JPH06170871A - Composite skin material and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a composite skin material, excellent in adhesive property to polyurethane foam and in cleanliness, by a method wherein an elastomer layer, consisting of ethylene/alpha-olefin copolymer rubber and polyolefin resin, is integrated with an olefin resin layer while complex dynamic viscosities of respective compositions are specified. CONSTITUTION:An elastomer layer is molded by powder molding employing a composition consisting of ethylene/alpha-olefin copolymer rubber and polyolefin resin or the partial crosslinking type composition, which are provided with a complex dynamic viscosity eta* (1) in a frequency of 1radian/sec at 250 deg.C of 1.5X10<5>poise or less and a Newtonian viscosity index, operated by a formula employing the eta* (1) and the complex dynamic viscosity eta* (100) in 100radian/sec is 0.67 or less. An olefin thermosetting resin layer is produced by powder molding employing the olefin thermosetting resin having the complex dynamic viscosity of 1X10<4>Poise or more in the frequency of 1radian/sec at 200 deg.C. According to this method, a composite skin material, excellent in the transferring property of a mold pattern also can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composite skin material comprising a layer molded from a powder composition containing a specific thermoplastic elastomer and a layer molded from a powder composition containing a specific synthetic resin, and the production thereof. Regarding the method.

[0002]

2. Description of the Related Art Conventionally, a skin material having a complicated pattern such as leather grain and stitch has been used for automobile interior parts and the like. It is also known that the skin material is produced by powder molding a vinyl chloride resin powder composition. However, since this skin material uses a vinyl chloride resin as a raw material, it is not only inferior in lightness but also generates an acidic substance by incineration at the time of disposal, causing air pollution, acid rain, etc. It has the disadvantage of being inferior in sex and is not completely satisfactory.

The inventors of the present invention have conducted studies to find a skin material free from such defects, and as a result, by powder-molding a powder composition containing a specific thermoplastic elastomer, the above-mentioned defects are eliminated and local thinning is achieved. It has already been proposed to find a skin material in which the pattern in the molding die is accurately transferred without pinholes or the like (EP-A 479,580).
issue). However, when using the skin material, a mixture of an isocyanate and a polyol is injected between the skin material and the base material, foamed, and cured to form a polyurethane foam layer, thereby producing a multilayer molded article. The adhesiveness with the polyurethane foam layer is not always sufficient, and in some cases, a problem of peeling during use occurred.

[0004]

Means for Solving the Problems As a result of intensive studies to solve such problems, the present inventors have found that a layer molded from a powder composition containing a specific thermoplastic elastomer and a specific synthetic resin are The present invention has been completed by finding out that a composite skin material composed of a layer molded from a powder composition containing the same has excellent adhesiveness to a polyurethane foam layer and further conducting various studies.

That is, the present invention provides a layer obtained by powder molding a powder composition containing the following (A) elastomer and a layer obtained by powder molding a powder composition containing the following (B) synthetic resin. The present invention provides a composite skin material and a method for producing the same. (A) From a thermoplastic elastomer composed of a composition of ethylene / α-olefin copolymer rubber and a polyolefin resin, or a partially cross-linked composition of ethylene / α-olefin copolymer rubber and a polyolefin resin Which has a complex dynamic viscosity η ^* (1) of 1.5 × 10 ⁵ at a frequency of 1 radian / sec at 250 ° C.
And the poise and the complex dynamic viscosity eta ^* (1) and the frequency 100 complex dynamic viscosity eta ^* (100) in radians / sec and the Newtonian viscosity index n calculated by the following equation 0.67 with Is a thermoplastic elastomer. ^{n = {logη * (1)} -logη * (100)} / 2 (B) a complex dynamic viscosity at a frequency of 1 radian / sec at 200 ℃ η ^* (1) olefinic at 1 × 10 ⁴ poise or more Thermoplastic synthetic resin.

The present invention will be described in detail below. The composite skin material of the present invention is the specific thermoplastic elastomer (A) described above.
It is characterized by comprising a layer obtained by powder molding a powder composition containing the above and a layer obtained by powder molding the powder composition containing the above specific synthetic resin (B). Examples of the ethylene / α-olefin copolymer rubber that is a component of the thermoplastic elastomer (A) include ethylene / propylene copolymer rubber and ethylene / α-olefin copolymer rubber.
Examples thereof include rubbers containing olefin as a main component, such as propylene / non-conjugated diene copolymer rubber. Examples of the non-conjugated diene include dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and the like. Among such ethylene / α-olefin copolymer rubbers, ethylene / propylene / ethylidene norbornene rubber (hereinafter referred to as EP
DM)), ethylene / propylene / dicyclopentadiene rubber and the like are more preferably used, and by using this, an elastomer excellent in heat resistance, tensile properties and the like can be obtained.

