JP2000007846A - Thermoplastic elastomer composition, powder of the same composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer composition capable of providing a molded product excellent in appearance and tensile characteristics even at a relatively low molding temperature such as about 210 deg.C in the thermoplastic elastomer composition consisting essentially of a polyolefin-based resin and a hydrogenated vinyl-aromatic compound-conjugated diene compound copolymer, a powder of the composition and the molded product prepared by using the powder. SOLUTION: This thermoplastic elastomer composition comprises 100 pts.wt. of a polyolefin-based resin and 10-250 pts.wt. of a hydrogenated vinyl-aromatic compound-conjugated diene compound copolymer and has <=3×104 P complex dynamic viscosity η* (0.1) at 210 deg.C. The powder of the thermoplastic elastomer composition comprises the thermoplastic elastomer composition. The molded product uses the powder of the thermoplastic elastomer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition, a powder of the composition, and a molded product obtained by powder-forming the powder. More specifically, the present invention relates to a thermoplastic elastomer composition containing a hydrogenated product of a polyolefin resin and a vinyl aromatic compound-conjugated diene compound copolymer as essential components, and has a relatively low temperature of about 210 ° C. Even at molding temperature,
The present invention relates to a thermoplastic elastomer composition capable of providing a molded article having excellent appearance and tensile properties, a powder of the composition, and a molded article obtained by using the powder.

[0002]

2. Description of the Related Art Conventionally, a sheet-like molded article having a complex uneven pattern such as a grain or a stitch on the surface has been used as a skin material for an automobile interior part or the like. As such a molded article, as an alternative to the conventional vinyl chloride-based resin molded article, an olefin-based thermoplastic elastomer comprising a block copolymer containing a polymer block of a crystalline polyolefin resin and styrene or a derivative thereof is pulverized. A molded product obtained by spin-molding and spray-molding the resulting powder has been proposed (see JP-A-7-96529 and JP-A-7-96532). However, when the powder obtained by pulverizing the thermoplastic elastomer is used in a powder slush molding method in which a shearing force from the outside is hardly applied and the molding cycle is as short as about 5 minutes, a relatively high temperature of about 210 ° C. When molded at a low temperature, the melt flow properties are insufficient, and there is a problem that the resulting molded article has poor appearance and insufficient rupture strength.

Further, a powder resin composition obtained by pulverizing a mixture of a polypropylene resin and a styrene-based thermoplastic elastomer containing a styrene polymer block, and a molded product obtained by subjecting it to powder slush molding have been proposed. (See Japanese Patent Application Laid-Open No. 7-82433).
However, also in this case, when molded at a relatively low temperature, such as about 210 ° C., the melt flow properties are insufficient, and the same problem is caused in that the obtained molded article has poor appearance and insufficient strength.

[0004]

Under such circumstances, an object of the present invention is to provide a polyolefin resin and a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer as essential components. A thermoplastic elastomer composition which can provide a molded article having excellent appearance and tensile properties even at a relatively low molding temperature of about 210 ° C., and a powder obtained by using the composition powder and the powder. It is in providing a molded object.

[0005]

That is, the first aspect of the present invention provides the following (a) 100 parts by weight and (b) 1
The present invention relates to a thermoplastic elastomer composition containing 0 to 250 parts by weight and having a complex dynamic viscosity η ^* (0.1) at 210 ° C. of 3 × 10 ⁴ poise or less. (A): Polyolefin-based resin (B): Hydrogenated product of vinyl aromatic compound-conjugated diene compound copolymer The second invention of the present invention relates to the thermoplastic elastomer composition powder of the first invention. It is related. A third aspect of the present invention relates to a powder molding method using the thermoplastic elastomer composition powder of the second aspect. The fourth invention of the present invention relates to a molded product obtained by powder molding the thermoplastic elastomer composition powder of the second invention. The fifth invention of the present invention relates to a two-layer molded product in which a foamed layer is laminated on one surface side of the molded product of the fourth invention. The sixth invention of the present invention relates to a multilayer molded product in which a thermoplastic resin core is laminated on one surface side of the molded product of the fourth invention. A seventh aspect of the present invention is directed to a method for producing a multilayer molded article according to the sixth aspect of the invention, in which a thermoplastic resin melt is supplied to one surface side of the molded article of the fourth aspect and pressurized. It is.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The component (a) of the present invention is a polyolefin resin, and is at least one selected from homopolymers or copolymers of olefins having high crystallinity. As the olefin, ethylene, propylene,
Examples thereof include olefins having 2 to 8 carbon atoms such as 1-butene, 1-hexene and 1-octene. Examples of (a) include polyethylene, polypropylene, poly (1-butene), and copolymers of propylene with other α-olefins (eg, 1-butene). (I)
Is propylene-ethylene copolymer resin or propylene-
When it is a 1-butene copolymer resin, the thermoplastic elastomer composition of the present invention is preferable in that it can provide a molded article having excellent heat resistance and flexibility. The crystallinity of (a) is 5
It is necessary to be 0% or more, and preferably 60% or more. Here, the crystallinity refers to the heat of fusion of the copolymer relative to the heat of fusion of a crystalline polyolefin homopolymer (stereoregularity of 99% or more) consisting of only the olefin unit having the highest content in the polyolefin resin. Indicates the ratio. The heat of fusion is determined by the DSC method.

A copolymer obtained by copolymerizing two or more monomers selected from ethylene and an α-olefin having 3 to 8 carbon atoms in two or more stages can also be used. For example, a copolymer obtained by homopolymerizing propylene in the first step and copolymerizing propylene with ethylene or an α-olefin other than propylene in the second step can be used.

[0008] From the viewpoint of the strength of the molded product obtained by the powder molding method, the melt flow rate (MFR) measured at 230 ° C under a load of 2.16 kgf in accordance with JIS K-7210 (a) is usually 20-500g / 10
Min, preferably 50 to 300 g / 10 min, particularly preferably 100 to 300 g / 10 min.

The component (b) of the present invention is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer.

Examples of the vinyl aromatic compound (b) include vinyl aromatic compounds having 8 to 12 carbon atoms such as styrene, p-methylstyrene and α-methylstyrene. Styrene is preferred from the viewpoint of price.

The conjugated diene compound (b) includes butadiene, isoprene, 1,3-pentadiene, 1,3-
Hexadiene and the like. These may be used alone or in combination of two or more.

