JP2002019029A - 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 polyolefin expandable composition containing 100 pts.wt. of a polyolefin thermoplastic elastomer obtained by the dynamic heat treatment of a mixture containing a polyolefin resin and ethylene-α-olefin copolymer rubber, 1-20 pts.wt. of polyolefin plastic, and a blowing agent and a skin layer of an ultra-high molecular weight polyolefin resin of 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]

The present invention relates to an olefin foam laminate having an olefin foam as a base layer and an ultrahigh molecular weight polyolefin resin or an olefin thermoplastic elastomer composition 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) Olefinic thermoplastic elastomer (A) 10
0 parts by weight and olefin-based thermoplastic (B)
And 1 to 20 parts by weight, the foaming agent (C) olefin-based foamable composition comprising (X ₁₎ of the foam (X ₂₎ consists of the base layer, the epidermis formed of ultrahigh molecular weight polyolefin resin (Y) An olefin-based foam laminate in which layers are laminated, wherein the olefin-based thermoplastic elastomer (A) is 5 to 60 parts by weight of a polyolefin resin (a-1), and is optionally non-conjugated with ethylene and an α-olefin. 40 to 95 parts by weight of an ethylene / α-olefin copolymer rubber (a-2) copolymerized with a polyene [where the total amount of the components (a-1) and (a-2) is 100 parts by weight Department. ] Is obtained by dynamically heat-treating the mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 5
0-100 mol%, melt flow rate (ASTM D
-1238-65T, 230 ° C, 2.16 kg load) is an olefin thermoplastic resin of 0.01 to 2 g / 10 min, and the ultrahigh molecular weight polyolefin resin (Y) has a limit measured in decalin at 135 ° C. An olefin foam laminate, which is an ultrahigh molecular weight polyolefin resin having a viscosity [η] of 3.5 to 8.3 dl / g. (2) Olefin-based thermoplastic elastomer (A) 10
0 parts by weight and olefin-based thermoplastic (B)
And 1 to 20 parts by weight, the foaming agent (C) olefin-based foamable composition comprising a foam (X ₁₎ a substrate layer made of (X _2), an olefinic thermoplastic elastomer composition (Z ₁₎
Olefin-based foamed laminate in which a skin layer made of olefin is laminated, wherein the olefin-based thermoplastic elastomer (A) requires 5 to 60 parts by weight of a polyolefin resin (a-1), and ethylene and an α-olefin. From 40 to 95 parts by weight of an ethylene / α-olefin copolymer rubber (a-2) copolymerized with a non-conjugated polyene
The total amount of the component (a-1) and the component (a-2) is 100
Parts by weight. Olefin-based thermoplastic elastomer obtained by dynamically heat-treating the mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 50 to 100 mol% and a melt flow rate (A
STM D-1238-65T, 230 ° C, 2.16k
g load) of 0.01 to 2 g / 10 min., wherein the olefin-based thermoplastic elastomer composition (Z ₁ ) is based on 100 parts by weight of the olefin-based thermoplastic elastomer (D). 0.5 to 25 parts by weight of organopolysiloxane (E), 0.5 to 10 parts by weight of fluoropolymer (F) and antistatic agent (G)
An olefin-based foamed laminate, which is an olefin-based thermoplastic elastomer composition containing at least one selected from the group consisting of 0.5 to 10 parts by weight in the above ratio. (3) Olefin-based thermoplastic elastomer (A) 10
0 parts by weight and olefin-based thermoplastic (B)
And 1 to 20 parts by weight, the foaming agent (C) an olefin foamable composition comprising a foam (X ₁₎ a substrate layer made of (X _2), an olefinic thermoplastic elastomer composition (Z ₂₎
Olefin-based foamed laminate in which a skin layer made of olefin is laminated, wherein the olefin-based thermoplastic elastomer (A) requires 5 to 60 parts by weight of a polyolefin resin (a-1), and ethylene and an α-olefin. From 40 to 95 parts by weight of an ethylene / α-olefin copolymer rubber (a-2) copolymerized with a non-conjugated polyene
The total amount of the component (a-1) and the component (a-2) is 100
Parts by weight. Olefin-based thermoplastic elastomer obtained by dynamically heat-treating the mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 50 to 100 mol% and a melt flow rate (A
STM D-1238-65T, 230 ° C, 2.16k
g load) of 0.01 to 2 g / 10 min., wherein the olefin-based thermoplastic elastomer composition (Z ₂ ) is based on 100 parts by weight of the olefin-based thermoplastic elastomer (D). An olefin foam laminate, which is an olefin thermoplastic elastomer composition containing the polyolefin resin (H) in a proportion of 5 to 200 parts by weight. (4) Olefin-based thermoplastic elastomer (A) 10
0 parts by weight and olefin-based thermoplastic (B)
And 1 to 20 parts by weight, the foaming agent (C) an olefin foamable composition comprising (X ₁₎ of the foam (X ₂₎ and the base layer made of an olefinic thermoplastic elastomer composition (Z ₃₎
Olefin-based foamed laminate in which a skin layer made of olefin is laminated, wherein the olefin-based thermoplastic elastomer (A) requires 5 to 60 parts by weight of a polyolefin resin (a-1), and ethylene and an α-olefin. From 40 to 95 parts by weight of an ethylene / α-olefin copolymer rubber (a-2) copolymerized with a non-conjugated polyene
The total amount of the component (a-1) and the component (a-2) is 100
Parts by weight. Olefin-based thermoplastic elastomer obtained by dynamically heat-treating the mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 50 to 100 mol% and a melt flow rate (A
STM D-1238-65T, 230 ° C, 2.16k
g load) of 0.01 to 2 g / 10 min olefinic thermoplastic plastic, wherein the olefinic thermoplastic elastomer composition (Z _3), the olefinic thermoplastic elastomer (D) 100 parts by weight, 0.5 to 25 parts by weight of organopolysiloxane (E), 0.5 to 10 parts by weight of fluoropolymer (F) and antistatic agent (G)
Olefin-based foaming, which is an olefin-based thermoplastic elastomer composition containing at least one selected from the group consisting of 0.5 to 10 parts by weight in the above ratio and further containing 5 to 200 parts by weight of the polyolefin resin (H) Laminate. (5) The olefin-based thermoplastic elastomer (D)
Crystalline polyolefin resin (d-1) and rubber (d-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 (H) 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 olefin foam laminate according to any one of the above (1) to (7), wherein the polyolefin resin (a-1) of the olefin thermoplastic elastomer (A) is a polypropylene resin. (9) The olefin-based thermoplastic elastomer (A)
Ethylene / α-olefin copolymer rubber (a-2) 1
10 to 200 parts by weight of a softener (a-
The olefin foam laminate according to any one of the above (1) to (8), further comprising 3). (10) Olefin-based thermoplastic elastomer (A)
Is a mixture of a polyolefin resin (a-1) and an ethylene / α-olefin-based copolymer rubber (a-2) or, if necessary, a mixture containing a softener (a-3) in the presence of a crosslinking agent. The olefin foam laminate according to any one of the above (1) to (9), which is a thermoplastic elastomer composition obtained by dynamically heat-treating the laminate. (11) Olefin-based thermoplastic (B)
Is an isotactic polypropylene or a propylene / α-olefin copolymer.
0) The olefin foam laminate according to any one of the above items. (12) The olefin foam laminate according to any one of the above (1) to (11), wherein the foaming agent (C) is an organic or inorganic pyrolytic foaming agent. (13) The content of the foaming agent (C) is from 0.5 to 100 parts by weight of the total of the olefin-based thermoplastic elastomer (A) and the olefin-based thermoplastic (B).
The olefin foam laminate according to any one of the above (1) to (12), which is 20 parts by weight. (14) The olefin foam laminate according to any one of the above (1) to (13), wherein the foam (X ₂ ) has an expansion ratio of 2 times or more. (15) Olefinic thermoplastic elastomer (D)
Is a crystalline polyolefin resin (d-1) and a rubber (d-
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.

