JPH11152380A - Thermoplastic elastomer composition, thermoplastic elastomer composition powder, and skin material consisting thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition and thermoplastic elastomer composition powder having good handling property, fluidity at processing and embossing transferability, and a skin material consisting thereof having good mechanical properties, heat resistance and designability. SOLUTION: The thermoplastic elastomer composition contains an olefinic thermoplastic elastomer (A) and an ethylenic resin (B) as essential components. Here, a propylenic polymer contained in the olefinic thermoplastic elastomer (A) exists as dispersed particles with an average particle size of 0.8 μm or smaller in the ethylenic resin (B), which is a matrix, confirmed by transmission electron microscopic observation. The thermoplastic elastomer composition further consists of multiple components including a propylenic resin (C) or a styrenic thermoplastic elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for a skin material such as a skin material of an automobile interior part, which has excellent workability and heat resistance.
The present invention relates to a thermoplastic composition elastomer composition having properties, a thermoplastic elastomer composition powder, and a skin material comprising the same.

[0002]

2. Description of the Related Art Conventionally, automotive interior materials such as instrument panels are mainly made of a polyolefin resin foam layer provided with a skin material such as a cloth material such as a polyvinyl chloride resin sheet, a thermoplastic elastomer sheet, and a tricot. Laminated or integrally molded, and further, an aggregate is bonded to the composite skin layer. Among these skin materials, polyvinyl chloride resin has been widely used because of its excellent surface hardness and flexibility. However, polyvinyl chloride resin is said to emit harmful substances such as dioxin when incinerated, and has a problem of environmental pollution. Therefore, in recent years,
As an alternative to polyvinyl chloride resin, the development of sheet products of thermoplastic elastomers has been developed. At the same time, the development of polyolefin-based resin powder, which can be recycled and incinerated, and is capable of powder-slush molding, which is commonly used for the molding of skin materials of polyvinyl chloride resin, heat-molds the powder by attaching it to the mold surface, It has been advanced.

[0003] For example, JP-A-59-1561 discloses that a partially crosslinked product of a polyolefin resin containing a carboxyl group or its anhydride group and an ethylene / α-olefin copolymer rubber, and optionally a polyolefin resin. A blended adhesive thermoplastic elastomer composition is shown. JP-A-1-103639 discloses a thermoplastic elastomer composition having a low bleed obtained by partially cross-linking a mixture of an oil-extended olefin-based copolymer rubber and an olefin-based resin. Further, Japanese Unexamined Patent Publication No.
No. 57310 discloses a thermoplastic elastomer composition containing a polyolefin resin and an ethylene / α-olefin-based copolymer rubber, and a thermoplastic elastomer molded article having a crimped pattern formed by slush molding the powder of the composition.

However, the composition proposed in the above-mentioned Japanese Patent Application Laid-Open No. 59-1561 is a composition intended for sheet molding, and therefore has a poor melt fluidity, making powder slush molding impossible. . Further, Japanese Patent Laid-Open No.
The composition proposed in JP-A-103639 has a problem that even if the composition is powdered, the grain transferability is poor because the composition has poor fluidity. Further, the composition proposed in JP-A-2-57310 has a problem that it is inferior in handleability.

[0005]

An object of the present invention is to provide a thermoplastic elastomer composition and a thermoplastic elastomer which are excellent in pulverizability at normal temperature, and excellent in heat resistance, fluidity during processing, and transferability of grain pattern. An object of the present invention is to provide a composition powder and a skin material comprising the same and excellent mechanical properties, heat resistance, and design properties.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the thermoplastic elastomer composition and powder having specific dispersed particles have been found to be easy to handle, flow, and heat-resistant. It has been found that the skin material composed of them has excellent mechanical properties, heat resistance, and transferability of a grain pattern, and has reached the present invention.

That is, the present invention comprises an olefin-based thermoplastic elastomer (A) and an ethylene-based resin (B) as essential components, and further includes a propylene-based resin (C) and / or a styrene-based thermoplastic elastomer (D). A thermoplastic elastomer composition, wherein a propylene polymer is present as dispersed particles having an average particle diameter of 0.8 μm or less according to a transmission electron microscope in an ethylene resin (B) as a matrix. A thermoplastic elastomer composition having an average particle diameter of 50 to 500 μm comprising the composition; and a skin material comprising the same.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The thermoplastic elastomer composition according to the present invention comprises an olefin-based thermoplastic elastomer (A) and an ethylene-based resin (B) as essential components, and further comprises a propylene-based resin (C) or a styrene-based thermoplastic elastomer (D). ), Or (A),
(B) and (C) are formed from four components including a styrene-based thermoplastic elastomer (D) in three components, and the kneaded product has a microstructure having specific dispersed particles.

