JP2003246887A - Thermoplastic elastomer composition for powder molding and thermoplastic elastomer composition powder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition for powder molding which gives a molten resin with good flowability, allows a powder slush molding, and is excellent in heat resistance, marring resistance, oil resistance and weatherability, and its powder. <P>SOLUTION: The thermoplastic elastomer composition for powder molding is characterized by comprising (a) 100 pts.wt. of a hydrogenated conjugated diene copolymer, (b) 20-200 pts.wt. of a petroleum-based hydrocarbon resin having a softening point of 80-170°C and a temperature, at which it has a melt viscosity of 10 P, of 120-250°C, and (c) 5-100 pts.wt. of a thermoplastic resin having a melting point measured by DSC of 70-140°C and a melt viscosity at 140°C of 400-100,000 cP. The powder comprises the composition. <P>COPYRIGHT: (C)2003,JPO

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 for powder molding and a powder from the composition, and more particularly to a powder molding having excellent fluidity even in powder slush molding with low shearing force. For a thermoplastic elastomer composition, and a thermoplastic elastomer composition powder from the composition.

[0002]

2. Description of the Related Art Conventionally, a doll face skin of a toy, a makeup or an esthetic doll, or an automobile inner layer component,
For example, a powder slush molding method using a thermoplastic resin or the like has been widely adopted for manufacturing skins for molded parts such as instrument panels and console boxes. As the thermoplastic resin for the skin material, a polyvinyl chloride resin has been used because the surface of the molded product can be provided with skin texture and stitches, and a molded product having a soft feel can be obtained.

In recent years, from the viewpoint of environmental problems, a thermoplastic elastomer or polyurethane resin has been used in place of the polyvinyl chloride resin, but in the powder slush molding method, the shearing force applied to the resin is used. Therefore, the molten resin needs to have good fluidity so as to form a uniform thickness over the entire mold. However, conventional thermoplastic elastomers have poor fluidity of molten resin, and the mold temperature is considerably higher than that of polyvinyl chloride resin. For example, sufficient fluidity is obtained unless the temperature is set to about 300 ° C. I can't. Therefore, as a result of repeatedly heating and cooling the mold, there is a problem that the mold is rapidly deteriorated due to metal fatigue.

As a method for improving the fluidity of a thermoplastic elastomer molten resin, a technique of subjecting a thermoplastic elastomer composition containing a polyurethane resin to injection molding has been disclosed (see, for example, Patent Document 1). However, the molten resin fluidity of the resin composition is not satisfactory for powder slush molding applications, and is also unsatisfactory with respect to weather resistance and heat resistance.

Further, the fluidity of the thermoplastic elastomer composition can be improved by blending the ethylene / vinyl acetate copolymer (EVA) and / or the saponified EVA and / or the ethylene / ethyl acrylate copolymer (EEA). However, the compositions containing these resins were not satisfactory in heat resistance, scratch resistance and oil resistance.

[0006]

[Patent Document 1] Japanese Patent Laid-Open No. 10-310617

[0007]

The object of the present invention is that the flowability of the molten resin is good even at lower mold temperatures, powder slush molding is possible, and it is excellent in heat resistance, scratch resistance, oil resistance and weather resistance. Another object of the present invention is to provide a thermoplastic elastomer composition for powder molding, and a thermoplastic elastomer composition powder using the same.

[0008]

In order to solve the above-mentioned problems, the present inventors have made various investigations to improve the fluidity of molten resin, and as a result, the hydrogenated conjugated diene-based copolymer has a specific petroleum content. It has been found that a thermoplastic resin composition for powder molding having excellent powder fluidity and melt resin fluidity in powder slush molding can be obtained by blending a resin and a specific thermoplastic resin in specific amounts, and the present invention Was completed.

That is, according to the first aspect of the present invention,
(A) 100 parts by weight of hydrogenated conjugated diene-based copolymer, (b)
20 to 200 parts by weight of a petroleum hydrocarbon resin having a softening point of 80 to 170 ° C. and a temperature of 120 to 250 ° C. at which the melt viscosity becomes 10 poise, and (c) a melting point of 70 to 140 ° C. measured by DSC, and 140 ° C melt viscosity is 400
Provided is a thermoplastic elastomer composition for powder molding, which comprises 5 to 100 parts by weight of a thermoplastic resin of 100,000 cps.

According to the second aspect of the present invention,
(A) The hydrogenated conjugated diene-based copolymer has a number average molecular weight of 1
The thermoplastic elastomer composition for powder molding according to the first invention is provided, which is characterized in that it is from 30,000 to 350,000.

Further, according to the third invention of the present invention, the invention further comprises (d) 1 to 100 parts by weight of a non-aromatic softening agent for rubber. A thermoplastic elastomer composition for powder molding is provided.

According to the fourth aspect of the present invention, further, (e) peroxide-decomposable olefin resin 1 to
The thermoplastic elastomer composition for powder molding according to any one of the first to third inventions is provided, which comprises 80 parts by weight.

Further, according to a fifth invention of the present invention, there is further provided (f) an organic peroxide in an amount of 0.01 to 3 parts by weight. A thermoplastic elastomer composition for powder molding is provided.

According to a sixth aspect of the present invention, the powder molding according to the fifth aspect is characterized in that it further comprises (g) 0.02 to 10 parts by weight of an ester crosslinking aid. A thermoplastic elastomer composition is provided.

According to a seventh aspect of the present invention, the first aspect
A powder obtained by pulverizing the thermoplastic elastomer composition for powder molding according to any one of claims 1 to 6, wherein 5% by weight or more of the powder has a size capable of passing through a 42-mesh screen. A plastic elastomer composition powder is provided.

According to the eighth aspect of the present invention, the seventh aspect
100 of the thermoplastic elastomer composition powder according to the invention
(H) powder fluidity improver 0.01 to 1 relative to parts by weight
Provided is a thermoplastic elastomer composition powder, which is characterized by containing 0 part by weight.

According to a ninth aspect of the present invention,
(H) The powder fluidity improver is styrene / (meth) acrylic acid ester-based composite resin particles, and the thermoplastic elastomer composition powder according to the eighth invention is provided.

According to the tenth aspect of the present invention,
(H) The powder fluidity improver is finely divided silica, and the thermoplastic elastomer composition powder according to the eighth invention is provided.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Each component of the resin composition of the present invention will be described below.

1. Component (1) Hydrogenated Conjugated Diene Copolymer Component (a) of Thermoplastic Elastomer Composition for Powder Molding Hydrogenated Conjugated Diene Copolymer Component (a) in Thermoplastic Elastomer Composition for Powder Molding of the Present Invention Is a copolymer obtained by hydrogenating or partially hydrogenating the conjugated diene-based moiety in the conjugated diene-based copolymer, and is represented by the following (a-
1)-(a-3) components are mentioned.

(A-1) Hydrogenated product of aromatic vinyl compound-conjugated diene compound random copolymer Hydrogenated product component of aromatic vinyl compound-conjugated diene compound random copolymer used in the present invention (a-1) Is a random copolymer of a conjugated diene compound and an aromatic vinyl compound, and the number average molecular weight thereof is preferably 5,0.
0 to 1,000,000, more preferably 1
30,000 to 350,000, and polydispersity (Mw /
The value of Mn) is 10 or less, and the content of vinyl bonds such as 1,2 bonds or 3,4 bonds in the conjugated diene portion is 5% or more, and preferably 20 to 90%.
If it is less than 5%, the resulting molded article will have a hard feel and will not meet the purpose of the present invention. Here, the content of the aromatic vinyl compound constituting the component (a-1) is 50% by weight or less, preferably 5 to 35% by weight. If it exceeds 50% by weight, the resulting molded article has a hard feel and does not meet the purpose of the present invention.

