JP2003089733A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition with which gasification, pinhole, blocking, or the like, in powder molding is solved, excellent in weather resistance, scratch resistance and heat resistance and capable of providing a molded product having smooth rear surface. SOLUTION: This thermoplastic resin composition is a pellet-like or powdery thermoplastic resin composition comprising (a) 10-95 wt.% polyolefin resin having at least one kind of hydrophilic functional group and selected from the group consisting of a saponified product of a ethylene-vinyl acetate copolymer, an ethylene-(meth)acrylate copolymer, an ethylene-(meth)acrylate copolymer and an ethylene-vinyl acetate copolymer and (b) 90-5 wt.% elastomer having a hydrophilic functional group, and the press sheet of the thermoplastic resin composition satisfies a specific Taber's abrasion resistance and heat resistance (change of length).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition for molding a powder, which comprises a polyolefin resin having a hydrophilic functional group and an elastomer having a hydrophilic functional group as main components.

[0002]

2. Description of the Related Art Powder molding is widely used for molding toys, automobile interior parts, etc. because it is suitable for molding complicated shapes, has a high material yield, and can easily make the thickness of molded products uniform. Has been. This powdery body molding is performed by bringing a pellet-shaped or powdered material into contact with the inner wall or outer wall of a heated mold to adhere the material to the mold and melt it. Due to such characteristics of powder molding, the material adhered to the mold does not melt in a short time to form pinholes in the molded product, transfer the “grain” on the mold surface, It is required that the material be spread to every detail.
In addition, during molding, the material that did not adhere to the mold is collected in the box and will be used again for the next molding.Therefore, part of the surface of the collected material will not be heated by the previous molding. It is also necessary to melt due to history and not cause aggregation of powders (hereinafter referred to as blocking).

Conventionally, as a raw material resin for molding powdery materials,
Polyvinyl chloride resins, polyolefin resins, thermoplastic polyurethane resins, etc. have been used, but each has the following drawbacks. Since the polyvinyl chloride resin contains a large amount of a low molecular weight plasticizer, there is a problem that the soft feeling is lost below the freezing point of the plasticizer. In addition, there is also a problem that the matting effect and the loss of softness due to the migration of the plasticizer to the surface of the molded product during long term use. The polyolefin resin is inexpensive and has excellent weather resistance, but has a drawback that it is inferior in powder formability and scratch resistance. Improvement of scratch resistance by surface decoration such as painting has been studied, but it is not practical because of high cost. The thermoplastic polyurethane resin has a problem that it has a long molding cycle and is apt to cause stringing and blocking during molding. Further, there is a problem that the back surface of the molded product is not smooth, and when the foamable resin is molded on the back surface in the post-processing, foamed gas leaks from the uneven portion. Further, there is a problem that it is expensive and inferior in weather resistance and flame retardancy.

[0004]

Therefore, the present invention solves the above-mentioned problems in powder molding, gasification during molding, pinholes, blocking, etc., and improves weather resistance, scratch resistance, and heat resistance. It is an object to provide a thermoplastic resin composition which is excellent and gives a molded product having a smooth back surface.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor contains a polyolefin resin having a specific hydrophilic functional group and an elastomer having a specific hydrophilic functional group. The resin composition has a specific amount of wear, heat resistance, gasification at the time of molding in powder molding, pinholes, blocking, etc. are solved, weather resistance, scratch resistance, excellent heat resistance, and, The present invention has been completed by finding that it is a thermoplastic resin composition that gives a molded product having a smooth back surface.

That is, according to the first aspect of the present invention,
(A) Saponified ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-
(Meth) acrylic acid copolymer, 10 to 95 mass% of a polyolefin resin having at least one hydrophilic functional group selected from the group of ethylene-vinyl acetate copolymer,
(B) A pellet-shaped or powder-shaped thermoplastic resin composition for molding a powder, which comprises an elastomer having a hydrophilic functional group and / or 90 to 5 mass% of the elastomer composition as a main component, There is provided a thermoplastic resin composition, characterized in that the press sheet of the thermoplastic resin composition satisfies the following. Taber abrasion resistance conforms to JIS K 7204,
Wear wheel CS-10, 250 g, when measured under the conditions of 100 rotations, the wear amount is 3 mg or less. When a test piece punched out from a press sheet into a No. 3 dumbbell shape was suspended in a gear oven at 110 ° C for 168 hours, the change in length was 2% or less.

According to the second aspect of the present invention,
(B) The elastomer and / or elastomer composition having a hydrophilic functional group comprises (bα) 10 to 95% by mass of a crosslinking agent-crosslinking elastomer having a hydrophilic functional group, and (bβ)
Crosslinking agent decomposable resin having hydrophilic functional group 90 to 5% by mass
The thermoplastic resin composition according to the first invention is provided.

According to the third aspect of the present invention,
(B) The total amount of [(bα) + (bβ)] in the elastomer and / or the elastomer composition having a hydrophilic functional group is 1
0.001 to (c) organic peroxide relative to 100 parts by mass
There is provided the thermoplastic resin composition according to the first or second invention, which comprises 5 parts by mass and 0.001 to 5 parts by mass of the crosslinking aid (d).

According to a fourth aspect of the present invention,
(B) The hydrophilic functional group-containing elastomer and / or (bα) the hydrophilic functional group-containing crosslinking agent crosslinkable elastomer of the elastomer composition is an ethylene-methyl acrylate-based copolymer elastomer, and (bβ) hydrophilic A thermoplastic resin composition according to any one of the first to third inventions, wherein the crosslinking agent decomposable resin having a functional group is a polyester resin.

Further, according to the fifth aspect of the present invention, 0.001 to 5 parts by mass of the crosslinking agent (c) is further added to 100 parts by mass of the components (a) and (b) in total. The thermoplastic resin composition according to any one of the first to fourth inventions is provided.

According to the sixth aspect of the present invention, 0.001 to 5 parts by mass of the component (c) crosslinking agent and 100 parts by mass of the component (a) and the component (b), and the component ( d) A thermoplastic resin composition according to any one of the first to fourth inventions, which further comprises 0.001 to 5 parts by mass of a crosslinking aid.

