JP2018028046A - Thermoplastic resin composition, method for producing the same and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that makes it possible to obtain a molding excelling in impact resistance, color development, flaw resistance, wiping flaw resistance, the persistence of the wiping flaw resistance, and squeak noise inhibitory effect, and a method for producing the same; and a molding excelling in impact resistance, color development, flaw resistance, wiping flaw resistance, the persistence of the wiping flaw resistance, and squeak noise inhibitory effect.SOLUTION: A thermoplastic resin composition contains: a graft copolymer (D) obtained by polymerization of a vinyl monomer mixture (m1) containing at least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylate in the presence of an ethylene-α-olefin copolymer; a methacrylate resin (G); and an antistatic agent (H).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article thereof.

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

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

  However, in the molded product made of the thermoplastic resin composition (1), the molded product has a high surface specific resistance value and is easily charged. For this reason, when the molded product is cleaned, there is a problem that deposits such as dust become an abrasive and the surface of the molded product is easily damaged.

As a thermoplastic resin composition that can obtain a molded product that has improved impact resistance and suppresses adhesion of dust and the like while maintaining the characteristics derived from a hard resin, for example, the following are known. .
(2) A thermoplastic resin composition in which an ASA resin and an antistatic agent are added to a methacrylic ester resin which is a hard resin (Patent Document 2).
(3) A thermoplastic resin composition in which an ABS resin, an antistatic agent, and a slidable filler are added to a methacrylic ester resin that is a hard resin (Patent Document 3).

However, in the molded article made of the thermoplastic resin composition of (2), although the adhesion of dust can be reduced by adding an antistatic agent, the scratch resistance is not sufficient, and the molded article is damaged when washed. There was a problem.
In the molded product made of the thermoplastic resin composition of (3), adhesion of dust is reduced by adding an antistatic agent. Further, the slidable filler added bleeds out on the surface of the molded product, thereby improving the slidability of the molded product and making it difficult to generate scratches. However, there is a problem that the slidable filler that has bleed out is washed away when the molded product is washed, and scratches during washing cannot be suppressed.

  Since the methacrylic acid ester resin is an amorphous (non-crystalline) resin, the friction coefficient (dynamic friction coefficient, fluctuation width of the dynamic friction coefficient) of the molded product is larger than that of the crystalline resins such as polyethylene, polypropylene, and polyacetal. For this reason, in molded products containing methacrylic ester resin, stick-slip phenomenon occurs in the mating parts of molded products due to vibrations of equipment, vibrations when starting and running automobiles, contact with parts, etc. There is a problem that occurs.

As a thermoplastic resin composition capable of obtaining a molded product having a small friction coefficient (dynamic friction coefficient, fluctuation width of the dynamic friction coefficient), for example, the following are proposed.
(4) A thermoplastic resin composition obtained by adding polyorganosiloxane as a lubricant to a methacrylic ester resin (Patent Document 4).

  In the molded product comprising the thermoplastic resin composition of (4), 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 and increasing the coefficient of friction. Make it smaller. However, the bleed-out lubricant deteriorates the surface appearance of the molded product, and there is a problem that the lubricity decreases with time due to the gradual loss of the lubricated lubricant. Further, there is a problem that dust or the like is likely to adhere to the molded product and is easily damaged when the molded product is washed.

JP 2005-132970 A JP 2004-346126 A JP 2007-051233 A Special table 2013-537252 gazette

  The present invention relates to a thermoplastic resin composition capable of obtaining a molded article excellent in impact resistance, color developability, scratch resistance, antistatic property, wiping resistance, wiping resistance, squeak noise suppression effect, and production thereof. The present invention provides a molded article excellent in the method, impact resistance, color development, scratch resistance, antistatic property, wiping resistance, wiping resistance, and squeak noise suppression effect.

The present invention includes the following aspects.
[1] Vinyl containing at least one vinyl monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters in the presence of an ethylene / α-olefin copolymer. A graft copolymer (D) obtained by polymerizing the monomer mixture (m1),
A methacrylate ester resin (G) obtained by polymerizing a vinyl-based monomer mixture (m3) containing a methacrylate ester;
A thermoplastic resin composition comprising an antistatic agent (H).
[2] The thermoplastic resin composition according to [1], wherein the ethylene / α-olefin copolymer is a crosslinked ethylene / α-olefin copolymer (C).
[3] Poly (meth) acrylic acid ester containing polyorganosiloxane (Ea), a unit derived from (meth) acrylic acid ester, a unit derived from a crosslinking agent and a unit derived from a graft crossing agent, or both At least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of a composite rubber-like polymer (E) comprising (Eb) The thermoplastic resin composition according to [1] or [2], further comprising a graft copolymer (F) obtained by polymerizing a vinyl monomer mixture (m2) containing.
[4] A molded article using the thermoplastic resin composition according to any one of [1] to [3].
[5] Vinyl containing at least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of an ethylene / α-olefin copolymer. A step of polymerizing the monomer mixture (m1) to obtain a graft copolymer (D);
A step of polymerizing a vinyl monomer mixture (m3) containing a methacrylate ester to obtain a methacrylate ester resin (G);
A step of mixing the graft copolymer (D), the methacrylic ester resin (G), and the antistatic agent (H) to obtain a thermoplastic resin composition; Method.
[6] The method for producing a thermoplastic resin composition according to [5], wherein the ethylene / α-olefin copolymer is a crosslinked ethylene / α-olefin copolymer (C).
[7] Poly (meth) acrylic acid ester containing polyorganosiloxane (Ea), 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, or both At least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of a composite rubber-like polymer (E) comprising (Eb) Further comprising a step of polymerizing a vinyl monomer mixture (m2) containing a graft copolymer (F),
In the step of obtaining the thermoplastic resin composition, the graft copolymer (D), the methacrylic ester resin (G), the antistatic agent (H), and the graft copolymer (F) are mixed. The method for producing the thermoplastic resin composition according to [5] or [6].

According to the thermoplastic resin composition of the present invention, a molded article having excellent impact resistance, color development, scratch resistance, antistatic properties, wiping resistance, wiping resistance, and squeak noise suppression effect can be obtained. .
According to the method for producing a thermoplastic resin composition of the present invention, a molded article excellent in impact resistance, color development, scratch resistance, antistatic property, wiping resistance, wiping resistance, and squeak noise suppression effect. Can be obtained.
The molded product of the present invention is excellent in impact resistance, color developability, scratch resistance, antistatic property, wiping resistance, durability of wiping resistance, and squeak noise suppression effect.

It is the schematic explaining the evaluation method of the abrasion resistance by car wash towel abrasion. It is the schematic explaining the evaluation method of a squeak noise suppression effect.

The following definitions of terms apply throughout this specification and the claims.
“(Meth) acrylic acid” means acrylic acid or methacrylic acid.
“(Meth) acrylic acid ester” means acrylic acid ester or methacrylic acid ester.
“Molded product” means a product formed by molding a thermoplastic resin composition.
“Scratch resistance” refers to scratch resistance (scratch resistance) and work gloves, car wash towels against scratches (scratches) that occur when scratching the surface of a molded product with a hard, pointed object such as a nail or pencil. 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 such as cloth.
“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 methacrylic ester resin (G), and an antistatic agent (H).
The thermoplastic resin composition of the present invention may contain a graft copolymer (F), other thermoplastic resins, and various additives as necessary within the range not impairing the effects of the present invention.

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

Specific examples of (α) include the following.
(Α1) A product obtained by polymerizing the vinyl monomer mixture (m1) in a solution containing the uncrosslinked ethylene / α-olefin copolymer (A).
(Α2) A product obtained by polymerizing a vinyl monomer mixture (m1) in an aqueous olefin resin dispersion (B) containing an uncrosslinked ethylene / α-olefin copolymer (A).

Specific examples of (β) include the following.
(Β1) A product obtained by polymerizing a vinyl monomer mixture (m1) in a solution containing a crosslinked ethylene / α-olefin copolymer (C).
(Β2) A product obtained by polymerizing the vinyl monomer mixture (m1) in an aqueous dispersion containing the crosslinked ethylene / α-olefin copolymer (C).

The graft copolymer (F) is the following (γ).
(Γ) obtained by polymerizing a vinyl monomer mixture (m2) in the presence of a composite rubber-like polymer (E) comprising a polyorganosiloxane (Ea) and a poly (meth) acrylate (Eb). Things.

The methacrylic ester resin (G) is the following (δ).
(Δ) A product obtained by polymerizing the vinyl monomer mixture (m3).
Hereinafter, each component ((A)-(H), (m1)-(m3) etc.) is demonstrated.

<Ethylene / α-olefin copolymer (A)>
The ethylene / α-olefin copolymer (A) includes 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. The ethylene / α-olefin copolymer (A) is uncrosslinked, that is, has no crosslinked structure.
The ethylene / α-olefin copolymer (A) may further contain a non-conjugated diene unit.

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

  Non-conjugated dienes include dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-cycloheptadiene, 1, 5-cyclooctadiene etc. are mentioned. Among these, dicyclopentadiene and / or 5-ethylidene-2-norbornene are preferable because the molded article obtained is further excellent in impact resistance and scratch resistance.

  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. 80 mass% is preferable and 50-75 mass% is more preferable. When the ethylene unit content is within the above range, the balance of the scratch resistance and impact resistance of the molded product is further improved.

