/g (B) of 1 to 15 pts.mass, a propylene polymer having melting point of 150°C or higher and intrinsic viscosity [η] measured in decalin at 135°C of 5 dl/g to 10 dl/g (C) of 0.1 to 5 pts.mass, and a styrene thermoplastic elastomer (D) of 30 to 70 pts.mass (total of components (A), (B), (C) and (D) is 100 pts.mass) and a layer (II) consisting of a thermoplastic elastomer in contact; a manufacturing method of the laminate; and a seal material consisting of the laminate, e.g. a seal material for automobile.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a sealing material using a thermoplastic elastomer composition suitable for coextrusion foam molding, and a method for producing the laminate.

  Ethylene / α-olefin / non-conjugated polyene copolymers such as ethylene / propylene / diene copolymer (EPDM) are generally excellent in weatherability, heat resistance and ozone resistance, for example, for automotive applications, concrete Are used in applications such as glass run channel products, window frame products or vulcanized rubber products such as hose products.

  Glass run channels and window frame products are used to prevent rain, wind and sound and are important sealing parts.

  The weather strip product of an automobile differs in composition depending on the part used, for example, the glass run channel usually consists of a two-layer composition of sponge rubber / solid rubber. Here, "sponge" means foam and "solid" means non-foam. Foam also includes what is called a slightly foamed, slightly foamed solid.

  At present, it is desirable to co-extrude the foam in the lower part of the glass run channel with the main body by coextrusion and to lower the density than the current product.

  However, when the foaming ratio is increased, there is a problem that the surface is roughened. Since the mainstream of the material used for the sponge part of the present glass run channel is a thermosetting elastomer, there is a problem that it is expensive and time-consuming.

  As a material used for the sponge portion of glass run channel, it is conceivable to use a dynamically cross-linked thermoplastic elastomer as described in Patent Document 1, but the foaming of the dynamically cross-linked thermoplastic elastomer is more than half of the volume Are difficult to foam, making it difficult to achieve high magnification and flexibility.

JP 2005-133090 A

  An object of the present invention is to provide a laminate comprising a thermoplastic elastomer excellent in both high foaming and surface skin.

  As a result of investigations to solve the above-mentioned problems, the present inventors replaced part of the island phase (for example, crosslinked EPDM) with a styrenic thermoplastic elastomer, whereby both high foaming and surface skin are good. Furthermore, they have found that the heat resistance is also equivalent to that of the olefin-based thermoplastic elastomer, and have completed the present invention.

That is, the gist of the present invention is as follows.
(1) Ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) 10 to 35 parts by mass, limiting viscosity [η] measured in decalin at 135 ° C. is 0.1 dl / 1-15 parts by mass of a propylene-based polymer (B) having a g or more and less than 5 dl / g, a melting point of 150 ° C. or more and an intrinsic viscosity [η] of 5 dl / g or more measured in decalin at 135 ° C. 0.1 to 5 parts by mass of a propylene-based polymer (C) or less and 30 to 70 parts by mass of a styrene-based thermoplastic elastomer (D) (components (A), (B), (C) and (D)) The laminated body which the layer (I) which consists of a resin foam containing 100 mass parts of, and the layer (II) which consists of thermoplastic elastomers contact | connects.
(2) Ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) 10 to 35 parts by mass, limiting viscosity [η] measured in decalin at 135 ° C. is 0.1 dl / 1-15 parts by mass of a propylene-based polymer (B) having a g or more and less than 5 dl / g, a melting point of 150 ° C. or more and an intrinsic viscosity [η] of 5 dl / g or more measured in decalin at 135 ° C. 0.1 to 5 parts by mass of a propylene-based polymer (C) or less and 30 to 70 parts by mass of a styrene-based thermoplastic elastomer (D) (components (A), (B), (C) and (D)) The total amount of (a) is 100 parts by mass) and 1 to 15 parts by mass of a foaming agent, and the laminate according to the above (1) including coextrusion molding using a thermoplastic elastomer composition. Production method.
(3) The sealing material which consists of a laminated body as described in said (1).
(4) The sealing material as described in said (3) which is a sealing material for motor vehicles.
(5) Ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) 10 to 35 parts by mass, limiting viscosity [η] measured in decalin at 135 ° C. is 0.1 dl / 1-15 parts by mass of a propylene-based polymer (B) having a g or more and less than 5 dl / g, a melting point of 150 ° C. or more and an intrinsic viscosity [η] of 5 dl / g or more measured in decalin at 135 ° C. 0.1 to 5 parts by mass of a propylene-based polymer (C) or less and 30 to 70 parts by mass of a styrene-based thermoplastic elastomer (D) (components (A), (B), (C) and (D)) The molded object which consists of a resin foam containing the total amount of 100 mass parts.

  According to the present invention, it is possible to provide a laminate which is made of a thermoplastic elastomer and which is excellent in both high foaming and surface skin.

  The present invention will be specifically described below.

  The laminate of the present invention comprises ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C) and styrene-based thermoplastic resin The layer (I) made of a resin foam containing an elastomer (D) is in contact with the layer (II) made of a thermoplastic elastomer.

[Ethylene-C 3-20 α-Olefin-Nonconjugated Polyene Copolymer (A)]
The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), which is one of the components of the layer (I) comprising a resin foam, is usually a unit derived from (a) ethylene And (b) a unit derived from α-olefin, 50/50 to 95/5, preferably 60/40 to 80/20, more preferably 65/35 to 75/25 [(a) / (b) In the range of the molar ratio of

  The α-olefin constituting the ethylene / C 3-20 α-olefin / non-conjugated polyene copolymer (A) according to the present invention is usually an α-olefin having 3 to 20 carbon atoms, 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 Be Among them, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.