The thermoplastic elastomer composition of the present invention comprises:
When the thermoplastic elastomer composition is used as a powder, the thermoplastic elastomer composition can be pulverized into a powder at room temperature (normal temperature pulverization). In order to enable cold grinding, the microstructure of the melt-kneaded thermoplastic elastomer composition needs to have specific dispersed particles.

That is, in the thermoplastic elastomer composition of the present invention, the ethylene resin (B) as a matrix
The propylene polymer therein is observed as a dispersed particle having an average particle diameter of 0.8 μm or less, preferably 0.5 μm or less by a transmission electron microscope. Here, the propylene-based polymer is contained in the olefin-based thermoplastic elastomer (A). On the other hand, the rubber component contained in the olefin-based thermoplastic elastomer (A) was analyzed by a transmission electron microscope using the same ethylene-based resin (B).
The particles are present as dispersed particles having an average particle diameter of 0.5 μm or more, usually 0.5 to 5 μm.

In the present invention, observation of dispersed particles of the melt-kneaded thermoplastic elastomer composition by such a transmission electron microscope (TEM) is performed as follows.
A sample for microstructure observation taken from the central part of the melt-kneaded product was added to a RuO ₄ (ruthenic acid) aqueous solution at room temperature for 5 to 10 minutes.
After immersion for a period of time, an ultra-thin section having a thickness of 50 to 100 μm is formed at room temperature using an ultramicrotome.
The section is observed using a transmission electron microscope JEM2000FX manufactured by JEOL Ltd. at 200 kV to determine the size of the dispersed particles of the rubber component contained in the propylene-based polymer and the olefin-based thermoplastic elastomer (A).

[0013] The microstructure of the thermoplastic elastomer composition of the present invention is affected by the composition of each component, the compatibility and the viscosity ratio between each component, and also the kneading conditions for obtaining the composition.

In the thermoplastic elastomer composition of the present invention, a preferable microstructure can be obtained by reducing the viscosity of a matrix component other than the rubber component of the olefin-based thermoplastic elastomer (A) containing a propylene-based polymer. .

FIGS. 1 to 3 show transmission electron microscope (TEM) photographs observed for the thermoplastic elastomer composition of the present invention.

FIG. 1 is a TEM photograph of the olefinic thermoplastic elastomer (A) at a magnification of 10,000 times alone,
EPDM in polypropylene matrix (photo, white)
(Photo, black) domain exists.

FIG. 2 shows a composition of olefin-based thermoplastic elastomer (A) / ethylene-based resin (B),
(A) / (B) = 100 parts by weight / 30 parts by weight of a TEM photograph at a magnification of 10,000 times. Small domain of polypropylene (white part) and E in ethylene resin matrix
There is a PDM domain. The size of the domain of this polypropylene is 0.5 μm to 2 μm.

FIG. 3 shows a composition of olefin-based thermoplastic elastomer (A) / ethylene-based resin (B),
It is a TEM photograph of (A) / (B) = 100 parts by weight / 150 parts by weight at a magnification of 60,000. Small domains of polypropylene and large domains of EPDM are found in the ethylene-based resin matrix. The size of the domain of polypropylene is 0.1 μm to 0.7 μm.

As described above, in the melt-kneaded product of the thermoplastic elastomer composition of the present invention, the propylene-based polymer contained in the olefin-based thermoplastic elastomer (A) contains 0% in the ethylene-based resin (B) as a matrix. The ethylene resin (B) matrix which is observed as finely dispersed particles having an average particle diameter of 0.2 μm and further contains a propylene-based polymer as finely dispersed particles as a rubber component contained in the olefinic thermoplastic elastomer (A) The particles have an average particle diameter of 1 μm and are present as dispersed particles having an average particle diameter larger than that of the propylene-based polymer.

Olefinic thermoplastic elastomer (A)
When the dispersed particles of the propylene-based polymer contained in the ethylene-based resin (B) become large and become dispersed particles having an average particle diameter of more than 0.8 μm, they are sieved on a 32 mesh screen when pulverized at room temperature. 5% by weight or more of unmilled material remains. Since the unground material cannot be used for powder slush molding, the yield is reduced. Further, pinholes are easily generated in the molded product, and the powder slush moldability becomes poor. Therefore, the propylene-based polymer contained in the olefin-based thermoplastic elastomer (A) or the propylene-based resin (C) added separately from the propylene-based polymer contained in the olefin-based thermoplastic elastomer (A) can be used. Including the entire propylene-based polymer,
If the average particle size of the dispersed particles present in the matrix of the ethylene resin (B) exceeds 0.8 μm, the particles cannot be practically pulverized at room temperature.

Hereinafter, each component forming the thermoplastic elastomer composition will be described.

