JPH09156009A - Thermoplastic elastomer laminated body and inner and outer parts for automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain inner and outer parts for automobile having excellent flaw resistance by using an olefin resin as a material. SOLUTION: Inner and outer parts for automobile are formed of a thermoplastic elastomer laminated body or further of a thermoplastic elastomer laminated body on which an intermediate layer is layered. The thermoplastic elastomer laminated body is formed of a skin layer consisting of a thermoplastic elastomer composition which contains components (A) and (B) mentioned below, and a base material layer consisting of a crosslinked polyethylene foamed body or a base material layer consisting of a crosslinked thermoplastic elastomer which contains a crystalline polyolefin resin and an olefin rubber. The component (A) is 10-50 pts.wt. of polyolefin composition consisting of an ultra-high- molecular-weight polyolefin and a polyolefin from a low-molecular-weight to a high-molecular-weight, and the component (B) is 90-50 pts.wt. of block copolymer consisting of a polymer block of styrene and an isoprene polymer block.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer laminate comprising a skin layer and a substrate layer, a thermoplastic elastomer laminate comprising a skin layer, an intermediate layer and a substrate layer, and these. The present invention relates to an automobile interior / exterior part made of a laminated body.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin has been widely used for automobile interior materials. An automobile interior material using vinyl chloride resin is a laminate in which the surface is textured by embossing and has a leather pattern, and a vinyl chloride resin layer is sequentially lined with a urethane foam layer and optionally a resin aggregate layer. Is used as. However, such a laminated body is manufactured through complicated steps. In addition, vinyl chloride resin produces harmful gas when incinerated,
There is a problem of polluting the environment.

Therefore, the inventors of the present application have proposed Japanese Patent Publication 1-14.
Japanese Patent No. 023 proposes a laminate of an olefinic thermoplastic elastomer that can be manufactured by a simple process.
This olefin thermoplastic elastomer laminate is composed of a blend of a partially cross-linked ethylene / α-olefin copolymer rubber and a polyolefin resin obtained by dynamically heat-treating it with an organic peroxide. It is composed of a thermoplastic elastomer layer having an embossed surface and a foam layer of polyethylene or polypropylene, is lightweight and can be recycled, and does not generate harmful gas when burned like vinyl chloride resin. Olefin-based thermoplastic elastomers have the advantages as described above, and thus have been widely used in recent years as energy-saving and resource-saving type materials from the viewpoint of protecting the global environment.

However, the conventional laminate made of an olefinic thermoplastic elastomer has a problem that it is inferior in scratch resistance as compared with a laminate made of a vinyl chloride resin, and its improvement is strongly desired.

Vinyl chloride resins are also widely used in side protection moldings, which are exterior parts of automobiles. Vinyl chloride resin is a very suitable material for automobile exterior parts because it has excellent scratch resistance and is inexpensive, but as mentioned above, vinyl chloride resin generates harmful gas when incinerated. Therefore, there is a problem of polluting the environment.

By the way, since olefin resins and olefin thermoplastic elastomers are lightweight and easy to recycle, they are widely used in automobile parts, industrial machine parts, electric / electronic parts, building materials, etc. as energy saving and resource saving type materials. It is used.

[0007] In recent years, from the viewpoint of protecting the global environment, in place of vinyl chloride resin, which emits harmful gas when incinerated,
Olefin-based resins or olefin-based thermoplastic elastomers that do not generate harmful gas have been used.

However, a conventional molded product made of an olefin resin or an olefin thermoplastic elastomer has a problem that it is inferior in scratch resistance as compared with a molded product made of a vinyl chloride resin, and its improvement is strongly desired. It is rare.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and uses an olefin resin as a material, which is excellent in scratch resistance, lightweight, and recycled. It is an object of the present invention to provide a thermoplastic elastomer laminate that does not easily generate harmful gas even when incinerated, and a vehicle interior / exterior part using the laminate.

[0010]

Means for Solving the Problems The inventors of the present invention have earnestly studied to obtain a thermoplastic elastomer laminate and a molded article having excellent scratch resistance, and have made a base material layer made of an olefin resin, a polyolefin composition and When a laminate comprising a skin layer formed from a thermoplastic elastomer composition containing a specific styrenic block copolymer in a specific ratio, or a laminate having an intermediate layer is prepared,
The inventors have found that a thermoplastic elastomer laminate that is lightweight, easy to recycle, produces no harmful gas even when incinerated, and has excellent scratch resistance, and completed the present invention.

That is, the present invention provides the following thermoplastic elastomer laminate and an automobile interior / exterior component comprising the same. (1) [I-] (A) Ultrahigh molecular weight polyolefin (a) having an intrinsic viscosity [η] measured in a 135 ° C decalin solvent in the range of 7 to 40 dl / g and 135 ° C decalin solvent. A polyolefin composition consisting essentially of a low to high molecular weight polyolefin (b) having an intrinsic viscosity [η] in the range of 0.1 to 5 dl / g, wherein the ultra high molecular weight polyolefin (a) is 15 to 4 relative to 100% by weight of the total of the molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b).
10 to 50 parts by weight of a polyolefin composition present in an amount of 0% by weight and having an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of 3.5 to 8.3 dl / g, and (B) A polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein isoprene is bonded at 1,2-position and 3,4-position with respect to all isoprene units. 90-50 parts by weight of an optionally hydrogenated block copolymer comprising a polymer or copolymer block (d) having a unit content of 40% or more [the total amount of components (A) and (B)] Is 100 parts by weight], which may be embossed with a thermoplastic elastomer composition [I-1], and [II-] (K) is cross-linked. Thermoplastic elastomer laminate characterized in that it consists also be polyethylene foam, or (L) be crosslinked consisting also be polypropylene foam substrate layer. (2) A portion containing the skin layer [I-], [II-] (M) crystalline polyolefin resin, or (N) crystalline polyolefin resin (p) and an olefin rubber (q). 1. A thermoplastic elastomer laminate comprising a base material layer made of a thermoplastic elastomer that is crosslinked physically or completely. (3) The skin layer of [I-], the base material layer of [II-], [III-] (M) crystalline polyolefin resin, or (N) crystalline polyolefin resin (p) and an olefin group. A partially or completely crosslinked thermoplastic elastomer containing rubber (q), and an intermediate layer laminated between the skin layer [I-] and the base material layer [II-]. A thermoplastic elastomer laminate characterized by being configured. (4) The thermoplastic elastomer composition [I-1] comprises, in addition to the components (A) and (B), a silicone oil (G),
At least one component selected from the group consisting of an ester (H) of an aliphatic alcohol and a dicarboxylic acid or a fatty acid, a fluoropolymer (I), and a higher fatty acid amide (J) is added to the components (A) and (B). 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the thermoplastic elastomer laminate according to any one of the above (1) to (3). (5) [I-] (A) Ultrahigh molecular weight polyolefin (a) having an intrinsic viscosity [η] measured in a 135 ° C decalin solvent in the range of 7 to 40 dl / g, and 135 ° C decalin solvent. A polyolefin composition consisting essentially of a low to high molecular weight polyolefin (b) having an intrinsic viscosity [η] in the range of 0.1 to 5 dl / g, wherein the ultra high molecular weight polyolefin (a) is 15 to 4 relative to 100% by weight of the total of the molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b).
10 to 50 parts by weight of a polyolefin composition present in an amount of 0% by weight and having an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of 3.5 to 8.3 dl / g.
(B) a polymer block (c) of styrene or a derivative thereof, which is an isoprene polymer block or an isoprene-butadiene copolymer block and is bonded at 1,2-position and 3,4-position with respect to all isoprene units. 90 to 25 parts by weight of an optionally hydrogenated block copolymer comprising a polymer or a copolymer block (d) having an isoprene unit content of 40% or more, (C) styrene or a derivative thereof. The polymer block (c) and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein the content of isoprene units bonded at 1,2-position and 3,4-position with respect to all isoprene units is 30. % Or less polymer or copolymer block (e) or butadiene polymer block (f)
0 to 30 parts by weight of an optionally hydrogenated block copolymer consisting of, (D) 0 to 40 parts by weight of olefin rubber, (E) 0 to 40 parts by weight of a softening agent, and (F) a crystalline polyolefin. A thermoplastic elastomer composition [I-2] comprising 0 to 50 parts by weight of a partially or completely crosslinked thermoplastic elastomer containing a resin (g) and an olefin rubber (h), Ingredient (C),
Contains at least one component selected from the group consisting of (D), (E) and (F) [components (A), (B),
The total amount of (C), (D), (E) and (F) is 100.
Parts by weight] and the components (A), (B), (C),
Thermoplastic elastomer in which the ratio of the total amount of components (A), (B), (C), (D) and (F) to the total amount of (D), (E) and (F) is 100 to 40% by weight. A thermoplastic elastomer laminate comprising a skin layer which may be embossed and which is composed of the composition [I-2], and a base material layer of the above [II-]. (6) A thermoplastic elastomer laminate comprising the skin layer [I-] and the base material layer [II-]. (7) A thermoplastic elastomer laminate comprising a skin layer [I-], a base material layer [II-], and an intermediate layer [III-]. (8) The thermoplastic elastomer composition [I-2] further comprises a silicone oil (G), an ester (H) of an aliphatic alcohol and a dicarboxylic acid or a fatty acid, a fluoropolymer (I), and a higher fatty acid amide (J ), At least one component selected from the group consisting of
0.01 to 10 parts by weight per 100 parts by weight of the total amount of (B), (C), (D), (E) and (F) is contained, and the above (5) to (). 7. The thermoplastic elastomer laminate according to any one of 7). (9) The thermoplastic elastomer laminate according to any one of (1) to (8) above, wherein an aggregate layer made of a polyolefin resin (Z) is laminated on the base material layer side. (10) A laminated body or a skin layer, an intermediate layer, and a base material, which is formed by preheating a skin layer and a base material layer on a molded aggregate product in which a polyolefin resin (Z) to be an aggregate layer is molded into a predetermined shape. The thermoplastic elastomer laminate according to (9) above, wherein the laminate comprising the layers is placed and thermoformed so that the base material layer and the aggregate layer are in contact with each other and integrated. (11) An automobile interior / exterior component, comprising the thermoplastic elastomer laminate according to any one of (1) to (10) above.

<< Skin Layer >> The skin layer constituting the thermoplastic elastomer laminate of the present invention comprises a thermoplastic elastomer composition [I-1] (containing a polyolefin composition (A) and a block copolymer (B). Hereinafter, it may be referred to as the first thermoplastic elastomer composition [I-1]),
Alternatively, in addition to the polyolefin composition (A) and the block copolymer (B), a block copolymer (C), an olefin rubber (D), a softening agent (E) and a thermoplastic elastomer (F) can be selected. Thermoplastic elastomer composition containing at least one selected component [I-
2] (hereinafter, the second thermoplastic elastomer composition [I-
2)).

The first or second thermoplastic elastomer composition [I-1] or [I- which constitutes the skin layer according to the present invention.
2] includes components (A), (B), (C), (D),
In addition to (E) and (F), if necessary, silicone oil (G), ester (H) of aliphatic alcohol and dicarboxylic acid or fatty acid, fluoropolymer (I), and higher fatty acid amide (J At least one component selected from the group consisting of

<< Polyolefin Composition (A) >> The polyolefin composition (A) used in the present invention has an intrinsic viscosity [η] of 7-40 dl / measured in a decalin solvent at 135 ° C.
g, preferably from 7 to 35 dl / g of ultra-high molecular weight polyolefin (a) and an intrinsic viscosity [η] measured in a 135 ° C decalin solvent of from 0.1 to 5 dl / g, preferably from 0.1 to 5 dl / g. A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin (b) in the range of 3 dl / g, wherein the ultra high molecular weight polyolefin (a) and the ultra high molecular weight polyolefin (a) are low to high molecular weight. 15-40% by weight, preferably 15-35%, based on 100% by weight of the total weight of the molecular weight polyolefin (b).
It is present in a proportion of wt% and has an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 3.5 to 8.3 dl / g, preferably 4.0 to 8.0 dl / g.