Specific examples of the nonconjugated polyene constituting the ethylene / C3-C20 α-olefin / nonconjugated polyene copolymer (A) according to 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- Chain non-conjugated dienes such as methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene and the like;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic non-conjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene and norbornadiene;
2,3-Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. Trienes and the like can be mentioned, and these non-conjugated polyenes can be used alone or in combination of two or more. Among these non-conjugated polyenes, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are preferable.

  The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) according to the present invention has an iodine value of usually 1 to 50, preferably 5 to 50, which is an indicator of the amount of non-conjugated polyene component. 40, more preferably in the range of 10-30. In addition, the total amount of non-conjugated polyenes is usually in the range of 2 to 20% by mass in the component [A].

  The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) according to the present invention has an intrinsic viscosity [η] of usually 1 to 10 dl / g, which is measured in decalin at 135 ° C. Preferably, it is in the range of 1.5 to 8 dl / g.

  The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) according to the present invention is a so-called oil-extended compounded with a softener, preferably a mineral oil-based softener, during its production. It may be rubber. 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 / C 3-20 α-olefin / non-conjugated polyene copolymer (A) according to the present invention is usually 10-250, preferably 30-150. In the range.

  The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) according to the present invention may be used alone or in combination of two or more.

  The ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) according to the present invention can be produced by a conventionally known method.

  The blending amount of ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) is ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), The amount is 10 to 35 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the total amount of the propylene-based polymer (B), the propylene-based polymer (C) and the styrene-based thermoplastic elastomer (D).

  Heat resistance falls that the compounding quantity of ethylene and a C3-C20 alpha-olefin nonconjugated polyene copolymer (A) is less than 10 mass parts, and when it exceeds 35 mass parts, high foaming magnification is carried out When it is used, the surface becomes rough.

[Propylene-based polymer (B)]
The propylene-based polymer (B) used in the present invention comprises a high molecular weight solid product obtained by polymerizing propylene alone, or propylene and one or more other monoolefins by the high pressure method or the low pressure method.

  As a suitable raw material olefin other than propylene of a propylene-based polymer (B), Preferably it is a C2- or 4-20 alpha-olefin, Specifically, 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. The polymerization mode may be random or block as long as a resinous material is obtained. These propylene polymers may be used alone or in combination of two or more.

  The propylene polymer (B) used in the present invention is preferably a propylene polymer having a propylene content of 40 mol% or more, more preferably a propylene polymer having a propylene content of 50 mol% or more.

  Among these propylene polymers, a propylene homopolymer, a propylene / ethylene block copolymer, a propylene / ethylene random copolymer, a propylene / ethylene / butene random copolymer and the like are particularly preferable.

  The propylene-based polymer (B) used in the present invention has an intrinsic viscosity [η] of 0.1 dl / g or more and 5 dl / g or less, preferably 0.5 to 5 dl / g, as measured in decalin at 135 ° C. is there. When the intrinsic viscosity [η] measured in decaline at 135 ° C. of the propylene-based polymer (B) is less than 0.1 dl / g, the foamability is significantly deteriorated, and when it is 5 dl / g or more, at the time of foaming The surface of the skin gets worse.

  The melting point of the propylene-based polymer (B) used in the present invention is usually 80 to 200 ° C., preferably 120 to 170 ° C., and more preferably 145 to 165 ° C.

  The propylene-based polymer (B) used in the present invention has a MFR (JIS K6721, 230 ° C., 2.16 kg load) generally in the range of 0.1 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min. is there.

  The steric structure of the propylene-based polymer (B) used in the present invention is preferably an isotactic structure, but a syndiotactic structure, a mixture of these structures, or a partially atactic structure is included. Can also be used.

  The propylene-based polymer (B) used in the present invention is polymerized by various known polymerization methods.

  The blending amount of the propylene-based polymer (B) is ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C) And 1 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the styrene-based thermoplastic elastomer (D).

  When the amount of the propylene-based polymer (B) is less than 1 part by mass, the foamability is significantly deteriorated, and when it is more than 15 parts by mass, the foam surface is deteriorated.

[Propylene-based polymer (C)]
As the propylene-based polymer (C), a propylene homopolymer and a propylene / ethylene block copolymer are preferable.

  The propylene-based polymer (C) used in the present invention has an intrinsic viscosity [η] measured in decalin of 135 ° C. of 5 dl / g or more and 10 dl / g or less, preferably 5 to 9.5 dl / g. When the intrinsic viscosity [η] measured in decaline at 135 ° C. of the propylene-based polymer (C) is less than 5 dl / g, the expansion ratio does not increase, and when it exceeds 10 dl / g, the extrusion appearance during foaming is Getting worse.

  The propylene-based polymer (C) used in the present invention has a melting point of 150 ° C. or higher, preferably in the range of 150 to 165 ° C. When the melting point of the propylene-based polymer (C) is less than 150 ° C., the heat resistance is deteriorated.

  The propylene-based polymer (C) used in the present invention has a MFR (JIS K6721, 230 ° C., 2.16 kg load) generally in the range of 0.1 to 100 g / 10 min, preferably 0.1 to 80 g / 10 min. is there.

  The propylene-based polymer (C) used in the present invention is polymerized by various known polymerization methods.

  The blending amount of the propylene-based polymer (C) is ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C) And 0.1 to 5 parts by mass, preferably 1 to 5 parts by mass, and more preferably 1 to 4 parts by mass with respect to 100 parts by mass of the total amount of the styrene-based thermoplastic elastomer (D).

  When the content of the propylene-based polymer (C) is less than 0.1 parts by mass, the extrusion appearance at the time of foaming is deteriorated, and when it exceeds 5 parts by mass, the reduction in hardness at the time of foaming is not achieved.