Examples of the aromatic vinyl compound in the component (a-1) include styrene, t-butylstyrene,
α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene, p-
One kind or two or more kinds can be selected from tertiary butyl styrene and the like, and styrene is preferable among them. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, and among them, butadiene, isoprene and combinations thereof are preferable.

The aromatic vinyl compound and the conjugated diene compound are bonded at random, and Corsov [I. M. Ko
Lthoff, J. et al. Polymer Sci. , Vo
l. 1p. 429 (1946)], it is preferable that the content of the block-shaped aromatic vinyl compound is 10% by weight or less, preferably 5% by weight or less in the total aromatic vinyl compound. Further, the copolymer is preferably one in which at least 90% of the aliphatic double bond based on the conjugated diene compound is hydrogenated.

Specific examples of the component (a-1) include hydrogenated styrene / butadiene random copolymer (HSBR).
Can be mentioned. In the present invention, the hydrogenated product of the aromatic vinyl compound-conjugated diene compound random copolymer may be used alone or in combination of two or more.

(A-2) Hydrogenated product of aromatic vinyl compound-conjugated diene compound block copolymer Hydrogenated product of aromatic vinyl compound-conjugated diene compound block copolymer (a-2) is an aromatic compound It is a polymer obtained by hydrogenating a block copolymer comprising at least two polymer blocks A containing a vinyl compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component. For example, A-B-A, B-A-B
It is obtained by hydrogenating a block copolymer of an aromatic vinyl compound-conjugated diene compound having a structure such as -A or A-B-A-B-A. Here, the polymer block A is preferably 40% by weight or less.

The polymer block A containing an aromatic vinyl compound as a main component may be a polymer consisting of an aromatic vinyl compound alone or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. Good. Further, the polymer block B containing a conjugated diene compound as a main component may be a polymer consisting only of the conjugated diene compound or a copolymer of the conjugated diene compound and an aromatic vinyl compound of less than 50% by weight.

As the aromatic vinyl compound constituting the component (a-2), for example, one kind or two or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. Among them, styrene is preferable. Further, as the conjugated diene compound, for example,
Butadiene, isoprene, 1,3-pentadiene, 2,
One kind or two or more kinds are selected from 3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable.

The microstructure in the polymer block B mainly composed of the conjugated diene compound can be arbitrarily selected. In the butadiene block, the 1,2-microstructure has a lower limit of 1% or more, preferably 5% or more, more preferably 10% or more, and an upper limit of 95% or less, preferably 80%.
Or less, more preferably 75% or less.

The hydrogenation rate of the hydrogenated copolymer of component (a-2) can be arbitrarily selected, and the heat deterioration resistance and the like are improved while maintaining the characteristics of the unhydrogenated block copolymer. In this case, the lower limit of the aliphatic double bond based on the conjugated diene is 3% or more, preferably 5% or more, more preferably 7 or more, even more preferably 9% or more, and the upper limit is less than 85%, preferably 80%. %, More preferably less than 75%, even more preferably less than 60%. In addition, the 1,2-vinyl bond after hydrogenation is 0.5
It is preferably -12%, more preferably less than 10%, still more preferably 5% or less, still more preferably 3% or less. Further, in the case of improving the heat deterioration resistance and the weather resistance, hydrogenation of 80% or more, preferably 90% or more is recommended.

In the polyisoprene block, 70 to 100% by weight of the isoprene compound is 1,4
Preference is given to those having a microstructure and in which at least 90% of the aliphatic double bonds based on said isoprene compound are hydrogenated.

The weight average molecular weight of the hydrogenated block copolymer having the above structure is preferably 10,000 to 35.
10,000, more preferably 20,000 to 300,0
00, more preferably 30,000 to 250,000
0, particularly preferably in the range of 50,000 to 150,000. The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less. The molecular structure of the hydrogenated block copolymer may be linear, branched, radial or any combination thereof.

If the number average molecular weight (Mn) is less than the above lower limit, the mechanical properties, heat resistance, scratch resistance, and oil resistance of the skin obtained by powder slush molding deteriorate. on the other hand,
When it exceeds the upper limit, the fluidity becomes poor and pinholes are generated in the molded product, resulting in poor moldability. The molecular weight in the present invention is a value determined by GPC based on polystyrene having a known molecular weight. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on each condition of the GPC such as the reference sample, the device, and the data processing method.

Specific examples of the hydrogenated block polymer component (a-2) include styrene-ethylene / butadiene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS), styrene- Ethylene-ethylene-propylene-styrene copolymer (SE
EPS), partially hydrogenated styrene-butadiene-styrene copolymer (SBBS) and the like. In the present invention, the hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer may be used alone,
You may mix and use 2 or more types.

As a method for producing these hydrogenated block copolymers, many methods have been proposed, and a typical method is, for example, the method described in Japanese Patent Publication No. 40-23798. A block copolymer obtained by block polymerization in an inert medium using a lithium catalyst or a Ziegler type catalyst is hydrogenated by a known method in the presence of a hydrogenation catalyst.

(A-3) Hydrogenated Product of Conjugated Diene Compound Block Copolymer As the hydrogenated product of (a-3) conjugated diene compound block copolymer, for example, a butadiene block copolymer is hydrogenated. A block copolymer (CEBC) having a crystalline ethylene block and an amorphous ethylene-butene block obtained by the above process may be used. In the present invention,
The hydrogenated product of the conjugated diene block copolymer may be used alone or in combination of two or more.

(2) Petroleum-based hydrocarbon resin component (b) The petroleum-based hydrocarbon resin component (b) used in the thermoplastic elastomer composition for powder molding of the present invention is a rubber dispersion of the resulting thermoplastic elastomer composition. It has good effects and the appearance of the molded product, and is effective in adjusting hardness and shrinkage. The petroleum-based hydrocarbon resin includes an aliphatic petroleum resin mainly composed of a C ₅ fraction, which is a by-product of steam cracking of petroleum, an aromatic petroleum resin mainly composed of a C ₉ fraction, and both. There is a C ₅ C ₉ copolymer resin to be copolymerized, etc., but it is not particularly limited as long as it is a petroleum hydrocarbon resin having a softening point and a melt viscosity in the ranges described below, but a copolymer system containing aromatics It is preferably a resin.

The softening point of the component (b) is 80 to 170 ° C, preferably 110 to 160 ° C. When the softening point is outside the above range, the balance of flexibility, compression set and molding processability of the obtained thermoplastic elastomer composition deteriorates.

The temperature at which the melt viscosity of the component (b) becomes 10 poise is 120 to 250 ° C., preferably 1
It is 50-240 degreeC. When the temperature at which the melt viscosity becomes 10 poise is less than 120 ° C, the rubber elasticity of the obtained thermoplastic elastomer composition deteriorates, and when it exceeds 250 ° C, the moldability of the obtained thermoplastic elastomer composition decreases.