According to a seventh aspect of the present invention, there is provided a method for producing a pellet-like or powder-like thermoplastic resin composition for forming a powdery body, the press sheet satisfying the following (a): At least one hydrophilicity selected from the group consisting of saponified ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene-vinyl acetate copolymer. 10 to 95% by mass of a polyolefin resin having a functional group,
(B) A method for producing a thermoplastic resin composition is provided, which comprises melt-kneading a component containing a hydrophilic functional group-containing elastomer and / or an elastomer composition of 90 to 5 mass% as a main component. Taber abrasion resistance conforms to JIS K 7204,
Wear wheel CS-10, 250 g, when measured under the conditions of 100 rotations, the wear amount is 3 mg or less. When a test piece punched out from a press sheet into a No. 3 dumbbell shape was suspended in a gear oven at 110 ° C for 168 hours, the change in length was 2% or less.

According to an eighth aspect of the present invention,
(B) The elastomer and / or elastomer composition having a hydrophilic functional group comprises (bα) 10 to 95% by mass of a crosslinking agent-crosslinking elastomer having a hydrophilic functional group, and (bβ)
Crosslinking agent decomposable resin having hydrophilic functional group 90 to 5% by mass
A method for producing a thermoplastic resin composition according to the seventh invention is provided, which comprises melt-kneading and.

According to a ninth aspect of the present invention, the first aspect
As a stage, (bα) cross-linking agent cross-linking elastomer having a hydrophilic functional group 10 to 95 mass%, (bβ) cross-linking agent decomposable resin having a hydrophilic functional group 90 to 5 mass%, [(b
α) + (bβ)] totaling 100 parts by mass, (c)
0.001 to 5 parts by mass of an organic peroxide and (d) 0.001 to 5 parts by mass of a cross-linking aid are melt-kneaded to produce (b) an elastomer having a hydrophilic functional group and / or an elastomer composition. In the second step, (a) a polyolefin resin having a hydrophilic functional group and (b) the elastomer having a hydrophilic functional group and / or an elastomer composition obtained in the first step are melt-kneaded. A method for producing the thermoplastic resin composition according to the seventh or eighth invention is provided.

According to the tenth aspect of the present invention,
(Bα) The cross-linking agent cross-linking elastomer having a hydrophilic functional group is an ethylene-methyl acrylate copolymer elastomer, and (bβ) the cross-linking agent decomposing type resin having a hydrophilic functional group is a polyester resin. A method for producing the thermoplastic resin composition according to any one of the seventh to ninth inventions is provided.

According to the eleventh invention of the present invention,
With respect to a total of 100 parts by mass of the component (a) and the component (b),
The method for producing a thermoplastic resin composition according to any one of the seventh to tenth inventions, characterized in that the component (c) further comprises 0.001 to 5 parts by mass of a crosslinking agent.

According to the twelfth aspect of the present invention, 0.001 to 5 parts by mass of the component (c) crosslinking agent and 100 parts by mass of the component (a) and the component (b) and the component ( d)
A method for producing a thermoplastic resin composition according to any one of the seventh to tenth inventions, characterized in that the method further comprises 0.001 to 5 parts by mass of a crosslinking aid.

According to a thirteenth invention of the present invention, there is provided a molded article comprising the thermoplastic resin composition according to any one of the first to sixth inventions.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Each component constituting the composition of the present invention will be described below. (1) (a) Polyolefin resin having hydrophilic functional group The polyolefin resin having hydrophilic functional group (a) used in the present invention is an ethylene-vinyl acetate copolymer (EV).
A), an ethylene-vinyl acetate copolymer saponified product (EVO
H), ethylene- (meth) acrylic acid ester copolymer (EEA, EMMA, EMA, etc.), ethylene- (meth)
It is at least one resin selected from the group of acrylic acid copolymers (EAA, EMAA, etc.) and may be used alone or in any combination. Among them, ethylene-vinyl acetate copolymer saponified product (EVOH)
It is preferable that the weather resistance and the smoothness of the back surface of the rotomolded article are good.

The EVOH has an ethylene unit content of 7
0-98 mol%, saponification degree of vinyl acetate component is 70 mol%
The above are preferable from the viewpoints of heat resistance, flexibility, and powder formability. More preferably, the ethylene unit content is 7
5-95 mol%, saponification degree of vinyl acetate component is 80 mol%
That is all.

The melt flow rate (MF) of the component (a)
R, according to JIS K6924-2, measured at 190 ° C. and a load of 21.18 N) is preferably 5 to 1000 g / 10 minutes, more preferably 10 to 500 g / 10 minutes. If the MFR is less than 5 g / 10 min, the fluidity is low and the powder formability tends to be insufficient, and if it exceeds 1000 g / 10 min, the mechanical properties and heat resistance tend to be poor.
When using a plurality of components (a), the MFR of the entire component (a) only needs to satisfy the above range, and each does not need to satisfy the above range. For example,
It is also possible to use a low MFR (less than 5 g / 10 min) as one of the components (a) to impart good mechanical properties while maintaining moldability.

When a polyolefin resin having no hydrophilic functional group is used in the component (a), the amount of heat of fusion per unit mass is large, and the powder formability is insufficient, which is not preferable. Further, in accordance with the properties of the component (a), the component (b) described below also has good powdery moldability by using a component having a hydrophilic functional group,
It can be a material exhibiting excellent physical properties. Also,
By using the component (a) and the component (b) together, the material properties such as flexibility can be adjusted according to the purpose of use.

(2) (b) Elastomer and / or Elastomer Composition Having Hydrophilic Functional Group The (b) elastomer and / or elastomer composition having a hydrophilic functional group used in the present invention mainly comprises carbon atoms and hydrogen atoms. , And an elastomer and / or an elastomer composition having a polar group composed of an oxygen atom, and specifically, a hydroxyl group, an ester group, a carboxyl group,
An elastomer and / or an elastomer composition having an ether group, a carbonyl group, or the like. The elastomer and / or the elastomer composition is a cross-linking agent cross-linking type or cross-linking agent decomposing type hydrophilic functional group-containing elastomer and / or elastomer composition, and can be preferably produced as follows.

