JPH09174727A - Laminate and automotive interior and exterior components using the laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent flaw resistance by utilizing a polyolefin material which has a light weight, is easily recyclable and generates no harmful gas even by incineration. SOLUTION: This laminate comprises [1] a skin layer made of a thermoplastic elastomer composition containing a thermoplastic elastomer A which contains a crystalline polyolefin resin (a) and a crosslinked olefin rubber (b) and poly-1-butene resin B in such a manner that the weight ratio [A/B] of the elastomer A to the poly-1-butene B is in a range of 95/5 to 5/95, and a base material layer formed of a thermoplastic elastomer A' containing a crystalline polyolefin resin a' and a crosslinked olefin rubber b', a crystalline polyolefin resin or a polyolefin resin foam.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate made of a polyolefin-based material and having excellent scratch resistance, and an automobile interior / exterior part using the same.

[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.

Further, vinyl chloride resin is widely used for side protection moldings which are exterior parts of automobiles. The vinyl chloride resin is excellent in scratch resistance and inexpensive, and is therefore a very suitable material for the above applications. However, the vinyl chloride resin has the above-mentioned problems.

By the way, since olefin resins and olefin thermoplastic elastomers are lightweight and easy to recycle, they are used as energy-saving and resource-saving type materials in automobile parts, industrial machine parts, electric / electronic parts, building materials, etc. Widely used. Further, in recent years, from the viewpoint of protecting the global environment, an olefin resin or an olefin thermoplastic elastomer that does not generate a harmful gas has come to be used in place of a vinyl chloride resin that generates a harmful gas when incinerated. .

However, a conventional molded product made of an olefin resin or an olefin thermoplastic elastomer has a drawback 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. ing.

[0006]

The object of the present invention is to make use of the advantages of the olefin polymer material such as light weight, easy recycle use, and generation of noxious gas even when incinerated, and scratch resistance. It is an object of the present invention to provide a material which is excellent in use and can be used for automobile interior and exterior parts. Another object of the present invention is to provide an automobile interior / exterior part using the above material.

[0007]

The above objects and advantages of the present invention are [1] (1) a thermoplastic elastomer (A) containing a crystalline polyolefin resin (a) and a crosslinked olefin rubber (b), and It contains the poly-1-butene resin (B), and (2) the weight ratio [(A) / (B)] of the thermoplastic elastomer (A) and the poly-1-butene resin (B) is 95 /
A thermoplastic elastomer (A ′) containing a skin layer made of a thermoplastic elastomer composition in the range of 5 to 5/95, and [II] a crystalline polyolefin resin (a ′) and a crosslinked olefin rubber (b ′). ), A base material layer formed from a crystalline polyolefin resin or a polyolefin resin foam, and an automobile exterior component and an automobile interior component using the laminate.

The present invention is described in detail below, and other objects and advantages of the present invention will be apparent.

First, the thermoplastic elastomer composition constituting the skin layer will be described. The thermoplastic elastomer composition will be described. The thermoplastic elastomer is
It contains a thermoplastic elastomer (A) and a poly-1-butene resin (B).

Thermoplastic Elastomer (A) [I] Crystalline Polyolefin Resin (a) As the crystalline polyolefin resin (a) constituting the thermoplastic elastomer, a homopolymer of α-olefin having 2 to 20 carbon atoms or A copolymer is mentioned. Specific examples of the crystalline polyolefin resin (a) include:
The following polymers or copolymers may be mentioned. (1) Ethylene homopolymer (manufacturing method may be low pressure method, high pressure method, etc.) (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 -Random copolymer of methyl-1-pentene and 20 mol% or less of other α-olefins. Other α-olefins as the comonomer include, for example, ethylene, 1-butene, 4-methyl-olefin. - pentene,
One or more kinds can be appropriately selected from 1-hexene, 1-octene and the like. In the above, the mol% of other α-olefin as a comonomer is based on all repeating units constituting the copolymer. Hereinafter, mol% of the olefin is based on all repeating units constituting the polymer similarly.