A commercially available product of the preferred example of the component (b) is an aromatic resin, particularly Endex 155 (Eastman C) which is a copolymer with an aromatic monomer.
Chemical Co., Ltd. or Kristalex 5140 (Eas, which is a copolymer of α-methylstyrene and styrene).
tman Chemical Co.).

The blending amount of the component (b) is 100 parts of the component (a).
It is 20 to 200 parts by weight, preferably 50 to 150 parts by weight, based on parts by weight. If the blending amount is less than 20 parts by weight, the resulting thermoplastic elastomer composition will be unusable as a product because of deterioration of pulverizability, deterioration of grain transferability, and generation of pinholes, resulting in deterioration of moldability. In addition, it is necessary to observe the presence or absence of pinholes with an optical microscope at a magnification of 30 times or more. When it exceeds 200 parts by weight, the hardness of the thermoplastic elastomer composition obtained becomes too high and the flexibility is lost, so that a product having a rubber-like feel cannot be obtained.

(3) Thermoplastic resin component (c) The thermoplastic resin component (c) in the thermoplastic elastomer composition for powder molding of the present invention is obtained by using together with the component (b). It improves the rubber dispersion of the product and the appearance of the molded product, and has the effect of adjusting the hardness and the shrinkage ratio.

The melting point (T
m) is 70 to 140 ° C., preferably 100 to 1
It is in the range of 20 ° C. When Tm is outside the above range,
The resulting thermoplastic elastomer composition has a poor balance of flexibility, compression set and moldability. And, the melt viscosity of the component (c) at 140 ° C. is 400 to 100,000.
It is 0 cps, preferably 500 to 10,000 cps. If the melt viscosity at 140 ° C. is less than 400 cps, the rubber elasticity of the obtained thermoplastic elastomer composition deteriorates,
When it exceeds 100,000 cps, the moldability of the obtained thermoplastic elastomer composition is deteriorated.

Examples of the thermoplastic resin component (c) include a nonpolar resin and / or a resin having a polar group. Examples of the non-polar resin include low molecular weight and low melting point resins of polyolefin such as polyethylene and polypropylene, and specific examples thereof include polyethylene wax. As the resin having a polar group, for example, ionomer, ethylene-acrylic acid copolymer,
Ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polyamide resin, polyamide thermoplastic elastomer, biodegradable polyester resin, polyester resin, polyester thermoplastic elastomer,
Examples thereof include low molecular weight and low melting point resins such as polyurethane resins and polyurethane thermoplastic elastomers. These thermoplastic resins may be used alone or in combination of two or more.

Preferred examples of the component (c) include polyethylene wax which is a nonpolar resin and biodegradable polyester resin which is a polar group-containing resin.

Examples of the polyethylene wax include branched chain homopolymer polyethylene. The polyethylene wax has a melting point of 101 ° C to 115 ° C and a density of 0.
91 g / cm ^{3 to} 0.93 g / cm ³ , Brookfield LVDVII + viscometer, spindle number SC4-1
The viscosity, measured at 8,60 rpm at 140 ° C., is approximately 6000 cps, and such a polyethylene wax is, for example, A-C735 polyethylene wax available from Allied Signal, Morristown, NJ, USA. is there.

As a biodegradable polyester resin
Can include biodegradable aliphatic polyester, etc.
Industrially, aliphatic dicarboxylic acid and excess diol
As a starting material, dehydration polycondensation reaction and dediol reaction
Incorporation of aromatic compounds
, Lactide ring-opening polymerization, lactic acid polycondensation, polymer
Quantified polycaprolactone, carbon monoxide and formalin
And polyglycolic acid synthesized from the above. Raw
Random aliphatic-aromatic among degradable aliphatic polyester
Copolyester is a copolymer of diol, fatty acid and aromatic acid.
A compound polyester resin, wherein the repeating unit is [-
{(OR¹-O)_a-(CO-R^Two-CO)_b}-
{(OR^Three-O)_c-(CO-Ar-CO)_d}-]
Is a polyester resin consisting of
Branching agent (BA)_xIncluding [-{(OR¹-O)_a−
(CO-R ^Two-CO)_b}-{(OR^Three-O)_c−
(CO-Ar-CO)_d}-] (BA)_xWith a structure like
It may be.

[0047] Here, in the above structural units, fatty acid residues: ^-CO-R 2 -CO- is a carbon atom 3 to 40, preferably a residue of 3-12 fatty acids, the fatty acid, for example , Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3
-Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,
Selected from the group consisting of 5-norbornanedicarboxylic acid,
4- (hydroxymethyl) cyclohexanecarboxylic acid,
Hydroxy acids such as hydroxypivalic acid, 6-hydroxyhexanoic acid, glycolic acid, lactic acid, and their ester-forming derivatives can also be used as the fatty acid component to make these copolyesters.

Aromatic acid residue: --CO--Ar--CO
-Is a residue of an aromatic acid having 8 to 40 carbon atoms, preferably 8 to 14 carbon atoms, and examples of the aromatic acid include 1,4
-Terephthalic acid, 1,3-terephthalic acid, 2,6-naphthoic acid, 1,5-naphthoic acid, their ester-forming derivatives and combinations thereof.

Further, the diol residue: --O--R ¹ --O--
And —O—R ³ —O— are residues of a diol having 2 to 20 carbon atoms, and examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,2- Dimethyl
1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 2,2,4-trimethyl-
1,6-hexanediol, thiodiethanol, 1,3
-Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,
3-cyclobutanediol, triethylene glycol,
It is selected from the group consisting of tetraethylene glycol and combinations thereof. The diol components may be the same or different.

Furthermore, a branching agent which is an optional component: (B
A) _x (where x represents the weight% of the branching agent, and is 0.01 to
10% by weight is preferable, and more preferably 0.1 to 1.0.
% By weight. ) Has a weight average molecular weight of preferably about 50 to 5,000, more preferably 92 to 3,000.
Examples of the polyol include a polyol having 0 to 3 hydroxy groups, a polycarboxylic acid having 3 or 4 carboxyl groups, or a hydroxy acid having 3 to 6 hydroxyl groups and carboxyl groups in total. For example, examples of low molecular weight polyols include glycerol, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis (hydroxy). Methyl) cyclohexane, tris (2-hydroxyethyl)
Included are isocyanurate and dipentaerythritol. High molecular weight polyol (Mw: 400 to 3,000)
Examples of 0) include triols derived by condensing C2-C3 alkylene oxides such as ethylene oxide and propylene oxide with a polyol initiator. Examples of the polycarboxylic acid include hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2- Ethanetricarboxylic acid, 1,3,5-
Mention may be made of pentanetricarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid, although acids may be used in this way, but preferably their lower alkyl esters or cyclic anhydrides are formed. Where possible, they are used in the form of their cyclic anhydrides. Hydroxy acids include malic acid, citric acid, tartaric acid, 3-hydroxyglutaric acid, mutic acid (or mucus acid), trihydroxyglutaric acid and 4- (β-hydroxyethyl) phthalic acid. Hydroxy acids contain three or more combinations of hydroxyl and carboxyl groups. Among these, a particularly preferable branching agent is
Examples include trimellitic acid, trimesic acid, pentaerythritol, trimethylolpropane and 1,2,4-butanetriol.

The biodegradable aliphatic polyester preferably used in the present invention includes polybutylene succinate (binary condensation product of succinic acid and 1,4-butanediol), polybutylene succinate adipate (succinic acid). And adipic acid, and a ternary condensate of 1,4-butanediol), polybutylene succinate terephthalate (succinic acid and terephthalic acid, and 1,4-butane).
And a ternary condensate of butanediol).