The ultra high molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b) as described above are, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-
Decene, 1-dodecene, 4-methyl-1-pentene, 3
It consists of a homopolymer or copolymer of α-olefin such as -methyl-1-pentene. In the present invention, an ethylene homopolymer and a copolymer of ethylene and 50 mol% or less of another α-olefin are preferable.

In the above polyolefin composition (A),
1 to 20% by weight of a liquid or solid lubricating oil may be added to the polyolefin composition (A). As the liquid lubricating oil, petroleum-based lubricating oil, synthetic lubricating oil or the like is used. Specific examples of the petroleum-based lubricating oil include liquid paraffin, spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, and cylinder oil. Specific examples of the synthetic lubricating oil include synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil, phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil, chlorinated biphenyl oil, silicone oil. Etc. are used.

As the above-mentioned solid lubricating oil, specifically, graphite and molybdenum disulfide are mainly used, but boron nitride, tungsten disulfide, lead oxide, glass powder, metallic soap and the like can also be used. it can. The solid lubricating oil can be used alone or in combination with the liquid lubricating oil. For example, the solid lubricating oil and the liquid lubricating oil can be used in the form of powder, sol, gel, suspenseoid, etc. It can be added to (A).

The above polyolefin composition (A) contains
If necessary, additives such as mineral oil-based softeners, heat stabilizers, antistatic agents, weathering stabilizers, antiaging agents, fillers, colorants, lubricants and the like are blended within a range that does not impair the object of the present invention. can do.

Polyolefin composition (A) as described above
Is 100 parts by weight in total of the polyolefin composition (A), the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F). To 10 to 50 parts by weight, preferably 15 to 40 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

<< Block Copolymer (B) >> The block copolymer (B) used in the present invention comprises a polymer block (c) of styrene or a derivative thereof and a specific isoprene polymer or a specific isoprene-butadiene copolymer. It is composed of a block (d) made of a polymer and may be hydrogenated.

The polymer component constituting the block (c) is styrene or its derivative. Specific examples of the styrene derivative include α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4. -Benzylstyrene, 4- (phenylbutyl) styrene, etc. may be mentioned. As the polymer component forming the block (c), styrene and α-methylstyrene are preferable.

The polymer or copolymer constituting the block (d) is an isoprene polymer or an isoprene-butadiene copolymer, which is in the 1,2-position and 3,4-position with respect to the entire isoprene unit shown below. Content of isoprene unit bonded at position 40% or more, preferably 45
% Or more.

[0023]

Embedded image

In the present invention, when the content of isoprene units bonded at the 1,2-position and the 3,4-position with respect to all isoprene units is 40% or more, a laminate having excellent scratch resistance is provided. To obtain a thermoplastic elastomer composition [I
-1] and [I-2] can be obtained.

The proportion of the polymer block (c) of styrene or its derivative in the block copolymer (B) is preferably 5 to 50% by weight, more preferably 10 to 45%.
% By weight. That is, the proportion of the above isoprene polymer block or isoprene-butadiene copolymer block (d) is preferably in the range of 95 to 50% by weight, more preferably 90 to 55% by weight.

In the present invention, the hydrogenated block copolymer (B) is preferred. When the hydrogenated block copolymer (B) is used, a thermoplastic elastomer composition capable of providing a laminate excellent in weather resistance and heat resistance [I
-1] and [I-2] are obtained.

The melt flow rate (MFR; ASTM D 123) of the block copolymer (B) used in the present invention.
8, 230 ° C., 2.16 kg load) is preferably 0.
01 to 30 g / 10 minutes, more preferably 0.01 to 1
It is in the range of 0 g / 10 minutes. When the block copolymer (B) having a melt flow rate in the above range is used, a thermoplastic elastomer composition [I-1] or [I-2] capable of providing a laminate excellent in scratch resistance Is obtained.

The block copolymer (B) used in the present invention is most preferably in the form of block (c) -block (d) -block (c), but is not limited thereto.

Such a block copolymer (B) can be produced, for example, by the following method. (1) A method in which styrene or a derivative thereof, isoprene or an isoprene-butadiene mixture is sequentially polymerized using an alkyllithium compound as an initiator. (2) A method of polymerizing styrene or a derivative thereof, followed by isoprene or a mixture of isoprene and butadiene, and coupling this with a coupling agent. (3) A method of sequentially polymerizing isoprene or an isoprene-butadiene mixture and then styrene or a derivative thereof using a dilithium compound as an initiator. Details of the method for producing the block copolymer (B) are described in, for example, JP-A 2-3
It is described in Japanese Patent No. 00250.

If the block copolymer (B) obtained by the above method is subjected to a hydrogenation treatment, a hydrogenated block copolymer (B) can be obtained. The block to be hydrogenated is an isoprene polymer block or an isoprene-butadiene copolymer block (d).

In the first thermoplastic elastomer composition [I-1] used in the present invention, the block copolymer (B) is 100 in the total amount of the polyolefin composition (A) and the block copolymer (B). 90 to 5 parts by weight
It is used in an amount of 0 part by weight, preferably 85 to 60 parts by weight.

In the second thermoplastic elastomer composition [I-2] used in the present invention, the block copolymer (B) includes the polyolefin composition (A), the block copolymer (B) and the block. 90 to 25 parts by weight, preferably 85 to 30 parts by weight, based on 100 parts by weight of the total amount of the copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F). Used in. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the block copolymer (B) is used in the above proportion, the thermoplastic elastomer composition [I-1 can provide a laminate excellent in heat resistance and scratch resistance and abrasion resistance. ], [I-2] are obtained.

<< Block Copolymer (C) >> The block copolymer (C) used in the present invention comprises a polymer block (c) of styrene or a derivative thereof and a specific isoprene polymer or a specific isoprene-butadiene copolymer. It is composed of a polymer block (e) or a butadiene polymer block (f) and may be hydrogenated.

The polymer component constituting the block (c) is styrene or its derivative, and examples thereof include the same compounds as those exemplified in the section of the block copolymer (B). As the polymer component forming the block (c), styrene and α-methylstyrene are preferable.

The polymer or copolymer forming the block (e) is an isoprene polymer or an isoprene-butadiene copolymer, and is bonded at the 1,2-position and the 3,4-position with respect to all isoprene units. The isoprene unit content is 30% or less, preferably 25% or less. In the present invention, 1,2 relative to all isoprene units
A thermoplastic elastomer composition [I-2] capable of providing a laminate having a good appearance when the content of isoprene units bonded at the -position and the 3,4-position is 30% or less.
Can be obtained.

Block copolymer (C) used in the present invention
May be composed of a block (c) and a block (e), or may be composed of a block (c) and a block (f) composed of a butadiene polymer.

The proportion of the polymer block (c) of styrene or its derivative in the block copolymer (C) is preferably 5 to 50% by weight, more preferably 10 to 45.
% By weight. That is, the ratio of the isoprene polymer block or the isoprene-butadiene copolymer block (e) or the butadiene polymer block (f) is preferably 95 to 50% by weight, more preferably 90 to 55% by weight. Is.

In the present invention, the hydrogenated block copolymer (C) is preferred. When the hydrogenated block copolymer (C) is used, a thermoplastic elastomer composition capable of providing a laminate excellent in weather resistance and heat resistance [I
-2] is obtained.

The melt flow rate (MFR; ASTM D 123) of the block copolymer (C) used in the present invention.
8, 230 ° C., 2.16 kg load) is preferably 0.
01 to 100 g / 10 minutes, more preferably 0.01 to
It is in the range of 50 g / 10 minutes. When the block copolymer (C) having a melt flow rate in the above range is used, a thermoplastic elastomer composition [I-2] capable of providing a laminate having excellent scratch resistance can be obtained.

The block form of the block copolymer (C) used in the present invention is most preferably block (c) -block (e) or (f) -block (c), but is not limited thereto. is not.

The optionally hydrogenated block copolymer (C) can be produced, for example, by the same method as the method for producing the block copolymer (B) described above. In the preparation of the hydrogenated block copolymer (C), the hydrogenated block is an isoprene polymer block, an isoprene-butadiene copolymer block (e), or a butadiene polymer block (f). Is.

In the present invention, the block copolymer (C) is a polyolefin composition (A), a block copolymer (B), a block copolymer (C), an olefin rubber (D), a softening agent ( 0 to 30 parts by weight based on 100 parts by weight of the total amount of E) and the thermoplastic elastomer (F),
Preferably 0 to 25 parts by weight, more preferably 0 to 20
Used in parts by weight. However, the above component (C),
Since (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the block copolymer (C) is used in the above proportion, it is excellent in scratch resistance and abrasion resistance, and
A thermoplastic elastomer composition [I-2] capable of providing a laminate having an excellent appearance is obtained.

<< Olefin-Based Rubber (D) >> The olefin-based rubber (D) used in the present invention is an amorphous random elastic copolymer mainly composed of an α-olefin having 2 to 20 carbon atoms, such as α. -Amorphous random elastic copolymers having an olefin content of 50 mol% or more are included. Further, in the present invention, within a range that does not impair the object of the present invention, an olefin rubber (D) and a rubber other than the olefin rubber (D), for example, styrene-butadiene rubber (SBR), nitrile rubber (NBR), Diene rubber such as natural rubber (NR) and butyl rubber (IIR), S
It is also possible to use it in combination with EBS, polyisobutylene rubber or the like.

The amorphous random elastic copolymer having an α-olefin content of 2 to 20 carbon atoms of 50 mol% or more is an α-olefin copolymer composed of two or more kinds of α-olefins, and 2 There are amorphous α-olefin copolymers composed of one or more α-olefins, α-olefin / non-conjugated diene copolymers composed of two or more α-olefins and non-conjugated dienes, and specifically, The following rubbers can be used.

(1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
50/50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [Ethylene / α-olefin (molar ratio) = about 90/10
50/50] (3) Propylene / α-olefin copolymer rubber [Propylene / α-olefin (molar ratio) = about 90/1
0-50 / 50] (4) Butene / α-olefin copolymer rubber [Butene / α-olefin (molar ratio) = about 90/10
50/50] As the α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1
-Hexene, 1-octene and the like.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene. The ethylene / α-olefin / (2) above in which such a non-conjugated diene is copolymerized
The iodine value of the non-conjugated diene copolymer rubber is preferably 25 or less. The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the above-mentioned copolymer rubbers (1) to (4) is 10 to 250, and particularly preferably 30 to 150.

In the present invention, the olefin rubber (D) is the polyolefin composition (A), the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softener (E). ) And 0 to 40 parts by weight based on 100 parts by weight of the total amount of the thermoplastic elastomer (F),
Preferably 0 to 30 parts by weight, more preferably 0 to 25
Used in parts by weight. However, the above component (C),
Since (D), (E) and (F) are optional components, these components may be 0 parts by weight. When the olefin rubber (D) is used in the above proportion, a thermoplastic elastomer composition [I-2] that can provide a laminate having excellent scratch resistance and flexibility is obtained.

<< Softening Agent (E) >> As the softening agent (E) used in the present invention, a softening agent usually used for rubber is suitable, and specifically, process oil, lubricating oil, paraffin, liquid paraffin, Petroleum-based substances such as polyethylene wax, polypropylene wax, petroleum asphalt, petrolatum; coal tars such as coal tar, coal tar pitch; castor oil, linseed oil, rapeseed oil, soybean oil,
Fatty oils such as coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid, erucic acid or the like Metal salts; synthetic polymers such as petroleum resin, coumarone indene resin, atactic polypropylene; dioctyl phthalate,
Ester plasticizers such as dioctyl adipate and dioctyl sebacate; other microcrystalline waxes;
Liquid polybutadiene or a modified or hydrogenated product thereof,
And liquid thiochol.