Specific examples of (b) include styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-isoprene block copolymer, styrene-butadiene-styrene block copolymer, and styrene- Examples include hydrogenated products of isoprene-styrene block copolymer or styrene-butadiene-isoprene-styrene block copolymer. Among these, a hydrogenated product of a styrene-butadiene-isoprene-styrene block copolymer is preferred from the viewpoint of cold resistance and heat resistance (no stickiness and glossiness) of the obtained molded article. In addition, "-" indicates the boundary between each copolymer block, and "•" indicates that two or more conjugated diene compounds are used in combination in the block.

The content of the vinyl aromatic compound (b) is as follows:
From the viewpoint that a molded article having excellent flexibility can be obtained, 50
% By weight or less, more preferably 2 to 20% by weight.
It is. If this content exceeds 50% by weight, the molded article obtained by molding the thermoplastic elastomer composition tends to be hard, and the feel tends to decrease.

(B) may be a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer containing a vinyl ester compound, an ethylenically unsaturated carboxylic acid ester compound or a vinyl nitrile compound. When these are used, when the obtained molded article is bonded to the polyurethane foam layer to produce a two-layer molded article or a composite molded article, an advantage that the adhesiveness is improved can be obtained.

The conjugated diene compound block (b) may contain a vinyl aromatic compound unit. In this case, the content of the unit is usually 10% by weight or less of the block.

The hydrogenation rate of (b) is usually 70% or more, preferably 80% or more, and more preferably 90% or more, from the viewpoint of light resistance and heat resistance of the obtained molded article.

In the conjugated diene compound block (b), the number of carbon atoms relative to the number of all hydrogenated conjugated diene units is 2
The proportion of the number of hydrogenated conjugated diene units having the above side chains varies depending on the type of the conjugated diene monomer used in the polymerization, but is usually 50% or more, preferably 60 to 95%. And more preferably 70 to 90% from the viewpoint of the flexibility of the obtained molded body. The percentage is
It can be determined by ¹ H-NMR measurement. Note that a block unit having a high ratio and a block unit having a low ratio may coexist in the block. In a block unit having a high ratio, the ratio is usually 70 to
In a block unit having a low ratio of 95%, the ratio is usually 30 to 70%. However, the ratio in the entire area in the block is preferably adjusted as described above.

The MFR (value obtained at 230 ° C. under a load of 2.16 kgf according to JIS K-7210) of (b) is 2 to 20 from the viewpoint of the strength of the obtained molded body.
0 g / 10 min is preferable, and more preferably 5 to 100 g / 10 min.
Min, particularly 10 to 100 g / 10 min, from the viewpoint of obtaining a molded article having excellent appearance and strength.

(B) is disclosed, for example, in Japanese Patent Application Laid-Open No. 2-36244.
JP, JP-A-3-72512, JP-A-7-11
It can be produced by the methods described in JP-A-8335, JP-A-5-70699, JP-A-56-38338 and JP-A-61-60739.

The thermoplastic elastomer composition of the present invention comprises:
In addition to the essential components (A) and (B), (C) 250 parts by weight or less of an ethylene-α-olefin copolymer,
Preferably, it may contain 150 parts by weight or less. When containing (c), without significantly reducing the powder moldability of the thermoplastic elastomer powder,
Provide a thermoplastic elastomer composition having excellent cost performance and cold resistance. If the content of (c) is excessive, the resulting molded article may have a sticky feeling.

The ethylene-α-olefin-based copolymer (c) is a copolymer of ethylene and α-olefin, a copolymer of ethylene-α-olefin and non-conjugated diene, and the like. A polymer having little or no crystallinity of less than 50%. Here, the crystallinity refers to a crystalline polyethylene homopolymer (stereoregularity of 99).
% Or more) of the copolymer. The heat of fusion is determined by the DSC method. Here, as the α-olefin, propylene, 1-butene, 3-
Α-olefins having 3 to 10 carbon atoms such as methyl-1-butene include dicyclopentadiene, 5-ethylidene 2-norbornene, 1,4-hexadiene, 1,5-cyclooctadiene and -Methylene-
Examples thereof include non-conjugated dienes having 5 to 15 carbon atoms such as 2-norbornene. Such ethylene-α-
Examples of the olefin-based copolymer include an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-propylene-5-ethylidene-2-norbornene copolymer (hereinafter, referred to as “EPDM”), and ethylene-propylene.
Examples include an ethylene / butylene / ethylene block copolymer and an ethylene / ethylene / propylene / ethylene block copolymer. These copolymers can be obtained by a copolymerization reaction of ethylene and α-olefin or a hydrogenation reaction after the polymerization of a conjugated diene compound such as butadiene or isoprene (see JP-A-3-74409). Such an ethylene-α-olefin-based copolymer may be crosslinked.

The α-olefin unit content in the ethylene-α-olefin copolymer is preferably in the range of 5 to 40% by weight, more preferably 10 to 35% by weight. α
-Olefin unit content and ethylene unit content are ¹³
It can be determined by a C-NMR method, infrared absorption spectroscopy, or the like. When a molded article is produced by a powder slush molding method using the powder of the thermoplastic elastomer composition of the present invention, from the viewpoint of the strength of the obtained molded article, the ethylene-α-olefin-based AS
The Mooney viscosity {ML _{1 + 4} (100 ° C.)} measured at 100 ° C. according to TM D-927-57T is preferably 1
It is in the range of 0 to 350, more preferably 15 to 300.

The thermoplastic elastomer composition of the present invention comprises:
Complex dynamic viscosity η ^* (0.1) at 210 ° C. is 3 × 1
0 ⁴ poise is of less, preferably 1 × 10 ² to 2
× 10 ⁴ poise.

The complex dynamic viscosity η ^* (ω) is calculated at a temperature of 210
° C, storage elastic modulus G 'at vibration frequency ω radian / sec
(Ω) and the loss elastic modulus G ″ (ω) are values calculated by the following equation (1). η ^* (0.1) is the value of the complex dynamic viscosity at ω = 0.1 rad / sec. η ^* (ω) = ｛[G ′ (ω)] ² + [G ″ (ω)] ² ｝ ^1/2 / ω (1)

When η ^* (0.1) exceeds the above upper limit,
The melt fluidity of the thermoplastic elastomer composition is inferior, and it tends to be difficult to produce a molded article by a molding method having a low shear rate during molding such as a powder slush molding method.

