JP6351152B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

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

Improving the impact resistance of the molded product not only expands the applications of the molded product, but also makes it extremely useful for industrial applications, such as enabling the molded product to be made thinner and larger. . Therefore, various techniques have been proposed so far for improving the impact resistance of the molded product. Among these methods, by using a rubber-reinforced resin material that combines a rubbery polymer and a hard resin, a method for improving the impact resistance of a molded product while maintaining the properties derived from the hard resin has already been industrialized. ing. Examples of such resin materials include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylic acid ester (ASA) resin, acrylonitrile-ethylene / α-olefin-styrene (AES) resin, or a hard resin thereof. The thermoplastic resin composition etc. which were added to are mentioned.
For example, the following are known as thermoplastic resin compositions capable of obtaining a molded article having improved impact resistance while maintaining the characteristics derived from the hard resin.
(1) A thermoplastic resin composition obtained by adding an AES resin to a methacrylic ester resin which is a hard resin (Patent Document 1).
(2) A thermoplastic resin composition in which an AES resin is added to a maleimide copolymer that is a hard resin (Patent Document 2).
(3) A thermoplastic resin composition obtained by adding an AES resin and an ASA resin to a methacrylic ester resin which is a hard resin (Patent Document 3).
However, in the thermoplastic resin compositions (1) and (2), it was necessary to add a large amount of AES resin in order to improve the impact resistance of the molded product. Therefore, in the obtained molded product, the surface hardness (scratch resistance) derived from the methacrylic ester resin and the heat resistance derived from the maleimide copolymer were remarkably 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 tended to have poor color development derived from a hard resin. .
In the thermoplastic resin composition of (3), AES resin and ASA resin are added in order to suppress a decrease in color developability of the molded product, but the impact resistance of the molded product is higher than when only the AES resin is added. Was low.

Rubber-reinforced resin materials are widely used in various fields such as office automation equipment, automobiles, and miscellaneous goods. However, in rubber-reinforced resin materials, stick-slip phenomenon occurs in switch parts of OA equipment, car audio fitting parts, etc. due to vibrations of equipment, vibrations at the start of a vehicle or running, etc., and squeak noise is generated. There was a problem.
In order to reduce the occurrence of squeak noise in a molded article of a rubber reinforced resin material, for example, it has been proposed to use the following thermoplastic resin composition.
(4) A thermoplastic resin composition obtained by adding 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 rubber-reinforced acrylonitrile-styrene resin containing ABS resin and AES resin (Patent Document 5).
(6) A thermoplastic resin composition in which polytetrafluoroethylene, low molecular weight oxidized polyethylene, or ultrahigh molecular weight polyethylene is added 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 product 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 product, thereby improving the lubricity of the molded product. Reduce the friction coefficient. However, there has been a problem that the bleed-out lubricant deteriorates the surface appearance of the molded product, and the bleed-out lubricant is gradually lost, so that the lubricity decreases with time.

JP 2005-132970 A JP 2004-352842 A JP 2004-346187 A Japanese Patent No. 2688619 JP 2011-174029 A JP 2011-168186 A

  The present invention provides a thermoplastic resin composition that has good fluidity, is excellent in scratch resistance, impact resistance, cold impact resistance, etc. of the obtained molded product, and can simultaneously suppress squeak noise and color development. With the goal. Further, the present invention provides a molded product that is excellent in scratch resistance, impact resistance, and cold impact resistance, and that can achieve both squeak noise suppression 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) was polymerized in the presence of the graft copolymer (D) obtained by polymerizing the vinyl monomer mixture (m1) and the crosslinked rubber-like polymer (E). A thermoplastic resin composition comprising: a graft copolymer (F) obtained by polymerization; and a methacrylate ester resin (G) obtained by polymerizing a vinyl monomer mixture (m3) containing a methacrylate ester. a is the following average particle diameter of the ethylene · alpha-olefin copolymer (a) is a 0.05Myuemu～0.18Myuemu the following average particle diameter of the rubbery polymer (E) is zero. 20 μm to 0.60 μm; ethylene / α-olefin copolymerization Of the total (100% by mass) of (A) and the rubbery polymer (E), the proportion of the ethylene / α-olefin copolymer (A) is 15 to 85% by mass, and the rubbery polymer (E ) Is a thermoplastic resin composition having a ratio of 85 to 15% by mass.
(Average particle size)
The average particle diameter of the ethylene / α-olefin copolymer (A) and the rubber-like polymer (E) is a volume average particle diameter measured using Nikkiso Co., Ltd. Microtrac and the measurement solvent as pure water.
[2] The rubbery polymer (E) is at least one rubbery polymer selected from diene rubber polymers, acrylic rubber polymers, and olefin rubber polymers. Thermoplastic resin composition.
[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] A molded product obtained by molding the thermoplastic resin composition according to any one of [1] to [3].

The thermoplastic resin composition of the present invention has good fluidity. Moreover, 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, color development, and squeak noise suppression effect.
The molded article of the present invention is excellent in scratch resistance, impact resistance, cold impact resistance, color development, and squeak noise suppression effect.

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

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

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention contains a graft copolymer (D), a graft copolymer (F), and a methacrylic ester resin (G). The thermoplastic resin composition of the present invention contains at least one of a styrenic copolymer (H), another thermoplastic resin, and various additives, as necessary, within a range not impairing the effects of the present invention. You may go out.
Details of each component will be described below.

[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). A vinyl monomer mixture (m1) in the presence of the cross-linked ethylene / α-olefin copolymer (C) in that the molded article has an excellent balance of scratch resistance, impact resistance, cold impact resistance and squeak noise suppression effect. ) Is preferred.
The graft copolymer (D) is an ethylene / α-olefin copolymer (A) in the presence of 50 to 80% by mass, and the vinyl monomer mixture (m1) is 20 to 50% by mass (provided that ethylene / α -The thing obtained by superposing | polymerizing olefin copolymer (A) and a vinyl-type monomer mixture (m1) is 100 mass%) is preferable. When the ethylene / α-olefin copolymer (A) is 50 to 80% by mass, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, and the balance of physical properties of the coloring property are further improved.
The graft ratio of the graft copolymer (D) is preferably 20 to 100% by mass from the viewpoint of the balance between the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, and the color development.

<Ethylene / α-olefin copolymer (A)>
The ethylene / α-olefin copolymer (A) comprises an ethylene unit and an α-olefin unit obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms by a known polymerization method. It is a copolymer.
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-icosene and 1-docosene. Among these α-olefins, α-olefins having 3 to 20 carbon atoms are preferable and propylene is particularly preferable from the viewpoint of impact resistance of the molded product.

