JP2002019028A - Foamed polyolefin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamed polyolefin laminate which is made of a recyclable olefin polymer, has a high expansion ratio and a soft touch, and is excellent in appearance, abrasion resistance, durability, and sliding characteristics. SOLUTION: In the foamed polyolefin laminate, a base material layer of a foamed polyethylene thermoplastic elastomer composition containing a polyethylene thermoplastic elastomer comprising a polyethylene resin and an ethylene-α- olefin copolymer 90-250 in Mooney viscosity ML1+4 (100 deg.C) and 70-95 mol% in ethylene content and a blowing agent and a skin layer of an ultra-high molecular weight polyolefin resin 3.5-8.3 dl/g in intrinsic viscosity, or a skin layer of a polyolefin thermoplastic elastomer composition containing at least one selected from the group consisting of a polyolefin thermoplastic elastomer, organopolysiloxane, a fluoropolymer, an antistatic agent, and a polyolefin resin are laminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin foam laminate in which a foam of an ethylene thermoplastic elastomer is used as a base layer and an ultrahigh molecular weight polyolefin resin or an olefin thermoplastic elastomer composition is used as a skin layer.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an elastomer foam, a natural rubber or a synthetic rubber is kneaded with a vulcanizing agent and a foaming agent, and the kneaded product is molded into a predetermined shape and heated. A method is known in which heating and foaming are performed to obtain an elastomer (vulcanized rubber) foam. However, in the conventional method as described above, when the rubber is molded into a predetermined shape by continuous extrusion, a step of kneading the compound into the rubber in batches in advance to obtain a kneaded product is performed before continuous extrusion. In order to easily supply the kneaded material to the extruder, it is necessary to perform a step of forming the kneaded material in a ribbon shape before continuous extrusion. As described above, the conventional methods as described above are disadvantageous in industrial production because the production steps are complicated and the vulcanization and foaming steps require considerable time.

[0003] As a method of solving such a problem,
For example, there is a method using a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a low density polyethylene, or a partially crosslinked thermoplastic elastomer composed of an olefin copolymer rubber and an olefin resin. According to this method, the above-described steps can be omitted.

However, conventionally used thermoplastic resins and thermoplastic elastomers are liable to be defoamed during foam molding, so that poor appearance is liable to occur, and the resulting foam has a low expansion ratio of at most 1.5. Since the foaming ratio is about twice, there is a problem that it is felt harder than rubber. In addition, even if a part that comes into contact with a person or an object or a part that repeatedly slides, such as a weather strip for an automobile or a sealing member for a door stop, is manufactured from a foam obtained by a conventional method, abrasion resistance and It has poor durability due to poor sliding characteristics, and is therefore difficult to use as a sliding member or the like.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the above-mentioned prior art, and it is made of a recyclable olefin polymer, and has a high foaming ratio and a flexible feel. An object of the present invention is to provide an olefin-based foam laminate having excellent appearance, abrasion resistance, durability, and sliding characteristics.

[0006]

The present invention is the following olefin foam laminate. (1) 5 to 60 parts by weight of a polyethylene resin (a-1) and an ethylene / α-olefin-based copolymer (a-2) 4
0 to 95 parts by weight [where the component (a-1) and the component (a-
2) The total amount of the components is 100 parts by weight. And a base layer made of a foam (X ₂ ) of an expandable ethylene thermoplastic elastomer composition (X ₁ ) containing a foaming agent (B) containing an ethylene thermoplastic elastomer (A) comprising: An olefin foam laminate in which a skin layer made of a high molecular weight polyolefin resin (Y) is laminated, wherein the ethylene / α-olefin copolymer (a-2) is composed of ethylene, α-olefin, and optionally The non-conjugated polyene copolymer used has Mooney viscosity ML
_{1 + 4} (100 ° C) 90-250, ethylene content 70
To 95 mol% of an ethylene / α-olefin copolymer, wherein the ultrahigh molecular weight polyolefin resin (Y) is
The intrinsic viscosity [η] measured in decalin at 35 ° C is 3.5 to 3.5.
An olefin-based foam laminate, which is an 8.3 dl / g ultra-high molecular weight polyolefin resin. (2) 5 to 60 parts by weight of polyethylene resin (a-1) and ethylene / α-olefin copolymer (a-2) 4
0 to 95 parts by weight [where the component (a-1) and the component (a-
2) The total amount of the components is 100 parts by weight. A base layer comprising a foam (X ₂ ) of an ethylene-based thermoplastic elastomer composition (X ₁ ) containing an ethylene-based thermoplastic elastomer (A) comprising a foaming agent and a foaming agent (B); An olefin foam laminate in which a skin layer made of the thermoplastic elastomer composition (Z ₁ ) is laminated, wherein the ethylene / α-olefin copolymer (a-
2) is a copolymer of ethylene, α-olefin and optionally used non-conjugated polyene, having an Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. An α-olefin-based copolymer, wherein the olefin-based thermoplastic elastomer composition (Z ₁ ) has an organopolysiloxane (D) content of 0.5 to 100 parts by weight based on 100 parts by weight of the olefin-based thermoplastic elastomer (C); 25 parts by weight, fluoropolymer (E)
0.5 to 10 parts by weight and antistatic agent (F) 0.5 to 1
An olefin-based foamed laminate, which is an olefin-based thermoplastic elastomer composition containing at least one selected from the group consisting of 0 parts by weight in the above ratio. (3) 5 to 60 parts by weight of polyethylene resin (a-1) and ethylene / α-olefin copolymer (a-2) 4
0 to 95 parts by weight [where the component (a-1) and the component (a-
2) The total amount of the components is 100 parts by weight. A base layer comprising a foam (X ₂ ) of an ethylene-based thermoplastic elastomer composition (X ₁ ) containing an ethylene-based thermoplastic elastomer (A) comprising a foaming agent and a foaming agent (B); An olefin foam laminate in which a skin layer made of a thermoplastic elastomer composition (Z ₂ ) is laminated, wherein the ethylene / α-olefin copolymer (a-
2) is a copolymer of ethylene, α-olefin and optionally used non-conjugated polyene, having an Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. An α-olefin-based copolymer, wherein the olefin-based thermoplastic elastomer composition (Z ₂ ) contains 5-200 parts by weight of the polyolefin resin (G) based on 100 parts by weight of the olefin-based thermoplastic elastomer (C); An olefin-based foamed laminate which is an olefin-based thermoplastic elastomer composition containing the olefin-based thermoplastic elastomer composition in an amount of 1 part by weight. (4) 5 to 60 parts by weight of polyethylene resin (a-1) and ethylene / α-olefin copolymer (a-2) 4
0 to 95 parts by weight [where the component (a-1) and the component (a-
2) The total amount of the components is 100 parts by weight. A base layer comprising a foam (X ₂ ) of an ethylene-based thermoplastic elastomer composition (X ₁ ) containing an ethylene-based thermoplastic elastomer (A) comprising a foaming agent and a foaming agent (B); An olefin foam laminate in which a skin layer made of a thermoplastic elastomer composition (Z ₃ ) is laminated, wherein the ethylene / α-olefin copolymer (a-
2) is a copolymer of ethylene, α-olefin and optionally used non-conjugated polyene, having an Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. An α-olefin-based copolymer, wherein the olefin-based thermoplastic elastomer composition (Z ₃ ) has an organopolysiloxane (D) content of 0.5 to 100 parts by weight based on 100 parts by weight of the olefin-based thermoplastic elastomer (C); 25 parts by weight, fluoropolymer (E)
0.5 to 10 parts by weight and antistatic agent (F) 0.5 to 1
At least one selected from the group consisting of 0 parts by weight is contained in the above ratio, and the polyolefin resin (G) is further contained in an amount of 5 to 2
An olefin foam laminate, which is an olefin thermoplastic elastomer composition containing 00 parts by weight. (5) The olefin-based thermoplastic elastomer (C)
Crystalline polyolefin resin (c-1) and rubber (c-2)
The olefin-based foamed laminate according to any one of the above (2) to (4), which is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing: (6) The olefin foam laminate according to the above (3) or (4), wherein the polyolefin resin (G) is an ultrahigh molecular weight polyolefin resin (Y). (7) When the ultrahigh molecular weight polyolefin resin (Y) is 13
Intrinsic viscosity [η] measured in 5 ° C decalin is 10 to 40
dl / g ultrahigh molecular weight polyolefin resin (y-1) 1
5 to 40 parts by weight and 85 to 60 parts by weight of a polyolefin resin (y-2) having an intrinsic viscosity [η] of 0.1 to 5 dl / g measured in decalin at 135 ° C. [where the component (y-1) And the total amount of the components (y-2) is 100 parts by weight. ] The olefin-based foamed laminate according to the above (1), (3), (4) or (6), which is an ultrahigh molecular weight polyolefin resin composition containing: (8) The ethylene-based thermoplastic elastomer (A) is a polypropylene resin (a-3) based on a total of 100 parts by weight of the polyethylene resin (a-1) and the ethylene / α-olefin-based copolymer (a-2). ), Wherein the olefin-based foamed laminate according to any one of the above (1) to (7), contains 30 parts by weight or less. (9) The olefin foam laminate according to any one of the above (1) to (8), wherein the foaming agent (B) is an organic or inorganic pyrolytic foaming agent. (10) The content of the foaming agent (B) is 0.5 to 2 with respect to 100 parts by weight of the ethylene-based thermoplastic elastomer (A).
The olefin foam laminate according to any one of the above (1) to (9), which is 0 parts by weight. (11) The olefin foam laminate according to any one of the above (1) to (10), wherein the foam (X ₂ ) has an expansion ratio of 2 times or more. (12) The ethylene-based thermoplastic elastomer (A)
A mixture of a polyethylene resin (a-1) and an ethylene / α-olefin-based copolymer (a-2) or, if necessary, a mixture containing a polypropylene resin (a-3) in the absence of a crosslinking agent. The olefin foam laminate according to any one of the above (1) to (11), which is a thermoplastic elastomer obtained by dynamic heat treatment. (13) Olefin-based thermoplastic elastomer (C)
Is a crystalline polyolefin resin (c-1) and a rubber (c-
The olefin-based foamed laminate according to any one of the above (2) to (4), which is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing (2) in the presence of a crosslinking agent.