The Mooney viscosity of the ethylene / α-olefin copolymer rubber (the Mooney viscosity measured at 100 ° C. according to ASTM D-927-57T (ML _{1 + 4} 100 ° C.)) is usually 130 or more and 350 or less, It is preferably 200 or more and 300 or less. Further, the ethylene / α-olefin copolymer rubber can be used in the form of an oil-extended olefin copolymer rubber by adding a mineral oil softener such as a paraffinic process oil to the ethylene / α-olefin copolymer rubber. In this case, not only the melt fluidity is improved but also the flexibility of the molded product is improved, which is preferable. The amount of the mineral oil-based softening agent added is usually 120 parts by weight or less, preferably 30 to 120 parts by weight, per 100 parts by weight of the ethylene / α-olefin-based copolymer rubber.

Further, as the polyolefin resin which is another component constituting the thermoplastic elastomer, polypropylene, a copolymer of propylene and ethylene, and a copolymer of propylene and an α-olefin other than propylene are preferably used. In particular, it is possible to reduce the hardness of the molded product by using a copolymer resin of propylene and butene.

If the melt flow rate of the polyolefin resin (MFR, measured according to JIS K-7210, 230 ° C., 2.16 kg load) is less than 20 g / 10 min, the powders melt and adhere to each other during powder molding. Since it becomes difficult and the strength of the molded product is reduced, 20 g / 10 min or more is usually used. It is preferably 50 g / 10 minutes or more.

The thermoplastic elastomer used in the present invention is a composition of the above ethylene / α-olefin copolymer rubber and a polyolefin resin, or a partially crosslinked composition obtained by dynamically crosslinking the composition. However, the weight ratio of the ethylene / α-olefin copolymer rubber to the olefin resin is usually 5:95 to 80:20.

In producing the partially crosslinked composition, an organic peroxide is usually used as a crosslinking agent. Dialkyl peroxide is preferably used as the organic peroxide. Further, in the presence of a crosslinking aid such as a bismaleimide compound, it is preferable to dynamically crosslink using a very small amount of organic peroxide. In this case, ethylene / α-
Olefin-based copolymer rubber is appropriately crosslinked to improve heat resistance and, at the same time, high flow is obtained. Ethylene / α-
The crosslinking assistant is used in an amount of 1.5 parts by weight or less, preferably 0.6 parts by weight or less, and the organic peroxide as a crosslinking agent is 0.2 parts by weight per 100 parts by weight of the total amount of the olefin copolymer rubber and the polyolefin resin. The amount used is not more than 0.1 part by weight, preferably not more than 0.1 part by weight, more preferably not more than 0.07 part by weight.
For dynamic crosslinking, a method of continuous kneading extrusion such as uniaxial kneading extrusion or biaxial kneading extrusion is suitable. In the case of biaxial kneading and extrusion, when extrusion cross-linking is carried out at a shear rate of <10 ³ sec ^-1 , the dispersed particle size of the ethylene / α-olefin copolymer rubber becomes large and it is difficult to realize the viscosity condition of the present invention. Therefore, it is preferable to carry out continuous extrusion crosslinking at a shear rate of ≧ 10 ³ sec ⁻¹ .

The thermoplastic elastomer in the present invention is
The complex dynamic viscosity η ^* (1) measured at 250 ° C and a frequency of 1 radian / second is 1.5 × 10 ⁵ poise or less, preferably 1.0 × 10
^{It is 5} poise or less. When it exceeds 1.5 × 10 ⁵ poise, the powder of the elastomer does not melt and flow on the mold surface, and cannot be molded by a powder molding method having a very low shear rate of 1 sec ⁻¹ or less during processing. Also, the complex dynamic viscosity η ^* (1) measured at 250 ° C and a frequency of 1 radian / second and the complex dynamic viscosity η ^* (100) measured at a frequency of 100 radian / second.
The Newtonian viscosity index n calculated by the following equation using and is 0.
It is 67 or less, preferably 0.60 or less. n = the ^{{logη * (1) -logη *} (100))} / 2 Newtonian viscosity index n exceeds 0.67, if frequency 1
Complex dynamic viscosity η ^* (1) measured in radians / second is 1.5 ×
Even if the porosity is 10 ⁵ poise or less, the frequency dependence of the complex dynamic viscosity becomes large, and the melted elastomer is produced by a molding method such as powder molding in which the molding pressure during molding is as small as 1 kg / cm ² or less. The heat fusion between the powder particles becomes incomplete, and a molded product having low mechanical properties tends to be obtained, which is not preferable.