Further, the biodegradable aliphatic polyester used in the present invention has a reactive group such as an isocyanate group or a urethane group for the purpose of modifying the functionality within a range not impairing the biodegradable function. It is also possible to introduce it inside.
Further, various copolymers such as a copolyester obtained by copolymerizing polylactic acid can be used.

As the biodegradable aliphatic polyester used in the present invention, those commercially available as biodegradable resins can be used. For example, as product names, Bionore (manufactured by Showa High Polymer Co., Ltd.), Easter
Bio (manufactured by Eastoman Chemicals),
Biopol (manufactured by Japan Monsanto), Biomax (D
uPont), Ecoflex (BASF), and the like, but a resin can be arbitrarily selected according to the application and characteristics.

The blending amount of the component (c) is 100 parts of the component (a).
It is 5 to 100 parts by weight, preferably 10 to 70 parts by weight, and more preferably 20 to 60 parts by weight with respect to parts by weight. If the blending amount is less than 5 parts by weight, the resulting thermoplastic elastomer composition is deteriorated in pulverizability, texture transfer property is reduced, and pinholes are generated, resulting in deterioration in moldability, which makes the product unusable as a product. If it exceeds 100 parts by weight, the moldability of the resulting thermoplastic elastomer composition will be poor, and the hardness of the thermoplastic elastomer composition will be too high, resulting in loss of flexibility and a rubber-like product cannot be obtained.

(4) Softener component for non-aromatic rubber (d) In the thermoplastic elastomer composition for powder molding of the present invention, a softener component (d) for non-aromatic rubber may be added, if necessary. It can be blended. The component (d) may be a non-aromatic mineral oil or a liquid or low molecular weight synthetic softening agent. The mineral oil softening agent used for rubber is a mixture of three aromatic ring, naphthene ring and paraffin chain, and paraffin chain carbon number occupies 50% or more of total carbon number. That is, those having a carbon number of naphthene ring of 30 to 40% are called naphthene type, and those having an aromatic carbon number of 30% or more are called aromatic type.

The mineral oil type rubber softening agents used as the component (d) in the present invention are paraffin type and naphthene type softeners in the above categories. The aromatic softening agent is not preferable because the component (a) becomes soluble due to its use and the crosslinking reaction is hindered so that desired improvement in physical properties cannot be achieved. As the component (d), paraffinic ones are preferable, and among paraffinic ones, those having less aromatic ring components are particularly preferable.

The properties of these non-aromatic softeners for rubber are such that the dynamic viscosity at 37.8 ° C. is 20 to 500 cS.
t, pour point is −10 to −15 ° C., flash point (COC) is 1
Those exhibiting 70 to 300 ° C. are preferable. Furthermore, the weight average molecular weight of the component (d) is preferably 100 to 2,000.

The blending amount of the component (d) is as follows.
The amount is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, and particularly preferably 5 to 20 parts by weight, relative to 100 parts by weight of the component (a). If it exceeds the upper limit, bleeding out of the softening agent is likely to occur, which may give tackiness to the final product, and the mechanical properties of the molded product may be deteriorated. Further, if the blending amount is less than the lower limit value,
No effect of addition is observed.

(5) Peroxide-decomposable olefin resin component (e) In the thermoplastic elastomer composition for powder molding of the present invention, a peroxide-decomposable olefin resin and / or a resin containing the peroxide-decomposable olefin resin may be added, if necessary. The polymer component (e) can be blended. The component (e) has the effects of improving the dispersion of the component (a) in the obtained thermoplastic elastomer composition, improving the appearance of the molded product, and improving the heat resistance and oil resistance.

The peroxide-decomposable olefin-based resin suitable as the component (e) in the present invention is rrrr in the pentad fraction by ¹³ C-nuclear magnetic resonance absorption method.
It is preferable that / l-mmmm is 20% or more. The melting peak temperature (Tm) determined by the differential scanning calorimetry is preferably 120 ° C or higher, more preferably 125 to 167 ° C. Furthermore, the melting enthalpy (ΔHm) determined by the differential scanning calorimetry is 1
00 J / g or less is preferable, and 20 to 83 is more preferable.
It is mJ / mg. The crystallinity can be estimated from Tm and ΔHm. When Tm and ΔHm are outside the above ranges, 1 of the obtained thermoplastic elastomer composition
The heat resistance and oil resistance at 00 ° C or higher are not improved.

As the peroxide-decomposing olefin resin, a high molecular weight homo-type polypropylene, for example,
Isotactic polypropylene or propylene and other small amounts of α-olefins such as ethylene, 1-butene,
Examples thereof include copolymers with 1-hexene, 4-methyl-1-pentene and the like.

The MFR of a peroxide-decomposing olefin resin (ASTM-D-1238, L condition, 23
0 ° C.) is preferably 0.1 to 1000 g / 10 minutes, more preferably 30 to 800 g / 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the moldability of the obtained thermoplastic elastomer composition will decrease, and if it exceeds 1000 g / 10 minutes, the mechanical properties and rubber elasticity of the obtained thermoplastic elastomer composition will deteriorate. Not preferable.

In addition to the above peroxide-decomposable olefin resin, the number average molecular weight (Mn) is 25,000 or more, and the weight average molecular weight (Mw) and the number average molecular weight (M
n) and a boiling heptane-soluble polypropylene having a ratio (Mw / Mn) of 7 or less and a melt index of 0.1 to 4 g
/ 10 minutes boiling heptane-insoluble polypropylene peroxide decomposition type olefin resin, boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more and an intrinsic viscosity [η] of 0.5 to 9.0 dl. / G
It is also possible to use a peroxide-decomposable olefinic resin composed of the boiling heptane-insoluble polypropylene.

The blending amount of the component (e) is as follows.
The amount is preferably 1 to 80 parts by weight, more preferably 3 to 50 parts by weight, and particularly preferably 5 to 20 parts by weight, relative to 100 parts by weight of the component (a). If it is less than the lower limit, the effect of addition is not recognized. On the other hand, when the amount exceeds the upper limit, the flexibility, rubber elasticity, and moldability of the obtained thermoplastic elastomer composition deteriorate.

(6) Organic peroxide component (f) In the thermoplastic elastomer composition for powder molding of the present invention, an organic peroxide component (f) can be added, if necessary. The component (f) is used in the case of performing dynamic crosslinking, and the thermoplastic elastomer composition obtained by performing appropriate dynamic crosslinking has pulverizability, oil resistance,
It has the effect of improving scratch resistance.

Examples of the component (f) include dicumyl peroxide, di-tert-butyl peroxide,
2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3
-Bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) benzene
-3,3,5-Trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert- Butyl peroxybenzoate,
Examples thereof include tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.

Of these, 2,5-dimethyl-2,5-di- (te is used in terms of odor, coloring and scorch stability.
Most preferred are rt-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene.

When compounding the component (f),
It is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 1 part by weight, and particularly preferably 0.1 to 0.5 part by weight, relative to 100 parts by weight of the component (a). If it is less than the lower limit, a sufficient crosslinking reaction cannot be obtained. The required crosslinking cannot be obtained. On the other hand, when the amount exceeds the upper limit, the crosslinking proceeds too much, resulting in poor dispersion of the crosslinked product.