As a method for obtaining the thermoplastic elastomer composition of the present invention, for example, the following method can be mentioned. That is, (a) and (b) and (c) if necessary may be melt-kneaded. In addition, after kneading or dynamically cross-linking all or several kinds selected from (a) and (b) and, if necessary, (c), the non-selected components are melt-kneaded. Can be. For example, the thermoplastic elastomer composition of the present invention in which (a) and / or (c) is intramolecularly and / or intermolecularly crosslinked, usually comprises (b) and (c) after dynamic crosslinking. And kneading after adding (b). Here, a single-screw extruder or a twin-screw extruder can be used for kneading. In addition, as for the compounding of various additives described later, for example, (a), (b), or (c) in which these additives are compounded in advance, or
It can be carried out by mixing the above components during kneading or dynamic crosslinking.

The dynamic crosslinking of the kneaded mixture can be carried out, for example, by kneading the kneaded mixture and a crosslinking agent under heating. As the crosslinking agent, usually, 2,5-dimethyl-2,5-di (tert-butylperoxyno) is used.
Organic peroxides such as hexane and dicumyl peroxide are used. The crosslinking agent is usually not more than 1 part by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the total of the components to be crosslinked among (A), (B) and if necessary (C).
0.8 parts by weight, more preferably 0.2 to 0.6 parts by weight. When an organic peroxide is used as a cross-linking agent, when dynamic cross-linking is performed in the presence of a cross-linking aid such as a bismaleimide compound, a thermoplastic elastomer composition that gives a molded article having excellent heat resistance can be obtained. Can be. In this case, the amount of the organic peroxide to be used is usually 0 per 100 parts by weight of the total of the components to be crosslinked among (a), (b) and, if necessary, (c). .8
Parts by weight or less, preferably 0.2 to 0.8 parts by weight, more preferably 0.4 to 0.6 parts by weight.

The amount of the crosslinking aid to be used is usually not more than 1.5 parts by weight, preferably not more than 1.5 parts by weight, per 100 parts by weight in total of (a), (b) and, if necessary, (c).
It is in the range of 0.2 to 1 part by weight, more preferably 0.4 to 0.8 part by weight. The crosslinking aid is preferably added before the addition of the crosslinking agent, and is usually added when the components to be crosslinked are preliminarily kneaded.

The cross-linking of (a), (b) and, if necessary, (c) is carried out by uniaxially extruding the components to be cross-linked, a cross-linking agent and, if necessary, a cross-linking assistant while heating. Under heating using an extruder or twin-screw extruder,
It can be performed by kneading in a temperature range of up to 250 ° C.

The thermoplastic elastomer composition of the present invention comprises:
For example, mineral oil-based softeners, heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based, and amide-based, anti-aging agents, weather-resistant stabilizers, antistatic agents, metallic soaps, waxes And other additives, coloring pigments and the like.

A thermoplastic elastomer composition containing a mineral oil-based softener can give a molded article having excellent melt fluidity and flexibility.

The thermoplastic elastomer composition containing a coloring pigment can give a molded article which is hardly decolored when the surface of the molded article is rubbed with a dry cloth or a cloth wetted with an organic solvent.

In addition, rubbery polymers such as natural rubber, butyl rubber, chloroprene rubber, epichlorohydrin rubber, acrylic rubber, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and saponified product thereof, ethylene- Other polymer components such as methyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer are contained within a range that does not impair the effects of the present invention. Is also good.

These additives and other polymer components are:
(A), (b) and, if necessary, (c) may be used by being contained in advance, or may be blended during or after the above-mentioned kneading or dynamic crosslinking.

In order to produce the thermoplastic elastomer composition of the present invention that satisfies the above-mentioned complex dynamic viscosity, the degree of the above-mentioned kneading and dynamic cross-linking, the components constituting the thermoplastic elastomer composition, And the amount thereof, the type and amount of a crosslinking agent and a crosslinking aid in dynamic crosslinking, the amount of the additive, the type of the additive and the amount thereof are appropriately selected. Above all, the shear rate in kneading and dynamic crosslinking greatly affects the above physical properties, and it is preferable to perform kneading and dynamic crosslinking at a shear rate of 1 × 10 ³ sec ⁻¹ or more.

The thermoplastic elastomer composition powder of the present invention can be powdered by a method such as a method of mechanically pulverizing the thermoplastic elastomer obtained by the above-mentioned method, a strand cut method, a die face cut method, a solvent treatment method or the like. It is manufactured by doing.

Here, as a method of mechanically pulverizing the thermoplastic elastomer composition, a freezing pulverization method or a normal temperature pulverization method can be used. The freeze-pulverization method is a method for preparing the thermoplastic elastomer composition at a temperature lower than its glass transition temperature, preferably -70 ° C.
Hereinafter, it is more preferable to cool the powder to -90 ° C or less, and pulverize while keeping the cooled state. It is also possible to pulverize the thermoplastic elastomer composition at a temperature higher than its glass transition temperature (normal temperature pulverization method), but the particle size of the obtained pulverized material tends to be uneven, and powder molding tends to be difficult. .

In order to grind the thermoplastic elastomer composition while keeping it in a cooled state, it is preferable to grind by a method with good grinding efficiency and low heat generation, for example, mechanical grinding using an impact grinder such as a ball mill. Method is used. The powder of the thermoplastic elastomer composition in this method has a size normally passing through a Tyler standard sieve 24 mesh (mesh size 700 μm × 700 μm), and preferably 28 mesh (mesh size 590 μm × 59).
0 μm), and more preferably 32 μm.
Mesh (aperture 500 μm × 500 μm), particularly preferably 42 mesh (aperture 355 μm × 355 μm)
Is the size that passes through.

The thermoplastic elastomer composition powder can also be produced by a strand cut method, a die face cut method, or a solvent treatment method. The powder obtained by these methods has a sphere-converted average particle diameter of 1.2 m.
m and a bulk specific gravity of 0.38 or more. The molded article of the present invention obtained from the thermoplastic elastomer composition powder obtained by these methods is used to mold a molded article having a complicated shape such as a convex portion as compared with the powder obtained by the mechanical pulverization method described above. It is excellent in that defects such as underfill and pinholes hardly occur in such cases.

