JP6954727B2 - Thermoplastic resin composition, its manufacturing method and molded product - Google Patents

Description

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

By improving the impact resistance of the molded product, not only the application of the molded product can be expanded, but also the molded product can be made thinner and larger, which makes it extremely useful in industry. .. Therefore, various methods have been proposed so far for improving the impact resistance of the molded product. Among these methods, a method of improving the impact resistance of a molded product while maintaining the characteristics derived from the hard resin by using a resin material in which a rubber polymer and a hard resin are combined 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 further hard resins. Examples thereof include a thermoplastic resin composition added to the above.

For example, the following is known as a thermoplastic resin composition capable of obtaining a molded product 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 acid ester resin which is a hard resin (Patent Document 1).

However, in the molded product made of the thermoplastic resin composition of (1), the surface specific resistance value of the molded product is high and the molded product is easily charged, so that dust and the like are likely to adhere to the molded product. Therefore, when cleaning the molded product, there is a problem that deposits such as dust become an abrasive and the surface of the molded product is easily scratched.

For example, the following is known as a thermoplastic resin composition capable of obtaining a molded product having improved impact resistance and suppressing adhesion of dust and the like while maintaining the characteristics derived from the hard resin. ..
(2) A thermoplastic resin composition obtained by adding an ASA resin and an antistatic agent to a methacrylic acid ester resin which is a hard resin (Patent Document 2).
(3) A thermoplastic resin composition obtained by adding an ABS resin, an antistatic agent, and a slidable filler to a methacrylic acid ester resin which is a hard resin (Patent Document 3).

However, in the molded product 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 product is scratched when washed. There was a problem.
In the molded product made of the thermoplastic resin composition of (3), the adhesion of dust is reduced by adding an antistatic agent. Further, the added slidable filler bleeds out to the surface of the molded product, thereby enhancing the slidability of the molded product and making it less likely to cause scratches. However, there is a problem that the bleed-out slidable filler is washed away during cleaning of the molded product, and scratches during cleaning cannot be suppressed.

Since the methacrylic acid ester resin is an amorphous 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 resin such as polyethylene, polypropylene, and polyacetal. Therefore, in a molded product containing a methacrylic acid ester resin, a stick-slip phenomenon occurs at the fitting portion of the molded product due to vibration of equipment, vibration when starting or running an automobile, contact with parts, etc., resulting in a squeak noise. 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, swing width of the dynamic friction coefficient), for example, the following has been proposed.
(4) A thermoplastic resin composition obtained by adding polyorganosiloxane as a lubricant to a methacrylic acid ester resin (Patent Document 4).

In the molded product made of the thermoplastic resin composition of (4), the lubricant added to the thermoplastic resin composition bleeds out to the surface of the molded product to improve the lubricity of the molded product and increase the coefficient of friction. Make it smaller. However, there is a problem that the bleed-out lubricant deteriorates the surface appearance of the molded product, or the lubricity deteriorates with the passage of time due to the gradual loss of the bouled-out lubricant. Further, there is a problem that dust or the like easily adheres to the molded product and is easily scratched when the molded product is washed.

Japanese Unexamined Patent Publication No. 2005-132970 Japanese Unexamined Patent Publication No. 2004-346126 Japanese Unexamined Patent Publication No. 2007-051233 Japanese Patent Application Laid-Open No. 2013-537252

INDUSTRIAL APPLICABILITY The present invention provides a thermoplastic resin composition capable of obtaining a molded product having excellent impact resistance, color development, scratch resistance, antistatic property, wipe resistance, wipe durability, and squeak noise suppressing effect, and production thereof. Provided are a method, and a molded product having excellent impact resistance, color development, scratch resistance, antistatic property, wipe resistance, wipe durability, and squeak noise suppressing effect.

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

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

It is the schematic explaining the evaluation method of the scratch resistance by the car wash towel wear. It is the schematic explaining the evaluation method of the squeak sound suppression effect.

The definitions of the following terms apply throughout the specification and claims.
"(Meta) acrylic acid" means acrylic acid or methacrylic acid.
"(Meta) acrylic acid ester" means an acrylic acid ester or a methacrylic acid ester.
The "molded article" means an article obtained by molding a thermoplastic resin composition.
"Scratch resistance" means scratch resistance (scratch resistance) to scratches (scratches) that occur when the surface of a molded product is scratched with a hard, sharp object such as a nail or pencil, and military hands and car wash towels. 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.
“Brightness (L ^* )” means ^{the lightness value (L *} ) among the color values in the ^{L *} a ^* b ^* color system adopted in JIS Z 8729.
The "SCE method" means a method of measuring color by removing specularly reflected light by an optical trap using a spectrocolorimeter compliant with JIS Z 8722.

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention contains a graft copolymer (D), a methacrylic acid ester resin (G), and an antistatic agent (H).
The thermoplastic resin composition of the present invention may contain a graft copolymer (F), another thermoplastic resin, and various additives, if necessary, as long as the effects of the present invention are not impaired.

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

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

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

The graft copolymer (F) is the following (γ).
Obtained by polymerizing a vinyl-based monomer mixture (m2) in the presence of a composite rubber-like polymer (E) composed of (γ) polyorganosiloxane (Ea) and poly (meth) acrylic acid ester (Eb). Monomer.

The methacrylic acid ester resin (G) is as follows (δ).
(Δ) A product obtained by polymerizing a vinyl-based monomer mixture (m3).
Hereinafter, each component ((A) to (H), (m1) to (m3), etc.) will be described.

<Ethylene / α-olefin copolymer (A)>
The ethylene / α-olefin copolymer (A) contains 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, it does not have a crosslinked structure.
The ethylene / α-olefin copolymer (A) may further contain unconjugated diene units.

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

Examples of non-conjugated diene include dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-cycloheptadiene, 1, Examples thereof include 5-cyclooctadiene. Of these, dicyclopentadiene and / or 5-ethylidene-2-norbornene are preferable because the obtained molded product is more excellent in impact resistance and scratch resistance.

