JP4659658B2 - Olefin-based thermoplastic elastomer foam laminate - Google Patents

Description

  The present invention relates to a foam laminate of an olefinic thermoplastic elastomer.

  Conventionally, as a method of producing an elastomer foam, a vulcanizing agent and a foaming agent are kneaded with natural rubber or synthetic rubber, and then the kneaded product is molded into a predetermined shape and heated to perform heating and foaming. Thus, a method of obtaining an elastomer (vulcanized rubber) foam is known. However, in the conventional method as described above, when the rubber is molded into a predetermined shape by continuous extrusion, the step of batch-kneading the compound into rubber in advance to obtain a kneaded product is performed before continuous extrusion. In order to make it easy to supply the kneaded product to the extruder, it is necessary to perform a step of forming the kneaded product into a ribbon shape in advance before continuous extrusion. Thus, the conventional methods as described above are disadvantageous in industrial production because the manufacturing process is complicated and the vulcanization and foaming processes require a considerable amount of time.

  As a method for solving such problems, for example, a thermoplastic resin such as ethylene / vinyl acetate copolymer, low density polyethylene, or a partially crosslinked thermoplastic elastomer comprising an olefin copolymer rubber and an olefin resin. There is a method of using. According to this method, the aforementioned steps can be omitted.

  However, the conventionally used thermoplastic resins and thermoplastic elastomers have a problem in that poor appearance tends to occur because they are easily defoamed during foam molding. In addition, even if parts such as weather strips for automobiles or seal members for door-to-door parts that are in contact with people or objects or parts that repeatedly slide are manufactured from foams obtained by conventional methods, wear resistance and It has the disadvantage of being inferior in scratch resistance.

For this reason, olefinic thermoplastic elastomers are rarely used as they are for parts that require wear resistance and scratch resistance, and surface treatment is performed (for example, Patent Document 1). The actual situation is that an improved version is used.
Japanese Patent Publication No. 3-070742

The present invention solves the problems associated with the prior art as described above, in which an olefinic thermoplastic elastomer excellent in wear resistance and scratch resistance is laminated on a conventional olefinic thermoplastic elastomer foam. Therefore, the present invention proposes a molded article that is excellent in moldability and part processability, and has excellent wear resistance and scratch resistance.

<Overview>
The olefinic thermoplastic elastomer foam laminate is
An olefinic thermoplastic elastomer composition (A) and / or an olefinic resin (B) containing an olefinic resin (a) and an ethylene copolymer rubber (b) as essential components, and a foaming agent (C). A base material layer comprising a foam (X ₂ ) of an olefin-based foamable composition (X ₁ );
An olefinic thermoplastic elastomer composition (D) comprising a syndiotactic α-olefin copolymer (c), another thermoplastic resin (d) and, if necessary, an ethylene copolymer rubber (e). ) -Based thermoplastic elastomer laminate.
(Here, the syndiotactic α-olefin copolymer (c) is
In ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution, the total absorption intensity at which the absorption of methyl groups of propylene units is observed at about 20.0 to 21.0 ppm based on tetramethylsilane is propylene. An absorption intensity of about 19.0 to 22.0 ppm attributed to methyl is 0.5 or more,
(C-1) a repeating unit derived from propylene;
(C-2) a repeating unit derived from ethylene;
(C-3) a repeating unit derived from at least one olefin selected from olefins having 4 to 20 carbon atoms, and, if necessary,
(C-4) consisting of repeating units derived from at least one polyene selected from conjugated polyenes and non-conjugated polyenes,
When the total amount of the unit (c-1), the unit (c-2) and the unit (c-3) is 100 mol%, the unit (c-1) is 30 to 79 mol%, and the unit (c- 2) It contains 1 to 30 mol% of units and 10 to 50 mol% of the above (c-3) units (provided that the total amount of (c-2) units and (c-3) units is 21 to 70) The (c-4) unit is 0 to 30 mol% with respect to 100 mol% of the total amount of the (c-1) unit, (c-2) unit and (c-3) unit. It is contained in quantity and is substantially a syndiotactic structure. )
Moreover, it is preferable that the said olefin type thermoplastic elastomer composition (D) contains ethylene-type copolymer rubber (e), and also it is desirable that the ethylene-type copolymer rubber (e) is bridge | crosslinked.

  Furthermore, it is desirable that the other thermoplastic resin (d) is a polypropylene having a melt flow rate in the range of 0.1 to 200 g / 10 min at 230 ° C. and a load of 2.16 kg.

  The syndiotactic α-olefin copolymer (c) has no melting peak measured by a differential scanning calorimeter (DSC), and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01. It is desirable that the molecular weight distribution by GPC is 4 or less and the glass transition temperature Tg is −5 ° C. or less.

  And it is preferable that the laminated body is manufactured by extrusion molding, injection molding, blow molding, or hollow molding.

    In the laminate according to the present invention, the syndiotactic α-olefin copolymer (c) may be crosslinked.

  The olefinic thermoplastic elastomer foam laminate as described above is excellent in moldability, heat resistance, scratch resistance, wear resistance and flexibility balance.

<Specific Description of the Invention>
Hereinafter, the olefinic thermoplastic elastomer foam laminate according to the present invention will be specifically described.

The olefinic thermoplastic elastomer foam laminate according to the present invention is an olefinic thermoplastic elastomer composition (A) and / or olefinic resin comprising an olefinic resin (a) and an ethylene copolymer rubber (b) as essential components. A base material layer comprising a foam (X ₂ ) of an olefin-based foamable composition (X ₁ ) containing (B) and a foaming agent (C);
An olefinic thermoplastic elastomer composition (D) comprising a syndiotactic α-olefin copolymer (c), another thermoplastic resin (d) and, if necessary, an ethylene copolymer rubber (e). ).

  The olefinic thermoplastic elastomer composition (D) is 1 to 99 parts by weight, preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, most preferably the syndiotactic α-olefin copolymer (c). 50 to 90 parts by weight and 99 to 1 part by weight of another thermoplastic resin (d), preferably 95 to 5 parts by weight, more preferably 90 to 10 parts by weight, most preferably 50 to 10 parts by weight, and If necessary, the ethylene copolymer rubber (e) is added in an amount of 5 to 1000 weights with respect to a total of 100 parts by weight of the syndiotactic α-olefin copolymer (c) and the other thermoplastic resin (d). Part, preferably 10 to 500 parts by weight, more preferably 15 to 300 parts by weight.

Olefin-based thermoplastic elastomer composition (A)
The olefinic thermoplastic elastomer composition (A) comprises an olefinic resin (a) and an ethylene copolymer rubber (b) as essential components.

<Olefin resin (a)>
The olefin resin (a) used in the present invention comprises a high molecular weight solid product obtained by polymerizing one or more monoolefins by either the high pressure method or the low pressure method. Examples of such a resin include isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

  Specific examples of suitable raw material olefins for the olefin resin (a) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 2-methyl-1- Examples include propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. These olefins may be used alone or in combination of two or more.

  The polymerization mode may be random type or block type, and any polymerization mode can be adopted as long as a resinous material is obtained. These olefinic resins may be used alone or in combination of two or more.

  Among these olefin resins (a), when heat resistance is required, a propylene polymer, specifically, a propylene homopolymer, a propylene / ethylene block copolymer, propylene / ethylene, or propylene / ethylene / butene random Copolymers are preferred.

  The polymerization form may be either isotactic or syndiotactic, but isotactic is particularly excellent in heat resistance.

  The olefin resin (a) used in the present invention has an MFR (ASTM D 1238-65T, 230 ° C.) of usually 0.01 to 100 g / 10 minutes, particularly 0.05 to 50 g / 10 minutes. preferable.

  The olefin resin (a) has a role of improving the fluidity and heat resistance of the composition.

  In the present invention, the olefin resin (a) is preferably 10 parts by weight or more and less than 80 parts by weight, more preferably 15 to 60 parts by weight with respect to 100 parts by weight of the total amount of the olefin resin and rubber. Used.

  When the olefin-based resin (a) is used in the above proportion, an olefin-based thermoplastic elastomer composition (A) excellent in heat resistance, flexibility and rubber elasticity and excellent in molding is obtained.