[Styrene-based thermoplastic elastomer (D)]
Specific examples of the styrene-based thermoplastic elastomer (D) used in the present invention include a styrene / isoprene block copolymer, a hydrogenated product of a styrene / isoprene block copolymer (SEP), a styrene / isoprene / styrene block Hydrogenated products of copolymer (SEPS; polystyrene / polyethylene / propylene / polystyrene block copolymer), styrene / butadiene copolymer, hydrogenated products of styrene / butadiene block copolymer (SEBS; polystyrene / polyethylene / butylene / butylene) Polystyrene block copolymer) and the like, and more specifically, Septon (manufactured by Kuraray Co., Ltd.), EARNESTON (manufactured by Kuraray Plastics Co., Ltd.), Hybler (HYBRAR) (manufactured by Kuraray Co., Ltd.), Clayton KRATON), Kraton G [Krat n Polymer company], Europrene SOLT [Versalis company], JSR-TR, JSR-SIS [JSR Co., Ltd.], Quintac [Nippon Zeon Co., Ltd.], Tuftec [Asahi Kasei Kogyo Co., Ltd.] (Trade name) or the like.

  The styrene-based thermoplastic elastomer (D) used in the present invention preferably has a type A hardness (instantaneous value) in accordance with JIS K6253 of 60 or less, and more preferably 1 to 50.

  The styrene thermoplastic elastomer (D) used in the present invention preferably has a styrene content of 15 wt% or less, and more preferably 5 to 14 wt%.

  The blending amount of the styrene-based thermoplastic elastomer (D) is ethylene / α-olefin / non-conjugated polyene copolymer (C) having 3 to 20 carbon atoms (A), propylene-based polymer (B), propylene-based polymer (C) And 30 to 70 parts by mass, preferably 35 to 65 parts by mass, with respect to 100 parts by mass of the total amount of the thermoplastic elastomer (D) and the styrene-based thermoplastic elastomer (D).

  When the blending amount of the styrene-based thermoplastic elastomer (D) is less than 30 parts by mass, the expansion ratio does not improve, and when it exceeds 70 parts by mass, the heat resistance decreases.

[Bubbling agent]
The resin foam in the present invention is the ethylene / C3-20 α-olefin / nonconjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C) and styrene described above. It is preferable to produce by adding and foaming a foaming agent together with the thermoplastic elastomer (D).

  As the foaming agent used in the present invention, an inorganic or organic thermal decomposition type foaming agent (chemical foaming agent), carbon dioxide, nitrogen and a mixture of carbon dioxide and nitrogen can be mentioned.

  Examples of the inorganic thermal decomposition type foaming agent include inorganic carbonates such as sodium hydrogencarbonate, sodium carbonate, ammonium hydrogencarbonate and ammonium carbonate, and nitrites such as ammonium nitrite.

  As an organic thermal decomposition type foaming agent, nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosotephthalamide, N, N'-dinitrosopentamethylenetetramine; azodicarbonamide, azobisiso. Azo compounds such as butyronitrile, azocyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), diphenyl sulfone-3,3 Sulfonyl hydrazide compounds such as' -disulfonyl hydrazide; Azide compounds such as calcium azide, 4,4'-diphenyl disulfonyl azide, p-toluene sulfonyl azide, thermally expandable microcapsules (eg, Sekisui Chemical Co., Ltd. trade name) : ADVA CELL EM), and the like.

  When carbon dioxide or nitrogen is used, the foaming composition is melted at 100 to 300 ° C. in a resin plasticizing cylinder, and the foaming composition and carbon dioxide or nitrogen are in a compatible state. Form a thermoplastic elastomer composition.

  As the foaming agent, ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C) and styrene-based thermoplastic elastomer (D) It is used in a proportion of usually 1 to 15 parts by mass, preferably 1 to 12 parts by mass with respect to 100 parts by mass of the total amount of

  Moreover, a foaming auxiliary can also be added as needed. The addition amount thereof is ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C) and styrene-based thermoplastic elastomer ( It is usually 0.01 to 10 parts by mass, preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the total amount of D).

  Examples of the foaming assistant include metal compounds such as zinc, calcium, lead, iron and barium, higher fatty acids such as stearic acid and metal salts thereof, and fine particle inorganic particles such as talc, barium sulfate and silica. Specifically, citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, tartaric acid, cyclohexane-1,2-dicarboxylic acid, camphoric acid, ethylenediaminetetraacetic acid, triethylenetetramine hexaacetic acid and polytrilotriacetic acid etc. Of an aliphatic carboxylic acid and an inorganic carbonic acid compound such as sodium hydrogencarbonate, sodium aluminum hydrogencarbonate and potassium hydrogencarbonate, and intermediates produced by these reactions, for example, polyvalent acids such as sodium dihydrogen citrate and potassium oxalate Mention may be made of salts of carboxylic acids.

  These foaming agents or foaming aids may be dry-blended before extrusion, and may be decomposed during extrusion, or may be melt-blended into pellets before addition.

[Other ingredients]
Examples of the foaming composition include the ethylene / C3-20 α-olefin / nonconjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C), and styrene. Components other than the thermoplastic elastomer (D) and the foaming agent, for example, other conventionally known resins (for example, non-peroxide cross-linked rubber-like substances) can be blended within the range not impairing the object of the present invention. Peroxide non-crosslinkable rubber-like substances are mixed with peroxide, for example, as in butyl rubber, polyisobutylene, atactic polypropylene, propylene / α-olefin copolymer rubber having a propylene content of 50 mol% or more, and heated. This refers to a hydrocarbon rubber-like substance which does not crosslink and does not decrease in fluidity even when it is kneaded. The compounding amount of the peroxide non-crosslinking rubber-like substance is ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C) And 25 parts by mass or less, preferably 20 parts by mass or less, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the styrene-based thermoplastic elastomer (D).

