JP2003191378A - Olefin expanded laminate and use application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin expanded laminate with such advantages that its recycling is easy, the expansion ratio is high with a feel of pliability and the characteristics such as appearance, abrasion resistance, durability and sliding are superb. <P>SOLUTION: This olefin expanded laminate comprises a skin layer formed of an ultra-high-molecular-weight polyolefin resin with an intrinsic viscosity of 3.5 to 8.3 dl/g, or a skin layer formed of an olefin thermoplastic elastomer composition containing an olefin thermoplastic elastomer and a lubricant, laminated on a base material layer formed of a polyethylene resin and an ethylene thermoplastic elastomer foam containing an ethylene/α-olefin copolymer with a Mooney viscosity ML<SB>1+4</SB>(100°C) of 90 to 250, and an ethylene content of 70 to 95 mol% or a base material layer formed of an olefin thermoplastic elastomer composition foam containing 100 pts.wt. of an olefin thermoplastic elastomer and 1 to 20 pts.wt. of an olefin thermoplastic plastic. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based foamed laminate comprising an olefin-based thermoplastic elastomer foam as a base layer and an ultrahigh molecular weight polyolefin resin or an olefin-based thermoplastic elastomer composition as a skin layer, and Regarding its use.

[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 then the kneaded material is molded into a predetermined shape and heated. A method is known in which vulcanization 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 previously kneading the compound into the rubber in a batch to obtain a kneaded product is performed before continuous extrusion. In addition, in order to easily supply the kneaded product to the extruder, a step of forming the kneaded product into a ribbon shape in advance needs to be performed before the continuous extrusion. As described above, the conventional method as described above is disadvantageous in industrial production because the manufacturing process is complicated and the vulcanization and foaming processes require a considerable amount of time.

As a method for solving such a problem,
For example, there is a method of using a thermoplastic resin such as an ethylene / vinyl acetate copolymer, 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 steps can be omitted.

However, the conventionally used thermoplastic resins and thermoplastic elastomers are liable to be defoamed during foam molding, resulting in poor appearance, and the resulting foams have a small expansion ratio, which is at most 1.5. Since the foaming ratio is about double, there is a problem that it feels harder than rubber. In addition, even if a part obtained by repeatedly sliding or sliding a part touching a person or an object, such as a weather strip for automobiles or a seal member of a door stop, is manufactured from a foam obtained by a conventional method, abrasion resistance and Since the sliding property is poor, the durability is poor, and thus it is 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, which is composed of a recyclable olefin polymer and has a high expansion ratio and a soft feel. The present invention is to provide an olefin foam laminate which is excellent in appearance, wear resistance, durability and sliding characteristics, and particularly excellent in wear resistance under adverse conditions. Another object of the present invention is to provide a sliding member, a weather strip for automobiles, and a sealing material for construction, which are made of the above olefin foam laminate.

[0006]

The present invention is the following olefinic foam laminates and uses. (1) An olefin foam laminate in which a base material layer made of a foam (X _F ) of an olefin thermoplastic elastomer (X) and a skin layer made of the following resin or elastomer composition are laminated. Y: Ultra-high molecular weight polyolefin resin having an intrinsic viscosity [η] of 3.5 to 8.3 dl / g measured in decalin at 135 ° C. Z: An olefinic thermoplastic elastomer composition containing an olefinic thermoplastic elastomer (C) and a lubricant (Z _L ). (2) The skin layer is a skin layer composed of an olefin-based thermoplastic elastomer composition (Z), and the olefin-based thermoplastic elastomer composition (Z) is based on 100 parts by weight of the olefin-based thermoplastic elastomer (C). Fatty acid amide 0.01-5 parts by weight, mineral oil 0.5-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5
Parts by weight, 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate, and an olefinic thermoplastic elastomer composition (Z _L ) containing at least one lubricant (Z _L ) selected from the group consisting of the above proportions. ₁₎ is the above (1) an olefin-based foam laminate according. (3) The olefinic thermoplastic elastomer (X) is
Compression set (70) measured according to JIS K 6262
Olefin-based foaming according to the above (1) or (2), which has a melt flow rate (230 ° C., 10 kg load) measured by JIS K 7120 of 0.1 g / 10 min or more, at 60 ° C. for 22 hours). Laminate. (4) The olefinic thermoplastic elastomer (X) is
5 to 60 parts by weight of a polyethylene resin (a-1) and 40 to 95 parts by weight of an ethylene / α-olefin copolymer (a-2) [wherein the component (a-1) and the component (a-2) are used. Is 100 parts by weight. ] An ethylene-based thermoplastic elastomer (A) consisting of
The α-olefin copolymer (a-2) is ethylene, α
A copolymer of olefins and optionally non-conjugated polyenes, with a Mooney viscosity ML _{1 + 4} (100
C) 90-250, ethylene content 70-95 mol%
The olefin foam laminate according to the above (1) or (2), which is the ethylene / α-olefin copolymer. (5) 5 to 60 parts by weight of polyethylene resin (a-1), and ethylene / α-olefin copolymer (a-2) 4
0-95 parts by weight [wherein component (a-1) and (a-
2) The total amount of the components is 100 parts by weight. ] An olefin foam laminate in which a base material layer made of a foam (X _F1 ) of an ethylene thermoplastic elastomer (A) and a skin layer made of an olefin thermoplastic elastomer composition (Z) are laminated. The ethylene / α-olefin copolymer (a-2) is a copolymer of ethylene, α-olefin and a non-conjugated polyene optionally used, and has a Mooney viscosity ML _{1 + 4} (100 C.) is 90 to 250 and the ethylene content is 70 to 95 mol%, and the olefin thermoplastic elastomer composition (Z) is an olefin thermoplastic elastomer (C) 100. Parts by weight,
0.5 to 25 parts by weight of organopolysiloxane (D), 0.5 to 10 parts by weight of fluoropolymer (E), 0.5 to 10 parts by weight of antistatic agent (F), polyolefin resin (G)
5 to 200 parts by weight, fatty acid amide 0.01 to 5 parts by weight,
Group consisting of 0.5 to 10 parts by weight of mineral oil, 0.01 to 5 parts by weight of metal soap, 0.01 to 5 parts by weight of esters, 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate. An olefin foam laminate which is an olefin thermoplastic elastomer composition containing at least one lubricant (Z _L ) selected from the above in the above proportions. (6) The olefinic thermoplastic elastomer (C) is
Crystalline polyolefin resin (c-1) and rubber (c-2)
The olefin-based foam laminate according to (5) above, which is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing and. (7) The polyolefin resin (G) has an intrinsic viscosity [η] measured in 135 ° C. decalin of 3.5 to 8.3 dl /
The olefin-based foam laminate according to the above (5) or (6), which is g of the ultrahigh molecular weight polyolefin resin (Y). (8) Ultra high molecular weight polyolefin resin (Y) is 13
Intrinsic viscosity [η] measured in 5 ° C decalin is 10-40
dl / g ultra high 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. [wherein (y-1) component And the total amount of the component (y-2) is 100 parts by weight. ] The olefinic foam laminate according to (7) above, which is an ultrahigh molecular weight polyolefin resin composition containing (9) The olefin-based thermoplastic elastomer composition (Z) is the olefin-based thermoplastic elastomer (C) 1
0.01 to 5 parts by weight of fatty acid amide, 0.5 to 10 parts by weight of mineral oil, 0.01 to 0.01 parts by weight of metal soap.
5 parts by weight, esters 0.01 to 5 parts by weight, calcium carbonate 0.01 to 5 parts by weight and silicate 0.01 to 5
The olefinic foam laminate according to the above (5) or (6), which is an olefinic thermoplastic elastomer composition (Z ₁ ) containing at least one lubricant (Z _L ) selected from the group consisting of parts by weight in the above proportion. . (10) The olefin-based thermoplastic elastomer composition (Z) is the olefin-based thermoplastic elastomer (C) 1
0.01 to 5 parts by weight of fatty acid amide as a lubricant (Z _L ), 0.5 to 10 parts by weight of mineral oil, 0.01 to 5 parts by weight of metal soap, and 0.01 to 5 parts by weight of esters with respect to 00 parts by weight. Part, at least one member selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate, and 5 to 200 parts by weight of a polyolefin resin (G) in the above proportions. The olefin-based foam laminate according to the above (5) or (6), which is a plastic elastomer composition (Z ₂ ). (11) The ethylene-based thermoplastic elastomer (A) is
The polypropylene resin (a-3) is contained in a proportion of 30 parts by weight or less with respect to a total of 100 parts by weight of the polyethylene resin (a-1) and the ethylene / α-olefin copolymer (a-2). The olefin-based foam laminate according to any one of (5) to (10) above. (12) The olefin foam laminate according to any one of (5) to (11) above, wherein the foam (X _F1 ) has a foaming ratio of 2 or more. (13) The ethylene-based thermoplastic elastomer (A) is
A mixture of a polyethylene resin (a-1) and an ethylene / α-olefin copolymer (a-2), or a mixture containing a polypropylene resin (a-3) as necessary, in the absence of a crosslinking agent. The olefin-based foam laminate according to any one of (5) to (12) above, which is a thermoplastic elastomer obtained by dynamic heat treatment. (14) Olefin-based thermoplastic elastomer (C)
Is a crystalline polyolefin resin (c-1) and rubber (c-
The olefin-based foam laminate according to any one of (5) to (13) above, which is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing 2) and 2). (15) The foam (X _F1 ) is a foam obtained by foaming a foamable ethylene-based thermoplastic elastomer composition (X ₁ ) containing an ethylene-based thermoplastic elastomer (A) and a foaming agent (B). The olefin-based foam laminate according to any one of (5) to (14) above. (16) The olefin-based foam laminate according to the above (15), wherein the foaming agent (B) is an organic or inorganic pyrolytic foaming agent. (17) 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 the above (15) or (16), which is 0 part by weight. (18) The ethylene-based thermoplastic elastomer (A) is
Compression set (70) measured according to JIS K 6262
60 ° C. or less for 22 hours) and a melt flow rate (230 ° C., 10 kg load) measured according to JIS K 7120 of 0.1 g / 10 min or more, (5) to (17) above. Olefin foam laminate. (19) Olefin-based thermoplastic elastomer (X)
Is 100 parts by weight of the olefinic thermoplastic elastomer (J) and 1 to 10 parts of the olefinic thermoplastic (K).
An olefin-based thermoplastic elastomer composition (X ₂ ) containing 20 parts by weight, wherein the olefin-based thermoplastic elastomer (J) is a polyolefin resin (j-1) 5
To 60 parts by weight, and ethylene / α-copolymerized with ethylene, α-olefin and optionally non-conjugated polyene
Olefin-based copolymer rubber (j-2) 40 to 95 parts by weight [wherein the total amount of the component (j-1) and the component (j-2) is 100 parts by weight. ] A olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing the above, wherein the olefin-based thermoplastic (K) is
Olefin content 50-100 mol%, melt flow rate (ASTM D-1238-65T, 230 ° C,
The olefin-based foam laminate according to the above (1) or (2), which is an olefin-based thermoplastic with a load of 2.16 kg) of 0.01 to 2 g / 10 minutes. (20) Olefin-based thermoplastic elastomer (J) 1
A base material layer made of a foam (X _F2 ) of an olefinic thermoplastic elastomer composition (X ₂ ) containing 00 parts by weight and 1 to 20 parts by weight of an olefinic thermoplastic (K), and an olefinic thermoplastic An olefin-based foam laminate in which a skin layer made of an elastomer composition (Z) is laminated, wherein the olefin-based thermoplastic elastomer (J) is 5 to 60 parts by weight of a polyolefin resin (j-1), and ethylene. 40 to 95 parts by weight of an ethylene / α-olefin-based copolymer rubber (j-2) obtained by copolymerization of an α-olefin with a non-conjugated polyene as necessary [wherein the component (j-1) and (j- 2) The total amount of ingredients is 1
It is 00 parts by weight. ] The olefinic thermoplastic elastomer (K) obtained by dynamically heat treating a mixture containing the above, wherein the olefinic thermoplastic (K) has an olefin content of 50 to 100 mol% and a melt flow rate (ASTM D-1238). -65T, 230 ° C, 2.1
6 kg load) is 0.01 to 2 g / 10 minutes, and the olefin-based thermoplastic elastomer composition (Z) is 100 parts by weight of the olefin-based thermoplastic elastomer (C). 0.5 to 25 parts by weight of polysiloxane (D), 0.5 to 10 parts by weight of fluoropolymer (E), antistatic agent (F) of 0.
5-10 parts by weight, polyolefin resin (G) 5-200
Parts by weight, fatty acid amide 0.01 to 5 parts by weight, mineral oil 0.5
-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5 parts by weight, calcium carbonate 0.01-
An olefin-based foamed laminate which is an olefin-based thermoplastic elastomer composition containing at least one lubricant (Z _L ) selected from the group consisting of 5 parts by weight and 0.01 to 5 parts by weight of silicate in the above proportion. (21) Olefin-based thermoplastic elastomer (C)
Is a crystalline polyolefin resin (c-1) and rubber (c-
The olefin-based foam laminate according to the above (20), which is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing and. (22) The above (19) or (2), wherein the polyolefin resin (G) is an ultrahigh molecular weight polyolefin resin (Y).
The olefin-based foam laminate according to 0). (23) Ultra high molecular weight polyolefin resin (Y) is 1
The intrinsic viscosity [η] measured in decalin at 35 ° C is 10 to 4
Ultra high molecular weight polyolefin resin (y-1) of 0 dl / g
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 135 ° C. decalin [wherein (y-1) component And the total amount of the component (y-2) is 100 parts by weight. ] The olefinic foam laminate according to the above (22), which is an ultrahigh molecular weight polyolefin resin composition containing: (24) The olefin-based thermoplastic elastomer composition (Z) is the olefin-based thermoplastic elastomer (C) 1
0.01 to 5 parts by weight of fatty acid amide, 0.5 to 10 parts by weight of mineral oil, 0.01 to 0.01 parts by weight of metal soap.
5 parts by weight, esters 0.01 to 5 parts by weight, calcium carbonate 0.01 to 5 parts by weight and silicate 0.01 to 5
The above (20) or (2) which is an olefinic thermoplastic elastomer composition (Z ₁ ) containing at least one lubricant (Z _L ) selected from the group consisting of parts by weight in the above proportion.
The olefin-based foam laminate according to 1). (25) The olefin-based thermoplastic elastomer composition (Z) is the olefin-based thermoplastic elastomer (C) 1
0.01 to 5 parts by weight of fatty acid amide as a lubricant (Z _L ), 0.5 to 10 parts by weight of mineral oil, 0.01 to 5 parts by weight of metal soap, and 0.01 to 5 parts by weight of esters with respect to 00 parts by weight. Part, at least one member selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate, and 5 to 200 parts by weight of a polyolefin resin (G) in the above proportions. The olefin-based foam laminate according to the above (20) or (21), which is a plastic elastomer composition (Z ₂ ). (26) The olefin foam laminate according to any of (20) to (25), wherein the polyolefin resin (j-1) of the olefin thermoplastic elastomer (J) is a polypropylene resin. (27) Olefin-based thermoplastic elastomer (J)
Is an ethylene / α-olefin copolymer rubber (j-
2) The olefin-based foam laminate according to any one of the above (20) to (26), further containing 10 to 200 parts by weight of the softening agent (j-3) with respect to 100 parts by weight. (28) Olefin-based thermoplastic elastomer (J)
Is a mixture of a polyolefin resin (j-1) and an ethylene / α-olefin copolymer rubber (j-2), or a mixture containing a softening agent (j-3) if necessary, and the presence of a crosslinking agent. The olefinic foam laminate according to any one of (19) to (27), which is a thermoplastic elastomer composition obtained by dynamically heat-treating below. (29) Olefin-based thermoplastic (K)
Is an isotactic polypropylene or a propylene / α-olefin copolymer, and the olefin foam laminate according to any one of (20) to (28) above. (30) The foam (X _F2 ) comprises 100 parts by weight of an olefinic thermoplastic elastomer (J), 1 to 20 parts by weight of an olefinic thermoplastic (K), and a foaming agent (B).
The olefinic foam laminate according to any one of (20) to (29) above, which is a foam obtained by foaming an olefinic foamable composition (X ₃ ) containing (31) The olefin foam laminate according to the above (30), wherein the foaming agent (B) is an organic or inorganic pyrolytic foaming agent. (32) The content of the foaming agent (B) is 0.5 to 100 parts by weight in total of the olefin-based thermoplastic elastomer (J) and the olefin-based thermoplastic (K).
The olefin foam laminate according to (30) or (31) above, which is 20 parts by weight. (33) The olefin foam laminate according to any one of (20) to (32), wherein the foam (X _F2 ) has a foaming ratio of 2 or more. (34) Olefin-based thermoplastic elastomer (C)
Is a crystalline polyolefin resin (c-1) and rubber (c-
The olefinic foam laminate according to any one of (20) to (33), which is an olefinic thermoplastic elastomer obtained by dynamically heat treating a mixture containing 2) and 2). (35) The olefin-based thermoplastic elastomer composition (X ₂ ) has a compression set (70 ° C., 22 hours) of 60% or less according to JIS K6262, and JIS K 71
Melt flow rate measured at 20 (230 ° C, 10k
The olefin-based foam laminate according to any one of (20) to (34) above, wherein the g load) is 0.1 g / 10 min or more. (36) A sliding member comprising the olefin foam laminate according to any one of (1) to (35). (37) A weather strip for an automobile, comprising the olefin foam laminate according to any one of (1) to (35). (38) A building sealing material comprising the olefin foam laminate according to any one of (1) to (35).

