JPH0760907A - Thermoplastic elastomer laminate - Google Patents

Abstract

PURPOSE:To achieve the enhancement of durability or easy reclamation by forming a base material layer and a skin layer from a thermoplastic elastomer consisting of a crystalline polyolefin resin and an olefinic resin and a thermoplastic elastomer consisting of a crystalline polyolefin resin and a specific block copolymer respectively. CONSTITUTION:A thermoplastic elastomer laminate is constituted of a base material layer and a skin layer. The base material layer is formed from a crosslinked thermoplastic elastomer [1] containing a crystalline polyolefin resin (A) and olefinic rubber (B). The skin layer is formed from a thermoplastic elastomer [2] consisting of 20-85 pts.wt. of the crystalline polyolefin resin (A) and 15-80 pts.wt. of a block polymer (C), which may be hydrogenated, consisting of a polymer block (a) of styrene or a derivative thereof and a copolymer block (b) wherein the content of the 1,2-bond and 3,4-bond in an isoprene polymer part are 40% or more [the total amt. of the components (A), (C) is 100 pts.wt.].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer laminate, and more particularly to an olefin-based thermoplastic elastomer laminate excellent in scratch resistance, which is suitable for use in, for example, automobile exterior parts.

[0002]

BACKGROUND OF THE INVENTION Conventionally, vinyl chloride resin has been widely used for side protection moldings 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, vinyl chloride resin has a problem of polluting the environment because it emits a harmful gas when incinerated.

By the way, since olefin thermoplastic elastomers are lightweight and easy to recycle, they are energy-saving and resource-saving type elastomers, especially automobile parts, industrial machine parts, electric / electronic parts as substitutes for vulcanized rubber. Widely used for building materials.

Further, in recent years, from the viewpoint of protecting the global environment, in place of vinyl chloride resin, which emits a harmful gas when incinerated,
Olefin-based thermoplastic elastomers that do not generate harmful gas have been used.

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

[0006] Therefore, the inventors of the present invention have earnestly studied to obtain a thermoplastic elastomer molding having excellent scratch resistance,
A base layer formed of a partially or completely crosslinked thermoplastic elastomer containing a crystalline polyolefin resin and an olefin rubber, and a crystalline polyolefin resin, and a specific block copolymer. We prepared a laminate consisting of a skin layer made of a thermoplastic elastomer containing it in a specific ratio. It was lightweight, easy to recycle, and did not generate harmful gas even when incinerated. It was found that a thermoplastic elastomer laminate excellent in heat resistance and heat resistance can be obtained, and the present invention has been completed.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, is lightweight and easy to recycle, and does not generate harmful gas even when incinerated. An object is to provide a thermoplastic elastomer laminate having excellent scratch resistance and heat resistance.

[0008]

SUMMARY OF THE INVENTION A first thermoplastic elastomer laminate according to the present invention comprises [I] a crystalline polyolefin resin (A) and an olefin rubber (B), partially or completely crosslinked. Layer formed of the thermoplastic elastomer [1] prepared above, [II] 20 to 85 parts by weight of a crystalline polyolefin resin (A), a polymer block (a) of styrene or a derivative thereof, and an isoprene weight. Hydrogen comprising a polymer block or an isoprene-butadiene copolymer block, the polymer or copolymer block (b) having a content of 1,2 bonds and 3,4 bonds in the isoprene polymer portion of 40% or more. A thermoplastic resin comprising 15 to 80 parts by weight of the block copolymer (C) which may be added [the total amount of the components (A) and (C) is 100 parts by weight]. It is characterized in that it is composed of a skin layer formed by formed by Sutoma [2].

The second thermoplastic elastomer laminate according to the present invention comprises [I] a crystalline polyolefin resin (A) and an olefin rubber (B), which is partially or completely crosslinked. Layer formed of the thermoplastic elastomer [1] prepared above, [II] 20 to 85 parts by weight of a crystalline polyolefin resin (A), a polymer block (a) of styrene or a derivative thereof, and an isoprene polymer. Block or isoprene-butadiene copolymer block, and hydrogenation comprising a polymer or copolymer block (b) in which the content of 1,2 bonds and 3,4 bonds in the isoprene polymer portion is 40% or more 12 to 80 parts by weight of the block copolymer (C) which may be contained,
And a polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein the content of 1,2 bonds and 3,4 bonds in the isoprene polymer portion is 30% or less. Optionally copolymerized block copolymer (D) consisting of a polymer or copolymer block (d) or a butadiene polymer block (e)
1 to 30 parts by weight [the total amount of components (A), (C) and (D) is 100 parts by weight] and a skin layer formed of a thermoplastic elastomer [3]. Is characterized by.

The thermoplastic elastomer forming the skin layer of the second thermoplastic elastomer laminate according to the present invention [3]
In addition to 20 to 85 parts by weight of the crystalline polyolefin resin (A), 12 to 80 parts by weight of the copolymer block (C) and 1 to 30 parts by weight of the copolymer block (D), an olefin rubber (B). 1 to 30 parts by weight and / or 1 to 30 parts by weight of the softening agent (E) [components (A), (B), (C),
The total amount of (D) and (E) is 100 parts by weight].

[0011]

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic elastomer laminate according to the present invention will be specifically described below. The thermoplastic elastomer laminate according to the present invention comprises a base material layer and a skin layer.

The base material layer contains a crystalline polyolefin resin (A) and an olefin rubber (B) and is a partially or completely crosslinked thermoplastic elastomer [1].
Is formed by.

The skin layer has a thermoplastic elastomer [2] containing a crystalline polyolefin resin (A) and a specific block copolymer (C) in a specific ratio, or a crystalline polyolefin resin (A). , A specific block copolymer (C) and a specific block copolymer (D) in a specific ratio, and are formed of a thermoplastic elastomer [3]. In the thermoplastic elastomer [3], in addition to the crystalline polyolefin resin (A), the block copolymers (C) and (D), if necessary, an olefin rubber (B) and a softening agent (E ) Can be blended in a specific ratio.