Ethylene-based thermoplastic elastomer (A) The ethylene-based thermoplastic elastomer (A) used as a raw material of the base layer in the present invention is a polyethylene resin (a-1) 5
To 60 parts by weight, preferably 10 to 50 parts by weight, and ethylene / α-olefin-based copolymer (a-2) 40 to 95
Parts by weight, preferably 50 to 90 parts by weight [where (a-
The total amount of the component (1) and the component (a-2) is 100 parts by weight. ]. The ethylene-based thermoplastic elastomer (A) may contain a polypropylene resin (a-3) as necessary, in addition to the component (a-1) and the component (a-2).

The ethylene-based thermoplastic elastomer (A) used in the present invention is a mixture containing the polyethylene resin (a-1) and the ethylene / α-olefin-based copolymer (a-2) in the above ratio, Accordingly, as described below, the mixture containing the polypropylene resin (a-3) is preferably an olefin-based thermoplastic elastomer obtained by dynamically heat-treating the mixture in the absence of a crosslinking agent. Polyethylene resin (a-1) and ethylene / α-olefin copolymer (a
-2), the rubber elasticity is excellent.

The polyethylene resin (a-
As 1), known polyethylene resins such as high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, and low-density polyethylene can be used without limitation, but linear low-density polyethylene is preferable, and a metallocene catalyst is particularly preferable. A linear low-density polyethylene polymerized by using is preferred.

The polyethylene resin (a-1) has a melt flow rate (MFR; ASTM D1238, 190 ° C.)
2.16 kg load) is 0.01 to 100 g / 10 min, preferably 0.01 to 50 g / 10 min. The ultrahigh molecular weight polyethylene having an MFR of less than 0.1 g / 10 min usually has an intrinsic viscosity [η] of 7 to 40 at 135 ° C. measured in decalin (decahydronaphthalene).
dl / g, and when such an ultrahigh molecular weight polyethylene is used as the polyethylene resin (a-1), 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 0.1 to
5 dl / g low to high molecular weight polyethylene 15
It is preferably used in the form of an ultra-high molecular weight polyethylene resin composition comprising -40% by weight and 85-60% by weight of ultra-high molecular weight polyethylene having an intrinsic viscosity [η] of 7-40 dl / g. The intrinsic viscosity [η] of the entire polyethylene resin composition is preferably from 3.5 to 8.3 dl / g.

The polyethylene resin (a-1) has a density of 0.3.
880-0.980 g / cm ³ , preferably 0.900
It is desirably 0.950 g / cm ³ . When a linear low-density polyethylene is used as the polyethylene resin (a-1), the MFR (ASTM D1238, 19)
0 ° C., 2.16 kg load) 0.1 to 30 g / 10 min.
Preferably 0.2 to 20 g / 10 min, density 0.880
０．９0.950 g / cm ³ , preferably 0.910-0.
It is desirable to use 940 g / cm ³ linear low density polyethylene.

When the linear low-density polyethylene is used as the polyethylene resin (a-1), the substrate layer is less likely to be rough and has less stickiness on the surface than when high-density polyethylene or medium-density polyethylene is used. Can be obtained.

The polyethylene resin (a-1) may be a homopolymer of ethylene or a copolymer of ethylene and a small amount, for example, 10 mol% or less, of another monomer. Examples of other monomers include α-olefins having 3 to 20, preferably 3 to 8 carbon atoms; vinyl monomers such as vinyl acetate and ethyl acrylate.
As the α-olefin used as another monomer, for example, propylene, 1-butene, 4-methyl-1-
Examples include pentene, 1-hexene and 1-octene. Other monomers can be used alone or in combination of two or more. The polyethylene resin (a-1) can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer (a-2) used in the present invention has a Mooney viscosity of ML _{1 + 4} (10
0 ° C.) is from 90 to 250, preferably from 100 to 200, more preferably from 110 to 180, and the ethylene content is from 70 to 250.
95 mol%, preferably 75 to 90 mol%, more preferably 75 to 85 mol% of ethylene / α-olefin copolymer. Here, the ethylene content refers to an ethylene content with respect to all α-olefins (including ethylene).

An ethylene / α-olefin copolymer (a
-2) is ethylene and having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms.
And a copolymer other than the α-olefin may be copolymerized. Examples of the monomer other than the α-olefin include a non-conjugated polyene. In addition, ethylene
The α-olefin-based copolymer (a-2) may be a random copolymer or a block copolymer.

The ethylene / α-olefin copolymer (a
Specific examples of -2) include an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated polyene copolymer. Among them, ethylene / α-olefin / non-conjugated polyene copolymer is preferred. In the ethylene / α-olefin copolymer (a-2), examples of the α-olefin to be copolymerized with ethylene include propylene, 1-butene, 1-pentene,
-Methyl-1-pentene, 1-hexene and 1-octene. The α-olefin can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer (a
In -2), the non-conjugated polyene copolymerized with ethylene and α-olefin includes, for example, non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene. . Non-conjugated polyenes can be used alone or in combination of two or more. The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer is usually 0.1.
It is 1-50, preferably 5-30. Ethylene ・ α-
The olefin-based copolymer (a-2) can be used alone or in combination of two or more.

As the polypropylene resin (a-3), a known polypropylene resin can be used without limitation.
Specific examples include the following polypropylene resins. 1) Propylene homopolymer 2) Random copolymer of propylene of 90 mol% or more and less than 10 mol% of other α-olefin (propylene
α-olefin random copolymer) 3) Block copolymer of propylene of 70 mol% or more and less than 30 mol% of other α-olefin (propylene
α-olefin block copolymer) Specific examples of the other α-olefin to be copolymerized with propylene include ethylene, 1-butene, and 4-methyl-
Examples thereof include α-olefins having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, such as 1-pentene, 1-hexene, and 1-octene.

As the polypropylene resin (a-3),
The propylene homopolymer (1) and the propylene / α-olefin random copolymer (2) are preferred.
(kg load) is preferably 0.1 to 50 g / 10 min. The polypropylene resin (a-3) can be used alone or in combination of two or more.

The content of the polypropylene resin (a-3) in the ethylene thermoplastic elastomer (A) used in the present invention depends on the polyethylene resin (a-1) and the ethylene / α-olefin copolymer (a- 30 parts by weight or less, preferably 2 to 3 parts by weight, based on 100 parts by weight in total of 2)
It is preferably 0 parts by weight, more preferably 5 to 20 parts by weight. When the content of the polypropylene resin (a-3) is in the above range, skin roughness is less likely to occur and the appearance is excellent,
In addition, a substrate layer with less stickiness can be obtained.

The ethylene thermoplastic elastomer (A) used in the present invention is excellent in rubber elasticity without cross-linking (vulcanization) using a cross-linking agent or a cross-linking aid. Further, the ethylene-based thermoplastic elastomer (A) used in the present invention is not a thermosetting elastic material such as a conventional vulcanized rubber but a thermoplastic elastomer, so that it can be easily recycled. In addition, since a cross-linking agent or the like is not required, a kneading step of the cross-linking agent or the like is not required, and the dynamic heat treatment can be easily and efficiently obtained in a single step, so that the cost is low.