The (b) hydrophilic functional group-containing elastomer and / or the elastomer composition is composed of (bα) hydrophilic functional group-containing crosslinker crosslinkable elastomer and (bβ) hydrophilic functional group-containing crosslinker decomposition type resin. And (c) a cross-linking agent,
(D) Obtained by melt-kneading in the presence or absence of a crosslinking aid.

(Bα) Crosslinking Agent Having Hydrophilic Functional Group As the crosslinkable elastomer, a (meth) acrylic acid-based elastomer, for example, ethylene, a (meth) acrylic acid ester, and an unsaturated hydrocarbon having a carboxyl group as a side chain are used. (Meth) acrylic acid-based terpolymer copolymers, polyacrylonitrile-based resins (acrylonitrile-butadiene rubber, acrylonitrile-acrylic acid ester-based copolymers), and the like, and organic peroxide crosslinking In the case of carrying out, a terpolymer elastomer of ethylene, an acrylic ester and an unsaturated hydrocarbon having a carboxyl group in the side chain is particularly preferable. (Bα) is a compound having a hydrophilic functional group, such as an organic peroxide or a sulfur compound,
In the presence of a cross-linking agent such as an amine compound or a metal soap cross-linking agent, the cross-linking reaction proceeds preferentially over the decomposition reaction, resulting in cross-linking. Among these, compounds in which the crosslinking reaction proceeds preferentially over the decomposition reaction in the presence of the organic peroxide and consequently the crosslinking occurs are particularly preferable.

Examples of the crosslinking agent decomposable resin having a hydrophilic functional group (bβ) include polyester resins, polyamide resins, polyurethane resins and the like. Among these, polyester resins are preferred. (Bβ) is
A compound in which the decomposition reaction takes precedence over the crosslinking reaction in the presence of the crosslinking agent. Examples of the polyester-based resin preferably used in the present invention include the following saturated polyester-based resin and polyester-based thermoplastic elastomer (COPE). Of these, saturated polyester resins are particularly preferable.

The saturated polyester resin of the (bβ) hydrophilic functional group-containing crosslinking agent decomposable resin of the present invention is a saturated polyester formed by copolycondensation of a dicarboxylic acid component and a diol component. Is an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid, an aliphatic dicarboxylic acid such as adipic acid, succinic acid or sebacic acid, and ethylene glycol rule as a diol component,
1,4-butanediol, diethylene glycol, neopentyl glycol and the like are used and copolycondensed by various combinations and changes in the blending amount. Of these, crystalline is preferable.

The method for producing the saturated polyester resin is arbitrary, but industrially, it is synthesized by a dehydration polycondensation reaction and a dediol reaction using an aliphatic dicarboxylic acid and an excess of diol as starting materials. Examples thereof include those introduced with an aromatic compound, ring-opening polymerization of lactide, polycondensation of lactic acid, polycaprolactone having a high molecular weight, and polyglycolic acid synthesized from carbon monoxide and formalin.

The structure of the saturated polyester resin is arbitrary.
However, among saturated aliphatic polyesters, aliphatic-aromatic
Group Random Copolyesters are diols, fatty acids, fragrances
A repeating unit of a copolyester resin of an aromatic acid
, [-{(OR¹-O) _a-(CO-R^Two-CO)
_b}-{(OR^Three-O)_c-(CO-Ar-C
O) _d}-] Is a polyester resin composed of
Branching agent (BA) _xIncluding [-{(OR¹
-O)_a-(CO-R^Two-CO)_b}-{(OR^Three−
O)_c-(CO-Ar-CO)_d}-] (BA)_xLike
It may have any structure.

[0030] 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, a 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. ) Is a polyol having a weight average molecular weight of preferably about 50 to 5000, more preferably 92 to 3000 and having 3 to 6 hydroxy groups,
Examples thereof include polycarboxylic acids having 3 or 4 carboxyl groups or hydroxy acids having a total of 3 to 6 hydroxyl groups and carboxyl groups. 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) isocyanurate and dipentaerythritol are mentioned. Examples of high molecular weight polyols (Mw: 400-3000) include triols derived by condensing C2-C3 alkylene oxides such as ethylene oxide and propylene oxide with a polyol initiator. As the polycarboxylic acid, hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid,
Benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid,
Examples include 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid, although acids may be used in this manner. Are preferably used in the form of their lower alkyl esters or their cyclic anhydrides, if they can be formed. 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, particularly preferable branching agents include trimellitic acid, trimesic acid, pentaerythritol, trimethylolpropane and 1,2,4-butanetriol.

Saturated polyester resins preferably used in the present invention include 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 (a ternary condensate of succinic acid and terephthalic acid, and 1,4-butanediol) and the like.

Further, in the saturated polyester resin used in the present invention, it is possible to introduce a reactive group such as an isocyanate group or a urethane group into the structure for the purpose of modifying the functionality. Further, various copolymers such as a copolyester obtained by copolymerizing polylactic acid can be used.

As the saturated polyester resin used in the present invention, those generally commercially available can be used. For example, as the product name, Byron GA3410
(Manufactured by Toyobo Co., Ltd.), Bionore (Showa Polymer Co., Ltd.)
Made), Easter Bio (Eastoman Ch)
bios (manufactured by Nippon Monsanto), Biomax (manufactured by DuPont), Ecofle
x (manufactured by BASF) and the like, but a resin can be arbitrarily selected according to the application and characteristics.

The weight average molecular weight of the saturated copolyester of the present invention is 3,000 to 50,000, preferably 100.
It is 00 to 30000. In use, the melting point of the copolyester is limited, but the melting point is 100
To 180 ° C, preferably 110 to 160 ° C, and more preferably 120 to 140 ° C.