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

The mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (A) is 17 × 10 ^{4 to} 35 × 10 ⁴ , and preferably 26 × 10 ^{4 to} 32 × 10 ⁴ . When the mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (A) is smaller than 17 × 10 ⁴ , the scratch resistance, impact resistance, cold impact resistance, and squeak noise suppression effect of the molded product can be obtained. Lower. On the other hand, when the mass 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 developability of the molded product are lowered. When the mass average molecular weight (Mw) is 26 × 10 ^{4 to} 32 × 10 ⁴ , the fluidity of the thermoplastic resin composition and the scratch resistance, impact resistance, cold impact resistance, and squeak noise suppression 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 scratch resistance, impact resistance, cold impact resistance, and squeak noise suppression effect of the molded product are lowered. . If 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 The cold shock resistance and squeak noise suppression effect are even better.

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

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

The method for producing the ethylene / α-olefin copolymer (A) is not limited. The ethylene / α-olefin copolymer (A) is usually produced by polymerizing ethylene and an α-olefin using a metallocene catalyst or a Ziegler-Natta catalyst.
As a metallocene catalyst, a catalyst obtained by combining an organic compound having a cyclopentadienyl skeleton with a transition metal (zirconium, titanium, hafnium, etc.), a metallocene complex in which a halogen atom or the like is coordinated, an organoaluminum compound, an organoboron compound, etc. Is mentioned.
Examples of the Ziegler-Natta catalyst include a catalyst in which a halide of a transition metal (titanium, vanadium, zirconium, hafnium, etc.) is combined with an organic aluminum compound, an organic boron compound, or the like.
Examples of the polymerization method include a method in which ethylene and an α-olefin are copolymerized in a solvent in the presence of the catalyst. Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may use the raw material alpha olefin as a solvent.
By changing the reaction conditions such as the supply amount of ethylene, α-olefin, the type and amount of molecular weight regulators such as hydrogen, the type and amount of catalyst, the reaction temperature, and the pressure, an ethylene / α-olefin copolymer (A ) Ethylene unit content, mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be adjusted.

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

The preparation method of 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 in which mechanical shearing force is applied and dispersed, and an aqueous medium containing an emulsifier is added; ethylene / α-olefin copolymer (A) is a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) And a method in which the mixture is dissolved in an aqueous medium, added to an aqueous medium and emulsified, and then sufficiently stirred to distill off the hydrocarbon solvent.
In preparing the aqueous olefin resin dispersion (B), an emulsifier, an acid-modified olefin polymer, and the like may be added as other components.

Examples of the emulsifier include known ones, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
The amount of the emulsifier added can suppress thermal coloring of the resulting thermoplastic resin composition, and the particle diameter control of the aqueous olefin resin dispersion (B) is easy, so that the ethylene / α-olefin copolymer (A) 1-8 mass parts is preferable with respect to 100 mass parts.

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

The method for adding the acid-modified olefin polymer is not limited. Crosslinking may be performed after mixing the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer, or the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer. You may mix, after each crosslinking process.
The mixing method of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer is not limited, 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 aqueous olefin resin dispersion (B) is 0.05 to 0.18 μm from the viewpoint of excellent physical properties of the molded product, and is 0.07 to 0.15 μm is preferable. 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 diameter of the ethylene / α-olefin copolymer (A) is smaller than 0.05 μm, the impact resistance and cold impact resistance of the molded product are lowered. When the average particle size of the ethylene / α-olefin copolymer (A) is larger than 0.6 μm, the impact resistance, cold impact resistance, color development, scratch resistance, and squeak noise suppression effect of the molded product are low. Become. When the average particle diameter of the ethylene / α-olefin copolymer (A) is 0.07 μm to 0.15 μm, the impact resistance, cold impact resistance, and color developability of the molded product are further improved.
The average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B) is the same as that of the ethylene / α-olefin copolymer (A) in the thermoplastic resin composition. It is confirmed by image analysis of an electron microscope that the average particle diameter is shown.
As a method for controlling the average particle size of the ethylene / α-olefin copolymer (A) in the olefin resin aqueous dispersion (B), the type or amount of the emulsifier, the type or content of the acid-modified olefin polymer, The method of adjusting the shear force, temperature conditions, etc. which are applied at the time of kneading is mentioned.

(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 crosslinking an uncrosslinked ethylene / α-olefin copolymer.
By crosslinking the uncrosslinked ethylene / α-olefin copolymer, the balance of the scratch resistance, impact resistance, cold impact resistance, color development, and squeak noise suppression effect of the molded product is further improved.

  The gel content of the cross-linked ethylene / α-olefin copolymer (C) is 35 to 75 in terms of a balance with the scratch resistance, impact resistance, cold impact resistance, color development, and squeak noise suppression effect of the molded product. % 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) a method of performing crosslinking treatment by adding an organic peroxide and, if necessary, a polyfunctional compound to the ethylene / α-olefin copolymer (A). (B) a method of performing a crosslinking treatment with ionizing radiation, and the like, and the method (a) is preferable from the viewpoint of impact resistance and color developability of the molded product.
Specifically, as the method of (a), an ethylene / α-olefin copolymer (A) or an aqueous olefin resin dispersion (B) is mixed with an organic peroxide and, if necessary, a multifunctional compound. The method of adding and heating is mentioned.
The gel content of the crosslinked ethylene / α-olefin copolymer (C) can be adjusted by adjusting the addition amount of organic peroxide and polyfunctional compound, heating temperature, heating time and the like.
The heating temperature varies depending on the type of organic peroxide. The heating temperature is preferably −5 ° C. to + 30 ° C., which is the 10-hour half-life temperature of the organic peroxide.
The heating time is preferably 3 to 15 hours.

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

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

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

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

As the organic peroxide, dialkyl such as dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, etc., because it is easy to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C). Peroxide compounds are particularly preferred.
The addition amount of the organic peroxide is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted to a range of 35 to 75% by mass, so that the ethylene / α-olefin copolymer (A ) 0.1 to 5 parts by mass is preferable with respect to 100 parts by mass.

The polyfunctional compound is used in combination with an organic peroxide as necessary in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C).
Examples of the multifunctional compound include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate, and the like. From the viewpoint of easily adjusting the gel content, divinylbenzene is preferable. A polyfunctional compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The addition amount of the polyfunctional compound is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted to 35 to 75% by mass, and thus the ethylene / α-olefin copolymer (A) 100 is used. 10 parts by mass or less is preferable with respect to parts by mass.