Olefin-based thermoplastic elastomer (A) The olefin-based thermoplastic elastomer (A) used as a raw material of the base layer in the present invention is a polyolefin resin (a-
1) 5 to 60 parts by weight, preferably 10 to 50 parts by weight, and an ethylene / α-olefin copolymer rubber (a-2)
40 to 95 parts by weight, preferably 50 to 90 parts by weight [where the total amount of the components (a-1) and (a-2) is 1
00 parts by weight. Is an olefinic thermoplastic elastomer obtained by dynamically heat-treating a mixture containing The olefin-based thermoplastic elastomer (A) comprises (a-1)
In addition to the component and the component (a-2), another component such as a softener (a-3) may be contained as necessary.

The olefin-based thermoplastic elastomer (A) used in the present invention is a mixture containing the polyolefin resin (a-1) and the ethylene / α-olefin-based copolymer rubber (a-2) in the above ratio, Depending on the softener (a
It is preferable to use an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing -3) or the like in the presence of a crosslinking agent, as described later. When the content of the polyolefin resin (a-1) and the content of the ethylene / α-olefin-based copolymer rubber (a-2) are within the above range, a foam (X ₂ ) having excellent flexibility can be obtained. In addition, an olefin foamable composition (X ₁ ) having good fluidity can be obtained.

The polyolefin resin (a-
1) is a resin comprising a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by a high-pressure method or a low-pressure method. Such resins include, for example, isotactic and syndiotactic monoolefin polymer or copolymer resins. These representative resins are commercially available.

Suitable raw material olefins for the polyolefin resin (a-1) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-hexene.
-Octene, 1-decene, 2-methyl-1-propene,
Α-olefins having 2 to 20 carbon atoms, such as 3-methyl-1-pentene, 4-methyl-1-pentene and 5-methyl-1-hexene. These olefins are used alone or in combination of two or more.

The polyolefin resin (a-1) is preferably a propylene homopolymer or a copolymer of propylene with another olefin as a main component. Specific examples of the copolymer include a propylene / ethylene copolymer, a propylene / 1-butene copolymer, a propylene / 1-hexene copolymer, and a propylene / 4-methyl-1-pentene copolymer. preferable.

The melt flow rate (MFR: ASTM D-1238-65) of the polyolefin resin (a-1)
T, 230 ° C, 2.16 kg load) is usually 0.01 to
100 g / 10 min, preferably 0.05 to 50 g / 10
Desirably within the range of minutes. The polyolefin resin (a-1) has a role of improving the fluidity of the composition and improving the heat resistance. Polyolefin resin (a-
1) can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer rubber (a-2) used in the present invention is an ethylene / α-olefin copolymer rubber and / or an ethylene / α-olefin / non-conjugated polyene copolymer rubber. Which is an elastic copolymer having an amorphous and random structure.

Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene,
1 to 3 carbon atoms such as 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene and 5-methyl-1-hexene
20 α-olefins. These olefins are used alone or in combination of two or more.

The non-conjugated polyene specifically includes dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, vinyl norbornene and the like.

As the ethylene / α-olefin copolymer rubber (a-2), 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. Particularly preferred are ethylene / propylene / non-conjugated polyene copolymer rubbers, especially ethylene / propylene / ethylidene norbornene copolymer rubber or ethylene / propylene / dicyclopentadiene copolymer rubber, and olefin-based heat having an appropriate cross-linked structure. It is particularly preferred in that a plastic elastomer (A) is obtained.

The ethylene / α-olefin copolymer rubber (a-2) used in the present invention has an ethylene content of 55 to 55.
It is desirably in the range of 95 mol%, preferably 60 to 90 mol%. Ethylene α- used in the present invention
The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the olefin copolymer rubber (a-2) is preferably in the range of 10 to 250, preferably 30 to 160. The iodine value of the ethylene / α-olefin copolymer rubber (a-2) is preferably 25 or less, and more preferably 5 to 25. Ethylene / α-olefin copolymer rubber (a
When the iodine value of -2) is 25 or less, an olefin-based thermoplastic elastomer (A) having an appropriate crosslinked structure can be obtained.

The ethylene / α-olefin copolymer rubber (a-2) may be used alone or in combination of two or more. In the present invention, ethylene / ethylene
The α-olefin-based copolymer rubber (a-2) and a rubber other than the ethylene / α-olefin-based copolymer rubber (a-2) can be used in combination.

Examples of the rubber other than the ethylene / α-olefin copolymer rubber (a-2) include, for example, a propylene / α-olefin copolymer rubber (propylene / α
-Olefin (molar ratio) = about 90/10 to 50/5
0), butene / α-olefin copolymer rubber (butene /
α-olefin (molar ratio) = about 90/10 to 50/5
0), butyl rubber, polyisobutylene rubber, styrene
Butadiene rubber (SBR) and its hydrogenated product (H
-SBR), styrene-butadiene block copolymer rubber (SBS) and its hydrogenated product (SEBS), styrene-isoprene block copolymer rubber (SIS) and its hydrogenated product (SEPS, HV-SIS), nitrile rubber (NBR), natural rubber (NR), silicone rubber and the like.