In the present invention, the softening agent (E) is a polyolefin composition (A), a block copolymer (B), a block copolymer (C), an olefin rubber (D), a softening agent (E). And total amount of thermoplastic elastomer (F) 1
0 to 40 parts by weight, preferably 0 to 3 with respect to 00 parts by weight
It is used in an amount of 0 part by weight, more preferably 0 to 20 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the softening agent (E) is used in the above proportion, a thermoplastic elastomer composition [I-2] having excellent fluidity during molding can be obtained. A molded article made of this thermoplastic elastomer composition [I-2] has good scratch resistance.

<< Thermoplastic Elastomer (F) >> The thermoplastic elastomer (F) used in the present invention comprises a crystalline polyolefin resin (g) and an olefin rubber (h). Examples of the crystalline polyolefin resin (g) include α-olefin homopolymers or copolymers having 2 to 20 carbon atoms.

Specific examples of the crystalline polyolefin resin (g) include the following polymers and copolymers. (1) Ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate or ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10 mol% or less of other α-olefin (5) Block copolymerization of propylene and 30 mol% or less of other α-olefin Combined (6) 1-butene homopolymer (7) Random copolymer of 1-butene and other α-olefin at 10 mol% or less (8) 4-Methyl-1-pentene homopolymer (9) 4 -Methyl-1-pentene and random copolymer of 20 mol% or less of other α-olefins (10) Intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 10 to 40 dl / g Molecular weight polyethylene (11) 15-40% by weight of ultra-high molecular weight polyethylene having an intrinsic viscosity [η] measured in 135 ° C decalin within the range of 10-40 dl / g and an intrinsic viscosity [η] measured in 135 ° C decalin ] Of 60 to 85% by weight of polyethylene in the range of 0.1 to 5 dl / g, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 3.5 to 8.3 d.
An ultra high molecular weight polyethylene composition in the range of 1 / g.

Specific examples of the above α-olefin include ethylene, propylene, 1-butene and 4-methyl-1.
-Pentene, 1-hexene, 1-octene and the like. Among the above crystalline polyolefin resins (g), propylene homopolymers, random copolymers of propylene and 10 mol% or less of other α-olefins, and propylene and 30 mol% or less of other α-olefins. Block copolymers are particularly preferred. The above crystalline polyolefin resins (g) can be used alone or in combination.

The crystalline polyolefin resin (g) used in the present invention has a melt flow rate (MFR; ASTM D).
1238, 230 ° C., 2.16 kg load) is preferably in the range of 0.01 to 100 g / 10 minutes, more preferably 0.3 to 70 g / 10 minutes. The crystallinity of the crystalline polyolefin resin (g) determined by the X-ray method is usually 5 to 100%, preferably 20 to 80%.

The crystalline polyolefin resin (g) constituting the thermoplastic elastomer (F) is the total amount 1 of the crystalline polyolefin resin (g) and the olefin rubber (h).
10 to 90 parts by weight, preferably 10
To 80 parts by weight, more preferably 20 to 70 parts by weight. When the thermoplastic elastomer (F) containing the crystalline polyolefin resin (g) in the above proportion is used, it is possible to provide a laminate excellent in scratch resistance and heat resistance, which is excellent in moldability. A plastic elastomer composition [I-2] is obtained.

As the olefin rubber (h), the above-mentioned olefin rubber (D) can be used. The olefin rubber (h) is a thermoplastic elastomer (F)
In it, it exists in a partially crosslinked state or a completely crosslinked state. In the present invention, it is preferable that the olefin rubber (h) is in a partially crosslinked state.

Further, in the present invention, an olefin rubber (h) and a rubber other than the olefin rubber (h) may be used in combination within a range not impairing the object of the present invention. Examples of the rubber other than the olefin rubber (h) include styrene-butadiene rubber (SB
R), nitrile rubber (NBR), natural rubber (NR), butyl rubber (IIR) and other diene rubbers, SEBS, polyisobutylene rubber and the like.

In the thermoplastic elastomer (F), the olefin rubber (h) is 10 to 90 parts by weight, preferably 20 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (g) and the olefin rubber (h). ~ 90
It is used in an amount of 30 parts by weight, more preferably 30 to 80 parts by weight.

When the olefin rubber (h) and a rubber other than the olefin rubber (h) are used in combination, the rubber other than the olefin rubber (h) is a crystalline polyolefin resin (g) and an olefin. It is used 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 system rubber (h).

The thermoplastic elastomer (F) containing the olefin rubber (h) in the above proportion, or the olefin rubber (h) and a rubber other than the olefin rubber (h) in the above proportion. When the thermoplastic elastomer (F) is used, a thermoplastic elastomer composition [I-2] that can provide a laminate having excellent scratch resistance and flexibility is obtained.

In the thermoplastic elastomer (F) used in the present invention, if necessary, a mineral oil type softener, a heat resistance stabilizer, an antistatic agent, a weather resistance stabilizer, an antiaging agent, a filler, a colorant, a lubricant. Additives such as can be added within a range that does not impair the object of the present invention.

The thermoplastic elastomer (F) preferably used in the present invention is a crystalline polypropylene resin (g).
And an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber (h), and these components are partially crosslinked in the thermoplastic elastomer (F). And the weight ratio of the crystalline polypropylene resin (g) to the olefin rubber (h) (crystalline polypropylene resin (g) / olefin rubber (h)) is 70/30 to 10
It is within the range of / 90.

More specific examples of the thermoplastic elastomer (F) preferably used in the present invention include 70 to 10 parts by weight of a crystalline polypropylene resin (g) and ethylene / propylene copolymer weight as an olefin rubber (h). Combined rubber or ethylene / propylene / diene copolymer rubber 30
To 90 parts by weight [the total amount of the crystalline polypropylene resin (g) and the olefin rubber (h) is 100 parts by weight], and a rubber other than the olefin rubber (h) 5 to 100 parts by weight.
The thermoplastic elastomer (F) is composed of 5 parts by weight and / or 5 to 100 parts by weight of a mineral oil-based softening agent, and the olefin rubber (h) is partially crosslinked.

The thermoplastic elastomer (F) used in the present invention is obtained by dynamically heat treating a blend containing a crystalline polyolefin resin (g) and an olefin rubber (h) in the presence of an organic peroxide. Can be obtained.

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

Among these, 2,5-dimethyl-2,5-di- (tert-) is preferable in terms of odor and scorch stability.
Butylperoxy) hexane, 2,5-dimethyl-2,
5-di- (tert-butylperoxy) hexyne-
3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane,
n-Butyl-4,4-bis (tert-butylperoxy) valerate is preferred, and 1,3-bis (te
Most preferred is (rt-butylperoxyisopropyl) benzene.

In the present invention, the organic peroxide is contained in an amount of 0.05 to 3% by weight, preferably 0.1 to 100% by weight of the total amount of the crystalline polyolefin resin (g) and the olefin rubber (h). Used at a ratio of 1% by weight.

In the present invention, sulfur, p-quinonedioxime, and
p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N,
Peroxy crosslinking aids such as N'-m-phenylenedimaleimide; or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc. A polyfunctional vinyl monomer such as a polyfunctional methacrylate monomer, vinyl butyrate, or vinyl stearate can be blended.

By using the above compound,
A uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin resin (g) and the olefin rubber (h), which are the main components of the above-mentioned substance to be crosslinked, and acts to solubilize the organic peroxide. The thermoplastic elastomer (F) has a uniform cross-linking effect due to heat treatment, and acts as a dispersant for organic peroxides, and has a good balance of fluidity and physical properties.
Is obtained.

In the present invention, the above-mentioned crosslinking aid or polyfunctional vinyl monomer is contained in an amount of 0.1 to 2% by weight, and particularly 0.3 to 1% by weight, based on the whole article to be crosslinked. It is preferably used in proportion. When the mixing ratio of the cross-linking aid or the polyfunctional vinyl monomer is within the above range, the thermoplastic elastomer (F) obtained is such that the cross-linking aid and the polyfunctional vinyl monomer remain as unreacted monomers in the elastomer. Therefore, there is no change in physical properties due to heat history during processing and molding, and it has excellent fluidity.

The above-mentioned "dynamically heat-treating" means kneading each of the above components in a molten state. The dynamic heat treatment is carried out by using a kneading device such as a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder, and preferably in a non-open type kneading device. The dynamic heat treatment is preferably performed in an inert gas such as nitrogen.

The kneading is preferably carried out at a temperature at which the half-life of the organic peroxide used is less than 1 minute. The kneading temperature is usually 150 to 280 ° C., preferably 170 to 2
40 ° C., kneading time is 1 to 20 minutes, preferably 1
~ 5 minutes. The shearing force applied during kneading is
Usually, the shear rate is 10 to 10 ⁴ sec ^-1 , preferably 1
It is determined within the range of 0 ² to 10 ⁴ sec ⁻¹ .

As described above, the olefin rubber (h)
A partially or completely crosslinked thermoplastic elastomer (F) can be obtained. Here, "partially crosslinked" means that the gel content (cyclohexane insoluble matter) measured by the following method is, for example, 10% or more, particularly 2%.
It refers to the case of 0% or more and less than 97%. In the present invention, the gel content is preferably 30% or more. Also, "completely crosslinked" means that the gel content (cyclohexane insoluble matter) measured by the following method is 98% or more and 100% or more.
Is the case. When the thermoplastic elastomer (F) having a gel content in the above range is used, the resulting thermoplastic elastomer composition [I-2] has good fluidity during molding, and is a laminate excellent in mechanical strength and heat resistance. Can be provided.

[Measurement Method of Gel Content (Cyclohexane Insoluble Content)] About 100 samples of thermoplastic elastomer (F) were used.
mg Weigh and cut into 0.5 mm x 0.5 mm x 0.5 mm strips, and the resulting strips are 30 m in a closed container.
Immerse in 1 liter of cyclohexane at 23 ° C. 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 (Q)".

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,
The corrected initial weight (P) is used. Here, the gel content (cyclohexane insoluble content) is calculated by the following equation.

## EQU1 ## Gel content [wt%] = [corrected final weight (Q)] / [corrected initial weight (P)] × 100

In the present invention, the thermoplastic elastomer (F) is the above-mentioned polyolefin composition (A), block copolymer (B), block copolymer (C), olefin rubber (D), softening agent. 0 to 50 parts by weight, preferably 0 to 40 parts by weight, and more preferably 0 to 100 parts by weight of the total amount of (E) and the thermoplastic elastomer (F).
It is used in a proportion of 30 parts by weight. However, the above component (C),
Since (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the thermoplastic elastomer (F) is used in the above proportion, a thermoplastic elastomer composition [I-2] which can provide a laminate excellent in heat resistance and scratch resistance is obtained.

<< Silicone oil (G), ester (H), fluoropolymer (I) and higher fatty acid amide (J) >> The silicone oil (G) used in the present invention is specifically dimethyl silicone oil or phenyl. Examples include methyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, modified silicone oil and the like. Of these, dimethyl silicone oil and phenylmethyl silicone oil are preferable.

The kinematic viscosity of this silicone oil (G) [J
IS K 2283, 25 ° C] is 10 to 30,000c
St, preferably 50 to 10,000 cSt, and more preferably 100 to 5,000 cSt.

The ester (H) used in the present invention is
It is an ester of an aliphatic alcohol and a dicarboxylic acid or a fatty acid. Specific examples of such an ester (H) include 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, and a beef tallow alcohol. An ester with propionic acid,
Beef tallow alcohol and butyric acid ester, stearyl alcohol and acetic acid ester, stearyl alcohol and propionic acid ester, stearyl alcohol and butyric acid ester, distearyl alcohol and phthalic acid ester, glycerin monooleate, glycerin monostearate Rate, 12-hydroxy stearate, glycerin tristearate, trimethylolpropane tristearate, pentaerythritol tetrastearate, butyl stearate, isobutyl stearate, stearic acid ester, oleic acid ester, behenic acid ester, calcium soap included Ester, isotridecyl stearate, cetyl palmitate, cetyl stearate, stearyl stearate, behenyl behenate, ethylene tannate montanate Glycol ester, montanic acid glycerol esters, montan 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, and montanic acid glycerin ester are preferable. Particularly preferred are esters of distearyl alcohol and phthalic acid, glycerin monostearate, and glyceryl montanate.