<Ethylene copolymer rubber (b)>
The ethylene copolymer rubber (b) used in the present invention is an amorphous random elastic copolymer rubber made of ethylene and an α-olefin having 3 to 20 carbon atoms, or ethylene and 3 to 3 carbon atoms. It is an amorphous random elastic copolymer rubber composed of 20 α-olefins and non-conjugated polyene.

  The ethylene / α-olefin molar ratio of such an ethylene copolymer (b) is usually 40/60 to 85/15, and among these, those in the range of 60/40 to 83/17 are preferred.

  Specific examples of the non-conjugated polyene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, and vinyl norbornene. Of these, ethylene / propylene / non-conjugated diene copolymer rubber and ethylene / 1-butene / non-conjugated diene copolymer rubber are preferred, and ethylene / propylene / non-conjugated diene copolymer rubber, particularly ethylene / propylene. -Ethylidene norbornene copolymer rubber and ethylene / propylene / vinyl norbornene copolymer rubber are particularly preferable in that a thermoplastic elastomer having an appropriate cross-linked structure can be obtained.

  The Mooney viscosity [ML1 + 4 (100 ° C.)] of the ethylene copolymer rubber (b) used in the present invention is preferably in the range of 50 to 300, preferably 100 to 200.

  Moreover, it is preferable that the iodine value of this ethylene-type copolymer rubber (b) is 3-30, and it is especially preferable that it exists in the range of 5-25. When the iodine value of the ethylene-based copolymer rubber (b) is in such a range, the thermoplastic elastomer composition (A) excellent in moldability and rubber elasticity is obtained by crosslinking in a balanced manner.

  The ethylene copolymer rubber (b) used in the present invention may be a so-called oil-extended product containing a softening agent. By using an oil-extended product, an elastomer composition having more flexibility can be obtained. As the softening agent that can be used for the oil-extended product, a softening agent that is usually used for rubber can be used.

Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly;
Synthetic oils such as low molecular weight ethylene / α-olefin random copolymers;
Coal tars such as coal tar and coal tar pitch;
Fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil;
Waxes such as tall oil, beeswax, carnauba wax, lanolin;
Fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate or metal salts thereof;
Synthetic polymer materials such as petroleum resin, coumarone indene resin, atactic polypropylene;
Ester plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate;
Other examples include microcrystalline wax, sub (factis), liquid polybutadiene, modified liquid polybutadiene, and liquid thiocol.
Among these softeners, paraffinic process oils or low-molecular-weight ethylene / α-olefin random copolymers are particularly preferred, and high-viscosity paraffinic process oils with a low content of low-molecular-weight components that tend to volatilize are particularly preferred. Particularly preferred. Here, the high-viscosity type means one having a kinematic viscosity at 40 ° C. in the range of 100 to 10,000 centistokes.

  In the present invention, the softener is used in a proportion of 150 parts by weight or less, preferably 2 to 100 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the ethylene copolymer rubber (b). .

  The ethylene copolymer rubber (b), which may be oil-extended as necessary, has a total amount of 100 parts by weight of the olefin resin (a) and the ethylene copolymer rubber (b). It is used in a proportion of 40 to 85 parts by weight, preferably 60 to 80 parts by weight.

  In the present invention, in addition to the ethylene copolymer rubber (b), a rubber other than the ethylene copolymer rubber (b) and the ethylene copolymer rubber (b) within a range not impairing the object of the present invention. Can also be used in combination. Examples of the rubber other than the ethylene copolymer rubber (b) include propylene / ethylene copolymer rubber (propylene content of 60 mol% or more), propylene / α-olefin copolymer rubber, styrene / butadiene rubber, and the like. Examples thereof include hydrogenated products, styrene / isoprene rubber and hydrogenated products thereof, polybutadiene rubber, polyisoprene rubber, nitrile rubber, butyl rubber, polybutylene rubber, natural rubber, and silicone rubber.

<Other ingredients>
In addition to the olefin resin (a) and the ethylene copolymer rubber (b), the olefin thermoplastic elastomer composition (A) according to the present invention may be blended with a softener and / or an inorganic filler. it can.

  As described above, the softening agent may be oil-extended into the ethylene copolymer rubber (b), or may be added later without oil-extended. In the case where the ethylene copolymer rubber (b) is added later without being oil-extended, the same softening agent as described above can be used.

  In the case where it is added later without oil-extended, the amount of the softening agent is 100 parts by weight with respect to the total amount of the olefin-based resin (a) and the ethylene-based copolymer rubber (b) together with the oil-extended component. 100 parts by weight or less, preferably 3 to 80 parts by weight, more preferably 5 to 50 parts by weight. When the softening agent is used in the above ratio, the resulting thermoplastic elastomer composition is excellent in fluidity during molding and does not deteriorate the mechanical properties of the molded product. In this invention, when the usage-amount of a softening agent exceeds 100 weight part, it exists in the tendency for the heat resistance of the thermoplastic elastomer composition obtained to fall.

  Specific examples of the inorganic filler used in the present invention include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, sulfuric acid. Examples include calcium, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, glass balloon, basic magnesium sulfate whisker, calcium titanate whisker, and aluminum borate whisker.

  In the present invention, the inorganic filler is a ratio of 100 parts by weight or less, preferably 2 to 30 parts by weight with respect to 100 parts by weight of the total amount of the olefin resin (a) and the ethylene copolymer rubber (b). Used in In this invention, when the usage-amount of an inorganic filler exceeds 100 weight part, there exists a tendency for the rubber elasticity of a heat resistant thermoplastic elastomer composition obtained and a moldability to fall.

  Further, in the present invention, a conventionally known heat stabilizer, anti-aging agent, weathering stabilizer, antistatic agent, crystal nucleating agent, higher fatty acid amide, metal in the olefinic thermoplastic elastomer composition (A) A lubricant such as soap, wax, silicone oil or the like can be added as long as the object of the present invention is not impaired.

  The olefinic thermoplastic elastomer composition (A) according to the present invention comprises the above-described olefinic resin (a) and ethylene copolymer rubber (b), and a softener and / or inorganic filler blended as necessary. After mixing with an agent, etc., it is obtained by dynamically heat-treating. Here, “dynamically heat-treating” means kneading in a molten state.

  In addition, by performing dynamic heat treatment in the presence of a crosslinking agent, a crosslinked olefinic thermoplastic elastomer composition (A) can be obtained, and by using a crosslinked olefinic thermoplastic elastomer, the present invention can be applied to the present invention. The applied heat resistance is further improved.

  The crosslinking agent used here is an organic peroxide, phenol resin, sulfur, hydrosilicone compound, amino resin, quinone or its derivative, amine compound, azo compound, epoxy compound, isocyanate, etc., thermosetting type The crosslinking agent generally used with rubber | gum is mentioned. Of these crosslinking agents, organic peroxides are particularly preferred.

Specific examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tart-butyl peroxide, 2,5-dimethyl-2,5-di- (tart-butylperoxy) hexane, 2, 5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tart-butylperoxyisopropyl) benzene, 1,1-bis (tart-butylperoxy) -3,3, 5-trimethylcyclohexane, n-butyl-4,4-bis (tar-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tart-butylperoxybenzoate, tart-butylperbenzoate , Tart-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tart-butylcumyl peroxide, etc. It is.

  Among these, 2,5-dimethyl-2,5-di- (tart-butylperoxy) hexane, 2,5-dimethyl-2,5-di- in terms of reactivity, odor and scorch stability Bifunctional organic peroxides such as (tart-butylperoxy) hexyne-3,1,3-bis (tart-butylperoxyisopropyl) benzene are particularly preferred. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane is most preferred.

  Such an organic peroxide is used in an amount of 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the whole object to be processed. When the amount of the organic peroxide is less than the above range, the resulting thermoplastic elastomer composition has a low degree of cross-linking, so that the heat resistance, tensile properties and rubber elasticity are not sufficient. Moreover, when there are more compounding quantities than the said range, the thermoplastic elastomer composition obtained may have a too high bridge | crosslinking degree, and may cause a moldability fall.

