JP2003340968A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate having excellent extrusion moldability, flaw resistance, oil resistance and soft feeling and further having excellent uniform spreadability, and embossing (embossing pattern) maintainability. <P>SOLUTION: The laminate is obtained by laminating a thermoplastic elastomer layer embossed on the surface and a base layer. In this laminate, the elastomer layer contains a thermoplastic elastomer composition which contains a block copolymer (component (a)) having a specific molecular weight and a specific structure, a softener (component (b)) for a hydrocarbon rubber, and an olefin resin (component (c)) so that a ratio of the component (b) to the total quantity of the component (a) and the component (b) is 20 to 80 wt.%, the ratio of the component (b) is 20 to 80 wt.%, and the component (c) is 1 to 300 pts.wt. per 100 pts.wt. of the total sum of the components (a) and (b). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate.
More specifically, the present invention relates to a laminate which is formed by laminating a thermoplastic elastomer layer and a base material layer, preferably a foam layer, and is effectively used as an interior material for automobiles.

[0002]

2. Description of the Related Art Conventionally, automobile interior sheets used for skins such as instrument panels and door trims have a polyvinyl chloride layer and a foam layer whose surface is embossed in a leather pattern and, if necessary, a resin. A laminate in which base material layers are sequentially laminated has been used. However, in order to eliminate the need for environmental issues such as weight reduction, recyclability, and easy incineration of automobile parts, heat resistance, cold resistance, heat aging resistance, light resistance, odor, and the appearance of a cheap material, polyolefin-based heat has recently been used. Plastic elastomer materials (hereinafter sometimes simply referred to as “TPO”) have begun to be put to practical use. Such TP
As O, for example, Japanese Patent Application Laid-Open No. 6-1888 discloses a sheet-shaped molded product having a base material of a composition containing an olefin copolymer rubber, an olefin copolymer and crystalline paraffin.

[0003]

However, in the conventional sheet-like laminate using TPO as a base material, a large amount of deposits (eyes) at the die outlet occurs during extrusion molding,
There was a problem that the surface of the molded product was contaminated and the extruder was stopped and cleaned to remove it, resulting in reduced productivity.
Furthermore, the scratch resistance was poor and it could not be used depending on the application. When the resin component is increased in order to improve the scratch resistance, the hardness increases and the desired softness cannot be obtained.
In addition, in a conventional sheet-like laminated body using TPO as a base material, in general, when the product is formed by secondary processing such as vacuum forming, pressure forming, stamping forming, the extensibility is insufficient and a product having a large drawing ratio is used. However, there were problems such as breakage and extremely thin walls. In addition, interior skin materials such as instrument panels and door trims have a leather-like texture, and the surface is embossed to prevent reflection.
When a sheet that has been pre-applied with is subjected to secondary processing such as vacuum forming, a texture flow (phenomenon (embossed pattern) becomes shallower) occurs due to heat and deformation during secondary processing, and the texture (embossed pattern) retainability is improved. There was a problem. In addition, in order to avoid such grain flow, a method such as vacuum forming using a female die with an embossed pattern (emboss pattern) is adopted, but even with this method, compared to the grain depth of the die There was a problem that the texture of the molded product became shallow.

The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in scratch resistance, oil resistance, soft feeling, uniform spreadability,
It is an object of the present invention to provide a laminate having excellent retention of embossed pattern.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by using a laminate obtained by laminating a specific styrene-based thermoplastic elastomer composition and a substrate layer, Based on the knowledge that the object of (1) can be achieved, the present invention has been completed. That is, the gist of the present invention is a laminate comprising a thermoplastic elastomer layer having a surface embossed and a base material layer, wherein the thermoplastic elastomer layer contains the following components (a) to (c). , The ratio of the component (a) to the total amount of the components (a) and (b) is 20 to 80.
%, The proportion of the component (b) is 20 to 80% by weight, and the thermoplastic elastomer composition comprises 1 to 300 parts by weight of the component (c) per 100 parts by weight of the total of the components (a) and (b). It exists in a laminate composed of objects. (A) A block copolymer having a weight average molecular weight of 80,000 to 500,000, which is a block copolymer represented by the general formula (I) and / or hydrogenation obtained by hydrogenating the block copolymer. Block copolymer.

