JPH09193300A - Laminate and automotive interior part items used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart an excellent scratch resistance to a laminate and apply the laminate to automotive interior parts by a method wherein the advantages of an olefin-based polymer material such as lightness, easy recycling and, in addition, no generation of noxious gas during incineration or the like are utilized. SOLUTION: A skin layer is made of a thermoplastic composition comprising a thermoplastic elastomer A including a crystalline polyolefin resin (a) and a crosslinked olefin-based rubber (b) and poly-1-butene resin B under the condition that the weight ratio (A/B) of the thermoplastic elastomer A and the poly-1- butene B lies within the region of 95/5-0/100. An intermediate layer is made of a thermoplastic elastomer A' including a crystalline polyolefin resin (a') and a crosslinked olefin-based rubber (b'). This laminate comprises a polyolefin resin foamed layer, which locates through the intermediate layer opposite to the skin layer.

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 material and having excellent scratch resistance, and an automobile interior part using the same.

[Prior art]

Conventionally, vinyl chloride resin has been widely used for automobile interior materials. An automobile interior member using a vinyl chloride resin is a laminate in which a vinyl chloride resin layer having a leather pattern with a textured surface by embossing 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. Also,
The vinyl chloride resin has a problem of polluting the environment because it emits a harmful gas when incinerated.

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, the conventional molded product made of an olefinic resin or olefinic 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.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to make use of the advantages of olefin polymer materials such as light weight, easy recycle use, and generation of no harmful gas even when incinerated, and scratch resistance. It is an object of the present invention to provide a laminate which is excellent in and can be used for automobile interior parts. Another object of the present invention is to provide an automobile interior part using the above laminate.

[0006]

The above objects and advantages of the present invention are [1] a thermoplastic elastomer (A) containing a crystalline polyolefin resin (a) and a crosslinked olefin rubber (b), and a poly-1-. Contains butene resin (B),
The weight ratio [(A) / (B)] of the thermoplastic elastomer (A) and the poly-1-butene (B) is 95/5 to 0.
/ 100 skin layer composed of a thermoplastic elastomer composition, [2] crystalline polyolefin resin (a ')
An intermediate layer composed of a thermoplastic elastomer (A ') containing a crosslinked olefin rubber (b'), and [3] a polyolefin resin foam located on the opposite side of the skin layer with the intermediate layer interposed therebetween. This is achieved by a layered body and an automobile interior part made of the layered body.

The present invention is described in detail below, with which other objects and advantages of the present invention will become apparent. First, the thermoplastic elastomer composition constituting the skin layer will be described. The thermoplastic elastomer contains the thermoplastic elastomer (A) and the poly-1-butene resin (B), including the case where the thermoplastic elastomer comprises only the poly-1-butene resin (B).

The crystalline polyolefin resin (a) constituting the thermoplastic elastomer has 2 to 20 carbon atoms.
[Alpha] -olefin homopolymers or copolymers. Specific examples of the crystalline polyolefin resin (a) include the following polymers or copolymers. (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.

The crosslinked olefin rubber (b), which is a component of the thermoplastic elastomer (A), has 2 to 2 carbon atoms.
0 is a crosslinked product of an α-olefin random copolymer rubber having an α-olefin content of 50 mol% or more. 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. α-
Specific examples of the olefin random copolymer rubber include rubbers represented by the following (1) to (4). (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10 to 50 /
50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90
(3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/10 to 5]
0/50] (4) 1-butene / α-olefin copolymer rubber [1-
Butene / α-olefin (molar ratio) = about 90/10 to 5
0/50]

Examples of the α-olefins (1) to (4) include ethylene, propylene, 1-butene, 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 [ML _{1 + 4} (121 ° C.)] of the copolymer rubbers of (1) to (4) is 10 to
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 obtained by crosslinking the above α-olefin random copolymer rubber.

From 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 crosslinked olefin rubber (b) is 100 in total of the crystalline polyolefin resin (a) and the crosslinked 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.