Olefinic thermoplastic elastomer (X) The olefinic thermoplastic elastomer (X) used as a raw material for the base material layer in the present invention usually comprises an olefin polymer and has a compression set (7) measured according to JIS K 6262.
0 ° C., 22 hours) is 60% or less, preferably 15 to 55
%, The melt flow rate (230 ° C., 10 kg load) measured by JIS K7120 is 0.1 g / 10 min or more, preferably 1 to 300 g / 10 min.

Olefinic thermoplastic elastomer (X)
The olefin-based polymer that constitutes C is usually 2 to 3 carbon atoms.
It is preferably a homopolymer of 0, preferably 2 to 20 olefins, a copolymer of olefins, or a copolymer of olefins with other monomers, and these can be used in combination of two or more. Examples of the monomer include α-olefin, cyclic olefin, conjugated polyene, non-conjugated polyene and the like. Of these, α-olefins and non-conjugated polyenes are particularly preferable. Other monomers such as vinyl acetate and ethyl acrylate can also be used within the range of 10 mol% or less.

Olefinic thermoplastic elastomer (X)
May be a mixture of two or more olefin polymers. The olefinic thermoplastic elastomer (X) is one or more kinds of olefinic polymers having a low comonomer content,
Mixtures with one or more olefinic polymers having a high comonomer content are particularly preferred. The olefinic thermoplastic elastomer (X) used in the present invention is not particularly limited as long as it is crosslinked or non-crosslinked as long as the compression set and the melt flow rate satisfy the above conditions.

The olefinic thermoplastic elastomer (X) used in the present invention includes 5 to 60 parts by weight of a polyethylene resin (a-1) described later and 40 to 40 parts of an ethylene / α-olefinic copolymer (a-2). 95 parts by weight [where
The total amount of the components (a-1) and (a-2) is 100.
Parts by weight. ] An olefinic thermoplastic elastomer composition comprising 100 parts by weight of an ethylene-based thermoplastic elastomer (A) or olefinic thermoplastic elastomer (J) and 1 to 20 parts by weight of an olefinic thermoplastic (K). (X ₂ ) and the like are preferable.

The olefinic thermoplastic elastomer (X) used in the present invention includes, in addition to the above-mentioned olefin polymer, if necessary, known softening agents, heat stabilizers, antiaging agents, weathering stabilizers, fillers, It may contain a colorant, a lubricant, etc. as long as the total compression set and melt flow rate satisfy the above conditions.

The base layer of the olefin foam laminate of the present invention is a foam (X _F ) obtained by foaming the olefin thermoplastic elastomer (X) with a foaming agent (B). Examples thereof include a foam (X _F1 ) and a foam (X _F2 ) described later.

The skin layer of the olefin foam laminate of the present invention is an ultrahigh molecular weight polyolefin resin (Y) having an intrinsic viscosity [η] of 3.5 to 8.3 dl / g measured in decalin at 135 ° C., or An olefin-based thermoplastic elastomer composition (Z) containing an olefin-based thermoplastic elastomer (C) and a lubricant (Z _L ) will be described in detail later.

[0014] - lubricant (Z _L) lubricants (Z _L) used as a raw material of the skin layer in the present invention may be a known which are formulated in general widely recognized plastic. For example, the ones described in p1037 to p1038 of the Chemical Handbook Applied Edition, Second Edition (edited by The Chemical Society of Japan, 1973, published by Maruzen Co., Ltd.) can be used. Specific examples thereof include organopolysiloxane (D), fluorine-based polymer (E), antistatic agent (F), polyolefin resin (G), fatty acid amide, mineral oil, metal soap, esters, calcium carbonate and silicate. . The lubricant (Z _L ) is at least one selected from the group consisting of fatty acid amide, mineral oil, metal soap, esters, calcium carbonate and silicate, or fatty acid amide, mineral oil, metal soap, ester, calcium carbonate and silicate. At least one selected from the group is preferably used in combination with the polyolefin resin (G). Some of the lubricant (Z _L ) components may be used as a softening agent, but the softener and the lubricant (Z _L ) to be blended with the olefinic thermoplastic elastomer (C) may be used.
The components such as mineral oil to be blended with may be the same or different.

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

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 proportion, or if necessary. Accordingly, it is preferable to be an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing a polypropylene resin (a-3), as described later, in the absence of a crosslinking agent. Further, the ethylene-based thermoplastic elastomer (A) has a compression set (70 ° C., 22 hours) measured by JIS K 6262 of 60% or less, preferably 15 to 55%, and a melt flow rate (230) measured by JIS K 7120. (° C, 10 kg load) is 0.1 g / 10 min or more, preferably 1 to 30
0 g / 10 min, more preferably 1-100 g / 1
A value of 0 min is desirable. Polyethylene resin (a
-1) and an ethylene / α-olefin copolymer (a-
When the content with 2) is in the above range, excellent rubber elasticity is exhibited.

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 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 D-1238, 190).
C., 2.16 kg load) is 0.01 to 100 g / 10
Min, preferably 0.01 to 50 g / 10 min. Ultrahigh molecular weight polyethylene having an MFR of less than 0.1 g / 10 minutes usually has an intrinsic viscosity [η] measured in decalin (decahydronaphthalene) of 135 ° C. of 7 to 7.
40 dl / g, and when such an ultrahigh molecular weight polyethylene is used as the polyethylene resin (a-1), the intrinsic viscosity [η] measured in decalin at 135 ° C. has a low molecular weight of 0.1 to 5 dl / g. To 15 to 40% by weight of high molecular weight polyethylene and an intrinsic viscosity [η] of 7 to 40d
It is preferably used in the form of an ultrahigh molecular weight polyethylene resin composition containing 1 / g of ultrahigh molecular weight polyethylene of 85 to 60% by weight, and the intrinsic viscosity [η] of the entire ultrahigh molecular weight polyethylene resin composition is 3. It is preferably 5 to 8.3 dl / g.

The polyethylene resin (a-1) has a density of 0.
880 to 0.980 g / cm ³ , preferably 0.900
It is desirable to be 0.950 g / cm ³ . When linear low-density polyethylene is used as the polyethylene resin (a-1), MFR (ASTM D-1238, 19
0 ° C, 2.16 kg load) is 0.1 to 30 g / 10 minutes,
Preferably 0.2 to 20 g / 10 minutes, density 0.880
-0.950 g / cm < ³ >, preferably 0.910-0.
It is desirable to use 940 g / cm ³ of linear low density polyethylene.

When a linear low-density polyethylene is used as the polyethylene resin (a-1), compared to a case where high-density polyethylene or medium-density polyethylene is used, roughening of the skin is less likely to occur and the surface of the base layer is less sticky. 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. The other monomer has 3 to 2 carbon atoms.
0, preferably 3 to 8 α-olefins; vinyl monomers such as vinyl acetate and ethyl acrylate. Examples of the α-olefin used as another monomer include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. The other monomers may be used alone or in combination of two or more.

The polyethylene resin (a-1) may 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 ML _{1 + 4.}
(100 ° C) is 90 to 250, preferably 100 to 20
0, more preferably 110 to 180, and the ethylene content is 70 to 95 mol%, preferably 75 to 90 mol%, and more preferably 75 to 85 mol%. Here, ethylene content is the total α
-Refers to the ethylene content relative to olefins (including ethylene).

Ethylene / α-olefin copolymer (a
-2) is ethylene and has 3 to 20 carbon atoms, preferably 3 to 8
The above-mentioned α-olefin may be used as the copolymer, or a monomer other than the α-olefin may be copolymerized. Examples of monomers other than α-olefins include non-conjugated polyenes. In addition, ethylene
The α-olefin copolymer (a-2) may be a random copolymer or a block copolymer.

Ethylene / α-olefin copolymer (a
Specific examples of -2) include ethylene / α-olefin copolymers and ethylene / α-olefin / non-conjugated polyene copolymers. Among these, ethylene / α-olefin / non-conjugated polyene copolymer is preferable. Examples of the α-olefin copolymerized with ethylene in the ethylene / α-olefin copolymer (a-2) include propylene, 1-butene, 1-pentene, and 4
-Methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned. The α-olefin may be used alone or in combination of two or more.

Ethylene / α-olefin copolymer (a
In -2), examples of the non-conjugated polyene copolymerized with ethylene and α-olefin include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene. . The non-conjugated polyene may 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.
It is 1 to 50, preferably 5 to 30. Ethylene / α-
The olefin copolymer (a-2) may be used alone or in combination of two or more.

As the polypropylene resin (a-3), known polypropylene resins can be used without limitation.
Specific examples include the following polypropylene resins and the like. 1) Propylene homopolymer 2) Random copolymer of 90 mol% or more propylene and less than 10 mol% other α-olefin (propylene
α-Olefin random copolymer) 3) A block copolymer (propylene · 70% by mole or more of propylene and less than 30% by mole of other α-olefin)
α-Olefin block copolymer) Specific examples of the other α-olefin copolymerized with propylene include ethylene, 1-butene, and 4-methyl-.
Examples thereof include 1-pentene, 1-hexene, 1-octene, and other α-olefins having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms. Examples of the polypropylene resin (a-3) include the propylene homopolymer of 1) and the propylene homopolymer of 2).
α-olefin random copolymers are preferred, especially MF
R (ASTM D-1238, 230 ° C, 2.16kg
The load) is preferably 0.1 to 50 g / 10 minutes. The polypropylene resin (a-3) may be used alone or in combination of two or more.

The content of the polypropylene resin (a-3) in the ethylene-based thermoplastic elastomer (A) used in the present invention is such that the polyethylene resin (a-1) and the ethylene / α-olefin-based copolymer (a- It is usually 30 parts by weight or less, preferably 2 to 3 with respect to 100 parts by weight in total of 2).
It is desirable that the amount is 0 parts by weight, and more preferably 5 to 20 parts by weight. When the content of the polypropylene resin (a-3) is in the above range, rough skin is less likely to occur and the appearance is excellent,
Moreover, it is possible to obtain a base material layer having less stickiness.

The ethylene-based thermoplastic elastomer (A) used in the present invention is excellent in rubber elasticity without being crosslinked (vulcanized) with a crosslinking agent or a crosslinking aid. Further, the ethylene-based thermoplastic elastomer (A) used in the present invention is not a thermosetting elastic body such as a conventional vulcanized rubber but a thermoplastic elastomer, so that it is easy to recycle. Further, 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 it can be obtained easily and efficiently in one step of dynamically heat-treating, so that it is inexpensive.

In the ethylene-based thermoplastic elastomer (A) used in the present invention, known softening agents, heat stabilizers, antiaging agents, weathering stabilizers may be added, if necessary, within a range not impairing the object of the present invention. Additives such as antistatic agents, fillers, coloring agents and lubricants can be added.

As the softening agent to be blended in the ethylene-based thermoplastic elastomer (A), a mineral oil-based softening agent is preferably used. The softening agent may be previously contained in the ethylene / α-olefin-based copolymer (a-2) as a extending oil. As such a mineral oil-based softening agent, a paraffin-based, naphthene-based, aromatic-based softening agent which is usually used for rubber is suitable.

.Ethylene type thermoplastic elastomer (A)
Production of ethylene-based thermoplastic elastomer (A) used in the present invention
Is preferably the above-mentioned polyethylene resin (a-1), the ethylene / α-olefin copolymer (a-2), and a resin or additive to be blended if necessary, in the absence of a cross-linking agent. It can be manufactured by mixing at a ratio of and heat treatment dynamically.

The above-mentioned "dynamically heat-treating" means melting the polyethylene resin (a-1), the ethylene / α-olefin copolymer (a-2), and the resins and additives to be blended if necessary. Kneading in the (melted) 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 or a twin-screw extruder, but it is performed using a twin-screw extruder. Is preferred. The dynamic heat treatment is preferably performed in a non-open type kneading device. It is also preferable to carry out in an inert gas such as nitrogen.

The condition for the dynamic heat treatment is that the kneading temperature is usually 150 to 280 ° C., preferably 170 to 240 ° C.
The kneading time is usually 1 to 20 minutes, preferably 1 to 5 minutes. The shearing force applied during kneading is usually 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 at a shear rate.
It is desirable to set it to 10 ⁴ sec ⁻¹ . When the dynamic heat treatment is performed using a twin-screw extruder, the following formula (1)
It is preferable to carry out under the conditions that preferably satisfy (1 ′), and more preferably (1 ″).

[0033]

[Equation 1] 4.8 <[(T-130) / 100] + 2.2logP + logQ-logR <7.0 (1) 5.0 <[(T-130) / 100] + 2.2logP + logQ-logR <6.8 ... (1) 1 ') 5.3 <[(T-130) / 100] + 2.2logP + logQ-logR <6.5 ... (1'') (in formulas (1), (1') and (1 ''), T is two The resin temperature (° C) at the die exit of the twin-screw extruder, P is the diameter of the screw of the twin-screw extruder (mm), Q is the maximum shearing speed (sec ^-1 ) received in the twin-screw extruder, and R is the twin-screw extrusion. extrusion rate of the machine is (kg / h). the maximum shear rate Q (sec ^-1)
Is obtained from the equation of Q = (P × π × S) / U. Here, P is the diameter (mm) of the screw of the twin-screw extruder, S is the screw rotation speed (rps) per second, 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 of. )

The ethylene-based thermoplastic elastomer (A) obtained by dynamic heat treatment using a twin-screw extruder in the absence of a cross-linking agent under the conditions satisfying the above formula (1) has tensile strength,
Excellent in permanent elongation, compression set and molding appearance.

In the method for producing the ethylene-based thermoplastic elastomer (A) used in the present invention, a crosslinking agent such as an organic peroxide and a vulcanization aid such as a divinyl compound, which are used in the conventional production of vulcanized rubber, etc. Without using the polyethylene resin (a-1) and the ethylene / α-olefin copolymer (a-2), or the polyethylene resin (a-
1), ethylene / α-olefin copolymer (a-2)
And to easily and efficiently produce an ethylene-based thermoplastic elastomer (A) having excellent rubber elasticity in one step by mixing resins and additives to be blended if necessary at the above-mentioned specific ratios and dynamically treating them. You can Further, since it is not necessary to use a cross-linking agent, a vulcanization aid, etc., and a complicated vulcanization step is not necessary, it is possible to manufacture at low cost.

The base layer of the foamed laminate of the present invention is a foam, and this foam is a foamable ethylene-based thermoplastic elastomer composition containing an ethylene-based thermoplastic elastomer (A) and a foaming agent (B). It can be obtained by foaming (X ₁ ).