(7) Ester-based cross-linking aid component (g) In the thermoplastic elastomer composition for powder molding of the present invention, an ester-based cross-linking aid component (g) may be added, if necessary. The component (g) is preferably used as a cross-linking aid during dynamic crosslinking, and can be added during the dynamic crosslinking treatment with the above-mentioned (f) organic peroxide so that a uniform and efficient crosslinking reaction can be carried out. You can In addition, by blending a large amount, a non-aromatic softening agent for rubber, particularly a low molecular weight paraffin oil, etc. can be appropriately cross-linked and bleed-out from the thermoplastic elastomer composition can be suppressed.

Examples of the component (g) include triallyl cyanurate, ethylene glycol dimethacrylate,
Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 9 to 14 repeating units of ethylene glycol, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1,8-octane Polyfunctional methacrylate compounds such as diol dimethacrylate, 1,9-nonanediol dimethacrylate,
Mention is made of polyfunctional acrylate compounds such as polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, and polyfunctional vinyl compounds such as vinyl butyrate or vinyl stearate. be able to. You may use these individually or in combination of 2 or more types. Among the above-mentioned crosslinking aids, a polyfunctional acrylate compound or a polyfunctional methacrylate compound is preferable, and triethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate is particularly preferable. These compounds are easy to handle, have an organic peroxide solubilizing action, and act as a dispersion aid for organic peroxides, so that crosslinking by heat treatment is performed uniformly and effectively, and balance between hardness and rubber elasticity is achieved. A good thermoplastic elastomer composition is obtained.

The blending amount of the component (g) is as follows.
It is preferably 0.02 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, and particularly preferably 0.2 to 1 part by weight, relative to 100 parts by weight of the component (a). If it is less than the lower limit, the crosslinking reaction is not sufficient. On the other hand, when the amount exceeds the upper limit, crosslinking proceeds too much, resulting in poor dispersion of the crosslinked product. Further, the blending amount of the component (h) is preferably about 1.0 to 3.0 times the blending amount of the organic peroxide component (g).

(8) Other components (i) In the thermoplastic elastomer composition for powder molding of the present invention, a heat stabilizer, an antioxidant, a light stabilizer, UV absorbers, crystal nucleating agents, antiblocking agents, sealability improving agents, release agents such as stearic acid and silicone oil, lubricants such as polyethylene wax, colorants, pigments, inorganic fillers such as alumina,
Foaming agent (organic, inorganic), flame retardant (hydrated metal compound,
Red phosphorus, ammonium polyphosphate, antimony, silicone) and the like can be added. Here, as the antioxidant, for example, 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4 , 4-dihydroxydiphenyl, tris (2
Examples thereof include phenol-based antioxidants such as -methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite-based antioxidants, and thioether-based antioxidants. Of these, phenol-based antioxidants and phosphite-based antioxidants are particularly preferable.

2. Production of Thermoplastic Elastomer Composition for Powder Molding The thermoplastic elastomer composition for powder molding of the present invention comprises the above components (a) to (c) or, if necessary, the components (d) to (d).
It can be produced by adding (g) and (i) and adding each component at the same time or in an arbitrary order and melt-kneading.

The melt-kneading method is not particularly limited, and a generally known method can be used. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. For example, a moderate L / D twin-screw extruder,
The above operation can be continuously performed by using a Banbury mixer, a pressure kneader or the like. Here, the temperature of the melt-kneading is preferably 160 to 220 ° C.

3. Thermoplastic Elastomer Composition Powder The thermoplastic elastomer composition powder of the present invention is obtained by pulverizing the pellets of the thermoplastic elastomer composition for powder molding obtained above by an appropriate method such as mechanical pulverization or solution pulverization. it can. In particular, freeze pulverization is preferable, and pulverization at a low temperature makes it possible to obtain a powder having a uniform shape and size. Further, this powder can also be prepared by forming the pellet of the thermoplastic elastomer composition into a fine pellet by reducing the hole diameter of the discharge port of the die.

The particle size distribution of the thermoplastic elastomer composition powder has a great influence on the fluidity thereof. If there are many coarse particles or the particle size distribution is wide, the moldability in slush molding is lowered and pinholes are generated. It is not easy to make a skin material with a uniform thickness. This particle size distribution is
It is preferred that 5 wt% or more of the particles pass through a 42 mesh screen. If the powder has such a particle size distribution,
It is possible to form a skin material having a uniform thickness without pinholes or the like.

The thermoplastic elastomer composition powder of the present invention can further improve the powder fluidity by incorporating the powder fluidity improver (h) which is fine powder particles. In particular, dry blending with powder having irregular shape crushed from low temperature to room temperature has a remarkable effect of improving fluidity, and dispersion failure and melting failure after slush molding using a thermoplastic elastomer powder are less likely to occur. Have the effect of

Examples of the powder fluidity improver (h) include composite resin particles (h-1) and hydrophobic inorganic oxide fine particles (h-).
2) etc. can be mentioned, and preferable examples will be described below.

(1) Composite Resin Particles (h-1) An example of the composite resin particles (h-1) that can be used in the thermoplastic elastomer composition powder of the present invention is (i) two or more in the molecule. A radically polymerizable ethylenically unsaturated group-containing monomer (crosslinking reaction monomer) and (ii) a monofunctional monomer having one polymerizable group in the molecule are used in an aqueous medium or a non-aqueous medium. It is obtained by copolymerization in an aqueous organic medium by emulsion polymerization, soap-free emulsion polymerization, suspension polymerization, NAD polymerization, precipitation polymerization, solution polymerization, etc., and if desired, isolation, pulverization and scoring. Emulsion polymerization, soap-free emulsion polymerization and NAD polymerization are suitable for obtaining particles of 0.02 to 0.6 μm, and precipitation polymerization is suitable for obtaining particles of 0.2 to 30 μm. Considering that fine particles having a predetermined particle size can be obtained, it is preferable to use emulsion polymerization or soap-free emulsion polymerization.

Examples of the above-mentioned (i) monomers having two or more radically polymerizable ethylenically unsaturated groups in the molecule (monomers for crosslinking reaction) include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylpropane trimethacrylate,
1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, penta Erythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol ataloxydimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1- Trishydroxymethylethane dimethacrylate, 1,1,1-trishydroxymethylethane trime Acrylate, 1,1,1-trihydroxy methyl propane diacrylate, 1,1,
1-trihydroxymethylpropane triacrylate,
1,1,1-trihydroxymethylpropane dimethacrylate, 1,1,1-trihydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene Etc.

On the other hand, examples of the monofunctional monomer (ii) having one polymerizable group in the molecule include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid. , Maleic acid, fumaric acid and the like; hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyputyl acrylate, hydroxyputyl methacrylate, allyl alcohol, methallyl Alcohol, etc .; Nitrogen-containing alkyl acrylate or methacrylate, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc .; Polymerizable amide, such as acrylic acid amide, methacrylic acid Etc .; Polymerizable nitriles such as acrylonitrile, methacrylonitrile, etc .; Alkyl acrylates or methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, etc .; Group compounds such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and the like; α-olefins such as ethylene, propylene and the like; vinyl compounds such as vinyl acetate, vinyl propionate and the like; diene compounds such as, for example: Butadiene, isoprene, etc .; Silicon-containing alkyl acrylates, methacrylates or silicon-containing vinyl compounds, such as γ-methacryloxypropyltrimethoxysilane, vinyl And the like fluorine-containing compound; trimethoxysilane, vinyltriethoxysilane and the like.