The content of ethylene units in the ethylene / α-olefin copolymer (A) is 45 to 5 when the total of all the constituent units constituting the ethylene / α-olefin copolymer (A) is 100% by mass. 80% by mass is preferable, and 50 to 75% by mass is more preferable. When the content of ethylene units is within the above range, the balance between scratch resistance and impact resistance of the molded product is further excellent.

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

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 . When the mass average molecular weight (Mw) is within the above range, the scratch resistance, color development property, impact resistance, and squeak noise suppressing effect of the molded product are further excellent.

The molecular weight distribution (Mw / number average molecular weight (Mn)) of the ethylene / α-olefin copolymer (A) is preferably 1.0 to 5.0, more preferably 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 excellent.

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 into 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 with an α-olefin or ethylene with an α-olefin and an unconjugated diene using a metallocene catalyst or a Ziegler-Natta catalyst. Manufactured.

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

Examples of the polymerization method include a method of copolymerizing ethylene and α-olefin or ethylene, α-olefin and unconjugated 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.). As the hydrocarbon solvent, one type may be used alone, or two or more types may be mixed and used. Further, the raw material α-olefin may be used as a solvent. At the time of polymerization, a molecular weight modifier such as hydrogen may be used.

Ethylene / α-olefin copolymer by changing the reaction conditions such as the supply amount of ethylene, α-olefin, and non-conjugated diene, the type and amount of the molecular weight modifier, the type and amount of the catalyst, the reaction temperature, and the pressure. 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 olefin resin aqueous dispersion (B) is obtained by dispersing an ethylene / α-olefin copolymer (A) in an aqueous medium.
The olefin resin aqueous dispersion (B) may contain an emulsifier, an acid-modified olefin polymer, or 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 the water-miscible organic solvent 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; and polyalkylene glycol. Alkyl ethers; lactams such as N-methyl-2-pyrrolidone and the like can be mentioned. 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 emulsifiers, and examples thereof include long-chain alkylcarboxylic acid salts, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
The content of the emulsifier in the olefin resin aqueous dispersion (B) can suppress the thermal coloring of the obtained thermoplastic resin composition, and the ethylene / α-olefin copolymer weight dispersed in the olefin resin aqueous dispersion (B). From the viewpoint that the particle size of the coalescence (A) can be easily controlled, 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 olefin polymers having a mass average molecular weight of 1,000 to 5,000 modified 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 dispersion (B) of the olefin resin is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (A). When the amount of the acid-modified olefin polymer added is within the above range, the balance between scratch resistance and impact resistance of the molded product is further excellent.

The method for preparing the olefin resin aqueous dispersion (B) is not limited. As a preparation method, for example, the ethylene / α-olefin copolymer (A) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw screw extruder, etc.) to obtain a mechanical shearing force. Method of giving, dispersing and adding to an aqueous medium; (b2) The ethylene / α-olefin copolymer (A) is dissolved in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) and added to the aqueous medium. After emulsifying the polymer, the mixture is sufficiently stirred to distill off the hydrocarbon solvent. When preparing the olefin resin aqueous dispersion (B), an acid-modified olefin polymer, an emulsifier or 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 of 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 Examples thereof include a method of dissolving the copolymer (A) and the acid-modified olefin polymer in a hydrocarbon solvent.
The method for mixing 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 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 the step of melt-kneading the mixture thereof.
The method of adding the emulsifier is not particularly limited. For example, a method similar to the method for adding the acid-modified olefin polymer can be mentioned. Further, in the method (b1) or (b2), a method of adding an emulsifier to an aqueous medium, a method of dissolving an emulsifier in a hydrocarbon solvent in the method (b2), and the like can be mentioned.

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

As a method for controlling the volume average particle size of the ethylene / α-olefin copolymer (A) dispersed in the olefin resin aqueous dispersion (B), the type or amount of the emulsifier and the type of the acid-modified olefin polymer Alternatively, a method of adjusting the content, the shearing force applied during kneading, the temperature conditions, and the like can be mentioned.

<Cross-linked 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 on the ethylene / α-olefin copolymer (A). By having a crosslinked structure, the impact resistance of the molded product is further excellent.

The gel content of the crosslinked ethylene / α-olefin copolymer (C) is preferably 35 to 75% by mass, more preferably 40 to 70% by 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) was dried with respect to the crosslinked ethylene / α-olefin copolymer (C) before swelling when it was swollen with toluene. The proportion of toluene insoluble. More specifically, it is obtained by the method described in the examples.

The crosslinked ethylene / α-olefin copolymer (C) is obtained by crosslinking the ethylene / α-olefin copolymer (A) or the olefin resin aqueous dispersion (B).
The cross-linking treatment of the ethylene / α-olefin copolymer (A) or the aqueous dispersion of the olefin resin (B) can be carried out by a known method. Examples of the method of the cross-linking treatment include (a) a method of adding an organic peroxide and a polyfunctional compound as needed to carry out the cross-linking treatment, and (b) a method of carrying out the cross-linking treatment with ionizing radiation. Therefore, the method (a) is preferable from the viewpoint of impact resistance and color development of the molded product.

Specifically, as the method (a), an ethylene / α-olefin copolymer (A) or an olefin resin aqueous dispersion (B) is mixed with an organic peroxide and, if necessary, a polyfunctional compound. Examples thereof include a method of adding and heating the mixture.
For example, when an organic peroxide and, if necessary, a polyfunctional compound are added to the ethylene / α-olefin copolymer (A), melt-kneaded, and pulverized, the crosslinked ethylene / α-olefin copolymer is obtained. The 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 cross-linking treatment, the cross-linked ethylene / α-olefin copolymer (C) aqueous dispersion is obtained. can get.
The gel content of the crosslinked ethylene / α-olefin copolymer (C) can be adjusted by adjusting the addition amount of the organic peroxide and the polyfunctional compound, the heating temperature, the heating time, and the like.
The heating temperature depends on the type of 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 peroxyester compound, a peroxyketal compound, a dialkylperoxide compound and the like. As the organic peroxide, one type may be used alone, or two or more types may be used in combination.