Thermoplastic Elastomer [1] As described above, the thermoplastic elastomer [1] used for forming the base material layer is a crystalline polyolefin resin (A).
And olefin rubber (B). [Crystalline Polyolefin Resin (A)] The crystalline polyolefin resin (A) includes α having 2 to 20 carbon atoms.
Examples include 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 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-olefins (5) Block copolymerization of propylene and 30 mol% or less of other α-olefins 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 other α up to 20 mol%
-Random copolymer with olefin As the above α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Examples include hexene and 1-octene.

Among the above crystalline polyolefin resins (A), a propylene homopolymer and a propylene / α-olefin copolymer containing propylene as a main component are particularly preferable. The crystalline polyolefin resin (A) as described above is
They can be used alone or in combination.

The crystalline polyolefin resin (A) has a melt flow rate (MFR; ASTM D 1238, 23).
0 ° C., 2.16 kg load, the same applies hereinafter) is preferably 0.
01 to 100 g / 10 minutes, more preferably 0.3 to 7
It is in the range of 0 g / 10 minutes.

The crystalline polyolefin resin (A)
Is usually 5 to 100% in crystallinity determined by X-ray method,
It is preferably in the range of 20 to 80%. In the present invention, the crystalline polyolefin resin (A) is usually 10 to 90 relative to 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the olefin rubber (B).
It is used in an amount of 10 parts by weight, preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight.

When the crystalline polyolefin resin (A) is used in the above proportion, a thermoplastic elastomer having excellent moldability and capable of providing a base material layer having excellent heat resistance can be obtained. [Olefin-based Rubber (B)] The olefin-based rubber (B) is an amorphous random elastic copolymer mainly composed of an α-olefin having 2 to 20 carbon atoms, and is composed of two or more α-olefins. -Amorphous α-olefin copolymers composed of olefins, α-olefin / non-conjugated diene copolymers composed of two or more kinds of α-olefins and non-conjugated dienes, and the specific examples are as follows. Rubber. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
To 50/50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
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] Specific examples of the α-olefin include the same α-olefins as the specific examples of the α-olefin constituting the crystalline polyolefin resin (A) described above.

Specific examples of the non-conjugated diene 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. Mooney viscosity [ML] of the copolymer rubber of the above (1) to (4)
_{1 + 4} (100 ° C)] is 10 to 250, especially 40 to 15
0 is preferred.

The olefin rubber (B) is present in the thermoplastic elastomer [1] in a partially crosslinked state or a completely crosslinked state. In the present invention, it is preferable that the olefin rubber (B) is in a partially crosslinked state.

Further, in the present invention, the olefin rubber (B) and a rubber other than the olefin rubber (B) may be used in combination within a range not impairing the object of the present invention.

Examples of rubbers other than the olefin rubber (B) include styrene-butadiene rubber (S
BR), nitrile rubber (NBR), natural rubber (NR),
Diene rubber such as butyl rubber (IIR), SEBS, polyisobutylene rubber and the like can be mentioned.

In the present invention, the olefin rubber (B) is usually 10 to 90 parts by weight, preferably 100 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the olefin rubber (B). Is used in an amount of 30 to 90 parts by weight, more preferably 40 to 80 parts by weight.

When the olefin rubber (B) and a rubber other than the olefin rubber (B) are used in combination, the rubber other than the olefin rubber (B) is a crystalline polyolefin resin (A) or It is used in a proportion 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 olefin rubber (B).

When the olefin-based rubber (B), or the olefin-based rubber (B) and a rubber other than the olefin-based rubber (B) are used in the above proportions, heat capable of providing a base material layer having excellent flexibility. A plastic elastomer is obtained. [Other Components] In the thermoplastic elastomer [1] used in the present invention, a mineral oil softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antiaging agent, a filler, a coloring agent may be added, if necessary. Additives such as agents and lubricants can be added within a range that does not impair the object of the present invention.

The thermoplastic elastomer [1] preferably used in the present invention is a crystalline polypropylene resin and an ethylene / α-olefin copolymer rubber or ethylene / α.
-Consisting of olefin / non-conjugated diene copolymer rubber,
In the thermoplastic elastomer [1], these components are present in a partially crosslinked state, and the weight compounding ratio of the crystalline polypropylene resin and the olefin rubber (crystalline polypropylene resin / olefin rubber) is 70 /. Thirty
Within the range of 10/90.

More specific examples of the thermoplastic elastomer [1] preferably used in the present invention include 70 to 10 parts by weight of a crystalline polypropylene resin and an ethylene / propylene copolymer rubber or ethylene / propylene as an olefin rubber. 30 to 90 parts by weight of diene copolymer rubber [total amount of crystalline polypropylene resin and olefinic rubber is 100 parts by weight], and 5 to 100 parts by weight of rubber other than olefinic rubber and / or mineral oil type The thermoplastic elastomer is composed of 5 to 100 parts by weight of a softening agent, and the olefin rubber is partially crosslinked.

The thermoplastic elastomer [1] used in the present invention is obtained by dynamically heat treating a blend containing a crystalline polyolefin resin (A) and an olefin rubber (B) in the presence of an organic peroxide. It can be obtained by

Specific examples of the above organic peroxide include:
Dicumyl peroxide, di-tert-butyl peroxide,
2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert- Butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl Examples thereof include peroxides, lauroyl peroxide, and tert-butyl cumyl peroxide.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-from the viewpoint of odor and stability of scorch. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 1,4-bis (tert-butylperoxy) valerate is preferred, and among them, 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

In the present invention, the organic peroxide is 0.05 to 3% by weight, preferably 0.1% to 100% by weight of the total amount of the crystalline polyolefin resin (A) and the olefin rubber (B). It is used in a proportion of 1 to 1% by weight.

In the present invention, during the partial crosslinking treatment with the above organic peroxide, sulfur, p-quinonedioxime, p,
Peroxy crosslinking aids such as p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, Or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinyl butyrate, vinyl stearate. Polyfunctional vinyl monomers can be included.