As the polyester thermoplastic elastomer (COPE) of the crosslinking agent decomposable resin having a hydrophilic functional group (bβ) used in the present invention, polyester is used as the hard segment in the molecule and the glass transition temperature (Tg) is used as the soft segment. Multiblock copolymers with low) polyethers or polyesters are preferred. For example, aromatic crystalline polyester such as polybutylene terephthalate is used as the hard segment, polyester / polyether type using polyether as the soft segment, aromatic crystalline polyester is used as the hard segment, and aliphatic type is used as the soft segment. Examples include polyester / polyester type using polyester.

Here, as the polyester / polyether type, for example, those synthesized by transesterification reaction and polycondensation reaction using dimethyl terephthalate, 1,4-butanediol, polytetramethylene glycol and the like as starting materials. Can be mentioned. Examples of the polyester / polyester type include those synthesized by transesterification reaction and ring-opening reaction using dimethyl terephthalate, 1,4-butanediol, ε-caprolactone and the like as starting materials.

In producing the component (b), the cross-linking agent cross-linking elastomer (bα) having a hydrophilic functional group and the cross-linking agent decomposable resin (bβ) having a hydrophilic functional group have a compounding ratio (bα) of 10 To 95% by mass is preferable, 20 to 90% by mass is more preferable, and 30 is particularly preferable.
˜80% by mass, (bβ) is preferably 90 to 5% by mass, more preferably 80 to 10% by mass, and particularly preferably 70 to 20% by mass. If the component (bα) is too small, the flexibility of the elastomer will be insufficient, and if it is too large, the powder formability will be adversely affected. Further, if the amount of the component (bβ) is small, the melt-kneading workability becomes low, which is not preferable.

As the cross-linking agent (c), which is optionally used during the production of the component (b) and / or when the components (a) and (b) are kneaded, organic peroxides and sulfur can be used. Examples thereof include compounds, amine compounds, metal soaps, and among them, organic peroxides are particularly preferable. (C) The organic peroxide generates radicals and causes the radicals to react in a chain to crosslink the (bα) components, the (bβ) components, and the (bα) and (bβ) components. Work. Examples of the component (c) include dicumyl peroxide, di-tert-butyl peroxide, 2,
5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t
ert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ter
t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, ter
Examples thereof include t-butyl cumyl peroxide. Of these, 2,5-dimethyl-2,5-di- (ter) is preferable from the viewpoint of odor, coloring, and scorch safety.
t-butylperoxy) hexane, 2,5-dimethyl-
2,5-di- (tert-butylperoxy) hexyne-3 is particularly preferred.

When the component (b) is produced and / or when the components (a) and (b) are kneaded, the amount of the component (c) used is as appropriate as the component (b). During production, the amount is 0.001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total of the (bα) component and the (bβ) component. If the blending amount is less than 0.001 part by mass, crosslinking cannot be sufficiently achieved and the resulting elastomer has low heat resistance and mechanical strength. On the other hand, when it exceeds 5 parts by mass, moldability is deteriorated. When the components (a) and (b) are kneaded, the total amount of the components (a) and (b) is 0.001 to 5 parts by mass, more preferably 0. It is 01 to 1 part by mass. If the blending amount is less than 0.001 part by mass, crosslinking cannot be sufficiently achieved,
The heat resistance and mechanical strength of the obtained elastomer will be low. On the other hand, when it exceeds 5 parts by mass, moldability is deteriorated.

When the component (b) is produced and / or when the components (a) and (b) are kneaded, the ester-based crosslinking aid is used as the crosslinking aid (d). Preferably, it can be blended during the crosslinking treatment with the above-mentioned (c) organic peroxide, whereby a uniform and efficient crosslinking reaction can be carried out. Specific examples of the component (d) include, for example, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol having a repeating number of ethylene glycol of 9 to 14. Dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate, 1,
Polyfunctional methacrylate compounds such as 9-nonanediol dimethacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate,
Mention may be made of multifunctional acrylate compounds such as neopentyl glycol diacrylate, propylene glycol diacrylate, multifunctional vinyl compounds such as vinyl butyrate or vinyl stearate. These may be used alone or in combination of two or more. Among these crosslinking aids, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,9-nonanediol dimethacrylate, and 2-methyl-1,8-octanediol dimethacrylate are particularly preferable.

The blending amount of the component (d) is used together with the organic peroxide (c), and when the component (b) is produced,
It is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total of the components (bα) and (bβ). If it exceeds 5 parts by mass, the degree of crosslinking is lowered due to self-polymerization, and the effect cannot be obtained. When kneading the components (a) and (b),
With respect to 100 parts by mass of the total of the components (a) and (b),
0.001 to 5 parts by mass, more preferably 0.01
~ 1 part by mass. If it exceeds 5 parts by mass, the degree of crosslinking is lowered due to self-polymerization, and the effect cannot be obtained.

(3) Mixing ratio of component (a) and component (b) The mixing ratio of component (a) and component (b) is 1 for component (a).
0 to 95% by mass, preferably 20 to 90% by mass,
The amount of the component (b) is 90 to 5% by mass, preferably 80 to 10% by mass. If the amount of the component (a) is less than 10% by mass (the amount of the component (b) exceeds 90% by mass), the cross-linking structure will be too much and the powder formability will be adversely affected. on the other hand,
When the amount of the component (a) exceeds 95% by mass (the amount of the component (b) is less than 5% by mass), the crosslinked structure is insufficient, and the scratch resistance,
Heat resistance does not improve.

(4) Thermoplastic Resin Composition The thermoplastic resin composition of the present invention comprises the above-mentioned component (b) produced as a first step, and the components (a) and (b) melted as a second step. Obtained by kneading. The obtained thermoplastic resin composition needs to be in the form of fine pellets or fine powder in order to maintain the powder formability. It is preferable to make it into a fine pellet form or a fine powder form by a freeze pulverizer or the like. In order to handle a complicated shape, it is preferable that the particle size is small, preferably 10 mesh pass, more preferably 20 mesh pass, and most preferably 30 mesh pass.

The thermoplastic resin composition of the present invention has the following physical properties as a press sheet, Taber abrasion resistance,
It is necessary to satisfy heat resistance (change in length).