[0006]

Embedded image A (BA) n and / or (AB) n (I) (wherein A is a vinyl aromatic hydrocarbon polymer block and B is an elastomeric polymer block) , N
Is an integer of 1 to 5. ) (B) Hydrocarbon-based rubber softening agent (c) Olefin-based resin

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) used in the present invention is
A block copolymer having a weight average molecular weight of 80,000 to 500,000, which is a block copolymer represented by the general formula (I) and / or a hydrogenated block obtained by hydrogenating the block copolymer. It is a copolymer.

In the block copolymer, the vinyl aromatic hydrocarbon polymer block (A) constitutes a hard segment and the elastomeric polymer block (B) constitutes a soft segment. A typical example of the block copolymer is A-
A block copolymer having a copolymer structure represented by B or A-B-A, in which the double bond of B may be partially or completely hydrogenated. Known as a plastic elastomer.

Examples of the vinyl aromatic hydrocarbon in the above vinyl aromatic hydrocarbon polymer block (A) include styrene, α-methylstyrene, o-, m-, p.
-Methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like are mentioned, and styrene is particularly preferable. As the elastomeric polymer block (B), as long as the elastomeric property is exhibited,
The type is not particularly limited, but conjugated dienes are preferred. Examples of the conjugated diene include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,
3-butadiene and the like are mentioned, and in particular, butadiene, isoprene, or 2/8 to 6 / of butadiene / isoprene.
A mixture of 4% by weight is preferred.

The content of the vinyl aromatic hydrocarbon polymer block (A) in the block copolymer is 10 to 50% by weight, preferably 15 to 45% by weight, more preferably 20.
-40% by weight. When the content of the polymer block of vinyl aromatic hydrocarbon is less than the above range, mechanical strength and heat resistance of the resulting laminate tend to be poor, while when it exceeds the above range, flexibility of the obtained laminate and rubber The elasticity is inferior, and the bleeding of the component (b), which is a softener for a hydrocarbon rubber, described later, tends to occur.

When only butadiene is used as the conjugated diene, the proportion of 1,2-bonds of the conjugated diene in the elastomeric polymer block (B) is usually 20 from the viewpoint of improving the feel of the laminate. -50%, preferably 25-45%. Further, the component (a) is preferably a hydrogenated block copolymer obtained by hydrogenation. Elastomeric polymer block (B) at this time
The hydrogenation rate of the double bond of 30% or more, preferably 5
It is 0% or more, more preferably 90% or more. When the hydrogenation rate is less than the above range, the laminated body tends to have poor weather resistance and heat resistance.

The weight average molecular weight of the block copolymer in the present invention is 8 as the polystyrene equivalent molecular weight measured by gel permeation chromatography.
It is 50,000 to 500,000, but preferably 1
0,000-450,000, more preferably 15
It is from 10,000 to 400,000. When the weight average molecular weight is less than 50,000, rubber elasticity and mechanical strength of the obtained laminate are poor and molding processability tends to be poor.
On the other hand, when the weight average molecular weight exceeds 500,000,
The moldability of the obtained laminate will be poor.

The method for producing the block copolymer may be any method as long as the above-mentioned structure and physical properties are obtained. For example, the method described in Japanese Patent Publication No. 40-23798, that is, the method of carrying out block polymerization in an inert solvent in the presence of a lithium catalyst can be employed. The hydrogenation treatment of these block copolymers is carried out, for example, in Japanese Examined Patent Publication No. 42-8704 and Japanese Examined Patent Publication No. 43-6636.
JP-A-59-133203, JP-A-60-
It can be carried out in the presence of a hydrogenation catalyst in an inert solvent according to the method described in JP-A-79005.