  In the present invention, in the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenyl Peroxy crosslinking aids such as guanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol Polyfunctional methacrylate monomers such as propane trimethacrylate and 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 the crystalline polyolefin resin (a) and the ethylene copolymer rubber (b), which are the main components of the cross-linked product, and an organic peroxide. Therefore, a thermoplastic elastomer composition having a uniform crosslinking effect by heat treatment and a balance between fluidity and physical properties can be obtained.

  The amount of the compound such as the above-mentioned crosslinking aid or polyfunctional vinyl monomer is usually 5 parts by weight or less, preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the whole object to be treated. Used in

  In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, Decomposition accelerators such as naphthenates such as manganese, magnesium, lead, and mercury may be used.

  The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature of the heat treatment ranges from the melting point of the crystalline polyolefin resin (a) to 300 ° C, and is usually 150 to 290 ° C, preferably 170 ° C to 270 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the applied shear force is in the range of 10 to 10,000 sac-1, preferably 100 to 50,000 sac-1 in terms of shear rate.

  As the kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a uniaxial or biaxial extruder can be used, and a non-open type apparatus is preferable, and among these, a biaxial extruder is particularly preferable.

  The olefinic thermoplastic elastomer (A) of the present invention is desirably statically heat-treated in hot air after the dynamic heat treatment as described above. The heat treatment is preferably performed at 80 to 130 ° C. for about 1 to 10 hours. By this heat treatment, residues of the crosslinking agent and the like can be removed, the odor of the obtained product can be reduced, or a product with good fogging properties can be obtained.

Olefin resin (B)
As the olefin resin (B) used in the present invention, the olefin resin (a) which is a raw material of the olefin thermoplastic elastomer can be used. In addition, the above-described inorganic filler, various additives, and stabilizers may be added as long as the characteristics are not impaired.

Foaming agent (C)
Examples of the foaming agent (C) to be blended in the raw material of the base material layer in the present invention include organic or inorganic pyrolytic foaming agents; water; hydrocarbon solvents, halogenated hydrocarbon solvents, etc .; nitrogen, carbon dioxide, propane And gases such as butane. As the foaming agent (C), an organic or inorganic pyrolytic foaming agent, water, carbon dioxide and the like are preferable.

  Specific examples of the inorganic pyrolytic foaming agent include sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite. Specific examples of the organic pyrolytic foaming agent include nitroso compounds such as N, N′-dimethyl-N, N′-dinitrosoterephthalamide and N, N′-dinitrosopentamethylenetetramine (DPT); Azo compounds such as azodicarbonamide (ADCA), azobisisobutyronitrile (AZBN), azobiscyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide (BSH), toluenesulfonyl hydrazide (TSH) ), P, p′-oxybis (benzenesulfonylhydrazide) (OBSH), sulfonylhydrazide compounds such as diphenylsulfone-3,3′-disulfonylhydrazide; calcium azide, 4,4′-diphenyldisulfonylazide, p-toluene Sulfonyl azide etc. Such as azide compounds, and the like.

  A foaming agent (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type. The foaming agent (C) is desirably used in a proportion of usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the olefinic thermoplastic elastomer (A).

The olefinic foamable composition (X ₁₎ used in the present invention, if necessary, can be blended foaming aid. Examples of foaming aids include compounds containing metals such as zinc, calcium, lead, iron, barium; organic acids such as citric acid, salicylic acid, phthalic acid, stearic acid, and oxalic acid; urea or derivatives thereof. The foaming assistant is usually used in a proportion of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the olefinic thermoplastic elastomer (A). The foaming assistant functions to lower the decomposition temperature of the foaming agent, accelerate the decomposition, and make the bubbles uniform.

The olefin-based foamable composition (X ₁ ) has a large amount of adsorption of inorganic porous powder that adsorbs inorganic gas, such as zeolite or inorganic gas, for the purpose of uniformly foaming at a high magnification, if necessary. A resin such as a polycarbonate resin or a nucleating agent for foaming can also be blended.

Furthermore, for the olefin-based foamable composition (X ₁ ), if necessary, fillers, heat stabilizers, anti-aging agents, weathering stabilizers, antistatic agents, wetting agents, metal soaps, waxes and other lubricants, pigments , Known additives such as dyes, flame retardants and anti-blocking agents can be blended within a range that does not impair the object of the present invention.

As the filler to be blended in the olefin-based foamable composition (X ₁ ), fillers usually used for rubber are suitable. Specifically, calcium carbonate, calcium silicate, clay, kaolin, talc, silica Diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, molybdenum disulfide, glass fiber, glass sphere, shirasu balloon, graphite, alumina and the like. These fillers are usually used in an amount of usually 40 parts by weight or less, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the olefinic thermoplastic elastomer (A).

Preparation of olefinic foamable composition (X ₁ ) The olefinic foamable composition (X ₁ ) comprises an olefinic thermoplastic elastomer (A) and / or an olefinic resin (B) and a foaming agent (C), as well as necessary. It can be prepared by blending a blending agent such as a foaming aid or a wetting agent blended according to the above. As a blending method, an olefin-based thermoplastic elastomer (A) and / or an olefin-based resin (B) and a foaming agent (C) are blended, and if necessary, blends such as foaming aids and wetting agents are blended with olefins. And a thermoplastic thermoplastic elastomer (A)) and / or an olefin resin (B) and a foaming agent (C). The olefin resin (B) and the foaming agent (C) may be mixed simultaneously or separately. When mixing separately, an olefin resin (B) can be mix | blended with an olefin type thermoplastic elastomer (A), and a foaming agent (C) can be mixed after that, and the order of this mixing may be reversed. .

  As a specific method of blending the olefinic thermoplastic elastomer (A) and / or the olefinic resin (B) and the foaming agent (C), for example, pellets of the olefinic thermoplastic elastomer (A) and / or olefinic resin. (B) and foaming agent (C) are once kneaded with a tumbler-type brabender, V-type brabender, ribbon blender, Henschel mixer, etc., and if necessary, an open-type mixing roll, non-release-type Banbury mixer, extrusion Examples of the method include kneading with a machine, a kneader, a continuous mixer, and the like. The weather resistance stabilizer, heat resistance stabilizer, anti-aging agent, pigment, dye and the like may be blended at any stage of the above process.

Base layer used in the present invention are the olefinic foamable composition foams _{(X 1) (X 2)} , can be obtained by heating for example olefinic foamable composition (X _1).

Olefin-based thermoplastic elastomer composition (D)
The olefinic thermoplastic elastomer composition (D) according to the present invention comprises a syndiotactic α-olefin copolymer (c), another thermoplastic resin (d), and an ethylene copolymer as required. It consists of rubber (e).

<Syndiotactic α-olefin copolymer (c)>
First, the syndiotactic α-olefin copolymer (c) will be described.

The syndiotactic α-olefin copolymer (c) according to the present invention is ¹³ C-NMR measured with a 1,2,4-trichlorobenzene solution, and the absorption of methyl groups of propylene units is based on tetramethylsilane. The total absorption intensity observed at about 20.0-21.0 ppm is 0.5 or more of the absorption intensity of about 19.0-22.0 ppm attributed to propylene methyl, preferably 0.6 or more, Preferably, it is 0.7 or more.

This syndiotactic structure is measured as follows. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And ¹³ C-NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 10,000 times or more. When the syndiotactic α-olefin copolymer (c) is in such a range, the syndiotactic property is excellent and the transparency, flexibility, and wear resistance tend to be excellent.