The average particle size of the cross-linked 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 product. preferable. When 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 are lowered. When the average particle size of the cross-linked ethylene / α-olefin copolymer (C) is larger than 0.6 μm, the impact resistance, cold impact resistance, color development, scratch resistance, and squeak noise suppression effect of the molded product Lower. When the average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) is 0.07 μm to 0.15 μm, the impact resistance, cold impact resistance, and color developability of the molded product are further improved.
In addition, the average particle diameter of the ethylene / α-olefin copolymer in the olefin resin aqueous dispersion (B) does not change before and after the crosslinking treatment.
The average particle size of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion is equal to the average particle size of the crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition. It is confirmed by image analysis of an electron microscope.

<Vinyl monomer mixture (m1)>
The vinyl monomer mixture (m1) is a vinyl monomer comprising one or more monomer units selected from the group of aromatic vinyl compounds, vinyl cyanide compounds and other vinyl monomers. It is a body mixture.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of the thermoplastic resin composition, the color development of the molded product, and the impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 65 to 82% by mass, more preferably 73 to 80% by mass, and further preferably 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 range, the color developability and impact resistance of the molded product are further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and still more preferably 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 developability and impact resistance of the molded product are further improved.

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

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

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

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

Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, and amino acid derivative salts.
Examples of nonionic surfactants include ordinary polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types.
Examples of the amphoteric surfactant include those having a carboxylate salt, sulfate ester salt, sulfonate salt, phosphate ester salt and the like in the anion portion and amine salts and quaternary ammonium salts in the cation portion.
The addition amount of the emulsifier is preferably 10 parts by mass or less with respect to 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 precipitation agent is added to the aqueous dispersion, and after heating and stirring, the precipitation agent is separated. And a precipitation method in which the precipitated graft copolymer (D) is washed with water, dehydrated and dried.
Examples of the precipitating agent include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. A precipitation agent may be used individually by 1 type, and may be used in combination of 2 or more type.
An antioxidant may be added to the aqueous dispersion containing the graft copolymer (D) as necessary.

As the method for producing the graft copolymer (D) by the 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. For example, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide are used. Moreover, the method of adding a polymerization initiator collectively or continuously is mentioned.

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

<Rubber 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 rubber-like polymers such as polyorganosiloxane-butyl acrylate composite rubber. These may be used alone or in combination of two or more.

  The diene rubber-like polymer (Ea) is a diene rubber polymer containing, for example, a diene component such as butadiene and isoprene, and, if necessary, a monomer component copolymerizable therewith as a constituent component. is there. Specific examples include polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene-styrene copolymer, and polychloroprene. These may be used individually by 1 type and may be used in combination of 2 or more type.

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

  The acrylic rubbery polymer (Eb) is a copolymer having one or both of a unit derived from a (meth) acrylic acid ester, a unit derived from a crosslinking agent, and a unit derived from a graft crossing agent. It is preferable. Examples of (meth) acrylic acid esters include (meth) acrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group, and acrylic acid esters having an aromatic hydrocarbon group (such as a phenyl group or a benzyl group). From the viewpoint of impact resistance of the molded product, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferable. One (meth) acrylic acid ester may be used alone, or two or more may be used in combination.

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

  The method for producing the acrylic rubber polymer (Eb) is not particularly limited. For example, a method of obtaining an aqueous dispersion of an acrylic rubber 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 crossing agent; A method of heteroaggregating or co-enlarging an aqueous dispersion of the acrylic rubber polymer (Eb) and an aqueous dispersion of another rubber component; an aqueous dispersion of an acrylic rubber-like polymer (Eb) or another rubber Examples thereof include a method of polymerizing a monomer mixture constituting the other in the presence of either one of the component aqueous dispersions to form a composite.

Examples of the olefin rubber polymer (Ec) include an ethylene / α-olefin copolymer and an ethylene-propylene-nonconjugated diene copolymer.
As the α-olefin of the ethylene / α-olefin copolymer, propylene having 1 to 3 carbon atoms, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-Icocene, 1-docosene and the like can be mentioned.
The ethylene-propylene-nonconjugated diene copolymer is a copolymer comprising an ethylene unit, a propylene unit, and a nonconjugated diene unit as a third component. Examples of the nonconjugated diene unit include dicyclopentadiene. , 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 rubber polymer (Ec) is not limited. For example, the olefin rubber 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 rubber 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.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may use the raw material alpha olefin as a solvent.

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

  The olefin rubber polymer (Ec) may be an aqueous dispersion. The method for preparing the aqueous dispersion of the olefin rubber polymer (Ec) is not limited. As a specific preparation method, for example, the olefin rubber polymer (Ec) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.), and dispersed by applying mechanical shearing force. The olefin rubber polymer (Ec) is dissolved in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) together with the emulsifier and added to the aqueous medium. After emulsification, a method of sufficiently stirring and distilling off the hydrocarbon solvent can be used. In preparing the aqueous dispersion of the olefin rubber polymer (Ec), an emulsifier, an acid-modified olefin polymer and the like may be added as other components.

Examples of the emulsifier include known ones, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
Examples of the acid-modified olefin polymer include those obtained by modifying an olefin polymer having a mass average molecular weight of 1,000 to 5,000 (polyethylene, polypropylene, etc.) with a compound having a functional group (such as an unsaturated carboxylic acid compound). It is done. Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, and the like.
The method for adding the acid-modified olefin polymer is not limited. The olefin rubber polymer (Ec) and the acid-modified olefin polymer may be mixed and then crosslinked, or the olefin rubber polymer (Ec) and the acid-modified olefin polymer may be crosslinked and then mixed. May be.

The average particle diameter of the rubber-like polymer (E) in the aqueous dispersion is 0.20 to 0.60 μm, preferably 0.30 to 0.50 μm, from the viewpoint of excellent physical properties of the molded product.
When the average particle diameter of the rubber-like polymer (E) is smaller than 0.20 μm, the impact resistance and cold impact resistance of the molded product are lowered. 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 developability of the molded product are lowered.
The average particle diameter of the rubber-like polymer (E) in the aqueous dispersion is equal to the average particle diameter of the rubber-like polymer (E) in the thermoplastic resin composition, which is confirmed by image analysis using an electron microscope. doing.