When a rubber other than the ethylene / α-olefin-based copolymer rubber (a-2) is used in combination with the ethylene / α-olefin-based copolymer rubber (a-2), -Olefin copolymer rubber (a-
The rubber other than 2) is 5 to 100 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the total of the ethylene / α-olefin copolymer rubber (a-2) and the polyolefin resin (a-1). It is desirable to use 40 parts by weight.

Olefinic thermoplastic elastomer (A)
May contain a softener (a-3). As the softener (a-3), a softener usually used for rubber can be used, and among them, a mineral oil-based softener and a synthetic softener are preferable. As such a mineral oil-based softener,
Examples include petroleum lubricating oils such as paraffinic, naphthenic, and aromatic oils, and liquid paraffin. As synthetic softeners, polyethylene wax, polypropylene wax,
Examples include petroleum asphalt and petrolatum.

Other softeners include coal tars such as coal tar and coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil, beeswax, Waxes such as carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid,
12-hydroxystearic acid, montanic acid, oleic acid,
Fatty acids such as erucic acid or metal salts thereof; synthetic polymers such as petroleum resin, coumarone indene resin, atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate; other microcrystalline wax, liquid polybutadiene Or modified products or hydrogenated products thereof, and liquid thiochol.

The softener (a-3) is used in an amount of 5 parts by weight based on 100 parts by weight of the ethylene / α-olefin copolymer rubber (a-2).
It is desirably used in an amount of from 200 to 200 parts by weight, preferably from 15 to 150 parts by weight, more preferably from 20 to 80 parts by weight. When the softener (a-3) is used at such a ratio,
The fluidity of the olefin-based foamable composition (X ₁ ) can be sufficiently improved without deteriorating physical properties such as heat resistance and tensile properties of the foam (X ₂ ). Softener (a-3)
May be added when the olefin-based thermoplastic elastomer (A) is produced, or may be previously added as an extender oil to the ethylene / α-olefin-based copolymer rubber (a-2) or the like.

The olefin thermoplastic elastomer (A) used in the present invention is not a thermosetting elastic material such as a conventional vulcanized rubber but a thermoplastic elastomer.
Easy to recycle. The olefin-based thermoplastic elastomer (A) used in the present invention may contain a known heat stabilizer, anti-aging agent, weather resistance stabilizer, antistatic agent, filler, if necessary, as long as the object of the present invention is not impaired. Additives such as colorants and lubricants can be blended.

Production of olefin-based thermoplastic elastomer (A) The olefin-based thermoplastic elastomer (A) used in the present invention comprises the above-mentioned polyolefin resin (a-1) and an ethylene / α-olefin-based copolymer rubber (a- It can be obtained by dynamically heat-treating a mixture of 2) and a softener (a-3) used as necessary.

Olefinic thermoplastic elastomer (A)
Is a polyolefin resin (a-1) and ethylene / α
-What is obtained by dynamically heat-treating a mixture of the olefin-based copolymer rubber (a-2) and, if necessary, a softener or the like in the presence of a crosslinking agent is preferable. Crosslinking agents that can be used for dynamic heat treatment include organic peroxides, sulfur, phenolic resins, amino resins, quinones and derivatives thereof, amine compounds, azo compounds, epoxy compounds, isocyanates, and the like. Crosslinking agents commonly used in curable rubbers are listed. 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 these, 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 100 parts by weight of a mixture of the polyolefin resin (a-1) and the ethylene / α-olefin-based copolymer rubber (a-2), and a softener used as necessary. For 0.
It is used in a proportion of from 0.5 to 3 parts by weight, preferably from 0.1 to 2 parts by weight.

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 is mainly composed of polyolefin resin (a-1) and ethylene / α
-Has good compatibility with the olefin copolymer rubber (a-2), and has an action of solubilizing an organic peroxide;
Since it acts as a dispersant for the organic peroxide, an olefin-based thermoplastic elastomer (A) having a uniform cross-linking effect by heat treatment and a good balance between fluidity and physical properties can be obtained.

The crosslinking assistant or the polyfunctional vinyl monomer as described above is used in an amount of 0.1 to 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" refers to kneading the above components in a molten state (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 device is preferable,
The kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The kneading temperature for dynamic heat treatment is usually 1
50-280 ° C, preferably 170-240 ° C,
The kneading time is desirably 1 to 20 minutes, preferably 1 to 5 minutes. The applied shear force is 1 as a shear rate.
0 to 1000 sec ^-1 , preferably 100 to 1000 s
ec ^-1 is desirable.

The olefinic thermoplastic elastomer (A) 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. When the gel content is 10% by weight or more, the foam (X ₂ ) is excellent in rubber properties such as heat resistance, tensile strength, flexibility, weather resistance, and rebound resilience, and is more suitable for recycling than vulcanized rubber. Is obtained.

[Measurement method of gel content] A thermoplastic elastomer sample was weighed in an amount of 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

-Olefin-based thermoplastic (B) The olefin-based thermoplastic (B) used in the present invention has an olefin content of 50 to 100 mol%, preferably 60 to 100 mol%, and an MFR (ASTM D-
1238-65T, 230 ° C, 2.16 kg load) is 0.01 to 2 g / 10 min, preferably 0.02 to 2 g.
/ 10 min α-olefin polymer or copolymer. Examples of such an olefin-based thermoplastic (B) include the polyolefin resin (a-1) satisfying the above physical properties. As the olefin-based thermoplastic (B), propylene homopolymer,
And a propylene content of 50 mol% or more, preferably 6
A 0-95 mol% propylene / α-olefin copolymer is particularly preferred.

Olefinic thermoplastic (B)
Has an MFR of 0.01 to 2 g / 10 minutes, so that the melt tension of the obtained olefin-based foamable composition (X ₁ ) can be improved, and a foam (X ₂ ) having a high expansion ratio can be obtained.
Can be obtained. The olefin-based thermoplastic (B) can be used alone or in combination of two or more.

Olefinic thermoplastic (B)
Is the olefinic thermoplastic elastomer (A) 10
1 to 20 parts by weight, preferably 1 to 10 parts by weight per 0 parts by weight
Used in parts by weight. When the olefin-based thermoplastic (B) is used in the above ratio, a foam (X ₂ ) having excellent flexibility and a high expansion ratio can be obtained.

