JP6291702B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a thermoplastic resin composition and a molded article thereof.

Improving the impact resistance of the molded product not only expands the applications of the molded product, but also makes it extremely useful for industrial applications, such as enabling the molded product to be made thinner and larger. . Therefore, various techniques have been proposed so far for improving the impact resistance of the molded product.
Among these methods, by using a resin material in which a rubber polymer and a hard resin are combined, a method for improving the impact resistance of a molded product while maintaining the characteristics derived from the hard resin has already been industrialized. . Examples of such resin materials include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylic acid ester (ASA) resin, acrylonitrile-ethylene / α-olefin-styrene (AES) resin, or a hard resin thereof. The thermoplastic resin composition etc. which were added to are mentioned.

For example, the following are known as thermoplastic resin compositions capable of obtaining a molded article having improved impact resistance while maintaining the characteristics derived from the hard resin.
(1) A thermoplastic resin composition obtained by adding an AES resin to a methacrylic ester resin which is a hard resin (Patent Document 1).
(2) A thermoplastic resin composition in which an AES resin is added to a maleimide copolymer that is a hard resin (Patent Document 2).
(3) A thermoplastic resin composition obtained by adding an AES resin and an ASA resin to a methacrylic ester resin which is a hard resin (Patent Document 3).

However, in the thermoplastic resin compositions of (1) and (2), it is necessary to add a large amount of AES resin in order to improve the impact resistance of the molded product. The surface hardness (scratch resistance) derived from the resin and the heat resistance derived from the maleimide copolymer are significantly reduced. In addition, since it is necessary to add an AES resin having a relatively large particle size in order to improve the impact resistance of the molded product, the color developability derived from the hard resin is reduced in the obtained molded product.
In the thermoplastic resin composition of (3), AES resin and ASA resin are added in order to suppress a decrease in color developability of the molded product, but the impact resistance of the molded product is higher than when only the AES resin is added. Is inferior.

JP 2005-132970 A JP 2004-352842 A JP 2004-346187 A

  The present invention is a thermoplastic resin composition having good flowability and excellent scratch resistance, impact resistance, cold shock resistance, color development, and lubricity of the obtained molded article, and scratch resistance, impact resistance, To provide molded products with excellent cold shock resistance, color development and lubricity.

The present invention includes the following aspects.
[1] An ethylene / α-olefin copolymer (A) having a mass average molecular weight (Mw) of 17 × 10 ^{4 to} 35 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1 to 3, or the ethylene / Graft copolymer obtained by polymerizing vinyl monomer component (m1) in the presence of crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking α-olefin copolymer (A). (D),
A graft copolymer (F) obtained by polymerizing the vinyl monomer component (m2) in the presence of the rubber-like polymer (E);
A methacrylate ester resin (G) obtained by polymerizing a vinyl-based monomer component (m3) containing a methacrylate ester;
Silica particles (H),
The average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) contained in the graft polymer (D) is 0.20 μm to 0.60 μm,
The rubbery polymer (E) contained in the graft copolymer (F) has an average particle size of 0.05 μm to 0.18 μm,
Of the total (100% by mass) of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the rubbery polymer (E), ethylene / α-olefin The ratio of the copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 15 to 85% by mass, and the ratio of the rubbery polymer (E) is 85 to 15% by mass. Thermoplastic resin composition.
[2] The graft copolymer (D) is obtained by polymerizing the vinyl monomer component (m1) in the presence of the crosslinked ethylene / α-olefin copolymer (C). The thermoplastic resin composition according to [1].
[3] A molded article using the thermoplastic resin composition according to [1] or [2].

The thermoplastic resin composition of the present invention has good fluidity. In addition, according to the thermoplastic resin composition of the present invention, a molded product having excellent scratch resistance, impact resistance, cold impact resistance, color developability, and lubricity can be obtained.
The molded article of the present invention is excellent in scratch resistance, impact resistance, cold impact resistance, color development, and lubricity.

It is the schematic explaining the abrasion-resistance test by gauze wear. It is the schematic explaining the evaluation method of lubricity.

The following definitions of terms apply throughout this specification and the claims.
“(Meth) acrylic acid” means acrylic acid or methacrylic acid.
“Molded product” means a product formed by molding a thermoplastic resin composition.
“Scratch resistance” refers to the resistance to scratches (scratch resistance) caused by scratching the surface of a molded article with a hard, pointed object such as a nail, and work gloves, gauze, cloth, etc. It means both scratch resistance (scratch resistance) against scratches (scratches) that occur when the surface of a molded product is rubbed with a soft material.
“Lightness (L ^* )” means the lightness value (L ^* ) of the color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729: 2004.
The “SCE method” means a method of measuring a color by using a spectrocolorimeter compliant with JIS Z 8722: 2009 and removing specularly reflected light with an optical trap.

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention contains a graft copolymer (D), a graft copolymer (F), a methacrylic ester resin (G), and silica particles (H). The thermoplastic resin composition of the present invention may contain a styrenic copolymer (I), other thermoplastic resins, and various additives as necessary within the range not impairing the effects of the present invention. .

The graft copolymer (D) is the following (α) or (β).
(Α) A product obtained by polymerizing the vinyl monomer component (m1) in the presence of the ethylene / α-olefin copolymer (A).
(Β) A product obtained by polymerizing the vinyl monomer component (m1) in the presence of the crosslinked ethylene / α-olefin copolymer (C).

  Specifically, the vinyl monomer component (m1) is polymerized in the olefin resin aqueous dispersion (B) which is an aqueous dispersion of the ethylene / α-olefin copolymer (A) as the (α). And those obtained by polymerizing the vinyl monomer component (m1) in a solution of the ethylene / α-olefin copolymer (A).

  Specifically, the (β) is obtained by polymerizing the vinyl monomer component (m1) in an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (C), Examples thereof include those obtained by polymerizing the vinyl monomer component (m1) in a solution of the α-olefin copolymer (C).

The graft copolymer (F) is obtained by polymerizing the vinyl monomer component (m2) in the presence of the rubber-like polymer (E).
The methacrylic ester resin (G) is obtained by polymerizing the vinyl monomer component (m3).
The styrene copolymer (I) is obtained by polymerizing the vinyl monomer component (m4).
Hereinafter, each component ((A)-(I), (m1)-(m4) etc.) is demonstrated.

<Ethylene / α-olefin copolymer (A)>
The ethylene / α-olefin copolymer (A) comprises an ethylene unit and an α-olefin unit obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms by a known polymerization method. It is a copolymer.

  Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-icosene, 1-docosene, etc. From the viewpoint of impact resistance, an α-olefin having 3 to 20 carbon atoms is preferable, and propylene is particularly preferable.

  The ethylene unit content of the ethylene / α-olefin copolymer (A) is 45 to 45% when the total of all the structural units constituting the ethylene / α-olefin copolymer (A) is 100% by mass. 65 mass% is preferable and 50-60 mass% is more preferable. When the ethylene unit content is within the above range, the balance of the scratch resistance, impact resistance, cold impact resistance, and lubricity of the molded product is further improved. In particular, when the ethylene unit content is 50 to 60% by mass, the scratch resistance, impact resistance, and cold impact resistance of the molded product are further improved.

The mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (A) is 17 × 10 ^{4 to} 35 × 10 ⁴ , and preferably 26 × 10 ^{4 to} 32 × 10 ⁴ . When the mass average molecular weight (Mw) is smaller than 17 × 10 ⁴ , the scratch resistance, impact resistance, cold impact resistance, and lubricity of the molded product are inferior. On the other hand, when the mass average molecular weight (Mw) is larger than 35 × 10 ⁴ , the fluidity of the thermoplastic resin composition and the color developability of the molded product are inferior. When the mass average molecular weight (Mw) is 26 × 10 ^{4 to} 32 × 10 ⁴ , the fluidity of the thermoplastic resin composition and the scratch resistance, impact resistance, and cold impact resistance of the molded product are further improved.

  The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (A) is 1 to 3, and preferably 1.9 to 2.5. When the molecular weight distribution (Mw / Mn) is larger than 3, the molded article has poor scratch resistance, impact resistance, cold impact resistance, and lubricity. When the molecular weight distribution (Mw / Mn) is 1.9 to 2.5, the fluidity of the thermoplastic resin composition, the scratch resistance and the impact resistance of the molded product are further improved.

  The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer (A) are values measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

  The degree of crystallinity of the ethylene / α-olefin copolymer (A) is preferably 0% to 30%, more preferably 1% to 30%. When the crystallinity is within the above range, the balance of scratch resistance, impact resistance, cold shock resistance and lubricity of the molded product is further improved. In particular, when the crystallinity is 1% to 30%, the scratch resistance, impact resistance, cold impact resistance, and lubricity are further improved. The crystallinity of the ethylene / α-olefin copolymer (A) is determined from the ratio of the peak area of the crystal by measuring X-ray diffraction.

  The method for producing the ethylene / α-olefin copolymer (A) is not limited. The ethylene / α-olefin copolymer (A) is usually produced by polymerizing ethylene and an α-olefin using a metallocene catalyst or a Ziegler-Natta catalyst.

As a metallocene catalyst, a catalyst obtained by combining an organic compound having a cyclopentadienyl skeleton with a transition metal (zirconium, titanium, hafnium, etc.), a metallocene complex in which a halogen atom or the like is coordinated, an organoaluminum compound, an organoboron compound, etc. Is mentioned.
Examples of the Ziegler-Natta catalyst include a catalyst in which a halide of a transition metal (titanium, vanadium, zirconium, hafnium, etc.) is combined with an organic aluminum compound, an organic boron compound, or the like.

  Examples of the polymerization method include a method in which ethylene and an α-olefin are copolymerized in a solvent in the presence of the catalyst. Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may use the raw material alpha olefin as a solvent.

  By changing the reaction conditions such as the supply amount of ethylene, α-olefin, the type and amount of molecular weight regulators such as hydrogen, the type and amount of catalyst, the reaction temperature, and the pressure, an ethylene / α-olefin copolymer (A ) Ethylene unit content, mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be adjusted.

<Olefin resin aqueous dispersion (B)>
The aqueous olefin resin dispersion (B) is obtained by dispersing the ethylene / α-olefin copolymer (A) in an aqueous medium.
The aqueous olefin resin dispersion (B) may contain an emulsifier, an acid-modified olefin polymer, and the like as other components.

Examples of the emulsifier include known ones, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
Since the content of the emulsifier in the aqueous olefin resin dispersion (B) can suppress the thermal coloring of the resulting thermoplastic resin composition, the particle size of the aqueous olefin resin dispersion (B) can be easily controlled. -1-8 mass parts is preferable with respect to 100 mass parts of alpha-olefin copolymer (A).