Taber abrasion resistance The Taber abrasion resistance of the press sheet of the thermoplastic resin composition is in accordance with JIS K 7204, and wear wheels CS-1
When measured under conditions of 0, 250 g, and 100 rotations, the amount of wear is 3 mg or less, preferably 2 mg or less, and more preferably 1.5 mg or less. The amount of wear is
It is an index of wear resistance, and a smaller value is preferable. If the abrasion resistance is more than 3 mg and the abrasion resistance is low, it is not preferable because the molded article is easily scratched when touched with a hand or wiped with a cloth.

Heat resistance (change in length) A test piece punched out from a press sheet of a thermoplastic resin composition into a No. 3 dumbbell shape was placed in a gear oven at 110 ° C.
When suspended for 8 hours, the change in length is 2% or less, preferably 1% or less, and more preferably 0.5% or less. The change in length is an index of heat resistance, and the smaller the value, the better. When the length change is more than 2% and the heat resistance is low, it is not preferable because when used for automobile interior parts exposed to high temperature, "grains" formed on the surface may flow.

(5) Other Ingredients The thermoplastic resin composition of the present invention contains various antioxidants such as phosphorus, phenol, sulfur and the like, antioxidants, and light within a range that does not impair the object of the present invention. Various weathering agents such as stabilizers and UV absorbers, modified silicone oils, silicone oils, waxes, acid amides, various lubricants such as fatty acids, fatty acid salts, various nucleating agents such as aromatic metal phosphates and gelols, Various plasticizers such as glycerin fatty acid ester type, aliphatic paraffin oil, aromatic paraffin oil, phthalic acid type, ester type, magnesium oxide,
Various fillers such as zinc oxide, magnesium hydroxide, calcium carbonate and talc, and additives such as various colorants can be used. In order to prevent troubles such as bleeding out on the surface of the molded product, those having a high compatibility with the thermoplastic resin composition of the present invention are preferable.

From the viewpoint of scratch resistance and dischargeability from the kneader at the time of production in the thermoplastic resin composition of the present invention,
It is preferable to use the polyethylene wax and the polyether-modified silicone oil in an amount of 0.2 to 10 parts by weight per 100 parts by weight of the total amount of the components (a) and (b).

[0052]

EXAMPLES The present invention will be specifically described by the following examples, but the present invention is not limited to these examples. The evaluation methods of physical properties used in the present invention are shown below.

(1) Taper wear resistance: temperature 200 ° C.,
3 minutes of residual heat, 3 minutes of clamping × pressure of 0.05 N / m ² -G,
Using a press sheet having a thickness of 1 mm obtained under the conditions of cold pressure for 3 minutes × pressure of 0.05 N / m ² -G as a sample, JIS K
In accordance with 7204, wear wheels CS-10, 250g, 1
The measurement was performed under the condition of 00 rotations. (2) Change in length (heat resistance): A test piece punched out from the above-mentioned press sheet into a No. 3 dumbbell shape was suspended in a gear oven at 110 ° C for 168 hours, and the change in length was measured. (3) Pinhole: The fine powdery thermoplastic resin composition was subjected to rotational molding under the conditions of a mold temperature of 240 ° C. and a mold rotation speed of 6 times, and the pinholes on the surface of the obtained molded product were observed. The following criteria were evaluated. ◯: There is no pinhole. Δ: There are some pinholes. X: There is a pinhole as a whole. (4) Smoothness of the back surface of the molded product: Using a gloss meter (MMX-202 manufactured by Murakami Color Research Laboratory), light was made incident on the back surface of the molded product after molding the powder at an incident angle of 60 degrees to measure the gloss value. . The following criteria were evaluated. ⊚: Gloss value of 50% or more ◯: Gloss value of 10% or more ×: Gloss value of less than 10% (5) Blocking: During powder molding, it is observed whether the material collected in the powder box is blocked due to heat history, The following criteria evaluated. ◯: Nothing at all. (0%) Δ: Slight blocking occurred. X: Remarkably blocked. (6) Tapered wear resistance of rotationally molded product: A test piece is cut out from a powdery molded product and conforms to JIS K 7204,
The wear wheel CS-10 was measured under the conditions of 250 g and 100 rotations. (7) Length change (heat resistance) of the powdery molded product: a test piece punched out from the powdery molded product into a No. 3 dumbbell shape at 110 ° C.
Was suspended in a gear oven for 168 hours, and the change in length was measured. (8) Tear strength: Based on JIS K 6252, the tear strength in the direction parallel to the rotation direction at the time of molding was measured.

Example 1 (1) First Step (Production of Component (b)) 70 parts by mass of ethylene / methyl acrylate copolymer elastomer (Baymac GLS) manufactured by Toray DuPont Co., Ltd., polyester system manufactured by Toyobo Co., Ltd. 30 parts by weight of resin (Vylon GA3410), as an organic peroxide,
0.06 parts by mass of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name of NOF CORPORATION: Perhexa 25B), 1,9- as a crosslinking aid
Nonanediol dimethacrylate and 2-methyl-1,
15:85 with 8-octanediol dimethacrylate
(Mass ratio) 0.11 parts by mass of a mixture (trade name of Shin-Nakamura Chemical Co., Ltd .: NK ester IND), and additives such as various stabilizers were compounded at a ratio shown in Table 1, and DS3-made by Moriyama Manufacturing Co. Melt-kneading was performed using a 7.5 MWH-H type pressure double-arm type kneader to obtain an elastomer (b-1) having a hydrophilic functional group having the composition shown in Table 1.

(2) Second stage (melt kneading of (a) and (b)) 25 parts by weight of Mersen H6922X, which is a saponification product of ethylene-vinyl acetate copolymer manufactured by Tosoh Corporation having the physical properties shown in Table 2, is used. 30 parts by mass of H6051 and the above (b
-1) Resin pellets obtained by melt-kneading 45 parts by mass with a TEM-37 type twin-screw kneading extruder of Toshiba Machine were freeze-pulverized into a fine powder of 30 mesh pass by a freeze-pulverizer of Toho Cold Energy Co., Ltd. To obtain a powdery thermoplastic resin composition for molding a powdery body. Next, the obtained powdery thermoplastic resin composition was subjected to rotational molding under conditions of a mold temperature of 250 ° C. and a mold rotation speed of 6 times to obtain a powdery molded product. The physical properties of the resin composition and the powder compact were evaluated. The results are shown in Table 3.