By using the above compound,
A uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is most preferred in the present invention. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin resin (A) and the olefin rubber (B), which are the main components of the above-mentioned substance to be crosslinked, and solubilizes the organic peroxide. Since it has a function of acting as a dispersant for the organic peroxide, a cross-linking effect by heat treatment is uniform, and a thermoplastic elastomer having a good balance of fluidity and physical properties can be 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, particularly 0.3 to 1% by weight, based on the whole article to be crosslinked. It is preferable to use it in a ratio of. When the blending ratio of the crosslinking aid or the polyfunctional vinyl monomer exceeds 2% by weight, when the blending amount of the organic peroxide is large, the crosslinking reaction proceeds too fast. Inferior, on the other hand, when the blending amount of the organic peroxide is small, the crosslinking aid and the polyfunctional vinyl monomer remain as unreacted monomers in the thermoplastic elastomer. Physical properties may change due to heat history. Therefore, the cross-linking aid and the polyfunctional vinyl monomer should not be blended in excess.

The above-mentioned "dynamically heat-treating" means kneading each of the above components in a molten state. 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 or the like is used. Among these, a non-open type kneading device is preferable. The kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The kneading 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 17
The temperature is 0 to 240 ° C., and the kneading time is 1 to 20 minutes, preferably 1 to 5 minutes. Also, the shearing force applied is
The shear rate is usually 10 to 10 ⁴ sec ^-1 , preferably 1
It is determined within the range of 0 ² to 10 ⁴ sec ⁻¹ .

Olefin rubber (B) as described above
A partially or completely crosslinked thermoplastic elastomer [1] 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, and particularly 20%.
% Or more and less than 98%. In the present invention, the gel content is preferably 30% or more. Further, "completely crosslinked" means that the gel content (cyclohexane insoluble content) measured by the following method is 98% or more 10
It means the case of 0%. When the gel content is in the above range,
The resulting thermoplastic elastomer [1] has good fluidity during molding and can provide a base material layer having excellent mechanical strength and heat resistance.

[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. 30m 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 (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,
The corrected initial weight (X) is used.

Here, the gel content (cyclohexane insoluble content) is calculated by the following equation. Gel content [% by weight] = [corrected final weight (Y)] ÷
[Corrected initial weight (X)] × 100 thermoplastic elastomer [2], [3] As described above, the thermoplastic elastomer used for forming the skin layer is a crystalline polyolefin resin (A).
And a thermoplastic elastomer [2] containing a specific block copolymer (C) in a specific ratio, or a crystalline polyolefin resin (A), a specific block copolymer (C) and a specific block copolymer There is a thermoplastic elastomer [3] containing the combination (D) in a specific ratio.
In the present invention, in the thermoplastic elastomer [3], in addition to the crystalline polyolefin resin (A), the block copolymers (C) and (D), if necessary, an olefin rubber (B). A softening agent (E) can be added. [Crystalline Polyolefin Resin (A)] The crystalline polyolefin resin (A) constituting the thermoplastic elastomers [2] and [3] is the crystalline polyolefin resin (A) constituting the thermoplastic elastomer [1]. ) Is the same.

In the thermoplastic elastomer [2],
The crystalline polyolefin resin (A) is 20 to 85 parts by weight, preferably 20 to 75 parts by weight, more preferably 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the block copolymer (C). Is used in a proportion of 20 to 60 parts by weight.

In the thermoplastic elastomer [3], the crystalline polyolefin resin (A) is the crystalline polyolefin resin (A), the block copolymer (C), the block copolymer (D), the olefin rubber. 20 to 85 based on 100 parts by weight of the total amount of (B) and the softening agent (E).
It is used in a proportion of parts by weight, preferably 20 to 75 parts by weight, more preferably 20 to 60 parts by weight. [Block Copolymer (C)] The block copolymer (C) constituting the thermoplastic elastomers [2] and [3] is a polymer block (a) of styrene or a derivative thereof and a specific isoprene polymer. It may be hydrogenated, which is composed of a block (b) composed of a polymer or a specific isoprene-butadiene copolymer.

The polymer component constituting the block (a) is styrene or its derivative. As the styrene derivative, specifically, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene,
4-dodecylstyrene, 2-ethyl-4-benzylstyrene,
4- (phenylbutyl) styrene and the like can be mentioned. As the polymer component constituting the block (a), styrene,
α-Methylstyrene is preferred.

The polymer or copolymer constituting the block (b) is an isoprene polymer or an isoprene-butadiene copolymer, and the 1,2 bond and the 3,4 bond in the isoprene polymer portion shown below are used. Content is 4
It is 0% or more, preferably 45% or more.

[0048]

[Chemical 1]

In the present invention, when the content of 1,2 bonds and 3,4 bonds in the isoprene polymer portion is 40% or more, it is possible to obtain a thermoplastic elastomer capable of providing a skin layer excellent in scratch resistance. You can

The proportion of the polymer block (a) of styrene or its derivative in the block copolymer (C) is preferably 5 to 50% by weight, more preferably 10 to 45%.
It is in the range of% by weight. That is, the proportion of the above isoprene polymer block or isoprene-butadiene copolymer block (b) 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 (C) is preferred. When the hydrogenated block copolymer (C) is used, a thermoplastic elastomer capable of providing a skin layer having more excellent weather resistance and heat resistance can be obtained.

The melt flow rate (MFR; ASTM D 1) of the block copolymer (C) used in the present invention.
238, 230 ℃, 2.16kg load, the same below)
It is preferably in the range of 0.01 to 30 g / 10 minutes, more preferably 0.01 to 10 g / 10 minutes. When the block copolymer (C) having a melt flow rate in the above range is used, a thermoplastic elastomer capable of providing a skin layer having excellent scratch resistance can be obtained.

The block form of the block copolymer (C) used in the present invention is most preferably block (a) -block (b) -block (a).
It is not limited to this.

Such a block copolymer (C) can be produced, for example, by the following method. (1) A method of sequentially polymerizing styrene or a derivative thereof, isoprene, or an isoprene-butadiene mixture using an alkyllithium compound as an initiator. (2) A method in which styrene or a derivative thereof, and then isoprene or a mixture of isoprene and butadiene are polymerized, and this is coupled 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 (C) are described, for example, in JP-A-2-300250 and JP-A-3-45646. Further, when the block copolymer (C) obtained by the above method is subjected to hydrogenation treatment, a hydrogenated block copolymer (C) can be obtained. The block to be hydrogenated is an isoprene polymer block or an isoprene-butadiene copolymer block (b).