  The total content of ethylene units and α-olefin units is preferably 90 to 100% by mass when the total of all the structural units constituting the ethylene / α-olefin copolymer (A) is 100% by mass. 95-99 mass% is more preferable. When the total content of ethylene units and α-olefin units is within the above range, the balance of scratch resistance and impact resistance of the molded product is further improved.

The mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (A) is preferably 4 × 10 ^{4 to} 35 × 10 ^{4, and} more preferably 17 × 10 ^{4 to} 32 × 10 ⁴ . If the mass average molecular weight (Mw) is within the above range, the scratch resistance, color developability, impact resistance, and squeak noise suppression effect of the molded product are further improved.

  The molecular weight distribution (Mw / number average molecular weight (Mn)) of the ethylene / α-olefin copolymer (A) is preferably from 1.0 to 5.0, more preferably from 1.9 to 4.0. When the molecular weight distribution (Mw / Mn) is within the above range, the scratch resistance, impact resistance, and squeak noise suppressing effect of the molded product are further improved.

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

  The method for producing the ethylene / α-olefin copolymer (A) is not limited. The ethylene / α-olefin copolymer (A) is usually obtained by copolymerizing ethylene and α-olefin or ethylene, α-olefin and non-conjugated diene using a metallocene catalyst or Ziegler-Natta catalyst. Manufactured.

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 Ziegler-Natta catalysts include catalysts obtained by combining halides of transition metals (titanium, vanadium, zirconium, hafnium, etc.) with organoaluminum compounds, organoboron compounds, and the like.

  Examples of the polymerization method include a method of copolymerizing ethylene and α-olefin or ethylene, α-olefin and non-conjugated diene in a solvent in the presence of a catalyst (metallocene catalyst or Ziegler-Natta 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. In the polymerization, a molecular weight regulator such as hydrogen may be used.

  By changing the reaction conditions such as supply amount of ethylene, α-olefin and non-conjugated diene, type and amount of molecular weight regulator, type and amount of catalyst, reaction temperature, pressure, etc., ethylene / α-olefin copolymer The ethylene unit content, mass average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of (A) can be adjusted.

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

  Examples of the aqueous medium include water, an organic solvent miscible with water (hereinafter, also referred to as “water-miscible organic solvent”), and a mixture thereof. Examples of water-miscible organic solvents include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; Alkyl ethers; and lactams such as N-methyl-2-pyrrolidone. As the aqueous medium, it is preferable to use only water or a mixture of water and a water-miscible organic solvent.

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

Examples of the acid-modified olefin polymer include those obtained by modifying an olefin polymer having a mass average molecular weight of 1,000 to 5,000 with a compound having a functional group.
Examples of the olefin polymer include polyethylene and polypropylene.
Examples of the compound having a functional group include unsaturated carboxylic acid compounds such as acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic acid monoamide.
The acid value of the acid-modified olefin polymer is preferably 20 to 40 mgKOH / g.
The content of the acid-modified olefin polymer in the aqueous olefin resin dispersion (B) is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (A). When the addition amount of the acid-modified olefin polymer is within the above range, the balance between scratch resistance and impact resistance of the molded product is further improved.

The preparation method of the olefin resin aqueous dispersion (B) is not limited. As the preparation method, for example, (b1) the ethylene / α-olefin copolymer (A) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.), and the mechanical shearing force is increased. (B2) The ethylene / α-olefin copolymer (A) is dissolved in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.), and then added to an aqueous medium. And then emulsifying and emulsifying the mixture, followed by sufficient stirring to distill off the hydrocarbon solvent. In preparing the aqueous olefin resin dispersion (B), an acid-modified olefin polymer, an emulsifier and the like may be added as other components.
In the method (b1), the temperature condition for melt kneading is preferably 150 to 250 ° C.

The method for adding the acid-modified olefin polymer is not limited. For example, in the method (b1), the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer are mixed and melt-kneaded, and in the method (b2), the ethylene / α-olefin is mixed. Examples thereof include a method of dissolving the copolymer (A) and the acid-modified olefin polymer in a hydrocarbon solvent.
The mixing method of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer is not particularly limited. Examples of the mixing method include a melt kneading method using a kneader, a Banbury mixer, a multi-screw extruder and the like. In this case, the step of mixing the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer may also serve as a step of melt-kneading the mixture.
The method for adding the emulsifier is not particularly limited. For example, the method similar to the addition method of an acid-modified olefin polymer is mentioned. Examples of the method (b1) or (b2) include a method of adding an emulsifier to an aqueous medium, and a method of dissolving the emulsifier in a hydrocarbon solvent in the method (b2).

The volume average particle diameter of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B) is 0.2 to 0.6 μm from the viewpoint of more excellent impact resistance and color developability of the molded product. Is preferable, and 0.3 to 0.5 μm is more preferable.
The volume average particle diameter is measured by the method described in Examples described later.
When the graft copolymer (D) is obtained using the aqueous olefin resin dispersion (B), the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B) is used. It has been confirmed by image analysis of an electron microscope that the volume average particle diameter of the same indicates the volume average particle diameter of the ethylene / α-olefin copolymer (A) in the thermoplastic resin composition as it is.

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

<Crosslinked ethylene / α-olefin copolymer (C)>
The crosslinked ethylene / α-olefin copolymer (C) is an ethylene / α-olefin copolymer having a crosslinked structure. Specifically, a crosslinked structure is formed in the ethylene / α-olefin copolymer (A). By having a crosslinked structure, the impact resistance of the molded product is further improved.

The gel content of the crosslinked ethylene / α-olefin copolymer (C) is preferably from 35 to 75 mass%, more preferably from 40 to 70 mass%, from the viewpoint of impact resistance of the molded product.
The gel content in the present invention means that the crosslinked ethylene / α-olefin copolymer (C) is swollen with toluene and dried with respect to the crosslinked ethylene / α-olefin copolymer (C) before swelling. This is the proportion of toluene insoluble matter. In detail, it calculates | requires by the method as described in an Example.

The crosslinked ethylene / α-olefin copolymer (C) is obtained by crosslinking the ethylene / α-olefin copolymer (A) or the aqueous olefin resin dispersion (B).
The crosslinking treatment of the ethylene / α-olefin copolymer (A) or the aqueous olefin resin dispersion (B) can be carried out by a known method. Examples of the crosslinking treatment method include (a) a method in which an organic peroxide and, if necessary, a polyfunctional compound are added to carry out a crosslinking treatment, and (b) a method in which a crosslinking treatment is performed with ionizing radiation. The method (a) is preferred from the viewpoint of impact resistance and color development 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.
For example, an organic peroxide and, if necessary, a polyfunctional compound are added to the ethylene / α-olefin copolymer (A), melt-kneaded, and pulverized to form a crosslinked ethylene / α-olefin copolymer. A powder of (C) is obtained. When an organic peroxide and, if necessary, a polyfunctional compound are added to the olefin resin aqueous dispersion (B) and subjected to crosslinking treatment, an aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C) is obtained. can get.
The 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.

As the organic peroxide, a dialkyl peroxide compound is particularly preferable because the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted.
Specific examples of the dialkyl peroxide compound include α, α′-bis (t-butylperoxy) 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.

  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. 0.1-5 mass parts is preferable with respect to mass parts.

When the ethylene / α-olefin copolymer (A) is crosslinked to obtain a crosslinked ethylene / α-olefin copolymer (C), an acid-modified olefin polymer is added to the ethylene / α-olefin copolymer (A). It may be added.
The acid-modified olefin polymer is the same as that mentioned in the description of the aqueous olefin resin dispersion (B). The amount of the acid-modified olefin polymer added is the same as the content of the acid-modified olefin polymer in the aqueous olefin resin dispersion (B), with respect to 100 parts by mass of the ethylene / α-olefin copolymer (A). 1-40 mass parts is preferable.
The method for adding the acid-modified olefin polymer is not limited. Crosslinking may be performed after mixing the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer, or the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer. You may mix, after each crosslinking process.
The mixing method of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer is not limited. Examples of the mixing method include a melt kneading method using a kneader, a Banbury mixer, a multi-screw extruder and the like.

  The volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) or the volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion is determined by the impact resistance of the molded product. In view of excellent color developability, 0.2 to 0.6 μm is preferable, and 0.3 to 0.5 μm is more preferable.

The crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the olefin resin aqueous dispersion (B) with an organic peroxide. The average particle diameter does not change with respect to the average particle diameter of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B).
When the graft copolymer (D) is obtained using an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (C), the crosslinked ethylene / α-olefin copolymer (C) It has been confirmed by image analysis of an electron microscope that the average particle size in the aqueous dispersion shows the average particle size of the crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition as it is.

<Vinyl single monomer mixture (m1)>
The vinyl monomer mixture (m1) contains at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester as a monomer.
The vinyl monomer mixture (m1) may further contain other vinyl monomers other than the aromatic vinyl compound, the vinyl cyanide compound, and the (meth) acrylic acid ester, if necessary.

  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 color developability and impact resistance of the molded product. 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 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.

  As (meth) acrylic acid ester, acrylic acid ester (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylic acid ester (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate) Etc.). Methyl methacrylate is preferable from the viewpoint of the color developability and impact resistance of the molded product. One (meth) acrylic acid ester may be used alone, or two or more may be used in combination.