Example 2 Example 1 was repeated except that the ethylene-vinyl acetate copolymer saponification product Mersen H6922X manufactured by Tosoh Corporation was changed to 60 parts by mass and the above (b-1) 40 parts by mass in the second step. A thermoplastic resin composition and a powdery compact were obtained in the same manner as in. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.

Example 3 In the first step, 55 parts by mass of ethylene / methyl acrylate copolymer elastomer (Baymack GLS) manufactured by Toray-Dupont Co., Ltd. and 45 parts by mass of polyester resin (Vylon GA3410) manufactured by Toyobo Co., Ltd. An elastomer (b-2) having a hydrophilic functional group having the composition shown in Table 2 was obtained in the same manner as in Example 1 except that the parts were changed.
In the second stage, a thermoplastic resin was prepared in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer saponified product Mersen H6922X manufactured by Tosoh Corporation was changed to 60 parts by mass and 40 parts by mass of the above (b-2). A composition and a powder compact were obtained. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.

Example 4 In the second stage, 25 parts by weight of the ethylene-vinyl acetate copolymer saponified product Mersen H6922X manufactured by Tosoh Corporation, 30 parts by mass of Mersen H6051 shown in Table 2, and (b-1) 45 parts by mass. Parts ratio, mersen H6922X
Was changed to 30 parts by mass, Mersen H6051 to 40 parts by mass, and (b-1) 30 parts by mass to obtain a thermoplastic resin composition and a powdery compact in the same manner as in Example 1.
The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.

Example 5 In the second stage, instead of 25 parts by mass of the saponified product of ethylene-vinyl acetate copolymer Mersen H6922X and 30 parts by mass of Mersen H6051 of Tosoh Corporation, Mitsui-DuPont Polychemical stock shown in Table 2 was used. EVAFLEX-EE, a company's ethylene-ethyl acrylate copolymer
25 parts by mass of AA-704 and EVAFLEX-EEA
Example 1 except that A-702 was changed to 30 parts by mass.
A thermoplastic resin composition and a powdery compact were obtained in the same manner as in. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.

Example 6 In the second step, EV which is an ethylene-ethyl acrylate copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd.
25 parts by mass of AFLEX-EEA A-704 and EVA
30 parts by mass of FLEX-EEA A-702, and (b
-1) Change the ratio of 45 parts by mass to EVAFLEX-EEA A
30 parts by mass of EVA-FLEX-EEA A-7
A thermoplastic resin composition and a powder compact were obtained in the same manner as in Example 5, except that 02 was changed to 40 parts by mass and (b-1) was changed to 30 parts by mass. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.
Shown in.

Example 7 In the first step, 40 parts by mass of ethylene-methyl acrylate copolymer elastomer (Baymack GLS) manufactured by Toray-Dupont Co., Ltd. and 60 parts by mass of polyester resin (Vylon GA3410) manufactured by Toyobo Co., Ltd. An elastomer (b-3) having a hydrophilic functional group shown in Table 1 was obtained in the same manner as in Example 1 except that the parts were changed. In the second stage, a thermoplastic resin was prepared in the same manner as in Example 1 except that the ethylene-vinyl acetate copolymer saponified product Mersen H6922X manufactured by Tosoh Corporation was changed to 60 parts by mass and 40 parts by mass of the above (b-3). A composition and a powder compact were obtained.
The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.

Example 8 Example 1 was repeated except that the ethylene-vinyl acetate copolymer saponification product Mersen H6920 manufactured by Tosoh Corporation was changed to 75 parts by mass and the above (b-2) 25 parts by mass in the second stage.
A thermoplastic resin composition and a powdery compact were obtained in the same manner as in. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.

Example 9 In the second stage, 6 of the ethylene-vinyl acetate copolymer saponification product Mersen 1H01A shown in Table 2 was used.
A thermoplastic resin composition and a powdery compact were obtained in the same manner as in Example 1 except that the amount was changed to 0 part by mass and the above (b-2) 40 parts by mass. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 3.

Example 10 (1) First Step (Production of Component (b)) 60 parts by mass of ethylene / methyl acrylate copolymer elastomer (Baymac GLS) manufactured by Toray DuPont Co., Ltd., polyester manufactured by Eastman Chemical Co., Ltd. 40 parts by mass of a resin (EASTAR BIO GP) as an organic peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name of NOF CORPORATION: Perhexa 25B) 0.06 parts by mass of 1,9-nonanediol dimethacrylate as a crosslinking aid and 2
0.15 parts by mass of a 15:85 (mass ratio) mixture with methyl-1,8-octanediol dimethacrylate (trade name of Shin Nakamura Chemical Co., Ltd .: NK ester IND), and further additives such as various stabilizers. Blended in a ratio shown in Table 1, melt-kneaded using a DS3-7.5MWH-H type pressure double-arm type kneader manufactured by Moriyama Seisakusho, and an elastomer having a hydrophilic functional group (having a composition shown in Table 1 ( b-4) was obtained.

(2) Second Step (Melting and Kneading of (a) and (b)) 30 parts by mass of MERSEN 1H01A which is a saponified ethylene-vinyl acetate copolymer manufactured by Tosoh Corporation having the physical properties shown in Table 2 and Mitsui・ Ethylene of DuPont Polychemical Co., Ltd.
40 vinyl acetate copolymer EVAFLEX EV40LX
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane (trade name of NOF CORPORATION: Perhexa) as 30 parts by mass of the above (b-4) as an organic peroxide. 25B) as 0.06 parts by mass, and as a crosslinking aid,
1 of 1,9-nonanediol dimethacrylate and 2-methyl-1,8-octanediol dimethacrylate
5:85 (mass ratio) mixture (trade name of Shin Nakamura Chemical Co., Ltd .: N
K ester IND) at a ratio of 0.11 parts by mass,
The resin pellets obtained by melt-kneading with a TEM-37 type twin-screw kneading extruder of Toshiba Machine Co., Ltd. are frozen and pulverized to a fine powder of 42 mesh pass, 200 mesh on by a freeze pulverizer of Toho Cold Energy Co., Ltd. A powdery thermoplastic resin composition for body molding was obtained. Next, the obtained powdery thermoplastic resin composition was subjected to rotational molding under conditions of a mold temperature of 250 ° C. and a mold rotation speed of 6 times to obtain a powdery molded product. The physical properties of the resin composition and the powder compact were evaluated. The results are shown in Table 3.