Blowing agent (B) Examples of the blowing agent (B) include organic or inorganic thermal decomposition type blowing agents; water; solvents such as hydrocarbon-based and halogenated hydrocarbon-based; nitrogen, carbon dioxide, propane, Examples include butane and other gases. As the foaming agent (B), an organic or inorganic thermal decomposition type foaming agent, water, carbon dioxide and the like are preferable. Specific examples of the inorganic thermal decomposition type foaming agent include sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrite and the like.

Specific examples of the organic thermal decomposition type foaming agent include N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine (DPT) and the like. Nitroso compounds; azodicarbonamide (ADCA), azobisisobutyronitrile (A
ZBN), azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, and other azo compounds; benzenesulfonyl hydrazide (BSH),
Toluenesulfonyl hydrazide (TSH), p, p'-
Oxybis (benzenesulfonyl hydrazide) (OBS
H), sulfonyl hydrazide compounds such as diphenyl sulfone-3,3′-disulfonyl hydrazide; calcium azide, 4,4′-diphenyl disulfonyl azide, p
-Azide compounds such as toluenesulfonyl azide. The foaming agent (B) may be used alone or in combination of two or more.
The foaming agent (B) is an ethylene-based thermoplastic elastomer (A)
It is desirable to use 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight.

If necessary, a foaming aid may be added to the expandable ethylene-based thermoplastic elastomer composition (X ₁ ). As a foaming aid, 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 and its derivatives are used. The foaming aid is usually 0.1 to 20 parts by weight, preferably 1 to 1 with respect to 100 parts by weight of the ethylene-based thermoplastic elastomer (A).
It is desirable to use 0 parts by weight. The foaming auxiliary agent has functions of lowering the decomposition temperature of the foaming agent, promoting decomposition, homogenizing bubbles, and the like. In addition, the expandable ethylene-based thermoplastic elastomer composition (X ₁ ) contains, if necessary, an inorganic porous powder that adsorbs an inorganic gas, such as zeolite or an inorganic gas, for the purpose of uniformly foaming at a high magnification. A resin having a large adsorption amount, for example, a polycarbonate resin, or a nucleating agent at the time of foaming may be blended.

Further, the expandable ethylene-based thermoplastic elastomer composition (X ₁ ) contains, if necessary, a filler, a heat resistance stabilizer, an antiaging agent, a weather resistance stabilizer, an antistatic agent, a wetting agent, a metal soap. Well-known additives such as lubricants such as wax, pigments, dyes, flame retardants, and antiblocking agents can be added within a range that does not impair the object of the present invention.

As the filler to be blended with the ethylene-based thermoplastic elastomer composition (X ₁ ), fillers usually used in rubber are suitable, and specifically, calcium carbonate, calcium silicate, clay, kaolin. , Talc, silica, diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, molybdenum disulfide, glass fiber, glass sphere, shirasu balloon, graphite, alumina and the like.
These fillers are preferably used 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 expandable ethylene-based thermoplastic elastomer composition (X ₁ ) The expandable ethylene-based thermoplastic elastomer composition (X ₁ ) comprises an ethylene-based thermoplastic elastomer (A) and a foaming agent (B). , And a blending agent such as a foaming aid and a wetting agent, which are blended as necessary. As a method of blending the ethylene-based thermoplastic elastomer (A) and the foaming agent (B), for example, the pellets of the ethylene-based thermoplastic elastomer (A) and the foaming agent (B) are once added to a tumbler type Brabender,
After kneading with a V-type Brabender, ribbon blender, Henschel mixer, etc., if necessary, kneading with an open mixing roll or a non-open Banbury mixer, extruder, kneader, continuous mixer, etc. can be used. . The weather resistance stabilizer, heat resistance stabilizer, antioxidant, pigment, dye and the like may be added at any stage of the above process.

To obtain the foam (X _F1 ) of the expandable ethylene-based thermoplastic elastomer composition (X ₁ ), for example, the expandable ethylene-based thermoplastic elastomer composition (X 1
There is a method of heating ₁ ).

In the present invention, an ultrahigh molecular weight polyolefin resin (Y) or an olefinic thermoplastic elastomer composition (Z) is used as a raw material for the skin layer.
At least one selected from the olefinic raw materials of 7) is preferable, and the olefinic thermoplastic elastomer composition (Z ₁ ) of 3) or the olefinic thermoplastic elastomer composition (Z ₂ ) of ₄ ) is particularly preferable. Can be used.

1) The above ultrahigh molecular weight polyolefin resin (Y) which is an ultrahigh molecular weight polyolefin resin having an intrinsic viscosity [η] measured in decalin at 135 ° C. of 3.5 to 8.3 dl / g 2) Olefin-based thermoplastic resin Organopolysiloxane (D) 0.5 to 100 parts by weight of elastomer (C)
25 parts by weight, fluoropolymer (E) 0.5 to 10 parts by weight, antistatic agent (F) 0.5 to 10 parts by weight, polyolefin resin (G) 5 to 200 parts by weight, fatty acid amide 0.0
1-5 parts by weight, mineral oil 0.5-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5 parts by weight,
Olefin-based thermoplastic elastomer composition (Z) 3) containing at least one lubricant (Z _L ) selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate in the above proportion. 0.01 to 5 parts by weight of fatty acid amide, 0.5 to 10 parts by weight of mineral oil, 0.01 to 5 parts by weight of metal soap, 0.01 to 0.01 parts of ester based on 100 parts by weight of the olefinic thermoplastic elastomer (C). 5 parts by weight, 0.01 to 5 parts by weight of calcium carbonate, and 0.01 to 5 parts by weight of silicate 0.01 to 5 parts by weight of at least one lubricant (Z _L ) selected from the group in the above proportion, an olefinic thermoplastic elastomer composition ( Z ₁ ) 4) Fatty acid amide 0.0 as a lubricant (Z _L ) based on 100 parts by weight of the olefinic thermoplastic elastomer (C)
1-5 parts by weight, mineral oil 0.5-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5 parts by weight,
Olefinic thermoplastic elastomer containing at least one selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate, and 5 to 200 parts by weight of a polyolefin resin (G) in the above ratio. the composition (Z ₂₎ 5) an olefin-based thermoplastic elastomer (C) 100 parts by weight of organopolysiloxane (D) 0.5 to
25 parts by weight, at least one lubricant (Z _L ) selected from the group consisting of 0.5 to 10 parts by weight of the fluoropolymer (E) and 0.5 to 10 parts by weight of the antistatic agent (F) in the above proportion. Olefinic thermoplastic elastomer composition containing (Z
₃ ) 6) An olefinic thermoplastic elastomer composition (Z ₄ ) containing the polyolefin resin (G) as a lubricant (Z _L ) in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the olefinic thermoplastic elastomer (C). 7) 0.5 to 25 parts by weight of an organopolysiloxane (D) as a lubricant (Z _L ) and 0.5 to 10 parts by weight of a fluoropolymer (E) with respect to 100 parts by weight of an olefinic thermoplastic elastomer (C). Parts, antistatic agent (F) 0.5 to
10 parts by weight, fatty acid amide 0.01 to 5 parts by weight, mineral oil 0.5 to 10 parts by weight, metal soap 0.01 to 5 parts by weight, esters 0.01 to 5 parts by weight, calcium carbonate 0.01 to 5 parts Parts by weight and at least one selected from the group consisting of 0.01 to 5 parts by weight of silicate and 5 to 200 parts by weight of a polyolefin resin (G) in the above proportions, an olefinic thermoplastic elastomer composition (Z ₅ ).

Ultra-high molecular weight polyolefin resin (Y) The ultra-high molecular weight polyolefin resin (Y) used as a raw material for the skin layer in the present invention has an intrinsic viscosity [η] of 3.5-8. It is an ultra high molecular weight polyolefin resin in the range of 3 dl / g, preferably 3.8 to 8.0 dl / g. The ultra-high 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,
A resin composition having an intrinsic viscosity [η] within the above range can be used.

When the ultra high molecular weight polyolefin resin (Y) is a resin composition, the ultra high 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 an ultrahigh molecular weight polyolefin resin (more preferably y-1) 15 to 40 parts by weight, polyolefin resin (y-2) 60 to 85 parts by weight, particularly preferably ultra-high molecular weight polyolefin resin (y-1) 18 to 3
It is an ultrahigh molecular weight polyolefin resin composition containing 5 parts by weight and 65 to 82 parts by weight of the polyolefin resin (y-2) (here, the total of both is 100 parts by weight).

The above ultra high molecular weight polyolefin resin (y
-1) and the polyolefin resin (y-2),
For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3-methyl-1-.
Examples include α-olefin homopolymers or copolymers such as pentene. As the ultrahigh molecular weight polyolefin resin (y-1) and the polyolefin resin (y-2), ethylene homopolymers and ethylene-based copolymers containing ethylene as a main component are preferable. The ultrahigh molecular weight polyolefin resin (Y) may contain a liquid or solid softening agent (lubricating oil).

As the liquid softening agent to be added to the ultra high molecular weight polyolefin resin (Y), mineral oil type softening agents, synthetic softening agents and the like are used. Specific examples of the mineral oil-based softening agent include petroleum-based lubricating oils such as paraffin-based and naphthene-based, liquid paraffin, spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, and cylinder oil. Specific examples of the synthetic softening agent include synthetic hydrocarbon oils, polyglycol oils, polyphenyl ether oils, ester oils,
Examples thereof include phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil, chlorinated biphenyl oil, silicone oil and the like.

As the solid softening agent, specifically, graphite and molybdenum disulfide are mainly used, but in addition, boron nitride, tungsten disulfide, lead oxide, glass powder,
Metal soap can be used.

The softening agents may be used alone or in combination of two or more. Further, a liquid softener and a solid softener may be used in combination, and for example, they may be blended in the form of powder, sol, gel or suspenseoid. It is desirable that the content of the softening agent is 1 to 20 parts by weight, preferably 3 to 15 parts by weight with respect to 100 parts by weight of the ultrahigh molecular weight polyolefin resin (Y). In addition, the ultra-high molecular weight polyolefin resin (Y) may include a heat resistance stabilizer, an antistatic agent, and
Additives such as a weather resistance stabilizer, an antiaging agent, a filler, a colorant, and a lubricant can be added within a range that does not impair the object of the present invention.

In the present invention, the olefinic thermoplastic elastomer composition (Z) can be used as the skin layer. The olefinic thermoplastic elastomer composition (Z) is the olefinic thermoplastic elastomer composition. (Z ₁ ) to (Z ₅ ) are preferable, and the olefinic thermoplastic elastomer composition (Z ₁ ) or (Z ₂ ) is particularly preferable.

Olefinic thermoplastic elastomer composition (Z ₁ ) to (Z ₅ ) Olefinic thermoplastic elastomer (C) The olefinic thermoplastic elastomer (C) used as a raw material for the skin layer in the present invention is a crystal. An olefin-based thermoplastic elastomer composed of a transparent polyolefin resin (c-1) and a rubber (c-2) can be used. The crystalline polyolefin resin (c-1) has 2 to 2 carbon atoms.
Examples of the homopolymers or copolymers of α-olefin of 0. Specific examples of the crystalline polyolefin resin (c-1) include the following.

(1) Ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method) (2) Ethylene and 10 mol% or less, preferably less than 10 mol% of other α-olefin or vinyl acetate , A copolymer with a vinyl monomer such as ethyl acrylate (3) a propylene homopolymer (4) a random copolymer of propylene and 10 mol% or less, preferably less than 10 mol% of other α-olefin (5) Block copolymer (6) 1-butene homopolymer (7) 1-butene with propylene and 30 mol% or less of other α-olefin, and 10 mol% or less, preferably less than 10 mol% of other α-. Random copolymer with olefin (8) 4-methyl-1-pentene homopolymer (9) 4-methyl-1-pentene and 20 mol% or less, preferably less than 20 mol% of other α-o. The random copolymers above α- olefin with fins, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.

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. For example, propylene / ethylene copolymer, propylene. Examples include 1-butene copolymer, propylene / 1-hexene copolymer, propylene-4-methyl-1-pentene copolymer and the like. MFR of crystalline polyolefin resin (c-1) (ASTM D-1238, 230
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 preferable. The olefin-based copolymer rubber used as the rubber (c-2) is an amorphous random elastic copolymer mainly composed of an α-olefin having 2 to 20 carbon atoms, and includes two or more α-olefins. And an α-olefin / non-conjugated polyene copolymer composed of two or more kinds of α-olefins and a non-conjugated diene.

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

Specific examples of the α-olefin include the same α-olefins as the specific examples of the α-olefin constituting the crystalline polyolefin (c-1). Specific examples of the non-conjugated polyene include non-conjugated dienes such as 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 kinds.

Specific examples of the rubber (c-2) include ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated polyene copolymer rubber, ethylene / 1-butene copolymer rubber, and ethylene / 1-. Butene / non-conjugated polyene copolymer rubber is preferred, especially ethylene / propylene /
A non-conjugated polyene copolymer rubber, particularly an ethylene / propylene / ethylidene norbornene copolymer rubber or an ethylene / propylene / dicyclopentadiene copolymer rubber is particularly preferable. The Mooney viscosity ML _{1 + 4} (100 ° C.) of these copolymer rubbers is 10 to 250, preferably 4
0-150 is desirable. The iodine value when the non-conjugated polyene is copolymerized 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 olefinic thermoplastic elastomer (C) used in the present invention, the weight compounding ratio (crystalline polyolefin resin / rubber) of the crystalline polyolefin resin (c-1) and the rubber (c-2) is usually 90. / 10 to 5/9
The range of 5, preferably 70/30 to 10/90 is desirable. When a combination of an olefin-based copolymer rubber and another rubber is used as the rubber (c-2),
It is desirable to add the other rubber 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 amount of the crystalline polyolefin resin (c-1) and the rubber (c-2). .

Olefinic thermoplastic elastomer (C)
If necessary, additives such as a softening agent, a heat resistance stabilizer, a weather resistance stabilizer, an antiaging agent, a filler, and a colorant can be added within a range that does not impair the object of the present invention. As the softening agent, a softening agent usually used for rubber can be used, but a mineral oil-based softening agent and a synthetic softening agent are preferable.

Olefinic thermoplastic elastomer (C)
As the mineral oil-based softening agent to be blended with, paraffin-based, naphthene-based, aromatic-based petroleum-based lubricating oils, liquid paraffin, etc., and as the synthetic softening agent, polyethylene wax, polypropylene wax, petroleum asphalt, vaseline, etc. can give. Furthermore, as other softening agents,
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, carnauba wax, lanolin and other waxes; ricinoleic acid, palmitic acid , Stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid, erucic acid and other fatty acids or metal salts thereof; petroleum resins, coumarone indene resins, synthetic polymers such as atactic polypropylene; dioctyl phthalate, dioctyl adipate, Other examples include ester plasticizers such as dioctyl sebacate; microcrystalline wax, liquid polybutadiene or its modified products or hydrogenated products, and liquid thiochol.

These softening agents 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, based on 100 parts by weight of the olefinic thermoplastic elastomer (C). Is desirable. These softening agents may be added at the time of producing the olefinic thermoplastic elastomer (C), or may be added in advance to the rubber (c-2) as an extending oil.

The olefinic thermoplastic elastomer (C) used in the present invention is the above-mentioned crystalline polyolefin resin (c
It is obtained by dynamically heat-treating a mixture of -1), rubber (c-2) and, if necessary, a softening agent and the like. Further, the rubber (c-2) can exist in all crosslinked states such as uncrosslinked, partially crosslinked or completely crosslinked in the olefinic thermoplastic elastomer (C).

In order to produce the olefinic thermoplastic elastomer (C) thus crosslinked, the crystalline polyolefin resin (c-1) and the rubber (c-2), and a softening agent used as necessary It is preferred to heat-treat the mixture of (1) dynamically in the presence of a crosslinking agent.