In the present invention, the olefin-based thermoplastic (B) is used in combination with the olefin-based thermoplastic elastomer (A) prepared by dynamic heat treatment, and the olefin-based thermoplastic (B) itself is a dynamic olefin-based thermoplastic (B). It is characterized by not being subjected to heat treatment. In preparing the olefin-based thermoplastic elastomer (A), the olefin-based thermoplastic plastic (B) is added together with the polyolefin resin (a-1) and the ethylene / α-olefin-based copolymer rubber (a-2). When mixed with an organic peroxide or the like and kneaded under heating, depending on the type of the olefin-based thermoplastic (B), the olefin-based thermoplastic (B) is thermally decomposed to reduce the molecular weight or to be crosslinked by heat. As a result, the desired foam (X ₂ ) cannot be obtained.

Blowing agent (C) In the present invention, the blowing agent (C) to be blended with the raw material of the base material layer is an organic or inorganic pyrolytic blowing agent; water; Solvents such as nitrogen, carbon dioxide, propane, butane and the like. As the foaming agent (C), 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 (C) can be used alone or in combination of two or more. It is desirable to use the foaming agent (C) 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 olefinic thermoplastic elastomer (A).

The olefinic foamable composition (X ₁ ) used in the present invention may optionally contain a foaming aid. As foaming aids, zinc, calcium, lead,
Compounds containing metals such as iron and barium; organic acids such as citric acid, salicylic acid, phthalic acid, stearic acid and oxalic acid;
Urea or a derivative thereof is used. The foaming aid is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer (A).
It is desirable to use them in 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 olefin-based foamable composition (X ₁ ) may, if necessary, be used for uniform foaming at a high magnification.
An inorganic porous powder that adsorbs the inorganic gas, for example, zeolite, a resin having a large amount of adsorbing the inorganic gas, for example, a polycarbonate resin, or a nucleating agent for foaming may be added.

Further, the olefin foamable composition (X ₁ )
If necessary, fillers, heat stabilizers, anti-aging agents, weather stabilizers, antistatic agents, wetting agents, metal soaps,
Known additives such as a lubricant such as wax, a pigment, a dye, a flame retardant, an anti-blocking 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 olefinic foamable composition (X ₁ ), fillers usually used for rubber are suitable, and specific examples thereof include calcium carbonate, calcium silicate, clay, kaolin, Examples include talc, silica, diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, molybdenum disulfide, glass fiber, glass sphere, shirasu balloon, graphite, and alumina. These fillers are usually 40 parts by weight or less, preferably 1 to 3 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer (A).
It is desirable to use 0 parts by weight.

Preparation of Olefinic Foamable Composition (X ₁ ) The olefinic foamable composition (X ₁ ) comprises an olefinic thermoplastic elastomer (A), an olefinic thermoplastic (B) and a blowing agent (C). And, if necessary, a compounding agent such as a foaming aid and a wetting agent. As a compounding method,
When the olefin-based thermoplastic elastomer (A) is blended with the olefin-based thermoplastic (B) and the foaming agent (C), and if necessary, a blending agent such as a foaming aid and a wetting agent, is blended. A method of blending B) and the foaming agent (C) is included.
The olefin-based thermoplastic (B) and the blowing agent (C) may be mixed simultaneously or separately. When mixed separately, the olefin-based thermoplastic elastomer (A) can be mixed with the olefin-based thermoplastic (B), and then the foaming agent (C) can be mixed. Is also good.

When the olefin-based thermoplastic elastomer (A) is prepared by mixing the olefin-based thermoplastic (B) and / or the blowing agent (C), the desired foam (X ₂ ) is obtained. Can not. When the olefin-based thermoplastic elastomer (A) is mixed with the olefin-based thermoplastic (B) and / or the blowing agent (C) when preparing the olefin-based thermoplastic elastomer (A), the olefin-based thermoplastic (B) may be mixed depending on the type of the olefin-based thermoplastic. (B) is thermally decomposed to reduce the molecular weight, or crosslinked by heat to gel, and the melt viscosity required to obtain the desired foam (X ₂ ) is greatly deviated, or the foaming agent (C) is decomposed. Or out of gas.

Specific methods for blending the olefin-based thermoplastic elastomer (A), the olefin-based thermoplastic (B) and the blowing agent (C) include, for example, pellets of the olefin-based thermoplastic elastomer (A), olefin-based thermoplastic elastomer (A). Once the thermoplastic (B) and the foaming agent (C) are kneaded with a tumbler-type Brabender, V-type Brabender, ribbon blender, Henschel mixer, etc., if necessary, an open-type mixing roll or a non-open-type Banbury Examples of the method include kneading with a mixer, an extruder, a kneader, a continuous mixer, or the like. Weather stabilizers, heat stabilizers, anti-aging agents, pigments, dyes, etc.
You may mix | blend at any stage of the said process.

The base layer used in the present invention is the foam of the olefin foamable composition _{(X 1) (X 2)} , be obtained by heating for example olefinic foamable composition (X ₁₎ it can.

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 (D) ) 100
0.5 parts by weight of the organopolysiloxane (E)
Olefin-based thermoplastic containing at least one selected from the group consisting of 0.5 to 25 parts by weight, a fluoropolymer (F) 0.5 to 10 parts by weight, and an antistatic agent (G) 0.5 to 10 parts by weight. Elastomer composition (Z ₁ ) 3) Olefinic thermoplastic elastomer (D) 100
5 to 20 parts by weight of the polyolefin resin (H)
Olefinic thermoplastic elastomer composition (Z ₂ ) containing 0 parts by weight 4) Olefinic thermoplastic elastomer (D) 100
0.5 parts by weight of the organopolysiloxane (E)
-25 parts by weight, at least one selected from the group consisting of 0.5-10 parts by weight of a fluoropolymer (F) and 0.5-10 parts by weight of an antistatic agent (G) in the above-mentioned ratio, and further comprising a polyolefin resin (H) in an amount of from 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 in decalin at 135 ° C. 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 in decalin at 135 ° C .; 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 softening agent is desirably 1 to 20 parts by weight, preferably 3 to 15 parts by weight, per 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.

[0059] As the olefin-based thermoplastic elastomer composition _{(Z 1) ~ (Z 3} ) · olefin thermoplastic elastomer (D) an olefin-based thermoplastic elastomer used as a raw material of the skin layer in the present invention (D), crystalline An olefin-based thermoplastic elastomer composed of a functional polyolefin resin (d-1) and a rubber (d-2) can be used.

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

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

Specific examples of the rubber (d-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 (d-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 olefinic thermoplastic elastomer (D) used in the present invention, the weight ratio of the crystalline polyolefin resin (d-1) to the rubber (d-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 (d-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 (d-1) and the rubber (d-2). .