Among the above crystalline polyolefin resins (a), a crystalline polypropylene resin is preferable, and a propylene homopolymer, a random copolymer of propylene and 10 mol% or less of α-olefin, and a propylene content of 50.
A propylene / α-olefin block copolymer of not less than mol% is particularly preferable. The crystalline polyolefin resin (a) as described above can be used alone or in combination. Melt flow rate of crystalline polyolefin resin (a) (MFR; ASTM D1238, 230 ° C.,
2.16 kg load, the same below) is preferably 0.01-1
00g / 10 minutes, more preferably 0.3 to 70g / 1
It is in the range of 0 minutes. The crystallinity of the crystalline polyolefin resin (a) determined by the X-ray method is usually 5-10.
It is in the range of 0%, preferably 20 to 80%.

In the thermoplastic elastomer (A), the crystalline polyolefin resin (a) is preferably 10 to 90 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (a) and the crosslinked olefin rubber (b). Parts, more preferably 10 to 80 parts by weight, still more preferably 10 to 70 parts by weight. When the crystalline polyolefin resin (a) is used in the above proportion, the thermoplastic elastomer composition of the present invention has good moldability, and the skin layer made of the composition has excellent scratch resistance and heat resistance.

[II] Crosslinked olefin rubber (b) The crosslinked olefin rubber (b) which is a component constituting the thermoplastic elastomer (A) has an α-olefin content of 2 to 20 carbon atoms of 50 mol% or more. It is a cross-linked product of α-olefin random copolymer rubber. Examples of the α-olefin random copolymer rubber include copolymer rubbers of two or more types of α-olefins and copolymer rubbers of two or more types of α-olefins and non-conjugated dienes. As the α-olefin random copolymer rubber, specifically, the following (1) to (4)
The rubber shown by can be illustrated. (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
To 50/50] (3) Propylene / α-olefin copolymer rubber [Propylene / α-olefin (molar ratio) = about 90/1
0-50 / 50] (4) 1-butene / α-olefin copolymer rubber [1-butene / α-olefin (molar ratio) = about 90/1
0-50 / 50]

Examples of the α-olefins (1) to (4) include ethylene, propylene, 1-butene and 4-.
One or more of methyl-1-pentene, 1-hexene, 1-octene and the like can be appropriately selected and used.

The non-conjugated diene preferably has 6 to 20 carbon atoms, and specific examples thereof include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene. . The iodine value of the ethylene / α-olefin / non-conjugated diene copolymer rubber of the above (2) in which such a non-conjugated diene is copolymerized is preferably 25 or less, 5
-20 are more preferable. The Mooney viscosity [ML1 + 4 (121 ° C.)] of the copolymer rubber of (1) to (4) above is 10.
˜250 is preferable, and 30 to 150 is particularly preferable.

The crystallinity of the α-olefin random copolymer rubber is preferably less than 20% as measured by X-ray method.

The crosslinked olefin rubber (b) is a crosslinked product of the above-mentioned α-olefin random copolymer rubber, but it is preferably in a partially crosslinked state. Here, the state of being partially crosslinked means the case where the gel content measured by the method described later is 20 to 97%.

From the α-olefin random copolymer rubber,
The crosslinked olefin rubber (b) can be obtained by a method known per se, for example, a method in which an α-olefin random copolymer is melt-kneaded in the presence of a small amount of a crosslinking agent. At this time, a thermoplastic elastomer (a) containing the crystalline polyolefin resin (a) and the crosslinked olefin rubber (b) is allowed to coexist with the crystalline polyolefin resin (a) in a single operation by the method described in detail later. It is also possible to produce A).

In the thermoplastic elastomer (A), the cross-linked olefin rubber (b) is 100 in total of the crystalline polyolefin resin (a) and the cross-linked olefin rubber (b).
10 to 90 parts by weight, preferably 20 to 9 parts by weight
It is used in an amount of 0 part by weight, more preferably 30 to 90 parts by weight.

[III] Preferable Thermoplastic Elastomer (A) and Method for Preparing Thermoplastic Elastomer (A) The thermoplastic elastomer (A) preferably used in the present invention is a crystalline polypropylene resin and a crosslinked ethylene / α-olefin copolymer. Polymer rubber or cross-linked ethylene
an α-olefin / non-conjugated diene copolymer rubber, which is present in the thermoplastic elastomer (A) in a partially crosslinked state, and which has a crystalline polypropylene resin and a crosslinked olefin rubber. Weight ratio (crystalline polypropylene resin / crosslinked olefin rubber) is 70
It is in the range of / 30 to 10/90.