In the present invention, when a partially crosslinked composition is used as the thermoplastic elastomer composition, an uncrosslinked ethylene-α-olefin copolymer rubber or ethylene-α-olefin copolymer resin is used as an elastomer.
By blending 50 parts by weight or less with 100 parts by weight, the flexibility of the molded product can be further improved. As the α-olefin in this case, propylene, butene and the like are used alone or in combination. Especially ethylene content 40 ~ 90
%, Preferably 70 to 85% by weight of ethylene-propylene copolymer rubber having a ML _{1 + 4} 100 ° C. of 50 or less is preferred.

The powder composition containing the thermoplastic elastomer in the present invention is usually produced by pulverizing the composition containing the thermoplastic elastomer as described above at a low temperature below the glass transition temperature. For example, a freeze pulverization method using liquid nitrogen is preferably used. The elastomer composition pellets cooled to −70 ° C. or lower, preferably −90 ° C. or lower can be obtained by a mechanical pulverization method using an impact pulverizer such as a hammer mill or a pin mill. Grinding at a temperature higher than −70 ° C. is not preferable because the particle size of the crushed elastomer powder becomes coarse and the powder moldability decreases. In order to prevent the polymer temperature from becoming higher than the glass transition temperature during the pulverization operation, a method that generates less heat and has high pulverization efficiency is preferable. Further, it is preferable that the crushing device itself is cooled by external cooling. The elastomer powder obtained is preferably pulverized to such an extent that 95% or more of the total weight of the elastomer powder passes through the Tyler standard sieve 32 mesh. If the cumulative rate on the 32 mesh screen exceeds 5%, it may be one of the causes of uneven thickness during pulverization and molding. This unevenness in thickness gives unevenness to the flexibility of the molded product and makes it easy to cause creases, which may be a factor that impairs the commercial value of the molded product.

Further, the powder composition of the present invention may contain an internally added release agent, and a methylpolysiloxane compound is preferably used as the internally added release agent. In this case, the methylpolysiloxane compound preferably has a viscosity at 25 ° C. of 20 centistokes or more, and more preferably 50 to 5000 centistokes.
If the viscosity becomes too high, the effect as a release agent decreases. The content of the internally added release agent is 10 in powder composition.
It is 2 parts by weight or less per 0 parts by weight, and when it is more than 2 parts by weight, heat fusion between the elastomer powders may be hindered, and only a molded product having poor mechanical properties may be obtained, and the surface of the mold may be deteriorated. The release agent may bleed and the mold may be contaminated, which is not preferable.

The internally added release agent can be incorporated at any time before and after pulverization. Further, the powder composition in the present invention is a known heat stabilizer such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine- or amide-based stabilizer, an antiaging agent, a weather resistance stabilizer, and an electrostatic charge. Inhibitor,
Lubricants such as metallic soap and wax, pigments for coloring and the like can be contained. When it is contained, it may be carried out at any time before and after pulverization.

The composite skin material of the present invention has a layer obtained by powder molding the above powder composition and a complex dynamic viscosity η ^* (1) of 1 × 10 ^{4 at} 200 ° C. and a frequency of 1 radian / sec.
It is characterized in that it comprises a layer obtained by powder molding a powder composition containing a specific synthetic resin called an olefinic thermoplastic synthetic resin having a poise or higher, but as such an olefinic thermoplastic synthetic resin, , For example,
Thermoplastic elastomer, polyethylene resin, polypropylene resin, etc. are used.

Here, as the thermoplastic elastomer,
For example, a thermoplastic elastomer composed of a composition of ethylene / α-olefin copolymer rubber and a polyolefin resin, a thermoplastic elastomer composed of a partially cross-linked composition of ethylene / α-olefin copolymer rubber and a polyolefin resin. Examples thereof include plastic elastomers.