The thermoplastic elastomer (A) preferably used in the present invention comprises a crystalline polypropylene resin and a crosslinked ethylene / α-olefin copolymer rubber or a crosslinked ethylene / α-olefin / non-conjugated diene copolymer rubber. In the thermoplastic elastomer (A), the components thereof are present in a partially crosslinked state, and the weight ratio of the crystalline polypropylene resin and the crosslinked olefin rubber (crystalline polypropylene resin / crosslinked olefin rubber).
Is in the range of 70/30 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.

As the thermoplastic elastomer (A), a blend containing the crystalline polyolefin resin (a) and the α-olefin random copolymer rubber is melted 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. Upon the crosslinking treatment with the organic peroxide, sulfur,
p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline,
Peroxy crosslinking aids such as nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide; or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol diethylene Polyfunctional methacrylate monomers such as methacrylate, trimethylolpropane trimethacrylate, allyl methacrylate and the like; and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using the above compounds,
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, especially 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.

Here, "crosslinked" 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.

[Method for measuring gel content (insoluble in cyclohexane)] About 100 mg of a sample of a thermoplastic elastomer was weighed and cut into a piece of 0.5 mm x 0.5 mm x 0.5 mm, which was 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, 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 was “corrected”. Initial weight (X) ". Here, the gel content (cyclohexane insoluble content) is calculated by the following mathematical formula.

[0030]

[Equation 1]

Poly 1-constituting the thermoplastic elastomer
As the butene resin (B), the (co) polymers exemplified in the following (1), (2) and (3) are 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.

The thermoplastic elastomer composition of the present invention comprises:
The thermoplastic elastomer (A) and the poly-1-butene resin (B) described above are included, including the case where the poly-1-butene resin (B) alone is included. The weight ratio [(A) / (B)] of these is 95/5 to 0/100.

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.

As the rubber other than the olefin rubber, for example, 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. However, they 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. Of these, esters of distearyl alcohol and phthalic acid, glycerin monooleate, glycerin monostearate and glyceryl montanate are preferred, and esters of distearyl alcohol and phthalic acid, glycerin monostearate and glyceryl montanate are particularly preferred.

Specific examples of the fluorine-based polymer (E) include polytetrafluoroethylene and vinylidene fluoride copolymer. Among them, polytetrafluoroethylene is preferable.

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 type 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), fluoropolymer (E) may be added, if necessary, when blending the above-mentioned respective components. 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.

The thermoplastic elastomer (A ') which forms the intermediate layer of the laminate of the present invention can be applied as it is, including the preferred embodiments, regarding the description of the thermoplastic elastomer (A). That is, the crystalline polyolefin resin (a ') and the crosslinked olefin rubber (b') constituting the thermoplastic elastomer (A ') are the crystalline (a) and the crosslinked olefin rubber (b) constituting the thermoplastic elastomer (A). This is applicable to b) including a preferable embodiment. Further, all the descriptions regarding the thermoplastic elastomer (A) regarding the optional components and the preparation method can be applied to the thermoplastic elastomer (A ′).

As the polyolefin resin foam constituting the polyolefin resin foam layer of the laminate of the present invention, polyethylene and polypropylene foams are preferable, and crosslinked foams thereof are more preferable. The crosslinked foam can be obtained by mixing polyethylene or polypropylene with a foaming agent and a crosslinking agent, and heating the mixture at a temperature equal to or higher than the softening point.