As a more specific example of the thermoplastic elastomer (A) that is preferably used, a crystalline polypropylene resin is used as the crystalline polyolefin resin (a), and a crosslinked ethylene / propylene copolymer rubber is used as the crosslinked olefin rubber (b). And at least one of crosslinked ethylene / propylene / non-conjugated diene copolymer rubber, and the polymerization ratio thereof is 70/30 to 90/10 [(a) / (b)].
Further, 5 to 100 parts by weight of a rubber other than the olefin-based rubber and / or a mineral oil-based softening agent which will be described later can be mentioned with respect to 100 parts by weight of the total amount of these components.

The thermoplastic elastomer (A) is obtained by melting a blend containing the crystalline polyolefin resin (a) and the α-olefin random copolymer rubber in the presence of a crosslinking agent such as an organic peroxide. , Can be obtained by kneading.

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, ter
Examples thereof include t-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.

Of these, 2,5-dimethyl-2,5-di- (tert-) is preferable in terms of odor and scorch stability.
Butylpentyloxy) hexane, 2,5-dimethyl-
2,5-Di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butyloxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane , N-
Butyl-4,4-bis (tert-butylperoxy)
Valerate is preferred, among which 1,3-bis (ter
Most preferred is t-butylperoxyisopropyl) benzene.

The organic peroxide is preferably 0.05 to 3 parts by weight, more preferably 0.1 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (a) and the α-olefin random copolymer rubber. It is used in a proportion of 1% by weight.

In the crosslinking treatment with the above organic peroxide,
Sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenediene Peroxy crosslinking aids such as maleimides; or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc. A polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be added.

By using the above compound,
A uniform and mild crosslinking reaction of the α-olefin random copolymer rubber can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin (a) and the α-olefin random copolymer rubber, has a function of solubilizing the organic peroxide, and disperses the organic peroxide. Since it functions as an agent, a thermoplastic elastomer (A) having uniform cross-linking by heat treatment and having a good balance of fluidity and physical properties can be obtained.

The above-mentioned crosslinking aid, polyfunctional methacrylate monomer or polyfunctional vinyl monomer is used in an amount of 0.1 to 2% by weight, particularly 0.1% by weight, based on the whole melt-kneaded product.
It is preferably used in a proportion of 3 to 1% by weight. Crosslinking aid,
When the compounding ratio of the polyfunctional methacrylate monomer or the polyfunctional vinyl monomer is within the above range, the thermoplastic elastomer (A) obtained is such that the crosslinking aid, the polyfunctional methacrylate monomer or the polyfunctional vinyl monomer is an elastomer. Since it rarely remains as an unreacted monomer in the product, the physical properties thereof are less likely to change due to heat history during processing, and the liquidity is excellent.

As the kneading device, a conventionally known kneading device,
For example, an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer and the like are used. Of these, a non-open type kneading device is preferable, and kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

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 280 ° C.
The temperature is 240 ° C., and the kneading time is 1 to 20 minutes, preferably 1 to 5 minutes. The shearing force applied is usually 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 at a shear rate.
It is in the range of ⁴ sec ^-1 . As described above, the thermoplastic elastomer (A) containing the crystalline polyolefin resin (a) and the crosslinked olefin rubber (b) can be obtained.

The term "crosslinked" as used herein means that the gel content (cyclohexane insoluble matter) measured by the following method is 10:
When it is more than%. In the present invention, the gel content of the thermoplastic elastomer is preferably 20% or more, more preferably 30% or more, and further preferably 4%.
0 to 70%. The thermoplastic elastomer (A) having a gel content in the above range has good rubber elasticity, and can provide a molded article excellent in mechanical strength and elongation at break.

[Determination of gel content (insoluble in cyclohexane)] About 100 mg of a thermoplastic elastomer sample was weighed and cut into 0.5 mm x 0.5 mm x 0.5 mm strips, which were then obtained. The strips are immersed in 30 ml of cyclohexane in a closed container 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, content, etc.) other than the polymer component from the weight of the dry residue is defined as "corrected final weight (Y)". On the other hand, from the weight of the sample, the weight of the cyclohexane-soluble component other than the polymer component (for example, the softening agent) and the cyclohexane-insoluble component other than the polymer component (fibrous filler, filler,
The value obtained by subtracting the weight of the pigment or the like) is defined as "corrected initial weight (X)". Here, the gel content (cyclohexane insoluble content) is calculated by the following mathematical formula.