  The syndiotactic α-olefin copolymer (c) according to the present invention is derived from an α-olefin having 1 to 30 mol% of ethylene component units, 30 to 79 mol% of propylene component units, and 4 to 20 carbon atoms. The component unit is 10 to 50 mol% (here, the total component unit amount in the copolymer (c) is 100 mol%, and the ethylene component unit and the component unit derived from an α-olefin having 4 to 20 carbon atoms) The total amount is 21 to 70 mol%), preferably 3 to 25 mol% of ethylene component units, 35 to 75 mol% of propylene component units, and 20 to 20 component units derived from α-olefins having 4 to 20 carbon atoms. 45 mol% (here, the total amount of the component units in the copolymer (c) is 100 mol%, and the total amount of ethylene component units and component units derived from α-olefins having 4 to 20 carbon atoms is 25 to 65) Is particularly preferred) 3 to 25 mol% of ethylene component units, 35 to 65 mol% of propylene component units, and 20 to 45 mol% of component units derived from α-olefins having 4 to 20 carbon atoms (wherein the copolymer (c) The total amount of the component units therein is 100 mol%, and the total amount of the ethylene component units and the component units derived from the α-olefin having 4 to 20 carbon atoms is 35 to 65 mol%), more preferably the ethylene component units. 5 to 25 mol%, propylene component unit is contained in 40 to 65 mol%, and component unit derived from α-olefin having 4 to 20 carbon atoms is contained (herein in the copolymer (I)) The total amount of the ethylene component unit and the component unit derived from an α-olefin having 4 to 20 carbon atoms is 35 to 60 mol%, with the total component unit amount being 100 mol%).

  Further, it is derived from at least one polyene selected from conjugated polyenes and non-conjugated polyenes with respect to 100 mol% of the total amount of ethylene component units, propylene component units, and component units derived from α-olefin having 4 to 20 carbon atoms. The repeating unit may be contained in an amount of 0 to 30 mol%, preferably 0 to 25 mol%.

  The syndiotactic α-olefin copolymer (c) containing an ethylene component, a propylene component, and a component derived from an α-olefin having 4 to 20 carbon atoms in such an amount has good compatibility with the thermoplastic resin. Thus, the resulting syndiotactic α-olefin copolymer tends to exhibit sufficient transparency, flexibility, rubber elasticity, and wear resistance.

  The α-olefin used in preparing the syndiotactic α-olefin copolymer (c) is not particularly limited as long as it has a carbon number of 4 to 20, preferably 4 to 12. These may be linear or branched.

  Specific examples of such α-olefins include 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptane, 1-octene, 1-nonene, 1-decene, 1-decene, Undecene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4, Examples include 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, and the like. 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1- Pentene is preferred, 1-butene, 1-hexene, 1-octene and 1-decene are preferred, and 1-butene is particularly preferred. These α-olefins can be used alone or in combination of two or more. For example, one α-olefin (i) selected from α-olefins having 4 to 20 carbon atoms and α-olefins selected from the α-olefins having 4 to 20 carbon atoms and different from the above (B) can be used in an amount ratio of (b) / (b) = (50 to 99 mol%) / (1 to 50 mol%) ((b) + (b) = 100 mol%). .

  The repeating unit derived from at least one polyene selected from a conjugated polyene and a non-conjugated polyene used in preparing the syndiotactic α-olefin copolymer (c) includes the following conjugated polyene and non-conjugated It is a repeating unit derived from at least one polyene selected from polyenes.

  Specific examples of the conjugated polyene include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene, 1- Phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene, Conjugated dienes such as 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-phenyl-1,3-butadiene; 1,3,5- Examples thereof include conjugated trienes such as hexatriene. Of these, butadiene, isoprene, pentadiene, hexadiene, and octadiene are preferable, and butadiene and isoprene are particularly preferable in terms of excellent copolymerizability.

Specific examples of non-conjugated polyenes include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4- Ethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5- Ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5- Methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7- Methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene , 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5- Nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7- Nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5- Decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6- Decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7- Decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 9-me Non-conjugated dienes such as Le 1,8 undecadiene;
6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl- 1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1,6- Octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4- Ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene- Non-conjugated trienes such as 1,7-nonadiene and 4-ethylidene-1,7-undecadiene It is below.

  Such non-conjugated polyene is preferable in that it has excellent wear resistance when crosslinked.

  Among these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene (DCPD), 4,8-dimethyl-1,4,8-decatriene (DMDT), 4-ethylidene-8- Methyl-1,7-nonadiene (EMND) is preferred. (C-3) Two or more types of units may be contained.

  In the syndiotactic α-olefin copolymer (c), a component unit derived from an aromatic vinyl compound such as styrene, a component unit derived from the polyene unsaturated compound (polyene) having two or more double bonds. , Component units composed of alcohol, carboxylic acid, amine, and derivatives thereof may be included.

  The syndiotactic α-olefin copolymer (c) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g. It is desirable to be. When the intrinsic viscosity [η] of the syndiotactic α-olefin copolymer (c) is within the above range, the properties such as weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, dynamic fatigue resistance, etc. It is a syndiotactic α-olefin copolymer excellent in.

  This syndiotactic α-olefin copolymer (c) has a single glass transition temperature, and the glass transition temperature Tg measured by a differential scanning calorimeter (DSC) is usually −5 ° C. or less, preferably Is preferably in the range of −10 ° C. or lower, particularly preferably −15 ° C. or lower. When the glass transition temperature Tg of the syndiotactic α-olefin copolymer (c) is within the above range, the cold resistance and the low temperature characteristics are excellent.

The molecular weight distribution measured by GPC (Mw / Mn, polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) is 4.0 or less, preferably 1.5 to 3.0. Within this range, transparency, scratch resistance, and impact resistance are improved, which is preferable.
Moreover, it is desirable that there is no melting peak measured by a differential scanning calorimeter (DSC). In this case, it is excellent in flexibility, scratch resistance, transparency, and whitening resistance.

[Production of Syndiotactic α-Olefin Copolymer (c)]
Such a syndiotactic α-olefin copolymer (c) can be obtained by copolymerizing propylene, ethylene and α-olefin in the presence of a metallocene catalyst shown below.

As such a metallocene catalyst,
(X) a transition metal compound represented by the following general formula (1);
(Y) (y-1) a compound that reacts with the transition metal M in the transition metal compound (c) to form an ionic complex,
(Y-2) an organoaluminum oxy compound,
(Y-3) at least one catalyst system comprising at least one compound selected from organoaluminum compounds.

[In the formula (1), M is Ti, Zr, Hf, Rn, Nd, Sm or Ru, and Cp ¹ and Cp ² are cyclopentadienyl group, indenyl group, fluorenyl group π-bonded to M, Or a derivative group thereof, X ¹ and X ² are anionic ligands or neutral Lewis base ligands, and Z is a C, O, B, S, Ge, Si or Sn atom, or these A group containing an atom. ]

Among the transition metal compounds represented by the general formula (1), a transition metal compound in which Cp ¹ and Cp ² are different groups can be mentioned, and more preferably any one group of Cp ¹ and Cp ² Transition metal compounds in which is a cyclopentadienyl group or a derivative group thereof and the other group is a fluorenyl group or a derivative group thereof. Among these, it is preferable that either one of Cp ¹ and Cp ^{2 is} a cyclopentadienyl group or a derivative group thereof, and the other group is a fluorenyl group or a derivative group thereof.

  In the present invention, as the catalyst for producing the syndiotactic α-olefin copolymer (c), a metallocene catalyst as described above is preferably used. A known titanium catalyst comprising a solid titanium catalyst component and an organoaluminum compound, or a vanadium catalyst comprising a soluble vanadium compound and an organoaluminum compound can also be used.

  In the present invention, ethylene, propylene and α-olefin are usually copolymerized in the liquid phase in the presence of the metallocene catalyst as described above. At this time, a hydrocarbon solvent is generally used, but propylene may be used as a solvent. Copolymerization can be carried out by either a batch method or a continuous method.

  When a metallocene catalyst is used and copolymerization is carried out by a batch method, the transition metal compound (x) in the polymerization system is usually 0.00005 to 1 mmol, preferably 0.0001 to 1 liter per polymerization volume. The amount used is 0.5 mmol.

  The ionized ionic compound (y-1) is a molar ratio of the ionized ionic compound to the transition metal compound (x) ((y-1) / (x)), and is 0.5 to 20, preferably 1 to 10. Is used in such an amount.