Another example of the composite resin particles (h-1) that can be used in the thermoplastic elastomer composition powder of the present invention is a three-dimensionally crosslinked condensed or polymerized resin particle having a diameter of 0.01 to 10 μm. Entangled structure with a linear vinyl resin having film-forming ability in the three-dimensional crosslinked resin particle body, which is obtained by solution polymerization of at least one compound having one polymerizable ethylenic unsaturated bond in the presence of Which is a composite resin particle having at least one compound (monomer) having one polymerizable ethylenically unsaturated bond in the presence of three-dimensionally crosslinked resin particles.
In order to solution polymerize the seeds, this monomer solution penetrates into the three-dimensional crosslinked particles to form a linear vinyl resin by polymerization or copolymerization. It is a complex structure with a chain vinyl resin and a special structure intertwined with each other.

The three-dimensionally crosslinked resin particle body is a three-dimensional resin having an average particle diameter of 0.01 μ to 10 μ, which is made of a condensation resin such as a polyester resin, an epoxy resin, an amino resin and a polymerization resin such as an acrylic resin or a vinyl resin. It is a crosslinked resin particle. Such crosslinked resin particles can be produced by various known methods such as emulsion polymerization method, NAD polymerization method or solution polymerization method. Depending on the production method, it may be used as it is, or the particles may be isolated or crushed before use.

The linear vinyl resin having film-forming ability is a polymer or copolymer obtained by addition polymerization of at least one compound having one polymerizable ethylenic unsaturated bond. As the polymerizable compound (monomer), any monomer used in the production of a linear acrylic resin or vinyl resin for paint is preferably used, and typical examples thereof include the following. it can. (I) a carboxyl group-containing monomer, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. (ii) a hydroxyl group-containing monomer,
For example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol, etc. (i
ii) Nitrogen-containing alkyl acrylate or methacrylate, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc., (iv) Polymerizable amide, for example, acrylic acid amide, methacrylic acid amide, etc., (v) Polymerizable nitrile, for example, acrylonitrile,
(Vi) alkyl acrylate or methacrylate such as methacrylonitrile, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate and the like, (vii) polymerizable aromatic compound, for example, styrene, α-methylstyrene,
Vinyltoluene, t-butylstyrene, etc. (viii)
Vinyl compounds such as vinyl acetate and vinyl propionate, and (ix) α-olefins such as ethylene and propylene. Monomers used to obtain a linear film-forming vinyl resin are not limited to the above, for example,
It may be a monomer having a glycidyl group. Although less preferred, a bifunctional monomer may be added if desired so long as it does not impair the film forming ability of the vinyl resin.

The composite resin particles can be easily produced by a conventional method of solution polymerizing at least one compound having one polymerizable ethylenic unsaturated bond as described above in the presence of three-dimensional crosslinked resin particles. To be That is, at least one of radical polymerization initiator such as organic peroxide or organic azo compound, solvent, three-dimensional crosslinked resin particles, and compound (monomer) having a polymerizable ethylenic unsaturated bond is charged into a reactor and heated. A solution polymerization method known to those skilled in the art is convenient, such as polymerization, a method of charging an organic solvent into a reactor and heating and dropping a polymerization initiator, three-dimensional crosslinked resin particles and monomers, or a combination thereof. Can be used for The composite resin particles obtained by the method as described above are not the ones in which the linear vinyl resin is simply attached to the three-dimensional crosslinked resin particles, and because of the special manufacturing method thereof, the three-dimensional crosslinked resin particles are Since the monomer solution enters and undergoes solution polymerization, the three-dimensional crosslinked resin particles and the linear film-forming vinyl resin are a complex having a structure in which they are intertwined with each other.

As the above (h-1) composite resin particles,
Styrene / (meth) acrylic acid ester-based composite resin particles are preferable, and examples of commercially available products include "Microgel" (trade name) sold by Nippon Paint Co., Ltd.

(2) Hydrophobic inorganic oxide fine particles (h-2) The hydrophobic inorganic oxide fine particles (h-2) that can be used in the thermoplastic elastomer composition powder of the present invention include:
Examples thereof include fine particle silica, titania, zirconia, zinc oxide, calcium oxide, magnesia, yttria and the like, and among them, fine particle silica or titania is preferable.

The specific surface area of the hydrophobic inorganic oxide fine particles is preferably 10 to 1000 m ² / g, more preferably 50 to 500 m ² / g, and the primary particle diameter is 1 to 1
00 μm is preferable, and more preferably 5 to 50 μm. If it is out of the above range, the flow effect cannot be obtained.

The hydrophobic inorganic oxide fine particles having such physical properties can be produced by surface-treating the inorganic oxide fine particles with a hydrophobizing agent. As a surface treatment method with a hydrophobizing agent, either a gas phase method or a liquid phase method can be adopted, but it is preferable to use hydrophobic inorganic oxide fine particles surface-treated by the gas phase method. The treatment method is disclosed in JP-B-41-17049 and JP-B-61-50.
The fluidized bed method described in Japanese Patent No. 882 etc. can be used.

The hydrophobizing agent is not particularly limited as long as it has sufficient fluidity, and can be appropriately selected from the compounds exemplified below. One kind of those hydrophobizing agents may be used, or two or more kinds thereof may be used in combination. In addition, two or more kinds of hydrophobic inorganic oxide fine particles surface-treated with different hydrophobizing agents may be mixed and used.

(I) Methylchlorosilane, ethylchlorosilane, propylchlorosilane, vinylchlorosilane,
Chlorosilanes such as phenylchlorosilane, (ii) dimethylpolysiloxane, polymerized silicon compounds such as silicone oil, (iii) alkoxysilanes such as methylmethoxysilane, methylethoxysilane, ethylmethoxysilane, vinylmethoxysilane and phenylmethoxysilane. , (Iv) Fluorinating agents such as diethylaminotrimethylsilane, carbonyl fluoride and hydrogen fluoride.

In particular, it is preferable to use fine particles of silica or fine particles of titania obtained by a gas phase oxidation method in a flame, and hydrophobic inorganic oxide fine particles whose surface is subjected to a hydrophobic treatment with a hydrophobizing agent. Silica or titania may be used alone in the surface treatment, and 2
One or more species may be mixed and used, and further, one compounded in the synthesis stage may be used.

The finely divided silica or finely divided titania obtained by the vapor phase oxidation method in a flame is generally known by the name of fumed silica or fumed titania, respectively. The manufacturing method thereof is described in JP-B-47-462.
74, JP-A-58-91031 and the like. The raw material may be a volatile and hydrolyzable compound, and examples of the silicon compound include tetrachlorosilane, halogenated silane such as trichlorosilane, tetramethoxysilane, trimethoxysilane, and the like.
Examples thereof include alkoxysilanes such as tetraethoxysilane, triethoxysilane, monomethyltrimethoxysilane, and dimethyldimethoxysilane. Among these, hydrophobic anhydrous amorphous silica obtained by reacting the hydroxyl group on the silica surface with monomethyltrichlorosilane, dimethyldichlorosilane or the like is preferable.

Commercially available products of the above-mentioned finely divided silica include "Roleoseal MT-10," manufactured by Tokuyama Corporation.
DM-10, DM-20, DM-30, DM-30
"S", "Nipsil" manufactured by Nippon Silica Industry Co., Ltd., "Silohobic" manufactured by Fuji Silysia Chemical Ltd., "Aerosil" manufactured by Nippon Aerosil Co., Ltd., and the like.