  Examples of other vinyl monomers include maleimide compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like. Another vinyl-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the above, the vinyl monomer mixture (m1) preferably contains an aromatic vinyl compound and a vinyl cyanide compound.

  In the vinyl monomer mixture (m1), the content of the aromatic vinyl compound is preferably 60 to 85% by mass with respect to the total mass (100% by mass) of the vinyl monomer mixture (m1), 62 to 80 mass% is more preferable. When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  15-40 mass% is preferable with respect to the total mass (100 mass%) of a vinyl-type monomer mixture (m1), and, as for the content rate of a vinyl cyanide compound, 20-38 mass% is more preferable. 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.

<Graft copolymer (D)>
The graft copolymer (D) is obtained by polymerizing the vinyl monomer mixture (m1) in the presence of an ethylene / α-olefin copolymer. Examples of the graft copolymer (D) include the above (α1), (α2), (β1), and (β2).
In the graft copolymer (D), it is difficult to specify how the ethylene / α-olefin copolymer and the vinyl monomer mixture (m1) are polymerized. That is, there is a situation (impossible / unpractical situation) that the graft copolymer (D) cannot be directly specified by its structure or characteristics or is almost impractical. Therefore, it is more appropriate to define “obtained by polymerizing the vinyl monomer component (m1) in the presence of the ethylene / α-olefin copolymer”.

  The graft copolymer (D) is a vinyl monomer mixture (m1) 20-50% by mass (provided that the ethylene / α-olefin copolymer is added) in the presence of 50-80% by mass of the ethylene / α-olefin copolymer. The total of the polymer and the vinyl monomer mixture (m1) is preferably 100% by mass). When the content ratio of the ethylene / α-olefin copolymer is 50 to 80% by mass, the impact resistance of the molded product and the physical property balance of color developability 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 impact resistance and color developability of the molded product.
The graft ratio is measured by the method described in Examples described later.

The graft copolymer (D) is a vinyl-based copolymer in the presence of an ethylene / α-olefin copolymer (ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer (C)). It is obtained by polymerizing the monomer mixture (m1). For example, the above (α1), (α2), (β1), and (β2) are obtained by the following methods (α1 ′), (α2 ′), (β1 ′), and (β2 ′), respectively.
(Α1 ′) A method of polymerizing the vinyl monomer mixture (m1) in a solution containing the ethylene / α-olefin copolymer (A).
(Α2 ′) A method of polymerizing a vinyl monomer mixture (m1) in an aqueous olefin resin dispersion (B) containing an ethylene / α-olefin copolymer (A).
(Β1 ′) A method of polymerizing the vinyl monomer mixture (m1) in a solution containing the crosslinked ethylene / α-olefin copolymer (C).
(Β2 ′) A method of polymerizing the vinyl monomer mixture (m1) in an aqueous dispersion containing the crosslinked ethylene / α-olefin copolymer (C).

  Examples of the polymerization method of the vinyl monomer mixture (m1) 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 the emulsion polymerization method, for example, an aqueous dispersion of an ethylene / α-olefin copolymer obtained by mixing a vinyl monomer mixture (m1) with an organic peroxide. The method of adding continuously to a body (for example, aqueous dispersion of olefin resin aqueous dispersion (B) or aqueous dispersion of crosslinked ethylene / α-olefin copolymer (C)) can be mentioned.
The polymerization conditions for emulsion polymerization are not particularly limited, and examples include polymerization conditions at 50 to 90 ° C. for 1.5 to 3.5 hours.
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, and avoids deterioration of impact resistance of the molded product. A combination of a product and a ferrous sulfate-chelating agent-reducing agent is preferred.
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 amount of the emulsifier added 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.

Examples of the method for producing the graft copolymer (D) by the solution polymerization method include an ethylene / α-olefin copolymer (for example, an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer). The method of adding a polymerization initiator and a vinyl-type monomer mixture (m1) to the solution which melt | dissolved (C)) in the solvent is mentioned.
As the solvent, an inert polymerization solvent used in usual radical polymerization can be used. For example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, halogen such as dichloromethylene and carbon tetrachloride. And hydrocarbons.
As the polymerization initiator used in the solution polymerization, a general initiator can be used, and examples thereof include organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide. It is done.
The addition method of a polymerization initiator is not specifically limited, For example, the method of adding collectively or continuously is mentioned.

  A graft copolymer (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Polyorganosiloxane (Ea)>
Although there is no restriction | limiting in particular as polyorganosiloxane (Ea), The polyorganosiloxane which has a vinyl polymerizable functional group is preferable, and contains vinyl polymerizable functional group with respect to the total number of moles of all the structural units which comprise polyorganosiloxane. Silicon having 0.3 to 3 mol% of siloxane units and 97 to 99.7 mol% of dimethylsiloxane units, and having 3 or more siloxane bonds with respect to the total number of moles of all silicon atoms in the polydimethylsiloxane A polyorganosiloxane having 1 mol% or less of atoms is more preferred.

  As a dimethylsiloxane which comprises polyorganosiloxane (Ea), the dimethylsiloxane type | system | group cyclic body of 3 or more member ring is mentioned, for example. Among these, a 3-membered to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

  The siloxane having a vinyl polymerizable functional group is not particularly limited as long as it has a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond, but the reactivity with dimethylsiloxane is considered. Then, the alkoxysilane compound which has a vinyl polymerizable functional group is preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, vinylphenylsiloxanes such as p-vinylphenyldimethoxymethylsilane, etc. Is mentioned. These vinyl polymerizable functional group-containing siloxanes can be used alone or in combination of two or more.

The polyorganosiloxane (Ea) may contain a siloxane-based crosslinking agent as a constituent component, if necessary.
Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The manufacturing method of polyorganosiloxane (Ea) is not limited. For example, it can be produced by the following method.
First, a siloxane-based crosslinking agent is added to a siloxane mixture composed of dimethylsiloxane and a siloxane having a vinyl polymerizable functional group, if necessary, and then emulsified with an emulsifier and water to disperse the siloxane mixture in an aqueous medium. A siloxane mixture aqueous dispersion is obtained. Next, the siloxane mixture aqueous dispersion is subjected to micronization treatment using a homomixer that makes fine particles by shearing force due to high-speed rotation, a homogenizer that makes fine particles by jet output from a high-pressure generator, and the like. Disperse particles (siloxane mixture) in the body are made fine. Here, it is preferable to use a high-pressure emulsifier such as a homogenizer because the particle size distribution of the polyorganosiloxane (Ea) becomes small. Next, the finely divided siloxane mixture aqueous dispersion is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction liquid is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash or sodium carbonate to stop the polymerization, thereby obtaining an aqueous dispersion in which polyorganosiloxane (Ea) is dispersed in the aqueous dispersion.

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

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

The volume average particle diameter of the polyorganosiloxane (Ea) in the aqueous dispersion is excellent in the color development property and scratch resistance of the molded product, and the viscosity increase and coagulation of the aqueous dispersion during production of the polyorganosiloxane (Ea). Since generation | occurrence | production of a lump (coagulum) can be prevented, 0.01-0.09 micrometer is preferable and 0.02-0.08 micrometer is more preferable.
As a method for controlling the volume average particle diameter of the polyorganosiloxane (Ea), for example, a method described in JP-A-5-279434 can be employed.

<Poly (meth) acrylic acid ester (Eb)>
The poly (meth) acrylic acid ester (Eb) is a copolymer having a unit derived from a (meth) acrylic acid ester and one or both of a unit derived from a crosslinking agent and a unit derived from a graft crossing agent.
In addition, in poly (meth) acrylic acid ester (Eb), (meth) acrylic acid ester corresponding to the cross-linking agent or graft crossing agent is a cross-linking agent or graft crossing agent, and does not correspond to (meth) acrylic acid ester. Shall.

  Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group; (meth) acrylic acid esters having an aromatic hydrocarbon group such as a phenyl group and a benzyl group. Can be mentioned. As (meth) acrylic acid ester, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferable. The (meth) acrylic acid ester can be used alone or in combination of two or more.

The cross-linking agent and the graft crossing agent each improve the impact resistance and color developability of the molded product.
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.

  In the poly (meth) acrylic acid ester (Eb), the total amount of the unit derived from the cross-linking agent and the unit derived from the graft crossing agent is excellent in impact resistance and color developability of the molded product. 0.1 to 5% by mass is preferable in the total 100% by mass of all units constituting the poly (meth) acrylic acid ester (Eb). 3 mass% is more preferable and 0.5-2 mass% is further more preferable.

<Composite rubbery polymer (E)>
The composite rubber-like polymer (E) is composed of polyorganosiloxane (Ea) and poly (meth) acrylic acid ester (Eb).

  1-20 mass% is preferable and, as for the content rate of polyorganosiloxane (Ea) with respect to the total mass (100 mass%) of a composite rubber-like polymer (E), 3-18 mass% is more preferable. If the content of the polyorganosiloxane (Ea) is not less than the lower limit of the above range, the impact resistance and scratch resistance of the molded product are more excellent, and if it is not more than the upper limit of the above range, the impact resistance is more excellent. .