  The organoaluminum oxy compound (y-2) has a molar ratio (Al / M) of aluminum atoms (Al) to transition metal atoms (M) in the transition metal compound (x) of 1 to 10000, preferably 10 to 5000. Is used in such an amount that The organoaluminum compound (y-3) is usually used in an amount of about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

The copolymerization reaction is usually carried out at a temperature in the range of −20 to 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C., and a pressure exceeding 0 to 80 kg / cm ² , preferably exceeding 0. In the range of ˜50 kg / cm ² .

  The reaction time (average residence time when polymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1.5 hours. It is.

  Ethylene, propylene and α-olefin are respectively supplied to the polymerization system in such an amount that a syndiotactic α-olefin copolymer (c) having a specific composition as described above can be obtained. In the copolymerization, a molecular weight regulator such as hydrogen can be used. When ethylene, propylene, and α-olefin are copolymerized as described above, the syndiotactic α-olefin copolymer (c) is usually obtained as a polymerization liquid containing the same. This polymerization solution is treated by a conventional method to obtain a syndiotactic α-olefin copolymer (c).

<Other thermoplastic resin (d)>
As other thermoplastic resins other than the syndiotactic α-olefin copolymer (c) according to the present invention, the melting point is 50 ° C. or higher, preferably 80 ° C. or higher, or the glass transition point when no melting point exists. Any thermoplastic resin having a temperature of 40 ° C. or higher, preferably 80 ° C. or higher can be used without particular limitation.

  Examples of the thermoplastic resin according to the present invention include polyolefin, polyamide, polyester, polyacetal, soft vinyl chloride, polyamide elastomer, polyester elastomer, polyurethane elastomer, and other crystalline thermoplastic resins, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS). ), Amorphous thermoplastic resins such as polycarbonate and polyphenylene oxide are used.

  Among these, polyolefin is most preferable, and specific examples of suitable raw material olefins for polyolefin include ethylene, propylene, 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. These olefins may be used alone or in combination of two or more. Examples of such polyolefins include olefin homopolymers such as polyethylene, polypropylene, poly-1-butene, polymethylpentene, and polymethylbutene, and olefin copolymers such as propylene / ethylene random copolymer. Among them, polypropylene, poly-1-butene, polymethylpentene, propylene / ethylene random copolymer, and propylene / ethylene block copolymer are preferable, and the melt flow rate at 230 ° C. and a load of 2.16 kg is preferably 0.1. Most preferred is polypropylene which is ~ 200 g / 10 min.

    As the polypropylene, either isotactic polypropylene or syndiotactic polypropylene may be used.

  The thermoplastic resins as described above may be used alone or in combination of two or more. Furthermore, a thermoplastic resin other than the above may be used together with the above thermoplastic resin.

<Ethylene copolymer rubber (e)>
The ethylene copolymer rubber (e) used in the present invention is an amorphous random elastic copolymer rubber made of ethylene and an α-olefin having 3 to 20 carbon atoms, or ethylene and 3 to 3 carbon atoms. It is an amorphous random elastic copolymer rubber composed of 20 α-olefins and non-conjugated polyene.

  The ethylene / α-olefin molar ratio of such an ethylene copolymer (C) is usually from 40/60 to 85/15, and among these, those in the range of 60/40 to 83/17 are preferred.

  Specific examples of the non-conjugated polyene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, and vinyl norbornene. Of these, ethylene / propylene / non-conjugated diene copolymer rubber and ethylene / 1-butene / non-conjugated diene copolymer rubber are preferred, and ethylene / propylene / non-conjugated diene copolymer rubber, particularly ethylene / propylene. -Ethylidene norbornene copolymer rubber and ethylene / propylene / vinyl norbornene copolymer rubber are particularly preferable.

  The Mooney viscosity [ML1 + 4 (100 ° C.)] of the ethylene copolymer rubber (e) used in the present invention is preferably in the range of 50 to 300, preferably 100 to 200.

  Moreover, it is preferable that the iodine number of this ethylene-type copolymer rubber (e) is 3-30, and it is especially preferable that it exists in the range of 5-25.

  The ethylene copolymer rubber (e) used in the present invention may be a so-called oil-extended product containing a softening agent. As the softening agent that can be used for the oil-extended product, a softening agent that is usually used for rubber can be used.

Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly;
Synthetic oils such as low molecular weight ethylene / α-olefin random copolymers;
Coal tars such as coal tar and coal tar pitch;
Fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil;
Waxes such as tall oil, beeswax, carnauba wax, lanolin;
Fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate or metal salts thereof;
Synthetic polymer materials such as petroleum resin, coumarone indene resin, atactic polypropylene;
Ester plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate;
Other examples include microcrystalline wax, sub (factis), liquid polybutadiene, modified liquid polybutadiene, and liquid thiocol.
Among these softeners, paraffinic process oils or low-molecular-weight ethylene / α-olefin random copolymers are particularly preferred, and high-viscosity paraffinic process oils with a low content of low-molecular-weight components that tend to volatilize are particularly preferred. Particularly preferred. Here, the high-viscosity type means one having a kinematic viscosity at 40 ° C. in the range of 100 to 10,000 centistokes.

  In the present invention, the softening agent is used in a proportion of 150 parts by weight or less, preferably 2 to 100 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the ethylene copolymer rubber (e). .

  In the present invention, in addition to the ethylene copolymer rubber (e), a rubber other than the ethylene copolymer rubber (e) and the ethylene copolymer rubber (e), as long as the object of the present invention is not impaired. Can also be used in combination. Examples of the rubber other than the ethylene copolymer rubber (e) include propylene / ethylene copolymer rubber (propylene content of 60 mol% or more), propylene / α-olefin copolymer rubber, styrene / butadiene rubber, and the like. Examples thereof include hydrogenated products, styrene / isoprene rubber and hydrogenated products thereof, polybutadiene rubber, polyisoprene rubber, nitrile rubber, butyl rubber, polybutylene rubber, natural rubber, and silicone rubber.

<Other ingredients>
The olefinic thermoplastic elastomer composition (D) according to the present invention comprises a syndiotactic α-olefinic copolymer (c) and another thermoplastic resin (d), and an ethylene copolymer used as necessary. In addition to rubber (e), softeners and / or inorganic fillers can be blended.

  As described above, the softening agent may be oil extended to the ethylene copolymer rubber (e), or may be added later without oil extension. In the case where the ethylene copolymer rubber (e) is added later without being oil-extended, the same softening agent as described above can be used.

  When added later without oil-extended, the amount of the softening agent is combined with the oil-extended, syndiotactic α-olefin copolymer (c) and other thermoplastic resins (b), as required. The total amount of ethylene copolymer rubber (e) used accordingly is 100 parts by weight or less, preferably 3 to 80 parts by weight, more preferably 5 to 50 parts by weight. When the softener is used in the above proportion, the resulting composition has excellent fluidity during molding and does not degrade the mechanical properties of the molded article. In this invention, when the usage-amount of a softener exceeds 100 weight part, it exists in the tendency for the heat resistance of the composition obtained to fall.

  Specific examples of the inorganic filler used in the present invention include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, sulfuric acid. Examples include calcium, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, glass balloon, basic magnesium sulfate whisker, calcium titanate whisker, and aluminum borate whisker.

  In the present invention, the inorganic filler is the sum of the syndiotactic α-olefin copolymer (c) and the other thermoplastic resin (d), and the ethylene copolymer rubber (e) used as necessary. The amount is 100 parts by weight or less, preferably 2 to 30 parts by weight with respect to 100 parts by weight. In this invention, when the usage-amount of an inorganic filler exceeds 100 weight part, there exists a tendency for the rubber elasticity of a composition obtained and a moldability to fall.