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

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

  The content of the aromatic vinyl compound is preferably 65 to 82% by mass, more preferably 73 to 80% by mass, and further preferably 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 range, the color developability and impact resistance of the molded product are further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and further preferably 20 to 25% by mass in 100% by mass of the vinyl monomer mixture (m2). When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  Examples of other vinyl monomers include methacrylate esters (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, pendyl methacrylate, phenyl methacrylate, etc.), maleimide compounds (N -Methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-tert-butylmaleimide, N-cycloalkylmale Amide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), N-aralkylmaleimide, etc.), acrylic acid ester (methyl acrylate, acrylic acid) Ethyl, propyl acrylate, butyl acrylate, etc.). Another vinyl-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

<Polymerization method of graft copolymer (F)>
Examples of the polymerization method of the graft copolymer (F) include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method).
For example, when the graft copolymer (F) is produced by emulsion polymerization, the vinyl monomer mixture (m2) is added to the aqueous dispersion of the rubber-like 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 radical polymerization initiators include peroxides, azo-based initiators, redox-based initiators in which an oxidizing agent and a reducing agent are combined, and redox-based initiators from the point that the graft polymerization reaction can be easily controlled. A sulfoxylate-based initiator in which ferrous sulfate-ethylenediaminetetraacetic acid disodium salt-longalite-hydroperoxide is combined is particularly preferable.

Preferred examples of emulsifiers include sodium or potassium salts of fatty acids (oleic acid, stearic acid, myristic acid, stearic acid, palmitic acid, etc.), sodium lauryl sulfate, sodium N-lauroyl sarcosine, dipotassium alkenyl succinate (octadede And dialkyl potassium succinate, dipotassium heptadecenyl succinate, dipotassium hexadecenyl succinate), sodium alkyldiphenyl ether disulfonate, and the like. An emulsifier may be used individually by 1 type and may be used in combination of 2 or more type.
In addition, you may use the emulsifier used in the case of manufacture of a rubber-like polymer (E) as it is. That is, the emulsifier contained in the aqueous dispersion of the rubber-like polymer (E) is used as it is, and it is not necessary to add an emulsifier at the time of graft polymerization, and an emulsifier is added at the time of graft polymerization as necessary. Also good.

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

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

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

[Methacrylate resin (G)]
The methacrylic ester resin (G) is obtained by polymerizing the vinyl monomer mixture (m3).
A methacrylic ester resin (G) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Vinyl monomer mixture (m3)>
The vinyl monomer mixture (m3) contains at least a methacrylic acid ester as an essential component, and is a maleimide compound, an aromatic vinyl compound, an acrylic acid ester, and other vinyl monomers copolymerizable with the methacrylic acid 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 scratch resistance and color developability of the molded product.
If the content of the methacrylic acid ester is 50 to 94% by mass, the content of the maleimide compound is 5 to 49% by mass, and the content of the aromatic vinyl compound is 1 to 45% by mass, the resistance of the molded product Scratch resistance, color development, impact resistance, and heat resistance are even better.

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

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

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

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

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

The method for polymerizing the methacrylic acid ester resin (G) is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, etc.).
As a method for producing a methacrylate ester resin (G) by emulsion polymerization, for example, a vinyl monomer mixture (m3), an emulsifier, a polymerization initiator, and a chain transfer agent are charged in a reactor and polymerized by heating. And the method of collect | recovering methacrylic ester resin (G) by the precipitation method from the aqueous dispersion containing methacrylic ester resin (G) is mentioned.
Examples of the emulsifier include usual emulsion polymerization emulsifiers (potassium rosinate, sodium alkylbenzenesulfonate, etc.).
Examples of the polymerization initiator include organic and inorganic peroxide initiators.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.
As the precipitation method, a method similar to that used when recovering the graft copolymer (D) from the aqueous dispersion can be employed.

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

[Styrene copolymer (H)]
The styrene copolymer (H) is obtained by polymerizing a vinyl monomer mixture (m4) containing an aromatic vinyl compound and a vinyl cyanide compound.
The polymerization method of 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, etc.). From the viewpoint of heat resistance of the molded product, suspension polymerization method and bulk polymerization method are available. 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-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Among these, styrene and α-methylstyrene are preferable from the viewpoint of the fluidity of the thermoplastic resin composition, the color developability of the molded product, and the impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 15 to 95% by mass in 100% by mass of the vinyl monomer 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. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 5 to 85% by mass in 100% by mass of the vinyl monomer 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 monomer mixture (m4) may contain a methacrylic acid ester and a maleimide compound as necessary.
Examples of the methacrylic acid ester and the maleimide compound include those exemplified in the vinyl monomer mixture (m3).

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

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

<Content of each component>
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). Among these, it is 15-85 mass%, and 30-70 mass% is preferable.
The ratio of the rubbery polymer (E) is 85 to 15% by mass in the total (100% by mass) of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E), and 30 to 30%. 70 mass% is preferable.
When the ratio of the ethylene / α-olefin copolymer (A) and the ratio of the rubbery polymer (E) are within the above ranges, impact resistance and cold impact resistance can be expressed with a small rubber content. Furthermore, it is excellent in scratch resistance, color development, and squeak noise suppression effect.

  The total content (rubber content) of the ethylene / α-olefin copolymer (A) and the rubbery polymer (E) is preferably 5 to 30% by mass in 100% by mass of the thermoplastic resin composition. 25 mass% is more preferable. 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 squeak noise suppressing effect are further improved.

  The total content of the graft copolymer (D) and the graft copolymer (F) in the thermoplastic resin composition is such that the graft copolymer (D), the graft copolymer (F), the methacrylate ester resin ( 5-40 mass% is preferable among the total 100 mass% of G) and a styrene-type copolymer (H), and 10-30 mass% is more preferable. If the total content of the graft copolymer (D) and the graft copolymer (F) is within the above range, the fluidity of the thermoplastic resin composition, the scratch resistance of the molded article, the impact resistance, and the cold impact resistance. Excellent balance of physical properties such as heat resistance, color development, squeak noise suppression effect, and heat resistance.

  The content of the methacrylic ester resin (G) in the thermoplastic resin composition is such that the graft copolymer (D), the graft copolymer (F), the methacrylic ester resin (G) and the styrene copolymer (H ) Is preferably 95 to 60% by mass, more preferably 90 to 70% by mass. If the content of the methacrylic ester resin (G) is within the above range, the flowability of the thermoplastic resin composition, scratch resistance of the molded product, impact resistance, cold impact resistance, color development, squeak noise suppression effect, Excellent balance of physical properties such as heat resistance.

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

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition is obtained by mixing the graft copolymer (D), the graft copolymer (F), the methacrylate ester resin (G), and, if necessary, the styrene copolymer (H). can get.