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 thereof include cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3 and the like.

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

The polyfunctional compound is used in combination with an organic peroxide, if necessary, in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C).
Examples of the polyfunctional compound include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene methacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate and the like. Divinylbenzene is preferable because the gel content can be easily adjusted. As the polyfunctional compound, one type may be used alone, or two or more types may be used in combination.

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

When the ethylene / α-olefin copolymer (A) is crosslinked to obtain a crosslinked ethylene / α-olefin copolymer (C), the ethylene / α-olefin copolymer (A) contains an acid-modified olefin polymer. It may be added.
The acid-modified olefin polymer is the same as that mentioned in the description of the olefin resin aqueous 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 olefin resin aqueous dispersion (B) with respect to 100 parts by mass of the ethylene / α-olefin copolymer (A). 1 to 40 parts by mass is preferable.
The method of adding the acid-modified olefin polymer is not limited. The ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer may be mixed and then subjected to a cross-linking treatment, or the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer may be mixed. Each may be crosslinked and then mixed.
The method for mixing 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 screw extruder and the like.

The volume average particle size of the crosslinked ethylene / α-olefin copolymer (C) or the volume average particle size of the crosslinked ethylene / α-olefin copolymer (C) in the aqueous dispersion is the impact resistance of the molded product. From the viewpoint of excellent color development, 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 size does not change with respect to the average particle size of the ethylene / α-olefin copolymer (A) in the aqueous dispersion (B) of the olefin resin.
When the graft copolymer (D) is obtained by using an aqueous dispersion of the 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 directly indicates the average particle size of the crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition.

<Vinyl-based single-volume mixture (m1)>
The vinyl-based monomer mixture (m1) contains at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters as monomers.
The vinyl-based monomer mixture (m1) may further contain other vinyl-based 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-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Styrene and α-methylstyrene are preferable from the viewpoint of color development and impact resistance of the molded product. One type of aromatic vinyl compound may be used alone, or two or more types may be used in combination.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the vinyl cyanide compound, one type may be used alone, or two or more types may be used in combination.

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

Examples of other vinyl-based monomers include maleimide-based compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like. As the other vinyl-based monomer, one type may be used alone, or two or more types may be used in combination.

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

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

The content of the vinyl cyanide compound is preferably 15 to 40% by mass, more preferably 20 to 38% by mass, based on the total mass (100% by mass) of the vinyl-based monomer mixture (m1). When the content of the vinyl cyanide compound is within the above range, the color development property and impact resistance of the molded product are further excellent.

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

The graft copolymer (D) contains 20 to 50% by mass of the vinyl-based monomer mixture (m1) in the presence of 50 to 80% by mass of the ethylene / α-olefin copolymer (however, both ethylene and α-olefin). The total of the polymer and the vinyl-based monomer mixture (m1) is 100% by mass), which is preferably obtained by copolymerizing. When the content ratio of the ethylene / α-olefin copolymer is 50 to 80% by mass, the physical property balance of impact resistance and color development of the molded product is further excellent.

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 development 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 simple polymer 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 polymer mixture (m1). For example, the above (α1), (α2), (β1), and (β2) can be obtained by the following methods (α1'), (α2'), (β1'), and (β2'), respectively.
(Α1') A method of polymerizing a vinyl-based monomer mixture (m1) in a solution containing an ethylene / α-olefin copolymer (A).
(Α2') A method of polymerizing a vinyl-based monomer mixture (m1) in an olefin resin aqueous dispersion (B) containing an ethylene / α-olefin copolymer (A).
(Β1') A method of polymerizing a vinyl-based monomer mixture (m1) in a solution containing a crosslinked ethylene / α-olefin copolymer (C).
(Β2') A method of polymerizing a vinyl-based monomer mixture (m1) in an aqueous dispersion containing a crosslinked ethylene / α-olefin copolymer (C).

Examples of the polymerization method of the vinyl-based monomer mixture (m1) include known polymerization methods (emulsification polymerization method, solution polymerization method, suspension polymerization method, massive polymerization method, etc.).

As a method for producing the graft copolymer (D) by the emulsion polymerization method, for example, a mixture of a vinyl-based monomer mixture (m1) and an organic peroxide is dispersed in an aqueous solution of an ethylene / α-olefin copolymer. Examples thereof include a method of continuously adding to a body (for example, an aqueous dispersion of an olefin resin aqueous dispersion (B) or an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (C)).
The polymerization conditions for emulsion polymerization are not particularly limited, and examples thereof include polymerization conditions at 50 to 90 ° C. for 1.5 to 3.5 hours.
The organic peroxide is preferably used as a redox-based initiator in which the organic peroxide, the transition metal, and the reducing agent are combined.
At the time of polymerization, a chain transfer agent, an emulsifier or the like may be used depending on the situation.

As a redox-based initiator, it is not necessary to keep the polymerization reaction conditions at a high temperature, deterioration of the ethylene / α-olefin copolymer can be avoided, and deterioration of the impact resistance of the molded product can be avoided. A combination of the product and a ferrous sulfate-chelating agent-reducing agent is preferable.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide and the like.
The redox-based initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of the chain transfer agent include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allyl sulphonic acid, metaallyl sulphonic acid, etc.). , Α-Methylstyrene dimer and the like, and mercaptans are preferable because the molecular weight can be easily adjusted. One type of chain transfer agent may be used alone, or two or more types may be used in combination.
The method of adding the chain transfer agent may be batch, split, or continuous.
The amount of the chain transfer agent added 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, amphoteric surfactants and the like.
Examples of the anionic surfactant include sulfate esters of higher alcohols, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, amino acid derivative salts and the like.
Examples of the nonionic surfactant include an alkyl ester type, an alkyl ether type, and an alkyl phenyl ether type of ordinary polyethylene glycol.
Examples of the amphoteric surfactant include those having a carboxylate, a sulfate ester salt, a sulfonate, a phosphate ester salt and the like in the anion portion, and an amine salt, a quaternary ammonium salt and the like 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-based 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 precipitate is added to the aqueous dispersion, heated and stirred, and then the precipitate is separated. Examples thereof include a precipitation method in which the precipitated graft copolymer (D) is washed with water, dehydrated, and dried.
Examples of the precipitant include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate and the like. As the precipitate, one type may be used alone, or two or more types may be used in combination.
If necessary, an antioxidant may be added to the aqueous dispersion containing the graft copolymer (D).