  Further, the olefinic thermoplastic elastomer composition (D) according to the present invention contains conventionally known additives such as heat stabilizers, anti-aging agents, weathering stabilizers, antistatic agents, crystal nucleating agents, and lubricants. It can add in the range which does not impair the objective of invention. In particular, the lubricant has the effect of further improving the scratch resistance and wear resistance of the resulting olefinic thermoplastic elastomer composition (D). Examples of the lubricant include higher fatty acid amide, metal soap, wax, silicone oil, Examples thereof include fluorine-based polymers. In the olefinic thermoplastic elastomer composition (D) according to the present invention, higher fatty acid amides, silicone oils, and fluoropolymers are used. Higher fatty acid amides include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behemic acid amide; unsaturated fatty acid amides such as erucic acid amide, oleic acid amide, brassic acid amide, and elaidic acid amide. Bis-fatty acid amides such as methylene bis-stearic acid amide, methylene bis-oleic acid amide, ethylene bis-stearic acid amide, ethylene bis-oleic acid amide; and the like as dimethyl silicone oil, phenyl methyl silicone oil, alkyl silicone oil , Fluorosilicone oil, tetramethyltetraphenyltrisiloxane, modified silicone oil, and the like, specifically, include polytetrafluoroethylene, vinylidene fluoride copolymer, etc. , Erucic acid amide, oleic acid amide, ethylene bis-oleic acid amide, dimethyl silicone oil, phenyl methyl silicone oil, alkyl silicone oil, polytetrafluoroethylene, vinylidene fluoride copolymer, particularly preferably erucic acid amide, oleic acid amide Dimethyl silicone oil and vinylidene fluoride copolymer are used.

The olefinic thermoplastic elastomer composition (D) is
Syndiotactic α-olefin copolymer (c) and other thermoplastic resins (d), ethylene copolymer rubber (e) used as necessary, and a softener blended as necessary It is obtained by mixing the inorganic filler and / or additives and / or additives and then dynamically molding the composition obtained by dynamic heat treatment into a desired shape. Here, “dynamically heat-treating” means kneading in a molten state.

  Here, all the components may be dynamically heat-treated at once, syndiotactic α-olefin copolymer (c) and other thermoplastic resin (d), ethylene used as necessary Syndiotactic after dynamically heat-treating in advance two or more of the copolymer rubbers (e) and softeners and / or inorganic fillers and / or additives blended as necessary It mix | blends with 1 or more types among the alpha-olefin copolymer (c) and other thermoplastic resin (b), and the ethylene-type copolymer rubber (e) used as needed, as needed. A softening agent and / or an inorganic filler and / or an additive may be added and dynamically heat-treated again.

  When the dynamic heat treatment is performed in the presence of a crosslinking agent, the ethylene copolymer rubber (e) can be crosslinked. By cross-linking the ethylene copolymer rubber (e), the heat resistance and rubber elasticity of the molding according to the present invention are improved. In addition, the syndiotactic α-olefin copolymer (c) can be crosslinked by performing dynamic heat treatment in the presence of a crosslinking agent. By crosslinking the syndiotactic α-olefin copolymer (c), the heat resistance and rubber elasticity of the molding according to the present invention are improved. In particular, since the syndiotactic α-olefin copolymer (c) contains the (c-4) unit, the crosslinking efficiency is increased, which contributes to improvement in heat resistance and rubber elasticity.

  The crosslinking agent used here is an organic peroxide, phenol resin, sulfur, hydrosilicone compound, amino resin, quinone or its derivative, amine compound, azo compound, epoxy compound, isocyanate, etc., thermosetting type The crosslinking agent generally used with rubber | gum is mentioned. Of these crosslinking agents, organic peroxides are particularly preferred.

Specific examples of the organic peroxide used in the present invention 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-butylperoxybenzoate, tert-butylperbenzoate Tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, and the like.

  Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- in terms of reactivity, odor, and scorch stability Bifunctional organic peroxides such as (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene are particularly preferred. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane is most preferred.

  Such an organic peroxide is used in an amount of 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the whole object to be processed.

  In the present invention, in the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenyl Peroxy crosslinking aids such as guanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol Polyfunctional methacrylate monomers such as propane trimethacrylate and 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 and syndiotactic α-olefin copolymer (c), which is the main component of the cross-linked product, other thermoplastic resin (d), ethylene copolymer rubber (e) It has a good compatibility with the organic peroxide, solubilizes the organic peroxide, and acts as a dispersant for the organic peroxide, so the crosslinking effect by heat treatment is uniform and the balance between fluidity and physical properties A good composition is obtained.

  The amount of the compound such as the above-mentioned crosslinking aid or polyfunctional vinyl monomer is usually 5 parts by weight or less, preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the whole object to be treated. Used in

  In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, Decomposition accelerators such as naphthenates such as manganese, magnesium, lead, and mercury may be used.

  The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature of heat processing is the range of 300 degreeC from melting | fusing point of another thermoplastic resin (B), and is 150-290 degreeC normally, Preferably it is 170 to 270 degreeC. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. The applied shearing force is in the range of 10 to 10,000 sec-1, preferably 100 to 50,000 sec-1, in terms of shear rate.

  As a kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a uniaxial or biaxial extruder can be used, and a non-open type apparatus is preferable.

  Furthermore, it is desirable that the heat treatment be performed statically in hot air after the dynamic heat treatment as described above. The heat treatment is preferably performed at 80 to 130 ° C. for about 1 to 10 hours. By this heat treatment, residues of the crosslinking agent and the like can be removed, the odor of the obtained product can be reduced, or a product with good fogging properties can be obtained.

Laminate Specific examples of the olefinic thermoplastic elastomer foam laminate according to the present invention include the following.
i) A sheet-like foamed laminate formed by laminating a surface layer made of an olefinic thermoplastic elastomer composition (D) on a base material layer made of an olefinic foam (X ₂ ).

<Preferred embodiment>
Molding method: Calender molding or extrusion foam molding from T-die Lamination method: Sequential method in which surface layer is laminated on base material layer after foam molding of sheet consisting of base material layer, or simultaneous in case of T die extrusion molding Multi-layer foam extrusion is possible Thickness of olefin-based foam (X ₂ ): 0.1 to 3 mm
Thickness of the olefinic thermoplastic elastomer composition (D): 0.01 to 1.0 mm
Application examples: Automotive interior skin materials (instrument panels, doors, ceiling skin materials), furniture sheets, wallpaper When used for automotive interior skin materials, they can be further laminated with olefinic or urethane foam materials. The surface may be embossed.
ii) a substrate layer comprising an olefin-based foam (X ₂₎ by extrusion foam molding of a multilayer, the olefinic thermoplastic elastomer composition (D) laminating a surface layer made of a multilayer extrusion foamed molded article.

<Preferred embodiment>
Molding method: Multilayer extrusion foam molding Lamination method: Simultaneous multilayer extrusion foam molding of base material layer and surface layer Thickness of base material layer made of olefinic foam (X ₂ ): 0.2 to 5 mm
Thickness of the olefinic thermoplastic elastomer composition (D): 0.01 to 1 mm
Application examples: Automotive exterior parts (various molding parts, seal parts), gasket members, and civil engineering construction members
iii) Laminated injection foam molded article in which a surface layer made of an olefinic thermoplastic elastomer composition (D) is laminated on a base material layer made of an olefinic foam (X ₂ ) by sequential injection foam molding or simultaneous injection foam molding. .

<Preferred embodiment>
Molding method: Sequential or simultaneous injection foam molding Laminating method: After injection foaming the olefinic foam (X ₂ ) as the base material, the surface layer olefinic thermoplastic elastomer composition (D) is injected, and the mold Thickness of simultaneous olefin-based foam (X ₂ ) in which a base material layer and a surface layer are simultaneously injected by successive injection foam molding or so-called sandwich molding to foam a laminated component: 0.3 to 5 mm
Thickness of the olefinic thermoplastic elastomer composition (D): 0.5 to 3 mm
Application examples: Automotive interior parts (handles, pillars, instrument panels, door trims, wheel house covers, console box covers, various levers, grips), household electrical appliance housings, sports equipment, daily necessities, miscellaneous goods
iv) Laminate extrusion in which a surface layer made of an olefinic thermoplastic elastomer composition (D) is laminated on a base material layer made of a thermoplastic elastomer composition (A) or an olefinic resin (B) by multilayer extrusion foaming blow molding. Molded body.