Examples of the foaming 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 (benzenesulfonylhydrazide), P, P'- Diphenyl-
Examples thereof include bis (sulfonyl hydrazide), benzenesulfonyl hydrazide, m-benzene-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, Poly (sulfone azide) compounds such as 6-benzene tris (sulfone azide), 4,4′-diphenylmethane bis (sulfone azide), 4,4′-diphenyl disulfide bis (sulfone azide); n-octadecyl Azidoformate, tetramethylene-bis (azidoformate), phenylazidoformate, 2,2-isopropylidene-bis (P,
P'-phenyl azidoformate), 2,2'-oxydiethyl-bis (azidoformate), 2,2'-ethylenedioxydiethyl-bis (azidoformate), 2,2 '
-Azidoformate compounds such as thiodiethyl-bis (azidoformate); m-phenylenediazide, 2,4,
Aromatic polyazide compounds such as 6-triazidobenzene and 4,4′-diazidophenylamine may be mentioned.

A method for producing a crosslinked foam is described in, for example, Japanese Examined Patent Publication No.
No. 9-25500, No. 40-25351, No. 40-25352, etc. are described in detail. 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. These foams are about 10-5
It is desirable that the expansion ratio is about 0 times.

If necessary, the polyolefin resin foam may contain additives such as a mineral oil type softener, a heat resistance stabilizer, an antistatic agent, a weather resistance stabilizer, an antiaging agent, a filler, a colorant and a lubricant. It can be blended within a range that does not impair the object of the invention.

The thickness of the skin layer of the laminate of the present invention is usually 0.01 to 1 mm, preferably 0.01 to 0.5 mm, and the thickness of the intermediate layer is usually 0.1 to 3 mm, preferably Is 0.3 to 2 mm, and the thickness of the polyolefin resin foam layer is
It is usually 0.5 to 10 mm, preferably 1 to 5 mm.
And the total thickness of the laminated body is usually 0.5 to 13 mm,
It is preferably 1 to 10 mm.

The laminate of the present invention can be produced by combining means known per se, an example of which is shown below. (1) A method of thermocompression-bonding a skin layer, an intermediate layer, and a polyolefin resin foam layer that have been formed into a sheet shape in advance by using a means such as a calender molding machine. (2) 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 to a sheet-shaped polyolefin resin foam layer.

When the laminate of the present invention is used for automobile interior parts, an aggregate layer may be provided on the laminate side for the purpose of imparting shape retention (rigidity). As the crystalline polyolefin resin, the same crystalline polyolefin resin (a) as that used in the thermoplastic elastomer is used. Among them, propylene homopolymer, propylene and 1
Random copolymers with 0 mol% or less of other α-olefins and block copolymers of propylene with 30 mol% or less of other α-olefins are preferable. The crystalline polyolefin resins can be used alone or in combination.

In the polyolefin resin used for forming the aggregate layer, wood powder, fiber pieces, inorganic fillers are used within the range not impairing the physical properties required for the aggregate layer or for the purpose of further improving the physical properties. Etc. can be mixed. These polyolefin resin aggregates are generally molded into a predetermined shape as an aggregate layer molded product in a state of, for example, a resin board, a plastic cardboard, or a resin felt.

The aggregate layer molded product obtained by molding the polyolefin resin or the composition thereof into a predetermined shape is placed so that the preheated foamed layer of the laminate of the present invention comes into contact with it, and thermoformed to form the present invention. Integrated with the laminated body of.

Automotive interior parts can be suitably produced from the laminate of the present invention by a method known per se. At this time, the skin layer has a thickness of 0.01 to 0.3 mm, the intermediate layer has a thickness of 0.2 to 2 mm, and the polyolefin resin foam layer has a thickness of 1
It is preferably ˜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 a dashboard, a wheel house cover, various pillars, sheets and the like. The skin layer may be embossed. When stacking aggregate layers, the thickness is 0.5-5 mm
It is preferred that

Since the surface layer of the automobile interior part of the present invention is formed of the thermoplastic elastomer composition, it is particularly excellent in scratch resistance. Further, since the thermoplastic elastomer is laminated on the skin layer, it has a feature that it is difficult to remove the embossed pattern, especially when the parts are processed. Further, since the foam layer is laminated, it is excellent in flexibility and cushioning property. Furthermore, the laminated body in which the aggregate layer is laminated,
Providing automobile interior parts with excellent strength and rigidity.