Examples of polyethylene resins include high-pressure polyethylene, low-pressure polyethylene, chain low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid ester-maleic anhydride. Acid terpolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate terpolymer, ethylene-
Glycidyl methacrylate-methacrylate terpolymers, ethylene-α-olefin copolymers, modified polyolefins, chlorinated polyethylene, and other thermoplastic synthetic resins containing ethylene as a main component are mentioned.

As the polypropylene resin, for example,
Homopolypropylene, a propylene-ethylene random copolymer, a propylene-ethylene block copolymer, a propylene-butene random copolymer, a propylene-ethylene-butene terpolymer, etc. are mentioned.

If the complex dynamic viscosity η ^* (1) at a frequency of 1 radian / sec at 200 ° C. is less than 1 × 10 ⁴ poise, these olefinic thermoplastic synthetic resins have insufficient adhesion to polyurethane foam. Since it peels off at the interface, it must be at least 1 × 10 ⁴ poise. Preferably 1.5 × 10 ⁵ poise or more, more preferably 2 × 10 ⁵
More than a poise.

The powder composition containing the synthetic resin of the present invention is a powder composition containing the olefinic thermoplastic synthetic resin as described above, but 95% or more of the total weight thereof passes through 32 mesh of Tyler standard sieve. The particle size is preferable. Further, two or more kinds of olefinic thermoplastic synthetic resin powders may be mixed and used.

The powder composition containing the synthetic resin according to the present invention may be a known heat stabilizer such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine- or amide-based stabilizer, and anti-aging agent. Agents, weather resistance stabilizers, antistatic agents, metallic soaps, lubricants such as waxes, and the like.

The composite skin material of the present invention comprises a layer obtained by powder molding the powder composition containing the elastomer (A) as described above and a powder composition containing the synthetic resin (B) as described above. It is characterized in that it is composed of a layer obtained by powder molding, in the powder molding, for example, fluidized-bed method, powder sintering method, electrostatic coating method, powder spraying method, powder rotation molding method. The powder slush molding method (Japanese Patent Laid-Open No. 58-132507) and the like are used. Among them, the powder slush molding method is preferable.

When the powder slush molding method is adopted,
For example, (1) a container containing a powder composition containing the elastomer of (A) and a mold having a complicated pattern inside which is heated to a temperature sufficiently higher than the melting temperature of the powder are integrated together, Powder is adhered to and melted in the cavity while rotating and / or rocking, and excess powder is discharged into the container. (2) Then, the container is removed, and the powder composition containing the synthetic resin of (B). The container containing is heated to a temperature sufficiently higher than the melting temperature of the powder.
The mold having the layer obtained in (1) was integrated in the same manner as above, and the powder composition containing the synthetic resin of (B) was obtained from the container in the same manner as above and obtained in (1) above. Adhered in layers,
A composite skin material can be produced by melting and discharging the excess powder composition into a container.

The mold heating system used for powder molding is not particularly limited, and examples thereof include a gas heating furnace system,
An electric heating furnace method, a heat medium oil circulation method, a dipping method in heat medium oil or heat fluidized sand, a high frequency induction heating method, and the like can be mentioned. In the step (1), the powder molding temperature is usually 180 to 300 ° C, preferably 2
It is 00-280 degreeC. In the step (2), the temperature is usually 150 to 270 ° C., preferably 150.
~ 250 ° C. The molding time is not particularly limited and is appropriately selected depending on the size of the molded body, the thickness of the molded body, and the like.

[0027]

As described above, the composite skin material of the present invention can be obtained. The composite skin material of the present invention is excellent not only in adhesiveness with polyurethane, but also in cleanliness, pattern transferability of a molding die, etc. Used in various fields. For example, in the automotive field, instrument panels, console boxes,
Armrests, headrests, door trims, rear panels, pillar trims, sun visors, luggage compartment trims, luggage compartment lids, airbag storage boxes, seat buckles, headliners, glove boxes, steering wheel covers, interior skin materials such as ceiling materials, kicking plates, and changes. It is suitable for interior parts such as lever boots and ceiling materials, spoilers, side moldings, license plate housings, mirror housings, air dam skirts, and mudguards.