Here, the sphere-equivalent average particle diameter is a particle diameter calculated as the diameter of a sphere having the same volume as the average volume of the thermoplastic elastomer composition powder obtained by calculating the average volume of the thermoplastic elastomer composition powder. It is a value calculated from the total weight of 100 pieces of the thermoplastic elastomer composition powder taken out arbitrarily and the density of the thermoplastic elastomer composition, preferably 1.0 mm or less, more preferably 0.1 mm or less.
０．９0.9 mm. When the sphere-equivalent average particle size exceeds 1.2 mm, heat fusion between powders during powder molding becomes insufficient, and pinholes and underfilling tend to occur in the obtained molded product.

[0041] The bulk specific gravity is defined as 100 m of the thermoplastic elastomer composition powder supplied from a bulk specific gravity measuring funnel to a bulk specific gravity measuring container in accordance with JIS K-6721.
It is a value calculated from the weight of 1 and is usually 0.38 or more, preferably 0.42 or more. Bulk specific gravity 0.38
If it is less than 3, depending on the inner surface shape of the mold, the powder adheres insufficiently on the surface of the mold during powder molding, and pinholes or underfilling tend to occur in the molded body.

The strand cutting method is a method in which a thermoplastic elastomer composition is melted by heat, extruded from a die to form a strand, and then the strand is taken or stretched and taken, and then cooled and cut (for example, see Japanese Unexamined Patent Publication No. No. 50-149747).
The die face cutting method is a method in which a thermoplastic elastomer composition is hot-melted and then cut near the discharge port of the die while extruding the same from a die into water. The solvent treatment method is a method in which a thermoplastic elastomer composition is pulverized at a temperature equal to or lower than its glass transition point, and then subjected to a solvent treatment to form a spheroid (for example, see JP-A-62-280226).
It is.

When manufactured by the strand cutting method, the discharge diameter of the die is usually in the range of 0.1 to 3 mm, preferably 0.2 to 2 mm, and the discharge speed from the die is usually 0.1 to 5 kg / hour / discharge. Outlet, preferably 0.5-3
The range of kg / hour / discharge port and the take-off speed of the strand are usually 1 to 100 m / min, preferably 5 to 50 m / min. The cut length after cooling is usually 1.4 mm or less, preferably 1.2 mm or less.

In the case of manufacturing by a die face cut method, the discharge diameter of the die is usually in the range of 0.1 to 3 mm, preferably 0.2 to 2 mm, and the discharge speed from the die is usually 0.1 to 5 kg / hour / hour. Discharge port, preferably 0.5 to 3
kg / hour / discharge port range. Usually 1 to 1000
A die having about the number of discharge ports is used. The die temperature is usually set at 150 to 350 ° C. If the die temperature is 150 ° C. or lower, there is a problem that the discharge port is clogged, and if the die temperature exceeds 350 ° C., there is a problem that the powder adheres to each other. The water temperature is usually set at 20 to 80C. If the water temperature is lower than 20 ° C., the problem of clogging of the discharge port occurs, and if the water temperature exceeds 80 ° C., the powder tends to adhere to each other.

When produced by a solvent treatment method, the thermoplastic elastomer composition has a temperature below its glass transition point,
Usually, it is pulverized at a temperature of -70 ° C or less, preferably -90 ° C or less, and then treated with a solvent. Here, the solvent treatment means that the pulverized thermoplastic elastomer composition is stirred in the presence of a dispersant and an emulsifier in a medium having a low compatibility with the pulverized thermoplastic elastomer composition, at or above the melting temperature of the thermoplastic elastomer composition, preferably This is a method of heating to a temperature 30 to 50 ° C. higher than the melting temperature to form a spheroid, then cooling and taking out.

As the medium in the solvent treatment, for example, ethylene glycol, polyethylene glycol,
Polypropylene glycol and the like are used, and the amount of use is usually 300 to 1000 parts by weight, preferably 400 to 80 parts by weight, based on 100 parts by weight of the thermoplastic elastomer used.
The range is 0 parts by weight.

Examples of the dispersant include ethylene-acrylic acid copolymer, silicic anhydride, titanium oxide and the like. The amount of the dispersant is usually 5 to 20 parts by weight, preferably 100 to 100 parts by weight of the thermoplastic elastomer used. Is 10-1
The range is 5 parts by weight.

Examples of the emulsifier include, but are not limited to, polyoxyethylene sorbitan monolaurate, polyethylene glycol monolaurate, sorbitan tristearate and the like. It is usually in the range of 3 to 15 parts by weight, preferably 5 to 10 parts by weight based on parts by weight.

The powder of the thermoplastic elastomer composition obtained by such a method has (d) a primary particle size of 30.
Fine powder having a size of 0 nm or less may be blended. Examples of the fine powder include powder pigments, inorganic oxides, vinyl chloride resins for pastes, and fatty acid metal salts. By blending (d), a powder having excellent powder fluidity can be obtained without lowering the meltability of the thermoplastic elastomer composition powder.

The primary particle size of (d) needs to be 300 nm or less, preferably 200 nm or less, more preferably 5 nm to 150 nm. Primary particle size is 300
If it exceeds nm, the powder flowability of the obtained thermoplastic elastomer powder may not be sufficiently improved. Here, the primary particle size means that a photograph of (d) is taken by a transmission electron microscope (TEM), about 1,000 particles are arbitrarily selected, the diameter of the particles is measured, and the diameter of these particles is determined. It is the value divided by the number of particles.

As the inorganic oxide, alumina, silica,
Alumina silica and the like can be mentioned.

Almost all aluminas have the chemical formula Al ₂
It is a fine powder composed of O ₃ units. Alumina has various crystal forms, and any of the crystal forms can be used. These are called α-alumina, β-alumina, γ-alumina, etc. depending on the crystal form. Alumina C (γ-alumina) manufactured by Degussa, AKP-G008 (α-alumina) manufactured by Sumitomo Chemical Co., Ltd.
And so on. Silica is a fine powder that is mostly composed of SiO ₂ units of the chemical formula. Manufactured by methods such as pulverization of natural diatomaceous earth and decomposition of sodium silicate. OX50 manufactured by Degussa Corporation and the like can be mentioned. Alumina silica is an inorganic oxide containing the aforementioned alumina and silica as main components. The surface of these inorganic oxides may be coated with poly (dimethylsiloxane) or the like, or may be surface-treated with a compound having a trimethylsilyl group or the like.