Specific examples of the automobile interior parts of the present invention include instrumental panels, steering wheels, pillar garnishes, airbag covers, door grabs, console boxes, shift knobs, assist grips, seat adjusters, louver garnishes, and garage openers. , Sun visor, rearview mirror cover,
A room mirror cover, a cup holder, a coin box, a resist, an ashtray upper, a door frame garnish, a door trim, an armrest, a column cover, an inner panel, a garage souper housing, a dashboard, a wheel house cover and the like can be mentioned.

[0064]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The raw materials used in the production of the thermoplastic elastomer composition in the examples are described below. (1) Thermoplastic elastomer (A) and (A ′) 20 parts by weight of polypropylene [MFR: 13 g / 10 minutes, crystallinity determined by X-ray method: 72%] as the crystalline polyolefin resin (a), and olefin As the rubber (b), ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber [ethylene content: 78 mol%,
Iodine number: 15, Mooney viscosity (ML _{1 + 4,} 121 ° C):
61] 80 parts by weight and 100 parts by weight of these mixtures, di-tert-butyl peroxide 50% by weight, divinylbenzene 40% by weight and paraffinic mineral oil 10
0.7 parts by weight of a mixture consisting of 10% by weight 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, a nitrogen atmosphere is introduced. Extruded below at 210 ° C. to produce pellets of thermoplastic elastomer (TPO). The gel content was 90%. This was used as the thermoplastic elastomers (A) and (A ').

(2) Poly 1-butene resin (B): 1-butene homopolymer MFR: 20 g / 10 minutes (230
(° C) (3) Silicone oil (C): manufactured by Toray Silicone Co.,
SH200 (4) Ester compound (D): Glycerin monostearate (5) Fluorine-based polymer (E): Polyvinylidene fluoride resin (KF polymer W-1000 manufactured by Kureha) (6) Higher fatty acid amide (F): Erucic acid amide

Examples 1 to 6 and Comparative Examples 1 and 2 (Preparation of Thermoplastic Elastomer Composition) Pellets of thermoplastic elastomer (A) and pellets of poly-1-butene resin (B) or crystalline polyolefin resin (a) After mixing the silicone oil (C), the ester compound (D), the fluoropolymer (E), and the higher fatty acid amide (F) in a ratio shown in Table 1, with a Henschel mixer,
The mixture was kneaded again with the extruder to produce thermoplastic elastomer composition pellets.

(Preparation of Laminated Product) Pellets of the thermoplastic elastomer (A ′) were heated at 220 ° C. 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 (A ') in a molten state extruded into a sheet at a take-off speed of 2.5 m / min, and a crosslinked foam sheet of polyethylene [Sekisui Chemical Co., Ltd., trade name software Ron, expansion ratio 30 times, thickness 3 mm] was passed through a pair of rolls to form a laminate (i).

Further, pellets of the thermoplastic elastomer composition were similarly formed into a sheet by a t-die extruder, and immediately laminated on the thermoplastic elastomer (A ') layer of the laminate (i) prepared in advance. At that time, the sheet of the thermoplastic elastomer composition is brought into contact with the side of the embossing roll having a roll temperature of 60 ° C., and the sheet of the laminate (i) is brought into contact with the side of the normal roll which is not heated, and the thermoplastic elastomer composition layer is An embossed laminate (ii) having a thickness of 0.1 mm and a thermoplastic elastomer layer of 1.0 mm was produced.

In addition to the laminated body (ii) obtained as described above, talc [Matsumura Sangyo Co., Ltd., trade name ET-5) 3
0% filled polypropylene [propylene / ethylene block copolymer, ethylene content 9 mol%, MFR (AS
TM D 1238-65T, 230 ° C., 2.16 kg load) 0.5] plastic hot-molded corrugated cardboard (pitch 10 mm, thickness 3 mm) to mold aggregates for automobile ceilings. Using a press
Press molding was performed for 40 seconds under heating and pressurizing conditions of 95 ° C. and 2 kg / cm ² , while the laminate (ii) preheated to 170 ° C. was placed on the aggregate molded product so that the foam layer was in contact therewith. Then, it was 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 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 results are shown in Table 1.