Further, the block copolymer as described above is
It can also be obtained by polymerizing styrene or a derivative thereof and an elastomeric block and coupling this with a coupling agent. It can also be obtained by polymerizing an elastomeric block using a dilithium compound as an initiator and then sequentially polymerizing styrene or a derivative thereof. Commercially available products of the above block copolymer include "KRAT
Examples of such products include "ON-G" (Shell Chemical Co.), "Septon" (Kuraray Co., Ltd.), and "Tuftec" (Asahi Kasei Co., Ltd.).

The component (b) used in the present invention is a hydrocarbon type softening agent for rubber. As the hydrocarbon-based softening agent for rubber, a hydrocarbon having a weight average molecular weight of usually 300 to 2,000, preferably 500 to 1,500 is used, and a mineral oil type hydrocarbon or a synthetic resin type hydrocarbon is suitable. . Generally, the mineral oil-based rubber softening agent is a mixture of aromatic hydrocarbons, naphthene-based hydrocarbons, and paraffin-based hydrocarbons. Aromatic hydrocarbons having a carbon content of 35% by weight or more based on the total carbon content are aromatic oils, and those having a naphthene-based hydrocarbon content of 30 to 45% by weight are naphthenic oils and paraffinic oils. The ratio of carbon in hydrocarbon is 5
Those with 0% by weight or more are called paraffin oils.
In the present invention, paraffinic oil is preferably used.

The kinematic viscosity of the paraffin oil at 40 ° C. is usually 20 to 800 cSt (centistokes), preferably 50 to 600 cSt, and the pour point is usually -40 to 0 ° C.
Preferably, the flash point (COC) is −30 to 0 ° C. and is usually 20.
The temperature is 0 to 400 ° C, preferably 250 to 350 ° C. The hydrocarbon-based softening agent for rubber (b) improves the fluidity of the obtained composition to contribute to the molding processability and also contributes to the improvement of the flexibility of the obtained sheet.

The component (c) used in the present invention is an olefin resin. As the olefin resin, propylene resin, ethylene resin, crystalline polybutene-1 resin,
Examples thereof include ethylene-based copolymer resins such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylic acid ester copolymer, and propylene-based resin is preferably used. To be Specific examples of the propylene-based resin include a propylene homopolymer, a propylene-ethylene random copolymer resin containing propylene as a main component, and a propylene-ethylene block copolymer resin. As the polymerization mode, any polymerization mode may be adopted as long as a resinous material can be obtained.

The propylene resin has a melt flow rate (JIS-K7210, 230 ° C., 21.2N load) of usually 0.05 to 200 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes. When a melt flow rate other than the above range is used, the uniform spreadability during secondary processing of the laminate tends to be poor. In the present invention, the composition ratio of each of the above components is as follows. That is, the ratio of the component (a) to the total amount of the components (a) and (b) is 20 to 80% by weight, preferably 25 to 75% by weight, and the ratio of the component (b) is 20 to.
It is 80% by weight, preferably 25 to 75% by weight. The proportion of component (a) is less than 20% by weight (the proportion of component (b) is 8
In the case of more than 0% by weight), the rubber elasticity of the composition obtained is inferior and the bleeding resistance of the softening agent is lowered, and the component (a)
If the ratio is more than 80% by weight (the ratio of the component (b) is less than 20% by weight), the oil resistance and molding processability of the resulting composition are poor. On the other hand, the ratio of component (c) is
It is 1 to 300 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight in total of (b). Ingredient (c)
If the amount is less than 1 part by weight, the moldability of the resulting composition is poor, and if it exceeds 300 parts by weight, the flexibility and rubber elasticity of the resulting composition are poor. The surface layer of the laminate of the present invention is a thermoplastic elastomer composition containing the components (a), (b), and (c). The TPO that has been used as the surface layer from the past is an organic peroxide. However, the thermoplastic elastomer composition of the present invention does not necessarily require dynamic heat treatment because of the pseudo-crosslinking caused by the polymer block of vinyl aromatic hydrocarbon. There is a feature that is not. However, also in the present invention, the heat treatment and the oil resistance of the laminate can be improved by performing the dynamic heat treatment, which is preferable.