The ethylene-based thermoplastic elastomer (A) used in the present invention may contain, if necessary, known softeners, heat-resistant stabilizers, anti-aging agents, and weather-resistant stabilizers as long as the object of the present invention is not impaired. And additives such as an antistatic agent, a filler, a coloring agent, and a lubricant. As the softener to be blended in the ethylene thermoplastic elastomer (A), a mineral oil softener is preferably used. As such a mineral oil-based softener, a paraffin-based, naphthene-based, aromatic-based softener and the like usually used for rubber are suitable.

Ethylene thermoplastic elastomer (A)
The ethylene thermoplastic elastomer (A) used in the present invention is preferably the above-mentioned polyethylene resin (a-1), ethylene / α-olefin copolymer (a-2) in the absence of a crosslinking agent. , And, if necessary, a resin and an additive to be blended at the above-mentioned specific ratio, and dynamically heat-treated.

The above-mentioned "dynamically heat-treating" means that the polyethylene resin (a-1), the ethylene / α-olefin copolymer (a-2), and the resin and additives to be blended if necessary are melted. Kneading in (melting) state. This dynamic heat treatment can be performed using a kneading device such as a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single screw extruder, and a twin screw extruder. Is preferred. The dynamic heat treatment is preferably performed in a closed kneading apparatus. Further, it is preferable to carry out in an inert gas such as nitrogen.

The conditions for the dynamic heat treatment are as follows: the kneading temperature is usually 150 to 280 ° C., preferably 170 to 240 ° C.
It is desirable that the kneading time is usually 1 to 20 minutes, preferably 1 to 5 minutes. The shearing force applied at the time of kneading is usually 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 sec at a shear rate.
It is desirable to set to 10 ⁴ sec ⁻¹ .

When the dynamic heat treatment is carried out using a twin screw extruder, the heat treatment may be carried out under the conditions satisfying the following formula (1), preferably (1 ′), more preferably (1 ″). preferable.

4.8 <[(T−130) / 100] +2.2 logP + logQ−logR <7.0 ... (1) 5.0 <[(T−130) / 100] + 2.2logP + logQ−logR <6.8… ( 1 ') 5.3 <[(T-130) / 100] + 2.2 logP + logQ-logR <6.5 ... (1'') (In the formulas (1), (1') and (1 ''), T is 2 Resin temperature at the die exit of the screw extruder (° C), P is the diameter of the screw of the twin screw extruder (mm), Q is the maximum shear rate received in the twin screw extruder (sec ^-1 ), R is the twin screw extruder The maximum shear rate Q (sec ^-1 )
Is obtained from the equation of Q = (P × π × S) / U. Here, P is the screw diameter (mm) of the twin-screw extruder, S is the screw rotation speed per second (rps), and U is the clearance (gap) between the barrel inner wall and the kneading segment (kneading segment) of the screw. Is the distance (mm) of the narrowest part. )

The ethylene thermoplastic elastomer (A) obtained by dynamically heat-treating using a twin-screw extruder in the absence of a crosslinking agent under the conditions satisfying the above formula (1) has a tensile strength,
Excellent in permanent elongation, compression set and molded appearance. In the method for producing the ethylene-based thermoplastic elastomer (A) used in the present invention, a cross-linking agent such as an organic peroxide or a vulcanization aid such as a divinyl compound used in the production of a conventional vulcanized rubber is used. The polyethylene resin (a-1)
And ethylene / α-olefin-based copolymer (a-
2) Alternatively, the polyethylene resin (a-1), the ethylene / α-olefin-based copolymer (a-2), and the resin and additives to be blended if necessary are mixed at the specific ratio and dynamically treated. Thereby, the ethylene-based thermoplastic elastomer (A) having excellent rubber elasticity can be easily and efficiently produced in one step. Further, since there is no need to use a crosslinking agent or a vulcanization aid, and a complicated vulcanization step is not required, it is possible to produce at low cost.

Blowing agent (B) In the present invention, the blowing agent (B) to be added to the raw material of the base material layer is an organic or inorganic pyrolytic blowing agent; water; a hydrocarbon type, a halogenated hydrocarbon type or the like. Solvents such as nitrogen, carbon dioxide, propane, butane and the like. As the foaming agent (B), an organic or inorganic pyrolytic foaming agent,
Water, carbon dioxide and the like are preferred.

Specific examples of the inorganic pyrolytic foaming agent include sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrite and the like. 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), azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide (BS)
H), toluenesulfonyl hydrazide (TSH), p,
p'-oxybis (benzenesulfonyl hydrazide)
(OBSH), sulfonyl hydrazide compounds such as diphenylsulfone-3,3'-disulfonyl hydrazide; and azide compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide and p-toluenesulfonyl azide.

The foaming agent (B) can be used alone or in combination of two or more. The foaming agent (B) is preferably used in a proportion of usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the ethylene-based thermoplastic elastomer (A).

The foaming ethylene-based thermoplastic elastomer composition (X ₁ ) may optionally contain a foaming aid. As foaming aids, zinc, calcium,
Compounds containing metals such as lead, iron and barium; organic acids such as citric acid, salicylic acid, phthalic acid, stearic acid and oxalic acid; urea or its derivatives are used. The foaming aid is usually 0.1 to 20 parts by weight, preferably 1 to 1 part by weight, per 100 parts by weight of the ethylene-based thermoplastic elastomer (A).
It is desirable to use 0 parts by weight. The foaming aid has functions such as lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and homogenizing the bubbles.

The foamable ethylene-based thermoplastic elastomer composition (X ₁ ) may contain, if necessary, an inorganic porous powder that adsorbs an inorganic gas, such as zeolite, for the purpose of uniformly foaming at a high magnification. A resin having a large amount of adsorption of an inorganic gas, for example, a polycarbonate resin, or a nucleating agent for foaming may be added.

The foamable ethylene-based thermoplastic elastomer composition (X ₁ ) may further contain a filler, a heat stabilizer, an antioxidant, a weather stabilizer, an antistatic agent, a wetting agent, a metal soap, if necessary. Known additives such as a lubricant such as wax, a pigment, a dye, a flame retardant, an antiblocking agent and the like can be blended within a range not to impair the object of the present invention.

As the filler to be added to the ethylene-based thermoplastic elastomer composition (X ₁ ), fillers usually used for rubber are suitable, and specific examples thereof include calcium carbonate, calcium silicate, clay, and 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.
It is desirable to use these fillers in an amount of usually 40 parts by weight or less, preferably 1 to 30 parts by weight, based on 100 parts by weight of the ethylene-based thermoplastic elastomer (A).

Preparation of foamable ethylene-based thermoplastic elastomer composition (X ₁ ) The foamable ethylene-based thermoplastic elastomer composition (X ₁ ) comprises an ethylene-based thermoplastic elastomer (A) and a foaming agent (B); In addition, it can be prepared by blending a blending agent such as a foaming assistant and a wetting agent blended as required.

As a method of blending the ethylene-based thermoplastic elastomer (A) and the foaming agent (B), for example, pellets of the ethylene-based thermoplastic elastomer (A) and the foaming agent (B) are once mixed with a tumbler type Brabender, a V-type. After kneading with a Brabender, ribbon blender, Henschel mixer or the like, if necessary, kneading with an open-type mixing roll, a non-open-type Banbury mixer, an extruder, a kneader, a continuous mixer, or the like can be given. Weather stabilizers, heat stabilizers, anti-aging agents, pigments, dyes, etc.
You may mix | blend at any stage of the said process.

The base layer of the present invention is the foamable ethylenic thermoplastic elastomer composition (X ₁₎ is a foam (X _2), for example, foamable ethylenic thermoplastic elastomer composition (X ₁₎ Can be obtained by heating.

In the present invention, the following 1) is used as a raw material for the skin layer.
At least one selected from the olefinic raw materials of (4) to (4).
Seeds can be used. 1) The ultrahigh molecular weight polyolefin resin (Y) which is an ultrahigh molecular weight polyolefin resin having an intrinsic viscosity [η] of 3.5 to 8.3 dl / g measured in decalin at 135 ° C. 2) An olefin-based thermoplastic elastomer (C) ) 100
0.5 parts by weight of organopolysiloxane (D)
Olefinic thermoplastic containing at least one selected from the group consisting of 0.5 to 25 parts by weight, a fluoropolymer (E) 0.5 to 10 parts by weight, and an antistatic agent (F) 0.5 to 10 parts by weight. Elastomer composition (Z ₁ ) 3) Olefinic thermoplastic elastomer (C) 100
5 to 20 parts by weight of the polyolefin resin (G)
Olefin-based thermoplastic elastomer composition (Z ₂ ) containing 0 parts by weight 4) Olefin-based thermoplastic elastomer (C) 100
0.5 parts by weight of organopolysiloxane (D)
-25 weight parts, 0.5-10 weight parts of a fluoropolymer (E) and 0.5-10 weight parts of an antistatic agent (F) in the above ratio, and a polyolefin resin. (G) in an amount of 5 to 200 parts by weight of an olefinic thermoplastic elastomer composition (Z
₃ )

Ultrahigh molecular weight polyolefin resin (Y) The ultrahigh molecular weight polyolefin resin (Y) used as a raw material of the skin layer in the present invention has an intrinsic viscosity [η] of 3.5 to 8.0 measured at 135 ° C in decalin. Ultra high molecular weight polyolefin resin in the range of 3 dl / g, preferably 3.8-8.0 dl / g. The ultrahigh molecular weight polyolefin resin (Y) may be a single resin or a composition containing two or more resins. In the case of a resin composition,
Those having an intrinsic viscosity [η] of the entire resin composition within the above range can be used.