Olefin-based thermoplastic elastomer (A) As the olefin-based thermoplastic elastomer (A) used in the present invention, any one generally belonging to olefin-based thermoplastic elastomers can be used. "Milastomer" (Mitsui Petrochemical Co., Ltd.)
Or a commercially available product such as "Sumitomo TPE" (manufactured by Sumitomo Chemical Co., Ltd.), or ethylene-propylene- (diene) -rubber (EPM,
An olefin-based thermoplastic elastomer obtained by compounding EPDM) with a polyolefin containing a propylene-based polymer can be used. Further, an olefin-based thermoplastic elastomer containing only an rubber component and not containing a crystalline propylene-based polymer, which is composed of an α-olefin copolymer, can be used in combination with a propylene-based resin (C) which is added separately.

It is preferable that the molded article obtained from the thermoplastic elastomer is a partially crosslinked olefin-based thermoplastic elastomer because of its excellent scratch resistance and heat resistance. Such partially crosslinked olefinic thermoplastic elastomers are disclosed in JP-B-53-34210, JP-B-56-15740, and JP-B-56-15.
No. 741, JP-B-56-15742, JP-B-58-56575, JP-B-59-30736 or JP-B-61-48537.

The olefin-based thermoplastic elastomer (A) used in the present invention has a JIS K7210-76, condition 14, load 2.
It is preferable that the melt flow rate (hereinafter, referred to as MFR) measured at 16 Kg and 230 ° C. is 20 to 100 g / 10 minutes.

Ethylene-based resin (B) The ethylene-based resin (B) used in the present invention is an ultra-low-density polyethylene, a very-low-density polyethylene, a low-density polyethylene, a medium-density polyethylene, a high-density polyethylene, and ethylene-vinyl acetate copolymer. It is at least one kind selected from coalescence. Above all, JIS K7210-76, condition 4, load 2.16 kg, MFR measured at 190 ° C is 2
0 to 200 g / 10 min, preferably 20 to 100 g / 1
Ethylene / α-olefin obtained by copolymerizing ethylene and an α-olefin having ³ to 20 carbon atoms for 0 minute and having a density of 0.865 to 0.945 g / cm ³ measured according to JIS K7112-80. Copolymer (B1) is preferred. Here, when the MFR is less than 20 g / 10 minutes, the molding fluidity of the obtained thermoplastic elastomer composition decreases. On the other hand, when it exceeds 200 g / 10 minutes, the mechanical strength is insufficient. When the density is less than 0.865 g / cm ³ , the heat resistance of the obtained thermoplastic elastomer decreases. On the other hand, when it exceeds 0.945 g / cm ³ , the flexibility resistance of the obtained thermoplastic elastomer decreases. Such an ethylene / α-olefin copolymer (B1)
Is a highly active Ziegler catalyst comprising a transition metal compound such as titanium and zirconium, a magnesium compound and an organoaluminum compound, or zirconium, hafnium,
It can be produced by copolymerizing ethylene and an α-olefin using a metallocene catalyst having at least one cyclopentadienyl group or substituted cyclopentadienyl group on a transition metal such as titanium.

Further, the ethylene / α-olefin copolymer (B1) has particularly excellent flexibility, emboss transferability and mechanical strength of the obtained thermoplastic elastomer composition. Mw) and monodispersity (Mw / M) represented by the ratio of the number average molecular weight (Mn).
Preferably, n) is in the range of 1.5 to 3, and has a characteristic that the melting point measured by a scanning differential calorimeter is substantially one. In addition, the thermoplastic elastomer composition used in the present invention has particularly excellent room-temperature pulverizability and excellent handling properties such as excellent flowability of the room-temperature pulverized powder. Therefore, JIS K7210-76, Condition 4, 190
JIS for MFR measured at a load of 2.16 kg
K7210-76, condition 7, 190 ° C, load 21.6
kg of MFR (HLMFR) (HLMF
(R / MFR) in the range of 20 to 50, preferably 22 to 45 is preferred. Ethylene with this property
The α-olefin copolymer (B1) can be produced using the above metallocene catalyst.

The α-olefin having 3 to 20 carbon atoms used for copolymerization with ethylene includes propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, Examples include pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

The ethylene-based resin (B) used in the present invention comprises 40 to 90% by weight of the above-mentioned ethylene / α-olefin copolymer (B1) at 190 ° C. and 2.16 kg.
Melt flow rate of load (JIS K7210-7
6) 20-200 g / 10 minutes and JIS K711
Density 0.920 to 0.945 g / c measured at 2-80
m ³ ethylene / α-olefin copolymer (B2) 60
It is preferred that the content is 10 to 10% by weight in order to balance the flexibility and heat resistance of the obtained thermoplastic elastomer composition.