Here, the dynamic heat treatment means kneading in a molten state or a semi-molten state. Usually, the dynamic heat treatment is carried out by uniformly mixing the above components and, if necessary, melt-kneading the mixture in the presence of an organic peroxide and a crosslinking aid. As the mixing device, a Henschel mixer, a ribbon blender, a V-type blender, etc. are used.
As the kneading device, a mixing roll, a kneader, a Banbury mixer, a Brabender plastograph, a single-screw or twin-screw extruder and the like are used.

The proportion of the organic peroxide used is usually 0.1 to 3 parts by weight, preferably 0.1 to 1 part by weight, and the proportion of the crosslinking aid used is 0.1 to 5 parts by weight, preferably Is 0.1 to 3 parts by weight, and the kneading temperature is usually
The temperature is 100 to 300 ° C., preferably 110 to 280 ° C., and the kneading time is usually 10 seconds to 30 minutes, preferably 20.
Seconds to 20 minutes. The state of the material during the dynamic heat treatment depends on the type of the material used and the temperature of the dynamic heat treatment, and is usually a semi-molten state or a molten state, but is not particularly limited. In the kneading, in addition to the method of kneading all the components at once, a kneading method of kneading the optional components and then adding the other remaining components and kneading may be adopted.

Examples of the above organic peroxides include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1 , 1-di (t-butylperoxy)-
Dialkyl peroxides such as 3,3,5-trimethylcyclohexane, t-butylperoxybenzoate,
t-butyl peroxyisopropyl carbonate, 2,
Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane and 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, acetyl peroxide, lauroyl peroxide, Examples thereof include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide and 2,4-dichlorobenzoyl peroxide, and hydroperoxides such as diisopropylbenzene hydroperoxide.
Of these, organic peroxides having a one-minute half-life temperature of 140 ° C. or higher are preferable. Examples of such organic peroxides include 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2, 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like can be mentioned.

Examples of the above-mentioned crosslinking aid include sulfur,
p-quinone dioxime, p-dinitrosobenzene, 1,
Peroxide crosslinking aids such as 3-diphenylguanidine and m-phenylene bismaleimide, polyfunctional vinyl compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate and diallyl phthalate, ethylene glycol di (meth) acrylate, Examples thereof include polyfunctional (meth) acrylate compounds such as diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate.

The composition according to the invention is preferably at least partially crosslinked by dynamic heat treatment.
By having a crosslinked structure, the gel fraction of the composition is increased, and rubber elasticity (compression set), oil resistance, etc. are improved. As used herein, "partially crosslinked" means that the gel fraction (cyclohexane insoluble matter) measured by the following method is
It means a case of 10% or more and less than 98%. Gel fraction 9
When it is 8% or more, it is said that it is completely crosslinked. The gel fraction of the composition of the present invention is preferably 30% or more.

The gel fraction (insoluble in cyclohexane) of the composition can be determined by the following method. About 100 mg of the composition was weighed and added to 50 ml of cyclohexane.
After impregnation at 3 ° C for 48 hours, the mixture was filtered, and the filtration residue was kept at room temperature for 7
Dry for 2 hours. According to these procedures, the gel fraction is determined by the symbols and formulas described below. W _ini : Initially weighed amount of thermoplastic elastomer (m
g) W _cini : Weight obtained by subtracting the weight of cyclohexane-soluble components (softening agent, etc.) from W _ini and the weight of cyclohexane-insoluble components (fillers, fillers, etc.) other than polymer components (mg) W _cxs : Cyclohexane dissolution , Weight after filtration and drying (m
g) W _ccxs : W _{cxs minus} the weight of cyclohexane insoluble components (fillers, fillers, etc.) other than the polymer component (mg) Fr _f : Cyclohexane insoluble component other than the polymer components contained in the thermoplastic elastomer ( (Filler, filler, etc.)
Fraction of. It can be determined by measuring the ash content. Fr _s : Fraction of cyclohexane soluble component (softening agent etc.) other than the polymer component contained in the thermoplastic elastomer. G
Determined by PC measurement. G%: gel fraction W _cini = W _ini * (1-Fr _f -F _{r s} ) W _ccxs = W _cxs -W _ini * _{F r f} G% = W _ccxs / W _cini * 100