Olefinic thermoplastic elastomer (D)
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 (D)
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 a proportion of 5 to 200 parts by weight, preferably 15 to 150 parts by weight, more preferably 20 to 80 parts by weight, per 100 parts by weight of the olefinic thermoplastic elastomer (D). Is desirable. These softeners may be added at the time of producing the olefin-based thermoplastic elastomer (D), or may be previously added to the rubber (d-2) as an extender oil.

The olefinic thermoplastic elastomer (D) used in the present invention is the same as the polyolefin resin (d-1)
And a rubber (d-2) and, if necessary, a mixture of a softener and the like, which is dynamically heat-treated. In the olefin-based thermoplastic elastomer (D), the rubber (d-2) is uncrosslinked, partially crosslinked, completely crosslinked, or the like.
It can be present in all cross-linked states.

To produce the crosslinked olefinic thermoplastic elastomer (D), a mixture of the polyolefin resin (d-1) and the rubber (d-2) and, if necessary, a softener and the like are used. Is dynamically heat-treated in the presence of a crosslinking agent. The method of dynamically heat-treating is the same as that of the olefin-based thermoplastic elastomer (A).

The olefinic thermoplastic elastomer (D) preferably used in the present invention has a gel content calculated by the above-mentioned method of 10% by weight or more, preferably 20% by weight or more, particularly preferably 45% by weight or more. It is desirable.

As the olefin thermoplastic elastomer (D) used for the skin layer of the present invention, the olefin thermoplastic elastomer (A) can be used. Since the olefin-based thermoplastic elastomer (D) constituting the skin layer of the olefin-based foam laminate of the present invention is composed of the crystalline polyolefin resin (d-1) and the rubber (d-2), it has excellent fluidity. . The polyolefin-based thermoplastic elastomer (D) as described above can be molded using a conventionally used molding apparatus such as compression molding, transfer molding, injection molding, and extrusion molding.

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

As the organopolysiloxane (E),
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 (E) can be used alone or in combination of two or more.

The organopolysiloxane (E) 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, since it has a very high viscosity, and may be a master batch with an olefin resin in order to enhance dispersibility in the olefin thermoplastic elastomer (D). . As the olefin resin used in this case, the crystalline polyolefin resin (d-1) used when producing the olefin thermoplastic elastomer (D), specifically, an ethylene homopolymer, ethylene and another α -Copolymers with olefins, propylene homopolymers, copolymers of propylene with other α-olefins, and the like.

The organopolysiloxane (E) can be used singly 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 (E) 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 (E) is in accordance with the olefin-based thermoplastic elastomer (D) 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 (E) is in the above range, the foamed laminate has excellent slidability, and the organopolysiloxane (E) does not cause any problem such as stickiness of the surface.

Fluoropolymer (F) As the fluoropolymer (F) used in the present invention, a known fluoropolymer containing a fluorine atom can be used without any limitation. By blending the fluoropolymer (F),
A skin layer having excellent slidability and wear resistance can be obtained. Examples of the fluorine-based polymer (F) 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 fluorine-based polymer (F) can be used alone or in combination of two or more.

The fluorinated polymer (F) is used in advance to improve the dispersibility with the olefinic thermoplastic elastomer (D) or to further enhance the effect of improving the sliding abrasion, in order to increase the effect of the olefinic resin and / or the known olefinic resin. 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 organopolysiloxane (F) masterbatch. 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 (F) is 0.5 to 10 parts by weight, preferably 100 to 100 parts by weight of the olefin-based thermoplastic elastomer (D). Is a ratio of 1 to 8 parts by weight. When the content of the fluoropolymer (F) is in the above range, the foamed laminate has excellent slidability.

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

Specific examples of the antistatic agent (G) 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 (G) is 1
The species can be used alone or in combination of two or more.

The antistatic agent (G) is used in advance to improve the dispersibility with the olefinic thermoplastic elastomer (D) 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 olefinic thermoplastic elastomer composition (Z ₁ ), the content of the antistatic agent (G) is preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer (D). Is a ratio of 1 to 8 parts by weight. When the content of the antistatic agent (G) is in the above range, the foamed laminate has excellent slidability, and disadvantages such as precipitation of the antistatic agent (G) on the surface and whitening (bleed out) occur. Absent.

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

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

In the olefin-based thermoplastic elastomer composition (Z ₂ ), the blending amount of the polyolefin resin (H) is 5 to 200 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the olefin-based thermoplastic elastomer (D). 18
0 parts by weight. When the olefin-based thermoplastic elastomer (D) and the polyolefin resin (H) are used at 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 (E), the fluoropolymer (F) and the antistatic agent (G), and the polyolefin resin (H) can be used in combination. . The content of such olefin-based thermoplastic elastomer composition in _{(Z 3) (E) ~} (H) 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, an antiaging agent. Additives such as fillers, coloring agents, lubricants, etc. can be incorporated within a range that does not impair the object 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 (D), organopolysiloxane (E), fluorine-based polymer (F)
And at least one selected from the group consisting of an antistatic agent (G), a polyolefin resin (H), and other additives added as necessary.

The olefin foam laminate of the present invention is characterized in that
Olefinic foamable composition (X ₁) Foam (X_Two)
A base layer comprising the above-mentioned ultra-high molecular weight polyolefin resin
Fatty (Y) or olefinic thermoplastic elastomer composition
Object (Z₁)-(Z_Three) And a skin layer
Body. The skin layer may be laminated on the entire surface of the base material layer.
Alternatively, it may be laminated on only a part of the base material layer,
Other layers may be stacked. Skin layer is one of base layer
When laminated only on the part, the part where the skin layer is not laminated
The base material layer may be exposed on the surface. What is the base layer and skin layer?
Although it may be laminated with an adhesive, it is fused
Is preferred. The thickness of the laminate is not particularly limited.
The thickness of the material layer is 0.1 to 50 mm, preferably 0.5 to 4
5 mm, the thickness of the skin layer is 5 μm to 10 mm, preferably
Desirably, it is 10 μm to 8 mm. Base layer
Foam (X_Two)) Is not particularly limited.
It is desirably up to 20 times, preferably 2 to 10 times.
In the present invention, an olefin-based thermoplastic
Since (B) is sufficiently foamed, the expansion ratio is at least 2 times.
Foam of expansion ratio (X_Two) Can be easily molded
Wear.

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 furthermore has good appearance, abrasion resistance, durability, and sliding properties. Is excellent. In addition, the laminate of the present invention can be easily produced and is recyclable, so that it is economically excellent.