Specific examples of the fluorine-based polymer (I) used in the present invention include polytetrafluoroethylene and vinylidene fluoride copolymer. Of these, polytetrafluoroethylene is preferred.

Specific examples of the higher fatty acid amide (J) used in the present invention include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide and behemic acid amide; erucic acid amide, oleic acid amide and brassidin. Unsaturated fatty acid amides such as acid amide and elaidic acid amide; methylenebisstearic acid amide,
Examples thereof include bis fatty acid amides such as methylene bis oleic acid amide, ethylene bis stearic acid amide, and ethylene bis oleic acid amide. Among these, erucamide, oleamide, and ethylenebisoleamide are preferred.

In the present invention, at least one component selected from the group consisting of the silicone oil (G), the ester (H), the fluoropolymer (I) and the higher fatty acid amide (J) is a polyolefin composition. (A),
0.0 based on 100 parts by weight of the total amount of the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F).
It is used in a proportion of 1 to 10 parts by weight, preferably 0.01 to 5 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the above silicone oil (G), ester (H), fluoropolymer (I) or higher fatty acid amide (J) is used in the above proportion, a thermoplastic elastomer excellent in scratch resistance is obtained. Composition [I-1],
[I-2] can be obtained.

<< Other Components >> In the present invention, in the thermoplastic elastomer compositions [I-1] and [I-2], if necessary, within the range not impairing the object of the present invention,
Additives such as known inorganic fillers, heat stabilizers, antiaging agents, weathering stabilizers, antistatic agents, metal soaps, and lubricants such as waxes can be added.

Specific examples of such inorganic fillers include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate and magnesium carbonate. , Molybdenum disulfide, glass fiber, glass sphere, shirasu balloon, graphite, alumina and the like.

Known heat resistance stabilizers, antiaging agents, and weather resistance stabilizers include phenol-based, sulfite-based, phenylalkane-based, phosphite-based, and amine-based stabilizers.

<< Thermoplastic Elastomer Composition [I-
2] >> Thermoplastic Elastomer Composition Used in the Present Invention [I
-2], the total of the polyolefin composition (A), the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F). Polymer component relative to the amount, that is, the polyolefin composition (A), the block copolymer (B),
The ratio of the total amount of the block copolymer (C), the olefin rubber (D) and the thermoplastic elastomer (F) is 100.
-40% by weight, preferably 100-50% by weight.

<< Thermoplastic Elastomer Composition [I-
1], Preparation of [I-2] >> The first thermoplastic elastomer composition [I-1] constituting the skin layer according to the present invention comprises a polyolefin composition (A) and a block copolymer (B).
And can be prepared by blending them in the above-mentioned proportions and performing a dynamic heat treatment in the absence of an organic peroxide.

The second thermoplastic elastomer composition [I-2] constituting the skin layer according to the present invention comprises a polyolefin composition (A), a block copolymer (B), and a block copolymer ( C), an olefin rubber (D), a softening agent (E), and at least one component selected from the group consisting of a thermoplastic elastomer (F) are mixed in the above-mentioned proportions, and no organic peroxide is present. It can be prepared by performing a dynamic heat treatment below.

In the preparation of the first and second thermoplastic elastomer compositions [I-1] and [I-2] used in the present invention, when the above-mentioned respective components are blended, if necessary, At least one component selected from the group consisting of silicone oil (G), ester (H), fluoropolymer (I), and higher fatty acid amide (J) can be blended.

As the dynamic heat treatment method, the dynamic heat treatment method described above in the preparation of the thermoplastic elastomer (F) is desirable. However, this dynamic heat treatment is performed in the absence of organic peroxide.

<Base Material Layer> The base material layer constituting the thermoplastic elastomer laminate of the present invention comprises a polyethylene or polypropylene foam (K or L), preferably a polyethylene or polypropylene crosslinked foam, or It comprises a crystalline polyolefin resin (M) or a partially or completely crosslinked thermoplastic elastomer (N) containing a crystalline polyolefin resin (p) and an olefin rubber (q).

The crosslinked foam (K or L) can be produced by heating a mixture containing polyethylene or polypropylene, a swelling agent and a crosslinking agent at a temperature equal to or higher than the softening point of the mixture. Examples of the swelling agent include azobis (formamide), diazoaminobenzene, N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosoterephthalimide, P, P'-oxy-. Bis (benzenesulfonyl semicarbazide), azobis (isobutyronitrile), P, P'-oxy-bis (benzenesulfonyl hydrazide), P, P'-diphenyl-bis (sulfonyl hydrazide), benzenesulfonyl hydrazide, m-benzene- Examples thereof include bis (sulfonyl hydrazide), monochlorotrifluoromethane, monochlorodifluoromethane, butane, pentane and hexane.

Examples of the cross-linking agent include 1,7-heptane-bis (sulfone azide), 1,11-undecane-bis (sulfone azide), 1,12-dodecane-bis (sulfone azide), 1 , 9,18-octadecane-tris (sulfone azide), poly (ethylene sulfone azide), 1,3-benzenebis (sulfone azide), 1-octyl-2,4,6-benzene tris (sulfone azide) ), 4,4′-diphenylmethane bis (sulfone azide), 4,4′-diphenyl disulfide bis (sulfone azide) and other poly (sulfone azide) compounds; n-octadecyl azidoformate, tetramethylene-bis (Azidoformate), phenyl azidoformate, 2,2-isopropylidene-bis (P, P'-phenyl) Jidohometo), 2,2 '
-Oxydiethyl-bis (azidoformate), 2,
Azidoformate compounds such as 2'-ethylenedioxydiethyl-bis (azidoformate) and 2,2'-thiodiethyl-bis (azidoformate); m-phenylenediazide, 2,4,6-triazidebenzene , 4, 4 '
-Aromatic polyazide compounds such as diazide phenylamine.

The method for producing the crosslinked foam is described in detail, for example, in Japanese Patent Publication Nos. 39-25500, 40-25351 and 40-25352. It is also possible to use a crosslinked foam that is crosslinked by radiation. Further, as the crosslinked foamed product, a commercially available product may be used as it is. When the thermoplastic elastomer laminate of the present invention is used as an automobile interior material, these foams preferably have a foaming ratio of about 10 to 50 times.

As the crystalline polyolefin resin (M) forming the base material layer of the thermoplastic elastomer laminate of the present invention, the crystalline polyolefin resin (g) described above, including the preferred embodiments, can be applied as it is. The crystalline polyolefin resin (M) may be used alone or in combination of two or more.

The thermoplastic elastomer (N) forming the base material layer is the same as the above-mentioned thermoplastic elastomer (F).
It can be applied as it is including the preferable embodiment.
That is, the thermoplastic elastomer (N) is composed of the crystalline polyolefin resin (p) and the olefin rubber (q), but these are the crystalline polyolefin resin (g) and the olefin system constituting the thermoplastic elastomer (F). The rubber (h) can be applied as it is, including the preferred embodiment. In addition, the thermoplastic elastomer (F)
All the optional components and the preparation method in (3) are also applied to the thermoplastic elastomer (N).

If necessary, the crystalline polyolefin resin (M) or the thermoplastic elastomer (N) forming the base material layer may include a mineral oil-based softener, a heat 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.

<< Intermediate Layer >> The crystalline polyolefin resin (M) forming the intermediate layer of the thermoplastic elastomer laminate of the present invention is the above-mentioned crystalline polyolefin resin (g).
Can be applied as is, including the preferred embodiments. The crystalline polyolefin resin (M) may be used alone or in combination of two or more.

As the thermoplastic elastomer (N), the above-mentioned thermoplastic elastomer (F) can be applied as it is, including the preferred embodiment. That is, the thermoplastic elastomer (N) is composed of the crystalline polyolefin resin (p) and the olefin rubber (q), but these are the crystalline polyolefin resin (g) and the olefin system constituting the thermoplastic elastomer (F). The rubber (h) can be applied as it is, including the preferred embodiment. Further, all the optional components and preparation methods for the thermoplastic elastomer (F) are also applicable to the thermoplastic elastomer (N). In the present invention, the intermediate layer is formed of the crystalline polyolefin resin (M) or the thermoplastic elastomer (N) as described above.

<< Aggregate Layer >> In the thermoplastic elastomer laminate of the present invention, an aggregate layer may be provided on the base material layer side for the purpose of imparting shape retention (rigidity). As the resin forming the aggregate layer, a polyolefin resin (Z), preferably a crystalline polyolefin resin (Z) can be used. Examples of the crystalline polyolefin resin (Z) include the same polymers or copolymers as the crystalline polyolefin resin (g). The crystalline polyolefin resin (g)
Among them, propylene homopolymer, random copolymer of propylene and 10 mol% or less of other α-olefin,
A block copolymer of propylene and 30 mol% or less of another α-olefin is preferable. The crystalline polyolefin resin (Z) can be used alone or in combination.

In the polyolefin resin (Z) used for forming the aggregate layer, wood powder, fiber pieces, inorganic filler, etc. are used within the range not impairing the required physical properties or for the purpose of further improving the physical properties. Can be mixed.
These polyolefin resin aggregates are generally molded into a predetermined shape in the state of resin board, plastic cardboard, resin felt, or the like.

As the aggregate layer, a laminated body composed of a skin layer and a base material layer which are preheated or a skin layer and an intermediate layer and a base are formed on an aggregate molded product obtained by molding the polyolefin resin (Z) into a predetermined shape. It is preferable that the laminated body including the material layer is placed so that the base material layer and the aggregate layer are in contact with each other, and thermoformed to be integrated.

<< Thermoplastic Elastomer Laminate, Automotive Interior Parts >> The thermoplastic elastomer laminate of the present invention comprises the above-mentioned skin layer and base material layer, or a skin layer, an intermediate layer and a base material layer, The aggregate layer may be further laminated on the base material layer side. The surface of the skin layer may be embossed.

When the thermoplastic elastomer laminate is composed of the skin layer and the base material layer, the skin layer made of the thermoplastic elastomer composition [I-1] or [I-2] and the polyethylene foam (K). Alternatively, a base material layer [II-] made of polypropylene foam (L), a crystalline polyolefin resin (M) or a thermoplastic elastomer.
A base material layer [II-] composed of (N) is laminated.

When the thermoplastic elastomer laminate comprises the above-mentioned skin layer, intermediate layer and base material layer, a skin layer comprising the thermoplastic elastomer composition [I-1] or [I-2] and a crystalline polyolefin. Intermediate layer [III-] made of resin (M) or thermoplastic elastomer (N)
And a base material layer [II-] made of polyethylene foam (K) or polypropylene foam (L). The thermoplastic elastomer laminate having the intermediate layer is excellent in scratch resistance and, at the same time, has a moldability, in particular, an embossed pattern is hard to disappear during processing of parts.

When the base material layer [II-] is formed of the crystalline polyolefin resin (M) or the thermoplastic elastomer (N), the crystalline polyolefin resin (M) and the thermoplastic elastomer (N), and the skin layer. Forming first and second thermoplastic elastomer compositions [I-
Since 1] and [I-2] can be subjected to coextrusion lamination processing, when the thermoplastic elastomer laminate of the present invention is produced, the base material layer and the skin layer are directly formed without a film (sheet) forming step. It can be laminated and is economical.

The thickness of each layer of the thermoplastic elastomer laminate of the present invention varies depending on the use of the laminate molded article and is not generally specified, but the thickness of the skin layer is usually 0.
It is 005 to 20 mm, preferably 0.01 to 0.5 mm, and the thickness of the base material layer is usually 0.1 to 50 mm, preferably 1 to 5 mm. When the intermediate layer is provided, the thickness of the intermediate layer is usually 0.1 to 3 mm, preferably 0.3 to 2 mm.
It is. The total thickness of the laminate (excluding the aggregate layer) is usually 0.1 to 70 m when the intermediate layer is not provided.
m, preferably 1 to 5.5 mm, and when an intermediate layer is provided, it is usually 0.2 to 73 mm, preferably 1.3 to 7.
5 mm. When the aggregate layers are laminated, the thickness is preferably 0.5 to 5 mm.