It does not restrict | limit especially as a manufacturing method of a composite rubber-like polymer (E). For example, a method of hetero-aggregating or co-enlarging an aqueous dispersion of polyorganosiloxane (Ea) and an aqueous dispersion of poly (meth) acrylic acid ester (Eb) produced separately, an aqueous solution of polyorganosiloxane (Ea) In any one of the dispersion and the aqueous dispersion of poly (meth) acrylic acid ester (Eb), a method in which the other polymer is formed and combined is exemplified. By these methods, an aqueous dispersion of the composite rubber-like polymer (E) is obtained.
As a method for producing the composite rubber-like polymer (E), since the impact resistance and color developability of the molded product are more excellent, a (meth) acrylic acid ester-based single dispersion is used in an aqueous dispersion of the polyorganosiloxane (Ea). A method of emulsion polymerization of a monomer mixture containing a monomer and one or both of a crosslinking agent and a graft crossing agent is preferred. For example, an emulsifier and the monomer mixture are added to an aqueous dispersion of polyorganosiloxane (Ea) at room temperature, the temperature is raised to 40 to 80 ° C., and a radical polymerization initiator is added to 0.5 to 3 By polymerizing for about an hour, an aqueous dispersion of the composite rubber-like polymer (E) is obtained.

Preferable specific examples of the emulsifier used in the emulsion polymerization include sodium or potassium salts of fatty acids such as oleic acid, stearic acid, myristic acid, stearic acid, palmitic acid, sodium lauryl sulfate, sodium N-lauroyl sarcosinate, alkenyl succinate. Examples include dipotassium acid, sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkylphenyl ether sulfate, and the like.
The emulsifier is preferably an acid type emulsifier having two or more functional groups in one molecule or a salt thereof from the viewpoint of further suppressing gas generation during the molding of the thermoplastic resin composition, and among them, dipotassium alkenyl succinate or alkyl Sodium diphenyl ether disulfonate is preferred.
Examples of the radical polymerization initiator include peroxides, azo initiators, redox initiators in which an oxidizing agent and a reducing agent are combined. Of these, redox initiators are preferable, and sulfoxylate initiators in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide are combined are particularly preferable.

The volume average particle diameter of the composite rubber-like polymer (E) dispersed in the aqueous dispersion is preferably 0.05 to 0.18 μm from the viewpoint of excellent impact resistance and color developability of the molded product, and is 0.07. -0.15 micrometer is more preferable.
Although it does not restrict | limit especially as a method of controlling the volume average particle diameter of a composite rubber-like polymer (E), The method of adjusting the kind or usage-amount of an emulsifier, etc. are mentioned.
When the graft copolymer (F) is obtained using an aqueous dispersion of the composite rubber-like polymer (E), the average particle of the composite rubber-like polymer (E) in the aqueous dispersion It has been confirmed by image analysis with an electron microscope that the diameter indicates the volume average particle diameter of the composite rubber-like polymer (E) in the thermoplastic resin composition as it is.

<Vinyl-based single amount mixture (m2)>
The vinyl monomer mixture (m2) contains at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester as a monomer.
The vinyl monomer mixture (m2) may further contain another vinyl monomer other than the aromatic vinyl compound, the vinyl cyanide compound, and the (meth) acrylic acid ester, if necessary.

  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. From the viewpoint of impact resistance, styrene and α-methylstyrene are preferable. 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 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.

  As (meth) acrylic acid ester, acrylic acid ester (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylic acid ester (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate) Etc.), and methyl methacrylate is preferred from the viewpoint of color developability and impact resistance of the molded product. One (meth) acrylic acid ester may be used alone, or two or more may be used in combination.

  Examples of other vinyl monomers include maleimide compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like. Another vinyl-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the above, the vinyl monomer mixture (m2) preferably contains an aromatic vinyl compound and a vinyl cyanide compound.

  In the vinyl monomer mixture (m2), the content of the aromatic vinyl compound is preferably 60 to 85 mass% with respect to the total mass (100 mass%) of the vinyl monomer mixture (m2), 62 to 80 mass% is more preferable. When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  The content of the vinyl cyanide compound is preferably 15 to 40% by mass and more preferably 20 to 38% by mass with respect to the total mass (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.

<Graft copolymer (F)>
The graft copolymer (F) is obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the composite rubber-like polymer (E).
In the graft copolymer (F), it is difficult to specify how the composite rubber-like polymer (E) and the vinyl monomer mixture (m2) are polymerized. That is, there is a situation (impossible / unpractical situation) that the graft copolymer (F) cannot be directly identified by its structure or characteristics, or is almost impractical. Therefore, it is more appropriate to define “obtained by polymerizing the vinyl monomer component (m2) in the presence of the composite rubber-like polymer (E)”.

In the presence of 20 to 90% by mass of the composite rubbery polymer (E), the graft copolymer (F) is 10 to 80% by mass of the vinyl monomer mixture (m2) (however, the composite rubbery polymer ( E) and the vinyl monomer mixture (m2) are preferably 100% by mass). The composite rubber-like polymer (E) is preferably 25 to 85% by mass. More preferably, it is obtained by polymerizing 15 to 75% by mass of the vinyl monomer mixture (m2) in the presence, and in the presence of 30 to 80% by mass of the composite rubber-like polymer (E). More preferably, the vinyl monomer mixture (m2) is obtained by polymerizing 20 to 70% by mass.
If the content of the composite rubber-like polymer (E) in the total 100% by mass of the composite rubber-like polymer (E) and the vinyl monomer mixture (m2) is within the above range, the graft copolymer ( The productivity of F) is good, and the color developability and impact resistance of the molded product are more excellent.

The graft copolymer (F) can be obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the composite rubber-like polymer (E).
Examples of the polymerization method of the vinyl monomer mixture (m2) include an emulsion polymerization method.
Production of the graft copolymer (F) by the emulsion polymerization method is performed, for example, by adding a vinyl monomer mixture (m2) to an aqueous dispersion of the composite rubber-like polymer (E), and then adding a vinyl monomer in the presence of an emulsifier. It can be carried out by radical polymerization of the monomer mixture (m2). Thereby, the aqueous dispersion of a graft copolymer (F) is obtained.
In the polymerization, various known chain transfer agents may be added in order to control the graft ratio and the molecular weight of the graft component.
The polymerization conditions for radical polymerization are not particularly limited, and examples include polymerization conditions at 60 to 90 ° C. for 1 to 4 hours.

  Examples of radical polymerization initiators used in radical polymerization include peroxides, azo initiators, redox initiators in which an oxidizing agent and a reducing agent are combined. Of these, redox initiators are preferable, and sulfoxylate initiators in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide are combined are particularly preferable.

  Examples of the emulsifier include those similar to the emulsifier used when the composite rubber-like polymer (E) is produced by an emulsion polymerization method. The emulsifier contained in the aqueous dispersion of the composite rubber-like polymer (E) is used as it is, and it is not necessary to add an emulsifier when the vinyl monomer mixture (m2) is polymerized. An emulsifier may be added during the polymerization of the monomer mixture (m2).

  The method of recovering the graft copolymer (F) from the aqueous dispersion of the graft copolymer (F) includes (i) an aqueous dispersion of the graft copolymer (F) in hot water in which a coagulant is dissolved. (Ii) by spraying an aqueous dispersion of the graft copolymer (F) in a heated atmosphere and semi-directly grafting. Examples thereof include a method (spray dry method) for recovering the copolymer (F).

  Examples of the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and metal salts such as calcium chloride, calcium acetate and aluminum sulfate. The coagulant is selected according to the emulsifier used in the polymerization. That is, when using only carboxylic acid soaps such as fatty acid soaps and rosin acid soaps, any coagulant may be used. When an emulsifier exhibiting stable emulsifying power is contained even in an acidic region such as sodium dodecylbenzenesulfonate, a metal salt must be used.

As a method for obtaining the dry graft copolymer (F) from the slurry graft copolymer (F), the emulsifier residue remaining in the slurry is eluted in water by washing, and then the following (i-1) ) Or (i-2).
(I-1) The slurry is dehydrated by a centrifugal dehydrator or a press dehydrator, and further dried by an air dryer or the like.
(I-2) The slurry is dehydrated and dried at the same time using a press dehydrator or an extruder.
After drying, the graft copolymer (F) is obtained in the form of powder or particles. Moreover, the graft copolymer (F) discharged | emitted from the press dehydrator or the extruder can also be sent directly to the extruder or molding machine which manufactures a thermoplastic resin composition.

  A graft copolymer (F) 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 a monomer.
The vinyl monomer mixture (m3) is selected from the group consisting of maleimide compounds, aromatic vinyl compounds, acrylic esters, and other vinyl monomers capable of co-polymerizing with methacrylic esters, if necessary. It may further contain at least one vinyl monomer.

  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, benzyl methacrylate, and phenyl methacrylate. From the viewpoint of further improving the heat resistance and impact resistance of the molded article, it is preferable to contain at least one of methyl methacrylate and ethyl methacrylate. 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). , Nt-butylmaleimide, etc.), N-cycloalkylmaleimide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.) and the like. . N-arylmaleimide is preferable and N-phenylmaleimide is particularly preferable from the viewpoint of further improving the heat resistance and impact resistance of the molded product. 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 preferred from the viewpoint that the molded product is further excellent in heat resistance and impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. 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.