The olefin foam laminate of the present invention is characterized in that
Olefinic foamable composition (X ₁) Foam (X_Two)
As the base layer, and the ultra-high molecular weight polyolefin resin described above.
(Y) or olefin-based thermoplastic elastomer composition
(Z₁)-(Z_Three) As a skin layer
Can be The lamination method depends on the shape, size, and requirements of the final product.
There is no particular limitation because it depends on the properties and the like.
The base material layer and the skin layer are extruded at the same time
Examples include a method of heat fusion. In this case, Olefi
Foaming composition (X₁) Is co-extrusion molding and heat fusion
When foaming, the foam (X_Two) To form the base material layer
I do. Such a heat-sealing method requires no adhesive.
The foam laminate can be easily obtained in one simple process.
In addition, the interlayer adhesion between the substrate layer and the skin layer is strong.

The olefin-based 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 an automotive weatherstrip including the olefin 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.

[0098]

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.

[0099]

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. The raw materials used in the examples are shown below.

● Polyolefin resin (a-11) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 50 g / 10 min, density = 0.91
0 g / cm ³ propylene / ethylene block copolymer, ethylene content = 8 mol% ● Ethylene / α-olefin copolymer rubber (a-2)
1) Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber having an ethylene content of 63 mol%, an iodine value of 13, and a Mooney viscosity of [ML _{1 + 4} (100 ° C.)] = 100 ● Oil-extended ethylene / α-olefin -Based copolymer rubber (a-
22) Addition of softener (a-31) to ethylene rubber of (a-11) ● Softener (a-31) Paraffin-based process oil [Idemitsu Kosan Co., Ltd., P
W-380, trademark] ● Olefin-based thermoplastic (B-1) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 0.3 g / 10 min, density = 0.9
10 g / cm ³ propylene homopolymer

● Blowing agent (C-1) Azodicarbonamide ● Ultrahigh molecular weight polyolefin composition (Y-1) Intrinsic viscosity [η] measured in decalin at 135 ° C. = 7.
Ultra high molecular weight polyethylene composition having 0 dl / g and density = 0.965 g / cm ³ Ultra high molecular weight polyethylene ([η] = 28 dl / g) / low molecular weight polyethylene ([η] = 0.73 dl / g) = 2
Rubber (d-11) Ethylene propylene / 5-ethylidene-2- having an ethylene content of 70 mol%, an iodine value of 12, and a Mooney viscosity of [ML _{1 + 4} (100 ° C.)] = 120 Norbornene copolymer rubber ● Polyolefin resin (d-21) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 13 g / 10 min, density = 0.91
g / cm ³ propylene / ethylene block copolymer,
Ethylene content = 3 mol%

● Organopolysiloxane (E-1) Silicon oil [manufactured by Toray Dow Corning Co., Ltd., S
H200 (3000 cSt, trademark)] Organopolysiloxane (E-2) Silicon oil-polypropylene masterbatch [BY27-002 (manufactured by Toray Dow Corning Co., Ltd., ultra-high molecular weight silicone oil content 50% by weight, trademark)] ● Fluoropolymer (F-1) Dynamer FX-9613, manufactured by Sumitomo 3M Limited
(Fluorine-based polymer content 90%, trademark) ● Antistatic agent (G-1) Kao Corporation, Electrostripper TS-6B,
Trademark ● Polyolefin resin (H-1) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 13 g / 10 min, density = 0.91
g / cm ³ propylene / ethylene block copolymer,
Ethylene content = 3 mol%

Example 1 (1) Production of olefin-based thermoplastic elastomer (A-1) 30 parts by weight of polyolefin resin (a-11) and 70 parts by weight of ethylene / α-olefin-based copolymer rubber (a-21) Parts under a nitrogen atmosphere using a Banbury mixer.
After kneading at 80 ° C. for 5 minutes, the mixture was passed through a sheeting roll and pellets were produced by a sheet cutter. Next, 100 parts by weight of the pellet and 1,3-bis (te) were added.
rt-butylperoxyisopropyl) benzene 0.3
A solution in which 0.3 parts by weight of divinylbenzene was dissolved and dispersed in parts by weight was mixed with a tumbler blender, and the solution was uniformly attached to the pellet surface. Next, the pellets were extruded at 210 ° C. under a nitrogen atmosphere using an extruder and subjected to dynamic heat treatment to obtain an olefin-based thermoplastic elastomer (A-1) having a gel content of 77% by weight.

(2) Production of laminate The olefin-based thermoplastic elastomer (A-
1) 100 parts by weight, 5 parts by weight of an olefin-based thermoplastic (B-1), and 1.5 parts by weight of a foaming agent (C-1) are mixed by a tumbler blender, and an olefin-based foamable composition is blended. did. 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) was co-extruded at a temperature of 230 ° C. to form a skin layer, and the base layer and the skin layer were heat-sealed to produce a weatherstrip shown in FIG. The expansion ratio of the obtained weather strip was 2.2 times.

The obtained weather strip was mounted on a test window frame, and a window glass having a thickness of 3.2 mm was fitted thereinto, and a durability test (a vertical repetition test of the window glass) was performed. As a result, the weatherstrip did not wear out even after 50,000 repetitions of the vertical glazing operation and maintained its function as a weatherstrip without abrasion.

Example 2 30 parts by weight of a polyolefin resin (a-11), 70 parts by weight of an ethylene / α-olefin copolymer rubber (a-21), and 50 parts by weight of a softener (a-31) were used. An olefin-based thermoplastic elastomer (A-2) was obtained in the same manner as in Example 1. The gel content of this olefinic thermoplastic elastomer (A-2) was 71% by weight. Next, the olefin-based thermoplastic elastomer (A-2)
Was used, and an olefin-based foamable composition was blended in the same manner as in Example 1, a weatherstrip was produced with the same skin layer as in Example 1, and a durability test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip. The foaming ratio of the obtained weather strip was 2.3 times.

Example 3 Ethylene / α-olefin copolymer rubber (a-21)
An olefin-based thermoplastic elastomer (A-3) was prepared in the same manner as in Example 1 except that 120 parts by weight of the oil-extended ethylene / α-olefin-based copolymer rubber (a-22) was used instead of 70 parts by weight. Obtained. The olefinic thermoplastic elastomer (A-3) had a gel content of 73% by weight. Then, using this olefinic thermoplastic elastomer (A-3), an olefinic foamable composition was blended 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 durable. The test was performed. As a result, the weatherstrip withstood 50,000 repetitive tests and maintained its function as a weatherstrip. The foaming ratio of the obtained weather strip was 2.3 times.