[0034]

[Equation 1]

Poly 1-butene resin (B) The poly 1-butene resin (B) constituting the thermoplastic elastomer is a (co) polymer exemplified by the following (1), (2) and (3). Is preferably used. (1) 1-Butene homopolymer (2) Random copolymer of 1-butene and 10 mol% or less of other α-olefin (3) 1-butene and 30 mol% or less of other α-olefin Block Copolymer of Other α-olefin as the comonomer specifically includes ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Among them, a homopolymer of 1-butene or a random copolymer of 1-butene containing 1-butene as a main component and ethylene or propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.

The poly-1-butene resins may be used alone or in combination of two or more. MFR (Mettle flow rate; ASTM D) of poly 1-butene resin (B)
1238, 230 ° C, 2.16 kg load) is 0.01-
The range of 30 is preferable.

Thermoplastic elastomer composition and its preparation
Production Method The thermoplastic elastomer composition of the present invention contains the above-mentioned thermoplastic elastomer (A) and poly-1-butene resin (B). And the weight ratio of these [(A)
/ (B)] is 60/40 to 5/95, preferably 59/41 to 10/90, and more preferably 55 /.
45 to 20/80.

The thermoplastic elastomer composition of the present invention may be blended with a rubber other than an olefin rubber as an optional component, if necessary, within a range not impairing the achievement of the object of the present invention.

Examples of rubbers other than olefin rubbers include styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), butyl rubber (II
Examples thereof include diene rubbers such as R) and polyisobutylene rubbers.

Rubbers other than the above-mentioned olefinic rubbers can be added at any stage of producing the thermoplastic elastomer composition of the present invention, but should be added at the stage of preparing the above-mentioned thermoplastic elastomer (A). Is preferred.
The rubber other than the olefin rubber is preferably used in a ratio of 40 parts by weight or less, more preferably 5 parts by weight, based on 100 parts by weight of the total amount of the crystalline olefin resin (a) and the crosslinked olefin rubber (b). Used in a proportion of up to 20 parts by weight. By using a rubber other than the olefin rubber, a thermoplastic elastomer composition having excellent flexibility can be obtained.

The thermoplastic elastomer composition of the present invention has a silicone oil (C), an ester compound (D), a fluoropolymer (E) and a higher fatty acid amide (F) for the purpose of improving scratch resistance. It is preferable to mix at least one selected from the group consisting of And the compounding quantity is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic elastomer (A) and the poly-1-butene resin (B). It is a department.

Specific examples of the silicone oil (C) include dimethyl silicone oil, phenylmethyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, modified silicone oil and the like. Among them, dimethyl silicone oil,
Phenylmethyl silicone oil is preferably used.

Kinematic viscosity of silicone oil (C) [JIS
K2283, 25 ° C] is 10 to 30,000 cS
t, preferably 50 to 10,000 cSt, more preferably 100 to 5,000 cSt.

The ester compound (D) is an ester of an aliphatic alcohol and a dicarboxylic acid or a fatty acid. As such an ester compound (D),
Specifically, esters of cetyl alcohol and acetic acid, esters of cetyl alcohol and propionic acid, esters of cetyl alcohol and butyric acid, esters of beef tallow alcohol and acetic acid, esters of beef tallow alcohol and propionic acid, tallow alcohol and butyric acid. Ester of stearyl alcohol and acetic acid, ester of stearyl alcohol and propionic acid, ester of stearyl alcohol and butyric acid, ester of distearyl alcohol and phthalic acid, glycerin monooleate, glycerin monostearate, glycerin 12 -Hydroxy stearate, glycerin tristearate, trimethylolpropane tristearate, pentaerythritol tetrastearate, butyl stearate, isobutyl stearate, stearic acid ether Tell, oleic acid ester, behenic acid ester, calcium soap-containing ester, isotridecyl stearate, cetyl palmitate, cetyl stearate, stearyl stearate, behenyl behenate, montanic acid ethylene glycol ester, montanic acid glycerin ester, Examples include montanic acid pentaerythritol ester, calcium-containing montanic acid ester, and the like. Among them, esters of distearyl alcohol and phthalic acid, glycerin monooleate, glycerin monostearate, glyceryl montanate are preferred, and esters of distearyl alcohol and phthalic acid, glycerin monostearate, glyceryl montanate are preferred. .