<Effect>
In the thermoplastic resin composition of the present invention described above, the presence of the ethylene / α-olefin copolymer (A) having a mass average molecular weight (Mw) and a molecular weight distribution (Mw / Mn) within specific ranges. The graft copolymer (D) obtained by polymerizing the vinyl monomer mixture (m1) below; and the vinyl monomer mixture (m2) polymerized in the presence of the rubber-like polymer (E) A graft copolymer (F) obtained in this manner; a methacrylate ester resin (G); an ethylene / α-olefin copolymer (A) and a rubbery polymer (E) in a thermoplastic resin composition Is a specific average particle size; since the ethylene / α-olefin copolymer (A) and the rubber-like polymer (E) in the thermoplastic resin composition are in a specific ratio, the fluidity is good. Yes, scratch resistance, color development, impact resistance, cold impact resistance, creaking It is possible to obtain a molded article having excellent noise suppression effect. Moreover, 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.
Examples of the molding method include injection molding, press molding, extrusion molding, vacuum molding, and blow molding.
Applications of molded products include vehicle interior / exterior parts, office equipment, home appliances, building materials, and the like.

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

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

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

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

<Measurement method of average particle diameter>
A microtrack (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.) was used. The average particle size (MV) measured using pure water as a measurement solvent was defined as the average particle size.
The ethylene / α-olefin copolymer (A) dispersed in the olefin resin aqueous dispersion (B), the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion, The average particle diameter of the rubber-like polymer (E) dispersed in the aqueous dispersion is 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 of C) and rubber-like polymer (E) was the same.

<Measurement method of gel content>
Coagulated powder sample [X1] 0.5 g obtained by coagulating an aqueous or solvent dispersion of the crosslinked ethylene / α-olefin copolymer (C) with dilute sulfuric acid, washing with water and drying, is 200 mL, 110 ° C. toluene. It was immersed in 5 hours, then filtered through a 200 mesh wire net, the residue was dried, the mass of the dried product [X2] was measured, and from the following formula (1), a crosslinked ethylene / α-olefin copolymer The gel content of (C) was determined.
Gel content rate (%) = dry substance amount [X2] (g) / coagulated powder sample mass [X1] (g) × 100 (1)

<Measurement method of graft ratio>
1 g of the graft copolymer (D) was added to 80 mL of acetone and heated to reflux at 65 to 70 ° C. for 3 hours to obtain a suspended acetone solution. The suspended acetone solution is centrifuged at 14,000 rpm for 30 minutes in a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.) to separate the precipitation component (acetone insoluble component) and the acetone solution (acetone soluble component). I took it. And the precipitation component (acetone insoluble component) was dried, the mass (Y (g)) was measured, and the graft ratio was computed from following formula (2). In 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 to determine Y. The rubber fraction is the solid content of the graft copolymer (D) of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C).
Graft rate (%) = {(Y-X × rubber fraction) / X × rubber fraction} × 100 (2)

<Melt-kneading 1>
Graft copolymer (D), graft copolymer (F), and methacrylic ester resin (G) are mixed, and the cylinder temperature is measured with a twin screw extruder ("PCM30" manufactured by Ikegai Co., Ltd.) with a screw diameter of 30 mm. Melt kneading was performed at 200 to 260 ° C. and 93.325 kPa vacuum to obtain a thermoplastic resin composition (1). Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

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

<Measurement of melt volume rate (MVR)>
With respect to the thermoplastic resin composition (2), MVR was measured in accordance with ISO 1133 standard. MVR serves as an index 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 are subjected to conditions of cylinder temperature 200 to 270 ° C. and mold temperature 60 ° C. with an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). Thus, 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 Charpy impact test and a molded product for measuring a deflection temperature under load (molded product (Ma1)).

<Injection molding 2>
The pellets of the thermoplastic resin composition (2) obtained by melt-kneading are subjected to conditions of cylinder temperature 200 to 270 ° C. and mold temperature 60 ° C. by an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). Thus, a molded product having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm was molded and used as a molded product for evaluating color development and a molded product for evaluating scratch resistance (molded product (Ma2)).

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

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

<Evaluation of cold shock resistance: falling ball impact test>
About the molded article (Ma2) temperature-controlled at -40 degreeC, the falling ball impact strength was measured according to JISK7211. A steel ball having a weight of 230 g was dropped from a height of 40 cm, and the presence or absence of cracks or cracks was confirmed. The test was performed on 10 sheets. As a result, 5 or more cracks or cracks occurred, x 3 to 4 cracks or cracks occurred, 1 or 2 cracks or cracks occurred. Were evaluated as ○, and those with no cracks or cracks were evaluated as ◎.

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

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

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

(Determination of scratch resistance)
A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded product (Mb) was calculated from the following formula (3). As the absolute value of ΔL ^* (mb−ma) is larger, the scratches are more conspicuous.
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)
When the absolute value of ΔL ^* (mb−ma) is 3.0 or less, the scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 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 the design of the molded product is impaired.

<Evaluation of scratch resistance>
As shown in FIG. 1, a rod-like jig 10 having a tip portion 11 formed in a hemispherical shape was prepared, and the tip portion 11 was covered with a laminated sheet 12 in which eight sheets of gauze were stacked. The tip portion 11 covered with the laminated sheet 12 is brought into contact with the surface of the molded product (Ma2) 13 so that the rod-shaped jig 10 is at a right angle, and the tip portion 11 is brought into contact with the surface of the molded product (Ma2) 13. Were slid in the horizontal direction (arrow direction in the figure) and reciprocated 100 times. At that time, the applied load was 1 kg. After reciprocating 100 times, the lightness L ^* of the surface of the scratched molded article (Mc) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mc)”.

(Determination of scratch resistance)
A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded article (Mc) was calculated from the following formula (4). As the absolute value of ΔL ^* (mc−ma) is larger, scratches are more conspicuous.
ΔL ^* (mc−ma) = L ^* (mc) −L ^* (ma) (4)
When the absolute value of ΔL ^* (mc−ma) is 3.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc-ma) is more than 3.0 to 7.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

(Evaluation of lubricity: before degreasing)
In the molded product (Ma3), when the test piece 21 having the rib structure 21a shown in FIG. 2 and the test piece 22 having a flat portion are used and a reciprocating motion is performed while applying a load of 500 g or 1 kg, a squeak noise is generated. Whether or not was evaluated according to the following criteria. Δ or more was considered to have lubricity.
(Double-circle): A squeak noise does not generate | occur | produce in any of load 500g and 1kg.
○: A small squeak noise is generated when the load is 1 kg, but not when the load is 500 g.
(Triangle | delta): A small squeak noise generate | occur | produces in any of the load 500g and the load 1kg.
X: A squeak noise is generated at both a load of 500 g and a load of 1 kg.