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. Examples thereof include a method of adding a polymerization initiator and a vinyl-based monomer mixture (m1) to a solution in which (C)) is dissolved in a solvent.
As the solvent, an inert polymerization solvent used in ordinary radical polymerization can be used, for example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methylethylketone and acetone, and halogens such as dichloromethylene and carbon tetrachloride. Examples include chemical hydrocarbons.
As the polymerization initiator used for solution polymerization, a general initiator can be used, and examples thereof include organic peroxides such as ketone peroxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and hydroperoxides. Be done.
The method of adding the polymerization initiator is not particularly limited, and examples thereof include a method of adding the polymerization initiator collectively or continuously.

As the graft copolymer (D), one type may be used alone, or two or more types may be used in combination.

<Polyorganosiloxane (Ea)>
The polyorganosiloxane (Ea) is not particularly limited, but a polyorganosiloxane having a vinyl polymerizable functional group is preferable, and the polyorganosiloxane contains a vinyl polymerizable functional group with respect to the total number of moles of all the constituent units constituting the polyorganosiloxane. Siloxane containing 0.3 to 3 mol% of siloxane unit and 97 to 99.7 mol% of dimethylsiloxane unit, and having 3 or more siloxane bonds with respect to the total number of moles of total silicon atoms in polydimethylsiloxane. Polyorganosiloxane having 1 mol% or less of atoms is more preferable.

Examples of the dimethylsiloxane constituting the polyorganosiloxane (Ea) include a dimethylsiloxane-based cyclic body having a 3-membered ring or more. Of these, those with a 3-membered ring to a 7-membered ring are preferable. Specific examples thereof 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 taken into consideration. Then, an alkoxysilane compound having a vinyl polymerizable functional group is preferable. Specifically, β-methacryloyloxyethyl dimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, Methacryloyloxysiloxane such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane, vinylphenylsiloxane such as p-vinylphenyldimethoxymethylsilane, etc. Can be 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 cross-linking agent as a constituent component, if necessary.
Examples of the siloxane-based cross-linking agent include trifunctional or tetra-functional silane-based cross-linking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The method for producing polyorganosiloxane (Ea) is not limited. For example, it can be produced by the following method.
First, a siloxane-based cross-linking agent was added to the siloxane mixture composed of dimethylsiloxane and 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. Obtain an aqueous dispersion of a siloxane mixture. Next, using a homomixer that atomizes by the shearing force of high-speed rotation, a homogenizer that atomizes by the jet output of a high-pressure generator, etc., the aqueous dispersion of the siloxane mixture is subjected to the atomization treatment to disperse the aqueous dispersion of the siloxane mixture. The dispersed particles (siloxane mixture) in the body are made into fine particles. Here, it is preferable to use a high-pressure emulsifying device such as a homogenizer because the distribution of the particle size of the polyorganosiloxane (Ea) becomes small. Next, the aqueous dispersion of the siloxane mixture treated for micronization is added to an aqueous acid solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction solution is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash, or sodium carbonate to terminate the polymerization, thereby obtaining an aqueous dispersion in which polyorganosiloxane (Ea) is dispersed in the aqueous dispersion.

In the production of the polyorganosiloxane (Ea), an anionic emulsifier is preferable as the 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 a solid content) of the siloxane mixture.

Examples of the acid catalyst used for the polymerization include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid and aliphatic substituted naphthalene sulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid and nitrate. These acid catalysts can be used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable because it is excellent in stabilizing the aqueous dispersion of polyorganosiloxane (Ea). Further, 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 development property of the thermoplastic resin composition as much as possible. It can be suppressed.

The volume average particle size of the polyorganosiloxane (Ea) in the aqueous dispersion is excellent in color development and scratch resistance of the molded product, and the viscosity and coagulation of the aqueous dispersion when producing the polyorganosiloxane (Ea) are increased. Since the generation of lumps (coagulum) can be prevented, 0.01 to 0.09 μm is preferable, and 0.02 to 0.08 μm is more preferable.
As a method for controlling the volume average particle size of the polyorganosiloxane (Ea), for example, the method described in JP-A-5-279434 can be adopted.

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

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 aromatic hydrocarbon groups such as phenyl group and benzyl group. Can be mentioned. As the (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 cross-linking agent improve the impact resistance and color development of the molded product, respectively.
Examples of the cross-linking agent include dimethacrylate compounds, and specific examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.
Examples of the graft crossing agent include allyl compounds, specifically, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like.

The total amount of the units derived from the cross-linking agent and the units derived from the graft cross-linking agent in the poly (meth) acrylic acid ester (Eb) is excellent in impact resistance and color development of the molded product, and during the production of the graft copolymer (F). Of the total 100% by mass of all the units constituting the poly (meth) acrylic acid ester (Eb), 0.1 to 5% by mass is preferable, and 0.2 to 5% by mass, because the amount of agglomerates (coagulum) is reduced. 3% by mass is more preferable, and 0.5 to 2% by mass is further preferable.

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

The content of the polyorganosiloxane (Ea) with respect to the total mass (100% by mass) of the composite rubber-like polymer (E) is preferably 1 to 20% by mass, more preferably 3 to 18% by mass. When the content of polyorganosiloxane (Ea) is at least the lower limit of the above range, the impact resistance and scratch resistance of the molded product are more excellent, and when it is at least the upper limit of the above range, the impact resistance is more excellent. ..