When the ultrahigh molecular weight polyolefin resin (Y) is a resin composition, an ultrahigh molecular weight polyolefin resin (y-1) having an intrinsic viscosity [η] of 10 to 40 dl / g measured at 135 ° C. in decalin; An ultrahigh molecular weight polyolefin resin composition containing a polyolefin resin (y-2) having an intrinsic viscosity [η] of 0.1 to 5 dl / g measured in decalin at 135 ° C. is preferable, and more preferably an ultrahigh molecular weight polyolefin resin ( y-1) 15 to 40 parts by weight, polyolefin resin (y-2) 60 to 85 parts by weight, particularly preferably ultrahigh molecular weight polyolefin resin (y-1) 18 to 3
This is an ultrahigh molecular weight polyolefin resin composition containing 5 parts by weight and 65 to 82 parts by weight of a polyolefin resin (y-2) (the total of both is 100 parts by weight).

The ultrahigh molecular weight polyolefin resin (y
-1) and the polyolefin resin (y-2) include:
For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3-methyl-1-
Examples thereof include α-olefin homopolymers and copolymers such as pentene. As the ultrahigh molecular weight polyolefin resin (y-1) and the polyolefin resin (y-2), an ethylene homopolymer and a copolymer containing ethylene and another α-olefin and containing ethylene as a main component are preferable.

The ultrahigh molecular weight polyolefin resin (Y) may contain a liquid or solid softener (lubricating oil). As the liquid softening agent to be mixed with the ultrahigh molecular weight polyolefin resin (Y), a mineral oil-based softening agent, a synthetic softening agent and the like are used. Specific examples of the mineral oil-based softener include petroleum-based lubricating oils such as paraffinic and naphthenic oils, liquid paraffin, spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, cylinder oil and the like. As the synthetic softener, specifically, synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil,
Examples include phosphate ester oils, polychlorotrifluoroethylene oils, fluoroester oils, chlorinated biphenyl oils, silicone oils and the like.

As the solid softening agent, specifically, graphite and molybdenum disulfide are mainly used. In addition, boron nitride, tungsten disulfide, lead oxide, glass powder,
Metal soap or the like can be used. The softeners can be used alone or in combination of two or more. Further, a liquid softener and a solid softener can be used in combination, and for example, can be blended in the form of a powder, a sol, a gel, a suspensoid or the like.

The content of the softener is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the ultrahigh molecular weight polyolefin resin (Y). The ultrahigh molecular weight polyolefin resin (Y) may optionally contain additives such as a heat stabilizer, an antistatic agent, a weather stabilizer, an antioxidant, a filler, a colorant, and a lubricant. Can be blended in a range that does not impair.

Olefin thermoplastic elastomer composition (Z ₁ ) to (Z ₃ ) Olefin thermoplastic elastomer (C) The olefin thermoplastic elastomer (C) used as a raw material of the skin layer in the present invention is a crystal. An olefin-based thermoplastic elastomer composed of a functional polyolefin resin (c-1) and a rubber (c-2) can be used.

The above-mentioned crystalline polyolefin resin (c-1)
Examples thereof include a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin resin (c-1) include the following (co) polymers. (1) Ethylene homopolymer (manufacturing method may be either low-pressure method or high-pressure method) (2) Co-polymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate or ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10 mol% or less of other α-olefin (5) Block copolymer of propylene and 30 mol% or less of other α-olefin (6) 1-butene homopolymer (7) Random copolymer of 1-butene and 10 mol% or less of other α-olefin (8) 4-methyl-1-pentene homopolymer (9) 4 Random copolymer of -methyl-1-pentene and 20 mol% or less of other α-olefins Specific examples of the α-olefins include ethylene, propylene, 1-butene, and 4-methyl. 1-pentene, 1-hexene, and 1-octene, and the like.

The crystalline polyolefin resin (c-1) is preferably a homopolymer of propylene or a copolymer of propylene containing propylene as a main component with other olefins, such as a propylene / ethylene copolymer or propylene. • 1-butene copolymer, propylene / 1-hexene copolymer, propylene / 4-methyl-1-pentene copolymer and the like. MFR (ASTM D1238, 230) of crystalline polyolefin resin (c-1)
° C, 2.16 kg load) is 0.01 to 100 g / 10
Min, preferably 0.1 to 50 g / 10 min.

The rubber (c-2) used in the present invention is not particularly limited, but an olefin copolymer rubber is preferred. The olefin copolymer rubber used as the rubber (c-2) is an amorphous random elastic copolymer containing an α-olefin having 2 to 20 carbon atoms as a main component, and two or more α-olefins. Α-olefin / non-conjugated diene copolymer comprising two or more α-olefins and a non-conjugated diene.

Specific examples of the olefin copolymer rubber used as the rubber (c-2) include the following rubbers. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10 to 50 /
50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90
/ 10 to 50/50] (3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/10 to 5]
0/50] (4) Butene / α-olefin copolymer rubber [butene /
α-olefin (molar ratio) = about 90/10 to 50/5
0]

Specific examples of the α-olefin include the same α-olefins as the specific examples of the α-olefin constituting the above-mentioned crystalline polyolefin (c-2). As the non-conjugated diene, specifically,
Examples thereof include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene. The rubber (c-2) can be used alone or in combination of two or more.

Specific examples of the rubber (c-2) include ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated polyene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1- Butene / non-conjugated polyene copolymer rubber is preferred, especially ethylene / propylene /
Non-conjugated polyene copolymer rubber, particularly ethylene / propylene / ethylidene norbornene copolymer rubber, or ethylene / propylene / dicyclopentadiene copolymer rubber is particularly preferred. The Mooney viscosity ML _{1 + 4} (100 ° C.) of these copolymer rubbers is 10 to 250, preferably 4 to 250.
0 to 150 is desirable. When the non-conjugated diene is copolymerized, the iodine value is preferably 25 or less.

The rubber (c-2) used in the present invention includes
In addition to the above olefin copolymer rubber, other rubber,
For example, styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), butyl rubber (II
R) and other diene rubbers, SEBS, polyisobutylene and the like.

In the olefin-based thermoplastic elastomer (C) used in the present invention, the weight ratio of the crystalline polyolefin resin (c-1) to the rubber (c-2) (crystalline polyolefin resin / rubber) is usually 90. / 10 to 5/9
5, preferably 70/30 to 10/90. When the olefin copolymer rubber and another rubber are used in combination as the rubber (c-2),
The other rubber is desirably compounded in an amount of 40 parts by weight or less, preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of the crystalline polyolefin resin (c-1) and the rubber (c-2). .

Olefinic thermoplastic elastomer (C)
In addition, if necessary, additives such as a softening agent, a heat stabilizer, a weather stabilizer, an antioxidant, a filler, a coloring agent, and a lubricant can be blended within a range that does not impair the purpose of the present invention. . As the softener, a softener usually used for rubber can be used, but a mineral oil-based softener and a synthetic softener are preferable.

Olefinic thermoplastic elastomer (C)
Mineral oil-based softeners to be blended in include paraffinic, naphthenic, and aromatic petroleum-based lubricating oils, liquid paraffin, and the like, and synthetic softeners include polyethylene wax, polypropylene wax, petroleum asphalt, and petrolatum. can give. Further, as other softeners,
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; ricinoleic acid, palmitic acid Fatty acids such as stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid and erucic acid or metal salts thereof; synthetic polymers such as petroleum resin, coumarone indene resin and atactic polypropylene; dioctyl phthalate, dioctyl adipate; Ester plasticizers such as dioctyl sebacate; and other examples include microcrystalline wax, liquid polybutadiene or a modified or hydrogenated product thereof, and liquid thiochol.

These softeners are used in an amount of 5 to 200 parts by weight, preferably 15 to 150 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer (C). Is desirable. These softeners may be added when the olefin-based thermoplastic elastomer (C) is produced, or may be added in advance to the rubber (c-2) as an extender oil.