When the thermoplastic elastomer laminate of the present invention is used as an automobile interior part, the skin layer generally has a thickness of about 0.01 to 2 mm, and the base material layer has a thickness of about 1 to 2.
The thickness of the intermediate layer is about 30 mm, the thickness of the intermediate layer when the intermediate layer is provided is 0.2 to 2 mm, and the thickness of the aggregate layer is about 0.5 to 5 mm. However, even in the case of such an application, the thickness of the skin layer is relatively thin in the ceiling material, and the dashboard,
A relatively thick laminate is used for wheel house covers, various pillars, sheets, and the like.

The thermoplastic elastomer laminate of the present invention comprises
It can be manufactured by combining means known per se, an example of which is shown below. (1) A method of thermocompression-bonding or heat-sealing a skin layer and a base material layer, which have been formed into a sheet shape in advance, using a means such as a calender molding machine. (2) A method of thermocompression-bonding or heat-sealing the skin layer, the intermediate layer, and the base material layer which have been formed into a sheet shape in advance by using a means such as a calender molding machine. (3) A method in which a skin layer and an intermediate layer are coextrusion-molded to prepare a laminate composed of these two layers, and this is thermocompression-bonded or heat-sealed to a base material layer made of a sheet-shaped foam.

When the base material layer is formed of the crystalline polyolefin resin (M) or the thermoplastic elastomer (N), the following method can be adopted. (4) in which either a method in which one sheet molded substrate layer or skin layer extruded, thermocompression bonding or heat sealing to the other layer that has a calendar molding. (5) A method in which a base material layer and a skin layer are simultaneously extrusion-molded by a multilayer extrusion molding machine and thermocompression-bonded or heat-sealed (coextrusion molding).

Further, in the present invention, a laminate comprising a base material layer and a skin layer is formed by a molding method (two-layer injection molding method) in which two kinds of molten resins are injected into a mold at different injection timings. You can also get Further, as in the case of the two-layer injection molding method, two types of molten resins are injected into the mold at different injection timings, that is, by a so-called sandwich injection molding method, a skin layer, a base material layer, and a skin layer in this order. A structured three-layer laminate can be obtained.

The laminated body in which the aggregate layers are laminated is, for example, a laminated body in which a skin layer and a base material layer are laminated, or a laminated body in which a skin layer, an intermediate layer and a base material layer are laminated, and an aggregate layer. It can be manufactured by stamping molding with a polyolefin resin (Z). In this case, a laminate comprising a preheated skin layer and a base material layer, or a laminate in which a skin layer, an intermediate layer and a base material layer are laminated, and the base material layer is placed on a mold to form an aggregate. It is preferable to perform thermoforming and integration with the resin to be the layer. The surface of the skin layer can be embossed using a roll for embossing when laminating the skin layer and the base material layer or laminating the skin layer and the intermediate layer.

The thermoplastic elastomer laminate of the present invention comprises
Since the skin layer is formed of the first or second thermoplastic elastomer composition [I-1] or [I-2],
Excellent in scratch resistance, deformation recovery, soft touch feeling, especially scratch resistance. Further, the laminate in which the base material layers made of the foam (K or L) are laminated has excellent flexibility and cushioning properties. The laminate in which the base material layer made of the crystalline polyolefin resin (M) or the thermoplastic elastomer (N) is laminated has excellent heat resistance, heat aging resistance and rigidity. A laminate in which the intermediate layers are laminated has moldability, and in particular, the embossed pattern does not easily disappear during processing of parts. Further, the laminated body in which the aggregate layers are laminated has strength and rigidity.

The thermoplastic elastomer laminate of the present invention has remarkably excellent interlayer adhesion between the layers, and further has mechanical strength, heat resistance, heat aging resistance, weather resistance, scratch resistance, abrasion resistance and dimensional stability. , Especially excellent in scratch resistance. Further, the thermoplastic elastomer laminate of the present invention is lighter in weight and easier to recycle than a polyvinyl chloride resin, does not generate harmful gas even when incinerated, and has a surface owing to overflow of a plasticizer or the like. There is no stickiness.

Therefore, the thermoplastic elastomer laminate of the present invention is used in applications requiring particularly scratch resistance, such as automobile interior parts, automobile exterior parts, furniture, building materials, home appliances housings, bags, suitcases, sports equipment, It can be effectively used for office supplies and miscellaneous goods. Among these, automobile interior parts and automobile exterior parts are particularly preferable, and they can be formed by coextrusion molding.

Specific examples of automobile interior parts include instrumental panels, steering wheels, pillar garnishes, airbag covers, door grabs, console boxes, shift knobs, assist grips, seat adjusters, louver garnishes, garage zipners, and sun visors. , Rearview mirror cover, room mirror cover, cup holder, coin box, resist, ashtray upper, door frame garnish, door trim, armrest, column cover, inner panel,
Examples include garage soup housings, dashboards, glass run channels, weather strips, etc. In addition, as a specific example of automobile exterior parts,
The side molding, garnish, window molding, wheel house cover, etc. can be mentioned.

[0121]

Industrial Applicability The thermoplastic elastomer laminate of the present invention comprises a skin layer made of a specific thermoplastic elastomer composition, a base layer made of polyethylene or polypropylene foam which may be crosslinked, or a crystalline polyolefin resin or Since it is composed of a base material layer made of a thermoplastic elastomer, it is excellent in scratch resistance, lightweight, easy to recycle and incinerate even though it uses a polyolefin resin as a material. However, no harmful gas is generated.

The thermoplastic elastomer laminate of the present invention having the intermediate layer has a good moldability, particularly the embossed pattern does not easily disappear during the processing of parts.

According to the present invention, in the above thermoplastic elastomer composition, silicone oil (G), ester (H) of aliphatic alcohol and dicarboxylic acid or fatty acid, fluoropolymer (I) or higher fatty acid amide (J) is added. By blending them, the scratch resistance can be further improved, and particularly in the case of a soft skin layer in which the ratio of the component (B) to the component (A) is large, excellent scratch resistance can be obtained.

Since the automobile interior / exterior parts of the present invention are composed of the above-mentioned thermoplastic elastomer laminate, even though the polyolefin composition is used as a material,
It has excellent scratch resistance, is lightweight, is easy to recycle, and does not generate harmful gas when incinerated.

[0125]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The raw materials used in the examples are described below. << Polyolefin composition (A) >> (A-1) Polyethylene composition: 23% by weight of ultrahigh molecular weight polyethylene having an intrinsic viscosity [η] of 28 dl / g measured in a decalin solvent at 135 ° C. and a decalin solvent at 135 ° C. A polyethylene composition consisting of 77% by weight of low molecular weight polyethylene having an intrinsic viscosity [η] measured in 0.73 dl / g [intrinsic viscosity [η] measured in a decalin solvent at 135 ° C .: 7.0 dl / g, Density: 0.965 g / c
m ³ ]

(A-2) Polyethylene composition: 135 ° C.
Has an intrinsic viscosity [η] of 14 dl measured in a decalin solvent
25% by weight of ultra high molecular weight polyethylene / g, 135 ° C
The intrinsic viscosity [η] measured in decalin solvent is 0.7d
Polyethylene composition consisting of 75% by weight of 1 / g low molecular weight polyethylene [Intrinsic viscosity [η] measured in decalin solvent at 135 ° C .: 3.9 dl / g, density: 0.965
g / cm ³ ] (A-3) Polyethylene: intrinsic viscosity [η] measured in decalin solvent at 135 ° C .; 3.7 dl / g, density;
968 g / cm ³

<< Block Copolymer (B) >> (B-1) Hydrogenated product of styrene / isoprene / styrene block copolymer: 1) Styrene content; 20% by weight 2) 1,2-based on all isoprene units Place and 3,4
Content of isoprene unit bonded at -position; 55% 3) MFR (ASTM D 1238-65T, 230
℃, 2.16kg load); 2.0g / 10 minutes

<< Block Copolymer (C) >> (C-1) Hydrogenated product of styrene / butadiene / styrene block copolymer: 1) Styrene content: 30% by weight 2) MFR (ASTM D 1238-65T, 230
(° C, 2.16 kg load); 1.5 g / 10 minutes (C-2) Hydrogenated product of styrene / butadiene / styrene block copolymer: 1) Styrene content; 30% by weight 2) MFR (ASTM D 1238- 65T, 230
℃, 2.16kg load); 2.5g / 10 minutes

<< Olefin Rubber (D) >> (D-1) Ethylene Propylene-5-Ethylidene-2
-Norbornene copolymer rubber: 1) ethylene content; 70 mol% 2) iodine value; 143) Mooney viscosity [ML _{1 + 4} (100 ° C.)]; 62 << softening agent (E) >> (E-1) Mineral oil-based process oil: Idemitsu Kosan Co., Ltd.
Made, PW-380 (trademark)

<< Thermoplastic Elastomer (F) >> (F-1) Olefinic Thermoplastic Elastomer Produced by the Following Method: Crystalline Polyolefin Resin (g)
20 parts by weight of polypropylene [MFR: 13 g / 10 minutes, crystallinity determined by X-ray method: 72%], and ethylene / propylene-5- as olefin rubber (h)
80 parts by weight of ethylidene-2-norbornene copolymer rubber [ethylene content: 70 mol%, iodine value: 12, Mooney viscosity (ML _{1 + 4} (100 ° C.)): 120] and 80 parts by weight of nitrogen were used. After kneading at 180 ° C. for 5 minutes in an atmosphere, the obtained kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets.

Then, 100 parts by weight of the square pellets,
0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene and 0.5 parts of divinylbenzene
After mixing with 1 part by weight with a Henschel mixer, the resulting mixture is extruded at 220 ° C. in a nitrogen atmosphere using a uniaxial extruder having L / D = 30 and a screw diameter of 50 mm to produce a thermoplastic elastomer (F -1) pellets were produced. The gel content of the obtained thermoplastic elastomer (F-1) was 84%.

(F-2) Olefin-based thermoplastic elastomer produced by the following method: Polypropylene [MFR (ASTM
D 1238, 230 ° C, 2.16 kg load): 13 g
/ 10 minutes, crystallinity determined by X-ray method: 72%] 30
Parts by weight, and an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber as an olefin rubber (h) [ethylene content: 70 mol%, iodine value: 12,
Mooney viscosity (ML _{1 + 4} (100 ° C.): 120] 70 parts by weight was kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and the resulting kneaded product was passed through a roll to form a sheet. And then cut with a sheet cutter to produce square pellets.
Parts by weight, 0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene, and 0.5 parts by weight of divinylbenzene were mixed by stirring with a Henschel mixer, and the resulting mixture was mixed with L / D = 30, screw diameter 5
220 mm in a nitrogen atmosphere using a 0 mm uniaxial extruder.
The pellets of the thermoplastic elastomer (F-2) were manufactured by extruding at 0 ° C. The resulting thermoplastic elastomer (F-
The gel content of 2) was 86%.