  Examples of the foaming composition include the ethylene / C3-20 α-olefin / nonconjugated polyene copolymer (A), propylene-based polymer (B), propylene-based polymer (C), and styrene. Components other than the thermoplastic elastomer (D) and the foaming agent, for example, conventionally known inorganic fillers, reinforcing materials, softeners, heat-resistant stabilizers (processing heat stabilizers), anti-aging agents, weathering stabilizers, antistatic agents Additives such as a nucleating agent, a coloring agent, and a lubricant can be blended within a range that does not impair the object of the present invention.

  Total amount of inorganic filler, reinforcing material, softener, heat resistant stabilizer (processing heat stabilizer), anti-aging agent, weather resistant stabilizer, antistatic agent, crystal nucleating agent, coloring agent and lubricant, ethylene, carbon atom number Based on 100 parts by mass of the total of 3 to 20 α-olefin / non-conjugated polyene copolymer (A), propylene polymer (B), propylene polymer (C) and styrene thermoplastic elastomer (D) The amount is usually 100 parts by mass or less, preferably 50 parts by mass or less, and more preferably 45 parts by mass or less.

  The softener is a softener commonly used for rubber. Specifically, for example, petroleum oils such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petrolatum; Synthetic oils such as low molecular weight ethylene / α-olefin random copolymer; coal tar and coal tar pitch Coal tars, etc .; Fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; Waxes such as tall oil, beeswax, carnauba wax and lanolin; Ricinoleic acid, palmitic acid, stearic acid, stearic acid Fatty acids such as barium and calcium stearate or metal salts thereof; synthetic polymers such as petroleum resin, coumarone indene resin and atactic polypropylene; ester based plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; and other microcrystalline waxes , Sa (Factice), liquid polybutadiene, modified liquid polybutadiene and liquid Thiokol and the like. Among them, paraffinic process oils are particularly preferred.

  When a softener is added to the composition for foaming, it may be added at the time of production of the composition for foaming, or ethylene / C3-C20 α-olefin / non-conjugated polyene co-weight in advance Containing a part of a combination (A), a styrene-based thermoplastic elastomer (D), or an ethylene / C3-20 α-olefin / non-conjugated polyene copolymer (A) and a propylene-based polymer (B) Although a softener may be added to the olefin thermoplastic elastomer and used, it is not limited thereto.

  Examples of the lubricant include higher fatty acid amides, metal soaps, waxes, silicone oils, fluorine-based polymers and the like. Among them, higher fatty acid amides, silicone oils and fluorine-based polymers are preferable.

  As higher fatty acid amides, saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, behemic acid amide, etc .; unsaturated fatty acid amides such as erucic acid amide, oleic acid amide, brushidic acid amide, elaidic acid amide And Methylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisstearic acid amide, bisfatty acid amides such as ethylenebisoleic acid amide, and the like.

  As silicone oil, dimethyl silicone oil, phenyl methyl silicone oil, alkyl silicone oil, fluoro silicone oil, tetramethyl tetraphenyl trisiloxane, modified silicone oil and the like can be mentioned.

  Examples of the fluorine-based polymer include polytetrafluoroethylene and vinylidene fluoride copolymer.

  As the inorganic filler, specifically, 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, glass fibers, glass spheres, silas balloon, basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers and the like can be mentioned.

[Olefin-based thermoplastic elastomer]
The propylene-based polymer (B) and the ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) may be present in a polyolefin-based fully or partially crosslinked thermoplastic elastomer .

Among such polyolefin-based fully or partially crosslinked thermoplastic elastomers, as a partially crosslinked thermoplastic elastomer, for example,
(1) A mixture comprising (a) peroxide-crosslinked olefin copolymer rubber and (b) peroxide-decomposable olefin plastic (propylene polymer (B)), or (a) peroxide-crosslinked olefin copolymer Mixture comprising polymer rubber, (b) peroxide-degradable olefin plastic (propylene polymer (B)), and (c) peroxide non-crosslinkable rubber-like substance and / or (d) mineral oil softener Partially cross-linked thermoplastic elastomer obtained by dynamically heat-treating in the presence of an organic peroxide,
(2) (a) peroxide crosslinkable olefin copolymer rubber, (b) peroxide decomposition olefin plastic (propylene polymer (B)), and (c) peroxide noncrosslinkable rubbery material and / or (E) a crosslinked rubber composition obtained by dynamically heat-treating a mixture comprising a mineral oil-based softener in the presence of an organic peroxide (or a phenol resin-based crosslinking agent); The partially crosslinked thermoplastic elastomer (and the completely crosslinked thermoplastic elastomer) etc. which compounded the polymer (B) uniformly are mentioned.

  The aforementioned (c) peroxide non-crosslinked rubber-like substance is, for example, a mixture with a peroxide such as polyisobutylene, butyl rubber, atactic polypropylene, propylene / α-olefin copolymer rubber having a propylene content of 50% by mole or more, etc. Also, it refers to a hydrocarbon-based rubbery substance which does not crosslink and is not lowered in fluidity even if it is kneaded under heating.

  The above-mentioned (d) mineral oil-based softeners usually weaken the intermolecular action of the rubber during roll processing of the rubber, and facilitate the processing, and also help to disperse the carbon black, white carbon, etc. It is a high-boiling petroleum fraction used for the purpose of reducing the hardness of vulcanized rubber and increasing its flexibility and elasticity, and is classified into paraffinic, naphthenic, aromatic and the like. Examples of mineral oil softeners include paraffinic process oils and naphthenic process oils.

  In the olefin-based thermoplastic elastomer preferably used in the present invention, the mass blending ratio ((b) / (a)) of (b) olefin-based plastic to (a) olefin-based copolymer rubber is usually 90/10 to 10 It is in the range of 10/90, preferably 70/30 to 15/85.