As the above-mentioned fluorine-based polymer (E), polytetrafluoroethylene is preferable among concrete examples of polytetrafluoroethylene, vinylidene fluoride copolymer and the like.

Specific examples of the higher fatty acid amide (F) include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide and hebemic acid amide; erucic acid amide, oleic acid amide and brassic acid amide. Unsaturated fatty acid amides such as elaidic acid amide; bis fatty acid amides such as methylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisstearic acid amide, and ethylenebisoleic acid amide. Among them, erucic acid amide, oleic acid amide, and ethylenebisoleic acid amide are preferable.

The components (C) to (E) may be blended in advance with at least one of the thermoplastic elastomer (A) and the poly-1-butene resin (B).

Further, in the present invention, in the thermoplastic elastomer composition, known mineral oil softeners, inorganic fillers and heat stabilizers may be added, if necessary, to the extent that the object of the present invention is not impaired. Additives such as antiaging agents, weathering stabilizers, antistatic agents, lubricants exemplified by metal soaps and waxes can be added. These may be mixed in advance with at least one of the thermoplastic elastomer (A) and the poly-1-butene resin (B).

Specific examples of such an inorganic filler 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.

Examples of known heat stabilizers, antiaging agents and weathering stabilizers include phenol type, sulfite type, phenylalkane type, phosphite type and amine type stabilizers.

The thermoplastic elastomer composition of the present invention comprises:
It can be prepared by blending the thermoplastic elastomer (A) and the poly-1-butene resin (B) in the above-described proportions and melt-kneading.

In the preparation of the thermoplastic elastomer composition of the present invention, silicone oil (C), ester compound (D), fluorine-based polymer (E) may be added, if necessary, when the above-mentioned components are blended. And at least one component selected from the group consisting of higher fatty acid amide (F), rubber other than olefin rubber, and other optional components described above.

As the above-mentioned melt-kneading method, the melt-kneading method described above in the preparation of the thermoplastic elastomer (A) is preferable.

Next, the thermoplastic elastomer (A '), the crystalline polyolefin resin and the olefin resin foam which form the base material layer of the laminate of the present invention will be described.
[I '] The thermoplastic elastomer (A') for forming a base material can be applied as it is to the thermoplastic elastomer (A '), including the description of the thermoplastic elastomer (A) including the preferable embodiments.

[II '] Crystalline Polyolefin Resin for Forming Base Material The following may be mentioned homopolymers or copolymers of α-olefins having 2 to 20 carbon atoms. (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 Copolymer (6) 1-butene homopolymer (7) Random copolymer of 1-butene and other α-olefin at 10 mol% or less (8) 4-Methyl-1-pentene homocopolymer (9) Random copolymer of 4-methyl-1-pentene and other α-olefin of 20 mol% or less (10) Intrinsic viscosity [η] measured in decalin at 135 ° C
High molecular weight polyethylene having a viscosity of 10 to 40 dl / g (11) Intrinsic viscosity [η] measured in 135 ° C decalin
Of 15 to 40% by weight of ultra-high molecular weight polyethylene in the range of 10 to 40 dl / g, and polyethylene 60 to which the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 5 dl / g. 85% by weight, 135 ° C
Intrinsic viscosity [η] measured in decalin is 3.5-8.3d
Ultra-high molecular weight polyethylene composition in the range of 1 / g Specific examples of the above α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1
-Hexene, 1-octene and the like.

Among the above crystalline polyolefin resins, propylene homopolymers, random copolymers of propylene and 10 mol% or less of other α-olefins, or propylene and 30 mol% or less of other α-olefins. It is particularly preferable to use the block copolymer of.

Melt flow rate of crystalline polyolefin resin (MFR; ASTM D1238, 230 ° C.,
2.16 kg load) is preferably in the range of 50 g / 10 minutes or less, more preferably 20 g / 10 minutes or less. The crystallinity of the crystalline polyolefin resin is usually 5 to 100%, preferably 20 to
It is in the range of 80%.