<Preferred embodiment>
Molding method: Multi-layer foam blow molding Lamination method: Thickness of olefin-based foam (X ₂ ) to be foam blow molded by laminating and extruding a base material layer and a surface layer from a die: 0.1 to 5 mm
Thickness of the olefinic thermoplastic elastomer composition (D): 0.1 to 2 mm
Application examples: automotive exterior parts (side molding, bumper fascia, spoiler, etc.), household electrical appliance housings, sporting goods, miscellaneous products Olefin-based foam (X ₂ ) and olefin-based thermoplastic elastomer composition ( D) can be bonded and laminated by heat fusion without using an adhesive.
v) A multilayer extruded hollow foam molded article obtained by laminating a surface layer made of an olefinic thermoplastic elastomer composition (D) on a hollow base material layer made of an olefinic foam (X ₂ ) by multilayer extrusion hollow molding.

<Preferred embodiment>
Molding method: Multilayer extrusion hollow foam molding Lamination method: Simultaneous multilayer extrusion hollow foam molding of base material layer and surface layer Thickness of hollow base material layer made of olefinic foam (X ₂ ): 0.2 to 5 mm
Thickness of the olefinic thermoplastic elastomer composition (D): 0.01 to 1 mm
Application examples: automotive exterior parts (weather strip parts, seal parts), and civil engineering components

[Example]
(Polymerization Example 1: Synthesis of syndiotactic propylene / butene / ethylene copolymer)
A 2000 ml polymerization apparatus sufficiently purged with nitrogen was charged with 100 ml of dry hexane, 480 g of 1-butene and triisobutylaluminum (1.0 mmol) at room temperature, and then the temperature of the polymerization apparatus was raised to 35 ° C. with propylene. Pressurized to 0.54 MPc and then pressurized to 0.62 MPc with ethylene. Thereafter, a toluene solution in which 0.005 mmol of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and 1.5 mmol of methylaluminoxane (produced by Tosoh Finechem) in contact with aluminum was added to the inside of the polymerization vessel. Polymerization was performed for 5 minutes while maintaining a temperature of 35 ° C. and an ethylene pressure of 0.62 MPc, and 20 ml of methanol was added to terminate the polymerization. After depressurization, a polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 36.1 g. The composition of the polymer was such that the propylene content was 61.3 mol%, the ethylene content was 10.3 mol%, the 1-butene content was 28.4 mol%, the intrinsic viscosity [η] was 2.67 dl / g, The transition temperature Tg was −27.7 ° C., there was no melting peak, and the molecular weight distribution by GPC was 2.0. In ¹³ C-NMR measured with 1,2,4-trichlorobenzene solution, the total absorption intensity at which the absorption of the methyl group of the propylene unit is observed at about 20.0 to 21.0 ppm based on tetramethylsilane is propylene. It was 0.8 with an absorption intensity of about 19.0 to 22.0 ppm attributed to methyl.

80 parts by weight of syndiotactic propylene / butene / ethylene copolymer obtained in Polymerization Example 1 and isotactic polypropylene (homopolymer, MFR (230 ° C., 2.16 kg load, hereinafter the same)) 0.5 (g / 10 minutes)) 20 parts by weight and 1 part by weight of carbon black masterbatch (for coloring in black) were kneaded with a twin-screw extruder set at 230 ° C. to obtain a composition (D-1). Further, a mineral oil softener is added to 100 parts by weight of an ethylene / propylene / 5-ethylidene-2-norbornene copolymer having an ethylene content of 78 mol%, an iodine value of 13 and a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 140. (Idemitsu Kosan Dyna Process Oil PW-380: trade name) 60 parts by weight of oil-extended EPDM pellets blended with 40 parts by weight, ethylene content 8% by weight, melt flow rate (ASTMD-1238-65T, 230 ° C., 2. 16 kg load) 10 g / 10 min propylene / ethylene block copolymer pellets 25 parts by weight, ethylene content 97 wt%, melt flow rate (ASTM D-1238-65T, 190 ° C., 2.16 kg load) 10 g / 10 min 15 parts by weight of ethylene 4-methyl-1-butene copolymer pellets, 1,3-bis tert-butylperoxyisopropyl) benzene 0.2 parts by weight and divinylbenzene 0.2 parts by weight are mixed with a tumbler blender, and the liquid mixture is uniformly attached to the surface of the mixed pellets. Extrusion was performed at 230 ° C. using a shaft extruder (TEM-50 manufactured by Toshiba Machine Co., Ltd.), and a dynamic heat treatment was performed to obtain a composition (A-1). Next, the composition (A-1) and the chemical foaming agent azodicarbonamide (Binihol DW # 6) were used as the foaming agent (C-1) in a two-layer laminating extruder comprising two single-screw extruders and one laminating die. : Eiwa Chemical Co., Ltd.) Foam (X ₂ ) obtained by foaming an olefin-based foamable composition (X ₁ ) added with 2 parts by weight per 100 parts by weight of the composition (A-1), and a composition (D The laminated body which consists of -1) was obtained. The laminated extrusion-molded product was in the form of a belt, the width was 5 cm, the thickness of the foam (X ₂ ) was 1.5 mm, and the thickness of the composition D-1 was 0.5 mm.

Further, the end of the obtained side molding was covered with cotton canvas # 10 using a 2 mm-thick specimen using a Gakushin abrasion tester made by Toyo Seiki Co., Ltd. The sample was worn at 23 ° C., the number of reciprocations of 100 times, the reciprocation speed of 33 times / min, and the stroke of 100 mm, and the gloss change rate ΔGloss before and after that was determined as follows.
ΔGloss = (Gloss before wear−Gloss after wear) / Gloss before wear × 100
ΔGloss under the above conditions was 8%.

[Comparative Example 1]
In Example 1, instead of the syndiotactic propylene / butene / ethylene copolymer obtained in Polymerization Example 1, a propylene / butene / ethylene copolymer having an existing isotactic structure (measured in 135 ° C. decalin). Intrinsic viscosity [η] is 2.5 dl / g, propylene content is 62 mol%, ethylene content is 10 mol%, 1-butene content is 28 mol%, molecular weight distribution (Mw / Mn) measured by GPC is 2.2) In the same manner as in Example 1, laminated extrusion foam molding was performed, and the gloss change rate ΔGloss was determined by the Gakushin abrasion test. ΔGloss was 73%.

In Example 1, instead of the isotactic polypropylene (homopolymer, MFR 0.5 (g / 10 min)) used in obtaining the composition (D-1), isotactic polypropylene (homopolymer, MFR13 ( g / 10 min)) to obtain a thermoplastic elastomer composition (D-2). From the thermoplastic elastomer composition (D-2) and the propylene homopolymer (B-1, MFR25 (g / 10 min)), the propylene homopolymer (B-1) and the foaming agent (C- 1) foam (X ₂ ) obtained by foaming an olefin-based foamable composition (X ₁ ) added with 2 parts by weight per 100 parts by weight of the composition (A-1), (base material, thickness 3 mm), heat Sequential injection foam molding was performed in the order of the plastic elastomer composition (D-2) (skin material thickness 1.5 mm) to obtain a laminated injection foam molded square plate (12 cm × 20 cm). Next, a Gakushin abrasion test was performed in the same manner as in Example 1 except that the thickness of the test piece was 4.5 mm, and the gloss change rate ΔGloss was obtained. ΔGloss was 9%.

[Comparative Example 2]
In Example 2, instead of the syndiotactic propylene / butene / ethylene copolymer obtained in Polymerization Example 1, a propylene / butene / ethylene copolymer having an existing isotactic structure (measured in decalin at 135 ° C.) Intrinsic viscosity [η] is 2.5 dl / g, propylene content is 62 mol%, ethylene content is 10 mol%, 1-butene content is 28 mol%, molecular weight distribution (Mw / Mn) measured by GPC is 2.2) In the same manner as in Example 2, sequential injection foaming was performed, and the gloss change rate ΔGloss was determined by the Gakushin abrasion test. ΔGloss was 78%.

Olefin-based foamable composition (X ₁ ) obtained by adding 2 parts by weight per 100 parts by weight of composition (A-1) and foaming agent (C-1) obtained in Example 1 A foam sheet having a thickness of 1.0 mm was formed by calender foam molding, and a 0.2 mm thick sheet of the composition (D-1) was laminated in the same manner as in Example 1 by thermal lamination while forming the sheet with a calendar molding machine. Then, a laminated foamed sheet molded body was obtained.