The ethylene / α-olefin copolymer (B
2) is JIS K7210-76, condition 4, 190 ° C
MFR measured at 20 to 200 g / 10 min, preferably 40 to 150 g / 10 min, and JIS K7112
The density measured at -80 is 0.920 to 0.945 g / c
m ³ , preferably 0.920 to 0.940 g / cm ³ . Here, the ethylene / α-olefin copolymer (B
When the MFR of 2) is less than 20 g / 10 minutes, the molding fluidity of the obtained thermoplastic elastomer composition is reduced. On the other hand, when the MFR exceeds 200 g / 10 minutes,
The mechanical strength of the obtained thermoplastic elastomer composition decreases. Further, if a density of less than 0.920 g / cm ^3, decreases the heat resistance of the thermoplastic elastomer composition obtained, the flexibility of the case, the thermoplastic elastomer composition obtained exceeding 0.945 g / cm ³ drops I do. Also,
The ethylene / α-olefin copolymer (B2) can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms using a highly active Ziegler catalyst or a metallocene catalyst.

Propylene Resin (C) The propylene resin (C) used in the present invention is a crystalline polypropylene polymer, a propylene homopolymer, a propylene random copolymer having a propylene content of 90 mol% or more. And a propylene-based block copolymer having a propylene content of 80 mol% or more. Since a thermoplastic elastomer composition having particularly excellent heat resistance can be obtained, its melting point by a scanning differential calorimeter is 145. It is preferably a crystalline polypropylene resin having a temperature of not less than ° C.

The propylene resin (C) used in the present invention is JIS because the thermoplastic elastomer composition obtained is excellent in grain transferability and mechanical strength.
It is preferable that the melt flow rate (MFR) measured at K7210-76, condition 14, load 2.16 Kg, and temperature at 230 ° C. is 20 to 100 g / 10 minutes.

Styrenic Thermoplastic Elastomer (D) The styrenic thermoplastic elastomer (D) used in the present invention is also referred to as a styrenic block copolymer and comprises the following hard segments and soft segments. . That is, at least one of the molecular terminals
One end is composed of a polymer block portion (hard segment) of styrene or a derivative thereof, and an intermediate portion sandwiched between the hard segments or a portion continuous with the hard segment is an isoprene polymer block, a butadiene polymer block, and isoprene-butadiene. It comprises at least one polymer block (soft segment) selected from copolymer blocks. Here, the unsaturated bond of the soft segment is preferably a hydrogenated styrene-based thermoplastic elastomer in order to improve weather resistance and heat resistance. Examples of the hydrogenated styrene-based thermoplastic elastomer include “Clayton G” (manufactured by Shell Japan, SEBS), “Toughtec H” (manufactured by Asahi Kasei Corporation, SEBS) and “Septon” (Kuraray) And SEPS).

As the styrene-based thermoplastic elastomer used in the present invention, the above-mentioned hydrogenated styrene-based thermoplastic elastomer can be used alone or in combination. Further, the hydrogenated styrene-based thermoplastic elastomer can be used in combination with another styrene-based thermoplastic elastomer as long as the heat resistance of the thermoplastic elastomer is not impaired.

The styrene-based thermoplastic elastomer (D) used as the component in the present invention is JIS K7210-76, Condition 1 because the obtained thermoplastic elastomer composition has more excellent grain transferability and mechanical strength.
4. The melt flow rate (MFR) measured at a load of 2.16 kg and a temperature of 230 ° C. is preferably 5 to 100 g / 10 minutes.

Mixing ratio of thermoplastic elastomer composition and production method The thermoplastic elastomer composition of the present invention comprises the above-mentioned olefinic thermoplastic elastomer (A) and ethylene resin (B) as essential components, and further comprises a propylene-based thermoplastic elastomer. It is a thermoplastic elastomer composition containing a resin (C) and a styrene-based thermoplastic elastomer (D).

Olefinic thermoplastic elastomer (A)
80 to 2 parts by weight of ethylene resin (B)
00 parts by weight, preferably 100 to 150 parts by weight, is blended as an essential component. When the amount of the ethylene-based resin (B) is less than 80 parts by weight, the flexibility of the obtained thermoplastic elastomer composition decreases. On the other hand, when the amount exceeds 200 parts by weight, the heat resistance of the obtained thermoplastic elastomer composition decreases.

Olefinic thermoplastic elastomer (A)
A propylene resin can be further blended with the ethylene resin (B) to improve heat resistance. The compounding amount is 3 to 50 parts by weight of the propylene-based resin (C) based on 100 parts by weight of the olefin-based thermoplastic elastomer (A). When the amount of the propylene-based resin (C) is less than 3 parts by weight, there is no improvement effect, and when the amount exceeds 50 parts by weight,
It is not preferable because the flexibility of the obtained thermoplastic elastomer composition decreases.

Further, in order to improve heat resistance, the two components (A) and (B), or (A), (B) and (C)
In addition, 3 to 50 parts by weight of a styrene-based thermoplastic elastomer (D) can be further blended with the above three components. When the amount of the styrene-based thermoplastic elastomer (D) is less than 3 parts by weight,
If the flexibility and heat resistance of the obtained thermoplastic elastomer composition decrease, and if it exceeds 50 parts by weight, it is not preferable because the fluidity of the obtained thermoplastic elastomer composition decreases.