[III '] Polyolefin Resin Foam for Forming Base Material The foam is preferably a polyethylene or polypropylene foam, more preferably a crosslinked foam. As a method for producing such a crosslinked foam, for example, Japanese Patent Publication No.
No. 25500, No. 40-25351, No. 40-25352 and the like describe methods using an azide cross-linking agent, and in addition to this, cross-linked foams by the radiation irradiation method are also known. Moreover, since these crosslinked foams are also commercially available, the commercially available products can be used as they are. When the 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.

In the above crystalline polyolefin resin and polyolefin resin foam, if necessary, a mineral oil softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antiaging agent, a filler, a coloring agent, Additives such as lubricants can be added within a range that does not impair the object of the present invention.

Laminate and Manufacturing Method Thereof The laminate of the present invention comprises the above-mentioned skin layer and base material layer. The method for laminating the base material layer and the skin layer differs depending on the shape, size and required physical properties of the final product and is not particularly limited, but examples thereof include the following laminating methods. (1) A method in which both layers, which are at least one of a base material layer and a skin layer, which have been formed in advance, are melted by heat and pressure using a calender roll molding machine, a compression molding machine, or the like at a temperature higher than the melting temperature. (2) A method in which a base material layer or a skin layer that has been formed into a sheet shape in advance is heat-pressure fused to the other layer that has been extrusion-molded and calendered. (3) A method in which a base material layer and a skin layer are simultaneously extrusion-molded by a multilayer extrusion molding machine and heat-sealed (coextrusion molding).

When the laminate is used for automobile exterior parts, the base material layer is preferably composed of a thermoplastic elastomer (A ') or a crystalline olefin resin. When used for automobile exterior parts, the thickness of the base material layer is preferably 0.1 to 50 mm, and the thickness of the skin layer is preferably 5 μm to 20 mm. Moreover, the thickness of the laminated body is 0.5 to 50 m.
m is preferable.

When the laminate is used for automobile interior parts, the base material layer is preferably made of polyolefin resin foam. When used for automobile interior parts, the thickness of the skin layer is 0.
The thickness of the base material layer is preferably 1 to 2 mm.
It is preferably 30 mm. Further, the thickness of the laminated body is preferably 1.1 to 30 mm. The thickness of the skin layer is relatively thin in the case of a ceiling material, and relatively thick in the case of dash bows, wheel house covers, various pillars, sheets and the like.

Further, the skin layer is used for any purpose,
It may be embossed if necessary.

Use of Laminate The laminate of the present invention has remarkably excellent interlayer adhesion between the base material layer and the skin layer, and further has mechanical strength, heat resistance, heat aging resistance, weather resistance, scratch resistance, and abrasion resistance. And excellent in dimensional stability, especially scratch resistance. Further, the thermoplastic elastomer laminate is lighter in weight and easier to recycle than polyvinyl chloride resin, and does not generate harmful gas even when incinerated.

Therefore, the thermoplastic elastomer laminate of the present invention is particularly used for applications requiring scratch resistance, such as automobile interior parts, automobile exterior parts, furniture, building materials, home appliance housings, shoes, suitcases, sports equipment, Office supplies,
It can be effectively used for purposes such as miscellaneous goods. Among these, it is particularly preferable to use it for automobile interior parts and automobile exterior parts, especially for automobile interior parts and automobile exterior parts suitable for 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, sun visors. , Rearview mirror cover, room mirror cover, cup holder, coin box, resist,
Examples include ashtray uppers, door frame garnishes, door trims, armrests, column covers, inner panels, garage opener housings, dashboards, wheel house covers and the like. Further, as a concrete example of the automobile exterior parts, a side molding garnish, a window molding and the like can be mentioned. In addition,
When using a polyolefin resin foam as the substrate,
Bone can be used for the purpose of improving strength. Bone agents themselves and methods of using them are well known and can be used.