In the field of home appliances / OA equipment, for example,
TV, video, washing machine, dryer, vacuum cleaner, cooler,
Suitable as an exterior member for air conditioners. In the field of sporting goods, for example, it is suitable for interior materials for boats, marine sports parts, etc., and in the field of construction and housing, for example, furniture, desks, chairs, gates, doors, fences, wall decoration materials, ceiling decoration materials, kitchens. Suitable for indoor floor materials such as washrooms and toilets, and can also be used for industrial products and miscellaneous goods.

[0029]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The surface appearance of the composite skin materials and the adhesiveness with the polyurethane foam in Examples and Comparative Examples were evaluated as follows. Surface appearance of the composite skin material The surface was visually observed and evaluated as follows. ◯: Meltability is good and no pinhole is observed. X: Poor meltability and pinholes are observed.

Contact between composite skin material and polyurethane foam
The adhesive composite skin material is placed in a mold for foamed polyurethane, and a semi-hard urethane resin of about 10 mm is foamed and laminated on the back surface of the skin material,
Then, after taking out from the mold, it was cut into a width of 25 mm to obtain a sample for a peel test. Using this sample, a 180 ° C. peel test between the composite skin material and polyurethane was conducted and evaluated as follows. ◯: Material peeling (adhesiveness at the interface is good) Δ: Partial interfacial peeling ×: Interface peeling (adhesiveness at the interface is bad) Adhesive composite skin material between the first layer and the second layer in the composite skin material Was subjected to a 180 ° peel test between the first layer and the second layer, and evaluated in the same manner as the evaluation of the adhesiveness between the composite skin material and the polyurethane foam.

Dynamic Viscoelasticity (1) Dynamic Viscoelasticity of Elastomer Dynamic Spectrometer made by Rheometrics
Using the RDS-7700 model, the dynamic viscoelasticity at a frequency of 1 radian / second and 100 radian / second at 250 ℃ was measured in parallel plate mode with an applied strain of 5%, and the complex dynamic viscosity η ^* (1)
And η ^* (100) were calculated. (2) Dynamic viscoelasticity of synthetic resin Using the same equipment as above, 50 ℃ to 250 ℃ at 4 ℃ / min.
The dynamic viscoelasticity at the time of heating up to was measured in a parallel plate mode, a frequency of 1 radian / sec, and an applied strain of 5%, and a complex dynamic viscosity η ^* (1) at 200 ° C. was calculated.

Example 1 (Preparation of Elastomer Powder Composition) EPDM (ML
_{1 + 4} 100 ° C. = 242, propylene content = 28% by weight,
Iodine value = 12) Per 100 parts by weight of mineral oil-based softener (registered trademark Diana Process PW-38 manufactured by Idemitsu Kosan Co., Ltd.
0) Oil-extended EPDM (ML _{1 + 4} 1 added with 100 parts by weight)
40 parts by weight at 00 ° C = 53) and propylene-ethylene random copolymer resin (ethylene content = 5% by weight, MFR
= 85 g / 10 minutes) and 60 parts by weight of a crosslinking aid (0.4% by weight of Sumitomo Chemical's registered trademark Sumifine BM-bismaleimide compound) were kneaded for 10 minutes using a Banbury mixer, and then an extruder was used. This was a pellet-shaped master batch for crosslinking (hereinafter referred to as MB).

This M. B. 100 parts by weight of organic peroxide (manufactured by Sanken Kako Co., Ltd., San Perox APO,
2,5-Dimethyl-2,5-bis (t-butylperoxy) hexane) (0.04 parts by weight) was added, and the mixture was mixed with a twin-screw kneader (manufactured by Japan Steel Works, registered trademark TEX-44) at 22.
Dynamic crosslinking was carried out at 0 ° C. to obtain elastomer composition pellets. The pellets were cooled to a temperature of −100 ° C. using liquid nitrogen and then frozen and pulverized to obtain a complex dynamic viscosity η.
^A thermoplastic elastomer powder for powder molding having a (1) of 3.1 × 10 ³ poise and a Newton viscosity index n of 0.24 was obtained. This powder passed through a 32 mesh Tyler standard sieve at 99% by weight.

(Preparation of Synthetic Resin Powder Composition)
Oil-extended EPD in the preparation of laster powder compositions
M as 70 parts, as a propylene-ethylene random copolymer
30 parts by weight of a copolymer having an MFR of 1.2 g / 10 min.
Outside is the same as when the above elastomer powder composition was prepared.
Thus, an elastomer powder was obtained. Melting this thing
Complex dynamic viscosity η at temperatures of 134 ° C and 200 ° C^*(1) is 3.
0 x 10 ^FiveIt was a poise.