(Evaluation of lubricity: after degreasing)
In the molded article (Ma3), the test piece 21 having the rib structure 21a shown in FIG. 2 and the test piece 22 having a flat portion are annealed at 60 ° C. for 10 days, and then the surfaces of the test piece 21 and the test piece 22 are isopropyl alcohol. The bleed component was removed by degreasing with. Generation | occurrence | production of the squeak noise after degreasing was investigated similarly to the lubricity evaluation method before degreasing, and the following reference | standard evaluated. △ or more is regarded as having a permanent lubricity.
(Double-circle): A squeak noise does not generate | occur | produce in any of load 500g and 1kg.
○: A small squeak noise is generated when the load is 1 kg, but not when the load is 500 g.
(Triangle | delta): A small squeak noise generate | occur | produces in any of the load 500g and the load 1kg.
X: A squeak noise is generated at both a load of 500 g and a load of 1 kg.

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

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1))
After fully substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ prepared to 8.0 mmol / L was added. ₅ ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was further added to 5 L / h. Hexane was continuously fed in an amount of 5 L / h. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene was supplied in an amount of 2000 L / h, propylene was supplied in an amount of 1000 L / h, hydrogen was supplied in an amount of 90 L / h, and a polymerization reaction was performed at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (A-1). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1). Table 1 shows the properties of the ethylene / propylene copolymer (A-1).

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

(Preparation of ethylene / propylene copolymer (A-6))
After sufficiently substituting a 20 L stainless steel tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and 110 L of propylene (standard state) and 800 mL of hydrogen were added. After heating to 40 ° C., it was pressurized with ethylene so that the total pressure was 0.6 MPa [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. Triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance is 0.16 mM in terms of boron, and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium chloride is 0. Polymerization was initiated by injecting 30 mL of a toluene solution containing 0004 mM with nitrogen. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gauge pressure]. Five minutes after the start of polymerization, 50 mL of methanol was inserted to stop the polymerization, and the pressure was released to atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-6). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-6). Table 2 shows the polymer 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) were mixed, and a twin screw extruder with a vacuum diameter of 30 mm (manufactured by Ikegai Co., Ltd. "PCM30") was melt-kneaded at 200 ° C and 93.325 kPa vacuum 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) is obtained in the same manner as the ethylene / propylene copolymer (A-3) except that VCl ₄ is used instead of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst. It was. Table 2 shows the polymer properties of the ethylene / propylene copolymer (A-8).

<Olefin resin aqueous dispersion component (B)>
(Preparation of aqueous dispersion of olefin resin (B-1))
100 parts of ethylene / propylene copolymer (A-1) and maleic anhydride-modified polyethylene (manufactured by Mitsui Chemicals, "Mitsui High Wax 2203A") as the acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 30 mg / g) 25 parts and 10 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture is supplied at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40), and water is supplied from a supply port provided in a vent portion of the twin screw extruder. While continuously supplying an aqueous solution obtained by mixing 1.5 parts of potassium oxide and 5.0 parts of ion exchange 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 the twin screw extruder and cooled to 90 ° C. Then, the solid discharged from the tip of the twin screw extruder is poured into warm water at 80 ° C., continuously dispersed, diluted to a solid content concentration of about 40% by mass, and an aqueous olefin resin dispersion (B -1) was obtained. Table 3 shows the average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in the aqueous olefin resin dispersion (B-1).

(Preparation of aqueous olefin resin dispersions (B-2) to (B-8))
As shown in Table 3, the olefin resin was the same as the olefin resin aqueous dispersion (B-1) except that (A-1) was changed to (A-2) to (A-8) as the A component. 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 olefin resin aqueous 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 the same as the olefin resin aqueous dispersion (B-3) except that the number of added parts of potassium oleate was changed. Got.
Table 4 shows the average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in each of the olefin resin aqueous dispersions (B-9) to (B-16).

<Crosslinked ethylene / α-olefin copolymer (C)>
(Preparation of crosslinked ethylene / α-olefin copolymer (C-1))
Ion exchange water was added to the olefin resin aqueous dispersion (B-1) (100 parts as a solid content) so that the solid concentration was 35%, and 0.5 parts of t-butylcumyl peroxide as an organic peroxide, As a polyfunctional compound, 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (C-1). Table 5 shows the gel content and average particle diameter of the crosslinked ethylene / α-olefin copolymer (C-1).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2) to (C-20))
As shown in Tables 5 to 7, the same as the crosslinked ethylene / α-olefin copolymer (C-1) except that the type of the aqueous olefin resin dispersion (B) and the addition amount of t-butylcumyl peroxide were changed. Thus, crosslinked ethylene / α-olefin copolymers (C-2) to (C-20) were obtained. Tables 5, 6 and 7 show the gel content and average particle size of the crosslinked ethylene / α-olefin copolymers (C-2) to (C-20).

(Preparation of crosslinked ethylene / α-olefin copolymer (C-21))
With respect to 100 parts of the ethylene / α-olefin copolymer (A-3), 0.5 part of α, α′-di (t-butylperoxy) diisopropylbenzene and 1.0 part of divinylbenzene as an organic peroxide, Were mixed and melt kneaded at 220 ° C. and 93.325 kPa vacuum using a twin screw extruder with a screw diameter of 30 mm and equipped with a vacuum vent (“Ikekai Co., Ltd.,“ PCM-30 ”). After melt-kneading, finely pulverized to obtain a crosslinked ethylene / α-olefin copolymer (C-21). Table 7 shows the gel content and average particle size of the crosslinked ethylene / α-olefin copolymer (C-21).

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1))
In a stainless steel polymerization tank equipped with a stirrer, the crosslinked ethylene / α-olefin copolymer (C-1) (70 parts as a solid content of the ethylene / propylene copolymer (A-1)) is placed, and the crosslinked ethylene / α-olefin is added. Ion exchange water is added to the copolymer (C-1) so that the solid content concentration is 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose are charged. The temperature was 80 ° C. Styrene (23.4 parts), acrylonitrile (6.6 parts) and cumene hydroperoxide (0.6 parts) were continuously added for 150 minutes, the polymerization temperature was kept at 80 ° C., and emulsion polymerization was carried out. Graft copolymer having an average particle size of 0.12 μm An aqueous dispersion containing the coalescence (D-1) was obtained. An antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1), solids are precipitated with sulfuric acid, and after washing, dehydration, and drying steps, the powdered graft copolymer ( D-1) was obtained. When the graft ratio of the graft copolymer (D-1) was measured, it was 30%. The results of the graft rate are also shown in Table 8. Moreover, it was 0.12 micrometer when the average particle diameter of the ethylene-alpha-olefin copolymer (A) in a thermoplastic resin composition was confirmed with the electron microscope.