The content of the component (h) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 3 parts by weight, and particularly preferably 100 parts by weight of the thermoplastic elastomer composition powder. It is 0.1 to 2 parts by weight. If the blending amount is less than 0.01 parts by weight, the fluidizing effect cannot be imparted, and if it exceeds 10 parts by weight, foreign matters are formed and the product appearance is deteriorated.

The component (h) can be blended by a dry blending method using a tumble mixer, a Henschel mixer, or the like, but can also be blended directly at the time of producing the thermoplastic elastomer composition for powder molding.

As a method of directly blending the thermoplastic elastomer composition for powder molding during production, for example, a crosslinking agent and a crosslinking aid are added to a component other than the component (h) powder fluidity improver and heated. Knead. As a kneading method, any method commonly used for rubber, plastic and the like can be satisfactorily used. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. By this step, a composition in which each component is uniformly dispersed can be obtained.

As a kneading method, it is preferable to use a twin-screw extruder having a L / D of 47 or more or a Banbury mixer because all the steps can be continuously performed. Further, for example, when kneading with a twin-screw extruder, the rotation speed of the screw is 80 to 350 rpm, preferably 80 to 20 rpm.
When it is carried out under the condition of 0 rpm, the dispersion of each component is good, and the product having good physical properties can be obtained.

In particular, in order to obtain a thermoplastic elastomer composition powder for slush molding which can be rapidly melted, the dynamic viscosity when the dynamic viscoelasticity is measured at a frequency of 6.28 rad / sec is 5 × 10 5. and ³ Pa · sec and composed temperature _{(T 1),} is preferably the difference between the temperature _{(T 2)} the dynamic viscosity of _{^{1 × 10 3 Pa · sec (}} T 2 -T 1) is 20 ° C. or less , More preferably 15 ° C. or lower, particularly preferably 12 ° C. or lower (usually 5 ° C. or higher), and the dynamic viscosity at 220 ° C. is 6 × 10 ² Pa.
It is preferably sec or less.

The temperatures T ₂ and T ₁ are both in the temperature range in which the thermoplastic elastomer composition is melting and the viscosity is decreasing, and the temperature difference (T ₂ −
The fact that T ₁ ) is 20 ° C. or lower means that the viscosity rapidly decreases as the temperature rises and then increases by crosslinking. With such a thermoplastic elastomer composition, the thermoplastic elastomer composition in the vicinity of the surface of the molding die is rapidly melted, a sufficient amount of the thermoplastic elastomer composition is attached, and the thermoplastic elastomer composition in a position apart from the vicinity of the surface is It is collected in a container without softening or melting. Also,
After that, crosslinking proceeds, and a thermoplastic elastomer composition which is not easily melted by heat is produced. As a result, it is possible to form a skin material having a uniform thickness and having an excellent appearance, feel, and the like, and in particular, there is no appearance defect in the thin portion, and it is possible to perform fine laser processing with high dimensional accuracy. It is preferable because it is possible.

When the temperature difference (T ₂ −T ₁ ) exceeds 20 ° C., thickening due to crosslinking starts before the viscosity is sufficiently lowered. Therefore, there is a problem that the time required for molding tends to be long, air is easily contained, and that this air remains as it is in the formed skin material.
Furthermore, the thermoplastic elastomer composition begins to melt even in the vicinity of the surface of the molding die, does not adhere to the surface of the molding die, and part of the thermoplastic elastomer composition collected in the container softens to form an agglomerated mass. In addition, since the time required for molding is long, cross-linking progresses, and the recovered thermoplastic elastomer composition may not be reused. Even if it can be reused, it does not melt promptly, and pinholes, etc. It causes the defect of.

The dynamic viscosity at a temperature of 220 ° C. at which the thermoplastic elastomer composition is completely melted is 6 × 10 ^2.
When it exceeds Pa · sec, the melted thermoplastic elastomer composition at the time of slush molding has a low fluidity and is inferior in moldability, and a skin material having a uniform thickness cannot be obtained.
Furthermore, it is not possible to obtain a skin material having an excellent appearance and feel, such as pinholes.

[0103]

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the examples. The evaluation methods and raw materials used in the examples are as follows.

1. Evaluation method (1) Molecular weight measurement method: The molecular weight is measured by GPC under the following conditions.
The molecular weight was determined using polystyrene as the standard. Eluent: dimethylformamide (DMF) Flow rate: 1.0 ml / min Detector: RI Column: Shodex KD-80M × 3 Column temperature: 40 ° C. (2) Hardness: Hardness after 15 seconds according to JIS K 6253 Was measured. (3) Tensile strength, elongation, 100% modulus: JIS
It measured based on K7161. Sample temperature is 250
130 × 130 × 2mm obtained by slush molding at ℃
A thick sheet was used, and the test piece was No. 3 dumbbell. (4) Melt viscosity measurement: ARES manufactured by Rheometrics
Measured temperature 220 with 1KFRTN-FCO-STD
The melt viscosity at a temperature of 6.28 rad / s and a strain of 3% Strain was measured. When the melt viscosity is 600 Pa · s or more, good slush moldability is not exhibited. (5) Angle of repose: The measurement was performed according to JIS H1902-1990. The powder was dropped from the funnel, and the tilt angle formed by the deposited powder and the substrate surface was measured. When the angle of repose is 43 ° or more, good powder fluidity is not exhibited. (6) Scratch resistance: The surface of the test piece was rubbed 1200 times with Campus cloth (Kanakin No. 3) from above while applying a load of 100 g, and the scratched state of the surface of the test piece was visually observed. The following criteria evaluated. ◯: Almost no scratches and no stain on the campus cloth. X: Scratches are noticeable or stains are attached to the campus cloth. (7) Heat resistance: The test piece was placed in an oven at 120 ° C for 16
After the test for 8 hours, the degree of holding of wrinkles on the surface of the test piece was visually observed and evaluated according to the following criteria. ◯: No melting and no grain flow. ×: Partial melting or grain flow occurred. (8) Bleed resistance: The extruded sheet, which was bent and fixed with a clip, was allowed to stand at room temperature and 120 ° C. for 168 hours, and visually observed for the presence of bleeding and blooming of low molecular weight substances, and evaluated according to the following criteria. ◯: Good ×: Poor (9) Releasability: Evaluated according to the following criteria when removing the molded product from the mold. ◯: The mold could be released from the mold without any problem, and no deformation was observed. X: A part of the molded product remained in the mold and / or the molded product taken out was deformed. (10) Number of pinholes on surface of molded product: optical microscope magnification 30
Double measurement was performed and evaluated according to the following criteria. ○: There is no pinhole. Δ: There are some pinholes. X: There is a pinhole as a whole. (11) Grain transfer property evaluation: The appearance was visually evaluated according to the following criteria. ◯: Both deep and shallow textures are transferred well. Δ: Transfer of shallow grain is bad. X: The transfer is poor in both deep and shallow wrinkles.