(Production of Composite Skin Material) A nickel flat plate wrinkled mold (30 cm × 30 cm) was heated in a gear oven at 300 ° C. When the mold surface temperature reaches 250 ° C, sprinkle the elastomer powder composition obtained above, discharge the excess powder composition after 7 seconds, and then sprinkle the synthetic resin powder composition obtained above. After 10 seconds, the excess powder composition was discharged. Then, the composite skin material was obtained by heating (post-heating) for 30 seconds in a gear oven at 240 ° C., cooling with water, and then removing from the mold. The evaluation results of this composite skin material and the composite skin material produced without post-heating are also shown in Table 1.

Example 2 In the production of the composite skin material of Example 1, a synthetic resin powder was used.
-As composition, polypropylene (Sumitomo Seika B-200
 , Melting temperature 167 ℃, complex dynamic viscosity η at 200 ℃ η ^*(1)
= 2.5 x 10^FiveExample except using crushed product (poise)
A composite skin material was produced in the same manner as in 1. Table of evaluation results
Shown in 1.

Example 3 In the production of the composite skin material of Example 1, an ethylene-vinyl acetate copolymer (K-2010 manufactured by Sumitomo Seika, a melting temperature of 77 ° C., a complex at 200 ° C.) was used as a synthetic resin powder composition. A composite skin material was produced in the same manner as in Example 1 except that a ground product having a dynamic viscosity η ^* (1) = 4.1 × 10 ⁴ poise) was used.
The evaluation results are shown in Table 1.

Example 4 (Preparation of synthetic resin powder composition) Synthetic resin of Example 1
In the preparation of the powder composition, 50 parts of oil-extended EPDM,
Propylene-ethylene random copolymer MFR =
Example except that 50 parts of copolymer of 85 g / 10 min were used
Eras in the same manner as in the preparation of the synthetic resin powder composition of 1.
Got Tomer Powder. The melting temperature of this product is 138 ℃,
Complex dynamic viscosity η at 200 ° C^*(1) is 1.6 x 10 ^FourPoise
Met. (Production of composite skin material) For production of the composite skin material of Example 1.
As a synthetic resin powder composition,
The same procedure as in Example 1 was carried out except that marp powder was used.
A synthetic skin material was manufactured. The evaluation results are shown in Table 1.

Example 5 (Preparation of elastomer powder composition) In the preparation of the elastomer powder composition of Example 1, propylene-
Instead of ethylene random copolymer, propylene-butene random copolymer (butene content = 24% by weight, MFR
= 90 g / 10 min) was used to obtain an elastomer powder composition in the same manner as in Example 1. The complex dynamic viscosity η ^* (1) of the product was 6.9 × 10 ³ poise and the Newton's viscosity index n was 0.39. (Production of Composite Skin Material) In the production of the composite skin material of Example 1, a composite skin material was produced in the same manner as in Example 1 except that the above elastomer powder composition was used as the elastomer powder composition. The evaluation results are shown in Table 1.

Comparative Example 1 In the production of the composite skin material of Example 1, a synthetic resin powder was used.
-As a composition, homopolypropylene (melting temperature 167
Complex dynamic viscosity η at ℃ and 200 ℃^*(1) = 2.1 x 10 ³Poi
The same as in Example 1 except that the frozen crushed product
To produce a composite skin material. The evaluation results are shown in Table 1.

Comparative Example 2 In the production of the composite skin material of Example 1, an ABS resin (melting temperature 175 ° C., 200 ° C.) was used as the synthetic resin powder composition.
Complex dynamic viscosity η ^* (1) = 1.3 × 10 ⁵ poise, grafting ratio 54.3%, rubber 15%, acrylonitrile-styrene (26% acrylonitrile) with a molecular weight of about 50000
A composite skin material was produced in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 3 In the production of the composite skin material of Example 1, a white pigment (PV-742 manufactured by Sumika Color Co., Ltd.
A composite skin material was produced in the same manner as in Example 1 except that (insoluble at 250 ° C.) was used. The evaluation results are shown in Table 1.