Example 4 30 parts by weight of polyolefin resin (a-11), 70 parts by weight of ethylene / α-olefin copolymer rubber (a-21), 50 parts by weight of softener (a-31), Butyl rubber (0.5% unsaturation, Mooney viscosity [ML1 + 4 (100
C))] and 30 parts by weight, and an olefin-based thermoplastic elastomer (A-4) was obtained in the same manner as in Example 1. This olefinic thermoplastic elastomer (A-4)
Was 81% by weight. Next, using this olefinic thermoplastic elastomer (A-4), an olefinic foamable composition is compounded in the same manner as in Example 1,
A weatherstrip was produced using the same skin layer as in Example 1, and a durability 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 2.6 times.

Example 5 (1) Production of olefin-based thermoplastic elastomer (D-1) 60 parts by weight of rubber (d-11) and 40 parts by weight of crystalline polyolefin-based resin (d-21) were mixed with a Banbury mixer. After kneading at 180 ° C. for 5 minutes in a nitrogen atmosphere using
The kneaded material was passed through a roll to form a sheet, which was cut by a sheet cutter to produce square pellets. Then
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 with a Henschel mixer. Next, this mixture was extruded at 210 ° C. in a nitrogen atmosphere using a twin screw extruder having an L / D of 40 and a screw diameter of 50 mm to obtain an olefin-based thermoplastic elastomer (D-1). The gel content of the obtained olefin-based thermoplastic elastomer (D-1) was 78% by weight as determined by the above method.

(2) Production of laminate The olefin-based thermoplastic elastomer (D-
1) 100 parts by weight of an organopolysiloxane (E-
1) 2 parts by weight were kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (Z-1) for a skin layer. This olefinic thermoplastic elastomer composition (Z
-1) and the same olefinic 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 survived the 000 repetition tests and maintained its function as a weatherstrip.

Example 6 100 parts by weight of the olefin-based thermoplastic elastomer (D-1) obtained in Example 5, 2 parts by weight of the organopolysiloxane (E-1), and 100 parts by weight of the organopolysiloxane (E-
2) 14 parts by weight were kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (Z-2) for a skin layer. This olefinic thermoplastic elastomer composition (Z
-2) and the same olefinic 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 survived the 000 repetition tests and maintained its function as a weatherstrip.

Example 7 100 parts by weight of the olefinic thermoplastic elastomer (D-1) obtained in Example 5 and a fluoropolymer (F-
1) 3 parts by weight were kneaded 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 olefinic 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 survived the 000 repetition tests and maintained its function as a weatherstrip.

Example 8 100 parts by weight of the olefin-based thermoplastic elastomer (D-1) obtained in Example 5 and 3 parts by weight of an antistatic agent (G-1) were kneaded with a twin-screw extruder to form a skin. An olefin-based thermoplastic elastomer composition (Z-4) for a layer was obtained. This olefin-based thermoplastic elastomer composition (Z-4);
A weatherstrip was prepared by co-extrusion of the same olefinic foamable composition as in Example 1, and a durability test was performed. As a result, the weatherstrip was 50,000
It survived zero repetition tests and maintained its function as a weatherstrip.

Example 9 100 parts by weight of the olefinic thermoplastic elastomer (D-1) obtained in Example 5 and 10 parts by weight of the ultrahigh molecular weight polyolefin composition (Y-1) were kneaded with a twin-screw extruder. And
An olefin-based thermoplastic elastomer composition (Z-5) for the skin layer was obtained. This olefin-based thermoplastic elastomer composition (Z-5) and the same olefin-based 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 10 100 parts by weight of the olefin thermoplastic elastomer (D-1) obtained in Example 5, 100 parts by weight of the ultrahigh molecular weight polyolefin composition (Y-1), and the organopolysiloxane (E- 1) 2 parts by weight were kneaded with a twin screw extruder, and the olefinic thermoplastic elastomer composition (Z-
6) was obtained. This olefin-based thermoplastic elastomer composition (Z-6) and the same olefin-based 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 11 100 parts by weight of the olefin-based thermoplastic elastomer (D-1) obtained in Example 5, 2 parts by weight of the organopolysiloxane (E-1), and the polyolefin resin (H-1)
30 parts by weight were kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (Z-7) for a skin layer.
This olefinic thermoplastic elastomer composition (Z-
7) and the same olefinic foamable composition as in Example 1 were co-extruded to produce a weatherstrip, and a durability test was performed. As a result, this weatherstrip
It survived the 000 repetition tests and maintained its function as a weatherstrip.

Comparative Example 1 A durability test was performed in the same manner as in Example 1 using a conventional weatherstrip (a laminated structure in which a nylon film was bonded to a soft vinyl chloride resin layer). As a result, 25,
After 000 times, breakage occurred on the contact surface with the window glass, and the frictional resistance with the window glass increased significantly, making it unusable for use.

[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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) C08L 23/00 C08L 23/00 23/08 23/08 91/00 91/00 F-term (reference) 4F070 AA12 AA13 AA15 AA16 AB08 AC94 AE02 AE12 GA05 GB08 GC08 4F074 AA16 AA17 AG02 BA02 BA13 BB02 CA22 CC04Y CC06X CE02 DA02 DA33 DA36 DA39 DA54 4F100 AK03A AK03B AL AK04A AK04A CA02H CA04A CA22B CA22H DJ01A EH20 GB07 GB32 GB71 GB87 JA06A JA08B JB16A JB16B JK09 JK11 JK16 4J002 AC03Y AC11Y AE05Y AG00Y BA01Y BB00X BB03X BB03Y BB05W BB12X BB12Y BB14X BB15W BB16X BK00Y CN02Y DE207 DE217 DF037 EA016 EF056 EG016 EH146 EQ017 EQ027 EQ037 ES007 FD02Y FD026 FD327 GL00 GN00

Claims (15)