<< Silicone oil (G) >> (G-1) Silicone oil: S manufactured by Toray Silicone Co., Ltd.
H200 (Trademark) << Ester (H) >> (H-1) Distearylphthalate << Fluorine-based polymer (I) >> (I-1) Polyvinylidene fluoride resin: KFHA W-1000 (trademark) manufactured by Kureha Co., Ltd. Higher fatty acid amide (J) >> (J-1) erucic acid amide (J-2) oleic acid amide (J-3) ethylenebisoleic acid amide

<< Crystalline Polyolefin Resin (M) >> (M-1) Polypropylene Homopolymer [MFR (AS
TM D 1238, 230 ° C., 2.16 kg load):
0.5g / 10 minutes]

<< Thermoplastic Elastomer (N) >> (N-1) Olefinic Thermoplastic Elastomer Produced by the Following Method: Crystalline Polyolefin Resin (p)
As polypropylene [MFR (ASTMD 123
8, 230 ° C., 2.16 kg load): 13 g / 10 minutes,
Crystallinity determined by X-ray method: 72%] 30 parts by weight,
As olefin rubber (q), ethylene, propylene,
Using a Banbury mixer, 70 parts by weight of 5-ethylidene-2-norbornene copolymer rubber [ethylene content: 70 mol%, iodine value: 12, Mooney viscosity (ML _{1 + 4} (100 ° C.): 120], 180 ℃ in nitrogen atmosphere
After kneading for 5 minutes, the obtained kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets. Then, 100 parts by weight of this square pellet,
0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene and 0.5 parts of divinylbenzene
After stirring and mixing 1 part by weight with a Henschel mixer, the resulting mixture is extruded at 220 ° C. in a nitrogen atmosphere using a uniaxial extruder with L / D = 30 and a screw diameter of 50 mm to produce a thermoplastic elastomer (N- The pellet of 1) was manufactured. The gel content of the obtained thermoplastic elastomer (N-1) was 86%.

(N-2) Polypropylene as a crystalline polyolefin resin (p) [MFR: 13 g / 10
Minutes, crystallinity determined by X-ray method: 72%] 20 parts by weight, and ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber as olefin rubber (q) [ethylene content: 78 mol% , Iodine value: 15, Mooney viscosity (ML _{1 + 4} , 121 ° C.): 61] 80 parts by weight, and 100 parts by weight of a mixture thereof, di-tert.
-Butyl peroxide 50% by weight, divinylbenzene 4
0.7 parts by weight of a mixture of 0% by weight and 10% by weight of paraffinic mineral oil was mixed by stirring with a Henschel mixer. Next, while supplying these mixtures into the cylinder from the hopper of the twin-screw extruder and directly injecting them into the cylinder part using a plunger pump so that the paraffinic process oil becomes 19 parts by weight, the mixture is heated at 210 ° C. under a nitrogen atmosphere. Extruded with thermoplastic elastomer (TP
O) pellets were produced. The gel content was 90%.

Example 1-1 After thoroughly mixing 40 parts by weight of the pellets of the polyethylene composition (A-1) and 60 parts by weight of the pellets of the block copolymer (B-1), L / D = 30, Screw diameter 50
The mixture was extruded at 220 ° C. in a nitrogen atmosphere using a twin-screw extruder of 2 mm to produce pellets of the thermoplastic elastomer composition. Further, the pellets of the thermoplastic elastomer composition were sheeted at 220 ° C. and a take-up speed of 25 m / min using a 90 mmφ T-die extruder (full flight screw, L / D = 26, coat hanger die) manufactured by Toshiba Corporation. Sheet-shaped thermoplastic elastomer composition in a melted state, and a cross-linked foam sheet of polyethylene [manufactured by Sekisui Chemical Co., Ltd., trade name Softlon,
A foaming ratio of 30 times and a thickness of 3 mm] were passed through a pair of rolls in a laminated state. At that time, the thermoplastic elastomer sheet was brought into contact with the embossing roll side at a roll temperature of 60 ° C., and the crosslinked foam sheet was brought into contact with the normal roll side which was not heated, and the skin layer had a thickness of 0.5 mm Manufactured body.

Separately from the laminate obtained as described above, polypropylene filled with 30% of talc [Matsumura Sangyo Co., Ltd., trade name ET-5] [propylene / ethylene block copolymer, ethylene content 9 mol %, MFR (ASTM
D 1238-65T, 230 ° C., 2.16 kg load): 0.5] A male and female hot mold for molding an automobile ceiling aggregate from a plastic cardboard (pitch 10 mm, thickness 3 mm) Using a press, press molding is performed for 40 seconds at 95 ° C. under a heating and pressurizing condition of ² kg / cm ² , while the laminate preheated to 170 ° C. is placed on the aggregate molded product, and again. Both were thermoformed and integrated by pressing to form an automobile ceiling material.

A felt cloth was placed on the smooth portion of the skin layer made of the thermoplastic elastomer composition of the obtained ceiling material,
Further, a weight was placed thereon so that a pressure of 200 g / cm ² was applied, and the ceiling material was reciprocated 100 times, and the scratch resistance was evaluated by the surface condition after the reciprocating operation. The evaluation criteria are as follows. Table 1 shows the results.

(5-level evaluation of scratch resistance) A: Almost no scratch is noticeable B: Scratch is slightly noticeable C: Scratch is noticeable D: Scratch is noticeable E: Surface is whitened

Example 1-2 In Example 1-1, the polyethylene composition (A-1)
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1-1, except that the amount was 85 parts by weight, and the ceiling material was molded in the same manner as in Example 1-1 to evaluate scratch resistance. went. Table 1 shows the results.

Example 1-3 In Example 1-1, the polyethylene composition (A-1)
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 30 parts by weight,
40 parts by weight of thermoplastic elastomer (F-
A pellet of the thermoplastic elastomer composition was produced in the same manner as in Example 1-1, except that 30 parts by weight of 1) was blended, and a ceiling material was formed in the same manner as in Example 1-1.
The scratch resistance was evaluated. Table 1 shows the results.

Example 1-4 30 parts by weight of polyethylene composition (A-1), 40 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and styrene / butadiene / styrene block 10 parts by weight of hydrogenated product (C-1) of copolymer, 10 parts by weight of ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (D-1), and mineral oil-based process oil (E- 1) 10 parts by weight of the mixture was kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and the resulting kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce a square pellet. did.

Then, this square pellet was mixed with L / D = 30,
Using a twin-screw extruder having a screw diameter of 50 mm, the pellets of the thermoplastic elastomer composition were manufactured by extruding at 220 ° C. in a nitrogen atmosphere. Further, a ceiling material was molded from the pellets of the thermoplastic elastomer composition in the same manner as in Example 1-1, and the scratch resistance was evaluated. Table 1 shows the results.

Example 1-5 The polyethylene composition (A-1) in Example 1-1.
The same procedure as in Example 1-1 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of silicone oil (G-1) were added. Pellets of the thermoplastic elastomer composition were manufactured, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 1 shows the results.

Example 1-6 In Example 1-1, the polyethylene composition (A-1)
Same as Example 1-1 except that 30 parts by weight, 70 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 1 part by weight of distearyl phthalate (H-1) were blended. Then, pellets of the thermoplastic elastomer composition were produced, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 1 shows the results.

Example 1-7 In Example 1-1, the polyethylene composition (A-1)
Example 1-1 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 5 parts by weight of polyvinylidene fluoride resin (I-1) were further added. Pellets of the thermoplastic elastomer composition were produced in the same manner as above, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 1 shows the results.

Example 1-8 In Example 1-1, the polyethylene composition (A-1)
Same as Example 1-1 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of erucamide (J-1) were blended. Then, pellets of the thermoplastic elastomer composition were produced, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 1 shows the results.

Example 1-9 In Example 1-1, the polyethylene composition (A-1)
Same as Example 1-1 except that 30 parts by weight, 70 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of oleic acid amide (J-2) were added. Then, pellets of the thermoplastic elastomer composition were produced, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 1 shows the results.

Example 1-10 In Example 1-1, the polyethylene composition (A-1)
Example 1-1 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of a styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of ethylenebisoleic acid amide (J-3) were blended. Pellets of the thermoplastic elastomer composition were produced in the same manner as above, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 1 shows the results.

Comparative Example 1-1 In Example 1-1, the polyethylene composition (A-1)
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1-1, except that the amount of the styrene / butadiene / styrene block copolymer hydrogenated product (C-1) was 85 parts by weight. Example 1-
A ceiling material was molded in the same manner as in 1, and the scratch resistance was evaluated. Table 1 shows the results.

Comparative Example 1-2 In Example 1-1, the polyethylene composition (A-1)
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 5 parts by weight and 9 parts by weight, respectively.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1-1, except that the amount was 5 parts by weight, and the ceiling material was molded in the same manner as in Example 1-1 to evaluate scratch resistance. went. Table 1 shows the results.

Comparative Example 1-3 In Example 1-1, the polyethylene composition (A-1)
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
15 parts by weight, and pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1-1, except that 70 parts by weight of the hydrogenated product (C-1) of styrene / butadiene / styrene block copolymer was added. Example 1
A ceiling material was molded in the same manner as in -1, and the scratch resistance was evaluated. Table 1 shows the results.

Comparative Example 1-4 A ceiling material was molded from 100 parts by weight of the pellets of the thermoplastic elastomer (F-1) in the same manner as in Example 1-1, and the scratch resistance was evaluated. Table 1 shows the results.

Comparative Example 1-5 100 parts by weight of the pellets of the thermoplastic elastomer (F-1) and 3 parts by weight of the erucic acid amide (J-1) were used in Example 1-1.
Extruded using a twin-screw extruder in the same manner as above to produce pellets of the thermoplastic elastomer composition. Furthermore, Example 1
A ceiling material was molded in the same manner as in -1, and the scratch resistance was evaluated. Table 1 shows the results.

[0156]

[Table 1]

Example 2-1 After thoroughly mixing 40 parts by weight of the pellets of the polyethylene composition (A-2) and 60 parts by weight of the pellets of the block copolymer (B-1), L / D = 30, Screw diameter 50
The mixture was extruded at 220 ° C. in a nitrogen atmosphere using a twin-screw extruder of 2 mm to produce pellets of the thermoplastic elastomer composition.

Then, polypropylene homopolymer (M
-1) is extrusion-molded at a temperature of 230 ° C., and the thermoplastic elastomer composition is coextrusion-laminated on the surface of the base layer (polypropylene homopolymer) and skin layer (thermoplastic elastomer composition). A laminated body constituted was obtained. The thickness of the base material layer of this laminate was 10 mm, and the thickness of the skin layer was 5.2 mm. The interlayer adhesion strength and the skin layer scratch resistance of the obtained laminate were evaluated by the following methods. Table 2 shows the results.

(A) Interlayer adhesion strength test Test method: 180 degree peel test Test piece: Width 25 mm, length 100 mm Peeling speed: 25 mm / min Interlayer adhesion strength: value obtained by dividing the peel load by the width of the test piece [unit: kgf / Cm]

(B) Scratch resistance test A felt cloth was placed on a smooth portion of the skin layer, and a weight was placed thereon so that a pressure of 200 g / cm ² was applied, and the cloth was reciprocated 100 times on the skin layer. The scratch resistance was evaluated based on the surface condition after the reciprocating operation. (Five-step evaluation of scratch resistance) A: Scratches are hardly noticeable B: Scratches are slightly noticeable C: Scratches are noticeable D: Scratches are noticeable E: Surface is whitened

Example 2-2 In Example 2-1, the polyethylene composition (A-2) is used.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 2-1 except that the amount was 85 parts by weight, and a laminate was formed in the same manner as in Example 2-1 to obtain interlayer adhesive strength and scratch resistance. The sex was evaluated. Table 2 shows the results.

Example 2-3 In Example 2-1, the polyethylene composition (A-2) was used.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 30 parts by weight,
40 parts by weight of thermoplastic elastomer (F-
2) A pellet of a thermoplastic elastomer composition was produced in the same manner as in Example 2-1, except that 30 parts by weight was blended, and a laminate was formed in the same manner as in Example 2-1.
The interlayer adhesion strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-4 30 parts by weight of polyethylene composition (A-2), 40 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and styrene / butadiene / styrene block 10 parts by weight of hydrogenated product (C-2) of copolymer, 10 parts by weight of ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (D-1), and mineral oil-based process oil (E- 1) 10 parts by weight was kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and the obtained kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce a square pellet. .