In the thermoplastic elastomer [2],
The block copolymer (C) is the total amount 1 of the crystalline polyolefin resin (A) and the block copolymer (C).
15 to 80 parts by weight, preferably 1 to 100 parts by weight
It is used in an amount of 5 to 70 parts by weight, more preferably 20 to 60 parts by weight.

In the thermoplastic elastomer [3], the block copolymer (C) is the crystalline polyolefin resin (A), the block copolymer (C), the block copolymer (D), the olefin described above. It is used in a proportion of 12 to 80 parts by weight, preferably 20 to 70 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the total amount of the system rubber (B) and the softening agent (E).

When the block copolymer (C) is used in the above proportion, a thermoplastic elastomer capable of providing a skin layer having excellent heat resistance and scratch resistance can be obtained. [Block Copolymer (D)] The block copolymer (D) constituting the thermoplastic elastomer [3] is composed of a polymer block (c) of styrene or a derivative thereof and a specific isoprene polymer or a specific isoprene polymer. It is composed of a block (b) made of an isoprene-butadiene copolymer or a butadiene polymer block (e) and may be hydrogenated.

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

The polymer or copolymer constituting the block (d) is an isoprene polymer block or an isoprene-butadiene copolymer block, which contains 1,2 bonds and 3,4 bonds in the isoprene polymer part. The amount is 30% or less, preferably 25% or less.

In the present invention, when the content of 1,2 bonds and 3,4 bonds in the isoprene polymer portion is 30% or less, it is possible to obtain a thermoplastic elastomer capable of providing a skin layer having a good appearance. it can.

The block copolymer (D) may be composed of the block (c) and the block (d), or may be composed of the block (c) and the block (e) composed of the butadiene polymer. May be.

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

In the present invention, the hydrogenated block copolymer (D) is preferred. When the hydrogenated block copolymer (D) is used, a thermoplastic elastomer capable of providing a skin layer having more excellent weather resistance and heat resistance can be obtained.

The melt flow rate (MFR; ASTM D 1) of the block copolymer (D) used in the present invention.
238, 230 ℃, 2.16kg load, the same below)
It is preferably 0.01 to 100 g / 10 minutes, more preferably 0.01 to 50 g / 10 minutes. When the block copolymer (D) having a melt flow rate in the above range is used, a thermoplastic elastomer capable of providing a skin layer having excellent scratch resistance can be obtained.

The block form of the block copolymer (D) used in the present invention is most preferably block (c) -block (d) or (e) -block (c), but is not limited thereto. Not a thing.

The optionally hydrogenated block copolymer (D) can be produced, for example, by the same method as the above-mentioned method for producing the block copolymer (C).

When the hydrogenated block copolymer is prepared, the hydrogenated block is an isoprene polymer block, an isoprene-butadiene copolymer block (d) or a butadiene polymer block (e). is there.

In the thermoplastic elastomer [3],
The block copolymer (D) is the total amount of the crystalline polyolefin resin (A), the block copolymer (C), the block copolymer (D), the olefin rubber (B) and the softening agent (E). 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 100 parts by weight.
It is used in a proportion of 20 parts by weight.

When the block copolymer (D) is used in the above proportion, a thermoplastic elastomer capable of providing a skin layer having excellent scratch resistance can be obtained. Further, a molded product obtained from this thermoplastic elastomer by injection molding has an excellent appearance. [Olefin Rubber (B)] In the thermoplastic elastomer [3], the olefin rubber (B) used as necessary is the same as the olefin rubber (B) constituting the thermoplastic elastomer [1] described above. is there. Specific examples of the olefin rubber (B) blended in the thermoplastic elastomer [3] include the above-listed copolymer rubbers (1) to (4) containing an α-olefin as a main component. The particularly preferred Mooney viscosity [ML _{1 + 4} (100 ° C.)] of these copolymer rubbers is in the range of 30 to 150.

Also in the thermoplastic elastomer [3], as in the case of the above-mentioned thermoplastic elastomer [1], the olefin rubber (B) and the olefin rubber ( It is also possible to use it in combination with a rubber other than B).

Examples of rubbers other than the olefin rubber (B) include styrene-butadiene rubber (S
BR), nitrile rubber (NBR), natural rubber (NR),
Diene rubber such as butyl rubber (IIR), SEBS, polyisobutylene rubber and the like can be mentioned.

In the thermoplastic elastomer [3],
The olefin rubber (B) is a crystalline polyolefin resin (A), an olefin rubber (B), a block copolymer (C), a block copolymer (D) and a softening agent (E), if necessary. 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and further preferably 5 to 100 parts by weight.
It is used in a proportion of 20 parts by weight.

When the olefinic rubber (B) is used in the above proportion, a thermoplastic elastomer which is excellent in flexibility and can provide a skin layer excellent in scratch resistance can be obtained. [Softening agent (E)] As the softening agent (E) used as necessary in the thermoplastic elastomer [3], a softening agent usually used for rubber is suitable, and specifically, a process oil, a lubricant Petroleum-based substances such as oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum; coal tars such as coal tar and coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil;
Waxes such as tall oil, beeswax, carnauba wax, lanolin, fatty acids such as ricinoleic acid, palmitic acid, stearic acid or metal salts thereof; synthetic polymers such as petroleum resin, coumarone indene resin, atactic polypropylene; dioctyl phthalate, Examples thereof include ester plasticizers such as dioctyl adipate and dioctyl sebacate; and microcrystalline wax, liquid polybutadiene or its modified products or hydrogenated products, and liquid thiochol.

In the thermoplastic elastomer [3],
The softening agent (E) is a crystalline polyolefin resin (A), an olefin rubber (B), a block copolymer (C), a block copolymer (D), and a softening agent (E), if necessary.
1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total amount of

When the softening agent (E) is used in the above proportion, a thermoplastic elastomer having excellent fluidity during molding can be obtained. The skin layer made of this thermoplastic elastomer is
Good scratch resistance. [Other Components] In the above thermoplastic elastomers [2] and [3], if necessary, an inorganic filler, a heat stabilizer, a weather stabilizer, an antioxidant, Additives such as antistatic agents can be added.