  When a combination of ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer and another rubber is used as the rubber, the other rubber is an olefin-based plastic (propylene-based polymer) It is mix | blended in the ratio of normally 40 mass parts or less, preferably 5-20 mass parts with respect to 100 mass parts of total amounts of (B) and rubber.

  The olefin-based thermoplastic elastomer preferably used in the present invention comprises crystalline polypropylene and an ethylene / C3-20 α-olefin / non-conjugated polyene copolymer (A) (rubber), and is an olefin-based thermal elastomer. An olefinic heat which exists in a partially crosslinked state in a plastic elastomer and has a mass blending ratio of crystalline polypropylene to rubber (crystalline polypropylene / rubber) in the range of 70/30 to 10/90. It is a plasticizing elastomer.

  More specific examples of the olefin-based thermoplastic elastomer preferably used in the present invention include ethylene and an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene copolymer (A) in an amount of 30 to 90 parts by mass and crystallinity. 70 to 10 parts by mass of polypropylene (B) [the total amount of components (A) and (B) is 100 parts by mass] and rubber and / or mineral oil-based softener 5 to 150 other than the component (A) Examples thereof include thermoplastic elastomers in which the component (A) is partially crosslinked, which is obtained by thermally treating a mixture of parts by mass dynamically in the presence of an organic peroxide.

  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 peroxyisopropyl carbonate, diacetyl peroxide Lauroyl peroxide, etc. tert- butyl cumyl peroxide.

  Among these, in terms of odor and scorch stability, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butyl) Peroxy) 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 is preferred, among which 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 1,3-bis (tert-butylperoxyisopropyl) benzene are most preferred.

  The organic peroxide is used usually in a proportion of 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, per 100 parts by mass of the total amount of crystalline polypropylene and rubber.

  Sulfur, p-quinonedioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrosobenzene, diphenyl guanidine, trimethylolpropane, N in the crosslinking treatment with the organic peroxide. Or a crosslinking assistant such as N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, or ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Multifunctional methacrylate monomers such as allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

  By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is most preferred in the present invention. Divinylbenzene is easy to handle, has good compatibility with crystalline polypropylene and rubber, which are the main components of the above-mentioned cross-linked product, and has the function of solubilizing organic peroxide, and a dispersant for organic peroxide Thus, the cross-linking effect of the heat treatment is homogeneous, and an olefin-based thermoplastic elastomer having well-balanced flowability and physical properties is obtained.

  When the olefin-based thermoplastic elastomer used in the present invention is produced using a phenol resin-based crosslinking agent as a crosslinking agent, a propylene-based polymer (B) and an uncrosslinked ethylene / α-olefin / nonconjugated polyene copolymer It is preferable to dynamically crosslink with a phenolic resin crosslinking agent. In the present invention, "dynamic crosslinking" refers to crosslinking while applying shear force to the mixture.

As a phenol resin type crosslinking agent, a halogenated phenol resin type crosslinking agent is mentioned.
Phenolic resin crosslinking agents are resole resins and are prepared by condensation of alkyl-substituted phenols or unsubstituted phenols with aldehydes in an alkaline medium, preferably by condensation with formaldehyde, or by condensation of difunctional phenolic dialcohols Is also preferred. The alkyl-substituted phenol is preferably an alkyl group substituted with 1 to about 10 carbon atoms. Furthermore, dimethylol phenols or phenol resins substituted with an alkyl group having 1 to about 10 carbon atoms in the p-position are preferred. The phenolic resin-based cured resin is typically a thermally crosslinkable resin, and is also referred to as a phenolic resin-based crosslinking agent or a phenolic resin.

  As an example of a phenol resin-based cured resin (phenol resin-based crosslinking agent), a compound represented by the following general formula (I) can be mentioned.

（式中、Ｑは、−ＣＨ_２−及び−ＣＨ_２−Ｏ−ＣＨ_２−から成る群から選ばれる二価の基であり、ｍは０又は１乃至２０の正の整数であり、Ｒ’は有機基である）。

(Wherein, Q is a divalent group selected from the group consisting of —CH ₂ — and —CH ₂ —O—CH ₂ —, m is a positive integer of 0 or 1 to 20, and R ′ is Is an organic group).

Preferably, Q is a divalent radical _-CH 2 -O-CH ₂ - and is, m is 0 or a positive integer of 1 to 10, R 'is an organic radical having less than 20 carbon atoms. More preferably, m is a positive integer of 0 or 1 to 5 and R ′ is an organic group having 4 to 12 carbon atoms. Specific examples thereof include alkylphenol formaldehyde resin, methylolated alkylphenol resin, halogenated alkylphenol resin and the like, preferably halogenated alkylphenol resin, and more preferably brominated hydroxyl group at the terminal.

（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）。

(In formula, n is an integer of 0-10, R is a C1-C15 saturated hydrocarbon group).

  As a product example of the said phenol-type cured resin, Takiroll (trademark) 201 (alkyl phenol formaldehyde resin, Taoka Chemical Industry Co., Ltd. product made), Takiroll (trademark) 250-I (the bromination rate 4% brominated alkylphenol) Formaldehyde resin, Taoka Chemical Industry Co., Ltd., Tackiroll (registered trademark) 250-III (brominated alkylphenol formaldehyde resin, Taoka Chemical Industry Co., Ltd.), PR-4507 (Gunei Chemical Industry Co., Ltd.) Vulkaresat 510E (Hoechst), Vulkaresat 532E (Hoechst), Vulkaresen E (Hoechst), Vulkaresen 105E (Hoechst), Vulkaresen 130E (Hoechst) Vulkaresol 315E (manufactured by Hoechst), Amberol ST 137X (manufactured by Rohm & Haas), Sumilite Resin (registered trademark) PR-22193 (manufactured by Sumitomo Durez Co., Ltd.), Symphorm-C-100 (manufactured by Anchor Chem.) Symphorm-C-1001 (Anchor Chem.), Tamanor (registered trademark) 531 (Arakawa Chemical Co., Ltd.), Schenectady SP 1059 (Schenectady Chem.), Schenectady SP 1045 (Schenectady Chem.), CRR -0803 (manufactured by U.C.C.), Schenectady SP 1055F (manufactured by Schenectady Chem., Brominated alkylphenol formaldehyde tree ), Schenectady SP1056 (manufactured by Schenectady Chem. Companies), CRM-0803 (Showa Union Synthesis Co., Ltd.), Vulkadur A (Bayer Corporation). Among them, halogenated phenol resin-based crosslinking agents are preferable, and brominated alkylphenol-formaldehyde resins such as Tackiroll (registered trademark) 250-I, Tackyroll (registered trademark) 250-III, and Schenectady SP 1055F can be more preferably used.