Examples of the acid-modified olefin polymer include those obtained by modifying an olefin polymer having a mass average molecular weight of 1,000 to 5,000 (polyethylene, polypropylene, etc.) with a compound having a functional group (such as an unsaturated carboxylic acid compound). It is done. Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, and the like.
The content of the acid-modified olefin polymer in the aqueous olefin resin dispersion (B) is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (A). When the addition amount of the acid-modified olefin polymer is within the above range, the balance between scratch resistance and impact resistance of the molded product is further improved.

  The preparation method of the olefin resin aqueous dispersion (B) is not limited. As a preparation method, for example, an ethylene / α-olefin copolymer (A) and, if necessary, an acid-modified olefin polymer are melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.). And then adding to an aqueous medium containing an emulsifier; an ethylene / α-olefin copolymer (A) and optionally an acid-modified olefin polymer in a hydrocarbon solvent (pentane, Hexane, heptane, benzene, toluene, xylene, etc.) together with an emulsifier, added to an aqueous medium and emulsified, and then sufficiently stirred to distill off the hydrocarbon solvent.

  The average particle diameter of the ethylene / α-olefin copolymer (A) in the olefin resin aqueous dispersion (B) is 0.20 to 0.60 μm from the viewpoint of excellent physical properties of the molded product, and is 0.30 to 0.30. 0.50 μm is preferable. When the average particle diameter is within the above range, the molded article is excellent in impact resistance, cold impact resistance, color development, scratch resistance and lubricity.

  As a method for controlling the average particle size of the ethylene / α-olefin copolymer (A) in the olefin resin aqueous dispersion (B), the type or amount of the emulsifier, the type or content of the acid-modified olefin polymer, The method of adjusting the shear force, temperature conditions, etc. which are applied at the time of kneading | mixing is mentioned.

<Crosslinked ethylene / α-olefin copolymer (C)>
The crosslinked ethylene / α-olefin copolymer (C) is obtained by crosslinking the ethylene / α-olefin copolymer (A).
By crosslinking the ethylene / α-olefin copolymer (A), the balance of scratch resistance, impact resistance, cold impact resistance, color developability and lubricity of the molded product is further improved.

The gel content of the crosslinked ethylene / α-olefin copolymer (C) is 35 to 75% by mass from the viewpoint of the balance of scratch resistance, impact resistance, cold impact resistance, color development, and lubricity of the molded product. Is preferable, 40-70 mass% is more preferable, 45-65 mass% is especially preferable.
The gel content means that the crosslinked ethylene / α-olefin copolymer (C) is swollen with toluene and the dried toluene insoluble to the crosslinked ethylene / α-olefin copolymer (C) before swelling. The ratio of minutes.

  The crosslinking treatment of the ethylene / α-olefin copolymer (A) can be carried out by a known method. As a crosslinking treatment method, (a) an organic peroxide and, if necessary, a polyfunctional compound are added to the ethylene / α-olefin copolymer (A) or the aqueous olefin resin dispersion (B). (B) A method of performing a crosslinking treatment with ionizing radiation, and the like, and the method (a) is preferred from the viewpoint of impact resistance and color developability of the molded product.

Specifically, as the method of (a), an ethylene / α-olefin copolymer (A) or an aqueous olefin resin dispersion (B) is mixed with an organic peroxide and, if necessary, a multifunctional compound. The method of adding and heating is mentioned.
The gel content of the crosslinked ethylene / α-olefin copolymer (C) can be adjusted by adjusting the addition amount of organic peroxide and polyfunctional compound, heating temperature, heating time and the like.
The heating temperature varies depending on the type of organic peroxide. The heating temperature is preferably −5 ° C. to + 30 ° C., which is the 10-hour half-life temperature of the organic peroxide.
The heating time is preferably 3 to 15 hours.

  The organic peroxide is for forming a crosslinked structure in the ethylene / α-olefin copolymer (A). Examples of the organic peroxide include a peroxy ester compound, a peroxy ketal compound, a dialkyl peroxide compound, and the like. An organic peroxide may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the peroxyester compound include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 -Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexyl peroxy 2-hexyl Hexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexano Ate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl Peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoe , Bis (t-butylperoxy) isophthalate.

  Specific examples of the peroxyketal compound include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) Examples include butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, and the like.

  Specific examples of the dialkyl peroxide compound include α, α′-bis (t-butyl peroxide) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butyl. Examples include cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

  As the organic peroxide, dialkyl such as dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, etc., because it is easy to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C). Peroxide compounds are particularly preferred.

  The addition amount of the organic peroxide is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted to a range of 35 to 75% by mass, so that the ethylene / α-olefin copolymer (A ) 0.1 to 5 parts by mass is preferable with respect to 100 parts by mass.

The polyfunctional compound is used in combination with an organic peroxide as necessary in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C).
Examples of the multifunctional compound include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate, and the like. From the viewpoint of easily adjusting the gel content, divinylbenzene is preferable. A polyfunctional compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the polyfunctional compound is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted to 35 to 75% by mass, and thus the ethylene / α-olefin copolymer (A) 100 is used. 10 parts by mass or less is preferable with respect to parts by mass.

  When an organic peroxide and, if necessary, a polyfunctional compound are added to the olefin resin aqueous dispersion (B) and subjected to crosslinking treatment, an aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C) is obtained. can get. The aqueous dispersion may contain an emulsifier, an acid-modified olefin polymer and the like as other components. Examples of the emulsifier and the acid-modified olefin polymer are the same as those described above. The acid-modified olefin polymer may be subjected to a crosslinking treatment.

  When an organic peroxide and, if necessary, a polyfunctional compound are added to the ethylene / α-olefin copolymer (A), melt-kneaded and pulverized, a crosslinked ethylene / α-olefin copolymer (C ) Powder is obtained. The powder may contain an acid-modified olefin polymer and the like as other components. Examples of the acid-modified olefin polymer are the same as described above. The acid-modified olefin polymer may be subjected to a crosslinking treatment.

The method for adding the acid-modified olefin polymer is not limited. Crosslinking may be performed after mixing the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer, or the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer. You may mix, after each crosslinking process.
The mixing method of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer is not limited. Examples of the mixing method include a melt kneading method using a kneader, a Banbury mixer, a multi-screw extruder and the like.

  The average particle size of the crosslinked ethylene / α-olefin copolymer (C) is 0.20 to 0.60 μm, preferably 0.30 to 0.50 μm, from the viewpoint of excellent physical properties of the molded product. When the average particle diameter is within the above range, the molded article is excellent in impact resistance, cold impact resistance, color development, scratch resistance and lubricity.

  The average particle size of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion obtained by adding an organic peroxide or the like to the aqueous dispersion of the olefin resin (B) is olefin resin aqueous dispersion. There is no change with respect to the average particle diameter of the ethylene / α-olefin copolymer (A) in the body (B).

<Vinyl monomer component (m1)>
The vinyl monomer component (m1) is composed of one or more monomers selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, and other vinyl monomers.
The vinyl monomer component (m1) preferably contains at least an aromatic vinyl compound and a vinyl cyanide compound.

  Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferable from the viewpoints of fluidity, color developability of molded products, and impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  65-82 mass% is preferable among 100 mass% of vinyl-type monomer components (m1), and, as for the content rate of an aromatic vinyl compound, 73-80 mass% is more preferable, and 75-80 mass% is further more preferable. When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and further preferably 20 to 25% by mass in 100% by mass of the vinyl monomer component (m1). When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  Other monomers include acrylic acid esters (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc.) ), Maleimide compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like. Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.

<Graft copolymer (D)>
The graft copolymer (D) polymerizes the vinyl monomer component (m1) in the presence of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C). Can be obtained.

  The graft copolymer (D) is a vinyl monomer component (in the presence of 50 to 80% by mass of an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C)). m1) 20-50% by mass (however, the total of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the vinyl monomer component (m1) is 100% by mass) %) Is preferred. When the ethylene / α-olefin copolymer (A) is 50 to 80% by mass, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, and the balance of physical properties of the coloring property are further improved.

  The graft ratio of the graft copolymer (D) is preferably 20 to 100% by mass from the viewpoint of the balance between the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, and the color development.

  Examples of the polymerization method include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.).

As a method for producing the graft copolymer (D) by emulsion polymerization, for example, an organic peroxide is mixed with the vinyl monomer component (m1), and then the vinyl monomer component (m1) is converted to olefin. Examples thereof include a method of continuously adding the aqueous resin dispersion (B) or the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C).
The organic peroxide is preferably used as a redox initiator that combines an organic peroxide, a transition metal, and a reducing agent.
In the polymerization, a chain transfer agent, an emulsifier or the like may be used depending on the situation.

The redox initiator does not require the polymerization reaction conditions to be at a high temperature, avoids deterioration of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C), and is molded. A combination of an organic peroxide and a ferrous sulfate-chelating agent-reducing agent is preferable from the viewpoint of avoiding a decrease in impact resistance of the product.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, and t-butyl hydroperoxide.
The redox initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of chain transfer agents include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allylsulfonic acid, methallylsulfonic acid, these Sodium salts, etc.), α-methylstyrene dimers, and the like, and mercaptans are preferred from the viewpoint of easy adjustment of the molecular weight. A chain transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
The addition amount of the chain transfer agent is preferably 2.0 parts by mass or less with respect to 100 parts by mass of the vinyl monomer component (m1).

Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, and amino acid derivative salts.
Examples of nonionic surfactants include ordinary polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types.
Examples of the amphoteric surfactant include those having a carboxylate salt, sulfate ester salt, sulfonate salt, phosphate ester salt and the like in the anion portion and amine salts and quaternary ammonium salts in the cation portion.
The amount of the emulsifier added is preferably 10 parts by mass or less with respect to 100 parts by mass of the vinyl monomer component (m1).

The graft copolymer (D) obtained by the emulsion polymerization method is in a state of being dispersed in water.
As a method for recovering the graft copolymer (D) from the aqueous dispersion containing the graft copolymer (D), for example, a precipitation agent is added to the aqueous dispersion, and after heating and stirring, the precipitation agent is separated. And a precipitation method in which the precipitated graft copolymer (D) is washed with water, dehydrated and dried.
Examples of the precipitating agent include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. A precipitation agent may be used individually by 1 type, and may be used in combination of 2 or more type.
An antioxidant may be added to the aqueous dispersion containing the graft copolymer (D) as necessary.

As a method for producing the graft copolymer (D) by the solution polymerization method, for example, an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C) is dissolved in a solvent. And a method of adding a polymerization initiator and a vinyl monomer component (m1).
As the solvent, an inert polymerization solvent used in ordinary radical polymerization is used, and aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, and halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride. Etc. are used.
As the polymerization initiator used for the solution polymerization, a general initiator is used. For example, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide are used. Moreover, as the addition method of a polymerization initiator, the method of adding collectively and the method of adding continuously are mentioned.