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

In the present invention, the thermoplastic elastomers [2] and [3] may not have a crosslinked structure, but preferably have a crosslinked structure. The thermoplastic elastomer [2] as described above is prepared by mixing the respective components of the crystalline polyolefin resin (A) and the block copolymer (C), and then operating in the presence or absence of an organic peroxide. Can be manufactured by heat treatment.

The thermoplastic elastomer [3] as described above includes the crystalline polyolefin resin (A), the block copolymer (C) and the block copolymer (D),
Further, it can be produced by mixing the respective components of the olefin rubber (B) and the softening agent (E) and then dynamically heat treating them in the presence or absence of an organic peroxide.
The dynamic heat treatment here is preferably performed by the method described above for the thermoplastic elastomer [1],
It can be carried out in the presence or absence of an organic peroxide. In the dynamic heat treatment performed in the presence of an organic peroxide, a crosslinking aid or a polyfunctional vinyl monomer can be used in addition to the organic peroxide. The organic peroxide, the crosslinking assistant and the polyfunctional vinyl monomer used here are the same as the organic peroxide, the crosslinking assistant and the polyfunctional vinyl monomer described above in the thermoplastic elastomer [1]. The conditions of the dynamic heat treatment performed in the presence of the organic peroxide are the same as those for the above-mentioned thermoplastic elastomer [1].

Since the thermoplastic elastomers [2] and [3] obtained as described above and the thermoplastic elastomer [1] can be subjected to coextrusion lamination processing, production of the thermoplastic elastomer laminate according to the present invention. At this time, the base material layer made of the thermoplastic elastomer [1] and the skin layer made of the thermoplastic elastomer [2] or [3] can be directly laminated without passing through the film (sheet) forming step, which is economical. Target.

Thermoplastic Elastomer Laminate As described above, the thermoplastic elastomer laminate according to the present invention includes a base material layer formed of the thermoplastic elastomer [1] and the thermoplastic elastomer [2] or [3]. And a skin layer formed by.

Therefore, the thermoplastic elastomer laminate according to the present invention can be obtained by laminating the above-mentioned base material layer and skin 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 of heat-sealing both layers using a calender roll molding machine, a compression molding machine, or the like at a temperature equal to or higher than the temperature at which at least one of the preformed base material layer and the skin layer is fused. (2) in which either one of the sheet shaped extruded substrate layer or skin layer, a method of thermal fusion to the other layer that has a calendar molding. (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).

Of these, the coextrusion molding of (3) above is preferable. In the present invention, it is also possible to obtain a laminate composed of a base material layer and a skin layer by a molding method (two-layer injection molding method) in which two types of molten resins are injected into a mold at different injection timings. it can. 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.

In the present invention, the thickness of the base material layer is 0.1.
It is generally preferable that the thickness is ˜50 mm, and the thickness of the skin layer is 5 μm to 20 mm. In the thermoplastic elastomer laminate according to the present invention, the base material layer comprises a partially or completely crosslinked thermoplastic elastomer containing a crystalline polyolefin resin (A) and an olefin rubber (B). Therefore, it is excellent in heat resistance, heat aging resistance and rubber elasticity.

The skin layer contains the crystalline polyolefin resin (A) and the block copolymer (C), further the block copolymer (D), the olefin rubber (B) and the softening agent (E) in a specific ratio. It is excellent in scratch resistance because it is composed of the thermoplastic elastomer contained in 1.

[0086]

The thermoplastic elastomer laminate according to the present invention is a partially or completely crosslinked thermoplastic elastomer containing the crystalline polyolefin resin (A) and the olefin rubber (B). The formed base material layer, the crystalline polyolefin resin (A) and the specific block copolymer (C), and further the specific block copolymer (D), the olefin rubber (B), the softening agent (E ) In a specific proportion, and a skin layer formed of a thermoplastic elastomer, the interlayer adhesion between the base material layer and the skin layer is remarkably excellent, and mechanical strength and heat resistance are high. Excellent in heat resistance, heat aging resistance, weather resistance, scratch resistance and dimensional stability.

The thermoplastic elastomer laminate according to the present invention is lighter in weight and easier to recycle than a polyvinyl chloride resin, and does not generate a harmful gas even when incinerated. There is no stickiness on the surface due to bleeding.

Therefore, the thermoplastic elastomer laminate according to the present invention can be used not only for applications where scratch resistance is required, for example, automotive exterior parts such as side protection moldings and wind moldings, automotive interior parts, but also for furniture. , Building materials, housings for home appliances, bags, suitcases, sporting goods, office supplies, miscellaneous goods, etc.

The present invention will be described below with reference to examples.
The invention is not limited to these examples.

[0090]

Example 1 [Preparation of Thermoplastic Elastomer for Forming Base Layer] Polypropylene as the crystalline polyolefin resin (A) [Melt flow rate (ASTM D 1238-65T, 230
℃, 2.16kg): 13g / 10 minutes, density 0.91g
/ Cm ³ , crystallinity determined by X-ray method: 72%, hereinafter abbreviated as (A-1)] 20 parts by weight, and ethylene / propylene-5-ethylidene-2- as olefin rubber (B)
Norbornene copolymer rubber [ethylene content: 70 mol%, iodine value: 12, Mooney viscosity ML _{1 + 4} (100
C): 120, hereinafter abbreviated as (B-1)] 80 parts by weight using a Banbury mixer in a nitrogen atmosphere at 180 ° C.
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.

Next, 100 parts by weight of the square pellets,
After 0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene and 0.5 parts by weight of divinylbenzene were mixed with stirring with a Henschel mixer, the resulting mixture was mixed with L / D = 30, screw. Using a uniaxial extruder having a diameter of 50 mm, it was extruded at 220 ° C. in a nitrogen atmosphere to produce pellets of a thermoplastic elastomer [hereinafter, abbreviated as TPE- (1)]. The gel content of the obtained TPE- (1) was 84%.