Examples of powder pigments include organic pigments such as azo, phthalocyanine, sulene, and dye lakes, oxides such as titanium oxide, molybdic acid chromate, selenium sulfide compounds, ferrocyan compounds, and carbon black. Are used.

These (d) are used alone or in combination of two or more having a primary particle size of 300 nm or less. For example, an inorganic oxide alone can be used, or a powdered pigment and an inorganic oxide can be used in combination.

When a powder pigment is used, a pigment supported on a carrier such as calcium carbonate, metal soap, or magnesium oxide can also be used. In this case, the primary particle size of the carrier is usually 10 μm or less, preferably 1 to 5 μm. In this case, the weight ratio between the powder pigment and the carrier is usually 2
0: 80-80: 20, preferably 25: 75-75:
25. In the case where a powder pigment supported on a carrier is used as (d), the weight of the carrier is not included. The case where the primary particle size of the carrier is more than 300 nm and 10 μm or less is included in (e) described later.

(D) The amount of the fine powder to be added is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the thermoplastic elastomer powder. If the amount is less than 0.1 part by weight, good powder flow characteristics and powder moldability cannot be obtained. If the amount exceeds 5 parts by weight, the heat-fusibility between the pulverized product particles is reduced, and the strength of the obtained molded body tends to be poor.

The method of blending (d) the fine powder with the pulverized thermoplastic elastomer is not particularly limited as long as (d) the fine powder is uniformly adhered to the pulverized thermoplastic elastomer. Not something. For example, a method of blending using a blender with a jacket, a high-speed rotary mixer, or the like can be used. Among them, a method of uniformly dispersing and preventing powder cohesion by applying a shearing force, such as a Henschel mixer or a super mixer, is preferred. The compounding is usually performed at room temperature.

The thermoplastic elastomer composition powder used in the present invention is used in addition to (d) the fine powder and 100 parts by weight of the thermoplastic elastomer composition powder ((however, (d) before blending)). , (E) the primary particle size is 300
0.1 to 5 parts by weight of powder having a size exceeding 10 nm and not more than 10 nm may be blended. Here, (e) may be mixed with (e) at the same time as (d) above, or after (d) is mixed, or (d) may be mixed after (e) is mixed. May be.

In this case, it is possible to obtain a thermoplastic elastomer composition powder which is more excellent in bulk specific gravity (packing properties) and coagulation resistance than when (e) is used alone. Examples of (e) include inorganic oxides such as alumina, silica, and alumina-silica, calcium carbonate, vinyl chloride resin for paste, and fatty acid metal salts similar to (d). (E) is added in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the pulverized thermoplastic elastomer. If the amount exceeds 5 parts by weight, the heat fusion between the thermoplastic elastomer powders of the present invention tends to decrease, and the strength of the obtained molded article tends to be poor. In this case, (e) and (d)
Is usually from 20:80 to 80:20, preferably from 25:75 to 60:40.

The above-mentioned thermoplastic elastomer composition powder can be applied to various powder molding methods such as a powder slush molding method, a fluid immersion method, an electrostatic coating method, a powder spraying method, and a powder rotational molding method. Particularly preferred examples of the powder molding method include a powder slush molding method including the following steps. First step: a step of supplying the thermoplastic elastomer composition powder of the present invention onto a molding surface of a mold heated to a melting temperature of the thermoplastic elastomer composition or higher. First, the thermoplastic elastomer composition powder is mixed with the composition. The product is supplied onto a molding surface of a mold heated to a temperature higher than the melting temperature of the product, usually from 160 to 320 ° C, preferably from 180 to 300 ° C. The mold is heated by, for example, a gas heating furnace method, a heat medium oil circulation method, a dipping method in heat medium oil or hot fluidized sand, a high-frequency induction heating method, or the like. Second step: a step of heating the powder obtained in the first step on the molding surface of the first step for a predetermined time, and fusing powders having at least their surfaces fused to each other. It is appropriately selected according to the thickness of the molded article to be formed. Third step: after a lapse of a predetermined time in the second step,
Step of recovering unfused powder Fourth step: If necessary, a step of further heating the mold on which the molten thermoplastic elastomer composition powder is placed. When heating, the mold is, for example, a gas heating furnace. Method, heat medium oil circulation method, immersion method in heat medium oil or hot fluidized sand,
It is heated by a high frequency induction heating method or the like. Fifth step: After the fourth step, the mold is cooled, and the sheet formed thereon is removed from the mold. Also, the molded article that has been subjected to powder molding with the thermoplastic elastomer composition powder of the present invention is When the mold is released from the mold, the adhesion to the inner surface of the mold may be increased. If the mold is forcibly removed, the obtained molded body may be broken. in this case,
The inner surface of the mold is preferably coated in advance with a silicon-based spray or a fluorine-based spray. It is also effective to add the above-mentioned lubricant internally during the production of the thermoplastic elastomer composition. The amount of the lubricant is usually 5 parts by weight or less, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the thermoplastic elastomer powder. If the amount of the lubricant exceeds 5 parts by weight, problems such as reduction in the strength of the obtained molded article and contamination of the mold surface may occur. In addition, the thermoplastic elastomer composition powder of the present invention containing a foaming agent is powder-molded and further foamed, whereby a foamed molded article can be produced.

The foaming agent may be contained in the powder or pellets in advance, or may be coated on the surface of the thermoplastic elastomer composition powder by a rotary mixer such as the aforementioned Henschel mixer.
The foaming agent may be blended after obtaining the thermoplastic elastomer composition powder by the above-described method, or may be blended simultaneously with the fine powder used in the present invention.

As the foaming agent, a pyrolytic foaming agent is usually used. Examples of such a pyrolytic foaming agent include azo compounds such as azodicarbonamide, 2,2′-azobisisobutyronitrile, and diazodiaminobenzene, benzenesulfonyl hydrazide, benzene-1,3-sulfonyl hydrazide, p- Sulfonyl hydrazide compounds such as toluenesulfonyl hydrazide, N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-
Examples include nitroso compounds such as N, N'-dimethylterephthalamide, azide compounds such as terephthalazide, and carbonates such as sodium bicarbonate, ammonium bicarbonate and ammonium carbonate. Among them, azodicarbonamide is preferably used. The compounding of the blowing agent is usually performed at a temperature equal to or lower than the decomposition temperature of the blowing agent. Further, the thermoplastic elastomer composition powder of the present invention may contain a foaming aid and a cell regulator together with the foaming agent.