Examples of the cross-linking agent that can be used during the dynamic heat treatment include organic peroxides, sulfur, phenol resins, amino resins, quinones and their derivatives, amine compounds, azo compounds, epoxy compounds and isocyanates. Other examples include crosslinking agents commonly used in thermosetting rubbers. Of these, organic peroxides are particularly preferable. Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy).
Hexane, 2,5-dimethyl-2,5-di- (tert
-Butylperoxy) hexyne-3,1,3-bis (t
ert-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, t
Examples thereof include ert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

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 among them, 1,3-bis (t
Most preferred is ert-butylperoxyisopropyl) benzene. In the present invention, the organic peroxide is 0.05 to 3 parts by weight, preferably 0.1 to 100 parts by weight of the total amount of the crystalline polyolefin resin (c-1) and the rubber (c-2). It is used in a proportion of 1 part 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-phenylenediene Peroxy crosslinking aids such as maleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyfunctional methacrylate monomers such as allyl methacrylate, A polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be added.

By using the above compounds,
A uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is most preferred in the present invention. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin resin (c-1) and rubber (c-2) which are the main components of the above-mentioned substance to be crosslinked, and solubilizes the organic peroxide. Since it has a function of acting as a dispersant for the organic peroxide, a cross-linking effect by heat treatment is uniform, and an olefinic thermoplastic elastomer (C) having a good balance of fluidity and physical properties can be obtained.

The above-mentioned crosslinking aid or polyfunctional vinyl monomer is used in an amount of 0.1% with respect to the whole article to be crosslinked.
It is desirable to use it in an amount of 3 to 3% by weight, preferably 0.3 to 2% by weight. When the mixing ratio of the cross-linking aid or the polyfunctional vinyl monomer is within the above range, the thermoplastic elastomer obtained does not have the cross-linking aid and the polyfunctional vinyl monomer remaining in the elastomer as an unreacted monomer. The physical properties do not change due to heat history during molding, and the fluidity is excellent.

The above-mentioned "dynamically heat treating" means kneading each of the above components 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 during the dynamic heat treatment is usually 1
50 to 280 ° C, preferably 170 to 240 ° C,
The kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. The shearing force applied is 100 sec ⁻¹ or more, preferably 500 to 10,000 as a shear rate.
It is desirable to set it to sec ^-1 .

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

[Measurement method of gel content] About 100 mg of a sample of a thermoplastic elastomer was weighed and measured to have a size of 0.5 mm × 0.5 m.
It is cut into m × 0.5 mm strips, and the strips obtained are then added to 30 ml of cyclohexane in a closed container at 23 ° C.
Soak for 48 hours. Next, this 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 component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the dry residue is defined 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, the softening agent) and the weight of the cyclohexane insoluble component other than the polymer component (fibrous filler, filler, pigment, etc.) from the weight of the sample is “corrected. Initial weight (X) ”.

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

As the olefinic thermoplastic elastomer (C) used in the skin layer of the present invention, the ethylene thermoplastic elastomer (A) may be used. Since the olefinic thermoplastic elastomer (C) constituting the skin layer of the olefinic foam laminate of the present invention comprises the crystalline polyolefin resin (c-1) and the rubber (c-2),
Excellent fluidity. The above-mentioned thermoplastic polyolefin-based elastomer (C) 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 the lubricant (Z _L ), known organopolysiloxanes 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 abrasion resistance can be obtained.

As the organopolysiloxane (D),
Specifically, dimethylpolysiloxane, methylphenylpolysiloxane, fluoropolysiloxane, tetramethyltetraphenylpolysiloxane, methylhydrogenpolysiloxane, epoxy modified, alkyl modified,
Examples include modified polysiloxanes such as amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkylpolyether-modified, epoxypolyether-modified and the like. Of these, dimethylpolysiloxane is preferred. The organopolysiloxane (D) may 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 cS.
Those of t are preferable. Among these, the viscosity [JI
SK2283, 25 ° C.] is 10 ⁶ cSt or more, the viscosity is very high. Therefore, in order to improve the dispersibility in the olefinic thermoplastic elastomer (C), even if it is a master batch with an olefinic resin. Good. As the olefin resin used in this case, the crystalline polyolefin resin (c-1) used when producing the olefin thermoplastic elastomer (C), specifically, ethylene homopolymer, ethylene and other α -Copolymers with olefins, propylene homopolymers, copolymers with propylene and other α-olefins, and the like.

The organopolysiloxane (D) may be used alone or in combination of two or more depending on its viscosity. Especially 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 high viscosity organopolysiloxanes of cSt.

In the olefinic thermoplastic elastomer composition (Z), the content of the organopolysiloxane (D) is such that the olefinic thermoplastic elastomer (C) 10
0.5 to 20 parts by weight, preferably 1 to 0 parts by weight
18 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 sticky surface.

Fluorine-based polymer (E) As the fluorine-based polymer (E) used as the lubricant (Z _L ), known fluorine-based polymers containing a fluorine atom can be used without limitation. By blending the fluoropolymer (E), a skin layer having excellent slidability and abrasion 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,
Examples thereof include tetrafluoroethylene / ethylene copolymer, vinylidene fluoride polymer, vinyl fluoride polymer and the like. The fluoropolymer (E) may be used alone or in combination of two or more.

The fluoropolymer (E) is previously known as an olefin resin and / or a known one in order to enhance the dispersibility with the olefin thermoplastic elastomer (C) or to further enhance the effect of improving the sliding wear resistance. It may be a masterbatch with the inorganic filler.
The olefin resin used here is the same as the olefin resin used in the masterbatch of the organopolysiloxane (D). Examples of the inorganic filler include calcium carbonate, titanium oxide, talc, clay and the like.

In the olefinic thermoplastic elastomer composition (Z), the content of the fluoropolymer (E) is 0.5 to 10 parts by weight, preferably 100 parts by weight of the olefinic thermoplastic elastomer (C). 1 to 8 parts by weight. When the content of the fluoropolymer (E) is within the above range, the foamed laminate has excellent slidability.

Antistatic Agent (F) As the antistatic agent (F) used as the lubricant (Z _L ), known antistatic agents generally used for resins can be used without limitation, and anionic activators and cationic activators can be used. Agents, nonionic activators, amphoteric activators and the like. 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 and N, N-bis (2-
Hydroxyethyl) stearylamine, stearyl monoglyceride, distearyl glyceride, tristearyl glyceride, polyoxyethylene lauryl amine capryl ester, stearyl diethanolamine monostearate and the like. Antistatic agent (F) is 1
The seeds may be used alone or in combination of two or more.

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

In the olefinic thermoplastic elastomer composition (Z), the content of the antistatic agent (F) is 0.5 to 10 parts by weight, preferably 100 parts by weight of the olefinic thermoplastic elastomer (C). 1 to 8 parts by weight. When the content of the antistatic agent (F) is within the above range, the foamed laminate has excellent slidability, and the antistatic agent (F)
There is no problem such as bleeding out by depositing on the surface.

Polyolefin resin (G) As the polyolefin resin (G) used as the lubricant (Z _L ), the above-mentioned olefinic thermoplastic elastomer (C) is used.
The crystalline polyolefin resin (c-1) used in 1. is preferable. Further, the polyolefin resin (G) used in the present invention may be the above-mentioned ultra high molecular weight polyolefin resin (Y).

In the olefinic thermoplastic elastomer composition (Z), the blending amount of the polyolefin resin (G) is 5 to 200 parts by weight, preferably 10 to 180 parts by weight, relative to 100 parts by weight of the olefinic thermoplastic elastomer (C).
Parts by weight. When the polyolefin resin (G) is in the above range, a skin layer having good moldability and molding appearance and excellent slidability and wear resistance can be obtained.

Specific examples of the fatty acid amide used as the lubricant (Z _L ) include stearamide, oxystearoamide, oleylamide, erucylamide, laurylamide, palmitylamide and behenamide, and the like fatty acid monoamide type; methylol. Amide, methylene bis stearamide, ethylene bis stearamide,
Amide type of higher fatty acid such as ethylene bis oleyl amide and ethylene bis lauryl amide; complex type amide such as stearyl oleyl amide, N-stearyl erucamide and N-oleyl palmitoamide; trade name of plastrosine and plastrosine S (Fujisawa Examples include special fatty acid amides marketed as Yakuhin Kogyo Co., Ltd. These may be used alone or as a mixture of two or more. The amount of the fatty acid amide compounded is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer (C). Within this range, the slidability, wear resistance and molding workability are excellent.

The esters used as the lubricant (Z _L ) are esters of aliphatic alcohol and dicarboxylic acid or fatty acid. As such ester, specifically, an ester of cetyl alcohol and acetic acid, an ester of cetyl alcohol and propionic acid, an ester of cetyl alcohol and butyric acid, an ester of beef tallow alcohol and acetic acid, beef tallow alcohol and propionic acid. Ester of beef tallow alcohol and butyric acid, ester of stearyl alcohol and acetic acid, ester of stearyl alcohol and propionic acid, ester of stearyl alcohol and butyric acid, ester of distearyl alcohol and phthalic acid, glycerin monooleate, Glycerin monostearate, 12-hydroxy stearate, glycerine tristearate, trimethylolpropane tristearate, pentaerythritol tetrastearate, butyl stearate, isobutyl stearate Stearate, oleate, behenate, calcium soap-containing ester, isotridecyl stearate, cetyl palmitate, cetyl stearate, stearyl stearate, behenyl behenate, montanic acid ethylene glycol ester, montanic acid glycerin Ester, montanic acid pentaerythritol ester,
Examples thereof include calcium-containing montanic acid ester.
Among these, esters of distearyl alcohol and phthalic acid, glycerin monooleate, glycerin monostearate, stearic acid ester, glyceryl montanate ester is preferable, particularly ester of distearyl alcohol and phthalic acid, glycerin monostearate, Glycerin montanate ester is preferred. The amount of the ester compounded is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer (C). Within this range, the slidability, wear resistance and molding workability are excellent.

The silicate used as the lubricant (Z _L ) is represented by the formula M ₂ O.mSiO ₂ .nH ₂ O (wherein M is an alkali metal atom, and m and n are SiO ₂ per mol of M ₂ O, respectively). ₂ or the number of moles of H ₂ O) is exemplified, and specific examples thereof include sodium silicate, potassium silicate, lithium silicate and the like. The amount of the silicate compounded is 0.01 to 5 parts by weight, preferably 0.05, relative to 100 parts by weight of the olefinic thermoplastic elastomer (C).
It is desirable that the amount is 3 parts by weight. Within this range, the slidability, wear resistance and molding workability are excellent.

In the olefinic thermoplastic elastomer composition, organopolysiloxane (D), fluoropolymer (E), antistatic agent (F), polyolefin resin (G), fatty acid amide, mineral oil, metal soap, esters The calcium carbonate and silicate may be used alone or in combination of two or more, and the combination is arbitrary. At least one selected from the group consisting of organopolysiloxane (D), fluoropolymer (E), antistatic agent (F), fatty acid amide, mineral oil, metal soap, esters, calcium carbonate and silicate, and a polyolefin resin It can be used in combination with (G). Of these, fatty acid amides, mineral oil, metal soaps, esters,
At least one selected from the group consisting of calcium carbonate and silicate is preferably used in combination with the polyolefin resin (G). The content of each component in such an olefinic thermoplastic elastomer composition (Z ₂ ) is as described above.

The olefin-based thermoplastic elastomer composition (Z) and the olefin-based thermoplastic elastomer compositions (Z ₁ ) to (Z ₅ ) may, if necessary, contain a mineral oil-based softening agent, a heat stabilizer, and a weather resistance. Stabilizer, anti-aging agent, filler,
Additives such as colorants can be added within a range that does not impair the object of the present invention.

The olefinic thermoplastic elastomer composition (Z) and the olefinic thermoplastic elastomer compositions (Z ₁ ) to (Z ₅ ) can be produced by a known method,
For example, olefin-based thermoplastic elastomer (C), fatty acid amide 0.01 to 5 parts by weight, mineral oil 0.5 to 10 parts by weight, metal soap 0.01 to 5 parts by weight, esters 0.
At least one selected from the group consisting of 01 to 5 parts by weight, 0.01 to 5 parts by weight of calcium carbonate, and 0.01 to 5 parts by weight of silicate, a polyolefin resin (G) and other additives added as necessary. It can be obtained by kneading the additives.

In the present invention, the foam (X
A foam of an olefinic thermoplastic elastomer composition (X ₂ ) containing 100 parts by weight of an olefinic thermoplastic elastomer (J) instead of _F1 ) and 1 to 20 parts by weight of an olefinic thermoplastic (K) ( X _F2 ) can also be used.

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

The olefinic thermoplastic elastomer (J) used in the present invention is a mixture containing the polyolefin resin (j-1) and the ethylene / α-olefinic copolymer rubber (j-2) in the above proportion, or is required. Depending on the softening agent (j
As described below, it is preferable that the olefin-based thermoplastic elastomer is obtained by dynamically heat-treating a mixture containing -3) and the like in the presence of a crosslinking agent. The olefinic thermoplastic elastomer (J) has a compression set (70 ° C., 22 hours) measured by JIS K 6262 of 60% or less, preferably 15 to 55%, and a melt flow rate (230) measured by JIS K 7120. (° C, 10 kg load) is 0.1 g / 10 min or more, preferably 1 to 30
It is preferably 0 g / 10 min. When the content of the polyolefin resin (j-1) and the ethylene / α-olefin copolymer rubber (j-2) is within the above range, a foam (X _F2 ) having excellent flexibility can be obtained. Also, an olefinic thermoplastic elastomer composition (X ₂ ) having good fluidity can be obtained.

The polyolefin resin (j-
1) is a resin composed of a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by a high pressure method or a low pressure method. Examples of such a resin include isotactic and syndiotactic monoolefin polymer or copolymer resins. These representative resins are commercially available.

Specific examples of suitable raw material olefins for the above polyolefin resin (j-1) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1
-Octene, 1-decene, 2-methyl-1-propene,
Examples thereof include 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 may be used alone or in combination of two or more.

As the polyolefin resin (j-1), a propylene homopolymer or a copolymer containing propylene as a main component with another olefin is preferable. 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.

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

The ethylene / α-olefin copolymer rubber (j-2) used in the present invention is an ethylene / α-olefin copolymer rubber and / or an ethylene / α-olefin / non-conjugated polyene copolymer rubber. And 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-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like having 3 to 10 carbon atoms.
There are 20 α-olefins. These olefins may be used alone or in combination of two or more. As the non-conjugated polyene, specifically, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene,
Examples thereof include methylene norbornene, ethylidene norbornene, vinyl norbornene and the like.

As the ethylene / α-olefin copolymer rubber (j-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 and the like are preferable. Particularly preferred is an ethylene / propylene / non-conjugated polyene copolymer rubber, especially an ethylene / propylene / ethylidene norbornene copolymer rubber or an ethylene / propylene / dicyclopentadiene copolymer rubber, which has an appropriate cross-linking structure. It is particularly preferable in that a plastic elastomer (J) can be obtained.

The ethylene / α-olefin copolymer rubber (j-2) used in the present invention has an ethylene content of 55 to 55.
It is desirable to be 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-based copolymer rubber (j-2) is in the range of 10 to 250, preferably 30 to 160.

The iodine value of the ethylene / α-olefin copolymer rubber (j-2) is 25 or less, preferably 5 or less.
It is desirable that it is ˜25. When the iodine value of the ethylene / α-olefin copolymer rubber (j-2) is 25 or less, the olefin thermoplastic elastomer (J) having an appropriate crosslinked structure can be obtained.

The ethylene / α-olefin copolymer rubber (j-2) may be used alone or in combination of two or more kinds. In the present invention, as long as the object of the present invention is not impaired, ethylene
The α-olefin-based copolymer rubber (j-2) and a rubber other than the ethylene / α-olefin-based copolymer rubber (j-2) can be used in combination.