(Preparation of graft copolymers (D-2) to (D-20))
As shown in Tables 8 to 11, the graft copolymer (D-2) was the same as the graft copolymer (D-1) except that the type of the crosslinked ethylene / α-olefin copolymer (C) was changed. ) To (D-20) were obtained. The graft ratios of the graft copolymers (D-2) to (D-20) are shown in Table 8, Table 9, Table 10, and Table 11.

(Preparation of graft copolymer (D-21))
In a stainless steel polymerization tank equipped with a stirrer, 70 parts of a crosslinked ethylene / α-olefin copolymer (C-21) and 300 parts of toluene were charged, and the contents were stirred and stirred uniformly at 70 ° C. for 1 hour. After sufficiently purging with nitrogen, 23.4 parts of styrene, 6.6 parts of acrylonitrile, 0.24 parts of t-dodecyl mercaptan and 0.22 parts of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was 110 ° C. The mixture was heated up to react for 4 hours. The internal temperature was raised to 120 ° C. and reacted for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum using a twin-screw extruder with a screw diameter of 30 mm and a vacuum vent (manufactured by Ikegai Co., Ltd., “PCM30”), pelletized, and graft copolymer (D -21) was obtained. The graft ratio of the graft copolymer (D-21) was measured and found to be 26%. The results are shown in Table 11.

(Preparation of graft copolymer (D-22))
As shown in Table 11, the grafted ethylene / α-olefin copolymer (C) was changed to an aqueous olefin resin dispersion (B-3), except that the graft copolymer (D-1) was used. A copolymer (D-22) was obtained. Table 11 shows the graft ratio of the graft copolymer (D-22).

<Rubber polymer (E)>
(Preparation of rubbery polymer (E-1))
100 parts of ethylene / propylene copolymer (A-3) and maleic anhydride-modified polyethylene (Mitsui Chemicals, "Mitsui High Wax 2203A", acid average molecular weight: 2,700, acid value: 30 mg / g) 25 parts and 7 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture is supplied at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40), and water is supplied from a supply port provided in a vent portion of the twin screw extruder. While continuously supplying an aqueous solution obtained by mixing 1.5 parts of potassium oxide and 5.0 parts of ion exchange 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 the twin screw extruder and cooled to 90 ° C. And the solid discharged from the front-end | tip of a twin screw extruder was thrown into 80 degreeC warm water, was continuously disperse | distributed, and it diluted to the solid content density | concentration vicinity of 40 mass%, and obtained the aqueous dispersion. Ion exchange water was added to the obtained aqueous dispersion (100 parts as a solid content) so that the solid content was 35%, 0.5 parts of t-butylcumyl peroxide as an organic peroxide, a polyfunctional compound 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to obtain a rubbery polymer (E-1) having an average particle size of 0.15 μm and a gel content of 50%.

(Preparation of rubber-like polymers (E-2) to (E-7))
As shown in Table 12, rubbery polymers (E-2) to (E-7) were obtained in the same manner as the rubbery polymer (E-1) except that the number of added emulsifiers was changed. Obtained. Table 12 shows the average particle diameters of the obtained rubber-like polymers (E-2) to (E-7).

(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 part of sodium organic sulfonate, 0.2 part of tert-decyl mercaptan, 0 potassium persulfate .3 parts and 0.14 parts of potassium hydroxide were charged. Next, polymerization was started by raising the temperature to 60 ° C. while stirring in a nitrogen atmosphere, and 5 parts of deionized water in which 0.1 part of potassium persulfate was dissolved when the polymerization rate was 65% was added to the pressure vessel. . Thereafter, the polymerization temperature was raised to 70 ° C., and the polymerization was completed with a reaction time of 13 hours and a polymerization conversion rate of 95% to obtain a latex having an average particle size of 80 nm and a solid content of 52.0%. To this latex, 2.5 parts of a 20% aqueous acetic acid solution as acetic acid was added and subjected to enlargement operation to obtain a rubber-like polymer (E-8) having an average particle size of 0.4 μm.

(Preparation of rubber-like polymer (E-9))
0.27 part of dipotassium alkenyl succinate, 175 parts of ion-exchanged water, 50 parts of n-butyl acrylate, 0.16 part of allyl methacrylate, 0.08 part of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of ethylenediaminetetraacetic acid disodium salt, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Furthermore, this state was maintained for 1 hour to obtain a rubbery polymer (E-9) having an average particle size of 0.40 μm.

(Preparation of rubbery polymer (E-10))
100 parts of an ethylene / propylene / non-conjugated diene copolymer (Mitsui Chemicals, "Tafmer TP3180") and maleic anhydride-modified polyethylene (Mitsui Chemicals, "Mitsui High Wax 2203A") as the acid-modified olefin polymer, mass average 25 parts of molecular weight: 2,700, acid value: 30 mg / g) and 3 parts of potassium oleate as an anionic emulsifier were mixed.
This mixture is supplied at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40), and water is supplied from a supply port provided in a vent portion of the twin screw extruder. While continuously supplying an aqueous solution obtained by mixing 0.5 part of potassium oxide and 2.4 parts of ion-exchanged water, it was heated to 220 ° C., melt-kneaded and extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the twin screw extruder and cooled to 90 ° C. And the solid discharged from the front-end | tip of a twin screw extruder was thrown into 80 degreeC warm water, was continuously disperse | distributed, and it diluted to the solid content density | concentration vicinity of 40 mass%, and obtained the aqueous dispersion. Ion exchange water was added to the obtained aqueous dispersion (100 parts as a solid content) so that the solid content was 35%, 0.5 parts of t-butylcumyl peroxide as an organic peroxide, a polyfunctional compound 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to obtain a rubber-like polymer (E-10) having an average particle size of 0.40 μm and a gel content of 50%.