The method for producing the composite rubber-like polymer (E) is not particularly limited. For example, a method for heteroaggregating or co-enhancing an aqueous dispersion of polyorganosiloxane (Ea) and an aqueous dispersion of poly (meth) acrylic acid ester (Eb) produced separately, an aqueous dispersion of polyorganosiloxane (Ea). Examples thereof include a method of forming a polymer of the other in one of the dispersion and the aqueous dispersion of the poly (meth) acrylic acid ester (Eb) to form a composite. By these methods, an aqueous dispersion of the composite rubber-like polymer (E) can be obtained.
As a method for producing the composite rubber-like polymer (E), since the molded product is more excellent in impact resistance and color development, a (meth) acrylic acid ester-based simple substance is used in an aqueous dispersion of polyorganosiloxane (Ea). A method of emulsion polymerization of a monomer mixture containing a weight and one or both of a cross-linking agent and a graft cross-linking agent is preferable. For example, at room temperature, an emulsifier and the monomer mixture are added to an aqueous dispersion of polyorganosiloxane (Ea) to raise the temperature to 40 to 80 ° C., and a radical polymerization initiator is added to 0.5 to 3 By polymerizing for about a time, an aqueous dispersion of the composite rubber-like polymer (E) can be obtained.

Preferred specific examples of emulsifiers used in emulsification polymerization are 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 thereof include dipotassium acid acid, sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkyl phenyl ether sulfate and the like.
As the emulsifier, an acid-type emulsifier having two or more functional groups in one molecule or a salt thereof is preferable from the viewpoint of further suppressing gas generation during 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-based initiators, and redox-based initiators in which an oxidizing agent and a reducing agent are combined. Of these, a redox-based initiator is preferable, and a sulfoxylate-based initiator that combines ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalit, and hydroperoxide is particularly preferable.

The volume average particle size of the composite rubber-like polymer (E) dispersed in the aqueous dispersion is preferably 0.05 to 0.18 μm, preferably 0.07, from the viewpoint of excellent impact resistance and color development of the molded product. ~ 0.15 μm is more preferable.
The method for controlling the volume average particle size of the composite rubber-like polymer (E) is not particularly limited, and examples thereof include a method for adjusting the type or amount of the emulsifier used.
When the graft copolymer (F) is obtained by using the aqueous dispersion of the composite rubber-like polymer (E), the average particles of the composite rubber-like polymer (E) in the aqueous dispersion. It has been confirmed by image analysis of an electron microscope that the diameter directly indicates the volume average particle size of the composite rubber-like polymer (E) in the thermoplastic resin composition.

<Vinyl-based single-volume mixture (m2)>
The vinyl-based monomer mixture (m2) contains at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters as monomers.
The vinyl-based monomer mixture (m2) may further contain other vinyl-based 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-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. From the viewpoint of impact resistance, styrene and α-methylstyrene are preferable. One type of aromatic vinyl compound may be used alone, or two or more types may be used in combination.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the vinyl cyanide compound, one type may be used alone, or two or more types may be used in combination.

Examples of (meth) acrylic acid esters include acrylic acid esters (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.) and methacrylic acid esters (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc.). Etc.), etc., and methyl methacrylate is preferable from the viewpoint of color development and impact resistance of the molded product. As the (meth) acrylic acid ester, one type may be used alone, or two or more types may be used in combination.

Examples of other vinyl-based monomers include maleimide-based compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like. As the other vinyl-based monomer, one type may be used alone, or two or more types may be used in combination.

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

In the vinyl-based monomer mixture (m2), the content of the aromatic vinyl compound is preferably 60 to 85% by mass, preferably 62 to 85% by mass, based on the total mass (100% by mass) of the vinyl-based monomer mixture (m2). 80% by mass is more preferable. When the content of the aromatic vinyl compound is within the above range, the color development property and impact resistance of the molded product are further excellent.

The content of the vinyl cyanide compound is preferably 15 to 40% by mass, more preferably 20 to 38% by mass, based on the total mass (100% by mass) of the vinyl-based monomer mixture (m2). When the content of the vinyl cyanide compound is within the above range, the color development property and impact resistance of the molded product are further excellent.

<Graft copolymer (F)>
The graft copolymer (F) is obtained by polymerizing a vinyl-based 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-based monomer mixture (m2) are polymerized. That is, there is a situation (impossible / impractical situation) in which the graft copolymer (F) cannot be directly specified by its structure or property, or is almost impractical. Therefore, it is more appropriate to define "the product obtained by polymerizing the vinyl-based monomer component (m2) in the presence of the composite rubber-like polymer (E)".

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

The graft copolymer (F) is obtained by polymerizing a vinyl-based monomer mixture (m2) in the presence of the composite rubber-like polymer (E).
Examples of the polymerization method of the vinyl-based monomer mixture (m2) include an emulsion polymerization method.
In the production of the graft copolymer (F) by the emulsion polymerization method, for example, a vinyl-based monomer mixture (m2) is added to an aqueous dispersion of the composite rubber-like polymer (E), and a vinyl-based simple polymer is produced in the presence of an emulsifier. This can be done by radically polymerizing the monomer mixture (m2). As a result, an aqueous dispersion of the graft copolymer (F) is obtained.
During 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 thereof include polymerization conditions at 60 to 90 ° C. for 1 to 4 hours.

Examples of the radical polymerization initiator used in the radical polymerization include peroxides, azo-based initiators, and redox-based initiators in which an oxidizing agent and a reducing agent are combined. Of these, a redox-based initiator is preferable, and a sulfoxylate-based initiator that combines ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalit, and hydroperoxide is particularly preferable.

Examples of the emulsifier include the same emulsifiers used when the composite rubber-like polymer (E) is produced by the 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 polymerizing the vinyl-based monomer mixture (m2), and if necessary, the vinyl-based polymer is used. An emulsifier may be added during the polymerization of the monomer mixture (m2).

As a method for recovering the graft copolymer (F) from the aqueous dispersion of the graft copolymer (F), (i) the aqueous dispersion of the graft copolymer (F) in hot water in which a coagulant is dissolved. (Wet method), (ii) Semi-direct grafting by spraying an aqueous dispersion of the graft copolymer (F) in a heated atmosphere. Examples thereof include a method of recovering the copolymer (F) (spray dry method).