  Further, as specific examples of crosslinking of thermoplastic vulcanized rubber with a phenol resin, US Pat. Nos. 4,311,628, 2,972,600 and 3,287,440 can be used. Although described, 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. Usually, a halogenated phenol resin-based crosslinking agent, preferably a brominated phenol resin-based crosslinking agent containing 2 to 10% by mass of bromine does not require a halogen donor, for example, iron oxide, titanium oxide, oxide It is used simultaneously with hydrogen halide scavengers such as magnesium, 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 scavengers accelerates the crosslinking action of the phenolic resin-based crosslinking agent, in the case of a rubber which is not easily vulcanized by the phenolic resin-based 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 phenolic resin based crosslinking agents, and includes metal oxides and halogen donors, Are 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, such as such crosslinking agents from Schenectady Chemicals, Inc. under the trade designation "SP-1045", "CRJ-352. , "SP-1055F" and "SP-1056". Similar functionally equivalent phenolic resin based crosslinkers can also be obtained from other suppliers.

  Phenolic resin-based crosslinking agents are suitable vulcanizing agents from the viewpoint of preventing fogging because generation of decomposition products is small. The phenolic resin based crosslinking agent is used in an amount sufficient to achieve essentially complete vulcanization of the rubber.

  The phenolic resin crosslinking agent is used in an amount of usually 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the ethylene / α-olefin / nonconjugated polyene copolymer. . By setting the compounding amount of the phenolic resin-based crosslinking agent in the above range, a composition having excellent moldability is obtained, and the obtained molded article has high strength and excellent oil resistance, and is sufficient. Has heat resistance and mechanical properties.

  In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, during dynamic crosslinking with a phenolic resin crosslinking agent. Peroxy crosslinking aids such as diphenyl guanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane Auxiliary agents such as polyfunctional methacrylate monomers such as trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

  A uniform and mild crosslinking reaction can be expected by using the auxiliaries. As the assistant, divinylbenzene is preferable. Divinylbenzene is easy to handle, has good compatibility with crystalline polypropylene and ethylene / α-olefin / nonconjugated polyene copolymer contained as a main component in the thermoplastic elastomer composition, and is a phenolic resin crosslinker In order to act as a solubilizing agent and act as a dispersing agent for the phenolic resin crosslinking agent, the crosslinking effect of the heat treatment is homogeneous, and a thermoplastic elastomer composition having well-balanced flowability and physical properties is obtained.

  The amount of the auxiliary agent is usually 2 parts by mass or less, preferably 0.3 to 1 parts by mass, with respect to 100 parts by mass of the ethylene / α-olefin / nonconjugated polyene copolymer.

  In addition, a dispersion accelerator may be used to accelerate the degradation of the phenolic resin crosslinking agent. Examples of decomposition accelerators include tertiary amines such as triethylamine, tributylamine and 2,4,6-tri (dimethylamino) phenol; aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury, etc. Naphthenic acid salts of naphthenic acid and various metals (eg, Pb, Co, Mn, Ca, Cu, Ni, Fe, Zn, rare earths) and the like can be mentioned.

  The crosslinking aid or multifunctional vinyl monomer as described above is used in a proportion of 0.01 to 5 parts by mass, in particular 0.05 to 3 parts by mass, with respect to 100 parts by mass of the whole to-be-crosslinked product. Is preferred. When the blending ratio of the crosslinking assistant or the polyfunctional vinyl monomer exceeds 5 parts by mass, the crosslinking reaction proceeds too fast when the blending amount of the organic peroxide is large, so that the obtained thermoplastic elastomer has fluidity. On the other hand, when the blending amount of the organic peroxide is small, the cross-linking coagent and the polyfunctional vinyl monomer remain as unreacted monomers in the thermoplastic elastomer, and the thermoplastic elastomer is thermally processed during processing and molding. Changes in physical properties occur due to history. Thus, the coagent and multifunctional vinyl monomer should not be incorporated in excess.

  The above-mentioned "dynamically heat-treated" refers to kneading each component as described above in a molten state. As the kneading apparatus, a conventionally known kneading apparatus such as an open mixing roll, a non-open Banbury mixer, an extruder, a kneader, a continuous mixer and the like are used. Among these, a non-open type kneading apparatus is preferable, and the kneading is preferably performed in the atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

Also, it is desirable that the kneading be performed at a temperature at which the half life of the organic peroxide used is less than one minute. The kneading temperature is usually 150 to 280 ° C., preferably 170 to 270 ° C., and the kneading time is usually 0.5 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is typically a shear rate, 10～50,000Sec ^-1, it is preferably determined in the range of 100~10,000sec ^-1.

  The completely crosslinked olefinic thermoplastic elastomer is prepared by changing the conditions such as the amount of organic peroxide used and the kneading time according to the method for preparing an olefinic thermoplastic elastomer described in (1) and (2) above. can do.