  In the case where better heat resistance is required for the molded article, the vinyl monomer mixture (m3) further contains one or both of a maleimide compound and an aromatic vinyl compound in addition to the methacrylic acid ester. It is preferable to include.

  In the vinyl monomer mixture (m3), the content of the methacrylic acid ester is excellent in the scratch resistance, coloring property, wiping resistance, and squeak noise suppression effect of the molded product. 50-100 mass% is preferable with respect to the total mass (100 mass%) of (m3).

  As a vinyl-type monomer mixture (m3), the content rate of methacrylic acid ester is 50-98 mass% with respect to the total mass (100 mass%) of a vinyl-type monomer mixture (m3), content of a maleimide-type compound It is particularly preferable that the ratio is 1 to 30% by mass and the content of the aromatic vinyl compound is 1 to 15% by mass. If the content of each of the methacrylic acid ester, maleimide compound and aromatic vinyl compound is within the above range, the scratch resistance, color development, wiping resistance, squeak noise suppressing effect and heat resistance of the molded product are further improved. .

<Methacrylate ester resin (G)>
The methacrylic ester resin (G) is obtained by polymerizing the vinyl-based monomer mixture (m3) and contains at least units derived from the methacrylic ester.

  The content of units derived from the methacrylic ester in the methacrylic ester resin (G) is excellent in that the molded article has excellent scratch resistance, color development, wiping resistance, and squeak noise suppression effect. 50-100 mass% is preferable with respect to the total mass (100 mass%) of all the units which comprise.

As a methacrylic ester resin (G), the content rate of the unit derived from a methacrylic ester is 50-98 mass%, and the content rate of the unit derived from a maleimide-type compound is 1 with respect to the total mass (100 mass%) of all the units. A copolymer having a content of -30% by mass and an aromatic vinyl compound-derived unit of 1-15% by mass is particularly preferred. If the methacrylic ester resin (G) has such a copolymer composition, the scratch resistance, color developability, wiping resistance, squeak noise suppressing effect and heat resistance of the molded product are further improved.
When the vinyl monomer mixture (m3) contains two or more types of monomers, the methacrylate ester resin (G) typically has random units derived from these two or more types of monomers. It is a random copolymer arranged in.

  The weight average molecular weight of the methacrylic ester resin (G) is preferably 100,000 to 300,000, and more preferably 120,000 to 220,000.

The methacrylic ester resin (G) can be obtained by polymerizing the vinyl monomer mixture (m3).
The polymerization method of the vinyl monomer mixture (m3) is not particularly 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.
The polymerization conditions for emulsion polymerization are not particularly limited, and examples include polymerization conditions at 40 to 120 ° C. for 1 to 15 hours.
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).
The polymerization conditions for suspension polymerization are not particularly limited, and examples include polymerization conditions at 40 to 120 ° C. for 1 to 15 hours.
Examples of the suspending agent include tricalcium phosphite and polyvinyl alcohol.
Examples of the suspension aid include sodium alkylbenzene sulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.

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

<Antistatic agent (H)>
Examples of the antistatic agent (H) include surfactants, conductive fillers, quaternary ammonium salts, and polymer antistatic agents.
Among the above, as the antistatic agent (H), it is excellent in durability of the antistatic effect, excellent in heat resistance in compounding by melt kneading with a resin component, and can be provided with antistatic properties by adding a small amount. Polymer antistatic agents are preferred.

  Although it does not restrict | limit especially as a polymeric antistatic agent, For example, the block copolymer etc. which have any one or both of a polyolefin-type block and a polyamide-type block, and a hydrophilic block are mentioned.

The polyolefin block includes a unit derived from an olefin monomer.
As a polyolefin-type monomer, a C2-C6 olefin is preferable, for example, ethylene, propylene, 1-butene etc. are mentioned. Of these olefins, at least one selected from ethylene and propylene is preferable, and at least propylene is particularly preferable.
Of the olefinic monomers, the proportion of propylene is preferably 80 mol% or more, particularly preferably 90 mol% or more, based on the total number of moles of olefinic monomers (100 mol%).
In the polyolefin block, the content of the unit derived from the olefin monomer is preferably 80 mol% or more, and 90 mol% or more with respect to the total number of moles (100 mol%) of all units constituting the polyolefin block. Particularly preferred.
The number average molecular weight of the polyolefin block is preferably 2000 to 50000, more preferably 3000 to 40000, and still more preferably 5000 to 30000.

Examples of the polyamide block include a block obtained by condensation of diamine and dicarboxylic acid, a block obtained by condensation of aminocarboxylic acid, a block obtained by ring-opening polymerization of lactam, and a copolymer block obtained from these components. Etc.
Examples of the diamine include aliphatic diamines having 4 to 20 carbon atoms such as hexamethylene diamine. Examples of the dicarboxylic acid include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedioic acid.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 4 to 20 carbon atoms such as 6-aminohexanoic acid and 12-aminododecanoic acid.
Examples of the lactam include a lactam having 4 to 20 carbon atoms such as caprolactam.

Examples of the hydrophilic block include polyether polymers (or nonionic polymers), cationic polymers, anionic polymers, and the like.
As the hydrophilic monomer constituting the hydrophilic block, alkylene oxide is preferable. Examples of the alkylene oxide include alkylene oxides having 2 to 6 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide. Of these, alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide are preferable.
Therefore, polyalkylene oxide is preferable as the hydrophilic block. The polyalkylene oxide is preferably a polyalkylene oxide having 2 to 6 carbon atoms in the alkylene oxide, and more preferably a polyalkylene oxide having 2 to 4 carbon atoms in the alkylene oxide. Specific examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polyethylene oxide-polypropylene oxide, and the like. The degree of polymerization of the polyalkylene oxide is preferably 2 to 300, more preferably 5 to 200, further preferably 10 to 150, particularly preferably 10 to 100, and most preferably 20 to 80.

The polyolefin block and the hydrophilic block are typically bonded via an ester bond, an amide bond, an ether bond, a urethane bond, an imide bond, or the like.
These bonds can be formed, for example, by modifying a polyolefin with a modifier and then introducing a hydrophilic block. For example, after introducing an active hydrogen atom by modifying a polyolefin with a modifier, it is introduced by addition polymerization of a hydrophilic monomer such as alkylene oxide. Examples of such modifiers include unsaturated carboxylic acids or their anhydrides (such as (anhydrous) maleic acid), lactams or aminocarboxylic acids (such as caprolactam), oxygen or ozone, hydroxylamine (such as 2-aminoethanol). , Diamine (such as ethylenediamine), and a mixture of two or more thereof.
Such an antistatic agent having a polyolefin block and a hydrophilic block can be obtained, for example, from Sanyo Chemical Industries, Ltd. under the trade name “Pelestat 300”.

The polyamide block and the hydrophilic block are typically bonded via an ester bond, an amide bond, an ether bond, a urethane bond, an imide bond, or the like.
These bonds can be formed, for example, by bonding a polyamide having a functional group at both ends and a polyether polymer with a glycidyl ether compound (for example, bisphenol A glycidyl ether).
Antistatic agents having such polyamide blocks and hydrophilic blocks are, for example, trade names “Pelestat (registered trademark) NC6321”, “Pelestat NC7530”, and “Peletron (registered trademark) AS” from Sanyo Chemical Industries, Ltd. Available.

  The number average molecular weight of the polymer antistatic agent is preferably 1000 or more, more preferably 1000 to 100,000, further preferably 2000 to 60000, particularly preferably 2000 to 50000, and most preferably 3000 to 20000.

These antistatic agents may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these antistatic agents, a block copolymer having a polyamide block and a hydrophilic block is preferable. In particular, polyether ester amide is preferred because it has good compatibility with the methacrylic ester resin (G) and has good color developability because of its close refractive index. Such antistatic agents are available from Sanyo Kasei Kogyo Co., Ltd. under the trade names “Pelestat (registered trademark) NC6321”, “Pelestat NC7530”, and “Peletron AS”.

The absolute value (difference in refractive index) of the value obtained by subtracting the refractive index of the methacrylate ester resin (G) from the refractive index of the polyether ester amide is preferably 0 to 0.05, because the color developability is excellent. 0 to 0.03 is more preferable, and 0 to 0.01 is more preferable.
Since the color developability tends to deteriorate when the refractive index of the methacrylate ester resin (G) is larger than the refractive index of the polyether ester amide, the refractive index of the polyether ester amide is the refractive index of the methacrylate ester resin (G). Is preferably the same as or larger than.
The refractive index is a value measured by an Abbe refractometer.

<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 (for example, nylon).

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

<Content of each component>
In the thermoplastic resin composition, the ethylene / α-olefin copolymer (ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer (C) contained in the graft copolymer (D) ) And the composite rubber-like polymer (E) contained in the graft copolymer (F), the ratio of the ethylene / α-olefin copolymer to the total mass (100% by mass) is 1 to 85% by mass. Preferably, 30 to 70% by mass is more preferable.
The ratio of the composite rubbery polymer (E) to the total mass (100% by mass) of the ethylene / α-olefin copolymer and the composite rubbery polymer (E) is preferably 15 to 99% by mass, 30-70 mass% is more preferable.
If the proportions of the ethylene / α-olefin copolymer and the composite rubber-like polymer (E) are within the above ranges, the impact resistance, color development, scratch resistance, wiping resistance, and squeaking of the molded product Sound suppression effect is even better.