The olefin-based thermoplastic elastomer (C) used in the present invention is the above-mentioned polyolefin resin (c-1)
And a rubber (c-2) and, if necessary, a mixture of a softener and the like, which is dynamically heat-treated. The rubber (c-2) is not crosslinked, partially crosslinked or completely crosslinked in the olefin thermoplastic elastomer (C).
It can be present in all cross-linked states.

In order to produce the olefinic thermoplastic elastomer (C) thus crosslinked, a mixture of the polyolefin resin (c-1) and the rubber (c-2) and, if necessary, a softener and the like are used. Is dynamically heat-treated in the presence of a crosslinking agent. Crosslinking agents that can be used when heat-treating dynamically include organic peroxides,
Crosslinking agents generally used in thermosetting rubbers, such as sulfur, phenolic resins, amino resins, quinones and derivatives thereof, amine compounds, azo compounds, epoxy compounds, isocyanates and the like can be mentioned. Among these, organic peroxides are particularly preferred.

As the above-mentioned organic peroxide, specifically,
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-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.

Among them, 2,5-dimethyl-2,5-di- (tert-) is preferable in terms of odor and scorch stability.
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 is preferred, and in particular, 1,3-bis (t
(tert-butylperoxyisopropyl) benzene is most preferred. In the present invention, the organic peroxide is used in an amount of 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the total amount of the crystalline polyolefin and the rubber.

In the crosslinking treatment with the above organic peroxide,
Sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylene Peroxy crosslinking aids such as maleimide, or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, Polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using a compound as described above,
A uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, and the polyolefin resin (c-1) and the rubber (c-
2) It has good compatibility with (2) and has a function of solubilizing organic peroxides, and works as a dispersant for organic peroxides. A balanced olefin-based thermoplastic elastomer (C) is obtained.

The crosslinking aid or the polyfunctional vinyl monomer as described above is used in an amount of 0.1% based on the whole to-be-crosslinked product.
It is desirable to use it at a ratio of -3% by weight, preferably 0.3-2% by weight. When the blending ratio of the crosslinking aid or the polyfunctional vinyl monomer is in the above range, the obtained thermoplastic elastomer is processed because the crosslinking aid and the polyfunctional vinyl monomer do not remain as unreacted monomers in the elastomer. There is no change in physical properties due to heat history during molding, and the fluidity is excellent.

The term "dynamically heat-treating" means that the above-mentioned components are kneaded in a molten state. As the kneading device, a known kneading device, for example, an open-type mixing roll, a non-open-type Banbury mixer, an extruder, a kneader, a continuous mixer, or the like is used. Among these, a non-open type kneading apparatus is preferable, and kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The kneading temperature for the dynamic heat treatment is usually 1
50-280 ° C, preferably 170-240 ° C,
The kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. The applied shearing force is a shear rate of 100 sec ^-1 or more, preferably 500 to 10,000.
It is preferably set to sec ^-1 .

The olefinic thermoplastic elastomer (C) preferably used in the present invention has a gel content calculated by the following of at least 10% by weight, preferably at least 20% by weight, particularly preferably at least 45% by weight. desirable.

[Measurement method of gel content] A thermoplastic elastomer sample was weighed to about 100 mg and weighed 0.5 mm × 0.5 m
m × 0.5 mm, then cut the obtained strip into 30 ml of cyclohexane at 23 ° C. in a closed container.
For 48 hours. Next, the sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. The value obtained by subtracting the weight of the cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the dried residue is referred to as “corrected final weight (Y)”. On the other hand, the value obtained by subtracting the weight of the cyclohexane-soluble component other than the polymer component (for example, a softener) and the weight of the cyclohexane-insoluble component other than the polymer component (fibrous filler, filler, pigment, etc.) from the sample weight is referred to as “corrected”. Initial weight (X) ".

Here, the gel content (cyclohexane-insoluble matter) is determined by the following equation. Gel content [wt%] = [corrected final weight (Y)] ÷
[Corrected initial weight (X)] × 100

As the olefin-based thermoplastic elastomer (C) used in the skin layer of the present invention, the above-mentioned ethylene-based thermoplastic elastomer (A) can also be used. Since the olefin-based thermoplastic elastomer (C) constituting the skin layer of the olefin-based foamed laminate of the present invention comprises a crystalline polyolefin resin (c-1) and a rubber (c-2),
Excellent fluidity. The polyolefin-based thermoplastic elastomer (C) as described above can be molded using a conventionally used molding apparatus such as compression molding, transfer molding, injection molding, and extrusion molding.

Organopolysiloxane (D) As the organopolysiloxane (D) used as a raw material of the skin layer in the present invention, a known organopolysiloxane having a —Si—O— bond in the main chain can be used without limitation.
By blending the organopolysiloxane (D),
A skin layer having excellent slidability and wear resistance can be obtained.

As the organopolysiloxane (D),
Specifically, dimethylpolysiloxane, methylphenylpolysiloxane, fluoropolysiloxane, tetramethyltetraphenylpolysiloxane, methylhydrogenpolysiloxane, etc., epoxy-modified, alkyl-modified,
Modified polysiloxanes such as amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkyl-polyether-modified, and epoxy-polyether-modified are exemplified. Of these, dimethylpolysiloxane is preferred. The organopolysiloxane (D) can be used alone or in combination of two or more.

The organopolysiloxane (D) has a viscosity [JIS K 2283, 25 ° C.] of 10 to 10 ⁷ cSt.
Are preferred. Among these, the viscosity [JIS
K2283, 25 ° C.] is 10 ⁶ cSt or more, which has an extremely high viscosity, and may be a master batch with an olefin resin in order to enhance dispersibility in the olefin thermoplastic elastomer (C). . As the olefin resin used in this case, the crystalline polyolefin resin (c-1) used for producing the olefin thermoplastic elastomer (C), specifically, an ethylene homopolymer, ethylene and another α -Copolymers with olefins, propylene homopolymers, and copolymers of propylene with other α-olefins.

The organopolysiloxane (D) can be used alone or in combination of two or more depending on its viscosity. Particularly, when two or more kinds are used in combination, the viscosity is 10 to 10 ⁶ cSt.
Low viscosity organopolysiloxane (D) and 10 ⁶ to 10 ⁷
It is preferred to use a combination of a cSt high viscosity organopolysiloxane.

In the olefin-based thermoplastic elastomer composition (Z ₁ ), the content of the organopolysiloxane (D) is controlled by the olefin-based thermoplastic elastomer (C) 1
0.5 to 20 parts by weight, preferably 1 to 100 parts by weight
１８18 parts by weight. When the content of the organopolysiloxane (D) is in the above range, the foamed laminate has excellent slidability, and the organopolysiloxane (D) does not cause a problem such as a sticky surface.

Fluoropolymer (E) As the fluoropolymer (E) used in the present invention, a known fluoropolymer containing a fluorine atom can be used without any limitation. By blending the fluoropolymer (E),
A skin layer having excellent slidability and wear resistance can be obtained. Examples of the fluorine-based polymer (E) used in the present invention include polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluorovinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, and fluorinated polymer. Vinylidene polymer, vinyl fluoride polymer and the like. The fluoropolymer (E) can be used alone or in combination of two or more.

The fluorinated polymer (E) is used in advance to improve the dispersibility with the olefinic thermoplastic elastomer (C) or to further enhance the effect of improving the sliding abrasion resistance. May be a masterbatch with the inorganic filler.
The olefin-based resin used here may be the same as the olefin-based resin used in the master batch of the organopolysiloxane (E). Examples of the inorganic filler include calcium carbonate, titanium oxide, talc, clay and the like.

In the olefin-based thermoplastic elastomer composition (Z ₁ ), the content of the fluoropolymer (E) is preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the olefin-based thermoplastic elastomer (C). Is a ratio of 1 to 8 parts by weight. When the content of the fluoropolymer (E) is in the above range, the foamed laminate has excellent slidability.

Antistatic agent (F) As the antistatic agent (F) used in the present invention, known antistatic agents generally used for resins can be used without limitation, and anionic, cationic and non-ionic surfactants can be used. Examples include ionic activators and amphoteric activators. By blending the antistatic agent (F), a skin layer having excellent slidability and abrasion resistance can be obtained.

Specific examples of the antistatic agent (F) include lauryl diethanolamine, N, N-bis (2-
(Hydroxyethyl) stearylamine, stearyl monoglyceride, distearyl glyceride, tristearyl glyceride, polyoxyethylene laurylamine caprylic ester, stearyldiethanolamine monostearate and the like. Antistatic agent (F) is 1
The species can be used alone or in combination of two or more.