<Rubber polymer (E)>
The rubbery polymer (E) is not particularly limited, and examples thereof include diene rubbery polymers, acrylic rubbery polymers, olefinic rubbery polymers, silicone rubbery polymers, and the like. System-acrylic composite rubbery polymer, silicone-acrylic composite rubbery polymer, and the like.
Among these, acrylic rubber-like polymer, olefin rubber-like polymer, silicone rubber-like polymer, and silicone-acrylic composite rubber-like polymer are preferred because of excellent weather resistance, and because of excellent impact resistance. Silicone-acrylic composite rubbery polymerization is more preferred. These may be used alone or in combination of two or more.

  The diene rubber-like polymer is, for example, a diene rubber-like polymer containing a diene component such as butadiene and isoprene and, if necessary, a monomer component copolymerizable with these as constituent components. Examples include polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene-styrene copolymer, polychloroprene, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Although the manufacturing method of a diene rubber-like polymer is not specifically limited, The well-known emulsion polymerization method is preferable. At that time, known emulsifiers, polymerization initiators, chain transfer agents and the like can be used. In controlling the particle diameter, a diene rubbery polymer having a small particle diameter may be produced in advance, and the particle diameter may be increased by a known enlargement treatment.

The acrylic rubber-like polymer is preferably a copolymer having one or both of a unit derived from a (meth) acrylic acid ester, a unit derived from a crosslinking agent, and a unit derived from a graft crossing agent. .
Examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group, and acrylic acid esters having an aromatic hydrocarbon group (such as a phenyl group or a benzyl group). From the viewpoint of impact resistance of the molded product, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferable. One (meth) acrylic acid ester may be used alone, or two or more may be used in combination.
Examples of the crosslinking agent include dimethacrylate compounds, and specific examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and the like.
Examples of the grafting agent include allyl compounds, specifically, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like.

  The method for producing the acrylic rubbery polymer is not particularly limited. For example, a method of obtaining an aqueous dispersion of an acrylic rubber-like polymer by emulsion polymerization of a monomer component containing (meth) acrylic acid ester and one or both of a crosslinking agent and a graft crossing agent, etc. It is done.

Examples of the olefin rubber-like polymer include an ethylene / α-olefin copolymer and an ethylene-propylene-nonconjugated diene copolymer.
Examples of the α-olefin of the ethylene / α-olefin copolymer include propylene having 3 or more carbon atoms, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene. 1-icosene, 1-docosene and the like. One α-olefin may be used alone, or two or more α-olefins may be used in combination.
The ethylene-propylene-nonconjugated diene copolymer is a copolymer comprising an ethylene unit, a propylene unit, and a nonconjugated diene unit that is a third component.
Examples of the non-conjugated diene of the ethylene-propylene-non-conjugated diene copolymer include dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1, Examples include 4-cycloheptadiene and 1,5-cyclooctadiene. A nonconjugated diene may be used individually by 1 type, and may be used in combination of 2 or more type.

The method for producing the olefin rubber-like polymer is not limited. For example, an olefin rubber-like polymer is usually produced by polymerizing ethylene and an α-olefin using a metallocene catalyst or a Ziegler-Natta catalyst.
Examples of the polymerization method include a method of copolymerizing ethylene and α-olefin in a solvent in the presence of a catalyst. Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may use the raw material alpha olefin as a solvent.

The olefin rubber-like polymer may be subjected to a crosslinking treatment.
The crosslinking treatment can be performed by a known method. As a method for the crosslinking treatment, the same method as that for obtaining the crosslinked ethylene / α-olefin copolymer (C) can be used.

The olefin rubber-like polymer may be an aqueous dispersion.
The aqueous dispersion of the olefin rubber-like polymer may contain an emulsifier, an acid-modified olefin polymer and the like as other components.

Examples of the emulsifier include known ones, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
Examples of the acid-modified olefin polymer include those obtained by modifying an olefin polymer having a mass average molecular weight of 1,000 to 5,000 (polyethylene, polypropylene, etc.) with a compound having a functional group (such as an unsaturated carboxylic acid compound). It is done. Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, and the like.

  The method for preparing the aqueous dispersion of the olefin rubber-like polymer is not limited. As a preparation method, for example, an olefin rubber-like polymer and, if necessary, an acid-modified olefin polymer are melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.), and mechanical shearing is performed. A method of dispersing by applying force and adding to an aqueous medium containing an emulsifier; an olefin rubber-like polymer and, if necessary, an acid-modified olefin polymer in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) ) And an emulsifier, added to an aqueous medium and emulsified, and then sufficiently stirred to distill off the hydrocarbon solvent.

  When the olefin rubber-like polymer is subjected to a crosslinking treatment, the method for adding the acid-modified olefin polymer is not limited. The olefin rubber-like polymer and the acid-modified olefin polymer may be mixed and then crosslinked, or the olefin rubber-like polymer and the acid-modified olefin polymer may be crosslinked and then mixed. .

The silicone rubbery polymer is preferably a polyorganosiloxane.
Although there is no restriction | limiting in particular as polyorganosiloxane, The polyorganosiloxane which has a vinyl polymerizable functional group is preferable, 0.3-3 mol% of siloxane units containing a vinyl polymerizable functional group, and dimethylsiloxane units 97-99 are included. More preferred is a polyorganosiloxane composed of 0.7 mol% and having 3 or more siloxane bonds in silicon atoms of 1 mol% or less with respect to all silicon atoms in polydimethylsiloxa.
The polyorganosiloxane may contain a siloxane-based crosslinking agent as a constituent component, if necessary.

  Examples of dimethylsiloxane include dimethylsiloxane-based cyclic bodies having three or more member rings, and among them, those having three to seven member rings are preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These can be used alone or in combination of two or more.

  The vinyl polymerizable functional group-containing siloxane is not limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond, but considering the reactivity with dimethylsiloxane, Various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane and γ-mercaptopropyl Examples include mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These vinyl polymerizable functional group-containing siloxanes can be used alone or in combination of two or more.

  Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The manufacturing method of polyorganosiloxane is not limited. For example, it can be produced by the following method.
First, a siloxane-based crosslinking agent is added to a siloxane mixture composed of dimethylsiloxane and a siloxane having a vinyl polymerizable functional group, if necessary, and then emulsified with an emulsifier and water to obtain an aqueous siloxane mixture dispersion. Next, the aqueous dispersion of the siloxane mixture is atomized using a homomixer that atomizes by a shearing force by high-speed rotation, a homogenizer that atomizes by a jet output from a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifier such as a homogenizer because the particle size distribution of the polyorganosiloxane becomes small. Next, the finely divided siloxane mixture aqueous dispersion is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction solution is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash, sodium carbonate, or the like, to terminate the polymerization, and obtain a polyorganosiloxane dispersed in an aqueous dispersion.

  In the production of the polyorganosiloxane, the emulsifier is preferably an anionic emulsifier. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are particularly preferable. These emulsifiers are used in the range of about 0.05 to 5 parts by mass with respect to 100 parts by mass (as solid content) of the siloxane mixture.

  Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable because it is excellent in the stabilizing action of the aqueous dispersion of polyorganosiloxane. In addition, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the emulsifier used in the aqueous dispersion of polyorganosiloxane can suppress the color development of the thermoplastic resin composition as much as possible. it can.

  The method for producing a composite rubber such as a diene-acrylic composite rubbery polymer or a silicone-acrylic composite rubbery polymer is not particularly limited. For example, a method of heteroaggregating or co-enlarging an aqueous dispersion of an acrylic rubbery polymer and an aqueous dispersion of another rubber component; an aqueous dispersion of an acrylic rubbery polymer or an aqueous dispersion of another rubber component And a method of polymerizing a monomer component constituting the other in the presence of either of them to form a composite. For example, in the presence of a diene rubber-like polymer or silicone rubber-like polymer, a monomer component containing (meth) acrylic acid ester and one or both of a crosslinking agent and a graft crossing agent is emulsion-polymerized. By doing so, a diene-acrylic composite rubbery polymer or a silicone-acrylic composite rubbery polymer is obtained.

<Vinyl monomer component (m2)>
The vinyl monomer component (m2) preferably contains at least an aromatic vinyl compound and a vinyl cyanide compound. In addition to the aromatic vinyl compound and the vinyl cyanide compound, the vinyl monomer component (m2) may contain other monomers copolymerizable therewith within a range not impairing the effects of the present invention.

  Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferable from the viewpoints of fluidity, color developability of molded products, and impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  65-82 mass% is preferable in 100 mass% of vinyl-type monomer components (m2), and the content rate of an aromatic vinyl compound has more preferable 73-80 mass%, and 75-80 mass% is further more preferable. When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and further preferably 20 to 25% by mass in 100% by mass of the vinyl monomer component (m2). When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  Other monomers include, for example, methacrylate esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-methacrylic acid t- Butyl, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, penzyl methacrylate, phenyl methacrylate, etc.), maleimide compounds (N-methyl) Maleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-tert-butylmaleimide, N-cycloalkylmaleimide ( -Cyclohexylmaleimide), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), N-aralkylmaleimide, etc.), acrylic acid ester (methyl acrylate, ethyl acrylate, acrylic) Propyl acid, butyl acrylate, etc.). Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.

<Graft copolymer (F)>
The graft copolymer (F) can be obtained by polymerizing the vinyl monomer component (m2) in the presence of the rubber-like polymer (E).

  The graft copolymer (F) is 20 to 80% by mass of the vinyl monomer component (m2) in the presence of 20 to 80% by mass of the rubbery polymer (E) (however, the rubbery polymer (E) And the vinyl monomer component (m2) is 100% by mass.) And is preferably obtained by polymerizing the rubber-like polymer (E) in the presence of 25 to 75% by mass. What was obtained by polymerizing 25 to 75% by mass of the monomeric monomer component (m2) is more preferable. In the presence of 30 to 70% by mass of the rubber-like polymer (E), the vinyl monomer component (m2) And more preferably obtained by polymerizing 30 to 70% by mass. When the ratio of the rubber-like polymer (E) is within the above range, the productivity of the graft copolymer (F) is good, and the color developability and impact resistance of the molded product are further improved.

Examples of the polymerization method of the graft copolymer (F) include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method).
For example, when produced by emulsion polymerization, a vinyl monomer component (m2) is added to an aqueous dispersion of a rubber-like polymer (E), and the vinyl monomer component (m2) is radicalized in the presence of an emulsifier. By polymerization, an aqueous dispersion of the graft copolymer (F) is obtained. At this time, various known chain transfer agents may be added in order to control the graft ratio and the molecular weight of the graft component.