Examples of rubbers other than the ethylene / α-olefin copolymer rubber (j-2) include, for example, propylene / α-olefin copolymer rubber (propylene / α).
-Olefin (molar ratio) = 90/10 to 50/50),
Butene / α-olefin copolymer rubber (butene / α-olefin (molar ratio) = 90/10 to 50/50), butyl rubber, polyisobutylene rubber, styrene / butadiene rubber (SBR), and hydrogenated products thereof (H -SB
R), styrene / butadiene block copolymer rubber (S
BS) and its hydrogenated products (SEBS), styrene
Examples thereof include isoprene block copolymer rubber (SIS) and hydrogenated products thereof (SEPS, HV-SIS), nitrile rubber (NBR), natural rubber (NR), silicone rubber and the like. When a rubber other than the ethylene / α-olefin copolymer rubber (j-2) is used in combination with the ethylene / α-olefin copolymer rubber (j-2), an ethylene / α-olefin rubber is used. Copolymer rubber (j-
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 amount of the ethylene / α-olefin copolymer rubber (j-2) and the polyolefin resin (j-1). It is desirable to use 40 parts by weight.

Olefin-based thermoplastic elastomer (J)
A softening agent (j-3) can be blended with. As the softening agent (j-3), a softening agent usually used for rubber can be used, but among them, a mineral oil softening agent and a synthetic softening agent are preferable. As such a mineral oil softener,
Examples thereof include petroleum-based lubricating oils such as paraffin-based, naphthene-based, and aromatic-based oils, liquid paraffin, and the like. As a synthetic softening agent, polyethylene wax, polypropylene wax,
Examples include petroleum asphalt and vaseline.

Further, as other softening agents, 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 resins, coumarone indene resins, atactic polypropylene; ester-based plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate; other microcrystalline wax, liquid polybutadiene Alternatively, modified products thereof, hydrogenated products, liquid thiochol, etc. may be mentioned.

The softening agent (j-3) was used in an amount of 5 parts by weight per 100 parts by weight of the ethylene / α-olefin copolymer rubber (j-2).
˜200 parts by weight, preferably 15 to 150 parts by weight, more preferably 20 to 80 parts by weight. When the softening agent (j-3) is used in such a ratio,
The fluidity of the olefinic thermoplastic elastomer composition (X ₂ ) can be sufficiently improved without lowering the physical properties such as heat resistance and tensile properties of the foam (X _F2 ).

The softening agent (j-3) may be added at the time of producing the olefinic thermoplastic elastomer (J), or may be previously added as an extending oil with an ethylene / α-olefinic copolymer rubber (j-2). It may be added to. The olefin-based thermoplastic elastomer (J) used in the present invention is a thermoplastic elastomer, not a thermosetting elastic body such as conventional vulcanized rubber, and is therefore easy to recycle.

The olefinic thermoplastic elastomer (J) used in the present invention contains, if necessary, known heat stabilizers, antiaging agents, weathering stabilizers, antistatic agents, as long as the object of the present invention is not impaired. Additives such as fillers, colorants and lubricants can be added.

Manufacture of olefinic thermoplastic elastomer (J) The olefinic thermoplastic elastomer (J) used in the present invention is the above-mentioned polyolefin resin (j-1) and ethylene / α-olefinic copolymer rubber (j- It is obtained by dynamically heat-treating a mixture of 2) and a softening agent (j-3) or the like used as necessary.

Olefin-based thermoplastic elastomer (J)
Is a polyolefin resin (j-1) and ethylene / α
-Olefin-based copolymer rubber (j-2), and those obtained by dynamically heat-treating a mixture of an optional softening agent and the like in the presence of a crosslinking agent are preferable. Examples of the cross-linking agent that can be used during the dynamic heat treatment include organic peroxides, sulfur, phenolic resins, amino resins, quinones and their derivatives, amine compounds, azo compounds, epoxy compounds, isocyanates, and the like. The cross-linking agent generally used in the curable rubber is mentioned. Of these, organic peroxides are particularly preferable.

Specific examples of the organic peroxide include:
Dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5
-Di- (tert-butylperoxy) hexyne-3,
1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-
Butyl-4,4-bis (tert-butylperoxy)
Valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate,
Examples thereof include tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide and tert-butyl cumyl peroxide.

Of 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 among them, 1,3-bis (t
Most preferred is ert-butylperoxyisopropyl) benzene. In the present invention, the organic peroxide is 100 parts by weight of a mixture of a polyolefin resin (j-1) and an ethylene / α-olefin copolymer rubber (j-2), and optionally a softening agent. For 0.
It is used in a proportion of 05 to 3 parts by weight, preferably 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-phenylenediene Peroxy crosslinking aids such as maleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyfunctional methacrylate monomers such as allyl methacrylate, A polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be added.

By using the above compound,
A uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is most preferred in the present invention. Divinylbenzene is easy to handle, and the polyolefin resin (j-1) and ethylene.
-Has good compatibility with the olefin-based copolymer rubber (j-2) and has an action of solubilizing the organic peroxide,
Since it acts as a dispersant for the organic peroxide, an olefinic thermoplastic elastomer (J) having a uniform cross-linking effect by heat treatment and a good balance of fluidity and physical properties can be obtained.

The above-mentioned crosslinking aid or polyfunctional vinyl monomer is used in an amount of 0.1 to 0.1% with respect to the whole article to be crosslinked.
It is desirable to use it in an amount of 3 to 3% by weight, preferably 0.3 to 2% by weight. When the mixing ratio of the cross-linking aid or the polyfunctional vinyl monomer is within the above range, the thermoplastic elastomer obtained does not have the cross-linking aid and the polyfunctional vinyl monomer remaining in the elastomer as an unreacted monomer. The physical properties do not change due to heat history during molding, and the fluidity is excellent.

The above-mentioned "dynamically heat-treating" means kneading the above-mentioned components 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 during the dynamic heat treatment is usually 1
50 to 280 ° C, preferably 170 to 240 ° C,
It is desirable that the kneading time is 1 to 20 minutes, preferably 1 to 5 minutes. The shear force applied is 1 as the shear rate.
0 to 1000 sec ^-1 , preferably 100 to 1000 s
It is desirable to set it as ec ^-1 .

The olefinic thermoplastic elastomer (J) preferably used in the present invention has a gel content calculated by the following of 10% by weight or more, preferably 20% by weight or more, and particularly preferably 45% by weight or more. desirable. When the gel content is 10% by weight or more, the rubber-like properties such as heat resistance, tensile strength, flexibility, weather resistance, and impact resilience are excellent, and the foam (X _F2 ) is more suitable for recycling than vulcanized rubber. Is obtained.

[Measurement method of gel content] About 100 mg of a sample of a thermoplastic elastomer was weighed and measured to have a size of 0.5 mm × 0.5 m.
It is cut into m × 0.5 mm strips, and the strips obtained are then added to 30 ml of cyclohexane in a closed container at 23 ° C.
Soak for 48 hours. Next, this 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 component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the dry residue is defined 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, the softening agent) and the weight of the cyclohexane insoluble component other than the polymer component (fibrous filler, filler, pigment, etc.) from the weight of the sample is “corrected. Initial weight (X) ”.

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

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

Olefin-based thermoplastic (K)
Has an MFR of 0.01 to 2 g / 10 minutes, the melt tension of the obtained olefinic thermoplastic elastomer composition (X ₂ ) can be improved, and a foam (X _F2 ) having a high expansion ratio is obtained. be able to. The olefinic thermoplastics (K) may be used alone or in combination of two or more.

Olefin-based thermoplastic (K)
Is the olefinic thermoplastic elastomer (J) 10
1 to 20 parts by weight, preferably 1 to 10 parts by weight, relative to 0 parts by weight
Used in proportions by weight. When the olefinic thermoplastic resin (K) is used in the above proportion, a foam (X _F2 ) having excellent flexibility and a high expansion ratio can be obtained.

In the present invention, the olefinic thermoplastic (K) is used in combination with the olefinic thermoplastic elastomer (J) prepared by dynamic heat treatment, and the olefinic thermoplastic (K) itself is dynamic. The feature is that it is not subjected to heat treatment. When preparing the olefin-based thermoplastic elastomer (J), the olefin-based thermoplastic (K) was added together with the polyolefin resin (j-1) and the ethylene / α-olefin-based copolymer rubber (j-2). , When mixed with an organic peroxide and kneaded under heating, the olefin-based thermoplastic (K) is thermally decomposed to have a smaller molecular weight depending on the type of the olefin-based thermoplastic (K), or is crosslinked by heat. And gelled, and the desired foam (X _F2 ) cannot be obtained.

The base material layer of the foamed laminate of the present invention is a foam, and this foam comprises an olefinic thermoplastic elastomer (J) and an olefinic thermoplastic (K).
When the blowing agent (B) and the olefinic foamable composition comprising a (X ₃₎ can be obtained by foaming. The foaming agent (B) is an olefinic thermoplastic elastomer (J) 10
It is desirable to use 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, relative to 0 parts by weight.

The olefinic foamable composition (X ₃ ) includes
If necessary, a foaming aid can be blended. As a foaming aid, a compound containing a metal such as zinc, calcium, lead, iron or barium; citric acid, salicylic acid, phthalic acid,
Organic acids such as stearic acid and oxalic acid; urea and its derivatives are used. The foaming aid is usually 0.1 part with respect to 100 parts by weight of the olefinic thermoplastic elastomer (J).
It is desirable to use 1 to 20 parts by weight, preferably 1 to 10 parts by weight. The foaming auxiliary agent has functions of lowering the decomposition temperature of the foaming agent, promoting decomposition, homogenizing bubbles, and the like.

If necessary, the olefinic foamable composition (X ₃ ) is used for the purpose of uniformly foaming at a high magnification.
It is also possible to add an inorganic porous powder that adsorbs an inorganic gas, such as zeolite, a resin having a large adsorption amount of an inorganic gas, such as a polycarbonate resin, or a nucleating agent for foaming.

Further, the olefinic foamable composition (X ₃ )
In addition, if necessary, a filler, a heat stabilizer, an antiaging agent, a weather stabilizer, an antistatic agent, a wetting agent, a metal soap,
Known additives such as a lubricant such as wax, a pigment, a dye, a flame retardant, an antiblocking agent and the like can be added within a range that does not impair the object of the present invention.

As the filler to be added to the olefinic foamable composition (X ₃ ), fillers usually used for rubber are suitable, and specifically, calcium carbonate, calcium silicate, clay, kaolin, Examples thereof include talc, silica, diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, molybdenum disulfide, glass fiber, glass spheres, shirasu balloon, graphite and alumina.

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 olefinic thermoplastic elastomer (J).

Preparation of olefinic foamable composition (X ₃ ) The olefinic foamable composition (X ₃ ) comprises an olefinic thermoplastic elastomer (J), an olefinic thermoplastic (K) and a foaming agent (B). ), And a blending agent such as a foaming aid and a wetting agent, which are blended as necessary. As a compounding method,
When the olefin-based thermoplastic elastomer (J) is blended with the olefin-based thermoplastic (K) and the foaming agent (B) and, if necessary, blended with a blending agent such as a foaming aid and a wetting agent, the olefin-based thermoplastic ( The method of adding K) and the foaming agent (B) may be mentioned. The olefin-based thermoplastic (K) and the foaming agent (B) may be mixed at the same time or separately. When they are mixed separately, the olefinic thermoplastic elastomer (J) may be blended with the olefinic thermoplastic (K), and then the foaming agent (B) may be blended. The mixing order may be reversed. Good.

When the olefinic thermoplastic resin (K) and / or the foaming agent (B) are mixed in preparing the olefinic thermoplastic elastomer (J), the intended foamed product (X _F2 ) is obtained. I can't. When the olefin-based thermoplastic (K) and / or the foaming agent (B) are mixed when preparing the olefin-based thermoplastic elastomer (J), the olefin-based thermoplastic (K) may be mixed depending on the type of the olefin-based thermoplastic (K). (K) is thermally decomposed to have a smaller molecular weight, or is crosslinked by heat to form a gel, and the desired foam (X
_The melt viscosity required to obtain _F2 ) is greatly deviated, or the foaming agent (B) decomposes and outgases.

Specific examples of the method for blending the olefin-based thermoplastic elastomer (J), the olefin-based thermoplastic (K) and the foaming agent (B) include, for example, pellets of the olefin-based thermoplastic elastomer (J) and olefin-based thermoplastic elastomer (J). Thermoplastic (K) and foaming agent (B) are once kneaded with a tumbler type Brabender, V type Brabender, ribbon blender, Henschel mixer, etc., and if necessary, an open type mixing roll or a non-open type Banbury. The method of kneading with a mixer, an extruder, a kneader, a continuous mixer, etc. can be mentioned. Weather resistance stabilizers, heat resistance stabilizers, antioxidants, pigments, dyes, etc.
It may be compounded at any stage of the above process.

A foam (X _F2 ) can be obtained by heating the above olefinic foamable composition (X ₃ ).
Even when the foam (X _F2 ) is used as the base material layer, the raw material for the skin layer is at least 1 selected from the olefin-based raw materials 1) to 7) as in the case of the foam (X _F1 ). The olefin-based thermoplastic elastomer composition (Z ₁ ) of 3) or the olefin-based thermoplastic elastomer composition (Z ₂ ) of ₄ ) is particularly preferred.

1) The above 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) Olefin-based thermoplastic resin Organopolysiloxane (D) 0.5 to 100 parts by weight of elastomer (C)
25 parts by weight, fluoropolymer (E) 0.5 to 10 parts by weight, antistatic agent (F) 0.5 to 10 parts by weight, polyolefin resin (G) 5 to 200 parts by weight, fatty acid amide 0.0
1-5 parts by weight, mineral oil 0.5-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5 parts by weight,
Olefin-based thermoplastic elastomer composition (Z) 3) containing at least one lubricant (Z _L ) selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate in the above proportion. 0.01 to 5 parts by weight of fatty acid amide, 0.5 to 10 parts by weight of mineral oil, 0.01 to 5 parts by weight of metal soap, 0.01 to 0.01 parts of ester based on 100 parts by weight of the olefinic thermoplastic elastomer (C). 5 parts by weight, 0.01 to 5 parts by weight of calcium carbonate, and 0.01 to 5 parts by weight of silicate 0.01 to 5 parts by weight of at least one lubricant (Z _L ) selected from the group in the above proportion, an olefinic thermoplastic elastomer composition ( Z ₁ ) 4) Fatty acid amide 0.0 as a lubricant (Z _L ) based on 100 parts by weight of the olefinic thermoplastic elastomer (C)
1-5 parts by weight, mineral oil 0.5-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5 parts by weight,
Olefinic thermoplastic elastomer containing at least one selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate, and 5 to 200 parts by weight of a polyolefin resin (G) in the above ratio. the composition (Z ₂₎ 5) an olefin-based thermoplastic elastomer (C) 100 parts by weight of organopolysiloxane (D) 0.5 to
25 parts by weight, at least one lubricant (Z _L ) selected from the group consisting of 0.5 to 10 parts by weight of the fluoropolymer (E) and 0.5 to 10 parts by weight of the antistatic agent (F) in the above proportion. Olefinic thermoplastic elastomer composition containing (Z
₃ ) 6) An olefinic thermoplastic elastomer composition (Z ₄ ) containing the polyolefin resin (G) as a lubricant (Z _L ) in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the olefinic thermoplastic elastomer (C). 7) 0.5 to 25 parts by weight of an organopolysiloxane (D) as a lubricant (Z _L ) and 0.5 to 10 parts by weight of a fluoropolymer (E) with respect to 100 parts by weight of an olefinic thermoplastic elastomer (C). Parts, antistatic agent (F) 0.5 to
10 parts by weight, fatty acid amide 0.01 to 5 parts by weight, mineral oil 0.5 to 10 parts by weight, metal soap 0.01 to 5 parts by weight, esters 0.01 to 5 parts by weight, calcium carbonate 0.01 to 5 parts Parts by weight and at least one selected from the group consisting of 0.01 to 5 parts by weight of silicate and 5 to 200 parts by weight of a polyolefin resin (G) in the above proportions, an olefinic thermoplastic elastomer composition (Z ₅ ).

As the olefinic thermoplastic elastomer (C), the olefinic thermoplastic elastomer (J) may be used.