  The Gakushin abrasion test was conducted in the same manner as in Example 1 except that the thickness of the test piece was 0.7 mm, and the gloss change rate ΔGloss was determined. ΔGloss was 5%.

[Comparative Example 3]
In Example 3, instead of the syndiotactic propylene / butene / ethylene copolymer obtained in Polymerization Example 1, a propylene / butene / ethylene copolymer having an existing isotactic structure (measured in 135 ° C. decalin). Intrinsic viscosity [η] is 2.5 dl / g, propylene content is 62 mol%, ethylene content is 10 mol%, 1-butene content is 28 mol%, molecular weight distribution (Mw / Mn) measured by GPC is 2.2) After obtaining the laminated sheet molded body in the same manner as in Example 3, the gloss change rate ΔGloss was determined by the Gakushin abrasion test. ΔGloss was 73%.

  25 parts by weight of isotactic polypropylene (homopolymer, MFR (230 ° C., 2.16 kg load, the same applies hereinafter) 5 (g / 10 min)), ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber oil 75 parts by weight of pellets (extended amount 40 parts (oil: mineral oil-based paraffin oil), Mooney viscosity ML1 + 4 (100 ° C.) 70, ethylene content 79 mol%, iodine value 11), A mixture of 0.2 parts by weight of 5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 0.3 parts by weight of divinylbenzene as a crosslinking aid is sufficiently stirred and mixed with a Henschel mixer and set to 160 ° C to 220 ° C. The resulting mixture was fed to a twin-screw extruder and subjected to dynamic crosslinking to produce a pellet of composition (I).

For 100 parts by weight of the pellet of composition (I),
35 parts by weight of propylene / butene / ethylene copolymer obtained in Polymerization Example 1 and isotactic polypropylene (homopolymer, MFR (230 ° C., 2.16 kg load, the same applies hereinafter) 0.5 (g / 10 min) 10 parts by weight and 1 part by weight of carbon black masterbatch (for coloring in black) were kneaded by a twin screw extruder set at 230 ° C. to obtain pellets of the composition (D-3). Olefin-based foamable composition (X ₁ ) obtained by adding 2 parts by weight of composition (A-1) obtained in Example 1 and foaming agent (C-1) to 100 parts by weight of composition (A-1). The foamed laminate comprising the foam (X ₂ ) and the composition (D-3) was obtained using a two-layer laminate extruder comprising two single-screw extruders and one laminate die. The laminated extrusion molded product was belt-shaped, the width was 5 cm, the thickness of the foam (X ₂ ) was 1.5 mm, and the thickness of the composition D-3 was 0.5 mm. A Gakushin abrasion test was performed in the same manner as in Example 1 to determine the gloss change rate ΔGloss. ΔGloss was 13%.

[Comparative Example 4]
In Example 4, instead of the syndiotactic propylene / butene / ethylene copolymer obtained in Polymerization Example 1, a propylene / butene / ethylene copolymer having an existing isotactic structure (measured in decalin at 135 ° C.). Intrinsic viscosity [η] is 2.5 dl / g, propylene content is 62 mol%, ethylene content is 10 mol%, 1-butene content is 28 mol%, molecular weight distribution (Mw / Mn) measured by GPC is 2.2) After obtaining a laminated laminate in the same manner as in Example 4, the gloss change rate ΔGloss was determined by the Gakushin abrasion test. ΔGloss was 78%.

In Example 1, instead of the composition (A-1), 30% by weight of a linear low density polyethylene (density: 0.920 g / cm ³ , MFR: 2.1 g / 10 min) and ethylene / propylene / diethylene Cyclopentadiene copolymer rubber (ethylene content; 77 mol%, Mooney viscosity ML _{1 + 4} (100 ° C.); 145, iodine value; 12) 70 wt% was mixed with a Henschel mixer, L / D = 30, screw diameter Using a 50 mm twin screw extruder, the composition (A-2) that was dynamically heat-treated and extruded at 220 ° C. was subjected to laminate extrusion foam molding in the same manner as in Example 1, and gloss was determined by Gakushin abrasion test. The change rate ΔGloss was determined. ΔGloss was 9%.

[Comparative Example 5]
In Example 5, instead of the syndiotactic propylene / butene / ethylene copolymer obtained in Polymerization Example 1, a propylene / butene / ethylene copolymer having an existing isotactic structure (measured in decalin at 135 ° C.) Intrinsic viscosity [η] is 2.5 dl / g, propylene content is 62 mol%, ethylene content is 10 mol%, 1-butene content is 28 mol%, molecular weight distribution (Mw / Mn) measured by GPC is 2.2) The laminate extrusion foaming was carried out in the same manner as in Example 5, and the gloss change rate ΔGloss was determined by the Gakushin abrasion test. ΔGloss was 75%.

  According to the present invention, by laminating a conventional olefinic foam with an olefinic thermoplastic elastomer excellent in wear resistance and scratch resistance, foaming is excellent in moldability, part workability, and scratch resistance. A shaped body can be proposed.

Claims (6)

An olefinic foamable composition (X) comprising an olefinic thermoplastic elastomer composition (A) having an olefinic resin (a) and an ethylene copolymer rubber (b) as essential components, and a foaming agent (C). ₁ ) a base material layer made of the foam (X ₂ );
Laminated on the base material layer, a syndiotactic α-olefin copolymer (c) and a polypropylene having a melt flow rate at 230 ° C. and a load of 2.16 kg within a range of 0.1 to 200 g / 10 min ( and a surface layer made of an olefinic thermoplastic elastomer composition (D) that does not contain a foaming agent (C), and an olefinic thermoplastic elastomer foam laminate.
(The syndiotactic α-olefin copolymer (c)
1,2,4-trichlorobenzene solution ¹³ C-NMR measured in the sum of the absorption intensity absorption of methyl group of the propylene units are observed referenced to tetramethylsilane 2 0.0～21.0Ppm is It is 0.5 or more in absorption intensity of 1 9.0～22.0Ppm that will be assigned to propylene methyl,
(C-1) a repeating unit derived from propylene;
(C-2) a repeating unit derived from ethylene;
(C-3) a repeating unit derived from at least one olefin selected from olefins having 4 to 20 carbon atoms, and, if necessary,
(C-4) consisting of repeating units derived from at least one polyene selected from conjugated polyenes and non-conjugated polyenes,
When the total amount of the unit (c-1), the unit (c-2) and the unit (c-3) is 100 mol%, the unit (c-1) is 30 to 79 mol%, and the unit (c- 2) 1-30 mol% of units and the above-mentioned (c-3) units in an amount of 10-50 mol% (however, the total amount of (c-2) units and (c-3) units is 21-70) Mol%),
Containing (c-4) unit in an amount of 0 to 30 mol% with respect to 100 mol% of the total amount of (c-1) unit, (c-2) unit and (c-3) unit, and substantially It is a syndiotactic structure. ) Before SL olefinic thermoplastic elastomer composition (D) further comprises the ethylene copolymer rubber (e), the olefin thermoplastic elastomer foamed laminate according to claim 1. The ethylene copolymer rubber (e) are cross-linked, olefinic thermoplastic elastomer foam laminate according to 請 Motomeko 2. The syndiotactic α-olefin copolymer (c) has no melting peak measured by a differential scanning calorimeter (DSC),
There intrinsic viscosity measured in a 135 ° C. decalin [eta] is in the range of 0.01 to 10 / g, the molecular weight distribution by GPC is 4 or less, and the glass transition temperature Tg of -5 ° C. or less, wherein Item 4. The olefinic thermoplastic elastomer foam laminate according to any one of Items 1 to 3 . The laminate is extrusion, injection molding, or blow molding is manufactured by blow molding, olefinic thermoplastic elastomer foam laminate according to any one of claims 1-4. Syndiotactic α- olefin copolymer (c) is cross-linked, olefinic thermoplastic elastomer foam laminate according to any one of claims 1-5.