Then, this square pellet was mixed with L / D = 30,
Using a twin-screw extruder having a screw diameter of 50 mm, the pellets of the thermoplastic elastomer composition were manufactured by extruding at 220 ° C. in a nitrogen atmosphere. Further, the pellets (skin layer) of the thermoplastic elastomer composition and the thermoplastic elastomer (N-1, substrate layer) were coextruded and laminated in the same manner as in Example 2-1, to form a laminate, and the interlayer was formed. The adhesive strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-5 The polyethylene composition (A-2) of Example 2-1.
30 parts by weight, 70 parts by weight of a hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of silicone oil (G-1) were added,
Pellets of the thermoplastic elastomer composition were manufactured in the same manner as in Example 2-1, and a laminate was further molded, and the interlayer adhesion strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-6 In Example 2-1, the polyethylene composition (A-2) is used.
Example 2-1 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of a styrene / isoprene / styrene block copolymer (B-1), and 1 part by weight of distearyl phthalate (H-1) were blended. In the same manner, pellets of the thermoplastic elastomer composition were produced, a laminate was formed, and the interlaminar adhesive strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-7 In Example 2-1, the polyethylene composition (A-2) is used.
Example 2 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of a styrene / isoprene / styrene block copolymer (B-1), and 5 parts by weight of a polyvinylidene fluoride resin (I-1) were blended. Pellets of the thermoplastic elastomer composition were produced in the same manner as in 1, and a laminate was further molded, and the interlayer adhesive strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-8 In Example 2-1, the polyethylene composition (A-2) is used.
Example 2-1 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of erucamide (J-1) were further mixed. In the same manner, pellets of the thermoplastic elastomer composition were produced, a laminate was formed, and the interlaminar adhesive strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-9 The polyethylene composition (A-2) of Example 2-1.
30 parts by weight, 70 parts by weight of a hydrogenated product of a styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of oleic acid amide (J-2) were added.
Pellets of the thermoplastic elastomer composition were manufactured in the same manner as in Example 2-1, and a laminate was further molded, and the interlayer adhesion strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-10 The polyethylene composition (A-2) of Example 2-1.
Example 2-except that 30 parts by weight, 70 parts by weight of a hydrogenated product of a styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of ethylenebisoleic acid amide (J-3) were blended. Pellets of the thermoplastic elastomer composition were produced in the same manner as in 1, and a laminate was further molded, and the interlayer adhesive strength and scratch resistance were evaluated. Table 2 shows the results.

Example 2-11 In Example 2-1, the polyethylene composition (A-2) was used.
Thermoplastic resin in the same manner as in Example 2-1 except that the compounding amount of the styrene-isoprene-styrene block copolymer (B-1) was changed to 70 parts by weight. Pellets of the elastomer composition were produced, a laminate was further formed, and the interlaminar adhesive strength and scratch resistance were evaluated. Table 2 shows the results.

Comparative Example 2-1 The polyethylene composition (A-2) in Example 2-1.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
Pellet of the thermoplastic elastomer composition was prepared in the same manner as in Example 2-1 except that the amount of the styrene / butadiene / styrene block copolymer hydrogenated product (C-2) was 85 parts by weight. Manufactured and further Example 2
A laminate was formed in the same manner as in -1, and the interlaminar adhesive strength and scratch resistance were evaluated. Table 2 shows the results.

Comparative Example 2-2 The polyethylene composition (A-2) of Example 2-1.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 5 parts by weight and 9 parts by weight, respectively.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 2-1 except that the amount was 5 parts by weight, and a laminate was formed in the same manner as in Example 2-1 to obtain interlayer adhesive strength and scratch resistance. The sex was evaluated. Table 2 shows the results.

Comparative Example 2-3 In Example 2-1, the polyethylene composition (A-2) is used.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
15 parts by weight, and pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 2-1 except that 70 parts by weight of the styrene / butadiene / styrene block copolymer hydrogenated product (C-2) was blended. The laminate was manufactured, and a laminate was formed in the same manner as in Example 2-1, and the interlayer adhesion strength and scratch resistance were evaluated. Table 2 shows the results.

Comparative Example 2-4 A laminate was molded from 100 parts by weight of the pellets of the thermoplastic elastomer (F-2) in the same manner as in Example 2-1, and the interlayer adhesive strength and scratch resistance were evaluated. . Table 2 shows the results.

Comparative Example 2-5 100 parts by weight of pellets of the thermoplastic elastomer (F-2) and 3 parts by weight of erucic acid amide (J-1) were used in Example 2-1.
Extrusion was carried out using a twin-screw extruder in the same manner as above to produce pellets of the thermoplastic elastomer composition. Furthermore, Example 2-
A laminate was molded in the same manner as in Example 1 and evaluated for interlayer adhesive strength and scratch resistance. Table 2 shows the results.

Comparative Example 2-6 In Example 2-2, the polyethylene composition (A-2)
Was performed in the same manner except that polyethylene (A-3) was used instead of. Table 2 shows the results.

Comparative Example 2-7 In Example 2-5, the polyethylene composition (A-2) was used.
Was performed in the same manner except that polyethylene (A-3) was used instead of. Table 2 shows the results.

[0179]

[Table 2]

Example 3-1 40 parts by weight of the polyethylene composition (A-1) pellets and 60 parts by weight of the block copolymer (B-1) pellets were thoroughly mixed, and L / D = 30, Screw diameter 50
The pellets of the thermoplastic elastomer composition [I-1] were produced by extruding at 220 ° C in a nitrogen atmosphere using a twin-screw extruder of mm.

[Preparation of Laminated Body] Pellets of the thermoplastic elastomer [N-2] were used for 220 using a 90 mmφ T-die extruder (full flight screw, L / D = 26, coat hanger die) manufactured by Toshiba Corporation. A sheet-shaped thermoplastic elastomer [N-2] which is extruded into a sheet at a temperature of 2.5 ° C and a take-up speed of 2.5 m / min;
Polyethylene crosslinked foam sheet [Sekisui Chemical Co., Ltd.,
Trade name: Softlon, foaming ratio 30 times, thickness 3 mm]
Was molded.

Further, the thermoplastic elastomer composition [I
Similarly, the pellet of [-1] was formed into a sheet with a t-die extruder, and immediately laminated with the laminate (i) prepared in advance. At that time, the thermoplastic elastomer composition [I-1] sheet is brought into contact with the embossing roll side at a roll temperature of 60 ° C., and the laminate (i) sheet is brought into contact with the unheated normal roll side, and the thermoplastic elastomer composition Composition [I-1] layer is 0.1 mm, thermoplastic elastomer [N
-2] An embossed laminate (ii) was produced in which the layer had a thickness of 1.0 mm.

Separately from the laminate obtained as described above, polypropylene filled with 30% of talc [Matsumura Sangyo Co., Ltd., trade name ET-5] [propylene / ethylene block copolymer, ethylene content 9 mol %, MFR (ASTM
D 1238-65T, 230 ° C., 2.16 kg load): 0.5] A male and female hot mold for molding an automobile ceiling aggregate from a plastic cardboard (pitch 10 mm, thickness 3 mm) Using a press, press molding was performed for 40 seconds at 95 ° C. under a heating and pressurizing condition of 2 kg / cm 2, while the laminate (ii) preheated to 140 ° C. was placed on the aggregate molded product. Then, they were pressed again to integrate them by thermoforming to form an automobile ceiling material.

A felt cloth was placed on the smooth portion of the skin layer made of the thermoplastic elastomer composition [I-1] of the obtained ceiling material, and a weight was placed thereon so that a pressure of 200 g / cm ² was applied. Then, the ceiling material was reciprocated 100 times, and the scratch resistance was evaluated based on the surface condition after the reciprocating operation. The evaluation criteria are as follows. Table 3 shows the results.

(5-level evaluation of scratch resistance) A: Almost no scratch is noticeable B: Scratch is slightly noticeable C: Scratch is noticeable D: Scratch is noticeable E: Surface is whitened

Further, the remaining standard of the embossed pattern on the edge portion of the obtained ceiling material was evaluated according to the following criteria. A: Almost unchanged from before molding B: Almost remaining C: Significantly remaining D: Somewhat remaining E: Not much remaining

Example 3-2 The polyethylene composition (A-1) of Example 3-1.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 3-1, except that the amount was 85 parts by weight, and the ceiling material was molded in the same manner as in Example 3-1, and the scratch resistance was evaluated. went. Table 3 shows the results.

Example 3-3 The polyethylene composition (A-1) of Example 3-1.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 30 parts by weight,
40 parts by weight of thermoplastic elastomer (F-
1) A pellet of a thermoplastic elastomer composition was produced in the same manner as in Example 3-1, except that 30 parts by weight was blended.
Furthermore, a ceiling material was molded in the same manner as in Example 3-1, and the scratch resistance was evaluated. Table 3 shows the results.

Example 3-4 30 parts by weight of polyethylene composition (A-1), 40 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and styrene / butadiene / styrene block 10 parts by weight of hydrogenated product (C-1) of copolymer, 10 parts by weight of ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (D-1), and mineral oil-based process oil (E- 1) 10 parts by weight of the mixture was kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and the resulting kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce a square pellet. did.

Then, this square pellet was mixed with L / D = 30,
Using a twin-screw extruder having a screw diameter of 50 mm, the pellets of the thermoplastic elastomer composition were manufactured by extruding at 220 ° C. in a nitrogen atmosphere. Further, a ceiling material was molded from the pellets of the thermoplastic elastomer composition in the same manner as in Example 3-1, and the scratch resistance was evaluated. Table 3 shows the results.

Example 3-5 The polyethylene composition (A-1) of Example 3-1.
Same as Example 3-1 except that 30 parts by weight, 70 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of silicone oil (G-1) were added. Pellets of the thermoplastic elastomer composition were manufactured, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 3 shows the results.

Example 3-6 The polyethylene composition (A-1) of Example 3-1.
Same as Example 3-1 except that 30 parts by weight, 70 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 1 part by weight of distearyl phthalate (H-1) were blended. Then, pellets of the thermoplastic elastomer composition were produced, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 3 shows the results.

Example 3-7 Polyethylene composition (A-1) in Example 3-1.
Example 3-1 except that 30 parts by weight, 70 parts by weight of a hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 5 parts by weight of polyvinylidene fluoride resin (I-1) were further added. Pellets of the thermoplastic elastomer composition were produced in the same manner as above, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 3 shows the results.

Example 3-8 The polyethylene composition (A-1) of Example 3-1.
Same as Example 3-1 except that 30 parts by weight, 70 parts by weight of hydrogenated product of styrene / isoprene / styrene block copolymer (B-1), and 3 parts by weight of erucic acid amide (J-1) were added. Then, pellets of the thermoplastic elastomer composition were produced, and the ceiling material was further molded, and the scratch resistance was evaluated. Table 3 shows the results.

Comparative Example 3-1 The polyethylene composition (A-1) in Example 3-1.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
A pellet of a thermoplastic elastomer composition was produced in the same manner as in Example 3-1, except that the amount of the styrene / butadiene / styrene block copolymer hydrogenated product (C-1) was 85 parts by weight. Example 3-
A ceiling material was molded in the same manner as in 1, and the scratch resistance was evaluated. Table 3 shows the results.

Comparative Example 3-2 The polyethylene composition (A-1) of Example 3-1.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 5 parts by weight and 9 parts by weight, respectively.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 3-1, except that the amount was 5 parts by weight, and the ceiling material was molded in the same manner as in Example 3-1, and the scratch resistance was evaluated. went. Table 3 shows the results.

Comparative Example 3-3 The polyethylene composition (A-1) in Example 3-1.
And styrene / isoprene / styrene block copolymer hydrogenated product (B-1) in an amount of 15 parts by weight,
A pellet of a thermoplastic elastomer composition was produced in the same manner as in Example 3-1 except that the amount of the styrene / butadiene / styrene block copolymer hydrogenated product (C-1) was 70 parts by weight. Example 3
A ceiling material was molded in the same manner as in -1, and the scratch resistance was evaluated. Table 3 shows the results.

Comparative Example 3-4 A ceiling material was molded from 100 parts by weight of the pellets of the thermoplastic elastomer (F-1) in the same manner as in Example 3-1, and the scratch resistance was evaluated. Table 3 shows the results.