  The total content (rubber content) of the ethylene / α-olefin copolymer and the composite rubber-like polymer (E) is the impact resistance, heat resistance, color development, and scratch resistance of the molded product. From the point which is excellent in balance, 5-25 mass% is preferable with respect to the total mass (100 mass%) of a thermoplastic resin composition, and 10-20 mass% is more preferable.

The total content of the graft copolymer (D) and the graft copolymer (F) is excellent in the balance of impact resistance, heat resistance, color development, and scratch resistance of the molded product. 7-50 mass% is preferable with respect to the total mass (100 mass%) of a coalescence (D), a graft copolymer (F), and methacrylic ester resin (G), and 14-40 mass% is more preferable.
In addition, the total mass of the graft copolymer (D), the graft copolymer (F), and the methacrylate ester resin (G) is the graft copolymer (D) when the graft copolymer (F) is not included. ) And the methacrylic ester resin (G) (equal to the following).

  The content of the methacrylic ester resin (G) is such that the graft copolymer (D) and the graft copolymer (F) have a good balance of impact resistance, heat resistance, color development, and scratch resistance of the molded product. ) And methacrylic acid ester resin (G) are preferably 93 to 50% by mass, more preferably 86 to 60% by mass, based on the total mass (100% by mass).

  The content of the antistatic agent (H) is such that the graft copolymer (D) and the graft are excellent in terms of the excellent balance of wiping-off scratch resistance, squeak noise suppression effect, impact resistance, color development, and antistatic properties of the molded product. 5-20 mass parts is preferable with respect to a total of 100 mass parts of a copolymer (F) and methacrylic ester resin (G), and 8-16 mass parts is more preferable.

<Volume average particle diameter>
Ethylene / α-olefin copolymer (ethylene / α-olefin copolymer (A) or crosslinked ethylene / α-olefin copolymer (C) contained in the graft copolymer (D) in the thermoplastic resin composition ) Is preferably 0.2 to 0.6 [mu] m, more preferably 0.3 to 0.5 [mu] m, from the viewpoint of excellent impact resistance and color developability of the molded product.

  The volume average particle size of the composite rubber-like polymer (E) contained in the graft copolymer (F) in the thermoplastic resin composition is from 0.05 to 0.05 because the impact resistance and color developability of the molded product are excellent. 0.18 μm is preferable, and 0.07 to 0.15 μm is more preferable.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention comprises a graft copolymer (D), a methacrylic ester resin (G), an antistatic agent (H), and other components (graft copolymer (F) as required. ), Other thermoplastic resins and additives).
As the graft copolymer (D), the methacrylic ester resin (G), and the graft copolymer (F), those obtained by the above procedure can be used.

<Effect>
The thermoplastic resin composition of the present invention described above is selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester in the presence of an ethylene / α-olefin copolymer. A graft copolymer (D) obtained by polymerizing the resulting vinyl monomer mixture (m1) containing at least one vinyl monomer; and a vinyl monomer mixture (m3) containing a methacrylate ester ) And the antistatic agent (H), so that it has impact resistance, color development, scratch resistance, antistatic properties, wiping resistance and wiping resistance. It is possible to obtain a molded article having excellent scratch durability and squeak noise suppression effect. Moreover, if the thing of a specific copolymer composition (for example, the composition of the said paragraph 0119) is used as methacrylic ester resin (G), it will be excellent also in heat resistance. Furthermore, even if heat resistance is imparted to the molded product, impact resistance is not impaired.
The thermoplastic resin composition of the present invention can provide a molded product having excellent scratch resistance, wiping resistance, durability of wiping resistance, and squeak noise suppression effect. Is possible.

"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.
The use of the molded product includes vehicle interior / exterior parts, office equipment, home appliances, building materials, etc., and vehicle interior / exterior parts are suitable.

  In the molded product of the present invention described above, since the thermoplastic resin composition of the present invention is used, impact resistance, coloring property, scratch resistance, antistatic property, wiping resistance, wiping resistance Excellent sustainability and squeak noise suppression effect. Furthermore, if the thing of a specific copolymer composition is used as methacrylic ester resin (G), it is 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)>
Using a GPC device (GPC: “GPC / V2000” manufactured by Waters, column: “Shodex AT-G + AT-806MS” manufactured by Showa Denko KK), using o-dichlorobenzene (145 ° C.) as a solvent, a mass average in terms of polystyrene Molecular weight (Mw) and number average molecular weight (Mn) were measured, and molecular weight distribution (Mw / Mn) was calculated.

<Method for measuring acid value>
The acid value was measured according to JIS K 2501.

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

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

<Measurement method of graft ratio>
1 g of the graft copolymer (D) is added to 80 mL of acetone, heated to reflux at 65 to 70 ° C. for 3 hours, and the resulting suspended acetone solution is added to a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.). The mixture was centrifuged at 14,000 rpm for 30 minutes to separate a precipitation component (acetone insoluble component) and an acetone solution (acetone soluble component). 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)

<Melting and kneading>
A graft copolymer (D), a methacrylic ester resin (G), an antistatic agent (H), and a graft copolymer (F) and other components are mixed as required in the formulations shown in Tables 8 to 11 described later. In addition, an organic dye ("NUBIAN PC-5596" manufactured by Orient Chemical Industry Co., Ltd.) is used for a total of 100 parts of the graft copolymer (D), graft copolymer (F) and methacrylate ester resin (G). ) 0.8 parts are mixed and colored, and melt kneaded at a cylinder temperature of 200 to 260 ° C. and 93.325 kPa vacuum using a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) A plastic resin composition was obtained. Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Creation of molded product for physical property evaluation 1>
The thermoplastic resin composition was injection-molded under conditions of a cylinder temperature of 200 to 270 ° C. and a mold temperature of 60 ° C. using an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). A black colored plate having a thickness of 3 mm) was obtained. This was made into the molded article (Ma).

<Creation of molded product for physical property evaluation 2>
The thermoplastic resin composition was injection-molded with an injection molding machine (Toshiba Machine Co., Ltd., “IS55FP-1.5A”) under the conditions of a cylinder temperature of 200 to 270 ° C. and a mold temperature of 60 ° C. A molded article for measuring a deflection temperature under load having a thickness of 10 mm and a thickness of 4 mm was obtained. This was designated as a molded product (Ma2).

<Creation of molded product for physical property evaluation 3>
The thermoplastic resin composition was injection molded by an injection molding machine (“SG150-SYCAPM IV” manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C., and the structure shown in FIG. Two types of molded articles (a test piece 21 having a rib structure 21a and a test piece 22 having a planar portion) were obtained.

<Evaluation of color development>
The lightness L ^* of the surface of the molded product (Ma) 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 impact resistance: falling ball impact strength measurement>
The molded product (Ma) temperature-controlled at −30 ° C. was used as a sample, and the falling ball impact strength was measured for each of the three samples. A steel ball having a weight of 200 g was dropped from a height of 10 cm, and if it was not cracked, the drop height was increased every 10 cm to check whether cracks or cracks occurred. The falling height at which two or more cracks or cracks did not occur in the three samples was defined as the falling ball impact height. The higher the falling ball impact height, the better the impact resistance.

<Evaluation of scratch resistance>
Using a pencil hardness tester, a 3H hardness pencil is pressed against the surface of the molded product (Ma) with a load of 750 g (7.35 N), and the molded product (Ma) is moved by about 5 cm in this state. The surface of the product (Ma) was scratched with a pencil, and the molded product (Ma) was scratched. A molded product (Mb) was obtained by scratching the molded product (Ma). 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 ^* (mb−ma) for the visibility of scratches on the molded product (Mb) was calculated from the following formula (3). As the absolute value of ΔL ^* (mb−ma) is larger, the scratches are more conspicuous.
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)

When the absolute value of ΔL ^* (mb−ma) is 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 11 formed in a hemispherical shape was prepared, and the tip 11 was covered with a car wash towel 12 (Joyfull Car Wash Towel 3p). The tip portion 11 covered with the car wash towel 12 is brought into contact with the surface of the molded product (Ma) 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 (Ma) 13. Were slid in the horizontal direction (in the direction of the double-headed arrow in the figure) and reciprocated 100 times to scratch the molded product (Ma). At that time, the applied load was 1 kg (9.8 N). A molded product (Mc) was obtained by scratching the molded product (Ma). 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 ^* (mc−ma) for the visibility 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 4.5 or less, the 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 4.5 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 antistatic properties>
(Dirt chamber test)
A molded product (Ma) that was allowed to stand for 24 hours at a temperature of 23 ° C. and a humidity of 65% was set in a dirt chamber test apparatus, and a test was performed in which 3 g of carbon black was blown for 5 minutes. The molded product (Ma) after the test was defined as a molded product (Md). This molded product (Md) was visually observed and evaluated according to the following evaluation criteria. When the evaluation of the dirt chamber test is Δ or more, it is said that the antistatic property is present.
○: A small amount of carbon black is uniformly attached or not attached at all.
Δ: A little more carbon black is uniformly attached, or a slight flower pattern (non-uniformly attached) is present.
X: Carbon black adheres unevenly throughout.