[Preparation of Thermoplastic Elastomer for Forming Skin Layer] Propylene homopolymer as crystalline polyolefin resin (A) [melt flow rate: 20 g / 10 minutes,
Crystallinity determined by X-ray method: 73%, the following (A-2)
50 parts by weight of pellets and styrene / isoprene / styrene block copolymer as a block copolymer (C) [styrene content: 20% by weight, 1,2 bonds and 3,4 bonds in the isoprene polymer part] Content:
After thoroughly mixing 50% by weight of pellets of 55%, melt flow rate: 2.5 g / 10 minutes, and abbreviated as (C-1) below, through a uniaxial extruder set at 220 ° C., a thermoplastic elastomer [below. , TPE- (2)].

[Preparation of Laminate] The above TPE- (1) was extrusion molded at a temperature of 230 ° C., and the above TPE- (2) was coextruded and laminated on the surface of the TPE- (1). A coextrusion laminate having a substrate layer thickness of 10 mm, a TPE- (2) skin layer thickness of 1.0 mm and a width of 5.2 mm was obtained.

With respect to the obtained laminate, changes in the interlaminar adhesive strength and the glossiness, which is an index of the scratch resistance of the surface of the skin layer, were measured by the following method. (A) Interlayer adhesive strength test Test method: 180 degree peeling test specimen: Width 25 mm, length 100 mm Tensile speed: 25 mm / min Interlayer adhesive strength: value obtained by dividing peeling load by width of test piece [unit: kgf / cm] (B) Scratch resistance test A 20 mm square felt cloth was placed on the surface of the skin layer 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 glossiness (JIS K 7105) was measured before and after the reciprocating operation. The change in glossiness was used to evaluate scratch resistance.

The results are shown in Table 1.

[0096]

Example 2 [Preparation of Thermoplastic Elastomer for Forming Skin Layer] Pellets 4 of (A-2) as crystalline polyolefin resin (A)
0 parts by weight, and as a block copolymer (C) (C-1)
50 parts by weight of pellets, and a styrene / isoprene / styrene block copolymer as a block copolymer (D) [styrene content: 30% by weight, 1,2 bond and 3,4 bond content in the isoprene polymer part: A thermoplastic elastomer [hereinafter abbreviated as TPE- (3)] in the same manner as in Example 1 from 10% by weight of pellets of 7%, melt flow rate: 8 g / 10 minutes, abbreviated as (D-1) below. Pellets were produced.

[Preparation of Laminate] The above TPE- (1) and TPE- (3) were coextruded and laminated in the same manner as in Example 1 to prepare TP.
A laminate composed of a base material layer made of E- (1) and a skin layer made of TPE- (3) was obtained.

With respect to the obtained laminate, changes in the interlaminar adhesive strength and the glossiness, which is an index of the scratch resistance of the surface of the skin layer, were measured according to the method described above. The results are shown in Table 1.

[0099]

Example 3 [Preparation of Thermoplastic Elastomer for Forming Skin Layer] Propylene-ethylene copolymer as crystalline polyolefin resin (A) [Ethylene content: 3.2 mol%, melt flow rate: 25 g / 10 min, X-ray Crystallinity determined by the method: 66%, 45 parts by weight of pellets (hereinafter abbreviated as (A-3)], a styrene polymer block, an isoprene-butadiene copolymer block, and a styrene polymer as a block copolymer (C). Hydrogenated product of block copolymer consisting of polymer block [styrene content: 20% by weight, butadiene content in isoprene / butadiene copolymer block: 12% by weight, isoprene polymer of isoprene / butadiene copolymer block] Partial 1,2 bonds and 3,4
Bond content: 60%, melt flow rate: 2.1 g /
10 minutes, 20 parts by weight of pellets (hereinafter abbreviated as C-2)] and a hydrogenated product of a styrene / butadiene / styrene block copolymer as a block copolymer (D) [styrene content: 40% by weight, Melt flow rate: 15g / 1
0 minutes, abbreviated as (D-2) below] 5 parts by weight of pellets,
Ethylene / butene copolymer rubber as olefin rubber (B) [ethylene content: 84 mol%, Mooney viscosity M
L _{1 + 4} (100 ° C): 15, abbreviated as (B-2) below] 1
0 parts by weight and 20 parts by weight of a mineral oil-based process oil [Idemitsu Kosan Co., Ltd., PW-380] as a softening agent (E),
In the same manner as in Example 1, the thermoplastic elastomer [hereinafter, T
PE- (4) is abbreviated].

[Preparation of Laminate] The above TPE- (1) and TPE- (4) were coextrusion laminated in the same manner as in Example 1 to prepare TP.
A laminate composed of a base material layer made of E- (1) and a skin layer made of TPE- (4) was obtained.

With respect to the obtained laminate, changes in the interlaminar adhesive strength and the glossiness, which is an index of the scratch resistance of the surface of the skin layer, were measured according to the method described above. The results are shown in Table 1.

[0102]

Example 4 [Preparation of Thermoplastic Elastomer for Forming Base Layer] Polypropylene as the crystalline polyolefin resin (A) [Melt flow rate (ASTM D 1238-65T, 230
° C, 2.16 kg: 11 g / 10 minutes, density: 0.91 g
/ Cm ³ , crystallinity determined by X-ray method: 70%, hereinafter abbreviated as (A-4)] 14 parts by weight of pellets, and 4 parts of paraffinic process oil as olefinic rubber (B).
0PHR oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber [ethylene content: 78 mol%, iodine value: 13, Mooney viscosity ML
_{1 + 4} (100 ° C.): 75, 64 parts by weight of pellets (hereinafter abbreviated as (B-3)] and butyl rubber as a rubber other than olefin rubber [Moonie viscosity ML _{1 + 4} (100 ° C.): 4
5, isoprene content: 1.0 mol%] and 14 parts by weight of pellets and 8 parts by weight of paraffinic process oil as a softening agent using a Banbury mixer in a nitrogen atmosphere,
After kneading at 180 ° C. 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 a square pellet.