The molded product obtained by molding the thermoplastic elastomer composition powder of the present invention is useful as a skin material, and a two-layer molded product in which a foam layer is laminated on one surface side is used as a skin material. May be used. Such a two-layer molded body can be integrally manufactured by a powder molding method (see Japanese Patent Application Laid-Open No. 5-473 or the like), or a separately manufactured foam is added to the molded body obtained above with an adhesive or the like. It can also be manufactured by a method of bonding.

In order to produce a two-layer molded product by the powder molding method, for example, a mold which may have a complicated pattern on its molding surface is heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition. The above-mentioned thermoplastic elastomer composition powder is supplied onto the molding surface of a mold, and the powders are thermally fused to each other to obtain a sheet-like melt on the molding surface, and then the extra powder which is not thermally fused. Is removed, and then a thermoplastic elastomer powder containing a foaming agent on the sheet-like melt (whether or not a fine powder is compounded or not) can be used. ) Is supplied, and the powders are thermally fused to each other to obtain a sheet-like molten material on the molding surface. Then, excess powder that has not been thermally fused is removed, and then further heated to expand the foam. Shape layers It is sufficient to.

Further, by a powder molding method, a three-layer molded article composed of the non-foamed layer (1) -foamed layer (2) -non-foamed layer (3) made of the thermoplastic elastomer of the present invention can be obtained. . In this case, the non-foamed layer (3) may be the same as or different from the non-foamed layer (1).

Further, as a thermoplastic polymer composition containing a foaming agent, a polyethylene foamable composition powder used in JP-A-7-228720 can be used. Fine powder used in the present invention may be blended with the polyethylene foamable composition powder.

A polyurethane foam may be used as the foam layer. In this case, since the adhesiveness between the thermoplastic elastomer composition of the present invention and polyurethane tends to be inferior, the adhesiveness is usually improved by pre-treating the adhesive surface of the molded article with a primer such as chlorinated polyethylene. Can be. The polyurethane foam is fixed at a predetermined position with a predetermined gap between the molded body and a core material described below,
A mixture of a polyol and a polyisocyanate is injected into the gap and foamed under pressure to be molded.

Such a molded article or a two-layer molded article is suitable as a skin material laminated on a thermoplastic resin core material. For example, the above-mentioned molded article is a multilayer material having a thermoplastic resin core material laminated on one surface side. It can be used for a molded article, and the two-layer molded article can be used for a multilayer molded article in which a thermoplastic resin core is laminated on the foam layer side.

As the thermoplastic resin in the thermoplastic resin core material, for example, a polyolefin such as polypropylene or polyethylene, or a thermoplastic resin such as an ABS (acrylonitrile-butadiene-styrene copolymer) resin is used. Among them, polypropylene is preferably used.

In such a multilayer molded article, for example, a thermoplastic resin melt is supplied to one surface side of the molded article and pressurized, or the thermoplastic resin melt is supplied to the foam layer side of the two-layer molded article, and heat treatment is performed. It can be easily manufactured by a pressing method.

The thermoplastic resin melt is a thermoplastic resin which is heated to a temperature higher than its melting temperature and is in a molten state. The supply of the thermoplastic resin melt may be before the pressurization or may be simultaneous with the pressurization. The pressurization may be performed by using a mold or the like, or may be performed by the supply pressure of the thermoplastic resin melt. Examples of such a molding method include an injection molding method, a low-pressure injection molding method, and a low-pressure compression molding method.

Specifically, for example, when the above-mentioned molded body is used as a skin material, the molded body is supplied between a pair of opened molds, and then, one surface side of the molded body and this After supplying or supplying the thermoplastic resin melt between one of the opposing molds, both molds may be clamped, and in the case of using a two-layer molded body as the skin material, an open pair is used. After supplying the two-layer molded body between the molds, and then supplying or while supplying the thermoplastic resin melt between the foamed layer of the molded body and one of the molds opposed thereto, the two molds are supplied. You only have to clamp the mold. Here, the opening / closing direction of the two dies is not particularly limited, and may be a vertical direction or a horizontal direction.

In the case where a molded product or a two-layer molded product produced using the above-mentioned powder molding die is used as the skin material,
The powder molding die can be used as one of the dies in the production of the multilayer molded body while holding the molded body or the two-layer molded body on the molding surface. According to this method,
Since the molded article or the two-layer molded article on which the pattern of the mold has been transferred is supplied between the molds without being separated from the mold, the pattern formed on the surface of the molded article is hardly destroyed, and the desired multilayer molding is performed. You can get the body.

The thermoplastic resin melt may be supplied after the clamping of both molds is completed. However, a multilayer molded article in which a molded article or a two-layer molded article as a skin material has a small displacement and the degree of pattern transfer is improved. It is preferable that both dies be clamped during or after supply while both dies are not closed.
The method of supplying the thermoplastic resin melt is not particularly limited. For example, the thermoplastic resin melt can be supplied from a resin passage provided in one of the molds facing the molded product or the two-layer molded product.
Alternatively, the supply nose of the molten resin may be inserted between the two dies to supply the molten resin, and thereafter, the supply nose may be retracted outside the system to close both the dies.

As the pair of dies, a pair of male and female dies in which the outer peripheral surface of one die and the inner peripheral surface of the other die can slide can be used. In this case, by keeping the clearance between the sliding surfaces of the two dies approximately equal to the thickness of the molded article or the two-layer molded article, a multilayer molded article having an extra skin material at its end can be obtained. By folding this extra skin material on the back surface of the multilayer molded body, a multilayer molded body whose end is covered with the skin material layer can be obtained.

Each of the molded bodies described above includes, for example, an instrument panel, a door trim, a console box, an armrest, a headrest, a glove box,
Automotive interior materials such as ceiling cover materials, cover materials such as chairs and chairs, stationery items such as mouse pads and file covers, saddle skins such as bicycles, handle grips, telephones, camera exteriors, and home appliance parts such as headphones. Can be used in various fields.