Example 11 (2) In the second step (melt kneading of (a) and (b)), 40 parts by mass of Mersen 1H01A which is a saponified ethylene-vinyl acetate copolymer manufactured by Tosoh Co., Ltd., Mitsui. 30 parts by mass of Evaflex EV40LX, an ethylene-vinyl acetate copolymer manufactured by DuPont Polychemical Co., Ltd., 30 parts by mass of the above (b-4), 2,5 as an organic peroxide.
-Dimethyl-2,5-di (t-butylperoxy) hexane (trade name of NOF CORPORATION: Perhexa 25B)
0.06 parts by mass, and a 15:85 (mass ratio) of 1,9-nonanediol dimethacrylate and 2-methyl-1,8-octanediol dimethacrylate as a crosslinking aid (Shin-Nakamura Chemical Co., Ltd.). Product Name: NK Ester IN
The same procedure as in Example 10 was carried out except that the ratio of D) was changed to 0.11 part by mass. The results are shown in Table 3.

Example 12 (2) In the second step (melt kneading of (a) and (b)), 20 parts by mass of Mersen 1H01A, which is a saponification product of ethylene-vinyl acetate copolymer manufactured by Tosoh Corporation, and Mersen H6051 were used. 20 parts by mass, 30 parts by mass of ethylene-vinyl acetate copolymer EVA45EV of Mitsui DuPont Polychemical Co., Ltd., 30 parts by mass of (b-4) above, and 2,5-dimethyl as an organic peroxide. -2,5
0.06 parts by mass of di (t-butylperoxy) hexane (trade name of NOF CORPORATION Perhexa 25B),
And as a crosslinking aid, a 15:85 (mass ratio) mixture of 1,9-nonanediol dimethacrylate and 2-methyl-1,8-octanediol dimethacrylate (trade name of Shin Nakamura Chemical Co., Ltd .: NK ester IND). Was performed in the same manner as in Example 10 except that the ratio was changed to 0.11 parts by mass. The results are shown in Table 3.

Comparative Example 1 In the first step, the organic peroxide 2,5-dimethyl-
6 parts by mass of 2,5-di (t-butylperoxy) hexane (trade name of NOF CORPORATION: Perhexa 25B),
A crosslinking aid 1,9-nonanediol dimethacrylate,
A 15:85 (mass ratio) mixture with 2-methyl-1,8-octanediol dimethacrylate (trade name of Shin Nakamura Chemical Co., Ltd .: NK ester IND) was changed to 6 parts by mass and Table 1 was used.
A thermoplastic resin composition and a rotomolded product were obtained in the same manner as in Example 1 except that the elastomer (P-1) having a hydrophilic functional group shown in 1 was obtained. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 4.
Shown in. Poor smoothness, heat resistance (change in length), and tear strength of pinholes and the back of molded products.

Comparative Example 2 In the first step, 5 parts by mass of ethylene / methyl acrylate copolymer elastomer (Baymack GLS) manufactured by Toray-Dupont Co., Ltd. and 95 parts by mass of polyester resin (Vylon GA3410) manufactured by Toyobo Co., Ltd. were used. Thermoplastic resin composition and rotation were carried out in the same manner as in Example 1 except that the elastomer (P-2) having a hydrophilic functional group shown in Table 1 was obtained in the same manner as in Example 1 except that the parts were changed. A molded body was obtained. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 4. Inferior in wear resistance, heat resistance (change in length) and tear strength.

Comparative Example 3 Hydrogenated styrene-butadiene elastomer (SBR) was used instead of the elastomer (b-1) having hydrophilic functional group.
A thermoplastic resin composition and a powder compact were obtained in the same manner as in Example 4 except that Dynaron 2324P manufactured by JSR Corporation was used. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 4. Poor physical properties such as wear resistance, heat resistance, and tear strength.

Comparative Example 4 In the first step, the organic peroxide 2,5-dimethyl-
6 parts by mass of 2,5-di (t-butylperoxy) hexane (trade name of NOF CORPORATION: Perhexa 25B),
A crosslinking aid 1,9-nonanediol dimethacrylate,
Hydrophilicity shown in Table 1 by changing the 15:85 (mass ratio) mixture with 2-methyl-1,8-octanediol dimethacrylate (trade name of Shin Nakamura Chemical Co., Ltd .: NK ester IND) to 0.11 parts by mass. Elastomer having a functional group (P-
A thermoplastic resin composition and a rotomolded product were obtained in the same manner as in Example 1 except that 3) was obtained. The physical properties of the obtained resin composition and powder compact were evaluated. The results are shown in Table 4. Poor smoothness, heat resistance (change in length), and tear strength of pinholes and the back of molded products.

In the first step, 0.06 of organic peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name of NOF CORPORATION, Perhexa 25B) was added. 15:85 (mass ratio) mixture of 1 part by mass of a crosslinking aid 1,9-nonanediol dimethacrylate and 2-methyl-1,8-octanediol dimethacrylate (trade name of Shin Nakamura Chemical Co., Ltd .: NK ester IN)
The elastomer (P-4) having a hydrophilic functional group shown in Table 1 in which D) is changed to 6.00 parts by mass has a poor appearance due to the self-polymer of the crosslinking aid.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

EFFECT OF THE INVENTION The thermoplastic resin composition for powder molding according to the present invention is excellent in weather resistance, scratch resistance and heat resistance, and solves gasification, pinholes, blocking, etc. during powder molding, Moreover, the molded product obtained by molding the powdery material becomes a molded product with a smooth back surface, and can be suitably used for toys and automobile interior parts.