As a method for producing the thermoplastic elastomer composition of the present invention, any method can be used as long as the thermoplastic elastomer composition of the present invention can be produced. After dry-blending a predetermined amount of the components with a mixer such as a Henschel mixer, a tumbler type blender, and a V type blender, the mixture is continuously or discontinuously supplied to a kneading machine such as a Banbury mixer, an extruder, a kneader or a mixer. After heating, melt-kneading, pelletizing by a known method.

The thermoplastic elastomer composition of the present invention comprises an olefinic thermoplastic elastomer (A) and an ethylene resin (B) as essential components by a known method of performing a dynamic heat treatment in the presence of an organic peroxide. May be used as a partially crosslinked thermoplastic elastomer composition. Organic peroxides used for partial crosslinking include di-t-butyl peroxide, di-cumyl peroxide, α, α ′
-Bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexyne-3 and the like, based on a total of 100% by weight of the thermoplastic elastomer composition.
It is blended at a ratio of 0.05 to 5% by weight. Further, a polyfunctional monomer such as divinylbenzene or an auxiliary for peroxy crosslinking may be used in combination.

Method for Producing Powder of Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention has excellent pulverizability at room temperature, and is cooled to a temperature of less than 0 ° C. using a refrigerant or a cooling equipment to be mechanically pulverized. It is not necessary to carry out mechanical grinding at room temperature. Here, normal temperature pulverization means that pulverization is usually performed at 0 to 50 ° C, preferably at 0 to 40 ° C. The average particle size is 50 to 500μ by a method such as a normal temperature pulverization method or a freeze pulverization method.
m, and the thermoplastic elastomer composition powder of the present invention has an average particle size of 50 to 50.
Since it has a thickness of 500 μm, it is excellent in handleability, and in particular, a product obtained when subjected to powder slush molding has excellent mechanical properties and design properties. Here, the room temperature pulverization means that the thermoplastic elastomer of the present invention is mechanically pulverized at room temperature using an impact type pulverizer such as a turbo mill.
This is a method for obtaining a thermoplastic elastomer powder that passes through a mesh sieve but does not pass through a 200 mesh sieve. Low-temperature pulverization refers to a process in which the thermoplastic elastomer composition of the present invention is reduced to 0% by a refrigerant such as liquid nitrogen or dry ice. It refers to a method of cooling to a temperature of less than ° C. and mechanically pulverizing. As a method for obtaining the thermoplastic elastomer composition powder of the present invention, it is preferable to use an ordinary temperature pulverization method which is excellent in cost because the pulverization equipment is simple and no additional equipment such as cooling is required.

Optional Ingredients The thermoplastic elastomer composition of the present invention may contain a modified polyolefin with an unsaturated carboxylic acid or anhydride for imparting adhesiveness, and the blending amount is 100 parts by weight of the thermoplastic elastomer composition. It is preferably 0 to 15 parts by weight based on the weight. Further, a mineral oil-based softening agent may be blended for imparting flexibility, and the blending amount does not decrease the heat resistance of the thermoplastic elastomer composition. Therefore, 100 parts by weight of the thermoplastic elastomer composition is used. It is preferably 0 to 10 parts by weight based on the weight.

The thermoplastic elastomer composition of the present invention comprises:
As long as it does not deviate from the object of the present invention, for example, phenol-based, phosphorus-based, amine-based, sulfur-based antioxidants, flame retardants, fillers, antistatic agents, ultraviolet absorbers, release agents, pigments, etc. May be added.

Method for Producing Skin Material The skin material of the present invention is obtained by subjecting the thermoplastic elastomer composition or the powder of the thermoplastic elastomer composition of the present invention to powder slush molding, compression molding, roll molding, or the like.
It can be obtained by molding by various molding methods such as extrusion molding and injection molding. The skin material of the present invention is preferably obtained by powder slush molding, since a skin material having excellent mechanical properties, heat resistance, and grain transferability can be obtained.

The thermoplastic elastomer composition, the thermoplastic elastomer composition powder and the skin material comprising the same according to the present invention can be used for automobile interior materials such as instrument panels, ceilings, doors, seats, pillars, steering wheels, handles, etc. Used as a skin material for furniture, miscellaneous goods, house lining, etc.

[0046]

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

In Examples and Comparative Examples, ethylene-α
-The Mw / Mn measurement and the melting point measurement of the olefin copolymer (B) were performed according to the following methods.

* Measurement of Mw / Mn (monodispersity) Gel permeation chromatography (manufactured by Nippon Millipore Co., Ltd., apparatus name "ALC / GPC150C" (column: manufactured by Tosoh Corporation, trade name "GMHHR-H") (S) "
3, solvent: 1,2,4-trichlorobenzene, temperature:
140 ° C, flow rate 1.0ml / min, injection concentration 1mg / 1m
1, injection volume 300 μl). The column elution volume was calibrated by the universal calibration method using standard polystyrene manufactured by Tosoh Corporation.