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

As a method for obtaining the dry graft copolymer (F) from the slurry-state graft copolymer (F), the emulsifier residue remaining in the slurry is eluted in water by washing, and then the following (i-1) is used. ) Or the method of performing the process of (i-2).
(I-1) The slurry is dehydrated with a centrifugal dehydrator or a press dehydrator, and further dried with an air flow dryer or the like.
(I-2) Dehydration and drying of the slurry are simultaneously carried out with a squeezing dehydrator, an extruder or the like.
After drying, the graft copolymer (F) is obtained in powder or particulate form. Further, the graft copolymer (F) discharged from the extrusion dehydrator or extruder can be directly sent to an extruder or molding machine for producing a thermoplastic resin composition.

As the graft copolymer (F), one type may be used alone, or two or more types may be used in combination.

<Vinyl-based monomer mixture (m3)>
The vinyl-based monomer mixture (m3) contains at least a methacrylic acid ester as a monomer.
The vinyl-based monomer mixture (m3) is selected from the group consisting of maleimide-based compounds, aromatic vinyl compounds, acrylic acid esters, and other vinyl-based monomers that can coweight with methacrylic acid esters, if necessary. It may further contain at least one vinyl-based monomer obtained.

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, and amyl methacrylate. Examples thereof include isoamyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate and the like. It is preferable to contain at least one of methyl methacrylate and ethyl methacrylate from the viewpoint of further excellent heat resistance and impact resistance of the molded product. As the methacrylic acid ester, one type may be used alone, or two or more types may be used in combination.

Examples of maleimide-based compounds include N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-i-propylmaleimide, Nn-butylmaleimide, N-i-butylmaleimide). , N-t-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 excellent heat resistance and impact resistance of the molded product. One type of maleimide-based compound may be used alone, or two or more types may be used in combination.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Styrene and α-methylstyrene are preferable from the viewpoint of further excellent heat resistance and impact resistance of the molded product. One type of aromatic vinyl compound may be used alone, or two or more types may be used in combination.

Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and the like. Methyl acrylate is preferable because the heat resistance and impact resistance of the molded product are further excellent. As the acrylic acid ester, one type may be used alone, or two or more types may be used in combination.

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

When better heat resistance is required for the molded product, the vinyl-based monomer mixture (m3) may further contain one or both of the maleimide-based compound and the aromatic vinyl compound in addition to the methacrylic acid ester. It is preferable to include it.

In the vinyl-based monomer mixture (m3), the content of the methacrylic ester is excellent in scratch resistance, color development, wiping resistance, and squeak noise suppressing effect of the molded product, and thus the vinyl-based monomer mixture. It is preferably 50 to 100% by mass with respect to the total mass (100% by mass) of (m3).

The vinyl-based monomer mixture (m3) contains a methacrylic ester content of 50 to 98% by mass and a maleimide-based compound with respect to the total mass (100% by mass) of the vinyl-based monomer mixture (m3). 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. When the content of each of the methacrylic acid ester, the maleimide compound, and the aromatic vinyl compound is within the above range, the scratch resistance, color development property, wiping scratch resistance, squeak noise suppressing effect, and heat resistance of the molded product are further excellent. ..

<Methacrylic acid ester resin (G)>
The methacrylic ester resin (G) is obtained by polymerizing a vinyl-based monomer mixture (m3), and contains at least a unit derived from the methacrylic ester.

The content of the unit derived from methacrylic acid ester in the methacrylic acid ester resin (G) is excellent in scratch resistance, color development, wiping resistance, and squeak noise suppressing effect of the molded product, and thus the methacrylic acid ester resin (G). ) Is preferably 50 to 100% by mass with respect to the total mass (100% by mass) of all the units constituting the above.

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

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

The methacrylic ester resin (G) is obtained by polymerizing a vinyl-based monomer mixture (m3).
The polymerization method of the vinyl-based monomer mixture (m3) is not particularly limited. Examples of the polymerization method include known polymerization methods (emulsification polymerization method, suspension polymerization method, solution polymerization method, etc.).

As a method for producing the methacrylic ester resin (G) by the emulsion polymerization method, for example, a vinyl monomer mixture (m3), an emulsifier, a polymerization initiator and a chain transfer agent are charged in a reactor and heated for polymerization. Then, a method of recovering the methacrylic ester resin (G) from the aqueous dispersion containing the methacrylic ester resin (G) by a precipitation method can be mentioned.
The polymerization conditions of emulsion polymerization are not particularly limited, and examples thereof include polymerization conditions of 40 to 120 ° C. for 1 to 15 hours.
Examples of the emulsifier include ordinary emulsifiers for emulsion polymerization (potassium rosinate, sodium alkylbenzene sulfonate, etc.).
Examples of the polymerization initiator include organic and inorganic peroxide-based initiators.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimers, terpenes and the like.
As the precipitation method, the same method as when recovering the graft copolymer (D) from the aqueous dispersion can be adopted.

As a method for producing the methacrylic ester resin (G) by the suspension polymerization method, for example, a vinyl-based monomer mixture (m3), a suspending agent, a suspending aid, a polymerization initiator, and a chain transfer agent are used in the reactor. Examples thereof include a method in which the mixture is charged, heated to polymerize, the slurry is dehydrated and dried, and the methacrylic ester resin (G) is recovered.
The polymerization conditions of suspension polymerization are not particularly limited, and examples thereof include polymerization conditions of 40 to 120 ° C. for 1 to 15 hours.
Examples of the suspending agent include tricalcium phosphite, polyvinyl alcohol and the like.
Examples of the suspension aid include sodium alkylbenzene sulfonate and the like.
Examples of the polymerization initiator include organic peroxides.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimers, terpenes and the like.

As the methacrylic acid ester resin (G), one type may be used alone, or two or more types may be used in combination.