[0077]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The following methods were used to evaluate the thermoplastic elastomer composition and the molded article. [1] Complex dynamic viscosity η ^* (0.1) Dynamic analyzer (RD) manufactured by Rheometrics
S-7700 type), the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ (ω) are converted to the vibration frequency ω = 0.1 radian /
The complex dynamic viscosity η ^* (0.1) was calculated by the above formula (1). The measurement was performed in a parallel plate mode, at an applied strain of 5%, and at a sample temperature of 210 ° C. [2] Ratio of the number of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to the number of all hydrogenated conjugated diene units in (b), using o-xylene-d10 as a solvent, 0.6 mg / m
It was determined by measuring the ¹ H-NMR spectrum (400 MHz) at ¹ concentration. [3] Evaluation of Appearance of Molded Article In the obtained molded article, the presence or absence of pinholes on the molding surface was visually checked, and evaluated by the following two steps. 1: A pinhole occurred on the molding surface. 2: No pinhole was formed on the molding surface. [4] Evaluation of tensile properties of molded product The obtained molded product was punched with a No. 1 dumbbell described in JIS K-6301 to obtain a test piece. This was measured using a tensile tester (AGS-500, manufactured by Shimadzu Corporation) in accordance with JIS.
According to the method described in K-6301, tensile strength and elongation at break were measured at 200 mm / min in an atmosphere at 23 ° C.

Example 1 [Production of thermoplastic elastomer composition powder] (b) 100 parts by weight of a propylene-ethylene copolymer resin [ethylene unit content 5% by weight, MFR = 220 g / 10 minutes], (b) Hydrogenated styrene-butadiene-isoprene-styrene block copolymer [water having a styrene unit content of 15% by weight, a hydrogenation ratio of 95%, and a side chain having 2 or more carbon atoms with respect to all hydrogenated conjugated diene units] The ratio of the added conjugated diene unit is 70%, MFR = 30 g / 10
100 parts by weight] and 50 parts by weight of an ethylene-propylene copolymer rubber [manufactured by Sumitomo Chemical Co., Ltd., SPO V0141, propylene unit content 27% by weight, MFR = 1 g / 10 minutes] using a twin-screw kneader. Speed 1.2 × 10
³ seconds ^-1 , kneading at a temperature of 180 ° C., the composition [η ^* (0.1)
= 8.0 × 10 ³ poise], which was cut using a cutting machine to obtain a granular material. After cooling to −120 ° C. using liquid nitrogen, the granules are pulverized while maintaining the cooling state, and then powdered with a thermoplastic elastomer composition [Tyler Standard Sieve 4]
Passes through 2 mesh (aperture 355 μm × 355 μm)]
I got

[Production of Molded Product by Powder Slush Molding Method] The obtained thermoplastic elastomer powder was placed on a nickel electroformed grain plate (30 cm) heated to a surface temperature of 210 ° C.
(X30 cm, thickness 3 mm), and after 18 seconds, excess powder not heat-sealed was removed. afterwards,
The sheet was heated in a heating furnace at 210 ° C. for 60 seconds, cooled, and then demolded to obtain a sheet-shaped molded body (thickness: 1 mm). Table 1 shows the evaluation results of the molded articles.

Example 2 Powder 1 of the thermoplastic elastomer composition obtained in Example 1
00 parts by weight of alumina (Alumina C, γ-
Alumina, primary particle diameter 13 nm) 1.0 part by weight using a super mixer (Kawada Seisakusho Co., Ltd., 5L super mixer SVM-5) at 23 ° C, 1500 rpm.
A molded article was obtained in the same manner as in Example 1 except that the mixture was mixed for minutes to obtain a thermoplastic elastomer composition powder.
Table 1 shows the evaluation results.

Example 3 A hydrogenated product of a styrene-butadiene-isoprene-styrene block copolymer [styrene unit content 1
5% by weight, hydrogenation ratio 90%, ratio of hydrogenated conjugated diene units having side chains having 2 or more carbon atoms to all hydrogenated conjugated diene units is 70%, MFR = 60 g / 10 min]. A molded article was obtained in the same manner as in Example 1, except for the presence of the resin. Table 1 shows the evaluation results.

Example 4 A hydrogenated product of a styrene-isoprene-styrene block copolymer [styrene unit content: 20% by weight, hydrogenation ratio: 95%, carbon number: 2 based on all hydrogenated conjugated diene units] The proportion of the hydrogenated conjugated diene units having the above side chains is 55%, MFR = 4 g / 10 min], 100 parts by weight, no ethylene-propylene copolymer rubber, and a paraffinic process oil [Idemitsu Kosan Company, PW-90]
A molded product was obtained in the same manner as in Example 1, except that 60 parts by weight was used. Table 1 shows the evaluation results.

Example 5 (b) A hydrogenated styrene-butadiene-styrene block copolymer [styrene unit content: 20% by weight, hydrogenation ratio: 95%, carbon number: 2 based on all hydrogenated conjugated diene units] Example 1 except that the proportion of the hydrogenated conjugated diene unit having the above side chain was 42%, MFR = 30 g / 10 min], 100 parts by weight, and the ethylene-propylene copolymer rubber was not used. The same operation was performed to obtain a molded body. Table 1 shows the evaluation results.

Comparative Example 1 Propylene resin [MFR = 60 g / 10 min] 100 parts by weight, styrene-isoprene-styrene block copolymer [styrene unit content 30% by weight, MFR = 5 g / 10
The ratio of the hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms to the total hydrogenated conjugated diene unit is 55.
%] And 40 parts by weight of paraffin-based process oil [PW-380, manufactured by Idemitsu Kosan Co., Ltd.] are kneaded using a twin-screw kneader at a shear rate of 1.2 × 10 ³ sec ^-1 and a temperature of 180 ° C. A molded product was obtained in the same manner as in Example 1 except that the obtained composition [η ^* (0.1) = 8.0 × 10 ⁴ poises] was used. Table 2 shows the evaluation results.

Comparative Example 2 Propylene resin [MFR = 60 g / 10 min] 100 parts by weight, hydrogenated styrene-isoprene-styrene block copolymer [styrene unit content 10% by weight, MFR = 5
g / 10 minutes, the proportion of the hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms to the total hydrogenated conjugated diene unit is 55%] 60 parts by weight and a paraffinic process oil [manufactured by Idemitsu Kosan Co., Ltd. PW-380] 40 parts by weight using a twin-screw kneader at a shear rate of 1.2 × 10 ³ sec ^-1 and a temperature of 180
Composition obtained by kneading at ℃ [η ^* (0.1) = 6.5 × 1
[0 ⁴ poise], a molded article was obtained in the same manner as in Example 1. Table 2 shows the evaluation results.