* Measurement of melting point Scanning differential calorimeter (DSC) (manufactured by PerkinElmer, Inc.)
The measurement was performed using the device name “DSC-7”. The sample was melted at 200 ° C. for 5 minutes in a DSC furnace, and then cooled at a cooling rate of 10 ° C./min to 30 ° C., and the solidified (crystallized) sample was heated at a rate of 10 ° C./min. The temperature at the position of the maximum peak of the obtained endothermic curve was measured as the melting point.

The thermoplastic elastomer compositions obtained in Examples and Comparative Examples were kneaded by the following method, and the average dispersed particle diameter was measured. Furthermore, room temperature pulverizability, powder slush moldability, and molded sheet properties (hardness, Vicat softening temperature) were evaluated.

* Production of thermoplastic elastomer composition After the respective components were added in a predetermined amount and dry blended, kneaded with a pressure kneader (DS3-7.5MHH-E type manufactured by Moriyama Seisakusho), rolled into a sheet, and pelletized. Was performed.

* Average dispersed particle diameter The average dispersed particle diameter of the propylene-based polymer of the thermoplastic elastomer composition pellets was measured by the method described above.

* Room temperature pulverizability The thermoplastic elastomer composition pellets obtained in Examples and Comparative Examples were pulverized by using a pulverizer having a 32 mesh sieve (Turbo Kogyo Co., Ltd., device name "Turbomill T-400") And room temperature pulverization at room temperature. Here, the room temperature pulverizability was evaluated based on the presence or absence of a 32 mesh-on unpulverized material.

* Powder slush moldability The powder of the thermoplastic elastomer composition obtained in each of Examples and Comparative Examples was attached to a uniaxial rotating powder slush molding apparatus at 300 mm × 300 mm and 250 m deep.
2 kg was placed in a stainless steel square container (hereinafter, referred to as a powder supply box). 300 mm × 300 m previously heated to 230 ° C. above the powder supply box
A nickel electroformed mold with a grain having a depth of 200 mm and a depth of 200 mm was attached by a clamp, and the powder supply box and the electroformed mold with the grain were simultaneously rotated left and right by 5 rotations each. Thereafter, the mold with a grain was hit with a wooden hammer two or three times to remove excess powder. The electroformed mold with a grain was removed from the supply box, heated and melted in a heating furnace at 300 ° C. for 30 seconds, cooled with water, and a molded product was taken out from the mold. Then, the powder slush moldability of the thermoplastic elastomer composition powder was evaluated based on the properties of the molded product obtained by desorption. The evaluation criteria for the powder slush moldability are shown below.

：: There is no pinhole in the molded product. Δ: There are some pinholes in the molded product. X: Pinholes are conspicuous in the molded product and the inner surface is poor in smoothness.

FIG. 4 is a plan view of the powder supply box used in the embodiment and the comparative example, FIG. 5 is an elevation view, and FIG. 6 is a side view. FIG. 7 shows a plan view of a nickel electroformed mold with a grain pattern, and FIG. 8 shows a side view.

* Hardness The hardness was measured according to JIS K6760 (D).

* Vicat softening temperature 10 mm × 10 mm × 4 according to JIS K7206
mm test piece, put the test piece in a heating tank, 1 kg
Was applied at a rate of 50 ° C./hour, and the temperature when the tip of the indenter penetrated 1 mm was defined as the Vicat softening temperature. The used samples are described below.

Olefinic Thermoplastic Elastomer (A) A1: "Milastermer M38" manufactured by Mitsui Petrochemical Co., Ltd.
00N "(MFR at 230 ° C = 54 g / 10 min, Shore D hardness 39)

Ethylene resin (B) B1: Ethylene / 1-octene (E / O) copolymer (trade name “Affinity SM135” manufactured by Dow Chemical Company)
0 ”) (MFR at density of 0.913 g / cm ³ , 190 ° C.)
30 g / 10 min, HLMFR / MFR = 26, Mw / M
n = 2.0, one for the DSC melting point of 106 ° C.) B2: Ethylene / 1-butene (E / B) copolymer (trade name “UC Polyethylene-LL MG3, manufactured by Nippon Unicar)
65 ”) (MF of density 0.932 g / cm ³ , 190 ° C.)
R = 110 g / 10 minutes)

Propylene resin (C) C1: manufactured by Tokuyama Corporation, trade name “MH493” (23
MFR at 0 ° C 60 g / 10 min, melting point 163 ° C)

Styrenic thermoplastic elastomer (D) D1: trade name "Clayton G1657" (manufactured by Shell Japan, SEBS) MFR at 230 ° C. = 8 g / 10 min.