<Graft copolymer (F)>
(Preparation of graft copolymer (F-1))
A rubber-like polymer (E-1) (50 parts as a solid content) is placed in a stainless polymerization tank equipped with a stirrer, ion-exchanged water is added so that the solid content concentration is 30%, and ferrous sulfate 0.006 is added. Part, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were charged, and the temperature was 80 ° C. 39 parts of styrene, 11 parts of acrylonitrile and 0.6 part of cumene hydroperoxide were continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. After the polymerization, an antioxidant is added to the aqueous dispersion containing the graft copolymer (F-1), solids are precipitated with sulfuric acid, and after washing, dehydration and drying, A polymer (F-1) was obtained.

(Adjustment of graft copolymers (F-2) to (F-7) and (F-10))
Except for changing the rubbery polymer (E-1) to rubbery polymers (E-2) to (E-7) and (E-10), the same procedure as for the graft copolymer (E-1) was performed. Graft copolymers (F-2) to (F-7) and (F-10) were obtained (Table 13).

(Preparation of graft copolymer (F-8))
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer, a rubber-like polymer (E-8) (50 parts as a solid content) is placed, and 0.3 parts of disproportionated potassium rosinate (Solid content), 0.01 parts of ferrous sulfate heptahydrate, 0.2 parts of sodium pyrophosphate, 0.5 parts of crystalline glucose, and the temperature in the reactor is increased to 60 ° C. while stirring. It was. 39 parts of styrene, 11 parts of acrylonitrile, 0.4 part of terrestrial decyl mercaptan and 0.35 part of cumene hydroperoxide were mixed and continuously dropped and supplied over 2 hours to perform graft polymerization. Meanwhile, the jacket temperature was controlled so as to keep the reactor internal temperature at 60 ° C. After completion of the dropwise addition, the temperature was raised to 70 ° C. and maintained for 1 hour to complete the graft polymerization reaction. After cooling, an antioxidant (dilauryl thiodipropionate) was added to obtain a latex of graft copolymer (F-8). The obtained latex of the graft copolymer (F-8) was put into a 2.5% aqueous sulfuric acid solution (80 ° C.) of 1 volume with stirring, and further held at 90 ° C. for 5 minutes to coagulate. Thus, a slurry of the graft copolymer (F-8) was obtained. The slurry was washed twice with water and dehydrated, and then left to stand at 70 ° C. overnight and dried to obtain a milky white powder graft copolymer (F-8).

(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 alkenyl succinate, and ions with respect to 50 parts (as a solid content) of the rubber-like polymer (E-9) An aqueous solution consisting of 10 parts of exchange water was added, and then a mixed liquid consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene, and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour for graft polymerization. . Five minutes after the completion of dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 11 A mixture consisting of 39 parts of styrene, 39 parts of styrene, 0.19 part of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropping, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of an antioxidant (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage W500) and alkenyl 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).

<Methacrylate ester resin (G)>
(Preparation of methacrylate resin (G-1))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan , 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered methacrylate resin (G-1). Table 14 shows the composition of the monomers.

(Preparation of methacrylate ester resin (G-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered methacrylate resin (G-2). Table 14 shows the composition of the monomers.

(Preparation of methacrylate resin (G-3) and (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.

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

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

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

<Other resins>
Polycarbonate: Novarex 7025R manufactured by Mitsubishi Engineering Plastics

[Example 1]
10 parts of graft copolymer (D-1), 14 parts of graft copolymer (F-1), 76 parts of methacrylic ester resin (G-1) are mixed and a twin screw extruder with a vacuum vent of 30 mm in screw diameter A thermoplastic resin composition was prepared by melt kneading at 240 ° C. and 93.325 kPa vacuum (“Ikegai Co., Ltd.,“ PCM30 ”). Table 16 shows the MVR of the thermoplastic resin composition.
The thermoplastic resin composition was pelletized and various molded articles were molded, and the impact resistance, cold impact resistance, color development, scratch resistance, scratch resistance, heat resistance and lubricity (squeak noise) were evaluated. The results are shown in Table 16.

[Examples 2 to 50]
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 22, and MVR was measured.
In addition, the thermoplastic resin composition of each example is pelletized, and various molded products are formed. ) Was evaluated. The results are shown in Tables 16-22.

[Comparative Examples 1-14]
A thermoplastic resin composition was prepared and MVR was measured in the same manner as in Example 1 except that the formulation was changed to the formulation shown in Table 23 and Table 24.
In addition, the thermoplastic resin composition of each comparative example is pelletized, and various molded products are formed. ) Was evaluated. The results are shown in Table 23 and Table 24.

The thermoplastic resin compositions of Examples 1 to 50 were excellent in fluidity. In addition, the molded articles obtained in Examples 1 to 50 were excellent in lubricity (squeak noise), impact resistance, cold impact resistance, heat resistance, color development, scratch resistance, and scratch resistance.
On the other hand, the molded products of Comparative Examples 1 to 14 did not have lubricity (squeak noise) characteristics, and the molded products had low impact resistance, cold impact resistance, and scratch resistance.

  The molded product obtained by molding the thermoplastic resin composition of the present invention is excellent in lubricity (squeaking noise), impact resistance, cold impact resistance, color development, scratch resistance and scratch resistance, It is useful as office equipment, home appliances, building materials, etc.

Claims (4)

In the presence of the 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, A graft copolymer (D) obtained by polymerizing the monomer mixture (m1);
A graft copolymer (F) obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the crosslinked rubber-like polymer (E);
A thermoplastic resin composition comprising a methacrylate monomer resin (G) obtained by polymerizing a vinyl monomer mixture (m3) containing a methacrylate ester,
The following average particle diameter of the ethylene · alpha-olefin copolymer (A) is a 0.05Myuemu～0.18Myuemu, the following average particle diameter of the rubbery polymer (E) is 0.20Myuemu～0. 60 μm,
The ratio 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 85% by mass. Yes, the thermoplastic resin composition whose rubber-like polymer (E) ratio is 85-15 mass%.
(Average particle size)
The average particle diameter of the ethylene / α-olefin copolymer (A) and the rubber-like polymer (E) is a volume average particle diameter measured using Nikkiso Co., Ltd. Microtrac and the measurement solvent as pure water.   The rubbery polymer (E) is at least one rubbery polymer selected from the group consisting of a diene rubber polymer, an acrylic rubber polymer, and an olefin rubber polymer. Thermoplastic resin composition.   The thermoplastic resin composition according to claim 1 or 2, wherein the ethylene / α-olefin copolymer (A) is a crosslinked ethylene / α-olefin copolymer (C).   The molded article which shape | molded the thermoplastic resin composition of any one of Claims 1-3.

Images