Comparative Example 3 Propylene resin [Hypol J74 manufactured by Mitsui Petrochemical Co., Ltd.]
0, MFR = 25 g / 10 min] 100 parts by weight and a hydrogenated product of styrene-butadiene-styrene block copolymer [Clayton G1657 manufactured by Shell Chemical Co., styrene unit content 13% by weight, MFR = 9 g / 10 min, water The ratio of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to all conjugated diene units added is 42%] 100 parts by weight is sheared at a rate of 1.2 × 10 ³ seconds using a biaxial kneader. ^-1 ,
Composition obtained by kneading at a temperature of 180 ° C. [η ^* (0.1) =
5.0 × 10 ⁴ poise], and a molded article was obtained in the same manner as in Example 1. Table 2 shows the evaluation results.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

As described above, according to the present invention, there is provided a thermoplastic elastomer composition containing a hydrogenated product of a polyolefin resin and a vinyl aromatic compound-conjugated diene compound copolymer as essential components. It was possible to provide a thermoplastic elastomer composition capable of providing a molded article having excellent appearance and tensile properties even at a relatively low molding temperature of about ° C, a powder of the composition, and a molded article obtained by using the powder.

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Claims (27)

[Claims] 1. The following (A) 100 parts by weight and (B) 1
A thermoplastic elastomer composition containing 0 to 250 parts by weight and having a complex dynamic viscosity η ^* (0.1) at 210 ° C. of 3 × 10 ⁴ poise or less. (A): Polyolefin resin (B): Hydrogenated product of vinyl aromatic compound-conjugated diene compound copolymer 2. The thermoplastic elastomer composition according to claim 1, which contains 100 parts by weight of (a), 10 to 250 parts by weight of (b), and 250 parts by weight or less of the following (c). (C): ethylene-α-olefin copolymer 3. The thermoplastic elastomer composition according to claim 1, wherein the vinyl aromatic compound (b) is styrene. 4. The thermoplastic elastomer composition according to claim 1, wherein the conjugated diene compound (b) is butadiene and / or isoprene. 5. A method according to claim 1, wherein (b) is a styrene-butadiene block copolymer, a styrene-isoprene block copolymer,
Styrene-butadiene / isoprene block copolymer,
The thermoplastic elastomer composition according to claim 1, which is a hydrogenated product of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, or a styrene-butadiene-isoprene-styrene block copolymer. 6. The thermoplastic elastomer composition according to claim 1, wherein (b) is a hydrogenated product of a styrene-butadiene-isoprene-styrene block copolymer. 7. The method according to claim 1, wherein (b) is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer containing a vinyl ester compound, an ethylenically unsaturated carboxylic acid ester compound or a vinyl nitrile compound. The thermoplastic elastomer composition as described in the above. 8. The heat according to claim 2, wherein (c) is an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-octene copolymer or an ethylene-ethylene / butylene-ethylene block copolymer. Plastic elastomer composition. 9. A thermoplastic elastomer composition powder comprising the thermoplastic elastomer composition according to claim 1. 10. The thermoplastic elastomer composition powder according to claim 9, which is produced by a mechanical grinding method. 11. The thermoplastic elastomer composition powder according to claim 9, which is produced by a strand cut method, a die face cut method, or a solvent treatment method. 12. The thermoplastic elastomer composition powder according to claim 11, which has an average sphere-equivalent particle size of 1.2 mm or less and a bulk specific gravity of 0.38 or more. 13. The thermoplastic elastomer composition powder according to claim 9, wherein 0.1 to 5 parts by weight of the following (d) is blended per 100 parts by weight of the thermoplastic elastomer composition powder. (D): Fine powder having a primary particle size of 300 nm or less 14. The thermoplastic elastomer composition powder according to claim 13, wherein the fine powder is a powder pigment, alumina, silica or alumina-silica. 15. The thermoplastic elastomer composition powder according to claim 9, further comprising:
14. The thermoplastic elastomer composition powder according to claim 13, which is contained in an amount of 0.1 to 5 parts by weight. (E) Powder having a primary particle size of more than 300 nm and 10 μm or less 16. The thermoplastic elastomer composition powder according to claim 15, wherein (e) is alumina, silica, alumina silica or calcium carbonate. 17. A powder molding method using the thermoplastic elastomer composition powder according to claim 9. 18. The powder molding method according to claim 17, comprising the following steps. First step: a step of supplying the thermoplastic elastomer composition powder according to claim 9 onto a molding surface of a mold heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition. Second step: molding surface of the first step The powder obtained in the first step above is heated for a predetermined time, and at least the powder whose surface is melted is fused together. Third step: After a predetermined time in the second step,
Step of recovering unfused powder Fourth step: If necessary, further heating the mold on which the molten thermoplastic elastomer composition powder is placed Fifth step: Cooling the mold and removing the sheet formed on it from the mold 19. A molded product obtained by powder molding the thermoplastic elastomer composition powder according to claim 9. 20. The molded product according to claim 19, which is obtained by the powder molding method according to claim 17. 21. A two-layer molded article comprising the molded article according to claim 19 and a foam layer laminated on one surface side. 22. A multilayer molded article comprising the molded article according to claim 19 and a thermoplastic resin core material laminated on one surface side. 23. A multilayer molded article comprising the thermoplastic resin core material laminated on the foam layer side of the two-layer molded article according to claim 21. 24. The method for producing a multilayer molded article according to claim 22, wherein a thermoplastic resin melt is supplied to one surface side of the molded article according to claim 19 and pressurized. 25. A thermoplastic resin melt is supplied to the foamed layer side of the two-layered molded article according to claim 21 and pressurized.
A method for producing the multilayer molded article according to the above. 26. The method according to claim 19, wherein the pair of molds is opened.
After supplying the molded body described above, and then supplying or supplying the thermoplastic resin melt between one surface side of the molded body and one mold opposite to the molded body, both molds are clamped. The method according to claim 24. 27. The method according to claim 21, wherein the pair of molds is opened.
After supplying the molded body described above, and then supplying or supplying the thermoplastic resin melt between one surface side of the molded body and one mold opposite to the molded body, both molds are clamped. The method according to claim 25.