Example 1 As an olefin-based thermoplastic elastomer (A), trade name “Milastomer M3800N” manufactured by Mitsui Petrochemical Co., Ltd.
(Sample A1) E / O copolymer (manufactured by Dow Chemical Company, trade name “Affinity SM1350” (density 0.913 g /
cm ³ , MFR at 190 ° C. 30 g / 10 min)) (Sample B)
1) After dry blending 100 parts by weight, a pressure kneader (manufactured by Moriyama Seisakusho, device name "DS3-7.5MHH-E")
The resulting mixture was kneaded in a mold), formed into a sheet with a roll, and then pelletized to obtain a thermoplastic elastomer composition pellet. When the average dispersed particle diameter of the propylene-based polymer contained in the olefin-based thermoplastic elastomer (A1) was measured by the above-mentioned TEM observation, the average particle diameter was 0.1.
It was 2 μm.

When the obtained thermoplastic elastomer composition pellets were pulverized according to the evaluation of the pulverizability at room temperature described above, the pulverizability of the thermoplastic elastomer composition at room temperature was good. A plastic elastomer composition powder was obtained.

When the powder slush moldability of the thermoplastic elastomer composition powder obtained by the above method was evaluated, the obtained molded product weighed 258 g and had a pinhole having a thickness of 1.1 mm. The product was excellent in uniformity of wall thickness with no grain pattern clearly reproduced in detail. Table 1 shows the results.

Example 2 In Example 1, an E / B copolymer (manufactured by Nippon Unicar,
Product name "NUC polyethylene-LL MG365",
(Density 0.932 g / cm ³ , MFR at 190 ° C. = 11
0 g / 10 min)) (Sample B2) and add Sample A 1:10
Sample B1: 50 parts by weight and Sample B2: 0 parts by weight
A thermoplastic elastomer composition powder having an average particle size of 149 μm was obtained in the same manner as in Example 1 except that the amount was changed to 50 parts by weight.

The obtained thermoplastic elastomer composition powder was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

The obtained thermoplastic elastomer composition has the following composition:
The propylene-based polymer contained in the olefin-based thermoplastic elastomer (A1) has an average dispersed particle size of 0.2 μm, has good pulverizability at normal temperature, and has powder slush obtained from the thermoplastic elastomer composition powder. The molded article had a weight of 260 g and a 1.1 mm-thick pinhole-free grain pattern, and was excellent in uniformity in thickness, in which a fine pattern was clearly reproduced in detail. Table 1 shows the results.

Example 3 In Example 2, as a propylene-based resin (C), “MH493” (trade name, manufactured by Tokuyama Corporation) (23)
MFR at 0 ° C., 60 g / 10 min, melting point 163 ° C., homopolymer) (sample C1) was added, and sample B1: 70 parts by weight, sample B2: 30 parts by weight, and sample C1: 20 parts by weight per 100 parts by weight of sample A. In the same manner as in Example 1, except that the above-mentioned parts were used, a thermoplastic elastomer composition powder having an average particle size of 159 μm was obtained.

The obtained thermoplastic elastomer composition powder was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

The obtained thermoplastic elastomer composition comprises:
The average dispersion particle diameter of the propylene-based polymer contained in the propylene-based resin (C) and the olefin-based thermoplastic elastomer (A1) is 0.3 μm, the pulverizability at ordinary temperature is good, and the thermoplastic elastomer composition The powder slush molded product obtained from the powder has a molded product weight of 250.
g, a 1.1 mm-thick grain-free pattern without pinholes was clearly reproduced sufficiently in detail, and the product was excellent in thickness uniformity. Table 1 shows the results.

Example 4 In Example 3, styrene-based thermoplastic elastomer (D): trade name “Clayton G1657” (manufactured by Shell Japan, SEBS) (sample D1) was added, and sample A1: 100 parts by weight was added. On the other hand, sample B1: 50 parts by weight,
A thermoplastic elastomer composition powder having an average particle diameter of 137 μm was obtained in the same manner as in Example 1, except that the sample B2 was 50 parts by weight, the sample C was 10 parts by weight, and the sample D was 20 parts by weight.

Further, the obtained thermoplastic elastomer composition powder was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

The obtained thermoplastic elastomer composition has the following composition:
The propylene-based polymer contained in the propylene-based resin (C) and the olefin-based thermoplastic elastomer (A1) has an average dispersed particle size of 0.25 μm, has good pulverizability at normal temperature, and has good thermoplasticity. The powder slush molded product obtained from the powder has a molded product weight of 25.
A 5 g, 1.1 mm thick pinhole-free grain pattern was clearly reproduced sufficiently in detail, and was excellent in thickness uniformity. Table 1 shows the results.

Comparative Example 1 In Example 3, with respect to 100 parts by weight of sample A, 50 parts by weight of sample B, 50 parts by weight of sample B2 and sample C
A thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that the amount was changed to 1:60 parts by weight.