<Evaluation of wiping resistance>
The molded product (Md) was washed with 200 mL of water and dried to obtain a molded product (Me).
As shown in FIG. 1, a rod-like jig 10 having a tip 11 formed in a hemispherical shape was prepared, and the tip 11 was covered with a car wash towel 12 (Joyfull Car Wash Towel 3p). The tip portion 11 covered with the car wash towel 12 is brought into contact with the surface of the molded product (Me) 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 (Me) 13. Were slid in the horizontal direction (in the direction of the double-headed arrow in the figure) and reciprocated 100 times to scratch the molded product (Me). At that time, the applied load was 1 kg (9.8 N). The carbon black adhering to the surface of the scratched molded product (Me) is washed away using a neutral surfactant (automobile detergent, manufactured by SOFT99 Corporation, “Car Shampoo”) and dried. A molded product (Mf) was obtained. The lightness L ^* of the surface of the molded product (Mf) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mf)”.

(Determination of wiping resistance)
The determination index ΔL ^* (mf−ma) for wiping-off resistance was calculated from the following formula (5). As the absolute value of ΔL ^* (mf−ma) is larger, the scratches are more conspicuous.
ΔL ^* (mf−ma) = L ^* (mf) −L ^* (ma) (5)

When the absolute value of ΔL ^* (mf−ma) is 4.5 or less, the scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mf−ma) is more than 4.5 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 ^* (mf−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

<Evaluation of durability of wiping resistance>
Set the molded product (Mf) left at a temperature of 23 ° C. and a humidity of 65% for 24 hours in a dirt chamber test apparatus, blow 3 g of carbon black for 5 minutes, and then wash the surface of the molded product with 200 mL of water and dry it. A molded product (Mg) was obtained.
As shown in FIG. 1, a rod-like jig 10 having a tip 11 formed in a hemispherical shape was prepared, and the tip 11 was covered with a car wash towel 12 (Joyfull Car Wash Towel 3p). The tip 11 covered with the car wash towel 12 is brought into contact with the surface of the molded product (Mg) 13 so that the rod-shaped jig 10 is at a right angle, and the tip 11 is brought into contact with the surface of the molded product (Mg) 13. Was slid in the horizontal direction (in the direction of the double-headed arrow in the figure) and reciprocated 100 times to scratch the molded product (Mg). At that time, the applied load was 1 kg (9.8 N). The carbon black adhering to the surface of the scratched molded product (Mg) is washed away with a neutral surfactant (automobile detergent, manufactured by SOFT99 Corporation, “Car Shampoo”) and dried. A molded product (Mh) was obtained. The lightness L ^* of the surface of the molded product (Mh) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mh)”.

(Determination of durability of wiping resistance)
The durability Δ (ΔL ^* ) of the wiping resistance of the molded product was calculated from the following formulas (6) to (7). The greater the absolute value of Δ (ΔL ^* ), the lower the durability of the wiping resistance.
ΔL ^* (mh−mf) = L ^* (mh) −L ^* (mf) (6)
Δ (ΔL ^* ) = ΔL ^* (mh−mf) −ΔL ^* (mf−ma) (7)

<Evaluation of squeak noise suppression effect>
As shown in FIG. 2, a test piece 21 having a rib structure 21 a is arranged on a test piece 22 having a flat portion, and a load of 500 g (4.9 N) or 1 kg (9.8 N) from above the test piece 21. The test piece 22 was reciprocated in the horizontal direction (in the direction of the double arrow in the figure). At this time, whether or not squeak noise was generated was examined and evaluated according to the following criteria. Δ or more is considered to have a squeak noise suppressing effect.
A: No squeak noise is generated at a load of 500 g (4.9 N) or 1 kg (9.8 N).
○: A small squeak noise is generated when the load is 1 kg (9.8 N), but not when the load is 500 g (4.9 N).
(Triangle | delta): A small squeak noise is heard in any of load 500g (4.9N) and 1 kg (9.8N).
X: A squeak noise is generated at both a load of 500 g (4.9 N) and 1 kg (9.8 N).

<Evaluation of heat resistance>
With respect to the molded article (Ma2), the deflection temperature under load (° C.) was measured by the flatwise method in accordance with ISO 75-1: 2004, 1.83 MPa, 4 mm.

<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), Polyorganosiloxane (Ea), composite rubber-like polymer (E), graft copolymer (F), methacrylic ester resin (G), antistatic agent (H), and silicone oil (I) were used.

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1))
After fully substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added to prepare ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ prepared to 8.0 mmol / L. 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 8 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).

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

(Preparation of olefin resin aqueous dispersions (B-2) to (B-5))
As shown in Table 2, the olefin resin aqueous solution was prepared in the same manner as in the preparation of the aqueous olefin resin dispersion (B-1) except that the number of added parts of potassium hydroxide during emulsification and the number of added parts of ion exchange water were changed. Dispersions (B-2) to (B-5) were obtained.
Table 2 shows the volume average particle diameter of the ethylene / α-olefin copolymer (A) dispersed in each of the olefin resin aqueous dispersions (B-2) to (B-5).

<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) to a solid content concentration of 35%, and 0.2 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 an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (C-1). Table 3 shows the gel content and volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (C-1).

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2) to (C-5))
As shown in Table 3, the crosslinked ethylene / α-olefin copolymer was prepared in the same manner as in the preparation of the crosslinked ethylene / α-olefin copolymer (C-1) except that the addition amount of t-butylcumyl peroxide was changed. An aqueous dispersion of polymers (C-2) to (C-5) was obtained. Table 3 shows the gel content and volume average particle diameter of the crosslinked ethylene / α-olefin copolymers (C-2) to (C-5).

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1))
An aqueous olefin resin dispersion (B-1) (70 parts as a solid content of the ethylene / propylene copolymer (A-1)) is placed in a stainless polymerization tank equipped with a stirrer, and an aqueous olefin resin dispersion (B-1). Ion-exchanged water was added to the solution so that the solid concentration was 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were added, and the temperature was set to 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 0.41 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%.
Moreover, in the Example mentioned later, when the average particle diameter of the ethylene-α-olefin copolymer (A) in the thermoplastic resin composition using the graft copolymer (D-1) was confirmed by an electron microscope, It was 0.41 μm.

(Preparation of graft copolymers (D-2) to (D-5))
As shown in Table 4, the graft copolymers (D-2) to (D-5) were the same as the graft copolymer (D-1) except that the type of the olefin resin aqueous dispersion (B) was changed. ) Table 4 shows the graft ratios of the graft copolymers (D-2) to (D-5).

(Preparation of graft copolymers (D-6) to (D-10))
Preparation of graft copolymer (D-1) except that olefin resin aqueous dispersion (B) was changed to an aqueous dispersion of crosslinked ethylene / α-olefin copolymer (C) as shown in Tables 4-5. In the same manner as above, graft copolymers (D-6) to (D-10) were obtained. The graft ratios of the graft copolymers (D-6) to (D-10) are shown in Tables 4 to 5.

(Preparation of graft copolymer (D-11))
In a stainless polymerization tank equipped with a stirrer, 70 parts of ethylene / α-olefin copolymer (A-1) and 300 parts of toluene were charged, and the contents were stirred and uniformly dissolved 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 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.), pelletized, and graft copolymer (D-11). ) When the graft ratio of the graft copolymer (D-11) was measured, it was 30%. Moreover, it was 0.4 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 copolymer (D-12))
As shown in Table 5, a graft copolymer (D-12) was obtained in the same manner as the preparation of the graft copolymer (D-1) except that styrene and acrylonitrile were changed to styrene and methyl methacrylate. It was. Table 5 shows the graft ratio of the graft copolymer (D-12).

(Preparation of graft copolymer (D-13))
In a pressure vessel equipped with a stirrer, 150 parts of deionized water, 100 parts of butadiene monomer, 3.0 parts of hardened fatty acid potassium soap, 0.3 part of sodium organic sulfonate, 0.2 part of tert-decyl mercaptan, 0 potassium persulfate .3 parts and 0.14 part of potassium hydroxide were added, the temperature was raised to 60 ° C. while stirring in a nitrogen atmosphere, and the polymerization was started. When the polymerization rate was 65%, 0.1 part of potassium persulfate was dissolved. 5 parts of deionized water was added to the pressure vessel and 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%, an average particle size of 0.08 μm, and a solid content of 52.0%. A latex of rubbery polymer (D-13-a) was obtained.
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 200 parts of ion-exchanged water (including water in polybutadiene latex), 0.3 part of disproportionated potassium rosinate (solid content) Then, 0.01 parts of ferrous sulfate heptahydrate, 0.2 parts of sodium pyrophosphate and 0.5 parts of crystalline glucose were charged and completely dissolved, and then latex of rubbery polymer (D-13-a) was added. As a solid content, 50 parts were added and mixed.
While stirring the contents in the reactor, the temperature is raised to 60 ° C., and a vinyl monomer mixture (m1) of 39 parts of styrene and 11 parts of acrylonitrile is continuously added dropwise over 2 hours for graft polymerization. It was. 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 (D-13).
The obtained graft copolymer (D-13) latex 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. A slurry of the graft copolymer (D-13) was obtained. Then, the slurry was washed with water and dehydrated twice, then allowed to stand at 70 ° C. overnight and dried to obtain a milky white powder graft copolymer (D-13).