Further, it is preferable to add an antioxidant to the thermoplastic elastomer composition used in the present invention. Examples of the antioxidant include 2,4-dimethyl-6-t.
-Butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6
-Di-t-butyl-4-ethylphenol, 2,4,6
-Tri-t-butylphenol, 2,5-di-t-butylhydroquinone, butylated hydroxyanisole, n
-Octadecyl-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and other monophenolic compounds, 4,
4'-dihydroxydiphenyl, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-)
Butylphenol), 4,4'-butylidene bis (3-
Methyl-6-t-butylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methylphenol and other bisphenol-based compounds, 1,1,3-tris (2'-methyl-4'-hydroxy-5'-t-butylphenyl) butane, 1,3,5
-Trimethyl-2,4,6-tris (3 ', 5'-di-
t-butyl-4′-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [β- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane and other polyphenol-based compounds, 2,2'-thiobis (4-methyl-6-)
t-butylphenol), 4,4′-thiobis (2-methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), and other thiobisphenol-based compounds, aldol-α- Naphthylamine,
Naphthylamines such as phenyl-α-naphthylamine and phenyl-β-naphthylamine, diphenylamines such as p-isopropoxydiphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β
-Naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-
Examples thereof include phenylenediamine-based compounds such as isopropyl-N′-phenyl-p-phenylenediamine. Among these, monophenolic, bisphenolic,
Polyphenol-based and thiobisphenol-based antioxidants of tri or higher are preferred. The proportion of the antioxidant used is usually 0.01 to 2% by weight, preferably 0.05 to 1% by weight, based on the total amount of the components (a) to (c).

Further, the composition of the present invention may be added, if necessary, within a range that does not impair the objects and effects of the present invention.
Other components can be blended. Such compounding ingredients include various resins and rubbers, glass fibers, carbon fibers, potassium titanate fibers, talc, mica, silica, titania, calcium carbonate, fillers such as carbon black, heat stabilizers, light stabilizers, Examples thereof include an ultraviolet absorber, a neutralizing agent, a lubricant, an antifogging agent, an antiblocking agent, an antistatic agent, a dispersant, a flame retardant, a conductivity-imparting agent, and a coloring agent. These are blended in advance with any of the above-mentioned components (a), (b) or (c), or are blended at any stage during mixing, melt-kneading and dynamic heat treatment of each component. It

The base material layer of the present invention can be freely selected according to the performance required for the laminate. Often used for the base layer are polyolefin resins typified by polypropylene or polyethylene, polyethylene terephthalate, polyester resins typified by polybutylene terephthalate, polystyrene, styrene elastic bodies (styrene / butadiene / styrene copolymer). Combined hydrogenated products, etc.), paper, cloth, metal foils such as aluminum sheets. The material used for these base material layers may be alone or 2
Mixtures of two or more kinds may be used, and various copolymers may be used, and the examples are not limited thereto.

The base material layer of the present invention is preferably a foam, and such a foam layer is preferably made of a foam of a polyethylene resin, a polypropylene resin, or a mixture thereof. Even more preferred are foams which are at least partially crosslinked. By using these foams, it is possible to obtain a laminate that is firmly fused with the thermoplastic elastomer layer of the present invention. The production of foams is described in JP-B-39-25500 and 40-2535.
As described in JP-A No. 1 and 40-25352, etc., azide foaming agents may be used as well as cross-linked foams by radiation. Further, a commercially available crosslinked foam can be used as it is. When the laminate is used as an automobile interior material, the expansion ratio of the foam is preferably about 5 to 50 times.