[0067]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Synthesis of component of thermoplastic elastomer (A-1) for skin layer) Polypropylene as crystalline polyolefin resin [MFR: 13 g / 10 min, crystallinity determined by X-ray method: 72%] 20 Parts by weight and ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber as an olefin rubber [ethylene content: 78 mol%, iodine value: 15, Mooney viscosity (ML1 + 4, 121 ° C.): 6
1] For 80 parts by weight and 100 parts by weight of these mixtures,
0.7 parts by weight of a mixture of 50% by weight of di-tert-butyl peroxide, 40% by weight of divinylbenzene and 10% by weight of paraffinic mineral oil were mixed with stirring by 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. Was extruded to produce pellets of the thermoplastic elastomer (A-1). Gel content is 9
It was 0%.

(Preparation of Thermoplastic Elastomer Composition for Forming Skin Layer) 90 parts by weight of pellets of the thermoplastic elastomer (A-1) and poly-1-butene resin (homopolymer, MF)
R: 20 g / 10 minutes) 10 parts by weight of pellets were mixed by a Henschel mixer, and then kneaded again by an extruder to produce thermoplastic elastomer composition pellets. (Preparation of Laminate) Crystalline polypropylene (P) (homopolymer, MFR: 15 g / 10 min) is extruded into a sheet at a temperature of 230 ° C., and the thermoplastic elastomer composition is formed into a sheet on the surface thereof. Was co-extruded and laminated to obtain a co-extruded laminate having a substrate layer thickness of 10 mm and a skin layer thickness of 2 mm.

With respect to the obtained laminate, the interlayer adhesive strength and the scratch resistance of the surface of the skin layer were measured according to the following methods. The results are shown in Table 1. (A) Interlayer adhesive strength test Test method: 180 degree peel test Test piece: Width 25 mm, length 100 mm Tensile speed: 25 mm / min (b) Scratch resistance test A 20 mm square felt cloth was placed on the surface layer surface of the laminate. ,
Furthermore, a weight was placed thereon so that a pressure of 200 g / cm ² was applied, the surface of the skin layer was reciprocated 100 times, and the scratch resistance was evaluated by 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

Examples 2 to 6 and Comparative Examples 1 and 2 (Preparation of Thermoplastic Elastomer for Forming Skin Layer) Pellets of thermoplastic elastomer (A-1) and the above polybutene-
1 resin pellets or crystalline polypropylene (P) pellets and silicone oil (C), ester compound (D), fluoropolymer (E), higher fatty acid amide (F) in the ratio shown in Table 1 in a Henschel mixer After mixing, the mixture was kneaded again with an extruder to produce thermoplastic elastomer composition pellets. In addition, the above (C) ~
The component (G) is as follows. Silicone oil (C): SH2 made by Toray Silicone Co., Ltd.
00 Ester compound (D): Glycerin monostearate Fluoropolymer (E): Polyvinylidene fluoride resin (KFHA Co., Ltd., KF polymer W-1000) Higher fatty acid amide (F): Erucamide

(Preparation of Laminate) A coextruded laminate was obtained in the same manner as in Example 1. With respect to the obtained laminate, the interlayer adhesion strength and the scratch resistance of the surface layer were measured in the same manner as in Example 1. The results are shown in Table 1.

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[Table 1]

Examples 7 to 12 and Comparative Examples 3 and 4 (Preparation of Thermoplastic Elastomer for Forming Skin Layer) Pellets of thermoplastic elastomer (A-1) and polybutene 1-butene resin, crystalline polypropylene resin (P ), Silicone oil (D), ester compound (D), fluoropolymer (E), and higher fatty acid amide (F) in the proportions shown in Table 2, respectively, in a Henschel mixer, and then kneaded again in the extruder to form a skin. Pellets of the forming thermoplastic elastomer composition were prepared.

Further, the pellets of the thermoplastic elastomer composition were used at a temperature of 220 ° C. and a take-up speed of 2. using a 90 mmφ T-die extruder (full flight screw, L / D = 26, coat hanger die) manufactured by Toshiba Corporation. 5m
The sheet-shaped thermoplastic elastomer composition in a melted state extruded in a sheet shape at a rate of 1 / min and a crosslinked foam sheet of polyethylene [manufactured by Sekisui Chemical Co., Ltd., trade name Softlon, foaming ratio 30 times, thickness 3 mm] and was passed through between a pair of rolls. At that time, the thermoplastic elastomer sheet is brought into contact with the embossing roll side at a roll temperature of 60 ° C., and the crosslinked foam sheet is brought into contact with the normal roll side which is not heated, and the skin layer has a thickness of 0.5 mm. A laminate was produced.