Then, 100 parts by weight of this square pellet,
A solution obtained by dissolving and dispersing 0.3 part by weight of 1,3-bis (tert-butylperoxyisopropylbenzene) in 0.5 part by weight of divinylbenzene is mixed by stirring with a tumbler blender, and the obtained solution is applied to the surface of the square pellets. It was applied uniformly.

Then, the pellets were extruded at 210 ° C. in a nitrogen atmosphere using a single screw extruder to produce pellets of a thermoplastic elastomer [hereinafter, abbreviated as TPE- (5)]. The gel content of the obtained TPE- (5) is 78%.
Met.

[Preparation of Thermoplastic Elastomer for Forming Skin Layer] As crystalline polyolefin resin (A) (A-3)
40 parts by weight of pellets, 30 parts by weight of (C-2) pellets as block copolymer [C], 10 parts by weight of (D-2) pellets as block copolymer (D), and olefin rubber (B) as ethylene, propylene, 5-
Ethylidene-2-norbornene copolymer rubber [ethylene content: 70 mol%, iodine value: 14, Mooney viscosity ML
_{1 + 4} (100 ° C): 62, abbreviated as (B-4) below] 20
A thermoplastic elastomer [hereinafter abbreviated as TPE- (6)] in the same manner as in Example 1 except that 0.3 parts by weight of dicumyl peroxide and 0.4 parts by weight of divinylbenzene were used.
Pellets were produced. The gel content of the obtained TPE- (6) was 58%.

[Preparation of Laminate] The above TPE- (5) and TPE- (6) were coextruded and laminated in the same manner as in Example 1 to prepare TP.
A laminate including a base material layer made of E- (5) and a skin layer made of TPE- (6) was obtained.

With respect to the obtained laminate, changes in the interlaminar adhesive strength and the glossiness, which is an index of the scratch resistance of the surface of the skin layer, were measured according to the method described above. The results are shown in Table 1.

[0108]

[Comparative example]

[Preparation of Thermoplastic Elastomer for Forming Skin Layer] Pellet 5 of (A-2) as crystalline polyolefin resin (A)
0 part by weight and (D-1) as a block copolymer (D)
In the same manner as in Example 1, thermoplastic elastomer [hereinafter abbreviated as TPE- (7)] pellets were produced from 50 parts by weight of the pellets of

[Preparation of Laminated Body] The above TPE- (1) and TPE- (7) were coextrusion laminated in the same manner as in Example 1 to prepare TP.
A laminate composed of a base material layer made of E- (1) and a skin layer made of TPE- (7) was obtained.

With respect to the obtained laminate, changes in the interlaminar adhesive strength and the glossiness, which is an index of the scratch resistance of the surface of the skin layer, were measured according to the above-mentioned method. The results are shown in Table 1.

[0111]

[Table 1]

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[Procedure amendment]

[Submission date] May 10, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

The second thermoplastic elastomer laminate according to the present invention comprises [I] a crystalline polyolefin resin (A) and an olefin rubber (B), which is partially or completely crosslinked. Layer formed of the thermoplastic elastomer [1] prepared above, [II] 20 to 85 parts by weight of a crystalline polyolefin resin (A), a polymer block (a) of styrene or a derivative thereof, and an isoprene polymer. Block or isoprene-butadiene copolymer block, and hydrogenation comprising a polymer or copolymer block (b) in which the content of 1,2 bonds and 3,4 bonds in the isoprene polymer portion is 40% or more 12 to 79 parts by weight of the block copolymer (C) which may be contained,
And a polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein the content of 1,2 bonds and 3,4 bonds in the isoprene polymer portion is 30% or less. Optionally copolymerized block copolymer (D) consisting of a polymer or copolymer block (d) or a butadiene polymer block (e)
1 to 30 parts by weight [the total amount of components (A), (C) and (D) is 100 parts by weight] and a skin layer formed of a thermoplastic elastomer [3]. Is characterized by.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The thermoplastic elastomer forming the skin layer of the second thermoplastic elastomer laminate according to the present invention [3]
A crystalline polyolefin resin (A) 20 to 85 parts by weight, the block copolymer (C). 12 to 79 parts by weight of Bed
In addition to 1 to 30 parts by weight of the lock copolymer (D), 1 to 30 parts by weight of the olefin rubber (B) and / or 1 to 30 parts by weight of the softening agent (E) [components (A), (B), (C),
The total amount of (D) and (E) is 100 parts by weight].

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

In the thermoplastic elastomer [2],
The crystalline polyolefin resin (A) is 20 to 85 parts by weight, preferably 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the block copolymer (C).
It is used in a proportion of 30 to 75 parts by weight, more preferably 40 to 60 parts by weight.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

In the thermoplastic elastomer [3], the crystalline polyolefin resin (A) is the crystalline polyolefin resin (A), the block copolymer (C), the block copolymer (D), the olefin rubber. 20 to 85 based on 100 parts by weight of the total amount of (B) and the softening agent (E).
It is used in a proportion of parts by weight, preferably 20 to 75 parts by weight, more preferably 20 to 60 parts by weight. However, I
The fin-based rubber (B) and the softening agent (E) are as described above.
In addition, since it is a component used as needed,
It may be 0 parts by weight. [Block Copolymer (C)] The block copolymer (C) constituting the thermoplastic elastomers [2] and [3] is a polymer block (a) of styrene or a derivative thereof and a specific isoprene polymer. It may be hydrogenated, which is composed of a block (b) composed of a polymer or a specific isoprene-butadiene copolymer.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

In the thermoplastic elastomer [2],
The block copolymer (C) is the total amount 1 of the crystalline polyolefin resin (A) and the block copolymer (C).
15 to 80 parts by weight, preferably 2 to 00 parts by weight
It is used in an amount of 5 to 70 parts by weight, and more preferably 40 to 60 parts by weight.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