(Preparation of graft copolymer (D-14))
0.7 parts of dipotassium alkenyl succinate, 175 parts of ion-exchanged water, 100 parts of n-butyl acrylate, 0.26 parts of allyl methacrylate, 0.14 parts of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.2 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 0.00026 parts of ferrous sulfate, 0.0008 parts of disodium ethylenediaminetetraacetate, 0.45 parts of Rongalite, and 10 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 (D-14-a) having an average particle size of 0.096 μm.
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, a dispersion of a rubber-like polymer (D-14-a) (solid content 50 parts) was put, and 0.15 parts of Rongalite, An aqueous solution consisting of 0.65 parts of dipotassium alkenyl succinate and 10 parts of ion-exchanged water was added, and then a mixed solution 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 to cause graft polymerization. Five minutes after the completion of the 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 6 A mixture of .2 parts, 18.8 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl succinic acid were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (D-14).

<Graft copolymer (F)>
(Preparation of polyorganosiloxane (Ea))
96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane mixture. To this was added 300 parts of ion-exchanged water in which 0.67 parts of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred at 10000 rpm / 2 minutes with a homomixer, and then passed once through the homogenizer at a pressure of 30 MPa to ensure stable premixing. An aqueous organosiloxane dispersion was obtained.
In addition, 2 parts of dodecylbenzenesulfonic acid and 98 parts of ion-exchanged water are injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. did. While this aqueous solution was heated to 85 ° C., the premixed organosiloxane aqueous dispersion was added dropwise over 4 hours, and the temperature was maintained for 1 hour after the completion of the addition and cooled. The reaction solution was allowed to stand at room temperature for 48 hours and then neutralized with an aqueous sodium hydroxide solution to obtain an aqueous dispersion of polyorganosiloxane (Ea). A part of the polyorganosiloxane (Ea) aqueous dispersion was dried at 170 ° C. for 30 minutes to obtain a solid content concentration of 17.3%. The volume average particle diameter of the polyorganosiloxane (Ea) dispersed in the aqueous dispersion was 0.05 μm.

(Preparation of graft copolymer (F-1))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 68.3 parts of an aqueous dispersion of polyorganosiloxane (Ea) and 0.75 part of sodium polyoxyethylene alkylphenyl ether sulfate were charged. 203 parts of ion exchange water was added and mixed. Thereafter, a mixture consisting of 61.8 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C, 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetic acid and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state is maintained for 1 hour to complete the polymerization of the acrylate component, and the unit derived from the polyorganosiloxane (Ea), the (meth) acrylic acid ester monomer and the crosslinking agent and / or the graft crossing agent An aqueous dispersion of a composite rubber-like polymer (E-1) comprising a poly (meth) acrylic acid ester containing Moreover, the volume average particle diameter of the composite rubber-like polymer (E-1) dispersed in the aqueous dispersion was 0.096 μm.
After the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Subsequently, 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide were dropped and polymerized over about 1 hour. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After holding for 1 hour after the completion of dropping, the mixture was cooled to obtain an aqueous dispersion of a graft copolymer (F-1) obtained by grafting an acrylonitrile-styrene copolymer onto a composite rubber-like polymer (E-1). . Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (F-1) was gradually dropped into the calcium acetate aqueous solution to be solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (F-1).
Table 6 shows the amount of polyorganosiloxane (Ea) used in obtaining the aqueous dispersion of the composite rubber polymer (E-1), the amount of emulsifier used, and the resulting composite rubber polymer (E- The volume average particle diameter of 1) is shown.

<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 7 shows the refractive indexes of the monomers and methacrylate resin (G-1) used.

(Preparation of methacrylate ester resin (G-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 98 parts of methyl methacrylate, 2 parts of N-phenylmaleimide, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 of n-octyl mercaptan Part, 0.7 parts of polyvinyl alcohol 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 7 shows the monomers used and the refractive indexes of the methacrylic acid ester resin (G-2).

(Preparation of methacrylate ester resin (G-3))
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 powdery methacrylic ester resin (G-3). Table 7 shows the monomers used and the refractive indexes of the methacrylate ester resin (G-3).

(Preparation of methacrylate ester resin (G-4))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 56 parts of methyl methacrylate, 29 parts of N-phenylmaleimide, 15 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-4). Table 7 shows the monomers used and the refractive indexes of the methacrylic acid ester resin (G-4).

(Preparation of methacrylic ester resin (G-5))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 53 parts of methyl methacrylate, 31 parts of N-phenylmaleimide, 16 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-5). Table 7 shows the refractive indexes of the monomers and methacrylic ester resin (G-5) used.

<Antistatic agent (H)>
As the antistatic agent (H), “Pelestat NC7530 (H1)” (refractive index 1.530) manufactured by Sanyo Chemical Industries, Ltd. was used.

<Silicone oil (I)>
“SH200-100cs” manufactured by Toray Dow Corning Co., Ltd. was used as the silicone oil (I).

[Example 1]
23 parts of graft copolymer (D-1), 77 parts of methacrylic ester resin (G-1), 4 parts of antistatic agent (H), organic dye (manufactured by Orient Chemical Industry Co., Ltd., “NUBIAN PC-5596” ) 0.8 part was mixed and melt-kneaded at 240 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (manufactured by Ikekai Co., Ltd., “PCM30”) to prepare a thermoplastic resin composition.
Pelletize thermoplastic resin composition, mold various molded products, impact resistance, heat resistance, color development, scratch resistance, scratch resistance, antistatic property, wiping resistance, wiping resistance The squeak noise suppression effect was evaluated. The results are shown in Table 8.

[Examples 2 to 26]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the formulation was changed to those shown in Tables 8 to 10.
Pelletize thermoplastic resin composition, mold various molded products, impact resistance, heat resistance, color development, scratch resistance, scratch resistance, antistatic property, wiping resistance, wiping resistance The squeak noise suppression effect was evaluated. The results are shown in Tables 8-10.

[Comparative Examples 1-6]
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 Table 11.
Pelletize thermoplastic resin composition, mold various molded products, impact resistance, heat resistance, color development, scratch resistance, scratch resistance, antistatic property, wiping resistance, wiping resistance The squeak noise suppression effect was evaluated. The results are shown in Table 11.

Molded articles obtained with the thermoplastic resin compositions of Examples 1 to 26 were impact resistant, heat resistant, color developing properties, scratch resistance, scratch resistance, antistatic properties, wiping resistance, and wiping resistance. The sustainability and the squeak noise suppression effect were excellent.
Therefore, when the thermoplastic resin composition of the present invention is used, impact resistance, heat resistance, color development, scratch resistance, scratch resistance, antistatic properties, wiping resistance, wiping resistance, creaking It can be seen that a molded product having an excellent sound suppression effect is obtained and can be applied to uses such as interior and exterior parts of vehicles, office equipment, home appliances, and building materials.

  On the other hand, in Comparative Examples 1 to 5 in which the graft copolymer (D) does not contain an ethylene / α-olefin copolymer and in Comparative Example 6 in which the antistatic agent (H) is not blended, Impact resistance, scratch resistance, antistatic properties, wiping resistance, durability of wiping resistance, and squeak noise suppression effect were low.

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

10 Jig 11 Tip 12 Car Wash Towel 13 Molded Product ((Ma), (Me), (Mg))
21 Test piece 21a Rib structure 22 Test piece

Claims (7)

A vinyl monomer comprising at least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of an ethylene / α-olefin copolymer. A graft copolymer (D) obtained by polymerizing the body mixture (m1);
A methacrylate ester resin (G) obtained by polymerizing a vinyl-based monomer mixture (m3) containing a methacrylate ester;
A thermoplastic resin composition comprising an antistatic agent (H).   The thermoplastic resin composition according to claim 1, wherein the ethylene / α-olefin copolymer is a crosslinked ethylene / α-olefin copolymer (C).   Poly (meth) acrylic acid ester (Eb) containing polyorganosiloxane (Ea), 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 Vinyl containing at least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of a composite rubber-like polymer (E) comprising The thermoplastic resin composition according to claim 1 or 2, further comprising a graft copolymer (F) obtained by polymerizing the monomer mixture (m2).   The molded article using the thermoplastic resin composition as described in any one of Claims 1-3. A vinyl monomer comprising at least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of an ethylene / α-olefin copolymer. Polymerizing the body mixture (m1) to obtain a graft copolymer (D);
A step of polymerizing a vinyl monomer mixture (m3) containing a methacrylate ester to obtain a methacrylate ester resin (G);
A step of mixing the graft copolymer (D), the methacrylic ester resin (G), and the antistatic agent (H) to obtain a thermoplastic resin composition; Method.   The method for producing a thermoplastic resin composition according to claim 5, wherein the ethylene / α-olefin copolymer is a crosslinked ethylene / α-olefin copolymer (C). Poly (meth) acrylic acid ester (Eb) containing polyorganosiloxane (Ea), 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 Vinyl containing at least one vinyl monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester in the presence of a composite rubber-like polymer (E) comprising Further comprising the step of polymerizing the monomer mixture (m2) to obtain the graft copolymer (F),
In the step of obtaining the thermoplastic resin composition, the graft copolymer (D), the methacrylic ester resin (G), the antistatic agent (H), and the graft copolymer (F) are mixed. A method for producing a thermoplastic resin composition according to claim 5 or 6.

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