Examples of radical polymerization initiators include peroxides, azo-based initiators, redox-based initiators in which an oxidizing agent and a reducing agent are combined, and redox-based initiators from the point that the graft polymerization reaction can be easily controlled. A sulfoxylate-based initiator in which ferrous sulfate-ethylenediaminetetraacetic acid disodium salt-longalite-hydroperoxide is combined is particularly preferable.
As an emulsifier, the emulsifier used in the case of manufacture of a rubber-like polymer (E) is mentioned. The emulsifier contained in the aqueous dispersion of the rubber-like polymer (E) is used as it is, and it is not necessary to add an emulsifier at the time of graft polymerization, or an emulsifier may be added at the time of graft polymerization as necessary. .

  As a method for recovering the graft copolymer (F) from the aqueous dispersion of the graft copolymer (F), the aqueous dispersion is poured into hot water in which a coagulant is dissolved, and coagulated in a slurry state. A method of recovering the graft copolymer (F) by spraying an aqueous dispersion of the graft copolymer (F) in a heated atmosphere (spray drying) Law).

  Examples of the coagulant include inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), metal salts (calcium chloride, calcium acetate, aluminum sulfate, etc.) and the like. The coagulant is selected according to the emulsifier used in the polymerization. That is, when only a sodium or potassium salt of a carboxylic acid such as a sodium or potassium salt of a fatty acid or a sodium or potassium salt of rosin acid is used as an emulsifier, any coagulant may be used. When an emulsifier exhibiting a stable emulsifying power even in an acidic region such as sodium dodecylbenzenesulfonate is included as an emulsifier, it is necessary to use a metal salt.

As a method for obtaining the dry graft copolymer (F) from the slurry graft copolymer (F), the emulsifier residue remaining in the slurry is eluted in water by washing, and (i) Examples include a method of dehydrating with a centrifugal dehydrator or a press dehydrator and further drying with an air flow dryer or the like, and (ii) a method of simultaneously performing dehydration and drying with a press dehydrator or an extruder.
After drying, the graft copolymer (F) is obtained in the form of powder or particles. Moreover, you may send the graft copolymer (F) discharged | emitted from the press dehydrator or the extruder directly to the extruder or molding machine which manufactures a thermoplastic resin composition.

<Vinyl monomer component (m3)>
The vinyl monomer component (m3) contains at least a methacrylic acid ester.
The vinyl monomer component (m3) includes, in addition to the methacrylic acid ester, a maleimide compound, an aromatic vinyl compound, an acrylic acid ester, and another vinyl monomer copolymerizable with the methacrylic acid ester. One or two or more selected monomers may be included within a range not impairing the effects of the present invention.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, Examples include isoamyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, penzyl methacrylate, phenyl methacrylate, and the like. From the viewpoint of superiority, at least one of methyl methacrylate and ethyl methacrylate is preferable. A methacrylic acid ester may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the methacrylic acid ester is preferably 50 to 100% by mass in 100% by mass of the vinyl monomer component (m3) from the viewpoint of scratch resistance and color developability of the molded product.

  Examples of maleimide compounds include N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide). , N-t-butylmaleimide, etc.), N-cycloalkylmaleimide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.) and the like. From the viewpoint of further improving the heat resistance and impact resistance of the molded product, N-arylmaleimide is preferred, and N-phenylmaleimide is particularly preferred. A maleimide type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferable from the viewpoint of further excellent impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and the like, and methyl acrylate is preferred from the viewpoint that the heat resistance and impact resistance of the molded product are further improved. One kind of acrylic acid ester may be used alone, or two or more kinds may be used in combination.

  Examples of other vinyl monomers include vinyl cyanide compounds (acrylonitrile, methacrylonitrile, etc.). Another vinyl-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The vinyl monomer component (m3) has a methacrylic acid ester content of 50 to 94 mass%, a maleimide compound content of 5 to 49 mass%, and an aromatic vinyl compound content of 1 to 45 mass%. It is preferable that When the content of each compound in 100% by mass of the vinyl monomer component (m3) is within the above range, the scratch resistance, color development, impact resistance, and heat resistance of the molded product are further improved.

<Methacrylate ester resin (G)>
The methacrylic ester resin (G) is obtained by polymerizing the vinyl monomer component (m3).
The polymerization method is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, etc.).

As a method for producing a methacrylic ester resin (G) by an emulsion polymerization method, for example, a vinyl monomer component (m3), an emulsifier, a polymerization initiator, and a chain transfer agent are charged in a reactor and polymerized by heating. And the method of collect | recovering methacrylic ester resin (G) by the precipitation method from the aqueous dispersion containing methacrylic ester resin (G) is mentioned.
Examples of the emulsifier include usual emulsion polymerization emulsifiers (potassium rosinate, sodium alkylbenzenesulfonate, etc.).
Examples of the polymerization initiator include organic and inorganic peroxide initiators.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.
As the precipitation method, a method similar to that used when recovering the graft copolymer (D) from the aqueous dispersion can be employed.

Examples of the method for producing a methacrylate ester resin (G) by suspension polymerization include, for example, a vinyl monomer component (m3), a suspending agent, a suspending aid, a polymerization initiator, and a chain transfer agent in a reactor. And heating to polymerize, and the slurry is dehydrated and dried to recover the methacrylic ester resin (G).
Examples of the suspending agent include tricalcium phosphite and polyvinyl alcohol.
Examples of the suspension aid include sodium alkylbenzene sulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.

  A methacrylic ester resin (G) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Silica particles (H)>
There is no restriction | limiting in particular as silica which comprises a silica particle (H), According to the objective, it can select suitably, For example, vapor phase method silica, crystalline silica, fused silica etc. are mentioned.

  The average particle diameter of the silica particles (H) is preferably 1 to 100 nm, more preferably 1 to 80 nm, and further preferably 1 to 50 nm. When the average particle diameter of the silica particles is within the above range, the obtained molded article has excellent scratch resistance and color developability.

  The surface of the silica particles (H) may be organically or may not be organically. It is preferable that the surface is made organic because the resulting molded article has good color developability and impact resistance.

Silica particles (H) may be synthesized according to the desired physical properties, or commercially available ones may be used.
Examples of commercially available aqueous silica particles include Snowtex OXS (acidic aqueous silica sol, manufactured by Nissan Chemical Industries, Ltd.), Snowtex OS (acidic aqueous silica sol, manufactured by Nissan Chemical Industries, Ltd.), Snowtex O (acidic aqueous solution). Silica sol, manufactured by Nissan Chemical Industries, Ltd., Snowtex O-40 (acidic aqueous silica sol, manufactured by Nissan Chemical Industries, Ltd.), Snowtex OL (acidic aqueous silica sol, manufactured by Nissan Chemical Industries, Ltd.), Snowtex OUP (Acid aqueous silica sol, manufactured by Nissan Chemical Industries, Ltd.).
Examples of commercially available silica particles having an organic surface include MEK-ST (methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), MEK-ST-MS (methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.). MEK-ST-UP (methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), MIBK-ST (methyl isobutyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), EAC-ST (ethyl acetate dispersed silica sol, Nissan Chemical Co., Ltd.) Kogyo Co., Ltd.), TOL-ST (toluene-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), PMA-ST (propylene glycol monomethyl ether acetate-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), and the like.

  There is no restriction | limiting in particular as a method of organicizing the surface of a silica particle, A well-known method is employable. For example, a method in which silanol groups on the surface of silica particles are reacted with an organic silane compound to form a covalent bond, and the surface of silica particles is reacted with a radically reactive silane compound and then polymerized by emulsion polymerization. And the like.

  Examples of organosilane compounds that can react with silanol groups on the surface of silica particles to form covalent bonds include silazane compounds, siloxane compounds, alkoxysilanes, alkoxysilane partial hydrolysates, alkoxysilane partial hydrolyzate oligomers. Is mentioned. An organic silane compound can be used individually by 1 type or in mixture of 2 or more types.

Examples of the silazane compound include hexamethyldisilazane and hexaethyldisilazane.
Examples of the siloxane compound include hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, hexaethyldisiloxane, and 3-glycol. Sidoxypropylpentamethyldisiloxane may be mentioned.

  Examples of the alkoxysilane include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. , Tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldiethoxysilane, n -Octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dode Rutrimethoxysilane, n-octadecyltriethoxysilane, phenyldimethylethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyl Trimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxy Propyltriethoxysilane, N- (β-aminoethyl)-(γ-aminopropyl) methyldimethoxysilane, N- (β-aminoethyl)-(γ-aminopropyl) trimethoxysilane, N- (β-aminoethyl) )-(Γ-aminopropyl) triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3- Isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecatrifluoropropyltrimethoxysilane, n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis (triethoxysilyl) ethane and hexaethoxydisiloxane .

  0.05-20 mass parts is preferable with respect to 100 mass parts of silica particles, and, as for the usage-amount of the organosilane compound used for organicization of the surface of a silica particle, 0.1-10 mass parts is more preferable. When the amount of the organic silane compound used is within the above range, the surface of the silica particles can be sufficiently organic, and the color development of the molded product becomes good.

<Vinyl monomer component (m4)>
The vinyl monomer component (m4) contains at least an aromatic vinyl compound and a vinyl cyanide compound.

  Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferable from the viewpoints of fluidity, color developability of molded products, and impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the aromatic vinyl compound is preferably 15 to 95% by mass in 100% by mass of the vinyl monomer component (m4). When the content of the aromatic vinyl compound is within the above range, the impact resistance of the molded product is further improved.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the vinyl cyanide compound is preferably 5 to 85% by mass in 100% by mass of the vinyl monomer component (m4). When the content of the vinyl cyanide compound is within the above range, the impact resistance of the molded product is further improved.

The vinyl monomer component (m4) may contain a methacrylic acid ester and a maleimide compound as necessary.
Examples of the methacrylic acid ester and the maleimide compound include those exemplified in the vinyl monomer component (m3).

<Styrene copolymer (I)>
The styrene copolymer (I) is obtained by polymerizing the vinyl monomer component (m4).
The polymerization method is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, etc.). From the viewpoint of heat resistance of the molded product, suspension polymerization method and bulk polymerization method are available. preferable.

<Other thermoplastic resins>
Other thermoplastic resins include, for example, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, poly Examples include arylate, liquid crystal polyester, polyethylene, polypropylene, and polyamide (nylon).

<Various additives>
Examples of various additives include antioxidants, lubricants, processing aids, pigments, fillers, silicone oils, paraffin oils, and the like.