Continued front page    F-term (reference) 4F071 AA15 AA28 AA32 AA33 AA43                       AA47 AC08 AE02 AE03 AF22                       AF45 AF54 BB03 BC01                 4J002 AE033 AE043 BB04W BB06W                       BB07W BB07X BB08W CF00X                       CF03X CF04X CF05X CP033                       EH007 EH017 EH077 EK006                       EK016 EK036 EK056 FD01                       FD07 FD09 FD146 FD157                       FD17 GC00 GN00

Claims (13)

[Claims] 1. A group of (a) a saponified product of an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid ester copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene-vinyl acetate copolymer. Polyolefin resins 10-9 having at least one hydrophilic functional group selected from
5% by mass and (b) an elastomer and / or elastomer composition having a hydrophilic functional group and / or 90 to 5% by mass of a main component are pellet-shaped or powder-shaped thermoplastic resin composition for powder molding. A thermoplastic resin composition, characterized in that the press sheet of the thermoplastic resin composition satisfies the following: Taber abrasion resistance conforms to JIS K 7204,
Wear wheel CS-10, 250 g, when measured under the conditions of 100 rotations, the wear amount is 3 mg or less. When a test piece punched out from a press sheet into a No. 3 dumbbell shape was suspended in a gear oven at 110 ° C for 168 hours, the change in length was 2% or less. 2. An elastomer and / or an elastomer composition having (b) a hydrophilic functional group comprises 10 to 95% by mass of a cross-linking agent-crosslinking elastomer (bα) having a hydrophilic functional group and (bβ) a hydrophilic functional group. The thermoplastic resin composition according to claim 1, which comprises 90 to 5% by mass of a crosslinker-decomposable resin having a group. 3. The (b) elastomer and / or elastomer composition having a hydrophilic functional group is [(bα) + (b
[beta]]] in total of 100 parts by mass, (c) 0.001 to 5 parts by mass of an organic peroxide, and (d) 0.00 of a crosslinking aid.
The thermoplastic resin composition according to claim 1, comprising 1 to 5 parts by mass. 4. The (b) elastomer having a hydrophilic functional group and / or (bα) the cross-linking agent cross-linking elastomer having a hydrophilic functional group of the elastomer composition is an ethylene-methyl acrylate copolymer elastomer. , (B
The thermoplastic resin composition according to any one of claims 1 to 3, wherein the cross-linking agent decomposable resin having a β) hydrophilic functional group is a polyester resin. 5. A total of 100 of the component (a) and the component (b).
Any one of claims 1 to 4, further comprising 0.001 to 5 parts by mass of the component (c) crosslinking agent with respect to parts by mass.
The thermoplastic resin composition according to item. 6. A total of 100 of the component (a) and the component (b).
The component (c) crosslinking agent 0.001 to 5 parts by mass and the component (d) crosslinking auxiliary agent 0.001 to 5 parts by mass relative to parts by mass are further included. The thermoplastic resin composition according to item 1. 7. A method for producing a pellet-like or powder-like thermoplastic resin composition for forming a powdery body, the press sheet of which satisfies the following: (a) a saponified product of an ethylene-vinyl acetate copolymer, Polyolefin resin 1 having at least one hydrophilic functional group selected from the group consisting of ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene-vinyl acetate copolymer
A method for producing a thermoplastic resin composition, comprising melt-kneading a component containing 0 to 95% by mass and (b) an elastomer having a hydrophilic functional group and / or 90 to 5% by mass of an elastomer composition as a main component. Taber abrasion resistance conforms to JIS K 7204,
Wear wheel CS-10, 250 g, when measured under the conditions of 100 rotations, the wear amount is 3 mg or less. When a test piece punched out from a press sheet into a No. 3 dumbbell shape was suspended in a gear oven at 110 ° C for 168 hours, the change in length was 2% or less. 8. An elastomer and / or an elastomer composition having (b) a hydrophilic functional group comprises 10 to 95% by mass of a cross-linking agent-crosslinking elastomer (bα) having a hydrophilic functional group and (bβ) a hydrophilic functional group. The method for producing a thermoplastic resin composition according to claim 7, wherein 90 to 5% by mass of a crosslinker-decomposable resin having a group is melt-kneaded. 9. A cross-linking agent cross-linking type elastomer having a hydrophilic functional group (bα) as a first step, 10 to 95% by mass,
(Bβ) Crosslinking agent decomposable resin 90 having a hydrophilic functional group
5% by mass, relative to 100 parts by mass of [(bα) + (bβ)], 0.001 to 5 parts by mass of (c) organic peroxide,
And (d) 0.001 to 5 parts by mass of a crosslinking aid is melt-kneaded to produce (b) an elastomer and / or elastomer composition having a hydrophilic functional group, and as a second step, (a)
9. The thermoplastic resin composition according to claim 7, wherein the polyolefin resin having a hydrophilic functional group and the (b) elastomer having a hydrophilic functional group obtained in the first step are melt-kneaded. Production method. 10. The crosslinking agent crosslinkable elastomer having a hydrophilic functional group (bα) is an ethylene-methyl acrylate copolymer elastomer, and the crosslinking agent decomposable resin having a hydrophilic functional group (bβ) is It is a polyester resin, The manufacturing method of the thermoplastic resin composition of any one of Claims 7-9 characterized by the above-mentioned. 11. A total of 10 of the component (a) and the component (b).
The method for producing a thermoplastic resin composition according to claim 7, further comprising 0.001 to 5 parts by mass of the component (c) crosslinking agent with respect to 0 parts by mass. 12. A total of 10 of the component (a) and the component (b).
Any one of claims 7 to 10, further comprising 0.001 to 5 parts by mass of the component (c) crosslinking agent and 0.001 to 5 parts by mass of the component (d) crosslinking aid with respect to 0 parts by mass. 2. The method for producing a thermoplastic resin composition according to item 1. 13. A molded product made of the thermoplastic resin composition according to claim 1.