The laminate of the present invention comprises the above-mentioned thermoplastic elastomer layer having an embossed surface and a foam layer. In embossing, for example, the following method is used. A sheet formed by extrusion molding, calendering, etc. is passed in a molten or semi-molten state between the embossing (embossing pattern) roll and a pressure roll such as a rubber roll, or the pre-rolled sheet is heated. Reheat with a drum or an infrared heater and pass it between a graining (embossing pattern) roll and a pressure roll such as a rubber roll, press a sheet using a die with an embossing pattern, and further embossing pattern This is a method in which the sheet is shaped and embossed (embossed patterning) simultaneously with the shaping of the sheet by vacuum forming using the attached male and female molds. In addition, the texture (embossed pattern) means a state in which the surface of the sheet is embossed into a relief pattern of unevenness such as a leather shape or a geometrical shape.

The laminated body of the thermoplastic elastomer layer and the foam layer of the present invention comprises a foamed sheet and a melted or semi-molten thermoplastic elastomer sheet formed by, for example, an extrusion molding method or a calendering method. It can be manufactured by overlapping and passing between a pair of rolls. At that time, the thermoplastic elastomer sheet is brought into contact with the roll side (for embossing) at a roll temperature of about 30 to 70 degrees, and the foam sheet is brought into contact with the unheated normal roll side. Alternatively, the thermoplastic elastomer sheet once extruded and cooled is heated again to be in a molten state or a semi-molten state and laminated in the same manner as above, or the sheet-like thermoplastic elastomer is pressed in a state of being laminated with a foam sheet. Method, two-layer injection molding method, etc.

The laminate of the present invention further comprises an aggregate, a foam,
Woven cloth such as cotton cloth, non-woven cloth, paper and the like can be laminated. Moreover, a coat layer can be applied to at least one surface of the laminate. Further, those obtained by shaping these laminated bodies by vacuum forming, pressure forming, etc. are also included in the laminated body of the present invention. The laminate of the present invention can be formed into a sheet-like molded product with a texture (embossed pattern) having a relief pattern such as leather or a geometrical pattern.
Specifically, it can be used as an interior skin material, particularly a sheet-like skin material used for an interior member in an automobile part, and more specifically, an instrument panel, a door trim, a console box, a ceiling material sheet, It can be suitably used as a skin material such as a handle pad or a seat for a seat.

[0032]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples without departing from the gist thereof. <Material> Component (a1): Hydrogenated product of styrene-butadiene block copolymer having styrene block-butadiene block-styrene block copolymer structure (styrene content 33% by weight, hydrogenation rate 98% or more, weight average) Molecular weight 245,000). Component (a2): Hydrogenated product of styrene-butadiene / isoprene block copolymer having styrene block-butadiene / isoprene block-styrene block copolymer structure (styrene content 30% by weight, hydrogenation rate 9
8% or more, weight average molecular weight 243,000). Component (a3): Partially hydrogenated product of styrene-butadiene block copolymer having styrene block-butadiene block-styrene block copolymer structure (styrene content 31% by weight, hydrogenation rate 56%, weight average molecular weight 100, 000). Component (a4) (for comparative example): Hydrogenated product of styrene-butadiene block copolymer having styrene block-butadiene block-styrene block copolymer structure (styrene content 29% by weight, hydrogenation rate 98% or more,
Weight average molecular weight 75,000). Component (b): Paraffin oil (weight average molecular weight 74
6, 40 ° C. kinematic viscosity 382 cSt, pour point −15 ° C., flash point 300 ° C., “PW380” manufactured by Idemitsu Kosan Co., Ltd.). Component (c): Propylene polymer resin (melt flow rate 0.9 g / 10 min) Crosslinking agent: 1,3-bis (t-butylperoxyisopropyl) benzene (POX) Crosslinking aid: divinylbenzene (DVB)