The antistatic agent (F) is used in advance to improve the dispersibility with the olefinic thermoplastic elastomer (C) or to further enhance the effect of improving the sliding abrasion, in order to improve the sliding abrasion resistance. It may be a masterbatch with an inorganic filler. Examples of the olefin resin and the inorganic filler used herein include the same as described above.

In the olefin-based thermoplastic elastomer composition (Z ₁ ), the content of the antistatic agent (F) is preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the olefin-based thermoplastic elastomer (C). Is a ratio of 1 to 8 parts by weight. When the content of the antistatic agent (F) is in the above range, the foamed laminate has excellent slidability, and disadvantages such as precipitation of the antistatic agent (F) on the surface and whitening (bleed out) occur. Absent.

The organopolysiloxane (D), the fluoropolymer (E) and the antistatic agent (F) can be used singly or in combination of two or more. Optional.

Polyolefin resin (G) As the polyolefin resin (G) used in the present invention, the crystalline polyolefin resin (c-1) used in the olefin-based thermoplastic elastomer (C) is preferable. Further, the polyolefin resin (G) used in the present invention may be the ultrahigh molecular weight polyolefin resin (Y).

In the olefin-based thermoplastic elastomer composition (Z ₂ ), the compounding amount of the polyolefin resin (G) is 5-200 parts by weight, preferably 10-200 parts by weight, per 100 parts by weight of the olefin-based thermoplastic elastomer (C). 18
0 parts by weight. When the olefin-based thermoplastic elastomer (C) and the polyolefin resin (G) are used in such a ratio, a skin layer having good moldability and molded appearance, and excellent in slidability and abrasion resistance can be obtained.

At least one selected from the group consisting of the organopolysiloxane (D), the fluoropolymer (E) and the antistatic agent (F) and the polyolefin resin (G) can be used in combination. . The content of such olefin-based thermoplastic elastomer composition in _{(Z 3) (D) ~} (G) is the same as defined above.

The olefin-based thermoplastic elastomer compositions (Z ₁ ) to (Z ₃ ) used as the raw material of the skin layer may contain, if necessary, a mineral oil-based softener, a heat stabilizer, a weather stabilizer, and an anti-aging agent. Additives such as fillers, colorants, and lubricants can be incorporated within a range that does not impair the purpose of the present invention.

The olefinic thermoplastic elastomer compositions (Z ₁ ) to (Z ₃ ) can be produced by a known method.
For example, olefin-based thermoplastic elastomer (C), organopolysiloxane (D), fluorine-based polymer (E)
And at least one selected from the group consisting of an antistatic agent (F), a polyolefin resin (G), and other additives added as necessary.

The olefin foam laminate of the present invention comprises a base layer comprising the foam (X ₂ ) of the ethylene thermoplastic elastomer composition (X ₁ ) and the ultrahigh molecular weight polyolefin resin (Y). or olefinic thermoplastic elastomer composition (Z ₁₎ ~ and a skin layer made of (Z ₃₎ is a laminate that is laminated. The skin layer may be laminated on the entire surface of the base material layer, may be laminated on only a part of the base material layer, or may be another layer. When the skin layer is laminated only on a part of the base material layer, the base material layer may be exposed on the surface where the skin layer is not laminated. The base layer and the skin layer may be laminated with an adhesive, but are preferably fused. The thickness of the laminate is not particularly limited, but the thickness of the base material layer is 0.1 to 50 mm, preferably 0.5 to 45 mm, and the thickness of the skin layer is 5 μm to 10 m.
m, preferably 10 μm to 8 mm.
Although the expansion ratio of the foam as a base material layer (X ₂₎ is not particularly limited, 1.1 to 15 times, preferably in the range 2 to 10 times. In the present invention, since the ethylene-based thermoplastic elastomer (A) sufficiently foams, a foam (X ₂ ) having a high foaming ratio of 2 times or more can be easily molded.

The olefin-based foam laminate of the present invention has a flexible feel because the base layer can have a high expansion ratio as described above, and further has appearance, abrasion resistance, durability, and sliding characteristics. Is excellent. In addition, the laminate of the present invention can be easily produced and is recyclable, so that it is economically excellent.

The foamed olefin-based laminate of the present invention comprises a foam (X ₂ ) of the above-mentioned ethylene-based thermoplastic elastomer composition (X ₁ ) as a base layer, and the above-mentioned ultrahigh molecular weight polyolefin resin (Y) or olefinic thermoplastic elastomer composition _{(Z 1) ~ (Z 3} ) is obtained by laminating a skin layer. The lamination method varies depending on the shape, size, required physical properties and the like of the final product, and is not particularly limited. Can be In this case, the ethylene-based thermoplastic elastomer composition (X ₁ )
Is foamed at the time of co-extrusion molding and heat fusion to form a foam (X
₂ ) to form a base material layer. Such a heat-sealing method does not require an adhesive, can easily obtain a foamed laminate in one simple step, and has strong interlayer adhesion between the base material layer and the skin layer.

The olefin foam laminate of the present invention can be suitably used for automobile parts such as automobile weather strips; building materials such as gaskets. As weather strips for automobiles, door weather strips,
Examples include a bonnet weather strip, a trunk room weather strip, a sunroof weather strip, a ventilator weather strip, and corner materials. Examples of building materials include building seal materials such as gaskets, airtight materials, joint materials, and door stop seal materials. In addition, golf club grip,
Leisure goods such as baseball bat grips, swimming fins, underwater glasses, hose protection materials, cushioning materials, and the like.

FIG. 1 shows an example of a cross-sectional structure of a weatherstrip for an automobile including the olefin-based foam laminate of the present invention. A weather strip 1 for an automobile shown in FIG. 1 has a thin plate-shaped core material 2 in a cross section and a sliding contact portion 3 provided on a surface of the core material 2 and curved so as to be in sliding contact with a window glass. It is composed of The sliding portion 3 is formed of the olefin foam laminate of the present invention in which the base material layer 4 and the skin layer 5 are laminated, and is provided so that the skin layer 5 is on the surface in sliding contact with the glass.

[0093]

The olefin foam laminate of the present invention has a high expansion ratio, a soft feel, and excellent appearance, abrasion resistance, durability and sliding properties. In addition, the laminate of the present invention can be easily produced, and since it is mainly composed of an olefin polymer, recycling is easy and economical.

[0094]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Production of Ethylene Thermoplastic Elastomer (A-1) Linear low density polyethylene (density: 0.920 g / cm)
³ , MFR; 2.1 g / 10 min, ethylene content;
0 mol%, 4-methyl-1-pentene content; 3.0 mol%) and 30 parts by weight of ethylene / propylene / dicyclopentadiene copolymer rubber (ethylene content: 77 mol%,
Mooney viscosity ML _{1 + 4} (100 ° C.); 145, iodine value; 12) 70 parts by weight were mixed with a Henschel mixer. Next, using a twin screw extruder with L / D = 30 and a screw diameter of 50 mm, the mixture is dynamically heat-treated at 220 ° C. in a nitrogen atmosphere and extruded to produce pellets of an ethylene-based thermoplastic elastomer (A-1). did.

(2) Ultra high molecular weight polyethylene composition (Y
-1) Intrinsic viscosity [η] of composition (Y-1) measured in 135 ° C decalin; 7.0 dl / g Intrinsic viscosity [η] measured in 135 ° C decalin 28 dl
/ G of ultra high molecular weight polyethylene resin (y-1) and 13
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.73 d
1 / g of a polyethylene resin (y-2) in a weight ratio of 23.
/ 77 ultra high molecular weight polyethylene composition.

(3) Production of laminate The ethylene-based thermoplastic elastomer (A-
1) 100 parts by weight and 3.0 parts by weight of a mixture (B-1) of 50 mol% of citric acid and 50 mol% of sodium hydrogen carbonate were mixed by a tumbler-type Brabender, and a foamable composition was blended. Next, the foamable composition is extruded at a die temperature of 150 ° C. to foam and mold the core material and the base layer, and at the same time, the ultrahigh molecular weight polyethylene composition (Y-1) of the above (2) is heated at a temperature of 230 ° C. The coextrusion molding is performed to form a skin layer, and the base layer and the skin layer are heat-sealed to form a skin layer as shown in FIG.
Was manufactured. The expansion ratio of the obtained weather strip was 4.8 times.

The obtained weatherstrip was mounted on a test window frame, and a window glass having a thickness of 3.2 mm was fitted thereto, and a durability test (upper and lower window glass test) was performed. As a result, the weatherstrip was free from wear and abrasion even after 50,000 repetitions of the up-and-down window glass test, and maintained its function as a weatherstrip.

Example 2 30 parts by weight of the linear low-density polyethylene used in Example 1, 70 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1, and a mineral oil softener (Paraffin oil, Idemitsu Kosan Co., Ltd., PW-
380, 40 parts by weight) to obtain an ethylene-based thermoplastic elastomer (A-2) in the same manner as in Example 1.