The olefin foam laminate of the present invention is
Foam (X_F1) Or foam (X _F2) Base layer
And the above-mentioned ultra high molecular weight polyolefin resin (Y),
Fin-based thermoplastic elastomer composition (Z) or ole
Fin-based thermoplastic elastomer composition (Z₁) ~ (Z_Five)
And a skin layer made of. The epidermis layer
It may be laminated on the entire surface of the base material layer, or a part of the base material layer
May be laminated only to the
May be. The skin layer is laminated only on a part of the base material layer.
When the surface layer is not laminated, the base layer is exposed on the surface.
You can put it out. The base material layer and the skin layer are laminated with an adhesive.
However, it is preferably fused. Stacking
The thickness of the body is not particularly limited, but the thickness of the base material layer is 0.1.
~ 50 mm, preferably 0.5-45 mm, skin layer thickness
Is 5 μm to 10 mm, preferably 10 μm to 8 mm
It is desirable to have. Foam (X_F1) Or
Foam (X_F2The expansion ratio of) is not particularly limited, but 1.
It is desired to be 1 to 20 times, preferably 2 to 10 times.
Yes. In the present invention, an ethylene-based thermoplastic elastomer
-(A) is fully foamed, so the expansion ratio is 2 times or more.
Foam with high expansion ratio (X_F1) Can be easily molded
it can. Also, olefinic thermoplastics (K)
Foams sufficiently, so the expansion ratio is more than 2 times
Rate of foam (X _F2), It can be easily molded.

The olefinic foam laminate of the present invention has a flexible feel because the base material layer can have a high expansion ratio as described above, and also has a good appearance, wear resistance, durability and sliding characteristics. Is excellent. Especially excellent in abrasion resistance under bad conditions. In addition, the laminate of the present invention can be easily manufactured and can be recycled, so that it is excellent in economic efficiency.

The olefinic foam laminate of the present invention is
Foam (X_F1) Or foam (X _F2) As the base layer,
The above-mentioned ultra high molecular weight polyolefin resin (Y), olefin
Thermoplastic elastomer composition (Z) or olefin
Thermoplastic elastomer composition (Z₁) ~ (Z_Five) Table
It is obtained by laminating as a skin layer. The lamination method is
It depends on the shape, size and required physical properties of the final product.
For example, but not limited to,
Method of co-extrusion and heat-sealing the skin and skin layer at the same time
Can be given. In this case, the ethylene-based thermoplastic elastomer
Mar composition (X ₁) Is for co-extrusion and heat fusion.
Foam to foam (X_F1), And a base material layer is formed. Well
Olefinic foamable composition (X₃) Is coextruded
Foam when heat-sealing_F2) And the base material
Form the layers. Adhesives are required for such heat fusion methods.
Obtaining a foam laminate easily in one simple process without the need
And the interlayer adhesion between the base layer and the skin layer is strong.
It

The olefinic foamed laminate of the present invention can be suitably used for automobile parts such as automobile weather strips; construction materials such as gaskets and sealants.
Examples of automotive weather strips include door weather strips, bonnet weather strips, luggage compartment weather strips, sunroof weather strips, ventilator weather strips, and corner materials. As building materials, gaskets,
Architectural sealing materials such as airtight, jointing materials and door-stop sealing materials are listed. In addition, golf club grips, baseball bat grips, swimming fins, leisure products such as underwater glasses, hose protection materials, cushioning materials and the like can be mentioned.

FIG. 1 shows an example of a cross-sectional structure of an automobile weather strip containing the olefin foam laminate of the present invention. The weather strip 1 for an automobile shown in FIG. 1 has a thin plate-shaped core member 2 in a cross section, and a sliding contact portion 3 provided on the surface of the core member 2 and curved so that a window glass is in sliding contact. It consists of and. The sliding contact portion 3 is composed 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 side in sliding contact with the glass.

The sliding member of the present invention is a sliding member made of the olefin foam laminate of the present invention. Since the sliding member of the present invention is composed of the olefin foam laminate of the present invention, it has a soft feel and is excellent in appearance, wear resistance, durability and sliding characteristics. In addition, it can be easily produced, and since it is mainly composed of an olefin polymer, it can be easily recycled and is excellent in economic efficiency.

The automobile weather strip of the present invention is an automobile weather strip comprising the olefin foam laminate of the present invention. Since the weather strip for automobiles of the present invention comprises the above-mentioned olefinic foam laminate of the present invention, it has a soft feel and is excellent in appearance, abrasion resistance, durability and sliding characteristics. In addition, it can be easily produced, and since it is mainly composed of an olefin polymer, it can be easily recycled and is excellent in economic efficiency.

The building sealing material of the present invention is a building sealing material comprising the olefin foam laminate of the present invention.
Since the building sealing material of the present invention is composed of the olefin foam laminate of the present invention, it has a soft feel and is excellent in appearance, wear resistance, durability and sliding characteristics. In addition, it can be easily produced, and since it is mainly composed of an olefin polymer, it can be easily recycled and is excellent in economic efficiency.

[0153]

As described above, the olefin foam laminate of the present invention has a high expansion ratio and a soft feel, and is excellent in appearance, abrasion resistance, durability and sliding characteristics. In particular, since it has excellent wear resistance under adverse conditions, it can be suitably used as a weather strip for automobiles. Further, the laminate of the present invention can be easily produced, and since the olefin polymer is used as a main raw material, it can be easily recycled and is excellent in economic efficiency.

[0154]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1-1: (1) Production of ethylene-based thermoplastic elastomer (A-1) Linear low-density polyethylene (density: 0.920 g / cm
³ , MFR; 2.1 g / 10 minutes, ethylene content; 97.
0 mol%, 4-methyl-1-pentene content; 3.0 mol%) 30 parts by weight, and 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 was dynamically heat-treated and extruded at 220 ° C. in a nitrogen atmosphere to produce pellets of an ethylene-based thermoplastic elastomer (A-1) did. A thickness of 12.7 m from the obtained ethylene-based thermoplastic elastomer (A-1)
m, a cylindrical sample having a diameter of 29.0 mm was injection-molded, and compression set (JIS K 6262, 70 ° C., 2
2 hours) was 46%. In addition, melt flow rate (JIS K712
0g, 230 ℃, 10kg load) measured, 2g
It was / 10 min.

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

(3) Production of Laminated Body The ethylene-based thermoplastic elastomer (A-
1) 100 parts by weight and 3.0 parts by weight of a mixture (B-1) of citric acid 50 mol% and sodium hydrogen carbonate 50 mol% were mixed with a tumbler type Brabender to blend a foamable composition. Then, this foamable composition is extrusion-molded at a die temperature of 150 ° C. to foam-mold the core material and the base material layer, and at the same time, the ultrahigh molecular weight polyethylene composition (Y-1) of (2) is heated at a temperature of 230 ° C. 1 to form a skin layer by coextrusion with a base material layer and heat-sealing the base layer and the skin layer.
The weather strip shown in was produced. The base material layer had a thickness of 2 mm, and the skin layer had a thickness of 100 μm. The foaming ratio of the obtained weather strip was 4.8 times.

The weather strip thus obtained was mounted on a test window frame, and a 3.2 mm-thick window glass was fitted therein, and a durability test (window glass repeated test) was performed. As a result, the weather strip maintained its function as a weather strip without fatigue and wear even after repeated tests of 50,000 times of window glass up and down.

Example 1-2: 30 parts by weight of the linear low-density polyethylene used in Example 1-1 and 70 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1-1. And a mineral oil-based softener (paraffin-based oil, manufactured by Idemitsu Kosan Co., Ltd., PW-380, trademark) 4
An ethylene-based thermoplastic elastomer (A-2) was obtained in the same manner as in Example 1-1, using 0 part by weight. Using the obtained ethylene-based thermoplastic elastomer (A-2),
In the same manner as in Example 1-1, compression set and MFR
Was measured. As a result, compression set is 46%, MFR
Was 4 g / 10 min.

Then, using this ethylene-based thermoplastic elastomer (A-2), a foamable composition was prepared in the same manner as in Example 1-1, and a weather strip with the same skin layer as in Example 1-1. Was prepared and a durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip. The foaming ratio of the obtained weather strip was 3.7 times.

Example 1-3: 15 parts by weight of the linear low-density polyethylene used in Example 1-1 and 85 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1-1. And propylene / ethylene random copolymer (MFR; 0.5 g / 10 minutes, ethylene content;
4 mol%) (PP-1) and 20 parts by weight were used to obtain an ethylene-based thermoplastic elastomer (A-3) in the same manner as in Example 1-1. Using the obtained ethylene-based thermoplastic elastomer (A-3), compression set and MFR were measured in the same manner as in Example 1-1. As a result, the compression set was 55% and the MFR was 2 g / 10 min.

Then, using this ethylene-based thermoplastic elastomer (A-3), a foamable composition was blended in the same manner as in Example 1-1, and a weather strip was formed with the same skin layer as in Example 1-1. It was produced and a durability test was conducted. as a result,
This weather strip withstood a repeated test of 50,000 times and maintained its function as a weather strip. The foaming ratio of the obtained weather strip was 3.0 times.

Example 1-4: 15 parts by weight of the linear low-density polyethylene used in Example 1-1 and 85 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1-1. And propylene homopolymer (MF
R; 1.5 g / 10 min) (PP-2) 20 parts by weight was used to obtain an ethylene-based thermoplastic elastomer (A-4) in the same manner as in Example 1-1. Using the obtained ethylene-based thermoplastic elastomer (A-4), compression set and MFR were measured in the same manner as in Example 1-1. As a result, the compression set was 57% and the MFR was 3g / 10m.
It was in.

Then, using this ethylene-based thermoplastic elastomer (A-4), a foamable composition was blended in the same manner as in Example 1-1, and a weather strip was formed with the same skin layer as in Example 1-1. It was produced and a durability test was conducted. as a result,
This weather strip withstood a repeated test of 50,000 times and maintained its function as a weather strip. The foaming ratio of the obtained weather strip was 2.8 times.

Example 1-5: 30 parts by weight of the linear low-density polyethylene used in Example 1-1 and the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1-1 were extended oils. Example 1 using 110 parts by weight of an oil-extended ethylene / propylene / dicyclopentadiene copolymer rubber blended with 40 parts by weight of paraffin oil (PW-380, trademark, manufactured by Idemitsu Kosan Co., Ltd.) Ethylene-based thermoplastic elastomer (A-5) in the same manner as -1
Got The obtained ethylene-based thermoplastic elastomer (A
-5) was used to measure compression set and MFR in the same manner as in Example 1-1. As a result, the compression set was 43% and the MFR was 4 g / 10 min.

Then, using this ethylene-based thermoplastic elastomer (A-5), a foamable composition was blended in the same manner as in Example 1-1, and a weather strip was formed with the same skin layer as in Example 1-1. It was produced and a durability test was conducted. as a result,
This weather strip withstood a repeated test of 50,000 times and maintained its function as a weather strip. The foaming ratio of the obtained weather strip was 3.8 times.

Example 1-6 (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) 60 parts by weight and polypropylene ((MFR (A
STM D-1238-65T, 230 ° C, 2.16k
g load); 13 g / 10 minutes, density; 0.91 g / c
m ³ and crystallinity by X-ray diffraction method; 72%) 40 parts by weight using a Banbury mixer in a nitrogen atmosphere at 18
Kneading was carried out at 0 ° C. for 5 minutes. Then, this kneaded material was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets. Then, with this square pellet,
0.2 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene and 0.2 parts of divinylbenzene
And 1 part by weight were mixed by stirring with a Henschel mixer. Next, this mixture was mixed with L / D = 40 and a screw diameter of 50 m.
olefin thermoplastic elastomer (C-1) extruded at 220 ° C. in a nitrogen atmosphere using a twin-screw extruder of m.
Got The gel content of the obtained olefinic thermoplastic elastomer (C-1) was 78% by weight as determined by the above method.

(2) Manufacture of Laminated Body Olefin-based thermoplastic elastomer (C-
1) 100 parts by weight and 2 parts by weight of silicone oil (manufactured by Toray Dow Corning Co., Ltd., SH200-3000cSt, trademark) (D-1) 2 parts by weight are kneaded with a twin-screw extruder to form an olefin system for the skin layer. Thermoplastic elastomer composition (Z1
-1) was obtained.

This olefinic thermoplastic elastomer composition (Z1-1) was coextruded with the same foamable composition as in Example 1-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 1-7: 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 1-6 and the silicone oil (D-
1) 2 parts by weight of silicone oil-polypropylene masterbatch (manufactured by Toray Dow Corning Co., BY
27-002 (ultra-high molecular weight silicone oil content 50% by weight) and 14 parts by weight of trademark (D-2) were kneaded with a twin-screw extruder to give an olefinic thermoplastic elastomer composition (Z1-2) for the skin layer. ) Got.

This olefinic thermoplastic elastomer composition (Z1-2) was coextruded with the same foamable composition as in Example 1-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 1-8: 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 1-6 and a fluoropolymer (manufactured by Sumitomo 3M Ltd.,
Dynamer FX-9613 (Fluorine-based polymer content 90
%) And 3 parts by weight of trademark (E-1) were kneaded with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z1-3) for the skin layer.

This olefinic thermoplastic elastomer composition (Z1-3) was coextruded with the same foamable composition as in Example 1-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 1-9: 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 1-6 and an antistatic agent (manufactured by Kao Corporation, Electrostripper TS-6B, 3 parts by weight of Trademark) (F-1) was kneaded with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z1-4) for the skin layer.

This olefinic thermoplastic elastomer composition (Z1-4) was coextruded with the same foamable composition as in Example 1-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 1-10: 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 1-6 and the ultra high molecular weight polyolefin composition (Y- used in Example 1-1) 1) 10 parts by weight were kneaded with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z1-5) for the skin layer.

This olefinic thermoplastic elastomer composition (Z1-5) was coextruded with the same foamable composition as in Example 1-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 1-11: 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 1-6 and the ultrahigh molecular weight polyolefin composition (Y- used in Example 1-1) 1) 100 parts by weight of the silicone oil (D-1) and 2 parts by weight of the silicone oil (D-1) were kneaded by a twin-screw extruder, and the olefinic thermoplastic elastomer composition for the skin layer (Z1-
6) was obtained.

This olefinic thermoplastic elastomer composition (Z1-6) was coextruded with the same foamable composition as in Example 1-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 1-12: 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 1-6 and the silicone oil (D-
1) 2 parts by weight and polypropylene (MFR (ASTM
D-1238-65T, 230 ° C., 2.16 kg load); 13 g / 10 minutes, density; 0.91 g / cm ³ (G
-1) Kneading with 30 parts by weight by a twin-screw extruder, and an olefinic thermoplastic elastomer composition for a skin layer (Z1-7)
Got

This olefinic thermoplastic elastomer composition (Z1-7) was coextruded with the same foamable composition as in Example 1-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 1-13: 100 parts by weight of the olefinic thermoplastic elastomer (C-1) obtained in Example 1-6 and 2 parts by weight of oleic acid amide were kneaded with a twin-screw extruder to form a skin. An olefinic thermoplastic elastomer composition (Z1-8) for a layer was obtained.

This olefinic thermoplastic elastomer composition (Z1-8) and the same foamable composition as in Example 1-1 were coextruded to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Comparative Example 1-1 Using a conventional weather strip (a laminated structure in which a nylon film is adhered to a soft vinyl chloride resin layer), a durability test was conducted in the same manner. As a result, the contact surface with the window glass was destroyed after 25,000 times, and the frictional resistance with the window glass was significantly increased, making it unusable.

The conditions of the dynamic heat treatment in the production of the above-mentioned ethylene-based thermoplastic elastomers (A-1), (A-2), (A-3), (A-4) and (A-5) are shown in Table 1. Shown in.