2. Raw material (1) Component (a): Hydrogenated block copolymer (HSBR)
JSR's Dynaron 1320P Styrene content: 10% by weight Specific gravity: 0.89 MFR: 3.5 g / 10 min (230 ° C · 2.16 kg) Number average molecular weight: 227,000 Weight average molecular weight: 295,000 Molecular weight distribution : 1.31 Hydrogenation rate: 90% or more (2) Component (b-1): Copolymer of aromatic monomer;
Endex155 (Trademark; Eastman Chemi
cal.), softening point; 151-155 ° C., specific gravity;
05, melt viscosity at 235 ° C .; 10 poise (3) component (b-2): copolymer of α-methylstyrene and styrene; Kristalex 5140 (trademark; Ea)
stman Chemical Co., Ltd.), softening point: 137
~ 143 ° C, specific gravity; 1.07, melt viscosity at 180 ° C; 1
0 Poise (4) Component (c): Polyethylene Wax; A-C73
5 (trademark; manufactured by Allied Signal Co., Ltd.), melting point; 110
℃, specific gravity; 0.92, melt viscosity of 140 ℃; 6000c
ps (5) Component (d): Non-aromatic rubber softener manufactured by Idemitsu Kosan Diana Process Oil PW-90 Type: Paraffin oil weight average molecular weight: 540 Aromatic component content: 0.1% or less (6 ) Component (e): Peroxide decomposition type olefin type resin: PP Mitsui Chemicals Co., Ltd. CJ700 MFR: 7 g / 10 min (230 ° C · 2.16 kg) Tm: 166 ° C ΔHm: 82 mJ / mg rrrr / l-mmmm : 97% (7) Component (f): Organic peroxide; manufactured by NOF CORPORATION Perhexa 25B (2,5-dimethyl-2,5-di (t-butylperoxide) hexane) (8) Component (g): Ester-based cross-linking aid; NK ester IND (2-methyl-1,8-octanediol dimethacrylate (85%), 1,9-nonanedioldi manufactured by Shin Nakamura Chemical Co., Ltd. Mixture of tacrylate (15%) (9) Component (h): Powder fluidity improver manufactured by Nippon Paint Co., Ltd. Microgel FS-102 Type: Styrene / (meth) acrylate crosslinked ultrafine particle size 0 0.08 μm Glass transition point: 102 ° C. Charge amount: −45 (10) Component (i): Antioxidant; Hindered phenol / phosphite / lactone-based composite antioxidant component (h): HP2215 (trademark; Ciba Specialty Chemicals) (Made by the company)

Examples 1 to 4 and Comparative Examples 1 to 4 In the component ratios shown in Table 1, components (a) to (e) and the antioxidant component (i) were first kneaded with a twin-screw extruder to obtain an organic compound. The peroxide component (f) and the crosslinking aid component (g) were added, and a dynamic crosslinking treatment was performed at a kneading temperature of 200 ° C., a screw rotation of 350 rpm, and an extruder discharge rate of 20 kg / hour. The obtained pellets were freeze-ground in a liquid nitrogen atmosphere to obtain a thermoplastic elastomer composition powder. The proportion of particles of the obtained powder which passed through a 42-mesh screen was 90% by weight.

Next, after the component (h) was dry blended with the obtained powder using a Henschel mixer, a sheet was formed by slush molding at a mold temperature of 250 ° C.
The obtained sheet was punched with a dumbbell to prepare various test pieces, and each evaluation was performed. The results are shown in Table 1.

[0108]

[Table 1]

As is clear from Table 1, the thermoplastic elastomer composition powder of the present invention had excellent fluidity which can be used for slush molding. On the other hand, in Comparative Examples 1 and 2, the compounding amount of the component (b) was out of the range of the present invention. When the amount of the component (b) is small, the pulverizability is deteriorated, the texture transfer property is deteriorated, and pinholes are generated, so that the moldability is deteriorated and the product cannot be used. When there are many components (b),
The hardness becomes too hard and the mechanical properties also deteriorate. In Comparative Examples 3 and 4, the compounding amount of the component (c) was out of the range of the present invention. When the amount of the component (c) is small, the pulverizability is deteriorated, the texture transfer property is deteriorated, and the pinhole is generated, so that the moldability is deteriorated and the product cannot be used. When the amount of the component (c) is large, the hardness becomes too hard and the mechanical properties also deteriorate.

[0110]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention is excellent in fluidity, heat resistance, scratch resistance, oil resistance and weather resistance, and can be used as a thermoplastic elastomer composition for powder molding. When used together with the powder fluidity improver, it exhibits excellent powder fluidity and molten resin fluidity and can be used as a powder slush molding material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 53/00 C08L 53/00 57/02 57/02 101/00 101/00 // B29K 9:00 B29K 9:00 F-term (reference) 4F070 AA12 AA13 AA18 AA68 AB11 AB23 AB24 AC23 AC43 AC56 AC83 AC94 AE02 AE08 AE09 DA46 DA58 DC07 4F205 AA03 AA13E AA21E AA45 AA46 AB04 AB07 AB01 AB01 AB01 BA01 AR02 AR11 AR20 AR11 GA20 AR11 GA20 AR11 AR20 GA11 BB12U BB12Y BB22Y BP01W BP02W CC16U CD00U CF00U CF00Y CF19Y CK02Y CL00Y DJ018 EH077 EK036 EK046 EK056 EK086 EU187 FD070 FD147 FD156 GN00

Claims (10)

[Claims] 1. (a) Hydrogenated conjugated diene-based copolymer 100
Parts by weight, (b) a softening point of 80 to 170 ° C., and a melt viscosity of 10
20 to 200 parts by weight of a petroleum hydrocarbon resin having a poise temperature of 120 to 250 ° C., and (c) a melting point of 70 to 140 ° C. measured by DSC and a melt viscosity of 140 to 100 ° C. of 400 to 100,000 cps. Plastic resin 5-10
A thermoplastic elastomer composition for powder molding, which comprises 0 part by weight. 2. The thermoplastic elastomer composition for powder molding according to claim 1, wherein the hydrogenated conjugated diene-based copolymer (a) has a number average molecular weight of 10,000 to 350,000. . 3. The thermoplastic elastomer composition for powder molding according to claim 1 or 2, further comprising (d) 1 to 100 parts by weight of a non-aromatic rubber softening agent. 4. The thermoplastic elastomer composition for powder molding according to any one of claims 1 to 3, further comprising (e) 1 to 80 parts by weight of a peroxide decomposing olefin resin. . 5. The (f) organic peroxide 0.
The thermoplastic elastomer composition for powder molding according to any one of claims 1 to 4, wherein the thermoplastic elastomer composition comprises 0.1 to 3 parts by weight. 6. Further, (g) an ester-based cross-linking aid of 0.
The thermoplastic elastomer composition for powder molding according to claim 5, wherein the thermoplastic elastomer composition comprises 02 to 10 parts by weight. 7. A powder obtained by pulverizing the thermoplastic elastomer composition for powder molding according to claim 1, wherein 5% by weight or more of the powder passes through a 42 mesh sieve. The thermoplastic elastomer composition powder is characterized by: 8. The thermoplastic resin composition according to claim 7, wherein 0.01 to 10 parts by weight of the powder fluidity improver (h) is added to 100 parts by weight of the thermoplastic elastomer composition powder according to claim 7. Elastomer composition powder. 9. (h) The powder fluidity improver is styrene.
9. The (meth) acrylic acid ester-based composite resin particles, the thermoplastic elastomer composition powder according to claim 8. 10. The thermoplastic elastomer composition powder according to claim 8, wherein (h) the powder fluidity improver is fine powder silica.