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: 0.5 g /
10 minutes], using a male and female hot press to mold an automobile ceiling aggregate from a plastic cardboard (pitch 10 mm, thickness 3 mm)
C., press molding for 40 seconds under a heating and pressurizing condition of ² kg / cm.sup.2, during which the laminate preheated to 170.degree. C. is placed on the aggregate molded product and pressed again to press both. Thermoforming was integrated 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 as to apply a pressure of 200 g / cm ² , and the ceiling material was reciprocated 100 times, and the scratch resistance was evaluated by the surface condition after the reciprocating operation.
Table 2 shows the results.

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[Table 2]

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EFFECTS OF THE INVENTION According to the present invention, there are provided a laminate which is lightweight, easy to recycle, does not generate a harmful gas even when incinerated, and has excellent scratch resistance, and an automobile interior / exterior component using the same. To be done.

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Claims (14)

[Claims] 1. A thermoplastic elastomer (A) containing [1] (1) a crystalline polyolefin resin (a) and a crosslinked olefin rubber (b) and a poly-1-butene resin (B), and (2) Weight ratio of thermoplastic elastomer (A) and poly 1-butene (B) [(A) /
(B)] contains a skin layer made of a thermoplastic elastomer composition in the range of 95/5 to 5/95, and [II] a crystalline polyolefin resin (a ′) and a crosslinked olefin rubber (b ′). A thermoplastic elastomer (A '), a base layer formed of a crystalline polyolefin resin or a polyolefin resin foam, and a laminate. 2. The plastic elastomer composition constituting the skin layer is at least one selected from the group consisting of silicone oil (C), ester compound (D), fluoropolymer (E) and higher fatty acid amide (F). The laminate according to claim 1, wherein the seed is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the thermoplastic elastomer (A) and the poly-1-butene resin (B). 3. The thermoplastic polyolefin (A) contains the crystalline polyolefin resin (a) in a total amount of 1 of the crystalline polyolefin resin (a) and the crosslinked olefin rubber (b).
10. 1 to 70 parts by weight relative to 00 parts by weight.
Or the laminate according to 2. 4. In the thermoplastic elastomer (A), at least one rubber selected from styrene / butadiene rubber, nitrile rubber, natural rubber, butyl rubber and polyisobutylene rubber and / or a mineral oil-based softening agent is crystalline. The laminate according to any one of claims 1 to 3, which is present in an amount of 5 to 100 parts by weight based on 100 parts by weight of the total amount of the polyolefin resin (a) and the crosslinked olefin rubber (b). 5. The crystalline polyolefin resin (a) is a crystalline polypropylene resin, and the crosslinked olefin rubber (b) is an ethylene / propylene random copolymer rubber or an ethylene / propylene / non-conjugated diene random copolymer rubber. The laminated body according to any one of claims 1 to 4, which is at least one of crosslinked rubbers. 6. The thermoplastic elastomer (A) is obtained by melting and kneading a crystalline polyolefin resin (a) and a crosslinked olefin rubber (b) in the presence of an organic peroxide. The laminate according to any one of the above. 7. The laminate according to claim 1, wherein the base material layer is formed of a crystalline polyolefin resin or a polyolefin resin foam. 8. The crystalline polyolefin resin of the base material layer,
The laminate according to claim 7, which is a crystalline polypropylene resin. 9. The polyolefin resin foam of the base material layer,
The laminate according to claim 7, which is a polyethylene foam or a polypropylene foam. 10. The laminate according to claim 7, wherein the polyolefin resin foam is crosslinked. 11. The laminate is for an automobile exterior part, wherein the base material layer has a thickness of 0.1 to 50 mm and the skin layer has a thickness of 5 μm.
The laminated body according to any one of claims 1 to 10, which has a thickness of 20 mm. 12. The laminate is for automobile interior parts, the base material layer has a thickness of 1 to 30 mm, and the skin layer has a thickness of 0.1.
It is 1-2 mm, The laminated body in any one of Claims 1-10. 13. An automobile exterior component comprising the laminate according to any one of claims 1 to 11. 14. An automobile interior part made of the laminated body according to any one of claims 1 to 10.