Comparative Example 4 (Preparation of Elastomer Powder Composition) EPDM (ML
_{1 + 4} 100 ° C. = 145, propylene content = 36% by weight,
Per 100 parts by weight of iodine value = 10) mineral oil-based softener (registered trademark Diana Process PW-38 manufactured by Idemitsu Kosan Co., Ltd.
0) 40 parts by weight of oil-extended EPDM (ML _{1 + 4} 10
52 parts by weight of 0 ° C. = 78), homopolypropylene (MFR
= 20 g / 10 min) and propylene-butene random copolymer resin (butene content = 24% by weight, MF)
21 parts by weight (R = 4 g / 10 minutes) and 0.2 parts by weight of a crosslinking aid (Sumifine BM-bismaleimide compound manufactured by Sumitomo Chemical Co., Ltd.) were kneaded using a Banbury mixer. To 100 parts by weight of this product, 0.23 of organic peroxide (Sanperox TY-1,3 manufactured by Sanken Kako Co., Ltd.)
Parts by weight were added, and dynamic crosslinking was performed using a biaxial kneader to obtain elastomer composition pellets. The pellets were freeze-ground in the same manner as in Example 1 to obtain a thermoplastic elastomer powder having a complex dynamic viscosity η ^* (1) of 1.9 × 10 ⁵ poise and a Newton's viscosity index n of 0.83. (Production of Composite Skin Material) In the production of the composite skin material of Example 1, a composite skin material was produced in the same manner as in Example 1 except that the above elastomer powder was used as the elastomer powder composition. The evaluation results are shown in Table 1.

Comparative Example 5 A skin material was produced in the same manner as in Example 1 except that the synthetic resin powder composition was not used. The evaluation results are shown in Table 1.

Table 1 Evaluation results of composite skin material Adhesion between the first layer of the skin material and polyurethane Surface appearance Adhesion of the second layer Post-heating No post-heating Yes Example 1 〇 〇 〇 〇 Example 2 〇 〇 〇 ○ Example 3 ○ ○ ○ ○ △ Example 4 ○ ○ ○ ○ △ Example 5 ○ ○ ○ ○ ○ Comparative Example 1 ○ ○ × × Comparative Example 2 ○ × ○ ○ Comparative Example 3 ○ − × × Comparative Example 4 × ○ ○ ○ △ Comparative Example 5 ○-△ ×

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadashi Hikasa 1-5 Anesaki Kaigan, Ichihara, Chiba Sumitomo Chemical Co., Ltd. Within the corporation

Claims (2)

[Claims] 1. A layer obtained by powder-molding a powder composition containing the following (A) elastomer, and a layer obtained by powder-molding a powder composition containing the following (B) synthetic resin. Composite skin material characterized by. (A) From a thermoplastic elastomer composed of a composition of ethylene / α-olefin copolymer rubber and a polyolefin resin, or a partially cross-linked composition of ethylene / α-olefin copolymer rubber and a polyolefin resin Which has a complex dynamic viscosity η ^* (1) of 1.5 × 10 ⁵ at a frequency of 1 radian / sec at 250 ° C.
Poise or less, and using the complex dynamic viscosity η ^* (1) and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second, the Newtonian viscosity index n calculated by the following equation is 0.67 or less. Is a thermoplastic elastomer. ^{n = {logη * (1)} -logη * (100)} / 2 (B) a complex dynamic viscosity at a frequency of 1 radian / sec at 200 ℃ η ^* (1) olefinic at 1 × 10 ⁴ poise or more Thermoplastic synthetic resin. 2. A powder composition containing the elastomer of the following (A) is powder-molded to form an elastomer layer, and then the powder composition containing the synthetic resin of the following (B) is powder-molded on the elastomer layer. By
A method for producing a composite skin material, characterized by integrating a synthetic resin layer. (A) From a thermoplastic elastomer composed of a composition of ethylene / α-olefin copolymer rubber and a polyolefin resin, or a partially cross-linked composition of ethylene / α-olefin copolymer rubber and a polyolefin resin Which has a complex dynamic viscosity η ^* (1) of 1.5 × 10 ⁵ at a frequency of 1 radian / sec at 250 ° C.
Poise or less, and using the complex dynamic viscosity η ^* (1) and the complex dynamic viscosity η ^* (100) at a frequency of 100 radians / second, the Newtonian viscosity index n calculated by the following equation is 0.67 or less. Is a thermoplastic elastomer. ^{n = {logη * (1)} -logη * (100)} / 2 (B) a complex dynamic viscosity at a frequency of 1 radian / sec at 200 ℃ η ^* (1) olefinic at 1 × 10 ⁴ poise or more Thermoplastic synthetic resin.