<Content of each component>
The ratio of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is the same as that of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer ( Of the total (100% by mass) of C) and the rubbery polymer (E), it is 15 to 85% by mass, preferably 30 to 70% by mass.
The ratio of the rubber-like polymer (E) is the sum of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the rubber-like polymer (E) (100% by mass). ) Is 85 to 15% by mass, preferably 30 to 70% by mass.
If the ratio of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the ratio of the diene rubbery polymer (E) are within the above ranges, the rubber content is small. It can exhibit impact resistance and cold impact resistance, and is excellent in scratch resistance, color development and lubricity.

  The total content (rubber content) of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the rubbery polymer (E) is a thermoplastic resin composition. 5-30 mass% is preferable in 100 mass%, and 10-25 mass% is more preferable. If the rubber content is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, the cold impact resistance, the scratch resistance, the color development and the lubricity are further improved.

  The total content of the graft copolymer (D) and the graft copolymer (F) is as follows: the graft copolymer (D), the graft copolymer (F), the methacrylate ester resin (G), and the styrene copolymer. 5-40 mass% is preferable among 100 mass% in total with coalescence (I), and 10-30 mass% is more preferable. If the total content of the graft copolymer (D) and the graft copolymer (F) is within the above range, the fluidity of the thermoplastic resin composition, the scratch resistance of the molded article, the impact resistance, and the cold impact resistance. Excellent balance of physical properties such as property, color developability, lubricity and heat resistance.

  The content of the methacrylic ester resin (G) is 100% by mass in total of the graft copolymer (D), the graft copolymer (F), the methacrylic ester resin (G), and the styrene copolymer (I). 95-60 mass% is preferable inside, and 90-70 mass% is more preferable. If the content of the methacrylic ester resin (G) is within the above range, the flowability of the thermoplastic resin composition, scratch resistance of the molded product, impact resistance, cold impact resistance, color development, lubricity, heat resistance Excellent physical property balance.

  The content of the silica particles (H) is 100 parts by mass in total of the graft copolymer (D), the graft copolymer (F), the methacrylic ester resin (G), and the styrene copolymer (I). 0.1-30 mass parts is preferable, and 1-15 mass parts is more preferable. When the content of the silica particles (H) is not less than the lower limit of the above range, the scratch resistance of the molded product tends to be excellent. There is a tendency.

  The total content of the styrene copolymer (I) is 100 masses of the graft copolymer (D), the graft copolymer (F), the methacrylic ester resin (G), and the styrene copolymer (I). % Is preferably 0 to 40% by mass, and more preferably 1 to 40% by mass from the viewpoint of fluidity of the thermoplastic resin composition, impact resistance of the molded article, cold impact resistance, and heat resistance.

<Average particle size>
The average particle size of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) contained in the graft copolymer (D) in the thermoplastic resin composition is 0.20. 0.60 μm, preferably 0.30 to 0.50 μm. When the average particle diameter is smaller than 0.20 μm, the impact resistance and cold impact resistance of the molded product are inferior. When the average particle diameter is larger than 0.60 μm, the molded article is inferior in impact resistance, cold impact resistance, color development, scratch resistance and lubricity. If the average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 0.30 μm to 0.50 μm, the impact resistance and cold impact resistance of the molded product Further, color developability, lubricity, and scratch resistance are further improved.

  The average particle diameter of the rubber-like polymer (E) contained in the graft copolymer (F) in the thermoplastic resin composition is 0.05 to 0.18 μm, and preferably 0.07 to 0.15 μm. When the average particle diameter is smaller than 0.05 μm, the impact resistance and cold impact resistance of the molded product are inferior. When the average particle size is larger than 0.18 μm, the impact resistance, cold impact resistance and color developability of the molded product are inferior.

When the graft copolymer (D) is obtained by polymerizing the vinyl monomer component (m1) in the aqueous olefin resin dispersion (B), the aqueous olefin resin dispersion (B) The average particle diameter of the ethylene / α-olefin copolymer (A) is the average particle size of the ethylene / α-olefin copolymer (A) contained in the graft copolymer (D) in the thermoplastic resin composition as it is. The diameter is confirmed by image analysis using an electron microscope.
When the graft copolymer (D) is obtained by polymerizing the vinyl monomer component (m1) in an aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C), Crosslinked ethylene / α-olefin copolymer in which the average particle size of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion is directly included in the graft copolymer (D) in the thermoplastic resin composition It is confirmed by image analysis of an electron microscope that the average particle diameter of (C) is shown.
When the graft copolymer (F) is obtained by polymerizing the vinyl monomer component (m2) in the aqueous dispersion of the rubber-like polymer (E), The average particle diameter of the rubber-like polymer (E) indicates the average particle diameter of the rubber-like polymer (E) contained in the graft copolymer (F) in the thermoplastic resin composition as it is. Confirmed by image analysis.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention comprises a graft copolymer (D), a graft copolymer (F), a methacrylic ester resin (G), silica particles (H), and other materials as required. It can be obtained by mixing the components (styrene copolymer (I), other thermoplastic resin, various additives).

In the production of the thermoplastic resin composition, the method of mixing each component is not particularly limited, and any method may be used as long as the silica particles (H) are uniformly dispersed in the thermoplastic resin composition. For example, the following methods (i) to (iv) are exemplified.
(I) The aqueous dispersion of the graft copolymer (D), the graft copolymer (F) or the methacrylic ester resin (G) is mixed with colloidal silica as an aqueous medium, and then solidified with an inorganic salt. The obtained coagulated product (graft copolymer (D), graft copolymer (F) or methacrylic ester resin (G) in which silica particles (H) are dispersed) is recovered, and the coagulated product and other components are collected. How to mix.
(Ii) After mixing the methacrylic ester resin (G) dissolved in an organic solvent and silica particles, or silica particles whose surface is organized, for example, organosilica sol, the organic solvent is removed to obtain silica particles ( A method of obtaining a methacrylic ester resin (G) in which H) is dispersed and mixing the methacrylic ester resin (G) with other components (such as a graft copolymer (D) and a graft copolymer (F)). .
(Iii) Silica particles or silica particles whose surface is organized, for example, an organic solvent of an organosilica sol is substituted with the aforementioned vinyl monomer component (m3) and then polymerized to obtain silica particles (H). A method of obtaining a dispersed methacrylic ester resin (G) and mixing the methacrylic ester resin (G) with a graft copolymer (D), a graft copolymer (F) and the like.
(Iv) The vinyl monomer component (m3) is graft-polymerized on silica particles treated with a radical polymerizable organosilane compound, then solidified, and the resulting solidified product (methacrylic acid in which silica particles (H) are dispersed) Ester resin (G)) and other components (graft copolymer (D), graft copolymer (F), etc.) are mixed.
Among these, by replacing the organic solvent of the organosilica sol with the vinyl monomer component (m3) and then performing suspension polymerization, a methacrylate ester resin (G) in which the silica particles (H) are uniformly dispersed is obtained. Thus, the method of mixing the methacrylic ester resin (G) containing the silica particles (H) in a uniformly dispersed state with the graft copolymer (D), the graft copolymer (F), etc., is the productivity of the thermoplastic resin, The resulting molded article is preferable because of good color developability.

<Effect>
In the thermoplastic resin composition of the present invention described above, the ethylene / α-olefin copolymer (A) having a mass average molecular weight (Mw) and a molecular weight distribution (Mw / Mn) within a specific range or this A graft copolymer (D) obtained by polymerizing the vinyl monomer component (m1) in the presence of a crosslinked ethylene / α-olefin copolymer (C) subjected to a crosslinking treatment, and a rubbery polymer ( E) a graft copolymer (F) obtained by polymerizing the vinyl monomer component (m2) in the presence of, a methacrylate ester resin (G), and silica particles (H), The ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the diene rubber-like polymer (E) in the plastic resin composition have a specific average particle diameter, Ethylene α-olefin in thermoplastic resin composition Since the specific ratio of the ethylene copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the diene rubber-like polymer (E) is good, the fluidity is good, and the scratch resistance A molded product excellent in stickiness, color development, impact resistance, cold impact resistance, and lubricity can be obtained. Moreover, even if heat resistance is imparted to the molded article, impact resistance is not impaired.

"Molding"
The molded article of the present invention can be obtained by molding the thermoplastic resin composition of the present invention by a known molding method.
Examples of the molding method include injection molding, press molding, extrusion molding, vacuum molding, and blow molding.
Applications of molded products include vehicle interior / exterior parts, office equipment, home appliances, building materials, and the like.

  In the molded article of the present invention described above, since the thermoplastic resin composition of the present invention is used, it is excellent in scratch resistance, color development, impact resistance, cold impact resistance, and lubricity. Moreover, if the thing of a specific copolymer composition is used as methacrylic ester resin (G), or a styrene-type copolymer (H) is used, it will be excellent also in heat resistance.

Hereinafter, an example is shown concretely. However, the present invention is not limited to these examples.
In the following, “%” means “mass%” and “part” means “part by mass”.
Various measurements and evaluation methods in the following examples and comparative examples are as follows.

<Measurement Method of Mass Average Molecular Weight (Mw), Molecular Weight Distribution (Mw / Mn)>
Mass average molecular weight in terms of polystyrene using GPC (GPC: “GPC / V2000” manufactured by Waters, column: “Shodex AT-G + AT-806MS” manufactured by Showa Denko KK) and o-dichlorobenzene (145 ° C.) as a solvent. (Mw), number average molecular weight (Mn) were measured, and molecular weight distribution (Mw / Mn) was calculated.

<Crystallinity>
It was determined from an X-ray diffraction spectrum measured using a wide-angle X-ray diffractometer RAD-RX manufactured by Rigaku Corporation.

<Measurement method of average particle diameter>
A volume average particle diameter (MV) measured using pure water as a measurement solvent was used as an average particle diameter using Microtrac (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.).
The ethylene / α-olefin copolymer (A) dispersed in the olefin resin aqueous dispersion (B), the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion, The average particle diameter of the rubber-like polymer (E) dispersed in the aqueous dispersion is the same as the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer in the thermoplastic resin composition. It was confirmed by image analysis with an electron microscope that the average particle diameter of (C) and the rubber-like polymer (E) was shown.

<Measurement method of gel content>
Coagulated powder sample [D1] 0.5 g obtained by coagulating an aqueous or solvent dispersion of the crosslinked ethylene / α-olefin copolymer (C) with dilute sulfuric acid, washing with water, and drying is 200 mL, 110 ° C. toluene. 5 hours, and then filtered through a 200 mesh wire mesh, the residue is dried, the mass of the dried product [D2] is measured, and from the following formula (1), a crosslinked ethylene / α-olefin copolymer The gel content of (C) was determined.
Gel content rate (%) = dry substance amount [D2] (g) / coagulated powder sample mass [D1] (g) × 100 (1)

<Melt-kneading 1>
Graft copolymer (D), graft copolymer (F), methacrylic ester resin (G), silica particles (H), and other components as required are mixed, and a twin screw extruder with a 30 mmφ vacuum vent (PCM30 manufactured by Ikegai Co., Ltd.) was subjected to melt kneading at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition (1). Further, after melt-kneading, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Melting and kneading 2>
Graft copolymer (D), graft copolymer (F), methacrylic ester resin (G), silica particles (H), carbon black with respect to a total amount of 100 parts mixed with other components as required 0.8 parts are mixed and melt kneaded at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa with a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.), and a thermoplastic resin composition (2) was obtained. Further, after melt-kneading, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Measurement of melt volume rate (MVR)>
With respect to the thermoplastic resin composition (1), MVR was measured in accordance with ISO 1133: 2011. In addition, MVR becomes a standard of the fluidity | liquidity of a thermoplastic resin composition.

<Injection molding 1>
The pellets of the thermoplastic resin composition (1) were molded by an injection molding machine (Toshiba Machine Co., Ltd., “IS55FP-1.5A”) under the conditions of a cylinder temperature of 200 to 270 ° C. and a mold temperature of 60 ° C. A molded product having a width of 10 mm and a thickness of 4 mm was obtained. The obtained molded product (molded product (Ma1)) was used as a molded product for Charpy impact test and a molded product for measuring deflection temperature under load.

<Injection molding 2>
The pellets of the thermoplastic resin composition (2) were molded by an injection molding machine (Toshiba Machine Co., Ltd., “IS55FP-1.5A”) under the conditions of a cylinder temperature of 200 to 270 ° C. and a mold temperature of 60 ° C. A molded product having a width of 100 mm and a thickness of 3 mm was obtained. The obtained molded product (molded product (Ma2)) is molded into a falling ball impact test, molded product for evaluation of color development, molded product for evaluation of scratch resistance, molded product for evaluation of scratch resistance, molded product for weather resistance evaluation. Used as.

<Injection molding 3>
The pellets of the thermoplastic resin composition (1) are molded by an injection molding machine (“SG150-SYCAPM IV” manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C., and the structure shown in FIG. Molded articles (test piece 21 and test piece 22) were obtained. The obtained molded product (molded product (Ma3)) was used as a molded product for evaluating lubricity.

<Evaluation of impact resistance: Charpy impact test>
The molded product (Ma1) was subjected to a Charpy impact test (notched) at 23 ° C. in accordance with ISO 179-1: 2010, and the Charpy impact strength was measured.

<Evaluation of cold shock resistance: falling ball impact test>
About the molded article (Ma2) temperature-controlled at -30 degreeC, the falling ball impact strength was measured in the following procedures. A steel ball having a weight of 230 g was dropped from a height of 10 cm onto a molded product (Ma2), and if it was not broken, the drop height was increased every 10 cm to confirm whether cracks or cracks occurred. The height obtained by subtracting 10 cm from the drop height at which three or more cracks or cracks occurred was taken as the cold ball impact resistance.

<Evaluation of heat resistance>
With respect to the molded article (Ma1), the deflection temperature under load (° C.) was measured by a flatwise method in accordance with ISO 75: 2004, 1.83 MPa, 4 mm.

<Evaluation of color development>
For the molded product (Ma2), the lightness L ^* was measured by the SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). The L ^* measured in this way is referred to as “L ^* (ma)”. The lower L ^* was, the more black the color was determined.

<Evaluation of scratch resistance>
Using a pencil hardness tester, a pencil with a hardness of 3H is pressed against the surface of the molded product (Ma2) with a load of 7.35 N, and the molded product (Ma2) is moved about 5 cm in this state, thereby moving the molded product (Ma2). ) Was scratched with a pencil to scratch the molded product (Ma2). The brightness L ^* of the surface of the scratched molded article (Mb) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mb)”.
From the above results, a determination index ΔL ^* for the visibility of scratches on the molded product (Mb) was calculated from the following formula (3). As the absolute value of ΔL ^* (mb−ma) is larger, the scratches are more conspicuous.
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)
When the absolute value of ΔL ^* (mb−ma) is 1 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 1.0 to 1.5 or less, scratches are hardly noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 1.5, scratches are conspicuous and the design of the molded product is impaired.

<Evaluation of scratch resistance>
As shown in FIG. 1, a rod-like jig 10 having a tip portion 11 formed in a hemispherical shape was prepared, and the tip portion 11 was covered with a laminated sheet 12 in which eight sheets of gauze were stacked. The tip portion 11 covered with the laminated sheet 12 is brought into contact with the surface of the molded product (Ma2) 13 so that the rod-shaped jig 10 is at a right angle, and the tip portion 11 is brought into contact with the surface of the molded product (Ma2) 13. Were slid in the horizontal direction (arrow direction in the figure) and reciprocated 100 times. At that time, the applied load was 9.8 N. After reciprocating 100 times, the lightness L ^* of the surface of the scratched molded article (Mc) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mc)”.
From the above results, a determination index ΔL ^* for the visibility of scratches on the molded product (Mc) was calculated from the following equation (4). As the absolute value of ΔL ^* (mc−ma) is larger, scratches are more conspicuous.
ΔL ^* (mc−ma) = L ^* (mc) −L ^* (ma) (4)
When the absolute value of ΔL ^* (mc-ma) is less than 3.0, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is 3.0 or more and 7.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

(Evaluation of lubricity: before degreasing)
In the molded product (Ma3), when the test piece 21 having the rib structure 21a shown in FIG. 2 and the test piece 22 having a flat surface portion are used and a reciprocating motion is performed while applying a load of 4.9N or 9.8N, the squeak is formed. It was investigated whether or not sound was generated. Evaluation was performed based on the following criteria from the occurrence of squeak noise and the number of tests that occurred when the same test was performed five times. Δ or more is considered to have lubricity and to suppress the occurrence of squeak noise.
A: No squeak noise is generated at any load of 4.9N and 9.8N.
○: A small squeak noise is generated when the load is 9.8N, but not when the load is 4.9N.
Δ: A squeak noise is generated at both a load of 4.9 N and a load of 9.8 N, but the number of tests generated is less than 4 at each load.
X: A squeak noise was generated at both a load of 4.9 N and a load of 9.8 N, and the generated number of tests was 4 or more at any load.

(Evaluation of lubricity: after degreasing)
In the molded article (Ma3), the test piece 21 having the rib structure 21a shown in FIG. 2 and the test piece 22 having a flat portion are annealed at 60 ° C. for 10 days, and then the surfaces of the test piece 21 and the test piece 22 are isopropyl alcohol. The bleed component was removed by degreasing with. Generation | occurrence | production of the base fingerprint after degreasing was investigated like the lubricity evaluation method before degreasing, and the following reference | standard evaluated. △ or more is regarded as having a permanent lubricity.
A: No squeak noise is generated at any load of 4.9N and 9.8N.
○: A small squeak noise is generated when the load is 9.8N, but not when the load is 4.9N.
Δ: A small squeak noise is generated at both the load 4.9N and the load 9.8N, but the number of tests generated is less than 4 at each load.
X: A squeak noise is generated at both a load of 4.9 N and a load of 9.8 N, and the number of generated tests is 4 or more at any load.

<Evaluation of weather resistance>
The molded product (Ma2) was treated for 1000 hours under conditions of a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall of 12 minutes) using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). Then, the degree of discoloration (ΔE) before and after the treatment was measured with a color difference meter and evaluated. The smaller the ΔE, the better the weather resistance.

<Each component>
In the following examples, the following ethylene / α-olefin copolymer (A), olefin resin aqueous dispersion component (B), crosslinked ethylene / α-olefin copolymer (C), graft copolymer (D), A graft copolymer (F), a methacrylic ester resin (G), a fluororesin (H), and a styrene copolymer (I) were used.

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1))
After fully substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ prepared to 8.0 mmol / L was added. ₅ ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was further added to 5 L / h. Hexane was continuously fed in an amount of 5 L / h. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene was supplied in an amount of 2000 L / h, propylene was supplied in an amount of 1000 L / h, hydrogen was supplied in an amount of 9 L / h, and a polymerization reaction was performed at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (A-1). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1). Table 1 shows the properties of the ethylene / propylene copolymer (A-1).

(Preparation of ethylene / propylene copolymers (A-2) to (A-5))
Except for changing the hydrogen supply amount as shown in Table 1, the ethylene / propylene copolymers (A-2) to (A-5) were changed in the same manner as the ethylene / propylene copolymer (A-1). Obtained. Table 1 shows the properties of the ethylene / propylene copolymers (A-2) to (A-5).

(Preparation of ethylene / propylene copolymer (A-6))
After sufficiently substituting a 20 L stainless steel tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and 110 L of propylene (standard state) and 800 mL of hydrogen were added. After heating to 40 ° C., it was pressurized with ethylene so that the total pressure was 0.6 MPa [gage]. When the internal pressure reached 0.6 MPa [gage], 10 mL of a 1.0 mM / mL hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance is 0.16 mM in terms of boron, and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium chloride is 0. Polymerization was initiated by injecting 30 mL of a toluene solution containing 0004 mM with nitrogen. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gage]. Five minutes after the start of polymerization, 50 mL of methanol was inserted to stop the polymerization, and the pressure was released to atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-6). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-6). Table 1 shows the properties of the ethylene / propylene copolymer (A-6).

(Preparation of ethylene / propylene copolymer (A-8))
An ethylene / propylene copolymer (A-8) is obtained in the same manner as the ethylene / propylene copolymer (A-3) except that VCl ₄ is used instead of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst. It was. Table 1 shows the properties of the ethylene / propylene copolymer (A-8).

(Preparation of ethylene / propylene copolymer (A-7))
30 parts of ethylene / propylene copolymer (A-3) and 70 parts of ethylene / propylene copolymer (A-8) are mixed, and a 30 mmφ vacuum vented twin screw extruder (“PCM30” manufactured by Ikegai Co., Ltd.) Was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-7). Table 1 shows the properties of the ethylene / propylene copolymer (A-7).

<Olefin resin aqueous dispersion component (B)>
(Preparation of aqueous dispersion of olefin resin (B-1))
100 parts of ethylene / propylene copolymer (A-1) and maleic anhydride-modified polyethylene (manufactured by Mitsui Chemicals, "Mitsui High Wax 2203A") as the acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 30 mg / g) 20 parts and 5 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture is supplied at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40), and water is supplied from a supply port provided in a vent portion of the twin screw extruder. While continuously supplying an aqueous solution obtained by mixing 0.5 part of potassium oxide and 2.4 parts of ion-exchanged water, it was heated to 220 ° C., melt-kneaded and extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the twin screw extruder and cooled to 90 ° C. Then, the solid discharged from the tip of the twin screw extruder is poured into warm water at 80 ° C., continuously dispersed, diluted to a solid content concentration of about 40% by mass, and an aqueous olefin resin dispersion (B -1) was obtained. Table 2 shows the average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B-1).

(Preparation of aqueous olefin resin dispersions (B-2) to (B-8))
As shown in Table 2, the olefin resin aqueous dispersion (B-) except that (A-1) was changed to (A-2) to (A-8) as the ethylene / α-olefin copolymer (A). In the same manner as in 1), olefin resin aqueous dispersions (B-2) to (B-8) were obtained.
Table 2 shows the average particle size of the ethylene / α-olefin copolymer (A) dispersed in each olefin resin aqueous dispersion (B-2) to (B-8).

(Preparation of aqueous olefin resin dispersions (B-9) to (B-16))
As shown in Table 3, the aqueous olefin resin dispersion was the same as the aqueous olefin resin dispersion (B-3) except that the number of added parts of potassium hydroxide during emulsification and the number of added parts of ion exchange water were changed. (B-9) to (B-16) were obtained.
Table 3 shows the average particle size of the ethylene / α-olefin copolymer (A) dispersed in each of the olefin resin aqueous dispersions (B-9) to (B-16).

<Crosslinked ethylene / α-olefin copolymer (C)>
(Preparation of crosslinked ethylene / α-olefin copolymer (C-1))
Ion exchange water was added to the olefin resin aqueous dispersion (B-1) (100 parts as a solid content) so that the solid content concentration was 35%, and 1 part of t-butylcumyl peroxide as an organic peroxide was obtained. As a functional compound, 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (C-1). Table 4 shows the gel content and average particle diameter of the crosslinked ethylene / α-olefin copolymer (C-1).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2) to (C-20))
As shown in Tables 4-6, the same as the crosslinked ethylene / α-olefin copolymer (C-1) except that the type of the olefin resin aqueous dispersion (B) and the amount of t-butylcumyl peroxide added were changed. Thus, crosslinked ethylene / α-olefin copolymers (C-2) to (C-20) were obtained. Tables 4 to 6 show the gel content and average particle size of the crosslinked ethylene / α-olefin copolymers (C-2) to (C-20).

(Preparation of crosslinked ethylene / α-olefin copolymer (C-21))
With respect to 100 parts of the ethylene / α-olefin copolymer (A-3), 0.5 part of α, α′-di (t-butylperoxy) diisopropylbenzene and 1.0 part of divinylbenzene as an organic peroxide, Are mixed and melt-kneaded at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (“Ikegai Co., Ltd.,“ PCM-30 ”), and then finely pulverized. -Obtained (alpha) -olefin copolymer (C-21). Table 6 shows the gel content and average particle size of the crosslinked ethylene / α-olefin copolymer (C-21).

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1))
In a stainless steel polymerization tank equipped with a stirrer, the crosslinked ethylene / α-olefin copolymer (C-1) (70 parts as a solid content of the ethylene / propylene copolymer (A-1)) is placed, and the crosslinked ethylene / α-olefin is added. Ion exchange water is added to the copolymer (C-1) so that the solid content concentration is 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose are charged. The temperature was 80 ° C. Styrene (23.4 parts), acrylonitrile (6.6 parts) and cumene hydroperoxide (0.6 parts) were continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. After the polymerization, an antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1), solids are precipitated with sulfuric acid, and after washing, dehydration and drying, A polymer (D-1) was obtained.

(Preparation of graft copolymers (D-2) to (D-20))
As shown in Tables 7 to 9, the graft copolymer (D-2) was the same as the graft copolymer (D-1) except that the type of the crosslinked ethylene / α-olefin copolymer (C) was changed. ) To (D-20) were obtained.

(Preparation of graft copolymer (D-21))
In a stainless steel polymerization tank equipped with a stirrer, 70 parts of a crosslinked ethylene / α-olefin copolymer (C-21) and 300 parts of toluene were charged, and the contents were stirred and stirred uniformly at 70 ° C. for 1 hour. After sufficiently purging with nitrogen, 23.4 parts of styrene, 6.6 parts of acrylonitrile, 0.24 parts of t-dodecyl mercaptan and 0.22 parts of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was 110 ° C. The mixture was heated up to react for 4 hours. The internal temperature was raised to 120 ° C. and reacted for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30”, manufactured by Ikegai Co., Ltd.), pelletized, and graft copolymer (D-21). ) The graft ratio of the graft copolymer (D-21) was measured and found to be 26%. When the average particle diameter of the ethylene / α-olefin copolymer (A) in the graft copolymer (D-21) was confirmed by an electron microscope, it was 0.39 μm.

(Preparation of graft copolymer (D-22))
As shown in Table 9, the grafted ethylene / α-olefin copolymer (C) was changed to an aqueous olefin resin dispersion (B-3), except that the graft copolymer (D-1) was used. A copolymer (D-22) was obtained.

<Graft copolymer (F)>
(Preparation of graft copolymer (F-1))
9 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture. To this was added an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of deionized water, stirred for 2 minutes at 10000 rpm with a homomixer, and then passed once through the homogenizer at a pressure of 20 MPa. A premixed organosiloxane latex was obtained.
On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of deionized water were charged into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirring device to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. . While this aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours. After the completion of the addition, the temperature was maintained for 1 hour, and then cooled to 40 ° C. or lower. Subsequently, this reaction product was neutralized to pH 7 with an aqueous caustic soda solution to complete the polymerization, whereby an aqueous polyorganosiloxane (Ea) dispersion (solid content concentration 16.8%) was obtained.

Next, 119.5 parts of an aqueous dispersion of polyorganosiloxane (Ea) and 0.8 part of sodium polyoxyethylene alkylphenyl ether sulfate are placed in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device. Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C, 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetic acid and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state is maintained for 1 hour, polymerization of the acrylate component is completed, and poly (siloxane) containing polyorganosiloxane (Ea), a (meth) acrylate monomer unit, a crosslinking agent and / or a graft crossing agent is contained. An aqueous dispersion of a composite rubber-like polymer (E-1) composed of a (meth) acrylic ester was obtained. The volume average particle diameter of the composite rubber-like polymer (E-1) dispersed in the aqueous dispersion was 0.08 μm.
After the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Subsequently, 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide were dropped and polymerized over about 1 hour. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After holding for 1 hour after the completion of dropping, the mixture was cooled to obtain an aqueous dispersion of a graft copolymer (F-1) obtained by grafting an acrylonitrile-styrene copolymer onto a composite rubber-like polymer (E-1). . Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (F-1) was gradually dropped into the calcium acetate aqueous solution to be solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (F-1).

(Preparation of graft copolymer (F-2))
In a reactor equipped with a reagent injection container, a condenser tube, a jacket heater and a stirrer, 119.5 parts of an aqueous polyorganosiloxane (Ea) dispersion and 0.94 part of sodium polyoxyethylene alkylphenyl ether sulfate were charged. 203 parts of ion exchange water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C, 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetic acid and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state is maintained for 1 hour, polymerization of the acrylate component is completed, and poly (siloxane) containing polyorganosiloxane (Ea), a (meth) acrylate monomer unit, a crosslinking agent and / or a graft crossing agent is contained. An aqueous dispersion of a composite rubber-like polymer (E-2) composed of a (meth) acrylic ester was obtained. The composite rubber-like polymer (E-2) dispersed in the aqueous dispersion had a volume average particle size of 0.04 μm.
After the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Subsequently, 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide were dropped and polymerized over about 1 hour. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was kept for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (F-2) obtained by grafting an acrylonitrile-styrene copolymer onto a composite rubber-like polymer (E-2). . Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (F-2) was gradually dropped into the calcium acetate aqueous solution to be solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (F-2).

(Preparation of graft copolymer (F-3))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous dispersion of polyorganosiloxane (Ea) and 0.9 part of sodium polyoxyethylene alkylphenyl ether sulfate were charged. 203 parts of ion exchange water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C, 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetic acid and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state is maintained for 1 hour, polymerization of the acrylate component is completed, and poly (siloxane) containing polyorganosiloxane (Ea), (meth) acrylic acid ester monomer units, a crosslinking agent and / or a graft crossing agent is contained. An aqueous dispersion of a composite rubber-like polymer (E-3) comprising (meth) acrylic acid ester was obtained. The volume average particle diameter of the composite rubber-like polymer (E-3) dispersed in the aqueous dispersion was 0.05 μm.
After the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Subsequently, 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide were dropped and polymerized over about 1 hour. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After holding for 1 hour after the completion of dropping, the mixture was cooled to obtain an aqueous dispersion of a graft copolymer (F-3) in which an acrylonitrile-styrene copolymer was grafted to the composite rubber-like polymer (E-3). . Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (F-3) was gradually dropped into the aqueous calcium acetate solution to be solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (F-3).

(Preparation of graft copolymer (F-4))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous dispersion of polyorganosiloxane (Ea) and 0.51 part of sodium polyoxyethylene alkylphenyl ether sulfate were charged. 203 parts of ion exchange water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C, 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetic acid and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state is maintained for 1 hour, polymerization of the acrylate component is completed, and poly (siloxane) containing polyorganosiloxane (Ea), a (meth) acrylate monomer unit, a crosslinking agent and / or a graft crossing agent is contained. An aqueous dispersion of a composite rubber-like polymer (E-4) composed of (meth) acrylic acid ester was obtained. The volume average particle diameter of the composite rubber-like polymer (E-4) dispersed in the aqueous dispersion was 0.18 μm.
After the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Subsequently, 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide were dropped and polymerized over about 1 hour. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After holding for 1 hour after the completion of dropping, the mixture was cooled to obtain an aqueous dispersion of a graft copolymer (F-4) obtained by grafting an acrylonitrile-styrene copolymer onto a composite rubber-like polymer (E-4). . Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (F-4) was gradually dropped into the calcium acetate aqueous solution to be solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (F-4).

(Preparation of graft copolymer (F-5))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 119.5 parts of an aqueous polyorganosiloxane (Ea) dispersion and 0.33 part of sodium polyoxyethylene alkylphenyl ether sulfate were charged. 203 parts of ion exchange water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C, 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetic acid and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state is maintained for 1 hour, polymerization of the acrylate component is completed, and poly (siloxane) containing polyorganosiloxane (Ea), a (meth) acrylate monomer unit, a crosslinking agent and / or a graft crossing agent is contained. An aqueous dispersion of a composite rubber-like polymer (E-5) composed of (meth) acrylate was obtained. The volume average particle diameter of the composite rubber-like polymer (E-5) dispersed in the aqueous dispersion was 0.24 μm.
After the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Subsequently, 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide were dropped and polymerized over about 1 hour. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was kept for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (F-5) obtained by grafting an acrylonitrile-styrene copolymer onto a composite rubber-like polymer (E-5). . Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (F-5) was gradually dropped into the calcium acetate aqueous solution to be solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft polymer (F-5).

(Preparation of graft copolymer (F-6))
In a pressure vessel equipped with a stirrer, 150 parts of deionized water, 100 parts of butadiene monomer, 3.0 parts of hardened fatty acid potassium soap, 0.3 part of sodium organic sulfonate, 0.2 part of tert-decyl mercaptan, 0 potassium persulfate .3 parts and 0.14 part of potassium hydroxide were added, the temperature was raised to 60 ° C. while stirring in a nitrogen atmosphere, and the polymerization was started. When the polymerization rate was 65%, 0.1 part of potassium persulfate was dissolved. 5 parts of the deionized water was added to the above pressure vessel, the polymerization temperature was raised to 70 ° C., the polymerization was completed at a reaction time of 13 hours and a polymerization conversion of 95%, an average particle size of 0.10 μm, and a solid content of 52.0%. A rubbery polymer (E-6) latex was obtained.
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 200 parts of ion-exchanged water (including water in polybutadiene latex), 0.3 part of disproportionated potassium rosinate (solid content) Then, 0.01 part of ferrous sulfate heptahydrate, 0.2 part of sodium pyrophosphate and 0.5 part of crystalline glucose were charged and completely dissolved, and then the latex of rubbery polymer (E-6) (solid content) 50 parts) was added and mixed.
While stirring the contents in the reactor, the temperature was raised to 60 ° C., and 39 parts of styrene and 11 parts of acrylonitrile were continuously added dropwise over 2 hours for graft polymerization. Meanwhile, the jacket temperature was controlled so as to keep the reactor internal temperature at 60 ° C. After completion of the dropwise addition, the temperature was raised to 70 ° C. and maintained for 1 hour to complete the graft polymerization reaction. After cooling, an antioxidant (dilauryl thiodipropionate) was added to obtain a latex of graft copolymer (F-6).
The obtained latex of the graft copolymer (F-6) was put into a 2.5% aqueous sulfuric acid solution (80 ° C.) of 1 volume with stirring, and further coagulated by holding at 90 ° C. for 5 minutes. Thus, a slurry of the graft copolymer (F-6) was obtained. The slurry was washed twice with water and dehydrated twice, then allowed to stand at 70 ° C. overnight and dried to obtain a milky white powder graft copolymer (F-6).

(Preparation of graft copolymer (F-7))
0.6 parts of dipotassium alkenyl succinate, 175 parts of ion exchange water, 50 parts of n-butyl acrylate, 0.16 part of allyl methacrylate, 0.08 part of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of ethylenediaminetetraacetic acid disodium salt, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Furthermore, this state was maintained for 1 hour to obtain a rubber-like polymer (E-7) having an average particle size of 0.11 μm.
While maintaining the internal temperature of the reactor at 75 ° C., 0.15 part of Rongalite, 0.65 part of dipotassium alkenyl succinate, and ions with respect to 50 parts (as a solid content) of the rubber-like polymer (E-7) An aqueous solution consisting of 10 parts of exchange water was added, and then a mixed liquid consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene, and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour for graft polymerization. . Five minutes after the completion of dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 11 A mixture consisting of 39 parts of styrene, 39 parts of styrene, 0.19 part of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl succinic acid were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (F-7).

  The average particle diameter of the rubber-like polymer (E) used in the preparation of the graft copolymers (F-1) to (F-7) and the rubber-like polymer (E) in the graft copolymer (F) is shown. 10 shows.

<Methacrylate ester resin (G)>
(Preparation of methacrylate resin (G-1))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan , 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered methacrylate resin (G-1). The amount of monomer used is shown in Table 11.

(Preparation of methacrylate ester resin (G-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered methacrylate resin (G-2). The amount of monomer used is shown in Table 11.

(Preparation of methacrylate resin (G-3) in which silica particles (H) are dispersed)
Silica particles (H) obtained by distilling off MEK-ST (organosilica sol manufactured by Nissan Chemical Industries, Ltd., dispersion medium: methyl ethyl ketone (MEK), average particle size 16 nm) in a stainless polymerization tank equipped with a stirrer 20 parts dispersed in a solution consisting of 79.2 parts methyl methacrylate and 0.8 parts methyl acrylate, 150 parts ion-exchanged water, 0.2 part 2,2′-azobis (isobutyronitrile) , 0.25 part of n-octyl mercaptan, 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic ester resin (G-3). Table 11 shows the amounts of monomer and silica particles used.

(Preparation of methacrylate resin (G-4) in which silica particles (H) are dispersed)
In a stainless polymerization tank equipped with a stirrer, 20 parts of silica particles (H) obtained by distilling off MEK of MEK-ST (organosilica sol manufactured by Nissan Chemical Industries, Ltd., dispersion medium: MEK, average particle diameter 16 nm) Dispersion dispersed in a solution consisting of 65.6 parts of methyl methacrylate, 9.6 parts of N-phenylmaleimide and 4.8 parts of styrene, 150 parts of ion-exchanged water, 2,2′-azobis (isobutyronitrile) 0.2 part, 0.25 part of n-octyl mercaptan, 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered methacrylate resin (G-4). Table 11 shows the amounts of monomer and silica particles used.

<Styrene copolymer (I)>
(Preparation of styrene copolymer (I-1))
In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, t -0.35 part of dodecyl mercaptan was charged and reacted at an initial temperature of 60 ° C for 5 hours. The temperature was raised to 120 ° C. and reacted for 4 hours. The contents were taken out to obtain a styrene copolymer (I-1). The amount of monomer used is shown in Table 12.

(Preparation of styrene copolymer (I-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 10 parts of methyl methacrylate, 22 parts of acrylonitrile, 68 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0 .25 parts, calcium hydroxyapatite 0.47 part, and potassium alkenyl succinate 0.003 part were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator and dehydrated, and dried to obtain a styrene copolymer (I-2). The amount of monomer used is shown in Table 12.

(Preparation of styrene copolymer (I-3))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 30 parts of N-phenylmaleimide, 15 parts of acrylonitrile, 55 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0.25 part, 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator, dehydrated, and dried to obtain a styrene copolymer (I-3). The amount of monomer used is shown in Table 12.

[Example 1]
Graft copolymer (D-2) 10 parts, Graft copolymer (F-1) 14 parts, Methacrylate resin (G-2) 36 parts, Methacrylate resin (G) dispersed with silica particles (H) -4) 50 parts (including 10 parts of silica particles (H)) were mixed and melted at 240 ° C. and 93.325 kPa vacuum in a 30 mmφ twin-screw extruder with a vacuum vent (Ikegai Co., Ltd., “PCM30”). The mixture was kneaded to prepare a thermoplastic resin composition. Table 13 shows the MVR of the thermoplastic resin composition.
The thermoplastic resin composition was pelletized and various molded articles were molded, and the impact resistance, cold impact resistance, color development, scratch resistance, scratch resistance, heat resistance and lubricity (squeak noise) were evaluated. The results are shown in Table 13.

[Examples 2-45]
Tables 13 to 18 (silica particles (H) (parts) in Tables 13 to 18 indicate the amount of silica particles (H) contained in the blended methacrylate resins (G-3) to (G-4). A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1 except that the formulation was changed to the formulation shown in FIG.
The thermoplastic resin composition was pelletized and various molded articles were molded, and the impact resistance, cold impact resistance, color development, scratch resistance, scratch resistance, heat resistance and lubricity (squeak noise) were evaluated. The results are shown in Tables 13-18.

[Comparative Examples 1-14]
Tables 19 to 20 (silica particles (H) (parts) in Tables 19 to 20 indicate the amount of silica particles (H) contained in the blended methacrylate resins (G-3) to (G-4). A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1 except that the formulation was changed to the formulation shown in FIG.
The thermoplastic resin composition was pelletized and various molded articles were molded, and the impact resistance, cold impact resistance, color development, scratch resistance, scratch resistance, heat resistance and lubricity (squeak noise) were evaluated. The results are shown in Tables 19-20.

The thermoplastic resin compositions of Examples 1 to 45 were excellent in fluidity. In addition, the molded products obtained in Examples 1 to 45 are excellent in scratch resistance, scratch resistance, impact resistance, cold impact resistance, color development, lubricity (squeak noise), heat resistance, and weather resistance. It was.
On the other hand, the molded products obtained in Comparative Examples 1 to 14 have one or more characteristics of scratch resistance, scratch resistance, impact resistance, cold impact resistance, color development, and lubricity (squeak noise). It was enough.

  Therefore, the thermoplastic resin composition of the present invention is excellent in fluidity, and when the thermoplastic resin composition of the present invention is used, it is excellent in scratch resistance, impact resistance, cold shock resistance, color development, and lubricity. It can be seen that the molded product can be applied to applications such as vehicle interior / exterior parts, office equipment, home appliances, and building materials.

  A molded article using the thermoplastic resin composition of the present invention is useful as a vehicle interior / exterior part, office equipment, home appliance, building material and the like.

10 Jig 11 Tip 12 Laminated Sheet 13 Molded Product (Ma2)
21 Test piece 21a Rib structure 22 Test piece

Claims (4)

The ethylene / α-olefin copolymer (A) or the ethylene / α-olefin having a mass average molecular weight (Mw) of 17 × 10 ^{4 to} 35 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1 to 3 Graft copolymer (D) obtained by polymerizing vinyl monomer component (m1) in the presence of crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking copolymer (A) When,
A graft copolymer (F) obtained by polymerizing the vinyl monomer component (m2) in the presence of the rubber-like polymer (E);
A methacrylate ester resin (G) obtained by polymerizing a vinyl-based monomer component (m3) containing a methacrylate ester;
Silica particles (H),
The average particle diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) contained in the graft polymer (D) is 0.20 μm to 0.60 μm,
The rubbery polymer (E) contained in the graft copolymer (F) has an average particle size of 0.05 μm to 0.18 μm,
Of the total (100% by mass) of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the rubbery polymer (E), ethylene / α-olefin The ratio of the copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) is 15 to 85% by mass, and the ratio of the rubbery polymer (E) is 85 to 15% by mass. Thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein the rubber-like polymer (E) is a silicone-acrylic composite rubber-like polymer. The graft copolymer (D) is obtained by polymerizing a vinyl monomer component (m1) in the presence of the crosslinked ethylene / α-olefin copolymer (C). The thermoplastic resin composition according to 1 or 2 . The molded article using the thermoplastic resin composition as described in any one of Claims 1-3.

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