(5 step 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 Also, the obtained ceiling The remaining standard of the embossed pattern on the edge of the 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

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[Table 1]

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EFFECTS OF THE INVENTION The laminate of the present invention is excellent in scratch resistance because it is lightweight, easy to recycle and uses the advantages of the olefin polymer material such as generating no harmful gas even when incinerated. It is possible to obtain automobile interior parts in which the embossed pattern does not easily disappear when the parts are processed.

Claims (10)

[Claims] 1. A crystalline polyolefin resin (a) [1]
Containing a thermoplastic elastomer (A) and a poly 1-butene resin (B) containing a crosslinkable olefin rubber (b) and a weight ratio of the thermoplastic elastomer (A) and the poly 1-butene (B) [(A) / (B)] is 95/5
From a thermoplastic elastomer (A ') containing a crystalline polyolefin resin (a') and a crosslinked olefin-based rubber (b '). And a [3] polyolefin resin foam layer located on the opposite side of the skin layer with the intermediate layer interposed therebetween. 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), wherein the crystalline polyolefin resin (a) is 100 in total of the crystalline olefin resin (a) and the crosslinked olefin rubber (b).
The crystalline polyolefin resin (a ') is present in the thermoplastic elastomer (A') in an amount of 10 to 70 parts by weight based on parts by weight, and the crystalline polyolefin resin (a ') and the crosslinked olefin rubber (b'). And 10 to 70 parts by weight relative to 100 parts by weight of the total amount of the above. 4. At least one rubber selected from styrene-butadiene rubber, nitrile rubber, natural rubber, butyl rubber and polyisobutylene rubber in the thermoplastic elastomer (A) and / or a mineral oil-based softening agent is a crystalline polyolefin. 5 to 100 parts by weight relative to 100 parts by weight of the total amount of the resin (a) and the crosslinked olefin rubber (b), and styrene / butadiene rubber, nitrile rubber, natural rubber in the thermoplastic elastomer (A '). At least one rubber and / or a mineral oil-based softening agent selected from butyl rubber and polyisobutylene rubber, per 100 parts by weight of the total amount of the crystalline polyolefin resin (a ′) and the crosslinked olefin rubber (b ′). 5 to 100 parts by weight of the laminated body according to any one of claims 1 to 3. 5. The crystalline polyolefin resins (a) and (a ′) are crystalline polypropylene resins, and the crosslinked olefin rubbers (b) and (b ′) are ethylene / propylene random copolymer rubber and ethylene / propylene. -The laminate according to any one of claims 1 to 4, which is a crosslinked rubber of at least one of non-conjugated diene random copolymer rubbers. 6. A thermoplastic elastomer (A) is obtained by kneading a crystalline polyolefin resin (a) and a cross-linked olefin rubber (b) in the presence of an organic peroxide while melting the thermoplastic elastomer (A). A ') is a crystalline polyolefin resin (a') and a crosslinked olefin rubber (b ')
The layered product according to any one of claims 1 to 5, which is obtained by kneading in the presence of an organic peroxide while being melted. 7. The laminate according to claim 1, wherein the polyolefin resin foam layer comprises a crosslinked polyethylene foam or a crosslinked polypropylene foam. 8. The laminate according to claim 1, further comprising an aggregate layer laminated on the polyolefin resin foam layer. 9. The laminate is for automobile interior parts, the skin layer has a thickness of 0.01 to 0.3 mm, the intermediate layer has a thickness of 0.2 to 2 mm, and a polyolefin resin foam. The layered product according to any one of claims 1 to 8, wherein the layer has a thickness of 1 to 30 mm. 10. An automobile interior part made of the laminate according to claim 1.