Next, using the obtained ethylene-based thermoplastic elastomer (A-2), a foamable composition was prepared in the same manner as in Example 1, and a weatherstrip was formed with the same skin layer as in Example 1. They were fabricated and subjected to a durability test. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip. In addition, the expansion ratio of the obtained weather strip was 3.7 times.

Example 3 15 parts by weight of the linear low-density polyethylene used in Example 1, 85 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1, and
Ethylene random copolymer (MFR; 0.5 g / 10
In addition, an ethylene-based thermoplastic elastomer (A-3) was obtained in the same manner as in Example 1 by using 20 parts by weight of (PP-1).

Next, a foaming composition was blended using the ethylene-based thermoplastic elastomer (A-3) in the same manner as in Example 1, and a weatherstrip was prepared with the same skin layer as in Example 1 to obtain a durability. The test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip.
The expansion ratio of the obtained weather strip was 3.0.
It was twice.

Example 4 15 parts by weight of the linear low-density polyethylene used in Example 1, 85 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1, and a propylene homopolymer ( MFR: 1.5 g / 10 min) (PP-2) 2
Using 0 parts by weight, an ethylene-based thermoplastic elastomer (A-4) was obtained in the same manner as in Example 1.

Next, a foaming composition was blended using the ethylene-based thermoplastic elastomer (A-4) in the same manner as in Example 1, and a weatherstrip was produced with the same skin layer as in Example 1 to obtain a durability. The test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip.
The expansion ratio of the obtained weather strip was 2.8.
It was twice.

Example 5 30 parts by weight of the linear low-density polyethylene used in Example 1 and the ethylene-propylene-dicyclopentadiene copolymer rubber used in Example 1 were extended oil (paraffin oil, Idemitsu Kosan Co., Ltd.). Using 110 parts by weight of an oil-extended ethylene-propylene-dicyclopentadiene copolymer rubber blended with 40 parts by weight of PW-380 (trade name, manufactured by Co., Ltd.) in the same manner as in Example 1, A plastic elastomer (A-5) was obtained.

Next, a foaming composition was compounded using the ethylene-based thermoplastic elastomer (A-5) in the same manner as in Example 1, and a weatherstrip was prepared with the same skin layer as in Example 1 to obtain a durability. The test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip.
The expansion ratio of the obtained weather strip was 3.8.
It was twice.

Example 6 (1) Production of olefinic thermoplastic elastomer (C-1) Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (ethylene content: 70 mol%, iodine value: 12, Mooney viscosity [ML _{1 + 4} (100 ° C)];
120) and 60 parts by weight of polypropylene ((MFR (A
STM-D-1238-65T, 230 ° C, 2.16k
g load); 13 g / 10 min, density; 0.91 g / c
m ³ ) was kneaded at 180 ° C. for 5 minutes in a nitrogen atmosphere using a Banbury mixer. Thereafter, the kneaded material was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets. Next, the square pellet, 0.2 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene, and 0.2 parts by weight of divinylbenzene were stirred and mixed by a Henschel mixer. Next, this mixture was mixed in a nitrogen atmosphere using a twin screw extruder having an L / D of 40 and a screw diameter of 50 mm.
Extruded at 220 ° C. to obtain an olefin-based thermoplastic elastomer (C-1). The gel content of the obtained olefin-based thermoplastic elastomer (C-1) was 78% by weight as determined by the above method.

(2) Production of Laminate The olefin-based thermoplastic elastomer (C-
1) 100 parts by weight and 2 parts by weight of a silicone oil (manufactured by Dow Corning Toray Co., Ltd., SH200-3000cSt, trademark) (D-1) are kneaded with a twin-screw extruder to obtain an olefin-based skin layer. Thermoplastic elastomer composition (Z-
1) was obtained. This olefinic thermoplastic elastomer composition (Z-1) and the same foamable composition as in Example 1 were co-extruded to produce a weather strip, and a durability test was performed. As a result, this weatherstrip is 50,
It survived 000 repetitions and maintained its function as a weatherstrip.

Example 7 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 6, 2 parts by weight of the silicone oil (D-1) used in Example 6, and silicone oil-polypropylene 14 parts by weight of a masterbatch (manufactured by Dow Corning Toray Co., Ltd., BY27-002 (ultra high molecular weight silicone oil content: 50% by weight), trademark) (D-2) is kneaded with a twin-screw extruder to form a skin layer. Olefinic thermoplastic elastomer composition (Z-2) was obtained. This olefinic thermoplastic elastomer composition (Z-2) and the same foamable composition as in Example 1 were co-extruded to produce a weather strip, and a durability test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip.

Example 8 100 parts by weight of the olefin-based thermoplastic elastomer (C-1) obtained in Example 6 was mixed with a fluorine-based polymer (Dynamer FX-9613 (manufactured by Sumitomo 3M Limited) with a fluorine-based polymer content of 90%). %) And 3 parts by weight of trademark (E-1) with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (Z-3) for a skin layer. This olefinic thermoplastic elastomer composition (Z-3) and the same foamable composition as in Example 1 were co-extruded to produce a weather strip, and a durability test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip.

Example 9 100 parts by weight of the olefin-based thermoplastic elastomer (C-1) obtained in Example 6 and an antistatic agent (trade name: Electrostripper TS-6B, manufactured by Kao Corporation) (F-
1) 3 parts by weight were kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (Z-4) for a skin layer. This olefinic thermoplastic elastomer composition (Z
-4) and the same foamable composition as in Example 1 were co-extruded to form a weather strip, and a durability test was performed.
As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip.

Example 10 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 6 and 10 parts by weight of the ultrahigh molecular weight polyolefin composition (Y-1) used in Example 1 were used. The mixture was kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (Z-5) for a skin layer. This olefinic thermoplastic elastomer composition (Z-5) and the same foamable composition as in Example 1 were co-extruded to form a weather strip, and a durability test was performed. As a result, the weatherstrip can withstand 50,000 repetitive tests,
The function as a weather strip was maintained.

Example 11 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 6, 100 parts by weight of the ultrahigh molecular weight polyolefin composition (Y-1) used in Example 1, 2 parts by weight of the silicone oil (D-1) was kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (Z-6) for a skin layer. This olefinic thermoplastic elastomer composition (Z-6) and the same foamable composition as in Example 1 were co-extruded to produce a weather strip,
A durability test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip.

Example 12 100 parts by weight of the olefin thermoplastic elastomer (C-1) obtained in Example 6, 2 parts by weight of the silicone oil (D-1) used in Example 1, and polypropylene (MF)
R (ASTM-D-1238-65T, 230 ° C, 2.
16 g load); 13 g / 10 min, density: 0.91 g /
cm ³ (G-1) and 30 parts by weight were kneaded with a twin-screw extruder.
An olefin-based thermoplastic elastomer composition (Z-7) for the skin layer was obtained. This olefinic thermoplastic elastomer composition (Z-7) and the same foamable composition as in Example 1 were co-extruded to produce a weather strip, and a durability test was performed. As a result, this weatherstrip
It withstood 50,000 repetition tests and maintained its function as a weatherstrip.

Comparative Example 1 A durability test was conducted in the same manner using a conventional weatherstrip (a laminated structure in which a nylon film was bonded to a soft vinyl chloride resin layer). As a result, destruction was caused at the contact surface with the window glass after 25,000 times, and the frictional resistance with the window glass was remarkably increased so that it could not be used.

The ethylene thermoplastic elastomers (A-1), (A-2), (A-3) and (A-4)
Table 1 shows the conditions of the dynamic heat treatment in the production of.