Comparative Example 3-5 100 parts by weight of pellets of the thermoplastic elastomer (F-1) and 3 parts by weight of erucic acid amide (J-1) were used in Example 3-1.
Extruded using a twin-screw extruder in the same manner as above to produce pellets of the thermoplastic elastomer composition. Further, Example 3
A ceiling material was molded in the same manner as in -1, and the scratch resistance was evaluated. Table 3 shows the results.

[0200]

[Table 3]

Claims (11)

[Claims] 1. An ultrahigh molecular weight polyolefin (a) [I-] (A) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 7 to 40 dl / g, and a 135 ° C. decalin solvent. Measured intrinsic viscosity [η] is 0.1-5d
A polyolefin composition consisting essentially of a low molecular weight or high molecular weight polyolefin (b) in the range of 1 / g, wherein the ultra high molecular weight polyolefin (a) and the ultra high molecular weight polyolefin (a) are low or high molecular weight. 15 based on 100% by weight of total molecular weight polyolefin (b)
Of 40 to 40% by weight, and the intrinsic viscosity [η] measured in a 135 ° C. decalin solvent is 3.5 to 8.3 dl /
10 to 50 parts by weight of the polyolefin composition in the range of g, and (B) a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein all isoprene units are contained. An optionally hydrogenated block copolymer consisting of a polymer or copolymer block (d) having an isoprene unit content of 40% or more bonded at the 1,2- and 3,4-positions relative to An embossed skin made of a thermoplastic elastomer composition [I-1] containing 90 to 50 parts by weight of coalesce (the total amount of components (A) and (B) is 100 parts by weight). A layer, and [II-] (K) a polyethylene foam which may be crosslinked, or (L) a base material layer which is made of a polypropylene foam which may be crosslinked. A thermoplastic elastomer laminate comprising: 2. An ultrahigh molecular weight polyolefin (a) [I-] (A) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 7 to 40 dl / g and a 135 ° C. decalin solvent. A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin (b) having a measured intrinsic viscosity [η] in the range of 0.1 to 5 dl / g, which is an ultra high molecular weight polyolefin (a).
However, the total weight of the ultra high molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b) is 100% by weight.
Present in a proportion of 15 to 40% by weight, and 135
The intrinsic viscosity [η] measured in a decalin solvent is 3.5 to
Polyolefin composition 10 in the range of 8.3 dl / g
To 50 parts by weight, and (B) a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, which are 1,2-positions and 3, with respect to all isoprene units. 90-50 parts by weight of an optionally hydrogenated block copolymer consisting of a polymer or copolymer block (d) having an isoprene unit content of 40% or more bonded at the 4-position [component ( The total amount of A) and (B) is 100 parts by weight], which may be embossed on the thermoplastic elastomer composition [I-1], and [II-] (M ) A crystalline polyolefin resin, or (N) a partially or completely crosslinked thermoplastic resin containing a crystalline polyolefin resin (p) and an olefin rubber (q). A thermoplastic elastomer laminate comprising a base material layer made of a elastomer. 3. An ultrahigh molecular weight polyolefin (a) [I-] (A) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 7 to 40 dl / g, and a 135 ° C. decalin solvent. A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin (b) having a measured intrinsic viscosity [η] in the range of 0.1 to 5 dl / g, which is an ultra high molecular weight polyolefin (a).
However, the total weight of the ultra high molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b) is 100% by weight.
Present in a proportion of 15 to 40% by weight, and 135
The intrinsic viscosity [η] measured in a decalin solvent is 3.5 to
Polyolefin composition 10 in the range of 8.3 dl / g
To 50 parts by weight, and (B) a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, which are 1,2-positions and 3, with respect to all isoprene units. 90-50 parts by weight of an optionally hydrogenated block copolymer consisting of a polymer or copolymer block (d) having an isoprene unit content of 40% or more bonded at the 4-position [component ( The total amount of A) and (B) is 100 parts by weight], which may be embossed on the thermoplastic elastomer composition [I-1], and [II-] (K ) Polyethylene foam which may be crosslinked, or (L) A base material layer which is made of polypropylene foam which may be crosslinked, and [III-] (M) crystalline polyolefin Fat, or (N) the crystalline polyolefin resin (p) and the olefin rubber (q) comprising a partially or fully crosslinked thermoplastic elastomers - made, the skin layer [I-]
And an intermediate layer laminated between the base material layer [II-] and the thermoplastic elastomer laminate. 4. A thermoplastic elastomer composition [I-1]
From the components (A) and (B), silicone oil (G), ester (H) of aliphatic alcohol and dicarboxylic acid or fatty acid, fluoropolymer (I), and higher fatty acid amide (J) The total amount of the components (A) and (B) is at least 1 selected from the group consisting of 1
0.01-10 weight part is contained with respect to 00 weight part, The thermoplastic elastomer laminated body in any one of the Claims 1 thru | or 3 characterized by the above-mentioned. 5. An ultrahigh molecular weight polyolefin (a) [I-] (A) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 7 to 40 dl / g, and a 135 ° C. decalin solvent. A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin (b) having a measured intrinsic viscosity [η] in the range of 0.1 to 5 dl / g, which is an ultra high molecular weight polyolefin (a).
However, the total weight of the ultra high molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b) is 100% by weight.
Present in a proportion of 15 to 40% by weight, and 135
The intrinsic viscosity [η] measured in a decalin solvent is 3.5 to
Polyolefin composition 10 in the range of 8.3 dl / g
To 50 parts by weight of (B) a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, which are 1,2-positions and 3,4 with respect to all isoprene units. 90-25 parts by weight of an optionally hydrogenated block copolymer comprising a polymer or a copolymer block (d) having an isoprene unit content of 40% or more bonded at the -position, (C) A polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein isoprene is bonded at 1,2-position and 3,4-position with respect to all isoprene units. A polymer or copolymer block (e) having a unit content of 30% or less, or a butadiene polymer block (f) Becomes good block copolymer 0-30 weight parts be hydrogenated, (D) an olefinic rubber 0-4
0 parts by weight, (E) 0 to 40 parts by weight of a softening agent, and (F)
A thermoplastic elastomer composition [I-2] containing 0 to 50 parts by weight of a partially or completely crosslinked thermoplastic elastomer containing a crystalline polyolefin resin (g) and an olefin rubber (h). And contains at least one component selected from the group consisting of components (C), (D), (E) and (F) [component (A),
The total amount of (B), (C), (D), (E) and (F) is 100 parts by weight], and the components (A), (B),
When the ratio of the total amount of the components (A), (B), (C), (D) and (F) to the total amount of (C), (D), (E) and (F) is 100 to 40% by weight. An embossed skin layer made of a thermoplastic elastomer composition [I-2], [II-] (K) optionally cross-linked polyethylene foam, or (L) cross-linked. And a base material layer made of a polypropylene foam which may be used. 6. An ultrahigh molecular weight polyolefin (a) [I-] (A) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 7 to 40 dl / g and a 135 ° C. decalin solvent. A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin (b) having a measured intrinsic viscosity [η] in the range of 0.1 to 5 dl / g, which is an ultra high molecular weight polyolefin (a).
However, the total weight of the ultra high molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b) is 100% by weight.
Present in a proportion of 15 to 40% by weight, and 135
The intrinsic viscosity [η] measured in a decalin solvent is 3.5 to
Polyolefin composition 10 in the range of 8.3 dl / g
To 50 parts by weight of (B) a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, which are 1,2-positions and 3,4 with respect to all isoprene units. 90-25 parts by weight of an optionally hydrogenated block copolymer comprising a polymer or a copolymer block (d) having an isoprene unit content of 40% or more bonded at the -position, (C) A polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein isoprene is bonded at 1,2-position and 3,4-position with respect to all isoprene units. From a polymer or copolymer block (e) having a unit content of 30% or less, or a butadiene polymer block (f) Optionally hydrogenated block copolymer 0-3
0 parts by weight, (D) 0 to 40 parts by weight of olefin rubber,
(E) 0 to 40 parts by weight of a softening agent, and (F) 0 to 50 parts by weight of a partially or completely crosslinked thermoplastic elastomer containing a crystalline polyolefin resin (g) and an olefin rubber (h). A thermoplastic elastomer composition [I-2] containing parts, wherein the components (C), (D),
Containing at least one component selected from the group consisting of (E) and (F) [components (A), (B), (C),
The total amount of (D), (E) and (F) is 100 parts by weight], and the components (A), (B), (C), (D),
The component (A) with respect to the total amount of (E) and (F),
The ratio of the total amount of (B), (C), (D) and (F) is 1
A thermoplastic elastomer composition [I-2] in an amount of 0 to 40% by weight, which may be embossed, and [II-] (M) crystalline polyolefin resin, or (N) crystalline A thermoplastic elastomer laminate comprising a base material layer made of a partially or completely crosslinked thermoplastic elastomer containing a polyolefin resin (p) and an olefin rubber (q). body. 7. An ultrahigh molecular weight polyolefin (a) [I-] (A) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 7 to 40 dl / g and a 135 ° C. decalin solvent. A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin (b) having a measured intrinsic viscosity [η] in the range of 0.1 to 5 dl / g, which is an ultra high molecular weight polyolefin (a).
However, the total weight of the ultra high molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b) is 100% by weight.
Present in a proportion of 15 to 40% by weight, and 135
The intrinsic viscosity [η] measured in a decalin solvent is 3.5 to
Polyolefin composition 10 in the range of 8.3 dl / g
To 50 parts by weight of (B) a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, which are 1,2-positions and 3,4 with respect to all isoprene units. 90-25 parts by weight of an optionally hydrogenated block copolymer comprising a polymer or a copolymer block (d) having an isoprene unit content of 40% or more bonded at the -position, (C) A polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein isoprene is bonded at 1,2-position and 3,4-position with respect to all isoprene units. A polymer or copolymer block (e) having a unit content of 30% or less, or a butadiene polymer block (f) Becomes good block copolymer 0-30 weight parts be hydrogenated, (D) an olefinic rubber 0-4
0 parts by weight, (E) 0 to 40 parts by weight of a softening agent, and (F)
A thermoplastic elastomer composition [I-2] containing 0 to 50 parts by weight of a partially or completely crosslinked thermoplastic elastomer containing a crystalline polyolefin resin (g) and an olefin rubber (h). And contains at least one component selected from the group consisting of components (C), (D), (E) and (F) [component (A),
The total amount of (B), (C), (D), (E) and (F) is 100 parts by weight], and the components (A), (B),
When the ratio of the total amount of the components (A), (B), (C), (D) and (F) to the total amount of (C), (D), (E) and (F) is 100 to 40% by weight. An embossed skin layer made of a thermoplastic elastomer composition [I-2], [II-] (K) optionally cross-linked polyethylene foam, or (L) cross-linked. Which may be a polypropylene foam, and a part containing [III-] (M) crystalline polyolefin resin, or (N) crystalline polyolefin resin (p) and olefin rubber (q). Made of a thermoplastic elastomer which is partially or completely crosslinked, and has a skin layer [I-]
And an intermediate layer laminated between the base material layer [II-] and the thermoplastic elastomer laminate. 8. A thermoplastic elastomer composition [I-2]
Is at least one component selected from the group consisting of silicone oil (G), ester of aliphatic alcohol and dicarboxylic acid or fatty acid (H), fluoropolymer (I), and higher fatty acid amide (J). , Components (A), (B), (C), (D), (E) and (F)
The thermoplastic elastomer laminate according to any one of claims 5 to 7, characterized in that it is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total. 9. The thermoplastic elastomer laminate according to claim 1, wherein an aggregate layer made of polyolefin resin (Z) is laminated on the base material layer side. 10. A laminated body comprising a preheated skin layer and a base material layer, or a skin layer and an intermediate layer, which are formed on an aggregate molded article in which a polyolefin resin (Z) to be an aggregate layer is molded into a predetermined shape. 10. The thermoplastic elastomer laminate according to claim 9, wherein the laminate comprising the base material layer is placed so that the base material layer and the aggregate layer are in contact with each other, and thermoformed to be integrated. . 11. An automobile interior / exterior part, comprising the thermoplastic elastomer laminate according to claim 1. Description: