JP6670087B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

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

  Improving the impact resistance of molded products not only expands the applications of molded products, but also makes it possible to cope with thinning and increasing the size of molded products, greatly increasing industrial utility. . Therefore, various methods have been proposed for improving the impact resistance of molded articles. Among these methods, a method for increasing the impact resistance of a molded product while maintaining characteristics derived from the hard resin by using a rubber-reinforced resin material combining a rubbery polymer and a hard resin has already been industrialized. ing. Examples of such a resin material include an acrylonitrile-butadiene-styrene (ABS) resin, an acrylonitrile-styrene-acrylic acid ester (ASA) resin, an acrylonitrile-ethylene-α-olefin-styrene (AES) resin, or a hard resin obtained by adding these resins. And the like.

As the thermoplastic resin composition capable of obtaining a molded article having improved impact resistance while retaining characteristics derived from a hard resin, for example, the following are known.
(1) A thermoplastic resin composition obtained by adding an AES resin to a methacrylic acid ester resin which is a hard resin (Patent Document 1).
(2) A thermoplastic resin composition obtained by adding an AES resin to a maleimide-based 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 as a hard resin (Patent Document 3).

However, in the thermoplastic resin compositions (1) and (2), it was necessary to add a large amount of AES resin in order to improve the impact resistance of the molded article. Therefore, in the obtained molded product, the surface hardness (scratch resistance) derived from the methacrylic acid ester resin and the heat resistance derived from the maleimide copolymer were 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 resulting molded product tends to have a lower coloring property derived from the hard resin. .
In the thermoplastic resin composition (3), an AES resin and an ASA resin are added in order to suppress a decrease in the coloring property of the molded article. However, the impact resistance of the molded article is higher than when only the AES resin is added. And cold shock resistance were low.

  BACKGROUND ART Rubber-reinforced resin materials are widely used in various fields such as OA equipment, automobiles, and miscellaneous goods as resin materials having an excellent balance of impact resistance, mechanical properties, and fluidity during molding of molded articles. However, in the rubber-reinforced resin material, a stick-slip phenomenon occurs in a switch portion of an OA device, a fitting portion of a car audio, and the like due to vibration of a device, vibration of a vehicle when starting or running, and the like, and a squeaking noise is generated. There was a problem.

In order to reduce the generation of squeak noise in a molded article of a rubber-reinforced resin material, for example, use of the following thermoplastic resin composition has been proposed.
(4) A thermoplastic resin composition obtained by adding a polyorganosiloxane as a lubricant to a rubber-reinforced styrene resin (Patent Document 4).
(5) A thermoplastic resin composition obtained by adding a silicone resin having a specific viscosity as a lubricant to a rubber-reinforced acrylonitrile-styrene resin containing an ABS resin and an AES resin (Patent Document 5).
(6) A thermoplastic resin composition obtained by adding polytetrafluoroethylene, low molecular weight oxidized polyethylene, or ultrahigh molecular weight polyethylene as a lubricant to a rubber reinforced styrene resin, an olefin resin, and a styrene-butadiene-styrene block copolymer ( Patent Document 6).

  In the molded article comprising the thermoplastic resin composition of (4) to (6), the lubricant added to the thermoplastic resin composition bleeds out to the surface of the molded article, thereby improving the lubricity of the molded article. , Reduces the friction coefficient and suppresses squeak noise. However, there has been a problem that the bleed-out lubricant deteriorates the surface appearance of the molded article, and the lubricating property decreases with time due to the gradual loss of the bleed-out lubricant.

JP 2005-132970 A JP 2004-352842 A JP 2004-346187 A Japanese Patent No. 2,688,619 JP 2011-174029 A JP 2011-168186 A

  The present invention is a thermoplastic resin composition that has good fluidity, is excellent in scratch resistance, impact resistance, cold impact resistance, heat resistance, and the like of the obtained molded article, and can achieve both suppression of squeak noise and color development. The purpose is to provide. Further, the present invention provides a molded article which is excellent in scratch resistance, impact resistance, cold impact resistance, heat resistance, etc., and can achieve both suppression of squeak noise and color development.

The present invention includes the following aspects.
[1] In the presence of 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 The vinyl monomer mixture (m2) is polymerized in the presence of the graft copolymer (D) obtained by polymerizing the vinyl monomer mixture (m1) and the rubbery polymer (E). And a methacrylic acid ester resin (G) obtained by polymerizing a graft copolymer (F) obtained as described above and a vinyl monomer mixture (m3) containing a methacrylic acid ester, and having a mass average molecular weight of 10,000. A thermoplastic resin composition comprising: a polyethylene-based resin (H), wherein the average particle diameter of the ethylene / α-olefin copolymer (A) is 0.05 to 0.18 μm; The rubber-like polymer (E) has an average particle size of 0.20 to 0.20. 60 μm, and the proportion of the ethylene / α-olefin copolymer (A) in the total (100% by mass) of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E) is 15 to A thermoplastic resin composition comprising 85% by mass and a rubber-like polymer (E) proportion of 85 to 15% by mass.
[2] The rubbery polymer (E) is at least one rubbery polymer selected from the group consisting of a diene rubbery polymer, an acrylic rubbery polymer, and an olefin rubbery polymer. The thermoplastic resin composition according to [1].
[3] The thermoplastic resin composition according to [1] or [2], wherein the ethylene / α-olefin copolymer (A) is a crosslinked ethylene / α-olefin copolymer (C).
[4] The thermoplastic resin composition according to any one of [1] to [3], wherein the polyethylene resin (H) is polyethylene oxide.
[5] A molded article obtained by molding the thermoplastic resin composition according to any one of [1] to [4].

The thermoplastic resin composition of the present invention has good fluidity. Further, according to the thermoplastic resin composition of the present invention, it is possible to obtain a molded article excellent in scratch resistance, impact resistance, cold impact resistance, heat resistance, coloring, and squeak noise suppressing effect.
The molded article of the present invention is excellent in scratch resistance, impact resistance, cold impact resistance, heat resistance, coloring, and squeak noise suppressing effect.

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

The following definitions of terms apply throughout the present specification and claims.
“(Meth) acrylic acid” is a general term for acrylic acid and methacrylic acid.
“Molded product” means a product obtained by molding the thermoplastic resin composition of the present invention.
"Scratch resistance" refers to the resistance to scratches (scratch resistance) caused by scratching the surface of a molded article with a hard and sharp object such as a nail or the like, and the gloves, gauze, cloth, etc. It means both scratch resistance (abrasion resistance) to scratches (abrasion) generated when the surface of a molded article is rubbed with a soft material.
“Lightness (L ^* )” means a lightness value (L ^* ) of the color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729.
The “SCE method” means a method of measuring a color by using a spectrocolorimeter based on JIS Z 8722 and removing specularly reflected light by an optical trap.

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention contains a graft copolymer (D), a graft copolymer (F), a methacrylate resin (G), and a polyethylene resin (H). The thermoplastic resin composition of the present invention contains at least one of a styrene copolymer (I), another thermoplastic resin, and various additives, as needed, within a range not to impair the effects of the present invention. You may go out.
Hereinafter, details of each component will be described.

[Graft copolymer (D)]
The graft copolymer (D) is obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the ethylene / α-olefin copolymer (A). In terms of the excellent balance of abrasion resistance, impact resistance, cold impact resistance, color development, and squeak noise suppression effect of the molded product, a vinyl monomer is used in the presence of the crosslinked ethylene / α-olefin copolymer (C). Those obtained by polymerizing the mixture (m1) are preferred.
The graft copolymer (D) is a vinyl monomer mixture (m1) 20 to 50% by mass (provided that the ethylene / α-olefin copolymer (A1) is 50 to 80% by mass) -A polymer obtained by polymerizing the olefin copolymer (A) and the vinyl monomer mixture (m1) in a total amount of 100% by mass is preferable. When the amount of 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 properties are further improved.
The graft ratio of the graft copolymer (D) is preferably from 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 coloring property.
It is difficult to specify how the graft copolymer (D) is polymerized between the ethylene / α-olefin copolymer (A) and the vinyl monomer mixture (m1). That is, there are circumstances (impossible / impractical circumstances) in which it is impossible or not practical to directly specify the graft copolymer (D) by its structure or properties.

<Ethylene / α-olefin copolymer (A)>
The ethylene / α-olefin copolymer (A) is composed of 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, and the like. Among these α-olefins, α-olefins having 3 to 20 carbon atoms are preferred, and propylene is particularly preferred, from the viewpoint of the impact resistance of the molded article.

  The content of ethylene units in 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% by mass is preferable, and 50 to 60% by mass is more preferable. When the content of the ethylene unit in the ethylene / α-olefin copolymer (A) is within the above range, the balance of the scratch resistance, the impact resistance, the cold impact resistance, and the squeak noise suppressing effect of the molded product is further excellent. In particular, when the content of the ethylene unit in the ethylene / α-olefin copolymer (A) is 50 to 60% by mass, the scratch resistance, impact resistance, cold impact resistance, and squeak noise suppressing effect of the molded product are further improved. improves.

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

  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) of the ethylene / α-olefin copolymer (A) is larger than 3, the molded article has low abrasion resistance, impact resistance, cold impact resistance, and squeak noise suppressing effect. . When the molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (A) is 1.9 to 2.5, the fluidity of the thermoplastic resin composition and the scratch resistance and impact resistance of the molded product , Cold shock resistance and squeak noise suppression effect are more excellent.

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

  The crystallinity of the ethylene / α-olefin copolymer (A) is preferably 0 to 30%, more preferably 1 to 30%. When the crystallinity of the ethylene / α-olefin copolymer (A) is within the above range, the molded product has a more excellent balance of scratch resistance, impact resistance, cold impact resistance, and squeak noise suppression effect. In particular, when the crystallinity is 1 to 30%, the abrasion resistance, impact resistance, cold impact resistance and squeak noise suppressing effect are further improved. The degree of crystallinity of the molded article is obtained by measuring X-ray diffraction and determining the ratio of the peak area of the crystal.

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 α-olefin using a metallocene catalyst or a Ziegler-Natta catalyst.
Examples of the metallocene catalyst include a catalyst obtained by combining an organic compound having a cyclopentadienyl skeleton, a metallocene complex in which a halogen atom or the like is coordinated with a transition metal (zirconium, titanium, hafnium, or the like), an organic aluminum compound, an organic boron compound, or the like. Is mentioned.
Examples of the Ziegler-Natta catalyst include a catalyst in which a halide of a transition metal (such as titanium, vanadium, zirconium, or hafnium) 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.). One type of hydrocarbon solvent may be used alone, or two or more types may be used in combination. Further, α-olefin as a raw material may be used as a solvent.
The ethylene / α-olefin copolymer (A) can be obtained by changing the supply conditions of ethylene and α-olefin, the type and amount of molecular weight regulator such as hydrogen, the type and amount of catalyst, the reaction temperature, the pressure, and other reaction conditions. ), The content of ethylene units, the mass average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) can be adjusted.

(Olefin resin aqueous dispersion (B))
The ethylene / α-olefin copolymer (A) may be an olefin resin aqueous dispersion (B) dispersed in an aqueous medium.

The method for preparing the olefin resin aqueous dispersion (B) is not limited. As a method for preparing the olefin resin aqueous dispersion (B), for example, the ethylene / α-olefin copolymer (A) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.). A method of dispersing by applying a mechanical shearing force and adding it to an aqueous medium containing an emulsifier; adding an ethylene / α-olefin copolymer (A) to a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) And then emulsifying the mixture by adding it to an aqueous medium and emulsifying the mixture with an aqueous medium, followed by sufficient stirring to distill off the hydrocarbon solvent.
In preparing the olefin resin aqueous dispersion (B), an emulsifier, an acid-modified olefin polymer, or the like may be added as other components.

Examples of the emulsifier include known ones, for example, a long-chain alkyl carboxylate, a sulfosuccinic acid alkyl ester salt, and an alkylbenzene sulfonate.
The addition amount of the emulsifier can suppress the thermal coloring of the obtained thermoplastic resin composition, and the particle diameter of the aqueous olefin resin dispersion (B) can be easily controlled, so that the ethylene / α-olefin copolymer (A) is used. 5 to 20 parts by mass per 100 parts by mass is preferred.

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 (eg, polyethylene or polypropylene) with a compound having a functional group (eg, an unsaturated carboxylic acid compound). Can be Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic monoamide.
The addition amount of the acid-modified olefin polymer is preferably 1 to 40 parts by mass based on 100 parts by mass of the ethylene / α-olefin copolymer (A). When the amount of the acid-modified olefin polymer is within the above range, the balance between the scratch resistance and the impact resistance of the molded product is further improved.

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

The average particle diameter of the ethylene / α-olefin copolymer (A) in the olefin resin aqueous dispersion (B) is 0.05 to 0.18 μm, and 0.07 to 0.15 μm is preferred. The average particle diameter in the present invention is a volume average particle diameter determined by a laser diffraction / scattering method.
When the average particle size of the ethylene / α-olefin copolymer (A) is smaller than 0.05 μm, the impact resistance and the cold impact resistance of the molded product become low. When the average particle size of the ethylene / α-olefin copolymer (A) is larger than 0.18 μm, the impact resistance, cold impact resistance, coloring, abrasion resistance, and squeak noise suppressing effect of the molded product are low. Become. When the average particle size of the ethylene / α-olefin copolymer (A) is from 0.07 μm to 0.15 μm, the impact resistance, cold impact resistance, and coloring of the molded product are further excellent.
The average particle size of the ethylene / α-olefin copolymer (A) dispersed in the olefin resin aqueous dispersion (B) is the same as that of the ethylene / α-olefin copolymer (A) in the thermoplastic resin composition. It has been confirmed by electron microscope image analysis that the particles have an average particle size.
The method for controlling the average particle size of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B) includes the type or amount of an emulsifier, the type or content of an acid-modified olefin polymer, A method of adjusting the shear force applied at the time of kneading, temperature conditions, and the like can be given.

(Crosslinked ethylene / α-olefin copolymer (C))
The ethylene / α-olefin copolymer (A) may be a crosslinked ethylene / α-olefin copolymer (C).
The crosslinked ethylene / α-olefin copolymer (C) is obtained by subjecting an uncrosslinked ethylene / α-olefin copolymer to a crosslinking treatment.
By cross-linking the uncrosslinked ethylene / α-olefin copolymer, the balance of the scratch resistance, impact resistance, cold impact resistance, color development, and squeak noise suppressing effect of the molded product is further improved.

  The gel content of the crosslinked ethylene / α-olefin copolymer (C) is from 35 to 75 in view of the balance between the scratch resistance, impact resistance, cold impact resistance, color development, and squeak noise suppressing effect of the molded article. % By mass is preferable, 40 to 70% by mass is more preferable, and 45 to 65% by mass is particularly preferable.

The crosslinking treatment of the ethylene / α-olefin copolymer (A) is performed by a known crosslinking method. As a specific crosslinking method, a method of adding an organic peroxide and, if necessary, a polyfunctional compound to the (α) ethylene / α-olefin copolymer (A) and performing a crosslinking treatment. (Β) a method of performing a cross-linking treatment by ionizing radiation, and the like, and the method (α) is preferred from the viewpoint of the impact resistance and the coloring property of the molded article.
As the method (α), specifically, 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). And heating.
The gel content of the crosslinked ethylene / α-olefin copolymer (C) can be adjusted by adjusting the addition amount of the organic peroxide and the polyfunctional compound, the heating temperature, the heating time, and the like.
The heating temperature depends on the type of the organic peroxide. The heating temperature is preferably from -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 peroxyester compound, a peroxyketal compound, a dialkyl peroxide compound, and the like. One kind of the organic peroxide may be used alone, or two or more kinds may be used in combination.

  Specific examples of the peroxyester compound include α, α′-bis (neodecanylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, -Cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexylperoxy 2-hexyl Hexanoate, t-butyl peroxy 2-hexyl hexanoate, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy 3,5,5-trimethylhexano Ethate, 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-butylperoxybenzoate , 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) 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-butylperoxide) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butyl Cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

Examples of the organic peroxide include dialkyl such as dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide because the gel content of the crosslinked ethylene / α-olefin copolymer (C) is easily adjusted. Peroxide compounds are particularly preferred.
The amount of the organic peroxide to be added is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted in the range of 35 to 75% by mass. ) 0.1 to 5.0 parts by mass per 100 parts by mass is preferred.

The polyfunctional compound is used in combination with an organic peroxide, if necessary, in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C).
Examples of the polyfunctional compound include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene methacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, and pentaerythritol tetraacrylate. And divinylbenzene is preferred because the gel content is easily adjusted. One of the polyfunctional compounds may be used alone, or two or more may be used in combination.
The amount of the polyfunctional compound to be added is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) is easily adjusted to 35 to 75% by mass, so that the ethylene / α-olefin copolymer (A) 100 It is preferably 10 parts by mass or less based on parts by mass.

The average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion is 0.05 to 0.18 μm, and 0.07 to 0.15 μm, from the viewpoint of excellent physical properties of the molded article. preferable. If the average particle size of the crosslinked ethylene / α-olefin copolymer (C) is smaller than 0.05 μm, the impact resistance and cold impact resistance of the molded product will be low. When the average particle size of the crosslinked ethylene / α-olefin copolymer (C) is larger than 0.18 μm, the impact resistance, cold impact resistance, coloring, abrasion resistance, and squeak noise suppressing effect of the molded product are reduced. Lower. When the average particle size of the crosslinked ethylene / α-olefin copolymer (C) is from 0.07 μm to 0.15 μm, the impact resistance, cold impact resistance, and coloring of the molded product are further excellent.
The average particle size of the ethylene / α-olefin copolymer in the aqueous olefin resin dispersion (B) does not change before and after the crosslinking treatment.
The average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion is equal to the average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition. Has been confirmed by image analysis with an electron microscope.

<Vinyl monomer mixture (m1)>
The vinyl monomer mixture (m1) is a vinyl monomer having one or more monomer units selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and another vinyl monomer. It is a body mixture.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of the thermoplastic resin composition, the coloring properties of the molded product, and the impact resistance. One kind of the aromatic vinyl compound may be used alone, or two or more kinds may be used in combination.
The content of the aromatic vinyl compound is preferably from 65 to 82% by mass, more preferably from 73 to 80% by mass, and still more preferably from 75 to 80% by mass in 100% by mass of the vinyl monomer mixture (m1). When the content of the aromatic vinyl compound is within the above-mentioned range, the color development and impact resistance of the molded product are further excellent.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the vinyl cyanide compound, one type may be used alone, or two or more types may be used in combination.
The content of the vinyl cyanide compound is preferably from 18 to 35% by mass, more preferably from 20 to 27% by mass, and still more preferably from 20 to 25% by mass in 100% by mass of the vinyl monomer mixture (m1). When the content of the vinyl cyanide compound is within the above range, the color development and impact resistance of the molded product are further improved.

  Other vinyl monomers include acrylates (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.) and methacrylates (methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid) Butyl, etc.) and maleimide-based compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.). As the other vinyl monomers, one type may be used alone, or two or more types may be used in combination.

<Method of polymerizing graft copolymer (D)>
Examples of the polymerization method for the graft copolymer (D) include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, and the like).
As a method for producing the graft copolymer (D) by the emulsion polymerization method, for example, an organic peroxide is mixed with a vinyl monomer mixture (m1), and then the vinyl monomer mixture (m1) is mixed with an olefin. A method of continuously adding the aqueous dispersion of the resin aqueous dispersion (B) or the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C) is exemplified. The organic peroxide is preferably used as a redox initiator obtained by combining an organic peroxide, a transition metal and a reducing agent. At the time of polymerization, a chain transfer agent, an emulsifier, and the like may be used depending on the situation.

As the redox initiator, there is no need to set the polymerization reaction temperature to high temperature, and the deterioration of the ethylene / α-olefin copolymer (A) or the cross-linked ethylene / α-olefin copolymer (C) is avoided, and the molding is performed. A combination of an organic peroxide and a ferrous sulfate-chelating agent-reducing agent is preferred from the viewpoint that a reduction in the impact resistance of the product can be avoided.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide and the like.
The redox-based initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of the chain transfer agent include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allyl sulfonic acid, methallyl sulfonic acid, And the like, and α-methylstyrene dimer, and mercaptans are preferred from the viewpoint that the molecular weight can be easily adjusted. One type of the chain transfer agent may be used alone, or two or more types may be used in combination.
The method of adding the chain transfer agent may be any of batch, division, and continuous.
The amount of the chain transfer agent to be added is preferably 2.0 parts by mass or less based on 100 parts by mass of the vinyl monomer mixture (m1).

Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include a higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, a phosphoric acid salt, a fatty acid salt, and an amino acid derivative salt.
Examples of the nonionic surfactant include the usual alkyl ester type, alkyl ether type, and alkyl phenyl ether type of polyethylene glycol.
Examples of the amphoteric surfactant include those having a carboxylate, a sulfate, a sulfonate, a phosphate and the like in the anion portion, and an amine salt and a quaternary ammonium salt in the cation portion.
The addition amount of the emulsifier is preferably 10 parts by mass or less based on 100 parts by mass of the vinyl monomer mixture (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 precipitant is added to the aqueous dispersion, heated and stirred, and then the precipitant is separated. And a precipitation method in which the precipitated graft copolymer (D) is washed with water, dehydrated, and dried.
Examples of the precipitant include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. As the precipitating agent, one type may be used alone, or two or more types may be used in combination.
If necessary, an antioxidant may be added to the aqueous dispersion containing the graft copolymer (D).

As a method for producing the graft copolymer (D) by a solution polymerization method, for example, an inert polymerization solvent used in ordinary radical polymerization is used, and aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, acetone and the like are used. Ketones, halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride are used.
As the polymerization initiator used for the solution polymerization, a general initiator is used, and for example, an organic peroxide such as a ketone peroxide, a dialkyl peroxide, a diacyl peroxide, a peroxyester, or a hydroperoxide is used. Moreover, the method of adding a polymerization initiator collectively or continuously is mentioned.

[Graft copolymer (F)]
The graft copolymer (F) is obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the rubbery polymer (E).
The graft copolymer (F) is a rubbery polymer (E) in the presence of 20 to 80% by mass of a vinyl monomer mixture (m2) 20 to 80% by mass (provided that the rubbery polymer (E) And the total amount of the vinyl monomer mixture (m2) is 100% by mass), and is preferably obtained by polymerizing a vinyl monomer in the presence of 25 to 75% by mass of the rubbery polymer (E). More preferably, the polymer mixture (m2) is obtained by polymerizing 25 to 75% by mass of the vinyl-based monomer mixture (m2) in the presence of 30 to 70% by mass of the rubbery polymer (E). Those obtained by polymerizing 70% by mass are more preferred. 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 development and impact resistance of the molded product are further excellent.
Note that it is difficult to specify how the rubbery polymer (E) and the vinyl monomer mixture (m2) are polymerized in the graft copolymer (F). That is, there are circumstances (impossible / impractical circumstances) in which it is impossible or not practical to directly specify the graft copolymer (F) by its structure or properties.

<Rubber-like polymer (E)>
The rubbery polymer (E) is not particularly limited, and examples thereof include a diene rubbery polymer (Ea), an acrylic rubbery polymer (Eb), and an olefin rubbery polymer (Ec). And silicone-based rubber-like polymers such as polyorganosiloxane-butyl acrylate composite rubber. These may be used alone or in combination of two or more.

  The diene rubbery polymer (Ea) is, for example, a diene rubbery polymer containing, as constituents, a diene component such as butadiene and isoprene and, if necessary, a monomer component copolymerizable therewith. It is. Specific examples include polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene-styrene copolymer, polychloroprene, and the like. These may be used alone or in combination of two or more.

  The method for producing the diene rubbery polymer (Ea) is not particularly limited, but a known emulsion polymerization method is preferred. In this case, known emulsifiers, polymerization initiators, chain transfer agents and the like can be used. In controlling the particle diameter, a diene rubber-like 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 rubbery polymer (Eb) is a copolymer having a unit derived from a (meth) acrylic acid ester and one or both of a unit derived from a crosslinking agent and a unit derived from a graft crossing agent. Is preferred. Examples of the (meth) acrylic ester include an alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, an acrylic ester having an aromatic hydrocarbon group (such as a phenyl group and a benzyl group), and the like. In view of the impact resistance of the molded product, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferred. (Meth) acrylic acid esters may be used alone or in combination of two or more.

Examples of the crosslinking agent include dimethacrylate compounds, and specific examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.
Examples of the graft crosslinking agent include allyl compounds, specifically, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like.

  The method for producing the acrylic rubbery polymer (Eb) is not particularly limited. For example, a method of obtaining an aqueous dispersion of an acrylic rubbery polymer (Eb) by emulsion polymerization of a monomer mixture containing (meth) acrylic acid ester and one or both of a crosslinking agent and a graft crosslinking agent. A method of heterocoagulating or co-blowing the aqueous dispersion of the acrylic rubber-like polymer (Eb) and the aqueous dispersion of another rubber component; an aqueous dispersion of the acrylic rubber-like polymer (Eb) or other And a method of polymerizing the monomer mixture constituting the other in the presence of one of the rubber component aqueous dispersions to form a composite.

Examples of the olefin-based rubbery polymer (Ec) include an ethylene / α-olefin copolymer and an ethylene-propylene-non-conjugated diene copolymer.
As the α-olefin of the ethylene / α olefin copolymer, propylene having 1 or more carbon atoms, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, Examples thereof include 1-icosene and 1-docosene.
The ethylene-propylene-non-conjugated diene copolymer is a copolymer composed of an ethylene unit, a propylene unit, and a non-conjugated diene unit as a third component. Examples of the non-conjugated diene unit include dicyclopentadiene. Or one or more of ethylidene norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, etc. it can.

The method for producing the olefin-based rubbery polymer (Ec) is not limited. For example, the olefin-based rubbery polymer (Ec) is usually produced by polymerizing ethylene and an α-olefin using a metallocene catalyst or a Ziegler-Natta catalyst.
Examples of the olefin rubbery polymer (Ec) polymerization method include a method of copolymerizing ethylene and an 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.). One type of hydrocarbon solvent may be used alone, or two or more types may be used in combination. Further, α-olefin as a raw material may be used as a solvent.

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

  The olefin rubbery polymer (Ec) may be an aqueous dispersion. The method for preparing the aqueous dispersion of the olefin-based rubbery polymer (Ec) is not limited. As a specific preparation method, for example, the olefin-based rubbery polymer (Ec) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.), and a mechanical shear force is applied. A method of dispersing and adding to an aqueous medium containing an emulsifier; dissolving the olefin-based rubbery polymer (Ec) in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) together with the emulsifier, and adding it to the aqueous medium After emulsification, the mixture is sufficiently stirred and the hydrocarbon solvent is distilled off. In preparing the aqueous dispersion of the olefin-based rubbery polymer (Ec), an emulsifier, an acid-modified olefin polymer, or the like may be added as other components.

Examples of the emulsifier include known ones, for example, a long-chain alkyl carboxylate, a sulfosuccinic acid alkyl ester salt, and an alkylbenzene sulfonate.
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 (eg, polyethylene or polypropylene) with a compound having a functional group (eg, an unsaturated carboxylic acid compound). Can be Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic monoamide.
The method for adding the acid-modified olefin polymer is not limited. After mixing the olefin-based rubbery polymer (Ec) and the acid-modified olefin polymer, a crosslinking treatment may be performed, or the olefin-based rubbery polymer (Ec) and the acid-modified olefin polymer may be subjected to a crosslinking treatment, respectively. It may be mixed later.

The average particle size of the rubbery polymer (E) in the aqueous dispersion is from 0.20 to 0.60 μm, preferably from 0.30 to 0.50 μm, from the viewpoint of excellent physical properties of the molded article.
When the average particle size of the rubber-like polymer (E) is smaller than 0.20 μm, the impact resistance and the cold impact resistance of the molded product become low. When the average particle diameter of the rubber-like polymer (E) is larger than 0.60 μm, the impact resistance, cold impact resistance, and color development of the molded product become low.
The average particle size of the rubber-like polymer (E) in the aqueous dispersion was confirmed to be equivalent to the average particle size of the rubber-like polymer (E) in the thermoplastic resin composition by image analysis with an electron microscope. are doing.

<Vinyl monomer mixture (m2)>
The vinyl monomer mixture (m2) is a vinyl monomer comprising one or more monomer units selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and another vinyl monomer. It is a body mixture.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Of these, styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of the thermoplastic resin composition, the color development of the molded product, and the impact resistance. One kind of the aromatic vinyl compound may be used alone, or two or more kinds may be used in combination.

  The content of the aromatic vinyl compound is preferably from 65 to 82% by mass, more preferably from 73 to 80% by mass, and still more preferably from 75 to 80% by mass in 100% by mass of the vinyl monomer mixture (m2). When the content of the aromatic vinyl compound is within the above-mentioned range, the color development and impact resistance of the molded product are further excellent.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the vinyl cyanide compound, one type may be used alone, or two or more types may be used in combination.
The content of the vinyl cyanide compound in 100% by mass of the vinyl monomer mixture (m2) is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and still more preferably 20 to 25% by mass. When the content of the vinyl cyanide compound is within the above range, the color development and impact resistance of the molded product are further improved.

  Examples of other vinyl monomers include, for example, methacrylates (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 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-based compounds (N -Methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-tert-butylmaleimide, N-cycloalkylmaleide Amide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), N-aralkylmaleimide, etc.), acrylate (methyl acrylate, acrylic acid) Ethyl, propyl acrylate, butyl acrylate, etc.). As the other vinyl monomers, one type may be used alone, or two or more types may be used in combination.

<Method for polymerizing graft copolymer (F)>
Examples of the polymerization method for the graft copolymer (F) include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method).
When the graft copolymer (F) is produced by, for example, emulsion polymerization, a vinyl monomer mixture (m2) is added to an aqueous dispersion of the rubbery polymer (E), and the vinyl copolymer is added in the presence of an emulsifier. It is produced by radical polymerization of the monomer mixture (m2). In order to control the graft ratio and the molecular weight of the graft component, various known chain transfer agents may be added.

  Examples of the radical polymerization initiator include peroxides, azo-based initiators, redox-based initiators obtained by combining an oxidizing agent and a reducing agent, and the like.From the viewpoint that the graft polymerization reaction can be easily controlled, a redox-based initiator is used. And a sulfoxylate-based initiator in which ferrous sulfate-ethylenediaminetetraacetic acid disodium salt-longarite-hydroperoxide is combined is particularly preferable.

Preferred specific examples of the emulsifier include sodium or potassium salts of fatty acids (such as oleic acid, stearic acid, myristic acid, stearic acid, and palmitic acid), sodium lauryl sulfate, sodium N-lauroyl sarcosinate, and dipotassium alkenyl succinate (octadede). Dipotassium senylsuccinate, dipotassium heptadecenylsuccinate, dipotassium hexadecenylsuccinate, etc.), and sodium alkyldiphenyletherdisulfonate. One emulsifier may be used alone, or two or more emulsifiers may be used in combination.
The emulsifier used in the production of the rubbery polymer (E) may be used as it is. That is, the emulsifier contained in the aqueous dispersion of the rubber-like polymer (E) is used as it is, and the emulsifier does not need to be added at the time of graft polymerization, or may be added at the time of graft polymerization as needed. Is also good.

  As a method for recovering the graft copolymer (F) from the aqueous dispersion of the graft copolymer (F), the aqueous dispersion is put into hot water in which a coagulant is dissolved, and the slurry is coagulated. (Wet method); a method of semi-directly recovering the graft copolymer (F) by spraying an aqueous dispersion of the graft copolymer (F) in a heated atmosphere (spray drying). Method).

  Examples of the coagulant include inorganic acids (such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid) and metal salts (such as calcium chloride, calcium acetate, and aluminum sulfate). 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 such as sodium dodecylbenzenesulfonate which exhibits stable emulsifying power even in an acidic region is contained as the emulsifier, it is necessary to use a metal salt.

  As a method of obtaining the graft copolymer (F) in a dry state from the graft copolymer (F) in a slurry state, the emulsifier residue remaining in the slurry is eluted into water by washing, and then (i) A method of dehydrating with a centrifugal dehydrator or a press dehydrator and further drying with a flash dryer or the like, (ii) a method of simultaneously performing dehydration and drying with a compression dehydrator, an extruder, or the like. After drying, the graft copolymer (F) is obtained in the form of powder or particles. Further, the graft copolymer (F) discharged from the compression dehydrator or the extruder may be directly sent to an extruder or a molding machine for producing a thermoplastic resin composition.

[Methacrylic ester resin (G)]
The methacrylate ester resin (G) is obtained by polymerizing a vinyl monomer mixture (m3).
As the methacrylate resin (G), one type may be used alone, or two or more types may be used in combination.

<Vinyl monomer mixture (m3)>
The vinyl monomer mixture (m3) contains at least a methacrylic ester as an essential component, and contains a maleimide compound, an aromatic vinyl compound, an acrylate ester, and another vinyl monomer copolymerizable with the methacrylic ester. Is a monomer mixture containing as an optional component.
The content of the methacrylic acid ester is preferably 50 to 100% by mass in 100% by mass of the vinyl monomer mixture (m3) from the viewpoint of the scratch resistance and the coloring property of the molded article.
If the content of the methacrylic acid ester is in the range of 50 to 94% by mass, the content of the maleimide-based compound is in the range of 5 to 49% by mass, and the content of the aromatic vinyl compound is in the range of 1 to 45% by mass, the molded article has a high durability. Excellent scratch resistance, coloring, impact resistance and heat resistance.
That is, the methacrylic acid ester resin (G) preferably contains at least a methacrylic acid ester unit, preferably 50 to 100% by mass of a methacrylic acid ester unit, 50 to 94% by mass of a methacrylic acid ester unit, and a maleimide compound unit. More preferably, it contains 5 to 49% by mass and 1 to 45% by mass of an aromatic vinyl compound unit.

  Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, Isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, penzyl methacrylate, phenyl methacrylate, and the like. From the viewpoint of being excellent, at least one of methyl methacrylate and ethyl methacrylate is preferable. The methacrylic acid esters may be used alone or in combination of two or more.

  As the maleimide-based compound, for example, N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide , Nt-butylmaleimide, etc.), N-cycloalkylmaleimide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.). N-arylmaleimide is preferable, and N-phenylmaleimide is particularly preferable, since the heat resistance and impact resistance of the molded product are further excellent. As the maleimide-based compound, one type may be used alone, or two or more types may be used in combination.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of further improving impact resistance. One kind of the aromatic vinyl compound may be used alone, or two or more kinds may be used in combination.

  Examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and the like. Methyl acrylate is preferable because the heat resistance and impact resistance of the molded product are more excellent. Acrylic esters may be used alone or in combination of two or more.

  Examples of other vinyl monomers include vinyl cyanide compounds (acrylonitrile, methacrylonitrile, etc.). As the other vinyl monomers, one type may be used alone, or two or more types may be used in combination.

The method for polymerizing the methacrylate resin (G) is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, and the like).
As a method for producing a methacrylic acid ester resin (G) by an emulsion polymerization method, for example, a vinyl monomer mixture (m3), an emulsifier, a polymerization initiator, and a chain transfer agent are charged into a reactor and heated to polymerize. And a method of recovering the methacrylate resin (G) from the aqueous dispersion containing the methacrylate resin (G) by a precipitation method.
Examples of the emulsifier include ordinary emulsifiers for emulsion polymerization (eg, potassium rosinate, sodium alkylbenzenesulfonate).
Examples of the polymerization initiator include organic and inorganic peroxide-based initiators.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.
As the precipitation method, the same method as that for recovering the graft copolymer (D) from the aqueous dispersion can be employed.

As a method for producing the methacrylate resin (G) by the suspension polymerization method, for example, a vinyl monomer mixture (m3), a suspending agent, a suspending aid, a polymerization initiator, and a chain transfer agent are placed in a reactor. And polymerizing by heating, and dehydrating and drying the slurry to recover the methacrylate resin (G).
Examples of the suspending agent include tricalcium phosphite, polyvinyl alcohol and the like.
Examples of the suspending aid include sodium alkylbenzenesulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.

[Polyethylene resin (H)]
The mass average molecular weight of the polyethylene resin (H) is less than 10,000, preferably from 2,000 to 4,000. When the mass average molecular weight of the polyethylene resin (H) is 10,000 or more, the impact resistance and the coloring property of the molded article tend to decrease. When the mass average molecular weight of the polyethylene resin (H) is from 2,000 to 4,000, the lubricating properties, impact resistance, cold impact resistance, coloring, scratch resistance and scratch resistance of the molded product are further excellent. .

  As the polyethylene resin (H), it is more preferable to use oxidized polyethylene obtained by oxidizing polyethylene by contact with oxygen or an oxygen-containing gas, since the molded article has more excellent scratch resistance and lubricity. Among the oxidized polyethylenes, an oxidized polyethylene having an acid value of 10 to 25 mgKOH / g, which represents the added amount of the acid component, is particularly preferable. When the acid value is in the range of 10 to 25 mgKOH / g, the effect of improving lubricity is more easily obtained, and the effect of suppressing squeak noise is further improved.

[Styrene-based copolymer (I)]
The styrene copolymer (I) is obtained by polymerizing a vinyl monomer mixture (m4) containing an aromatic vinyl compound and a vinyl cyanide compound.
The polymerization method for the vinyl monomer mixture (m4) is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, and the like). From the viewpoint of heat resistance of molded articles, suspension polymerization method and bulk polymerization method are used. preferable.

<Vinyl monomer mixture (m4)>
The vinyl monomer mixture (m4) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Of these, styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of the thermoplastic resin composition, the color development of the molded product, and the impact resistance. One kind of the aromatic vinyl compound may be used alone, or two or more kinds may be used in combination.
The content of the aromatic vinyl compound is preferably from 15 to 95% by mass in 100% by mass of the vinyl monomer mixture (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. As the vinyl cyanide compound, one type may be used alone, or two or more types may be used in combination.
The content of the vinyl cyanide compound is preferably from 5 to 85% by mass in 100% by mass of the vinyl monomer mixture (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-based monomer mixture (m4) may contain a methacrylic acid ester and a maleimide-based compound, if necessary.
Examples of the methacrylic acid ester and the maleimide-based compound include those exemplified for the vinyl-based monomer mixture (m3).

[Other thermoplastic resins]
Examples of other thermoplastic resins (other resins) include polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, polyacetal, modified polyphenylene ether (modified PPE), and ethylene-vinyl acetate. Copolymers, polyarylates, liquid crystal polyesters, polyethylenes (excluding those having a mass average molecular weight of less than 10,000), polypropylene, fluororesins, polyamides (nylons), and the like.

[Various additives]
Examples of various additives include antioxidants, lubricants, processing aids, pigments, fillers, silicone oil, paraffin oil, and the like.

[Content of each component]
In the thermoplastic resin composition, the proportion of the ethylene / α-olefin copolymer (A) is the sum of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E) (100% by mass). Of these, the content is 15 to 85% by mass, and preferably 30 to 70% by mass.
The proportion of the rubbery polymer (E) is 85 to 15% by mass of the total (100% by mass) of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E), 70% by mass is preferred.
When the proportion of the ethylene / α-olefin copolymer (A) is more than 85% by mass (the proportion of the rubbery polymer (E) is less than 15% by mass), the impact resistance and the cold resistance of the molded article are reduced. Impact properties are reduced. When the proportion of the ethylene / α-olefin copolymer (A) is less than 15% by mass (the proportion of the rubbery polymer (E) is more than 85% by mass), the impact resistance and cold resistance of the molded product are reduced. Impact, abrasion resistance, coloring, and squeak noise suppression effects are reduced.
When the proportion of the ethylene / α-olefin copolymer (A) and the proportion of the rubbery polymer (E) are within the above ranges, impact resistance and cold impact resistance can be exhibited with a small rubber content. Further, it is also excellent in scratch resistance, coloring, and squeak noise suppressing effect.

  The total content (rubber content) of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E) is as follows: the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester. The total amount is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, in the total of 100% by mass of the resin (G) and the styrene-based copolymer (I). When 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 squeaking noise suppressing effect are further excellent.

  The total content of the graft copolymer (D) and the graft copolymer (F) in the thermoplastic resin composition is determined based on the graft copolymer (D), the graft copolymer (F), and the methacrylate resin ( 5 to 40% by mass, preferably 10 to 30% by mass, of the total 100% by mass of G) and the styrene-based copolymer (I). 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 product, the impact resistance, and the cold impact resistance Excellent balance of physical properties such as properties, coloring properties, squeak noise suppression effect, heat resistance and the like.

  The content of the methacrylate ester resin (G) in the thermoplastic resin composition is determined based on the graft copolymer (D), the graft copolymer (F), the methacrylate ester resin (G), and the styrene copolymer (I). ) Is preferably 95 to 60% by mass, and more preferably 90 to 70% by mass in the total 100% by mass. If the content of the methacrylic acid ester resin (G) is within the above range, the fluidity of the thermoplastic resin composition, the scratch resistance of the molded product, the impact resistance, the cold impact resistance, the coloring property, the squeaking noise suppressing effect, etc. Has excellent physical property balance. In particular, when the content of the methacrylic acid ester resin (G) is 60% by mass or more, the molded product is more excellent in scratch resistance, scratch resistance, and coloration. Better impact, abrasion and cold impact resistance.

  The blending amount of the polyethylene resin (H) in the thermoplastic resin composition depends on the graft copolymer (D), the graft copolymer (F), the methacrylate ester resin (G) and the styrene copolymer (I). Is preferably 0.5 to 4.0 parts by mass, more preferably 1.0 to 2.0 parts by mass, based on 100 parts by mass of the total. When the content of the polyethylene resin (H) is within the above range, impact resistance, lubricity, and the surface appearance of the molded product are more excellent. In particular, if the blending amount of the polyethylene resin (H) is 0.5 parts by mass or more, the effect of improving lubricity is more likely to be obtained, and the squeak noise suppressing effect is more excellent, and if it is 4.0 parts by mass or less. The impact resistance and surface appearance of the molded product are further improved.

  The content of the styrene-based copolymer (I) in the thermoplastic resin composition is determined based on the graft copolymer (D), the graft copolymer (F), the methacrylate resin (G), and the styrene-based copolymer ( 0 to 40% by mass is preferable in 100% by mass of the total of I), and 1 to 40% by mass is more preferable from the viewpoint of the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, the cold impact resistance, and the heat resistance. .

[Method for producing thermoplastic resin composition]
The thermoplastic resin composition comprises a graft copolymer (D), a graft copolymer (F), a methacrylate resin (G), a polyethylene resin (H), and, if necessary, a styrene copolymer (I). ), And other thermoplastic resins and various additives. Specifically, the method for producing a thermoplastic resin composition preferably includes the following steps (a) to (d).
Step (a): a step of polymerizing a vinyl monomer mixture (m1) in the presence of an ethylene / α-olefin copolymer (A) to obtain a graft copolymer (D).
Step (b): a step of polymerizing the vinyl monomer mixture (m2) in the presence of the rubbery polymer (E) to obtain a graft copolymer (F).
Step (c): a step of polymerizing a vinyl monomer mixture (m3) containing a methacrylate to obtain a methacrylate resin (G).
Step (d): a step of mixing the graft copolymer (D), the graft copolymer (F), the methacrylate resin (G), and the polyethylene resin (H).

In the step (a), an aqueous olefin resin dispersion (B) or a crosslinked ethylene / α-olefin copolymer (C) may be used instead of the ethylene / α-olefin copolymer (A).
In the step (d), the proportion of the ethylene / α-olefin copolymer (A) is 15% of the total (100% by mass) of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E). The graft copolymer (D), the graft copolymer (F), the methacrylic ester resin (G), and the polyethylene such that the proportion of the rubbery polymer (E) is 85 to 15% by mass. Mix with the resin (H). Further, if necessary, the styrene copolymer (I), another thermoplastic resin and various additives may be further mixed.

[Effects]
In the thermoplastic resin composition of the present invention described above, the presence of the ethylene / α-olefin copolymer (A) having a weight average molecular weight (Mw) and a molecular weight distribution (Mw / Mn) within a specific range. A graft copolymer (D) obtained by polymerizing a vinyl monomer mixture (m1) below; and a vinyl monomer mixture (m2) in the presence of a rubbery polymer (E). Containing a graft copolymer (F) obtained as described above; a methacrylate resin (G); and a polyethylene resin (H) having a mass average molecular weight in a specific range, and containing ethylene in the thermoplastic resin composition. The α-olefin copolymer (A) and the rubbery polymer (E) have specific average particle diameters; the ethylene / α-olefin copolymer (A) and the rubbery weight in the thermoplastic resin composition Good fluidity due to the specific ratio of coalescence (E) , And the addition, it is possible to obtain scratch resistance, coloring property, impact resistance, low temperature impact resistance, a molded article having excellent squeak noise suppression effect. Even if heat resistance is imparted to the molded product, impact resistance and cold impact resistance are 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. That is, the molded article of the present invention comprises the thermoplastic resin composition of the present invention.
Examples of the molding method include an injection molding method, a press molding method, an extrusion molding method, a vacuum molding method, a blow molding method, and the like.
Applications of the molded article include interior and exterior parts of vehicles, office equipment, home appliances, building materials, and the like.

  In the above-described molded article of the present invention, since the thermoplastic resin composition of the present invention is used, scratch resistance, impact resistance, cold impact resistance, heat resistance, coloring, and squeak noise suppression effects are improved. Excellent. If a methacrylate resin (G) having a specific copolymer composition or a styrene-based copolymer (I) is used, the heat resistance is further improved.

Hereinafter, specific examples will be described. However, the present invention is not limited to these examples.
“%” Described below means “% by mass”, and “parts” means “parts by mass”.
Various measurement and evaluation methods in the following examples and comparative examples are as follows.

"Measurement and evaluation"
<Measuring method of mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn)>
GPC (GPC: manufactured by Waters, "GPC / V2000"; column: Showa Denko, manufactured by Shodex AT-G + AT-806MS), using o-dichlorobenzene (145 ° C) as a solvent, and a mass in terms of polystyrene. The average molecular weight (Mw) and the number average molecular weight (Mn) were measured, and the molecular weight distribution (Mw / Mn) was calculated.

<Method of measuring 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 size>
A microtrack ("Nanotrack 150" manufactured by Nikkiso Co., Ltd.) was used. The volume average particle diameter (MV) measured using pure water as a measurement solvent was defined as the average particle diameter.
Incidentally, an ethylene / α-olefin copolymer (A) dispersed in the olefin resin aqueous dispersion (B), a crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion, The average particle diameter of the rubbery polymer (E) dispersed in the aqueous dispersion is such that the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer ( It was confirmed by image analysis with an electron microscope that the average particle diameter became equivalent to that of C) or the rubber-like polymer (E).

<Method for measuring gel content>
An aqueous or solvent dispersion of the cross-linked ethylene / α-olefin copolymer (C) is coagulated with dilute sulfuric acid, washed with water and dried, and 0.5 g of a coagulated powder sample [X1] is obtained by adding 200 mL of toluene at 110 ° C. Immersed in the mixture for 5 hours, and then filtered through a 200-mesh wire gauze. The residue was dried, and the mass of the dried product [X2] was measured. From the following formula (1), the crosslinked ethylene / α-olefin copolymer was obtained. The gel content of (C) was determined.
Gel content (%) = Amount of dry substance [X2] (g) / mass of coagulated powder sample [X1] (g) × 100 (1)

<Method for measuring graft ratio>
1 g of the graft copolymer (D) was added to 80 mL of acetone, and heated under reflux at 65 to 70 ° C. for 3 hours to obtain a suspended acetone solution. The suspended acetone solution was centrifuged at 14,000 rpm for 30 minutes using a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., "CR21E") to separate the precipitated component (acetone insoluble component) and the acetone solution (acetone soluble component). I took it out. Then, the precipitated component (acetone-insoluble component) was dried, its mass (Y (g)) was measured, and the graft ratio was calculated from the following equation (2). In the formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (D), and X is the total mass (g) of the graft copolymer (D) used for obtaining Y. The rubber fraction is the solid content of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) of the graft copolymer (D).
Graft rate (%) = {(YX × Rubber fraction) / X × Rubber fraction} × 100 (2)

<Method of measuring acid value>
It was measured according to JIS K2501.

<Melting and kneading 1>
A graft copolymer (D), a graft copolymer (F), a methacrylate resin (G), and a polyethylene resin (H) are mixed, and a twin-screw extruder having a screw diameter of 30 mm and having a vacuum vent (manufactured by Ikegai Co., Ltd. With “PCM30”), the mixture was melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition (1). After melt-kneading as needed, pelletization was performed using a pelletizer ("SH-type pelletizer" manufactured by Soken Co., Ltd.).

<Melting and kneading 2>
A total of 100 parts of the graft copolymer (D), the graft copolymer (F) and the methacrylic acid ester resin (G) was mixed with 100 parts of the polyethylene resin (H) and 0.8 parts of carbon black. Melt kneading was performed at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa using a twin screw extruder with a vacuum vent having a diameter of 30 mm (manufactured by Ikegai Co., Ltd., “PCM30”) to obtain a thermoplastic resin composition (2). . After melt-kneading as needed, pelletization was performed using a pelletizer ("SH-type pelletizer" manufactured by Soken Co., Ltd.).

<Measurement of melt volume rate (MVR)>
The thermoplastic resin composition (2) was measured according to the ISO 1133 standard. The MVR is a measure of the fluidity of the thermoplastic resin composition, and the higher the MVR value, the higher the fluidity.

<Injection molding 1>
The pellets of the thermoplastic resin composition (1) obtained by melt-kneading were molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., “IS55FP-1.5A”) at a cylinder temperature of 200 to 270 ° C. and a mold temperature of 60 ° C. A molded product having a length of 80 mm, a width of 10 mm and a thickness of 4 mm was molded and used as a molded product for a Charpy impact test and a molded product for measuring deflection temperature under load (molded product (Ma1)).

<Injection molding 2>
The pellets of the thermoplastic resin composition (2) obtained by melt-kneading were subjected to injection molding machine (manufactured by Toshiba Machine Co., Ltd., "IS55FP-1.5A") at a cylinder temperature of 200 to 270 ° C and a mold temperature of 60 ° C. Then, a molded product having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm is molded, and a molded product for a falling ball impact test, a molded product for evaluating color development, a molded product for evaluating scratch resistance, a molded product for evaluating surface appearance (molded product ( Ma2)).

<Injection molding 3>
The pellets of the thermoplastic resin composition (1) obtained by melt-kneading are molded by an injection molding machine (“SG150-SYCAPM IV” manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. Molded articles (test pieces 21 and 22) having the structure shown in FIG. 2 were molded and used as molded articles for lubricity evaluation (molded articles (Ma3)).

<Evaluation of impact resistance: Charpy impact test>
The molded product (Ma1) was subjected to a Charpy impact test (with a notch) at 23 ° C. in accordance with the ISO 179 standard to measure the Charpy impact strength.

<Evaluation of cold shock resistance: falling ball impact test>
The falling ball impact strength of the molded article (Ma2) adjusted to -40 ° C was measured in accordance with JIS K7211. A steel ball weighing 230 g was dropped from a height of 40 cm, and the presence or absence of cracks and cracks was checked. The test was performed on 10 sheets, and evaluated according to the following criteria.
A: No cracks or cracks occurred.
：: One or two cracks or cracks occurred.
Δ: 3 to 4 cracks or cracks occurred.
×: The number of cracks and cracks is 5 or more.

<Evaluation of heat resistance>
For the molded product (Ma1), the deflection temperature under load (° C.) was measured by a flatwise method at 1.83 MPa and 4 mm in accordance with the ISO test method 75 standard.

<Evaluation of color development>
For the molded product (Ma2), the lightness L ^* was measured by an SCE method using a spectrophotometer (manufactured by Konica Minolta Optics, "CM-3500d"). L ^* measured in this manner is referred to as “L ^* (ma)”. The lower the L ^* , the blacker the color and the better the color developability.

<Evaluation of scratch resistance>
(Evaluation of scratch resistance)
Using a pencil hardness tester, a pencil having a hardness of 3H is pressed against the surface of the molded article (Ma2) with a load of 750 g, and the molded article (Ma2) is moved by about 5 cm in that state, thereby obtaining a molded article (Ma2). The surface was scratched with a pencil, and the molded product (Ma2) was scratched. The lightness L ^* of the surface of the damaged molded article (Mb) was measured by an SCE method using a spectrophotometer. L ^* measured in this manner is referred to as “L ^* (mb)”.

(Judgment of scratch resistance)
The judgment index ΔL ^* of the degree of conspicuousness of scratches on the molded article (Mb) was calculated from the following equation (3). The larger the absolute value of ΔL ^* (mb-ma), the more noticeable the scratch.
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)
When the absolute value of ΔL ^* (mb-ma) is 3.0 or less, scratches are not conspicuous and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb-ma) is more than 3.0 to 7.0 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 7.0, scratches are conspicuous and impair the design of a molded product.

(Evaluation of scratch resistance)
As shown in FIG. 1, a rod-shaped jig 10 having a hemispherical tip 11 was prepared, and the tip 11 was covered with a laminated sheet 12 on which eight gauze sheets were stacked. The tip 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 perpendicular to the surface of the molded product (Ma2) 13. Was reciprocated 100 times in the horizontal direction (the direction of the arrow in the figure). At this time, the applied load was 1 kg. After reciprocating 100 times, the lightness L ^* of the surface of the damaged molded article (Mc) was measured by an SCE method using a spectrophotometer. L ^* measured in this manner is referred to as “L ^* (mc)”.

(Judgment of scratch resistance)
The judgment index ΔL ^* of the degree of conspicuousness of scratches on the molded article (Mc) was calculated from the following equation (4). The larger the absolute value of ΔL ^* (mc-ma), the more noticeable the scratch.
ΔL ^* (mc−ma) = L ^* (mc) −L ^* (ma) (4)
When the absolute value of ΔL ^* (mc-ma) is 3.0 or less, scratches are not conspicuous and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc-ma) is more than 3.0 to 7.0 or less, scratches are not conspicuous, 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), a squeak sound is generated when the test piece 21 having the rib structure 21a and the test piece 22 having the flat portion shown in FIG. 2 are reciprocated while applying a load of 500 g or 1 kg. It was examined whether or not it was, and evaluated according to the following criteria. Δ or more was regarded as having lubricity.
◎: No squeak noise is generated under any of the load of 500 g and 1 kg.
：: A small squeak sound is generated when the load is 1 kg, but not when the load is 500 g.
Δ: Small squeak noise is generated at both the load of 500 g and the load of 1 kg.
×: A squeak sound is generated at both the load of 500 g and the load of 1 kg.

<Evaluation of lubricity: after degreasing>
In the molded product (Ma3), after the test piece 21 having the rib structure 21a and the test piece 22 having the flat portion shown in FIG. 2 were annealed at 60 ° C. for 10 days, the surfaces of the test piece 21 and the test piece 22 were isopropyl alcohol. The bleed component was removed by degreasing with the above. The occurrence of squeak noise after degreasing was examined in the same manner as in the method for evaluating lubricity before degreasing, and evaluated according to the following criteria. Δ or more was regarded as having lubricity persistence.
◎: No squeak noise is generated under any of the load of 500 g and 1 kg.
：: A small squeak sound is generated when the load is 1 kg, but not when the load is 500 g.
Δ: Small squeak noise is generated at both the load of 500 g and the load of 1 kg.
×: A squeak sound is generated at both the load of 500 g and the load of 1 kg.

<Evaluation of molded product surface appearance>
The surface condition of the molded article (Ma2) was visually observed and evaluated according to the following criteria.
：: Good without appearance defects such as silver streaks.
Δ: Slight appearance defects such as silver streaks are slightly recognized, but are less noticeable.
X: The appearance defect such as silver streak is remarkable and the appearance is inferior.

`` Various ingredients ''
In the following examples, the following ethylene / α-olefin copolymer (A), olefin resin aqueous dispersion (B), crosslinked ethylene / α-olefin copolymer (C), graft copolymer (D), rubber Polymer (E), graft copolymer (F), methacrylate resin (G), polyethylene resin (H), styrene copolymer (I), and other resins were used.

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1))
After sufficiently replacing the 20 L stainless steel polymerization tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ adjusted 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 was further added as a catalyst at 5 L / h. And hexane was continuously supplied in an amount of 5 L / h. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization tank so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene was supplied at a rate of 2000 L / h, propylene was supplied at a rate of 1000 L / h, and hydrogen was supplied at a rate of 90 L / h, and the polymerization reaction was carried out at 35 ° C.
A polymerization reaction was carried out under the above conditions to obtain a polymerization solution containing the ethylene / propylene copolymer (A-1). The resulting polymerization solution was decalcified 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 that the supply amount of hydrogen was changed as shown in Table 1, the ethylene / propylene copolymers (A-2) to (A-5) were prepared 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 replacing the 20 L stainless steel polymerization 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 became 0.6 MPa [gauge pressure]. When the internal pressure reached 0.6 MPa [gauge pressure], 10 mL of a 1.0 mM / mL hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. 0.16 mM of previously prepared triphenylcarbenium (tetrakispentafluorophenyl) borate in terms of boron and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium chloride in 0% 30 mL of a toluene solution containing 0.0004 mM was injected with nitrogen to initiate polymerization. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gauge pressure]. Five minutes after the start of the polymerization, 50 mL of methanol was inserted to stop the polymerization, and the pressure was released to the atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-6). The resulting polymerization solution was demineralized with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-6). Table 2 shows the properties of the ethylene / propylene copolymer (A-6).

(Preparation of ethylene / propylene copolymer (A-7))
30 parts of ethylene / propylene copolymer (A-3) and 70 parts of the following ethylene / propylene copolymer (A-8) are mixed, and a twin-screw extruder having a screw diameter of 30 mm and a vacuum vent (manufactured by Ikegai Co., Ltd .; The mixture was melt-kneaded at 200 ° C. and 93.325 kPa vacuum in “PCM30” to prepare an ethylene / propylene copolymer (A-7). Table 2 shows the properties of the ethylene / propylene copolymer (A-7).

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

<Olefin resin aqueous dispersion (B)>
(Preparation of olefin resin aqueous dispersion (B-1))
100 parts of ethylene / propylene copolymer (A-1) and maleic anhydride-modified polyethylene ("Mitsui High Wax 2203A", manufactured by Mitsui Chemicals, Inc., acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 25 parts of 30 mg KOH / g) and 10 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture was supplied at 4 kg / h from a hopper of a twin-screw extruder (manufactured by Ikegai Co., Ltd., "PCM30", L / D = 40), and water was supplied from a supply port provided at a vent portion of the twin-screw extruder. While continuously supplying an aqueous solution obtained by mixing 1.5 parts of potassium oxide and 5.0 parts of ion-exchanged water, the mixture 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 a 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 concentration of about 40% by mass, and the aqueous olefin resin dispersion (B -1) was obtained. Table 3 shows the average particle size 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 3, except that (A-1) was changed from (A-2) to (A-8) as the component A, the olefin resin was prepared in the same manner as the olefin resin aqueous dispersion (B-1). Aqueous dispersions (B-2) to (B-8) were obtained.
Table 3 shows the average particle size of the ethylene / α-olefin copolymer (A) dispersed in each of the aqueous olefin resin dispersions (B-2) to (B-8).

(Preparation of aqueous olefin resin dispersions (B-9) to (B-16))
As shown in Table 4, the olefin resin aqueous dispersions (B-9) to (B-16) were prepared in the same manner as the olefin resin aqueous dispersion (B-3) except that the number of added potassium oleate was changed. I got
Table 4 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-exchanged water was added to the olefin resin aqueous dispersion (B-1) (100 parts as solids) so as to have a solid concentration of 35%, and 0.5 parts of t-butylcumyl peroxide was used as an organic peroxide. One part of divinylbenzene was added as a polyfunctional compound and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (C-1). Table 5 shows the gel content and the average particle size 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 5 to 7, except that the type of the olefin resin aqueous dispersion (B) and the addition amount of t-butylcumyl peroxide were changed, the crosslinked ethylene / α-olefin copolymer (C-1) was used. Similarly, crosslinked ethylene / α-olefin copolymers (C-2) to (C-20) were obtained. Tables 5 to 7 show the gel content and the average particle size of the crosslinked ethylene / α-olefin copolymers (C-2) to (C-20).

(Preparation of crosslinked ethylene / α-olefin copolymer (C-21))
For 100 parts of the ethylene / α-olefin copolymer (A-3), 0.5 parts of α, α′-di (t-butylperoxy) diisopropylbenzene and 1.0 part of divinylbenzene were used as organic peroxides. And melt-kneaded at 220 ° C. and 93.325 kPa vacuum using a twin screw extruder with a screw diameter of 30 mm and a vacuum vent (manufactured by Ikegai Co., Ltd., “PCM-30”). After melt-kneading, the mixture was finely pulverized to obtain a crosslinked ethylene / α-olefin copolymer (C-21). Table 7 shows the gel content and the average particle size of the crosslinked ethylene / α-olefin copolymer (C-21).

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1))
A crosslinked ethylene / α-olefin copolymer (C-1) (70 parts as a solid content of the ethylene / propylene copolymer (A-1)) is put into a stainless steel polymerization tank equipped with a stirrer, and the crosslinked ethylene / α-olefin is added. Ion-exchanged water was added to the copolymer (C-1) so that the solid content concentration became 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were charged, The temperature was 80 ° C. 23.4 parts of styrene, 6.6 parts of acrylonitrile and 0.6 part of cumene hydroperoxide were continuously added for 150 minutes, emulsion polymerization was carried out while keeping the polymerization temperature at 80 ° C., and graft copolymer having an average particle diameter of 0.12 μm was obtained. An aqueous dispersion containing the union (D-1) was obtained. An antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1), the solid content is precipitated with sulfuric acid, and the powdered graft copolymer ( D-1) was obtained. It was 30% when the graft ratio of the graft copolymer (D-1) was measured. The results of the graft ratio are also shown in Table 8. The average particle size of the ethylene / α-olefin copolymer (A) in the thermoplastic resin composition was confirmed by an electron microscope, and was found to be 0.12 μm.

(Preparation of Graft Copolymers (D-2) to (D-20))
As shown in Tables 8 to 11, except that the type of the crosslinked ethylene / α-olefin copolymer (C) was changed, the graft copolymer (D-) was prepared in the same manner as the graft copolymer (D-1). 2) to (D-20) were obtained. Tables 8 to 11 show the graft ratios of the graft copolymers (D-2) to (D-20).

(Preparation of graft copolymer (D-21))
70 parts of a crosslinked ethylene / α-olefin copolymer (C-21) and 300 parts of toluene were charged into a stainless steel polymerization tank equipped with a stirrer, and the contents were uniformly stirred at 70 ° C. for 1 hour. After sufficiently purging with nitrogen, 23.4 parts of styrene, 6.6 parts of acrylonitrile, 0.24 part of t-dodecylmercaptan, and 0.22 part of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was increased to 110 ° C. The reaction was allowed to react for 4 hours. The internal temperature was raised to 120 ° C., and the reaction was performed for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C, and 0.2 parts of octadecyl-3- (3,5-di-t-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 component is substantially devolatilized at 220 ° C. and 93.325 kPa vacuum using a twin screw extruder with a screw diameter of 30 mm and a vacuum vent (manufactured by Ikegai Co., Ltd., “PCM30”), pelletized, and the graft copolymer (D -21) was obtained. It was 26% when the graft ratio of the graft copolymer (D-21) was measured. Table 11 shows the results.

(Preparation of Graft Copolymer (D-22))
As shown in Table 11, except that the crosslinked ethylene / α-olefin copolymer (C) was changed to the olefin resin aqueous dispersion (B-3), the grafting was carried out in the same manner as the graft copolymer (D-1). A copolymer (D-22) was obtained. Table 11 shows the graft ratio of the graft copolymer (D-22).

<Rubber-like polymer (E)>
(Preparation of rubbery polymer (E-1))
100 parts of ethylene / propylene copolymer (A-3) and maleic anhydride-modified polyethylene ("Mitsui High Wax 2203A", manufactured by Mitsui Chemicals, Inc., acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 25 parts of 30 mg KOH / g) and 7 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture was supplied at 4 kg / h from a hopper of a twin-screw extruder (manufactured by Ikegai Co., Ltd., "PCM30", L / D = 40), and water was supplied from a supply port provided at a vent portion of the twin-screw extruder. While continuously supplying an aqueous solution in which 1.5 parts of potassium oxide and 5.0 parts of ion-exchanged water were mixed, the mixture 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 a twin-screw extruder, and cooled to 90 ° C. Then, the solid discharged from the tip of the twin-screw extruder was put into warm water at 80 ° C., continuously dispersed, and diluted to a solid concentration of about 40% by mass to obtain an aqueous dispersion. Ion-exchanged water was added to the obtained aqueous dispersion (100 parts as solids) so that the solid content concentration became 35%, 0.5 parts of t-butylcumyl peroxide as an organic peroxide, a polyfunctional compound Was reacted at 130 ° C. for 5 hours to obtain a rubber-like polymer (E-1) having an average particle size of 0.15 μm and a gel content of 50%. Table 12 shows the results of the average particle diameter. The rubber-like polymer (E-1) is an olefin-based rubber-like polymer (Ec).

(Preparation of rubbery polymers (E-2) to (E-7))
As shown in Table 12, rubber-like polymers (E-2) to (E-7) were prepared in the same manner as for rubber-like polymer (E-1) except that the number of emulsifiers added during emulsification was changed. Obtained. Table 12 shows average particle sizes of the obtained rubbery polymers (E-2) to (E-7). The rubbery polymers (E-2) to (E-7) are olefin-based rubbery polymers (Ec).

(Preparation of rubbery polymer (E-8))
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 parts of organic sodium sulfonate, 0.2 parts of t-dodecyl mercaptan, 0 parts of potassium persulfate .3 parts and 0.14 parts of potassium hydroxide. Next, the temperature was raised to 60 ° C. while stirring under a nitrogen atmosphere to initiate polymerization. When the polymerization rate was 65%, 5 parts of deionized water in which 0.1 part of potassium persulfate was dissolved was added to the pressure-resistant container. . Thereafter, the polymerization temperature was raised to 70 ° C., the polymerization was completed at a polymerization conversion of 95% for a reaction time of 13 hours, and a latex having an average particle diameter of 80 nm and a solid content of 52.0% was obtained. To this latex, 2.5 parts of a 20% aqueous acetic acid solution as acetic acid was added, and the operation of enlarging was performed to obtain a rubbery polymer (E-8) having an average particle diameter of 0.4 μm. Table 12 shows the results of the average particle diameter. The rubbery polymer (E-8) is a diene rubbery polymer (Ea).

(Preparation of rubbery polymer (E-9))
0.54 parts of dipotassium alkenyl succinate, 350 parts of ion-exchanged water, 100 parts of n-butyl acrylate, 0.32 parts of allyl methacrylate, 0.16 parts of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.2 part of the mixture was charged to the reactor. The inside of the reactor was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.0003 parts of ferrous sulfate, 0.0009 parts of ethylenediaminetetraacetic acid disodium salt, 0.48 parts of Rongalite, and 10 parts of ion-exchanged water was added. The polymerization was started, and the internal temperature was raised to 75 ° C. Further, this state was maintained for 1 hour to obtain a rubbery polymer (E-9) having an average particle diameter of 0.40 μm. Table 12 shows the results of the average particle diameter. The rubber-like polymer (E-9) is an acrylic rubber-like polymer (Eb).

(Preparation of rubbery polymer (E-10))
100 parts of an ethylene / propylene / non-conjugated diene copolymer (manufactured by Mitsui Chemicals, "Tuffmer TP3180") and maleic anhydride-modified polyethylene (Mitsui High Wax 2203A, manufactured by Mitsui Chemicals, Inc.) as an acid-modified olefin polymer, mass average 25 parts of (molecular weight: 2,700, acid value: 30 mg KOH / g) and 3 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture was supplied at 4 kg / h from a hopper of a twin-screw extruder (manufactured by Ikegai Co., Ltd., "PCM30", L / D = 40), and water was supplied from a supply port provided at a vent portion of the twin-screw extruder. While continuously supplying an aqueous solution in which 0.5 part of potassium oxide and 2.4 parts of ion-exchanged water were mixed, the mixture 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 a twin-screw extruder, and cooled to 90 ° C. Then, the solid discharged from the tip of the twin-screw extruder was put into warm water at 80 ° C., continuously dispersed, and diluted to a solid concentration of about 40% by mass to obtain an aqueous dispersion. Ion-exchanged water was added to the obtained aqueous dispersion (100 parts as solids) so that the solid content concentration became 35%, 0.5 parts of t-butylcumyl peroxide as an organic peroxide, a polyfunctional compound Was reacted at 130 ° C. for 5 hours to obtain a rubbery polymer (E-10) having an average particle diameter of 0.40 μm and a gel content of 50%. Table 12 shows the results of the average particle diameter. The rubber-like polymer (E-10) is an olefin-based rubber-like polymer (Ec).

<Graft copolymer (F)>
(Preparation of graft copolymer (F-1))
A rubbery polymer (E-1) (50 parts as a solid content) was placed in a stainless steel polymerization tank equipped with a stirrer, and ion-exchanged water was added so that the solid content concentration became 30%. , 0.3 parts of sodium pyrophosphate and 0.35 parts of fructose, and the temperature was adjusted to 80 ° C. 39 parts of styrene, 11 parts of acrylonitrile and 0.6 part of cumene hydroperoxide were continuously added for 150 minutes, and emulsion polymerization was carried out while keeping the polymerization temperature at 80 ° C. After the polymerization, an antioxidant was added to the aqueous dispersion containing the graft copolymer (F-1), and the solid content was precipitated with sulfuric acid. Polymer (F-1) was obtained. Table 13 shows the rubber content in the graft copolymer (F).

(Preparation of Graft Copolymers (F-2) to (F-7), (F-10))
Except having changed rubber-like polymer (E-1) into rubber-like polymers (E-2)-(E-7) and (E-10), it carried out similarly to graft copolymer (E-1). And graft copolymers (F-2) to (F-7) and (F-10). Table 13 shows the rubber content in the graft copolymer (F).

(Preparation of graft copolymer (F-8))
The rubbery polymer (E-8) (50 parts as a solid content) was placed in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, and 0.3 parts of disproportionated potassium rosinate was added. (Solid content), 0.01 part of ferrous sulfate heptahydrate, 0.2 part of sodium pyrophosphate and 0.5 part of crystalline glucose were charged, and the temperature in the reactor was raised to 60 ° C. while stirring. Was. 39 parts of styrene, 11 parts of acrylonitrile, 0.4 part of t-dodecyl mercaptan, and 0.35 part of cumene hydroperoxide were mixed, continuously dropped and supplied over 2 hours, and graft-polymerized. During that time, the jacket temperature was controlled so as to maintain the reactor internal temperature at 60 ° C. After completion of the dropwise addition, the temperature was raised to 70 ° C., and the temperature was further maintained for 1 hour to complete the graft polymerization reaction. After cooling, an antioxidant (dilauryl thiodipropionate) was added to obtain a latex of the graft copolymer (F-8). The obtained latex of the graft copolymer (F-8) is poured into a 2.5% aqueous sulfuric acid solution (80 ° C.) of 1 volume of the latex under stirring, and further coagulated by holding at 90 ° C. for 5 minutes. Thus, a slurry of the graft copolymer (F-8) was obtained. After repeating washing and dehydration of the slurry twice, the slurry was allowed to stand at 70 ° C. overnight and dried to obtain a milky white powder graft copolymer (F-8). Table 13 shows the rubber content in the graft copolymer (F).

(Preparation of graft copolymer (F-9))
While maintaining the internal temperature of the reactor at 75 ° C, 0.15 part of Rongalite, 0.65 part of dipotassium alkenylsuccinate, and 40 parts of solid polymer as rubbery polymer (E-9), An aqueous solution consisting of 10 parts of exchanged water was added, and then a mixed solution consisting of 5 parts of acrylonitrile, 15 parts of styrene, and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour to carry out graft polymerization. Five minutes after the completion of the dropwise addition, an aqueous solution consisting of 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 9 was added. , 31 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 parts of n-octylmercaptan were dropped over 1 hour to carry out graft polymerization. After completion of the dropwise addition, the internal temperature was maintained at 75 ° C. for 10 minutes, and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of an antioxidant (Antage W500, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and alkenyl succinate 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-9). Table 13 shows the rubber content in the graft copolymer (F).

<Methacrylic acid ester resin (G)>
(Preparation of Methacrylate Resin (G-1))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged 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 parts of calcium hydroxyapatite and 0.003 parts of potassium alkenyl succinate. The reaction was carried out for 3 hours at an internal temperature of the polymerization tank of 75 ° C., and the reaction was carried out at 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylate resin (G-1). Table 14 shows the composition of the monomers.

(Preparation of Methacrylate Resin (G-2))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged 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 0.25 parts of mercaptan and 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set to 75 ° C., and the reaction was performed for 3 hours. The temperature was raised to 90 ° C., and the reaction was performed for 1 hour. The content was extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylate resin (G-2). Table 14 shows the composition of the monomers.

(Preparation of Methacrylate Resin (G-3), (G-4))
As shown in Table 14, except that the type of the vinyl monomer mixture (m3) was changed, the methacrylic ester resin (G-3), (G- 4) was obtained. Table 14 shows the composition of the monomers.

<Polyethylene resin (H)>
(Polyethylene resin (H-1))
As the polyethylene resin (H-1), "Mitsui High Wax 4052E" manufactured by Mitsui Chemicals, Inc., mass average molecular weight: 3,000, acid value: 20 mgKOH / g was used.

(Polyethylene resin (H-2))
As the polyethylene resin (H-2), “Mitsui High Wax 320MP”, mass average molecular weight: 3,000, acid value: 1 mgKOH / g, manufactured by Mitsui Chemicals, Inc. was used.

(Polyethylene resin (H-3))
As the polyethylene resin (H-3), “Mitsui High Wax 320P”, manufactured by Mitsui Chemicals, Inc., mass average molecular weight: 3,000, acid value: 0 mgKOH / g was used.

<Styrene-based copolymer (I)>
(Preparation of styrene copolymer (I-1))
120 parts of ion-exchanged water, 0.1 part of polyvinyl alcohol, 0.3 parts of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, 75 parts of t -0.35 parts 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 the reaction was performed for 4 hours. The contents were taken out to obtain a styrene copolymer (I-1). Table 15 shows the composition of the monomers.

(Preparation of styrene copolymer (I-2))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged water, 10 parts of methyl methacrylate, 22 parts of acrylonitrile, 68 parts of styrene, 0.2 parts of 2,2′-azobis (isobutyronitrile), 0.2 parts of n-octyl mercaptan 0 .25 parts, 0.47 parts of calcium hydroxyapatite, and 0.003 parts of potassium alkenyl succinate were charged, the internal temperature was raised to 75 ° C., and the mixture was reacted for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, washed and dehydrated by a centrifugal dehydrator repeatedly, and dried to obtain a styrene-based copolymer (I-2). Table 15 shows the composition of the monomers.

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

<Other resins>
Polycarbonate (PC): manufactured by Mitsubishi Engineering-Plastics, NOVAREX 7025R

[Example 1]
10 parts of graft copolymer (D-2), 14 parts of graft copolymer (F-4), 76 parts of methacrylate resin (G-2), and 1 part of polyethylene resin (H-1) were mixed, The mixture was melt-kneaded at 240 ° C. and 93.325 kPa vacuum using a twin-screw extruder with a screw diameter of 30 mm and a vacuum vent (manufactured by Ikegai Co., Ltd., “PCM30”) to prepare a thermoplastic resin composition (1).
Separately, 10 parts of graft copolymer (D-2), 14 parts of graft copolymer (F-4), 76 parts of methacrylate resin (G-2), 1 part of polyethylene resin (H-1), carbon 0.8 parts of black were mixed and melt-kneaded at 240 ° C. and 93.325 kPa vacuum in a twin-screw extruder with a screw diameter of 30 mm and a vacuum vent (“PCM30”, manufactured by Ikegai Co., Ltd.) to obtain a thermoplastic resin composition (2 ) Was prepared.
Table 16 shows the MVR of the thermoplastic resin composition (2).
The thermoplastic resin composition (1) or the thermoplastic resin composition (2) is pelletized, and various molded articles are formed, and the resulting article has impact resistance, cold impact resistance, coloring, scratch resistance, abrasion resistance, and heat resistance. The lubricity (squeaking noise) and the surface appearance of the molded product were evaluated. Table 16 shows the results.

[Examples 2-57]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the formulation was changed to the formulation shown in Tables 16 to 23, and the MVR was measured.
In addition, the thermoplastic resin composition of each example was pelletized, and various molded articles were molded, and the impact resistance, the cold impact resistance, the coloring, the scratch resistance, the abrasion resistance, the heat resistance, the lubricity (squeaking noise) ) And the surface appearance of the molded product was evaluated. The results are shown in Tables 16 to 23.

[Comparative Examples 1 to 15]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the formulation was changed to the formulation shown in Tables 24 and 25, and the MVR was measured.
Further, the thermoplastic resin composition of each comparative example was pelletized, and various molded articles were molded, and then subjected to impact resistance, cold impact resistance, coloring, scratch resistance, abrasion resistance, heat resistance, lubricity (squeaking noise). ) And the surface appearance of the molded product was evaluated. The results are shown in Tables 24 and 25.

The thermoplastic resin compositions of Examples 1 to 57 were excellent in fluidity. Further, the molded products obtained in Examples 1 to 57 were excellent in lubricity (squeak noise), impact resistance, cold impact resistance, heat resistance, coloring, scratch resistance, and scratch resistance. In particular, the blending amount of the polyethylene resin (H) is based on 100 parts by mass of the total of the graft copolymer (D), the graft copolymer (F), the methacrylate resin (G), and the styrene copolymer (I). On the other hand, the molded products obtained in Examples 1 to 56, which were 0.5 to 4.0 parts by mass, were also excellent in surface appearance.
On the other hand, the molded articles of Comparative Examples 1 to 15 did not have lubricity (squeaking noise) characteristics, or had low impact resistance, cold impact resistance, and abrasion resistance.

  The molded article obtained by molding the thermoplastic resin composition of the present invention is excellent in lubricity (squeak noise), impact resistance, cold impact resistance, coloring, scratch resistance, and scratch resistance, and is used for vehicle interior and exterior parts. Useful as office equipment, home appliances, building materials, etc.

Reference Signs List 10 jig 11 tip 12 laminated sheet 13 molded product (Ma2)
21 Test piece 21a Rib structure 22 Test piece

Claims (5)

Existence of 50 to 80% by mass of 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 Below, 20-50 mass% of vinyl monomer mixture (m1) (however, the total of the ethylene / α-olefin copolymer (A) and the vinyl monomer mixture (m1) is 100 mass%. A) a graft copolymer (D) obtained by polymerizing
In the presence of 20 to 80% by mass of the rubbery polymer (E), 20 to 80% by mass of the vinyl monomer mixture (m2) (provided that the rubbery polymer (E) and the vinyl monomer mixture (m2 Is a total of 100% by mass.) , And a graft copolymer (F) obtained by polymerization of
A methacrylate resin (G) obtained by polymerizing a vinyl monomer mixture (m3) containing a methacrylate,
A polyethylene resin (H) having a mass average molecular weight of less than 10,000, and a thermoplastic resin composition comprising:
The thermoplastic resin composition may include a styrene-based copolymer (I) obtained by polymerizing a vinyl-based monomer mixture (m4) containing an aromatic vinyl compound and a vinyl cyanide compound,
The average particle diameter of the ethylene / α-olefin copolymer (A) is 0.05 to 0.18 μm, the average particle diameter of the rubbery polymer (E) is 0.20 to 0.60 μm, These average particle diameters are the volume average particle diameters determined by the laser diffraction / scattering method,
In the total (100% by mass) of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E), the proportion of the ethylene / α-olefin copolymer (A) is 15 to 85% by mass. , proportion 85-15% by mass of the rubber-like polymer (E) is,
The ethylene unit content of the ethylene / α-olefin copolymer (A) is 45 to 45 when the total of all the constituent units constituting the ethylene / α-olefin copolymer (A) is 100% by mass. 60% by mass,
The vinyl-based monomer mixture (m1) contains 65 to 82% by mass of an aromatic vinyl compound and 18 to 35% by mass of a vinyl cyanide compound in 100% by mass of the vinyl-based monomer mixture (m1),
The vinyl-based monomer mixture (m2) contains 65 to 82% by mass of an aromatic vinyl compound and 18 to 35% by mass of a vinyl cyanide compound in 100% by mass of the vinyl-based monomer mixture (m2),
The total content of the graft copolymer (D) and the graft copolymer (F) in the thermoplastic resin composition is as follows: the graft copolymer (D), the graft copolymer (F), the methacrylate resin ( G) and 5.1 to 54.9% by mass in a total of 100% by mass of the styrenic copolymer (I),
The content of the methacrylate resin (G) in the thermoplastic resin composition may be determined according to the graft copolymer (D), the graft copolymer (F), the methacrylate ester resin (G), and the styrene copolymer (I). ) Of 94.9 to 45.1% by mass in a total of 100% by mass,
The content of the styrene-based copolymer (I) in the thermoplastic resin composition is determined based on the graft copolymer (D), the graft copolymer (F), the methacrylate resin (G), and the styrene-based copolymer ( 0 to 38% by mass in the total 100% by mass of I),
The content of the polyethylene-based resin (H) in the thermoplastic resin composition is determined based on the graft copolymer (D), the graft copolymer (F), the methacrylate ester resin (G), and the styrene-based copolymer (I). total 100 parts by mass, Ru 0.5 to 5 parts by mass der, thermoplastic resin composition.   The rubbery polymer (E) is at least one rubbery polymer selected from the group consisting of a diene rubbery polymer, an acrylic rubbery polymer, and an olefin rubbery polymer. 5. The thermoplastic resin composition according to item 1. Ethylene · alpha-olefin copolymer (A), the ethylene · alpha-olefin copolymer (A) to crosslinking treatment and the crosslinked ethylene · alpha-olefin copolymer as (C), the vinyl monomer mixture The thermoplastic resin composition according to claim 1 or 2, which is subjected to polymerization with (m1) .   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyethylene resin (H) is a polyethylene oxide.   A molded article obtained by molding the thermoplastic resin composition according to claim 1.

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