<Antistatic agent (H)>
Examples of the antistatic agent (H) include a surfactant, a conductive filler, a quaternary ammonium salt, a polymer antistatic agent and the like.
Among the above, the antistatic agent (H) has excellent sustainability of the antistatic effect, excellent heat resistance in compounding by melting and kneading with the resin component, and can impart antistatic property by adding a small amount. , Polymer antistatic agents are preferred.

The polymer antistatic agent is not particularly limited, and examples thereof include block copolymers having either or both of a polyolefin-based block and a polyamide-based block and a hydrophilic block.

The polyolefin-based block contains a unit derived from an olefin-based monomer.
As the polyolefin-based monomer, an olefin having 2 to 6 carbon atoms is preferable, and examples thereof include ethylene, propylene, and 1-butene. Of these olefins, at least one selected from ethylene and propylene is preferable, and at least propylene is particularly preferable.
The proportion of propylene in the olefin-based monomer is preferably 80 mol% or more, particularly preferably 90 mol% or more, based on the total number of moles (100 mol%) of the olefin-based monomer.
In the polyolefin-based block, the content of the unit derived from the olefin-based monomer is preferably 80 mol% or more, preferably 90 mol% or more, based on the total number of moles (100 mol%) of all the units constituting the polyolefin-based block. Especially preferable.
The number average molecular weight of the polyolefin-based block is preferably 2000 to 50000, more preferably 3000 to 40,000, and even more preferably 5000 to 30000.

Examples of the polyamide-based block include a block obtained by condensation of a diamine and a dicarboxylic acid, a block obtained by condensation of an aminocarboxylic acid, a block obtained by ring-opening polymerization of lactam, and a copolymerization block obtained from these components. And so on.
Examples of the diamine include aliphatic diamines having 4 to 20 carbon atoms such as hexamethylenediamine. 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-aminocaproic acid and 12-aminododecanoic acid.
Examples of the lactam include lactam having 4 to 20 carbon atoms such as caprolactam.

Examples of the hydrophilic block include a polyether polymer (or a nonionic polymer), a cationic polymer, an anionic polymer and the like.
As the hydrophilic monomer constituting the hydrophilic block, an 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, as the hydrophilic block, polyalkylene oxide is preferable. As the polyalkylene oxide, a polyalkylene oxide having 2 to 6 carbon atoms is preferable, and a polyalkylene oxide having 2 to 4 carbon atoms is more preferable. 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-based 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 the polyolefin with a denaturing agent and then introducing a hydrophilic block. For example, it is introduced by modifying polyolefin with a denaturing agent to introduce an active hydrogen atom, and then adding and polymerizing a hydrophilic monomer such as alkylene oxide. Examples of such modifiers include unsaturated carboxylic acids or anhydrides thereof (such as (maleic anhydride) maleic acid), lactams or aminocarboxylic acids (such as caprolactam), oxygen or ozone, and hydroxylamines (such as 2-aminoethanol). , Diamine (ethylenediamine, etc.), a mixture of two or more of these, and the like.
An antistatic agent having such a polyolefin-based block and a hydrophilic block can be obtained from, for example, Sanyo Chemical Industries, Ltd. under the trade name "Perestat 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 functional groups at both ends and a polyether polymer with a glycidyl ether compound (for example, bisphenol A glycidyl ether or the like).
Antistatic agents having such a polyamide block and a hydrophilic block are, for example, from Sanyo Chemical Industries, Ltd. under the trade names "Perestat (registered trademark) NC6321", "Perestat NC7530", and "Perectron (registered trademark) AS". 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.

One of these antistatic agents may be used alone, or two or more thereof may be used in combination.
Among these antistatic agents, a block copolymer having a polyamide-based block and a hydrophilic-based block is preferable. In particular, a polyether ester amide is preferable because it has good compatibility with the methacrylic acid ester resin (G) and has good color development due to its close refractive index. As such an antistatic agent, for example, it can be obtained from Sanyo Chemical Industries, Ltd. under the trade names "Perestat (registered trademark) NC6321", "Perestat NC7530", and "Perectron 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 from the viewpoint of excellent color development. 0 to 0.03 is more preferable, and 0 to 0.01 is even more preferable.
When the refractive index of the methacrylic acid ester resin (G) is larger than the refractive index of the polyether ester amide, the color development property tends to deteriorate. Therefore, the refractive index of the polyether ester amide is the refractive index of the methacrylic acid ester resin (G). Preferably greater than or equal to.
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 thereof include allylate, liquid crystal polyester, polyethylene, polypropylene, fluororesin, polyamide (for example, nylon) and the like.

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

<Contents of each component>
In the thermoplastic resin composition, the ethylene / α-olefin copolymer (ethylene / α-olefin copolymer (A) or the 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. It is preferably 30 to 70% by mass, more preferably 30 to 70% by mass.
The ratio of the composite rubber-like polymer (E) to the total mass (100% by mass) of the ethylene / α-olefin copolymer and the composite rubber-like polymer (E) is preferably 15 to 99% by mass. More preferably, it is 30 to 70% by mass.
When the ratios of the ethylene / α-olefin copolymer and the composite rubber-like polymer (E) are within the above ranges, the molded product has impact resistance, color development, scratch resistance, wiping scratch resistance, and squeak. The 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 property, and scratch resistance of the molded product. From the viewpoint of excellent balance, 5 to 25% by mass is preferable, and 10 to 20% by mass is more preferable with respect to the total mass (100% by mass) of the thermoplastic resin composition.

The total content of the graft copolymer (D) and the graft copolymer (F) has an excellent balance of impact resistance, heat resistance, color development property, and scratch resistance of the molded product, and thus has a graft copolymer weight. 7 to 50% by mass is preferable, and 14 to 40% by mass is more preferable with respect to the total mass (100% by mass) of the coalescence (D), the graft copolymer (F) and the methacrylic acid ester resin (G).
When the total mass of the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester resin (G) does not include the graft copolymer (F), the graft copolymer (D) ) And the total mass of the methacrylic acid ester resin (G) (the same applies hereinafter).