  The olefin-based thermoplastic elastomer used in the present invention preferably has a type A hardness (instantaneous value) according to JIS K6253 of 60 or more. The type A hardness (instantaneous value) is usually 1 to 98, preferably 60 to 98, more preferably 70 to 98, and particularly preferably 80 to 98.

  The olefin thermoplastic elastomer used in the present invention has a melt flow rate (MFR: ISO 1133, 230 ° C., load 2.16 kg) measured at 230 ° C. and a load of 2.16 kg, usually 0.1 to 100 g / 10 min, preferably It is in the range of 1 to 100 g / 10 min.

[Composition for foaming]
The foaming composition used in the present invention comprises 10 to 35 parts by mass, preferably 10 to 30 parts by mass of an ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms, preferably a propylene-based polymer (B) 1 to 15 parts by mass, preferably 1 to 10 parts by mass, propylene-based polymer (C) 0.1 to 5 parts by mass, preferably 1 to 5 parts by mass, more preferably 1 to 4 parts by mass, styrene 30 to 70 parts by mass of thermoplastic elastomer (D), preferably 35 to 65 parts by mass (the total amount of components (A), (B), (C) and (D) is 100 parts by mass) and a foaming agent It contains 1 to 15 parts by mass.

  The foaming composition used in the present invention comprises an ethylene / C3-20 α-olefin / non-conjugated polyene copolymer (A), a propylene-based polymer (B), a propylene-based polymer which is at least partially crosslinked. The polymer (C) and the styrenic thermoplastic elastomer (D), and if necessary, the softener and further the other components may be melt-kneaded and then granulated or pulverized.

  The thermoplastic elastomer composition of the present invention has a part of the propylene-based polymer (B) and an uncrosslinked ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer in view of flowability adjustment A mixture containing (A), an organic peroxide, and, if necessary, other components, is dynamically heat-treated to partially or completely crosslinked ethylene / C 3 -C 20 α-olefin・ After preparing an olefin-based thermoplastic elastomer containing a nonconjugated polyene copolymer (A), the remaining propylene-based polymer (B), the propylene-based polymer (C), and the styrene-based thermoplastic elastomer (B) It is preferable to manufacture by a method of granulating or grinding after melt-kneading a foaming agent and, if necessary, other components.

  As a kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single screw or twin screw extruder, etc. can be used, but a non-open type apparatus is preferable.

  The laminate of the present invention comprises a foamable composition for forming the layer (I) of the resin foam obtained as described above and a thermoplastic elastomer composition for forming the layer (II) of the thermoplastic elastomer. The product can be produced by heating by coextrusion and foaming and heat sealing.

  Although there is no restriction | limiting in particular as a thermoplastic elastomer composition which forms layer (II) which consists of a thermoplastic elastomer, An olefin type thermoplastic elastomer composition and a styrene-type thermoplastic elastomer composition are mentioned.

  The laminate of the present invention is applied, for example, as a seal material used for door seals, hood seals, automobile seal materials used for trunk seals, truck container seals, construction gaskets (for example, bathroom door seals).

  EXAMPLES The present invention will be more specifically described below based on examples, but the present invention is not limited to these examples.

The measuring method and evaluation method of the physical property implemented below are as follows.
[Melting point (Tm)]
The melting point (Tm) of the polymer was measured by a differential scanning calorimeter (DSC) with a DSC220C apparatus manufactured by Seiko Instruments Inc. 7-12 mg of samples obtained from the polymerization were sealed in an aluminum pan and heated from room temperature to 200C at 10C / min. The sample was held at 200 ° C. for 5 minutes for complete melting and then cooled at 10 ° C./min to −50 ° C. After 5 minutes at -50 ° C, the sample was reheated to 200 ° C at 10 ° C / min. The peak temperature on the high temperature side of the endothermic curve at this second (second) heating was adopted as the melting point (Tm).

[Intrinsic viscosity]
The intrinsic viscosity [η] of the polymer was measured at 135 ° C. using a decalin solvent.
[MFR (g / 10 min)]
According to JIS K6721, it measured at 230 ° C under load of 2.16 kg and 10 kg.

[Shore A hardness]
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.

[Compression set (CS)]
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 Co., Ltd.), and then cold pressed for 5 minutes at room temperature to obtain a 2 mm-thick press sheet Made.

  The 2 mm-thick press sheets produced as described above were laminated in accordance with JIS K6250, and a compression set test was conducted in accordance with JIS K6262.

  The test conditions are compression using 25% thickness, 70 ° C., 24 hours condition using laminated sheet of 12 mm thickness (4 sheets of 3 mm thickness), and measured after lapse of 30 minutes after strain removal (compression) did.

[Penetration temperature]
In accordance with JIS K7196, using a TMA 5200 (manufactured by Seiko Instruments Inc.) using a test piece having a thickness of 2 mm, a load of 50 g / cm ² is applied using an indenter having a diameter of 1 mm under nitrogen stream at 2 ° C. It implemented on the temperature rising conditions of / min, and read the penetration temperature.

[Extrusion foam evaluation]
8 parts by mass of a foaming agent is added to a blend obtained by kneading at a processing speed of 50 kg per hour at 220 ° C. in an extruder (product number KTX-46, manufactured by Kobe Steel Co., Ltd.) to carry out extrusion foaming The Foaming agent was dry blended ADVANCELL ^TM EM P501E1 made of Sekisui Chemical.

  Using this dry blend, using a 65 mm single screw extruder (No. OSE-65, manufactured by Nagata Mfg. Co., Ltd.) using a nozzle 2 mm wide, C1 / C2 / C3 / C4 / C5 / C5 / C6 / C7 / C7 / C8 = 170 ° C. Extrusion was carried out at / 180 ° C./190° C./210° C./220° C./200° C./200° C./200° C., and a pull-out extrusion evaluation was performed at 3 m / min.