[Table 1]

Note in Table 1 The unit of the blending 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: Ethylene / propylene / dicyclopentadiene copolymer rubber 100 parts by weight of paraffin as extender oil System oil (made by Idemitsu Kosan Co., Ltd., PW-38
Oil-extended ethylene / propylene / dicyclopentadiene copolymer rubber * 4 PP-1: propylene / ethylene copolymer * 5 PP-2: propylene homopolymer * 6 paraffin oil : Mineral oil softener (PW-380, trademark, manufactured by Idemitsu Kosan Co., Ltd.) * 7 T: Resin temperature (° C) at the die exit of the twin-screw extruder * 8 P: Screw diameter of the twin-screw extruder (Mm) * 9 Q: Maximum shear rate received in the twin-screw extruder (sec)
^-1 ) * 10 R: Extrusion amount of twin-screw extruder (kg / h) * 11 S: Screw rotation speed (rps) in 1 second * 12 U: Between barrel inner wall and kneading segment (kneading segment) of screw Clearance
(Mm) * 13 Formula (1): [(T-130) / 100] + 2.2logP
+ LogQ-logR

The components used in the following Examples and Comparative Examples are as follows. ● Polyolefin resin (j-11) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 50 g / 10 minutes, density = 0.91
0 g / cm ³ propylene / ethylene block copolymer, ethylene content = 8 mol% ● Ethylene / α-olefin copolymer rubber (j-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 [ML _{1 + 4} (100 ° C.)] = 100 ● Oil-extended ethylene / α-olefin Type copolymer rubber (j-
22) A softening agent (j-31) is added to the ethylene rubber of (j-21) ● Softening agent (j-31) Paraffin-based process oil [made by Idemitsu Kosan Co., Ltd., P
W-380, trademark]

● Olefin-based thermoplastic (K
-1) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 0.3 g / 10 minutes, density = 0.9
Propylene homopolymer of 10 g / cm ³ ● Blowing agent (B-2) Azodicarbonamide ● Ultra high 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
3/77 weight ratio

Rubber (c-11) Ethylene content = 70 mol%, iodine value = 12, Mooney viscosity [ML _{1 + 4} (100 ° C.)] = 120 Ethylene / propylene / 5-ethylidene-2-norbornene co-polymer Polymer rubber Polyolefin resin (c-21) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 13 g / 10 minutes, density = 0.91
g / cm ³ propylene / ethylene block copolymer,
Ethylene content = 3 mol% Organopolysiloxane (D-1) Silicone oil [manufactured by Toray Dow Corning Co., Ltd.,
SH200 (3000 cSt, trademark)] Organopolysiloxane (D-2) Silicone oil-polypropylene masterbatch [Toray Dow Corning Incorporated, BY27-002 (ultra high molecular weight silicone oil content 50% by weight, trademark)]

Fluorine polymer (E-1) Dynamer FX-9613 manufactured by Sumitomo 3M Limited
(Fluorine polymer content 90%, trademark) Antistatic agent (F-1) Electrostripper TS-6B, manufactured by Kao Corporation.
Trademark ● Polyolefin resin (G-2) MFR (ASTM D-1238-65T, 230 ° C,
2.16 kg load) = 13 g / 10 minutes, density = 0.91
g / cm ³ propylene / ethylene block copolymer,
Ethylene content = 3 mol%

Example 2-1: (1) Production of olefinic thermoplastic elastomer (J-1) 30 parts by weight of polyolefin resin (j-11) and ethylene / α-olefinic copolymer rubber (j-21) ) 70 parts by weight with a Banbury mixer under a nitrogen atmosphere, 1
The mixture was kneaded at 80 ° C. for 5 minutes, passed through a sheeting roll, and pellets were manufactured with a sheet cutter. Next, 100 parts by weight of this pellet and 1,3-bis (te
rt-Butylperoxyisopropyl) benzene 0.3
A solution in which 0.3 part by weight of divinylbenzene was dissolved and dispersed was mixed with a tumbler blender, and this solution was uniformly attached to the pellet surface. Next, the pellets were extruded at 210 ° C. in a nitrogen atmosphere using an extruder and subjected to dynamic heat treatment to obtain an olefin-based thermoplastic elastomer (J-1) having a gel content of 77% by weight. The obtained olefinic thermoplastic elastomer (J-
1) 100 parts by weight and 5 parts by weight of an olefinic thermoplastic (K-1) were extruded at 210 ° C. in a nitrogen atmosphere using an extruder to produce pellets of an olefinic thermoplastic elastomer composition. A cylindrical sample having a thickness of 12.7 mm and a diameter of 29.0 mm was injection-molded from this pellet, and compression set (JIS K 6262,
It was 36% when measured at 70 ° C. for 22 hours.
In addition, melt flow rate (JIS
K 7120, 230 ° C., 10 kg load) was measured and found to be 33 g / 10 min.

(2) Manufacture of Laminated Body Olefin-based thermoplastic elastomer (J-
1) 100 parts by weight, 5 parts by weight of an olefinic thermoplastic (K-1), and 1.5 parts by weight of a foaming agent (B-2) are mixed by a tumbler blender to blend an olefinic foamable composition. did. Then, this foamable composition is extrusion-molded at a die temperature of 150 ° C. to foam-mold the core material and the base material layer, and at the same time, the ultra high molecular weight polyethylene composition (Y
1) was coextruded at a temperature of 230 ° C. to form a skin layer, and the base material layer and the skin layer were heat-sealed to produce the weather strip shown in FIG. 1. Base layer thickness is 2m
m, and the thickness of the epidermis layer was 100 μm. The expansion ratio of the obtained weather strip was 2.2 times.

The weather strip thus obtained was mounted on a test window frame, and a 3.2 mm-thick window glass was fitted to perform a durability test (upper and lower repeated test of the window glass). As a result, the weather strip maintained its function as a weather strip without wear and tear even after repeated 50,000 times of repeated window glass up and down tests.

Example 2-2: Polyolefin resin (j-
11) 30 parts by weight, 70 parts by weight of ethylene / α-olefin copolymer rubber (j-21), and a softening agent (j-3
1) Using 50 parts by weight, an olefinic thermoplastic elastomer (J-2) was obtained in the same manner as in Example 2-1.
The gel content of this olefinic thermoplastic elastomer (J-2) was 71% by weight. Further, the compression set and the MFR were measured in the same manner as in Example 2-1 using the above-mentioned olefin-based thermoplastic elastomer (J-2) and olefin-based thermoplastic (K-1). As a result, the compression set was 35% and the MFR was 37 g / 10 mi.
It was n.

Then, an olefinic foamable composition was blended using the above olefinic thermoplastic elastomer (J-2) in the same manner as in Example 2-1. Then, a weather strip was prepared with the same skin layer as in Example 2-1,
A durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip. Further, the expansion ratio of the obtained weather strip was 2.3 times.

Example 2-3: Oil-extended ethylene / α-olefin copolymer rubber (j-22) instead of 70 parts by weight of ethylene / α-olefin copolymer rubber (j-21)
An olefinic thermoplastic elastomer (J-3) was obtained in the same manner as in Example 2-1, except that 120 parts by weight was used. This olefinic thermoplastic elastomer (J-3)
Had a gel content of 73% by weight. Further, the compression set and the MFR were measured in the same manner as in Example 2-1 using the olefin thermoplastic elastomer (J-3) and the olefin thermoplastic (K-1). As a result, the compression set was 35% and the MFR was 37 g / 10 mi.
It was n.

Then, an olefinic foamable composition was blended using the above olefinic thermoplastic elastomer (J-3) in the same manner as in Example 2-1. Then, a weather strip was prepared with the same skin layer as in Example 2-1,
A durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip. Further, the expansion ratio of the obtained weather strip was 2.3 times.

Example 2-4: Polyolefin resin (j-
11) 30 parts by weight, 70 parts by weight of ethylene / α-olefin copolymer rubber (j-21), and a softening agent (j-3
1) 50 parts by weight and 30 parts by weight of butyl rubber (unsaturation degree 0.5%, Mooney viscosity [ML _{1 + 4} (100 ° C.)] 40) were used, and an olefinic compound was prepared in the same manner as in Example 2-1. A thermoplastic elastomer (J-4) was obtained. The gel content of this olefinic thermoplastic elastomer (J-4) was 81% by weight. Further, an olefin-based thermoplastic elastomer (J-4) and an olefin-based thermoplastic (K-
Using 1) and, the compression set and the MFR were measured in the same manner as in Example 2-1. As a result, the compression set was 33% and the MFR was 42 g / 10 min.

Next, an olefinic foamable composition was blended using the above olefinic thermoplastic elastomer (J-4) in the same manner as in Example 2-1. Then, a weather strip was prepared with the same skin layer as in Example 2-1,
A durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip. Moreover, the expansion ratio of the obtained weather strip was 2.6 times.

Example 2-5: (1) Production of olefinic thermoplastic elastomer (C-2) 60 parts by weight of rubber (c-11) and crystalline polyolefin resin (c-21) (X-ray diffraction method) Crystallinity according to: 72
%) 40 parts by weight with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then the kneaded product is passed through a roll to form a sheet, which is cut with a sheet cutter to produce square pellets. . Next, the square pellets, 0.2 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene, and 0.2 parts by weight of divinylbenzene were mixed by stirring with a Henschel mixer.
Next, this mixture was mixed with L / D = 40 and a screw diameter of 5
Using a 0 mm twin-screw extruder, extruding at 210 ° C. in a nitrogen atmosphere, the olefin-based thermoplastic elastomer (C-
2) was obtained. The gel content of the obtained olefinic thermoplastic elastomer (C-2) was 78% by weight as determined by the above method.

(2) Production of Laminated Product The olefinic thermoplastic elastomer (C-
2) 100 parts by weight of organopolysiloxane (D-
1) 2 parts by weight were kneaded with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z2-1) for the skin layer. This olefinic thermoplastic elastomer composition (Z
2-1) and the same olefinic foamable composition as in Example 2-1 are coextruded to produce a weather strip,
A durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 2-6: 100 parts by weight of the olefinic thermoplastic elastomer (C-2) obtained in Example 2-5, 2 parts by weight of organopolysiloxane (D-1),
14 parts by weight of organopolysiloxane (D-2) was kneaded with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z2-2) for the skin layer.

This olefinic thermoplastic elastomer composition (Z2-2) was coextruded with the same olefinic foamable composition as in Example 2-1, a weather strip was prepared, and a durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 2-7: 100 parts by weight of the olefinic thermoplastic elastomer (C-2) obtained in Example 2-5 and 3 parts by weight of a fluoropolymer (E-1) were used in a twin-screw extruder. And kneaded to obtain an olefinic thermoplastic elastomer composition (Z2-3) for the skin layer.

This olefinic thermoplastic elastomer composition (Z2-3) and the same olefinic foamable composition as in Example 2-1 were coextruded to prepare a weather strip, and a durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 2-8: 100 parts by weight of the olefinic thermoplastic elastomer (C-2) obtained in Example 2-5 and 3 parts by weight of antistatic agent (F-1) were used in a twin-screw extruder. And kneaded to obtain an olefinic thermoplastic elastomer composition (Z2-4) for the skin layer.

This olefinic thermoplastic elastomer composition (Z2-4) and the same olefinic foamable composition as in Example 2-1 were coextruded to prepare a weather strip, and a durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 2-9: 100 parts by weight of the olefinic thermoplastic elastomer (C-2) obtained in Example 2-5, and an ultrahigh molecular weight polyolefin composition (Y-1) 10
This was kneaded with 2 parts by weight with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z2-5) for the skin layer.

This olefinic thermoplastic elastomer composition (Z2-5) was coextruded with the same olefinic foamable composition as in Example 2-1 to prepare a weather strip, and a durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 2-10: 100 parts by weight of the olefinic thermoplastic elastomer (C-2) obtained in Example 2-5 and an ultrahigh molecular weight polyolefin composition (Y-1) 1
00 parts by weight and 2 parts by weight of organopolysiloxane (D-1) were kneaded with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z2-6) for the skin layer.

This olefinic thermoplastic elastomer composition (Z2-6) was coextruded with the same olefinic foamable composition as in Example 2-1, a weather strip was prepared, and a durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 2-11: 100 parts by weight of the olefinic thermoplastic elastomer (C-2) obtained in Example 2-5, 2 parts by weight of an organopolysiloxane (D-1), and a polyolefin resin (G -2) 30 parts by weight was kneaded with a twin-screw extruder to obtain an olefinic thermoplastic elastomer composition (Z2-7) for the skin layer.

This olefinic thermoplastic elastomer composition (Z2-7) was coextruded with the same olefinic foamable composition as in Example 2-1, a weather strip was prepared, and a durability test was conducted. As a result, this weather strip survived a repeated test of 50,000 times and maintained its function as a weather strip.

Example 2-12: 100 parts by weight of the olefinic thermoplastic elastomer (C-2) obtained in Example 2-5 and 2 parts by weight of oleic acid amide were kneaded with a twin-screw extruder to form a skin. An olefinic thermoplastic elastomer composition (Z2-8) for a layer was obtained.

This olefinic thermoplastic elastomer composition (Z2-8) and the same foamable composition as in Example 2-1 were coextruded to prepare a weather strip, and a durability test was conducted. As a result, this weather strip
It survived a repeated test of 50,000 times and maintained its function as a weather strip.

Comparative Example 2-1 Using a conventional weather strip (a laminated structure in which a nylon film is adhered to a soft vinyl chloride resin layer), a durability test was conducted in the same manner as in Example 2-1. As a result, the contact surface with the window glass was destroyed after 25,000 times, and the frictional resistance with the window glass was significantly increased, making it unusable.

Example 3-1: The sliding contact portion 3 was cut out from the weather strip of Example 2-11 (see FIG. 1) to give a test piece, and as shown in FIG. (Width 20 mm, height 30 mm, thickness 4.5 mm) 7 was contacted. In the sliding wear tester, this glass wear element 7
Then, a load of 3 kg was applied in the direction of arrow X, the sliding contact part 3 was reciprocated with a stroke of 100 mm in the direction of arrow Y, and the abrasion test with muddy water was performed. Here, initial and wear frequency 10
Muddy water (water: sand = 3: 1) was added dropwise to the contact portion every 0.5 times with 0.5 ml spoid. The abrasion state was evaluated after 5000 times of abrasion. The results are shown in Table 2.

Comparative Examples 3-1 to 3-3: Instead of the test piece used in Example 3-1, an olefinic thermoplastic elastomer (J-1) for the base material layer of Example 2-1 was used. Example 2-
No. 11 test piece (Comparative Example 3-1) comprising a non-foamed laminate in which the olefinic thermoplastic elastomer composition (Z2-7) for the skin layer was laminated, and the foamed base material layer single layer of Example 2-1. Was used (Comparative Example 3-2), and a test piece (Comparative Example 3-3) having a single skin layer made of the olefinic thermoplastic elastomer composition (Z2-7) of Example 2-11 was used. Except for the above, the abrasion test with muddy water was performed in the same manner as in Example 3-1. The results are shown in Table 2.

[0219]

[Table 2] * 1 Evaluation: 5 with almost no wear, 3 with partial wear, 1 with significant wear, and 4 or 3 with a state of wear between 5 and 3. The value between 2 and 1 was set as 2.

Example 3-2: The foamed laminates of this invention were tested for flexibility. That is, the weather strip of Example 2-11 was used as a test piece, and the test piece was pressed to test whether or not a sponge-like soft touch was obtained.
The results are shown in Table 3.

Comparative Examples 3-4 to 3-6: Instead of the test piece used in Example 3-2, an olefinic thermoplastic elastomer (J-1) for the base material layer of Example 2-1 was used. Example 2-
Test piece (Comparative Example 3-4) comprising a non-foamed laminate in which the olefinic thermoplastic elastomer composition (Z2-7) for the skin layer of Example 11 was laminated, and the foamed base material layer single layer of Example 2-1. Was used (Comparative Example 3-5), and a test piece (Comparative Example 3-6) having a single skin layer made of the olefinic thermoplastic elastomer composition (Z2-7) of Example 2-11 was used. Except for this, the same method as in Example 3-2 was used for the test. The results are shown in Table 3.

[0222]

[Table 3] * 1 Evaluation: A sponge-like soft feel was given as 5, a resin-like hard feel was taken as 1, and an intermediate feel was obtained as a soft feel. It was set to 4, 3, 2.

[Brief description of drawings]

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

FIG. 2 is a perspective view showing a method of a wear test with muddy water carried out in an example.