<Molding Method> (1) Manufacture of Laminated Product A thermoplastic elastomer composition was manufactured by Watanabe Koki Co., Ltd.
mφ extruder (single flight type screw) T
From the die, cylinder temperature 190 ℃, die temperature 210
Width of 250 m under conditions of ℃ and screw rotation speed of 70 rpm
A sheet having a thickness of m and a thickness of 0.35 mm is extruded, and then the sheet is passed between a roll for embossing (emboss patterning) (30 ° C.) and a pressure-bonding rubber roll. At this time, a polypropylene resin crosslinked foam sheet (expansion ratio 10 times, thickness 1 m
m) was passed over the pressure-bonded rubber roll in an overlapping manner to produce a laminate of a thermoplastic elastomer composition and a cross-linked foam of polypropylene resin. (2) After the vacuum-formed laminate was heated with an infrared heater until the surface temperature reached from 100 ° C to 130 ° C, the expansion rate was 200.
Female pull vacuum forming was performed so that
Asano Laboratory Co., Ltd. "Vacuum forming machine FCP-4APA-
W-30-L "). <Evaluation method> (1) Molding workability: Molding workability was determined to be good when there was no problem in molding under the above-mentioned molding conditions and there was no remarkable appearance defect in the obtained laminate. (2) Eyes: The state of deposits on the die outlet during the above-mentioned molding was visually observed and evaluated on the basis of the following 5 grades.

5: Very low 4 ... Low 3 ... Normal 2 ... High 1 ... Very high (3) Soft feeling: The surface of the laminate was touched by hand and the touch was evaluated according to the following 5 grades. A surface having a sticky feeling is not suitable for the purpose of the present invention, but in that case, it is described as (sticky).

5 ... Very soft 4 ... Soft 3 ... Normal 2 ... Hard 1 ... Very hard (4) Scratch resistance: A pencil (hardness H) was applied to the surface of the thermoplastic elastomer layer of the laminate in accordance with JIS K5401. After scratching with a load of 500 g to remove the carbon powder on the surface, the surface was visually observed and evaluated according to the following two stages.

○: No scratches △: Almost no scratches ×: Scratches (5) Retainability of embossed pattern after vacuum forming:
Tokyo Seimitsu Co., Ltd. surface roughness profile measuring machine (Surfcom 57
0A) was used to measure the grain depth before and after vacuum forming at the same location of the laminate, and the average roughness of 10 points was obtained. The ratio of the average roughness after vacuum forming to the average roughness before vacuum forming was determined and defined as Rz residual rate (%). Depending on the value of Rz residual rate, the following 4
The grade was evaluated.

Residual Rz 50% or more ...... ◎ 40% or more and less than 50% …… ○ 35% or more and less than 40% …… △ Less than 35% ………… (6) Breakage: Laminate surface during vacuum forming Was visually observed and evaluated according to the following three grades.

∘: No torn parts were observed ×: No torn parts were observed (7) Oil resistance: A single-layer sheet of the thermoplastic elastomer composition was dipped in light liquid paraffin and left at 80 ° C. for 24 hours. did. After the immersion, the sample was taken out, the oil adhering to the surface was wiped off, and the weight was measured. The weight change rate before and after immersion was calculated by the following formula.

ΔW = (W2-W1) * 100 / W1 ΔW: weight change rate (%) W1: mass in air before immersion W2: mass in air after immersion Examples 1 to 5 and Comparative Examples 1-2 (Production of Thermoplastic Elastomer) Tetrakis [methylene- 3- (3 ', 5'-di-
t-Butyl-4′-hydroxyphenyl) propionate] methane (trade name “Irganox 1010” manufactured by Ciba Specialty Chemicals) was added in an amount of 0.1 part by weight, and POX and DVB in the amounts shown in Table 1 were further added. , L /
Using a twin-screw extruder having a diameter of 41 and a cylinder diameter of 44 mm, the temperature was set to 110 to 180 ° C. to melt and knead the mixture, which was extruded in a strand form from a die and cut to obtain pellets of the thermoplastic elastomer composition. It was Then, using the obtained pellets, a laminate was manufactured by the above method and evaluated. The evaluation results are shown in Table 1.