In the thermoplastic elastomer [3], the block copolymer (C) is the crystalline polyolefin resin (A), the block copolymer (C), the block copolymer (D), the olefin described above. It is used in a proportion of 12 to 79 parts by weight, preferably 20 to 70 parts by weight, and more preferably 20 to 60 parts by weight, based on 100 parts by weight of the total amount of the system rubber (B) and the softening agent (E). However, Olef
The in-line rubber (B) and the softening agent (E) are as described above.
Since it is an ingredient used as needed, it is 0
It may be part.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

In the thermoplastic elastomer [3],
The block copolymer (D) is the total amount of the crystalline polyolefin resin (A), the block copolymer (C), the block copolymer (D), the olefin rubber (B) and the softening agent (E). 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 100 parts by weight.
It is used in a proportion of 20 parts by weight. However, olefin-based
The rubber (B) and the softening agent (E) are required as described above.
Since it is a component used according to the
May be.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction content]

In the thermoplastic elastomer [3],
The olefin rubber (B) is a crystalline polyolefin resin (A), an olefin rubber (B), a block copolymer (C), a block copolymer (D) and a softening agent (E), if necessary. 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and further preferably 5 to 100 parts by weight.
It is used in a proportion of 20 parts by weight. However, softener (E)
Is a component used as necessary as described above.
Therefore, it may be 0 parts by weight.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

In the thermoplastic elastomer [3],
The softening agent (E) is a crystalline polyolefin resin (A), an olefin rubber (B), a block copolymer (C), a block copolymer (D), and a softening agent (E), if necessary.
1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total amount of However, olefin rubber
As described above, (B) is a component that is used as necessary.
Since it is a minute, it may be 0 parts by weight.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0099

[Correction method] Change

[Correction content]

[0099]

Example 3 [Preparation of Thermoplastic Elastomer for Forming Skin Layer] Propylene-ethylene copolymer as crystalline polyolefin resin (A) [Ethylene content: 3.2 mol%, melt flow rate: 25 g / 10 min, X-ray Crystallinity determined by the method: 66%, 64 parts by weight of pellets of (A-3) hereinafter, styrene polymer block, isoprene-butadiene copolymer block and styrene polymer as block copolymer (C) Hydrogenated product of block copolymer consisting of polymer block [styrene content: 20% by weight, butadiene content in isoprene / butadiene copolymer block: 12% by weight, isoprene polymer of isoprene / butadiene copolymer block] Partial 1,2 bonds and 3,4
Bond content: 60%, melt flow rate: 2.1 g /
10 minutes, hereinafter abbreviated as (C-2)] 29 parts by weight of a pellet, and a hydrogenated product of a styrene / butadiene / styrene block copolymer as a block copolymer (D) [styrene content: 40% by weight, Melt flow rate: 15g / 1
0 minutes, abbreviated as (D-2) below] 7 parts by weight of pellets,
Ethylene / butene copolymer rubber as olefin rubber (B) [ethylene content: 84 mol%, Mooney viscosity M
L _{1 + 4} (100 ° C.): 15, abbreviated as (B-2) below] 1
From 4 parts by weight and 29 parts by weight of a mineral oil-based process oil [Idemitsu Kosan Co., Ltd., PW-380] as a softening agent (E),
In the same manner as in Example 1, the thermoplastic elastomer [hereinafter, T
PE- (4) is abbreviated].

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0105

[Correction method] Change

[Correction content]

[Preparation of Thermoplastic Elastomer for Forming Skin Layer] As crystalline polyolefin resin (A) (A-3)
50 parts by weight of pellets, 37.5 parts by weight of (C-2) pellets as the block copolymer (C) , and 12.5 parts by weight of (D-2) pellets as the block copolymer (D). An ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber as the olefin rubber (B) [ethylene content: 70 mol%, iodine value: 14, Mooney viscosity ML _{1 + 4} (100 ° C.): 62, Hereinafter, abbreviated as (B-4)] 25 parts by weight, 0.38 parts by weight of dicumyl peroxide, and 0.5 parts by weight of divinylbenzene are used in the same manner as in Example 1 to prepare a thermoplastic elastomer [hereinafter, TPE- (6).
Abbreviated]. Obtained TPE-
The gel content of (6) was 58%.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0111

[Correction method] Change

[Correction content]

[0111]

[Table 1]

Claims (3)

[Claims] 1. A group formed of [I] a crystalline polyolefin resin (A) and an olefin rubber (B), which is formed of a partially or completely crosslinked thermoplastic elastomer [1]. A material layer, [II] 20 to 85 parts by weight of a crystalline polyolefin resin (A), and a polymer block (a) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, An optionally hydrogenated block copolymer (C) 15 comprising a polymer or copolymer block (b) having a 1,2 bond and 3,4 bond content of 40% or more in the isoprene polymer part.
-80 parts by weight [total amount of components (A) and (C) is 10
Thermoplastic elastomer [2]
And a skin layer formed of the thermoplastic elastomer laminate. 2. A group formed of a partially or completely crosslinked thermoplastic elastomer [1] containing [I] a crystalline polyolefin resin (A) and an olefin rubber (B). A material layer, [II] 20 to 85 parts by weight of a crystalline polyolefin resin (A), a polymer block (a) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein isoprene An optionally hydrogenated block copolymer (C) 12 comprising a polymer or copolymer block (b) having a content of 1,2 bonds and 3,4 bonds in the polymer portion of 40% or more.
To 80 parts by weight, and a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein 1,2 bonds and 3,4 bonds are contained in the isoprene polymer part. 1-30 parts by weight of an optionally hydrogenated block copolymer (D) consisting of a polymer or copolymer block (d) or a butadiene polymer block (e) in an amount of 30% or less [component The total amount of (A), (C) and (D) is 100 parts by weight] and a skin layer formed of a thermoplastic elastomer [3]. Laminate. 3. The thermoplastic elastomer [3] comprises 20 to 85 parts by weight of a crystalline polyolefin resin (A), 12 to 80 parts by weight of a copolymer block (C) and 1 to 30 parts of a copolymer block (D). In addition to 1 part by weight, 1 to 30 parts by weight of olefin rubber (B) and / or 1 to 1 of softening agent (E)
30 parts by weight [the total amount of components (A), (B), (C), (D) and (E) is 100 parts by weight]. Thermoplastic elastomer laminate.