[Explanation of symbols]

1 Weather strip 2 core material 3 Sliding contact 4 Base material layer 5 epidermis 7 glass wearer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/098 C08K 5/098 5/10 5/10 5/20 5/20 C08L 23/00 C08L 23 / 00 57/02 57/02 // (C08L 23/00 C08L 83:04 83:04) F-term (reference) 4F074 AA17A AA21 AA24A AA54A AA98 BA01 BA02 BA03 BA12 BA13 CA22 4F100 AA08B AH02B AH03B AK03A AK03B AK04A62AAK52A62AAK52A62AAK52A62AAK52A62A62A62 AL09B AN00A BA02 CA19B CA22A DJ01A GB07 GB32 JA05A JA06B JA11A JB16A JB16B JK01A YY00A YY00B 4J002 AE053 BB00Y BB03W BB05X BD124 CP023 CP034 FD FD FD FD FD 017 FD FD FD FD 176 FD FD FD 174 FD 017 FD FD FD 174 FD FD FD GD FD FD 174 FD FD 174 FD 174 FD 017 FD FD FD 174 FD 017 FD FD FD to FD FD FD 174 to FD FD FD FD to 17

Claims (38)

[Claims] 1. An olefin-based foam laminate in which a base layer made of a foam (X _F ) of an olefin-based thermoplastic elastomer (X) and a skin layer made of the following resin or elastomer composition are laminated. Y: Ultra-high molecular weight polyolefin resin having an intrinsic viscosity [η] of 3.5 to 8.3 dl / g measured in decalin at 135 ° C. Z: An olefinic thermoplastic elastomer composition containing an olefinic thermoplastic elastomer (C) and a lubricant (Z _L ). 2. A skin layer comprising the olefinic thermoplastic elastomer composition (Z), wherein the olefinic thermoplastic elastomer composition (Z) is 100 parts by weight of the olefinic thermoplastic elastomer (C). 0.01 to 5 parts by weight of fatty acid amide, 0.5 to 10 parts by weight of mineral oil, 0.01 to 5 parts by weight of metal soap, and esters of 0.
Olefinic thermoplastic elastomer composition containing at least one lubricant (Z _L ) selected from the group consisting of 01 to 5 parts by weight, calcium carbonate 0.01 to 5 parts by weight, and silicate 0.01 to 5 parts by weight in the above proportion. The olefinic foam laminate according to claim 1, which is a product (Z ₁ ). 3. The olefin-based thermoplastic elastomer (X) has a compression set (70 ° C., 22 hours) of 60% or less according to JIS K6262, and JIS K 712.
Melt flow rate measured at 0 (230 ° C, 10 kg
The olefin-based foam laminate according to claim 1 or 2, having a load of 0.1 g / 10 min or more. 4. The olefinic thermoplastic elastomer (X) comprises 5 to 60 parts by weight of a polyethylene resin (a-1) and an ethylene / α-olefinic copolymer (a-2) 4.
0-95 parts by weight [wherein component (a-1) and (a-
2) The total amount of the components is 100 parts by weight. ] The ethylene-based thermoplastic elastomer (A), wherein the ethylene / α-olefin copolymer (a-2) is a copolymer of ethylene, α-olefin and a non-conjugated polyene optionally used. And the Mooney viscosity ML _{1 + 4}
(100 ° C) 90-250, ethylene content 70-9
The olefinic foam laminate according to claim 1 or 2, which is a 5 mol% ethylene / α-olefinic copolymer. 5. A polyethylene resin (a-1) in an amount of 5 to 60 parts by weight and an ethylene / α-olefin copolymer (a-
2) 40 to 95 parts by weight [here, the total amount of the component (a-1) and the component (a-2) is 100 parts by weight. ] An olefin foam laminate in which a base material layer made of a foam (X _F1 ) of an ethylene thermoplastic elastomer (A) and a skin layer made of an olefin thermoplastic elastomer composition (Z) are laminated. Which is the ethylene / α-olefin copolymer (a-2)
Is a copolymer of ethylene, α-olefin and optionally a non-conjugated polyene, having a Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. An olefin-based copolymer, the olefin-based thermoplastic elastomer composition (Z)
Is 0.5 to 100 parts by weight of the olefinic thermoplastic elastomer (C).
25 parts by weight, fluoropolymer (E) 0.5 to 10 parts by weight, antistatic agent (F) 0.5 to 10 parts by weight, polyolefin resin (G) 5 to 200 parts by weight, fatty acid amide 0.0
1-5 parts by weight, mineral oil 0.5-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5 parts by weight,
Olefin-based foaming which is an olefin-based thermoplastic elastomer composition containing at least one lubricant (Z _L ) selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate in the above proportion. Laminate. 6. An olefin-based thermoplastic elastomer (C) obtained by dynamically heat-treating a mixture containing a crystalline polyolefin resin (c-1) and a rubber (c-2). The olefinic foam laminate according to claim 5. 7. The polyolefin resin (G) has a temperature of 135 ° C.
The intrinsic viscosity [η] measured in decalin is 3.5 to 8.3.
The olefin-based foam laminate according to claim 5 or 6, which is a dl / g ultrahigh molecular weight polyolefin resin (Y). 8. Ultra high molecular weight polyolefin resin (Y)
However, the intrinsic viscosity [η] measured in decalin at 135 ° C is 1
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] measured in 135 ° C decalin of 0.1 to 5 dl / g [where (y-
The total amount of the component 1) and the component (y-2) is 100 parts by weight. ] The olefinic foam laminate according to claim 7, which is an ultrahigh molecular weight polyolefin resin composition containing 9. The olefinic thermoplastic elastomer composition (Z) is an olefinic thermoplastic elastomer (C).
0.01 to 5 parts by weight of fatty acid amide, 0.5 to 10 parts by weight of mineral oil, and 0.01 to 100 parts by weight of metal soap per 100 parts by weight.
5 parts by weight, esters 0.01 to 5 parts by weight, calcium carbonate 0.01 to 5 parts by weight and silicate 0.01 to 5
The olefinic foam laminate according to claim 5 or 6, which is an olefinic thermoplastic elastomer composition (Z ₁ ) containing at least one lubricant (Z _L ) selected from the group consisting of parts by weight in the above proportion. 10. The olefinic thermoplastic elastomer composition (Z) comprises 0.01 to 5 parts by weight of a fatty acid amide as a lubricant (Z _L ) and 0 mineral oil per 100 parts by weight of the olefinic thermoplastic elastomer (C). 0.5 to 10 parts by weight, 0.01 to 5 parts by weight of metal soap, and esters of 0.
At least one selected from the group consisting of 01 to 5 parts by weight, 0.01 to 5 parts by weight of calcium carbonate, and 0.01 to 5 parts by weight of silicate; and a polyolefin resin (G) 5 to
The olefinic foam laminate according to claim 5 or 6, which is an olefinic thermoplastic elastomer composition (Z ₂ ) containing 200 parts by weight in the above ratio. 11. An ethylene-based thermoplastic elastomer (A) comprises a polypropylene resin (a) based on 100 parts by weight of a total of a polyethylene resin (a-1) and an ethylene / α-olefin-based copolymer (a-2). The olefin-based foam laminate according to any one of claims 5 to 10, which contains -3) in an amount of 30 parts by weight or less. 12. The olefin foam laminate according to claim 5, wherein the foam (X _F1 ) has a foaming ratio of 2 or more. 13. An ethylene-based thermoplastic elastomer (A) comprises 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 a mixture containing a polypropylene resin (a-3) as necessary in the absence of a crosslinking agent. The olefin-based foam laminate according to any one of claims 5 to 12, which is 14. An olefinic thermoplastic elastomer (C) is 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 foam laminate according to any one of claims 5 to 13, which is an olefin-based thermoplastic elastomer. 15. A foam (X _F1 ) obtained by foaming a foamable ethylene-based thermoplastic elastomer composition (X ₁ ) containing an ethylene-based thermoplastic elastomer (A) and a foaming agent (B). The olefinic foam laminate according to any one of claims 5 to 14, which is a body. 16. The olefin foam laminate according to claim 15, wherein the foaming agent (B) is an organic or inorganic pyrolytic foaming agent. 17. The content of the foaming agent (B) is 0.1% by weight based on 100 parts by weight of the ethylene-based thermoplastic elastomer (A).
The olefin foam laminate according to claim 15 or 16, which is 5 to 20 parts by weight. 18. The ethylene-based thermoplastic elastomer (A) has a compression set (70 ° C., 22 hours) of 60% or less according to JIS K6262, and JIS K 712.
Melt flow rate measured at 0 (230 ° C, 10 kg
The olefin foam laminate according to any one of claims 5 to 17, having a load of 0.1 g / 10 min or more. 19. The olefinic thermoplastic elastomer (X) is an olefinic thermoplastic elastomer (J) 1.
An olefin-based thermoplastic elastomer composition (X ₂ ) containing 00 parts by weight and 1 to 20 parts by weight of an olefin-based thermoplastic (K), wherein the olefin-based thermoplastic elastomer (J) is a polyolefin resin ( j-1) 5 to 60 parts by weight and 40 to 95 parts by weight of ethylene / α-olefin copolymer rubber (j-2) obtained by copolymerizing ethylene, α-olefin and, if necessary, a non-conjugated polyene [here. Then, the total amount of the component (j-1) and the component (j-2) is 100 parts by weight. ] The olefin-based thermoplastic elastomer (K) obtained by dynamically heat-treating a mixture containing the above, wherein the olefin-based thermoplastic (K) has an olefin content of 50 to 100 mol% and a melt flow rate (ASTM D-1238). -65T, 230 ° C, 2.
The olefin-based foam laminate according to claim 1 or 2, which is an olefin-based thermoplastic having a load of 16 kg) of 0.01 to 2 g / 10 minutes. 20. A foam (X) of an olefinic thermoplastic elastomer composition (X ₂ ) containing 100 parts by weight of an olefinic thermoplastic elastomer (J) and 1 to 20 parts by weight of an olefinic thermoplastic (K). An olefin foam laminate in which a base material layer made of _F2 ) and a skin layer made of an olefin thermoplastic elastomer composition (Z) are laminated, wherein the olefin thermoplastic elastomer (J) is a polyolefin resin. (J-1) 5 to 60 parts by weight, and ethylene / α-olefin copolymer rubber (j-2) 40 to 95 parts by weight obtained by copolymerizing ethylene, α-olefin and optionally a non-conjugated polyene [ Here, the total amount of the component (j-1) and the component (j-2) is 100 parts by weight. ] The olefin-based thermoplastic elastomer (K) obtained by dynamically heat-treating a mixture containing the above, wherein the olefin-based thermoplastic (K) has an olefin content of 50 to 100 mol% and a melt flow rate (ASTM D-1238). -65T, 230 ° C, 2.
16 kg load) is 0.01 to 2 g / 10 min olefin-based thermoplastic, and the olefin-based thermoplastic elastomer composition (Z)
Is 0.5 to 100 parts by weight of the olefinic thermoplastic elastomer (C).
25 parts by weight, fluoropolymer (E) 0.5 to 10 parts by weight, antistatic agent (F) 0.5 to 10 parts by weight, polyolefin resin (G) 5 to 200 parts by weight, fatty acid amide 0.0
1-5 parts by weight, mineral oil 0.5-10 parts by weight, metal soap 0.01-5 parts by weight, esters 0.01-5 parts by weight,
Olefin-based foaming which is an olefin-based thermoplastic elastomer composition containing at least one lubricant (Z _L ) selected from the group consisting of 0.01 to 5 parts by weight of calcium carbonate and 0.01 to 5 parts by weight of silicate in the above proportion. Laminate. 21. An olefinic thermoplastic elastomer (C), which is obtained by dynamically heat-treating a mixture containing a crystalline polyolefin resin (c-1) and a rubber (c-2). 20.
The olefinic foam laminate described. 22. The olefin foam laminate according to claim 19 or 20, wherein the polyolefin resin (G) is an ultrahigh molecular weight polyolefin resin (Y). 23. Ultra high molecular weight polyolefin resin (Y)
However, the intrinsic viscosity [η] measured in decalin at 135 ° C is 1
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] measured in 135 ° C decalin of 0.1 to 5 dl / g [where (y-
The total amount of the component 1) and the component (y-2) is 100 parts by weight. The olefin-based foam laminate according to claim 22, which is an ultrahigh molecular weight polyolefin resin composition containing 24. The olefin-based thermoplastic elastomer composition (Z) contains 0.01 to 100 parts by weight of a fatty acid amide with respect to 100 parts by weight of the olefin-based thermoplastic elastomer (C).
5 parts by weight, mineral oil 0.5 to 10 parts by weight, metal soap 0.
01-5 parts by weight, esters 0.01-5 parts by weight, calcium carbonate 0.01-5 parts by weight and silicate 0.0.
The olefinic thermoplastic elastomer composition (Z ₁ ) containing at least one lubricant (Z _L ) selected from the group consisting of 1 to 5 parts by weight in the above proportion.
The olefinic foam laminate described. 25. The olefinic thermoplastic elastomer composition (Z) comprises 0.01 to 5 parts by weight of a fatty acid amide as a lubricant (Z _L ) and 0 parts of mineral oil based on 100 parts by weight of the olefinic thermoplastic elastomer (C). 0.5 to 10 parts by weight, 0.01 to 5 parts by weight of metal soap, and esters of 0.
At least one selected from the group consisting of 01 to 5 parts by weight, 0.01 to 5 parts by weight of calcium carbonate, and 0.01 to 5 parts by weight of silicate; and a polyolefin resin (G) 5 to
The olefinic thermoplastic elastomer composition (Z ₂ ) containing 200 parts by weight in the above proportion.
The olefin foam laminate according to 1. 26. The olefin-based foam laminate according to claim 20, wherein the polyolefin resin (j-1) of the olefin-based thermoplastic elastomer (J) is a polypropylene resin. 27. The olefinic thermoplastic elastomer (J) contains 10 to 200 parts by weight of a softening agent (j-3) based on 100 parts by weight of an ethylene / α-olefinic copolymer rubber (j-2). The olefinic foam laminate according to any one of claims 20 to 26, which further contains. 28. The olefinic thermoplastic elastomer (J) comprises a polyolefin resin (j-1) and ethylene.
a mixture with an α-olefin copolymer rubber (j-2),
Alternatively, if necessary, a mixture containing a softening agent (j-3),
The olefin foam laminate according to any one of claims 19 to 27, which is a thermoplastic elastomer composition obtained by dynamically heat-treating in the presence of a crosslinking agent. 29. The olefin foam laminate according to claim 20, wherein the olefin thermoplastic (K) is isotactic polypropylene or a propylene / α-olefin copolymer. 30. An olefin whose foam (X _F2 ) contains 100 parts by weight of an olefinic thermoplastic elastomer (J), 1 to 20 parts by weight of an olefinic thermoplastic (K), and a blowing agent (B). The olefinic foam laminate according to any one of claims 20 to 29, which is a foam obtained by foaming the foamable composition (X ₃ ). 31. The olefin foam laminate according to claim 30, wherein the foaming agent (B) is an organic or inorganic pyrolytic foaming agent. 32. The content of the foaming agent (B) is 0.5 to 20 parts by weight based on 100 parts by weight of the total of the olefinic thermoplastic elastomer (J) and the olefinic thermoplastic (K). Item 30. An olefin-based foam laminate according to Item 30 or 31. 33. The olefin-based foam laminate according to claim 20, wherein the foam (X _F2 ) has a foaming ratio of 2 or more. 34. An olefinic thermoplastic elastomer (C) is 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 foam laminate according to any one of claims 20 to 33, which is an olefin-based thermoplastic elastomer. 35. The olefinic thermoplastic elastomer composition (X ₂ ) has a compression set (70 ° C., 22 hours) of 60% or less as measured by JIS K 6262, and JIS.
Melt flow rate measured by K 7120 (230
The olefin foam laminate according to any one of claims 20 to 34, which has a temperature of 10 ° C and a load of 10 kg of 0.1 g / 10 min or more. 36. A sliding member comprising the olefin foam laminate according to any one of claims 1 to 35. 37. A weather strip for an automobile, comprising the olefin foam laminate according to any one of claims 1 to 35. 38. A building sealing material comprising the olefin foam laminate according to any one of claims 1 to 35.