The obtained thermoplastic elastomer composition comprises:
The average dispersed particle size of the propylene-based polymer contained in the propylene-based resin (C) and the olefin-based thermoplastic elastomer (A1) was 0.9 μm. The obtained thermoplastic elastomer composition was pulverized at room temperature, but 15% by weight of unpulverized material remained on a 32-mesh sieve, and the pulverization was not performed at room temperature.
The powder slush molded product of the powder obtained by normal-temperature pulverization except for the one remaining on the 32 mesh sieve had pinholes, grain patterns were not clear, and the details were not sufficiently reproduced in detail.

[0077]

[Table 1]

[0078]

Industrial Applicability The thermoplastic elastomer composition of the present invention has excellent heat resistance and fluidity, and the powder obtained from the thermoplastic elastomer composition has an imprint pattern transfer property at the time of forming a skin material during slush molding. It is excellent.

[Brief description of the drawings]

FIG. 1 is a transmission electron microscope (TEM) photograph of the thermoplastic elastomer composition of the present invention.

FIG. 2 is a transmission electron microscope (TEM) photograph of the thermoplastic elastomer composition of the present invention.

FIG. 3 is a transmission electron microscope (TEM) photograph of the thermoplastic elastomer composition of the present invention.

FIG. 4 is a plan view of a powder supply box for powder slush molding used in Examples and Comparative Examples.

FIG. 5 is an elevation view of a powder supply box for powder slush molding used in Examples and Comparative Examples.

FIG. 6 is a side view of a powder supply box for powder slush molding used in Examples and Comparative Examples.

FIG. 7 is a plan view of a nickel electroforming mold with a grain for powder slush molding used in Examples and Comparative Examples.

FIG. 8 is a side view of a nickel electroforming mold with a grain for powder slush molding used in Examples and Comparative Examples.

[Explanation of symbols]

 1: Uniaxial rotation handle 2: Leather grain pattern surface (one surface only)

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Claims (14)

[Claims] 1. A thermoplastic elastomer composition comprising an olefin-based thermoplastic elastomer (A) and an ethylene-based resin (B), wherein the olefin-based thermoplastic elastomer is contained in an ethylene-based resin (B) which is a matrix when observed by a transmission electron microscope. A thermoplastic elastomer composition, wherein the propylene-based polymer contained in the thermoplastic elastomer (A) is dispersed and present as particles having an average particle diameter of 0.8 μm or less. 2. A thermoplastic elastomer composition comprising an olefin-based thermoplastic elastomer (A), an ethylene-based resin (B) and a propylene-based resin (C),
In the transmission electron microscope observation, the propylene-based polymer contained 0.8 μm in the ethylene-based resin (B) as a matrix.
m. A thermoplastic elastomer composition which is dispersed and present as particles having an average particle size of not more than m. 3. The thermoplastic elastomer composition according to claim 1, further comprising a styrene-based thermoplastic elastomer (D). 4. A thermoplastic elastomer composition comprising the thermoplastic elastomer composition according to claim 2, further comprising a styrene-based thermoplastic elastomer (D). 5. An ethylene resin (B) 8 based on 100 parts by weight of the olefin thermoplastic elastomer (A).
The thermoplastic elastomer composition according to any one of claims 1 to 4, comprising 0 to 200 parts by weight. 6. An ethylene-based resin (B) 8 per 100 parts by weight of the olefin-based thermoplastic elastomer (A).
0 to 200 parts by weight and propylene resin (C) 3 to 50
The thermoplastic elastomer composition according to claim 2 or 4, comprising parts by weight. 7. An ethylene resin (B) 8 based on 100 parts by weight of the olefin thermoplastic elastomer (A).
The thermoplastic elastomer composition according to claim 3, comprising 0 to 200 parts by weight and 3 to 50 parts by weight of the styrene-based thermoplastic elastomer (D). 8. An ethylene resin (B) 8 per 100 parts by weight of the olefin thermoplastic elastomer (A).
0 to 200 parts by weight and propylene resin (C) 3 to 50
The thermoplastic elastomer composition according to claim 4, further comprising 3 to 50 parts by weight of the styrene-based thermoplastic elastomer (D). 9. The gel dispersion has a monodispersity (weight-average molecular weight / number-average molecular weight) in the range of 1.5 to 3.0 in gel permeation chromatography, and a melting point substantially determined by differential scanning calorimetry. 9. The thermoplastic elastomer composition according to claim 1, wherein one of the ethylene-based resins (B) is used. 10. The method according to claim 1, wherein:
13. A thermoplastic elastomer composition powder comprising the thermoplastic elastomer composition described in the item 6 and having an average particle size of 50 to 500 μm. 11. The method according to claim 1, wherein
The thermoplastic elastomer composition powder according to claim 10, which is obtained by pulverizing the thermoplastic elastomer composition according to the above item at ordinary temperature. 12. The method according to claim 1, wherein:
A skin material comprising the thermoplastic elastomer composition described in the above item. 13. A skin material obtained by molding the thermoplastic elastomer composition powder according to claim 10 or 11. 14. A skin material obtained by subjecting the thermoplastic elastomer composition powder according to claim 10 or 11 to powder slush molding.