[Claims] 1. An olefinic foamable composition (X ₁ ) comprising 100 parts by weight of an olefinic thermoplastic elastomer (A), 1 to 20 parts by weight of an olefinic thermoplastic (B), and a foaming agent (C). A) an olefinic foam laminate in which a base layer made of the foam (X ₂ )) and a skin layer made of an ultrahigh molecular weight polyolefin resin (Y) are laminated, wherein the olefinic thermoplastic elastomer (A) Is a polyolefin resin (a-1) in an amount of 5 to 60 parts by weight, and ethylene / α-olefin-based copolymer rubber (a-2) in which ethylene and an α-olefin and, if necessary, a non-conjugated polyene are copolymerized. 95 parts by weight [the total amount of the components (a-1) and (a-2) is 100 parts by weight. An olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 50 to 100 mol% and a melt flow rate (ASTM D-1238). -65T, 230 ° C, 2.
Olefin-based thermoplastic plastic having a load of 16 kg) of 0.01 to 2 g / 10 minutes, and the ultrahigh molecular weight polyolefin resin (Y) is 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. An olefinic foamable composition (X ₁ ) comprising 100 parts by weight of an olefinic thermoplastic elastomer (A), 1 to 20 parts by weight of an olefinic thermoplastic (B), and a foaming agent (C). A) a foamed olefin-based laminate in which a base layer made of the foam (X ₂ )) and a skin layer made of the olefin-based thermoplastic elastomer composition (Z ₁ ) are laminated; (A) is a polyolefin resin (a-1) of 5 to 60 parts by weight, and an ethylene / α-olefin-based copolymer rubber (a-2) obtained by copolymerizing ethylene, an α-olefin and, if necessary, a non-conjugated polyene. ) 40 to 95 parts by weight [where the total amount of the components (a-1) and (a-2) is 100 parts by weight. An olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 50 to 100 mol% and a melt flow rate (ASTM D-1238). -65T, 230 ° C, 2.
An olefin-based thermoplastic plastic having a load of 16 kg / min) of 0.01 to 2 g / 10 minutes, wherein the olefin-based thermoplastic elastomer composition (Z ₁ )
Is the organopolysiloxane (E) 0.5 to 100 parts by weight of the olefinic thermoplastic elastomer (D).
An olefinic thermoplastic elastomer containing at least one selected from the group consisting of 25 parts by weight, 0.5 to 10 parts by weight of a fluoropolymer (F) and 0.5 to 10 parts by weight of an antistatic agent (G) in the above ratio An olefin-based foam laminate, which is a composition. 3. An olefinic foamable composition (X ₁ ) comprising 100 parts by weight of an olefinic thermoplastic elastomer (A), 1 to 20 parts by weight of an olefinic thermoplastic (B), and a foaming agent (C). A) an olefin-based foam laminate in which a base layer made of the foam (X ₂ )) and a skin layer made of the olefin-based thermoplastic elastomer composition (Z ₂ ) are laminated; (A) is a polyolefin resin (a-1) of 5 to 60 parts by weight, and an ethylene / α-olefin-based copolymer rubber (a-2) obtained by copolymerizing ethylene, an α-olefin and, if necessary, a non-conjugated polyene. ) 40 to 95 parts by weight [where the total amount of the components (a-1) and (a-2) is 100 parts by weight. An olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 50 to 100 mol% and a melt flow rate (ASTM D-1238). -65T, 230 ° C, 2.
An olefin-based thermoplastic elastomer having a load of 16 kg / min. Of 0.01 to 2 g / 10 minutes, wherein the olefin-based thermoplastic elastomer composition (Z ₂ )
Is a polyolefin resin (H) in an amount of 5 to 200 parts by weight per 100 parts by weight of the olefinic thermoplastic elastomer (D).
An olefin-based foamed laminate, which is an olefin-based thermoplastic elastomer composition contained in parts by weight. 4. An olefinic foamable composition (X ₁ ) comprising 100 parts by weight of an olefinic thermoplastic elastomer (A), 1 to 20 parts by weight of an olefinic thermoplastic (B), and a foaming agent (C). A) an olefinic foam laminate in which a base layer made of the foam (X ₂ )) and a skin layer made of the olefinic thermoplastic elastomer composition (Z ₃ ) are laminated; (A) is a polyolefin resin (a-1) of 5 to 60 parts by weight, and an ethylene / α-olefin-based copolymer rubber (a-2) obtained by copolymerizing ethylene, an α-olefin and, if necessary, a non-conjugated polyene. ) 40 to 95 parts by weight [where the total amount of the components (a-1) and (a-2) is 100 parts by weight. An olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing the olefin-based thermoplastic elastomer (B), wherein the olefin-based thermoplastic (B) has an olefin content of 50 to 100 mol% and a melt flow rate (ASTM D-1238). -65T, 230 ° C, 2.
16kg load) is 0.01 to 2 g / 10 min olefinic thermoplastic plastic, wherein the olefinic thermoplastic elastomer composition (Z ₃₎
Is the organopolysiloxane (E) 0.5 to 100 parts by weight of the olefinic thermoplastic elastomer (D).
25 parts by weight, at least one selected from the group consisting of 0.5 to 10 parts by weight of a fluoropolymer (F) and 0.5 to 10 parts by weight of an antistatic agent (G) in the above ratio, and further comprising a polyolefin resin ( An olefin foam laminate, which is an olefin thermoplastic elastomer composition containing H) in an amount of 5 to 200 parts by weight. 5. An olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing a crystalline polyolefin resin (d-1) and a rubber (d-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 (H) 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. The olefin foam laminate according to claim 1, wherein the polyolefin resin (a-1) of the olefin thermoplastic elastomer (A) is a polypropylene resin. 9. The olefin-based thermoplastic elastomer (A) contains 10 to 200 parts by weight of a softener (a-3) based on 100 parts by weight of an ethylene / α-olefin-based copolymer rubber (a-2). The olefin foam laminate according to any one of claims 1 to 8, further comprising: 10. An olefin-based thermoplastic elastomer (A) comprising a polyolefin resin (a-1) and ethylene.
a mixture with an α-olefin copolymer rubber (a-2),
Or optionally a mixture containing a softener (a-3),
The olefin-based foam laminate according to any one of claims 1 to 9, which is a thermoplastic elastomer composition obtained by dynamically heat-treating in the presence of a crosslinking agent. 11. The olefin foam laminate according to claim 1, wherein the olefin thermoplastic plastic (B) is an isotactic polypropylene or a propylene / α-olefin copolymer. 12. The olefin foam laminate according to claim 1, wherein the foaming agent (C) is an organic or inorganic pyrolytic foaming agent. 13. The content of the blowing agent (C) is 0.5 to 20 parts by weight based on 100 parts by weight of the total of the olefin-based thermoplastic elastomer (A) and the olefin-based thermoplastic (B). Item 13. The olefin foam laminate according to any one of Items 1 to 12. 14. The olefin foam laminate according to claim 1, wherein the foam (X ₂ ) has an expansion ratio of 2 times or more. 15. An olefinic thermoplastic elastomer (D) obtained by dynamically heat-treating a mixture containing a crystalline polyolefin resin (d-1) and a rubber (d-2) in the presence of a crosslinking agent. The olefin foam laminate according to any one of claims 2 to 4, which is an olefin thermoplastic elastomer obtained.