[0117]

[Table 1]

Note in Table 1 The unit of the amount of each component is parts by weight. * 1 PE: linear low-density polyethylene * 2 EPDM: ethylene-propylene-dicyclopentadiene copolymer rubber * 3 Oil-extended EPDM: paraffin as an extension oil in 100 parts by weight of ethylene-propylene-dicyclopentadiene copolymer rubber Oil (PW-38, manufactured by Idemitsu Kosan Co., Ltd.)
Oil, ethylene / propylene / dicyclopentadiene copolymer rubber * 4 PP-1: propylene / ethylene copolymer * 5 PP-2: propylene homopolymer * 6 Paraffin oil : Mineral oil-based softening agent (PW-380, trade name, manufactured by Idemitsu Kosan Co., Ltd.) * 7 T: Resin temperature at die exit of twin-screw extruder (° C) * 8 P: Screw diameter of twin-screw extruder (Mm) * 9 Q: Maximum shear rate received in the twin-screw extruder (sec)
^-1 ) * 10 R: extrusion rate of twin-screw extruder (kg / h) * 11 S: number of screw revolutions per second (rps) * 12 U: between barrel inner wall and screw kneading segment (kneading segment) Clearance (gap)
Distance of the narrowest part of (mm) * 13 Equation (1): [(T-130) / 100] + 2.2logP
+ LogQ-logR

[Brief description of the drawings]

FIG. 1 is a perspective view of an automotive weather strip including an olefin-based foam laminate of the present invention, in which a cross section is illustrated as an end face.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Weather strip 2 Core material 3 Sliding part 4 Base material layer 5 Skin layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/06 C08L 23/06 23/08 23/08 23/12 23/12 23/16 23/16 51 / 00 51/00 // (C08L 51/00 (C08L 51/00 83:04 83:04 27:12) 27:12) F-term (reference) 4F074 AA00 AA05 AA16 AA17 AA24 AA25 AA26 AA38 AA90 AA98 AB01 AB05 AG02 AG07 BA03 BA07 BB02 BB28 CA22 CC04W CC06W DA02 DA39 DA59 4F100 AK03B AK04A AK04B AK04K AK07A AK17B AK17H AK52B AK52H AK62A AK63J02 J02A07B02A02A02A01B AC01W AC07W AC08W BB00W BB00X BB00Z BB001 BB03W BB04W BB04Z BB05W BB05X BB11Z BB12W BB123 BB14W BB143 BB15W BB15X BB153 BB17W BB17Z BB18W BB19Z BD123 CP133 BD0205 062 CP082 CP092 CP182 DA006 DE016 DE026 DE226 DE246 DF036 EA006 EA016 EB006 EH047 EH057 EK038 EK048 EK058 EK068 EK088 EN107 EN127 EQ016 EQ036 ES006 EV266 EV286 FD105 FD107 FD158 FD326 GC00 GL00 GN00

Claims (13)

[Claims] 1. A polyethylene resin (a-1) (5 to 60 parts by weight) and an ethylene / α-olefin copolymer (a-
2) 40 to 95 parts by weight [where the total amount of the components (a-1) and (a-2) is 100 parts by weight. A base layer made of a foam (X ₂ ) of an ethylene thermoplastic elastomer composition (X ₁ ) containing an ethylene thermoplastic elastomer (A) comprising a foaming agent and a foaming agent (B); An olefin-based foam laminate in which a skin layer made of a high molecular weight polyolefin resin (Y) is laminated, wherein the ethylene / α-olefin-based copolymer (a-2)
Is a copolymer of ethylene, α-olefin and optionally used non-conjugated polyene, having an Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. -An olefin-based copolymer, wherein the ultrahigh molecular weight polyolefin resin (Y) is at 135 ° C;
The intrinsic viscosity [η] measured in decalin is 3.5 to 8.3.
An olefin foam laminate which is a dl / g ultra-high molecular weight polyolefin resin. 2. 5 to 60 parts by weight of a polyethylene resin (a-1) and an ethylene / α-olefin copolymer (a-
2) 40 to 95 parts by weight [where the total amount of the components (a-1) and (a-2) is 100 parts by weight. A base layer comprising a foam (X ₂ ) of a foamable ethylene thermoplastic elastomer composition (X ₁ ) containing a foaming agent (B) and an ethylene thermoplastic elastomer (A) comprising: And a skin layer comprising a thermoplastic elastomer composition (Z ₁ ), wherein the ethylene / α-olefin copolymer (a-2)
Is a copolymer of ethylene, α-olefin and optionally used non-conjugated polyene, having an Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. -An olefin-based copolymer, wherein the olefin-based thermoplastic elastomer composition (Z ₁ )
Is an organopolysiloxane (D) in an amount of from 0.5 to 100 parts by weight of the olefin-based thermoplastic elastomer (C).
An olefinic thermoplastic elastomer containing at least one selected from the group consisting of 25 parts by weight, a fluoropolymer (E) 0.5 to 10 parts by weight, and an antistatic agent (F) 0.5 to 10 parts by weight in the above ratio An olefin-based foam laminate, which is a composition. 3. A polyethylene resin (a-1) (5 to 60 parts by weight) and an ethylene / α-olefin copolymer (a-
2) 40 to 95 parts by weight [where the total amount of the components (a-1) and (a-2) is 100 parts by weight. A base layer comprising a foam (X ₂ ) of a foamable ethylene thermoplastic elastomer composition (X ₁ ) containing a foaming agent (B) and an ethylene thermoplastic elastomer (A) comprising: An olefin foam laminate in which a skin layer made of a thermoplastic elastomer composition (Z ₂ ) is laminated, wherein the ethylene / α-olefin copolymer (a-2)
Is a copolymer of ethylene, α-olefin and optionally used non-conjugated polyene, having an Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. -An olefin-based copolymer, wherein the olefin-based thermoplastic elastomer composition (Z ₂ )
Is a polyolefin resin (G) in an amount of 5 to 200 parts by weight per 100 parts by weight of the olefinic thermoplastic elastomer (C).
An olefin-based foamed laminate, which is an olefin-based thermoplastic elastomer composition contained in parts by weight. 4. A polyethylene resin (a-1) (5 to 60 parts by weight) and an ethylene / α-olefin copolymer (a-
2) 40 to 95 parts by weight [where the total amount of the components (a-1) and (a-2) is 100 parts by weight. A base layer comprising a foam (X ₂ ) of a foamable ethylene thermoplastic elastomer composition (X ₁ ) containing a foaming agent (B) and an ethylene thermoplastic elastomer (A) comprising: An olefin foam laminate in which a skin layer made of a thermoplastic elastomer composition (Z ₃ ) is laminated, wherein the ethylene / α-olefin copolymer (a-2)
Is a copolymer of ethylene, α-olefin and optionally used non-conjugated polyene, having an Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. -An olefin-based copolymer, wherein the olefin-based thermoplastic elastomer composition (Z ₃ )
Is an organopolysiloxane (D) in an amount of from 0.5 to 100 parts by weight of the olefin-based thermoplastic elastomer (C).
25 parts by weight, at least one selected from the group consisting of 0.5 to 10 parts by weight of a fluoropolymer (E) and 0.5 to 10 parts by weight of an antistatic agent (F) in the above ratio, and further comprising a polyolefin resin ( An olefin foam laminate, which is an olefin thermoplastic elastomer composition containing G) in an amount of 5 to 200 parts by weight. 5. An olefinic thermoplastic elastomer obtained by dynamically heat-treating a mixture containing a crystalline polyolefin resin (c-1) and a rubber (c-2). The olefin foam laminate according to any one of claims 2 to 4, wherein 6. The olefin foam laminate according to claim 3, wherein the polyolefin resin (G) is an ultrahigh molecular weight polyolefin resin (Y). 7. Ultra high molecular weight polyolefin resin (Y)
Has an intrinsic viscosity [η] of 1 at 135 ° C in decalin.
0-40 dl / g ultra-high molecular weight polyolefin resin (y
-1) 15 to 40 parts by weight and 85 to 60 parts by weight of a polyolefin resin (y-2) having an intrinsic viscosity [η] of 0.1 to 5 dl / g measured in decalin at 135 ° C. [where (y-
The total amount of the component (1) and the component (y-2) is 100 parts by weight. The olefin-based foamed laminate according to claim 1, 3, 4 or 6, which is an ultrahigh molecular weight polyolefin resin composition containing: 8. An ethylene-based thermoplastic elastomer (A)
Is a polyethylene resin (a-1) and ethylene-α-
The olefin according to any one of claims 1 to 7, wherein the polypropylene resin (a-3) is contained in a proportion of 30 parts by weight or less based on 100 parts by weight of the total of the olefin-based copolymer (a-2). Based foam laminate. 9. The olefin foam laminate according to claim 1, wherein the foaming agent (B) is an organic or inorganic pyrolytic foaming agent. 10. The content of the foaming agent (B) is 0.1 to 100 parts by weight of the ethylene thermoplastic elastomer (A).
The olefin foam laminate according to any one of claims 1 to 9, wherein the amount is 5 to 20 parts by weight. 11. The olefin foam laminate according to claim 1, wherein the foam (X ₂ ) has an expansion ratio of 2 times or more. 12. An ethylene-based thermoplastic elastomer (A) comprising a polyethylene resin (a-1) and ethylene-α
-A thermoplastic elastomer obtained by dynamically heat-treating a mixture with an olefin-based copolymer (a-2) or, if necessary, a mixture containing a polypropylene resin (a-3) in the absence of a crosslinking agent. The olefin foam laminate according to any one of claims 1 to 11, wherein 13. An olefinic thermoplastic elastomer (C) obtained by dynamically heat-treating a mixture containing a crystalline polyolefin resin (c-1) and a rubber (c-2) in the presence of a crosslinking agent. The olefin-based foamed laminate according to any one of claims 2 to 4, which is an olefin-based thermoplastic elastomer obtained.