The surface skin evaluation was performed by the slipperiness of the surface skin. When a finger tip was made to slide sideways and touched the obtained extrusion-molded article, evaluation was made according to the following criteria.
○: The extruded foam surface is not caught on the finger when touched and slides smoothly :: The extruded foam surface is slightly hooked on the finger when touched and there is a sense of resistance to moving the finger laterally X: when touched There is a feeling that the finger is caught on the surface of the molded product and it is resistant to move the finger laterally

The state of the foam cell (foamability) was evaluated as follows.
○: uniform bubble condition, bubble breaking, no tearing observed Δ: bubble condition non-uniform, bubble breaking, tearing partially observed ×: bubble breaking, tearing, etc. severe Or swelling occurs and can not be evaluated

[Example 1] The composition of the preparation methods ethylene-alpha-olefin-non-conjugated polyene (A) as the ethylene-propylene-diene copolymer rubber (MITSUI ^EPT TM 3072EPM: Mitsui Chemicals Co., Ltd., ethylene content = 64 mass %, diene content = 5.4 wt%, Mooney viscosity ML (1 + 4) 125 ℃ = 51, oil extension amount = 40 (PHR)) 65 parts by weight, the propylene polymer (B) as Prime Polypro ^TM J707G (Prime polymer Ltd., propylene / ethylene block copolymer, 15 parts by mass of intrinsic viscosity [極限] 1.7 dl / g, butyl rubber as another component: trade name IIR065 (manufactured by Exxon Mobil Chemical, degree of unsaturation: 0.8 mol %, Mooney viscosity ML (1 + 8) 125 ° C .: 20 parts by mass, and paraffinic process oil: trade name die 10 parts by mass of Na Process Oil PW-100 (made by Idemitsu Kosan Co., Ltd.) is mixed beforehand with a closed mixer [Kobe Steel Co., Ltd. Mixtron BB16] and sheeted into a sheeting roll, and then made by a pelletizer made by Korai Iron Works Co., Ltd. Square pellets were produced.

The angular pellets 47.5 parts by mass of the propylene-based copolymer as a propylene-based polymer (C) (trade name: Prime Polypro ^TM VP103W, manufactured by Prime Polymer Co., MFR (JIS K6721,230 ℃, 2.16kg load ) 3.0 g / 10 min, an intrinsic viscosity [η] 8.5dl / g, durometer D50) 2.5 parts by weight, the propylene polymer (B) as Prime Polypro ^TM J739E (block polypropylene, manufactured by Prime polymer Co., Intrinsic viscosity [η] 1.2 dl / g, MFR (JIS K 6721, 230 ° C, 2.16 kg load) 90 g / 10 min, 2.5 parts by mass of melting point 162 ° C., and septon as a styrene-based thermoplastic elastomer (D) ^TM 2063 (made by Kuraray, Shore A hardness 36 according to JIS K6253, styrene content 13 w t%) 47.5 parts by mass of an extruder (No. KTX-30, manufactured by Kobe Steel, Ltd., cylinder temperature: C1: 50 ° C., C2: 90 ° C., C3: 100 ° C., C4: 120 ° C., C5: 180) C6: 200 ° C., C7 to C14: 200 ° C., die temperature: 200 ° C., screw rotation speed: 500 rpm, extrusion amount: 40 kg / h) to obtain pellets of a thermoplastic elastomer composition. The formulations and results are shown in Table 1.

Comparative Examples 1 to 5
Pellets of a thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the components and the amount thereof were changed as shown in Table 1. The results are shown in Table 1.

  From the results shown in Table 1, it is understood that the thermoplastic elastomer composition of Example 1 is excellent in both high foaming and surface skin.

Claims (5)

  Ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) 10 to 35 parts by mass, limiting viscosity [η] measured in decalin at 135 ° C. is 0.1 dl / g or more, 1-15 parts by mass of a propylene-based polymer (B) less than 5 dl / g, melting point 150 ° C. or more, and intrinsic viscosity [η] measured in decalin at 135 ° C. is 5 dl / g or more and 10 dl / g or less 0.1-5 parts by mass of the propylene-based polymer (C), and 30-70 parts by mass of the styrene-based thermoplastic elastomer (D) (total amount of the components (A), (B), (C) and (D) The laminated body in which the layer (I) which consists of a resin foam which contains 100 mass parts), and the layer (II) which consists of thermoplastic elastomer contact.   Ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) 10 to 35 parts by mass, limiting viscosity [η] measured in decalin at 135 ° C. is 0.1 dl / g or more, 1-15 parts by mass of a propylene-based polymer (B) less than 5 dl / g, melting point 150 ° C. or more, and intrinsic viscosity [η] measured in decalin at 135 ° C. is 5 dl / g or more and 10 dl / g or less 0.1 to 5 parts by mass of a propylene-based polymer (C), 30 to 70 parts by mass of a styrene-based thermoplastic elastomer (D) (total amount of components (A), (B), (C) and (D) The method for producing a laminate according to claim 1, comprising coextrusion molding using a composition comprising 100 parts by mass of 1 to 15 parts by mass of a foaming agent and a thermoplastic elastomer composition.   A sealing material comprising the laminate according to claim 1.   The sealing material according to claim 3, which is a sealing material for automobiles.   Ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer (A) 10 to 35 parts by mass, limiting viscosity [η] measured in decalin at 135 ° C. is 0.1 dl / g or more, 1-15 parts by mass of a propylene-based polymer (B) less than 5 dl / g, melting point 150 ° C. or more, and intrinsic viscosity [η] measured in decalin at 135 ° C. is 5 dl / g or more and 10 dl / g or less 0.1-5 parts by mass of the propylene-based polymer (C), and 30-70 parts by mass of the styrene-based thermoplastic elastomer (D) (total amount of the components (A), (B), (C) and (D) The molded object which consists of a resin foam containing 100 mass parts.