Comparative Example 3 An olefinic thermoplastic elastomer (trade name "Thermolane 36" which is a dynamically cross-linked product of a blend of an ethylene-propylene-non-conjugated diene copolymer rubber and polypropylene.
02N ”manufactured by Mitsubishi Chemical Co., Ltd.)
An evaluation was made. The evaluation results are shown in Table 1. <Evaluation of Results> 1) In Comparative Example 1, since the component (a4) having a weight average molecular weight outside the range of the present invention is used, the moldability is poor as compared with the corresponding Examples 1 and 2. It has a sticky feeling, scratch resistance, texture retention after vacuum forming, vacuum forming breakage, and poor oil resistance. 2) In Comparative Example 2, since the component (a4) having a weight average molecular weight outside the range of the present invention is used, the moldability is poor and the sticky feeling is felt as compared with the corresponding Examples 3, 4, and 5. Yes, scratch resistance, texture retention after vacuum forming, vacuum forming breakage, and oil resistance are inferior. 3) In Comparative Example 3, the olefinic thermoplastic elastomer is used, and as compared with the corresponding Examples 1 to 5, generation of eye blemishes is recognized, scratch resistance, wrinkle retention after vacuum forming,
The oil resistance is inferior.

[0041]

[Table 1]

[0042]

According to the present invention described above, a laminate having excellent extrusion moldability, scratch resistance, oil resistance, soft feeling, and uniform spreadability and texture (embossed pattern) retention is provided. , Interior materials of automobile parts, such as instrument panel, door trim, console box, ceiling material sheet, handle pad, and other skin materials, seat leather seats, furniture skin materials, etc. The industrial value of the invention is remarkable.

Continued front page    F-term (reference) 4F100 AK03A AK03B AK04B AK07A                       AK07B AK12A AK29A AL02A                       AL05B AL06A AL09A AT00B                       BA02 BA07 CA04A DD01A                       DJ01B EJ05B EJ39A GB33                       JA07A JB01 JB16A JK14                       YY00A                 4J002 AE05Y BB02X BB06X BB07X                       BB08X BB11X BB15X BB16X                       BP01W FD02Z GF00

Claims (8)

[Claims] 1. A laminate comprising a thermoplastic elastomer layer whose surface is embossed and a base material layer, wherein:
The thermoplastic elastomer layer contains the following components (a) to (c), and the ratio of the component (a) to the total amount of the components (a) and (b) is 20 to 80% by weight, and the component (b). Is 20 to 80% by weight, and the total of the components (a) and (b) is 10
A laminate comprising a thermoplastic elastomer composition having 1 to 300 parts by weight of the component (c) per 0 parts by weight. (A) Weight average molecular weight of 80,000 to 500,000
Which is a block copolymer represented by the general formula (I) and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer. Embedded image A (BA) n and / or (AB) n (I) (wherein A is a vinyl aromatic hydrocarbon polymer block and B is an elastomeric polymer block) , N
Is an integer of 1 to 5. ) (B) Hydrocarbon-based rubber softening agent (c) Olefin-based resin 2. A in general formula (I) is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block or a butadiene-isoprene polymer block, and A is contained in component (a). Quantity is 10-50
The laminate according to claim 1, which is in weight%. 3. The composition according to claim 1, wherein B in the general formula (I) is an elastomeric polymer block of a conjugated diene.
The laminated body according to. 4. The laminate according to claim 1, wherein the thermoplastic elastomer composition is at least partially crosslinked. 5. The layered product according to claim 1, wherein the component (c) is a propylene polymer. 6. The laminate according to claim 1, wherein the base material layer is made of a polyolefin resin. 7. The laminate according to claim 1, wherein the base material layer is made of a foam of a polyethylene resin, a polypropylene resin, or a mixture thereof. 8. The foamed product is crosslinked.
The laminated body according to.