The content of the methacrylic acid ester resin (G) is excellent in the balance of impact resistance, heat resistance, color development property, and scratch resistance of the molded product, and thus the graft copolymer (D) and the graft copolymer (F). ) And the methacrylic acid ester resin (G), 93 to 50% by mass is preferable, and 86 to 60% by mass is more preferable with respect to the total mass (100% by mass).

The content of the antistatic agent (H) is excellent in the balance between wiping scratch resistance, squeak noise suppressing effect, impact resistance, color development property, and antistatic property of the molded product, and thus the graft copolymer (D) and the graft. 5 to 20 parts by mass is preferable, and 8 to 16 parts by mass is more preferable with respect to 100 parts by mass of the total of the copolymer (F) and the methacrylic acid ester resin (G).

<Volume average particle size>
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 μm, more preferably 0.3 to 0.5 μm, from the viewpoint of excellent impact resistance and color development 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 0.05 to 0.05 because the molded product is excellent in impact resistance and color development. 0.18 μm is preferable, and 0.07 to 0.15 μm is more preferable.

<Manufacturing method of thermoplastic resin composition>
The thermoplastic resin composition of the present invention comprises a graft copolymer (D), a methacrylate ester resin (G), an antioxidant (H), and other components (graft copolymer (F)) as required. ), Other thermoplastic resins, additives).
As the graft copolymer (D), the methacrylic acid 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 a vinyl-based monomer mixture (m1) containing at least one of the above-mentioned vinyl-based monomers; and a vinyl-based monomer mixture containing a methacrylate ester (m3). ) Is contained in the methacrylic acid ester resin (G) obtained by polymerizing; and the antistatic agent (H). It is possible to obtain a molded product having excellent scratch durability and squeak noise suppressing effect. Further, if a specific copolymer composition (for example, the composition described in paragraph 0119) is used as the methacrylic acid ester resin (G), the heat resistance is also excellent. Further, even if heat resistance is imparted to the molded product, the impact resistance is not impaired.
Since the thermoplastic resin composition of the present invention can obtain a molded product having excellent scratch resistance, wipe resistance, durability of wipe resistance, and squeak noise suppressing effect, it can also be used in vehicle interior / exterior parts. It is possible.

"Molding"
The molded product of the present invention is obtained by molding the thermoplastic resin composition of the present invention by a known molding method.
Examples of the molding method include an injection molding method, a press molding method, an extrusion molding method, a vacuum forming method, a blow molding method and the like.
Examples of the use of the molded product include vehicle interior / exterior parts, office equipment, home appliances, building materials, etc., and vehicle interior / exterior parts are preferable.

Since the molded product of the present invention described above uses the thermoplastic resin composition of the present invention, it has impact resistance, color development, scratch resistance, antistatic property, wipe resistance, and wipe resistance. Has excellent sustainability and squeak noise suppression effect. Further, if a methacrylic acid ester resin (G) having a specific copolymer composition is used, the heat resistance is also excellent.

Specific examples will be shown below. However, the present invention is not limited to these examples.
In the following, "%" means "mass%" and "parts" means "parts by mass".
Various measurement and evaluation methods in the following examples and comparative examples are as follows.

<Measurement method of mass average molecular weight (Mw) and 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), using o-dichlorobenzene (145 ° C.) as a solvent, mass average in terms of polystyrene The molecular weight (Mw) and the number average molecular weight molecular weight (Mn) were measured, and the molecular weight distribution (Mw / Mn) was calculated.

<Measurement method of acid value>
The acid value was measured according to JIS K 2501.

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

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

<Measurement method of graft rate>
1 g of the graft copolymer (D) was added to 80 mL of acetone, heated and refluxed at 65 to 70 ° C. for 3 hours, and the obtained suspended acetone solution was placed in a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.). Then, the mixture was centrifuged at 14,000 rpm for 30 minutes to separate a precipitate component (acetone insoluble component) and an acetone solution (acetone soluble component). Then, the precipitated component (acetone insoluble component) was dried, its mass (Y (g)) was measured, and the graft ratio was calculated from the following formula (2). In the formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (D), and X is the total mass (g) of the graft copolymer (D) used in determining Y. The rubber content is the solid content of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) of the graft copolymer (D).
Graft ratio (%) = {(YX x rubber fraction) / (X x rubber fraction)} x 100 ... (2)

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

<Creation of molded products for physical property evaluation 1>
The thermoplastic resin composition is injection-molded by an injection molding machine (manufactured by 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. to 100 × 100 mm (100 × 100 mm). A black colored plate having a thickness of 3 mm) was obtained. This was designated as a molded product (Ma).

<Creation of molded products for physical property evaluation 2>
The thermoplastic resin composition is injection-molded by an injection molding machine (manufactured by 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., and has a length of 80 mm and a width of 80 mm. A molded product for measuring the deflection temperature under load with a thickness of 10 mm and a thickness of 4 mm was obtained. This was designated as a molded product (Ma2).

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

<Evaluation of color development>
^{The brightness 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). ^{Let L *} measured in this way be "L ^* (ma)". The ^{lower the L *} , the blacker the color, and the better the color development.

<Evaluation of impact resistance: Measurement of falling ball impact strength>
A molded product (Ma) whose temperature was adjusted to −30 ° C. was used as a sample, and the impact strength of falling balls was measured for each of the three samples. A steel ball weighing 200 g was dropped from a height of 10 cm, and if it did not crack, the drop height was increased every 10 cm to check for cracks and cracks. The drop height at which two or more cracks or cracks did not occur in the three samples was defined as the drop impact height. The higher the impact height of the falling ball, the better the impact resistance.

<Evaluation of scratch resistance>
Using a pencil hardness tester, a pencil with a hardness of 3H is pressed against the surface of the molded product (Ma) with a load of 750 g (7.35N), and in that state, the molded product (Ma) is moved by about 5 cm to form the product. The surface of the product (Ma) was scratched with a pencil to scratch the molded product (Ma). A product (Mb) in which the molded product (Ma) was scratched was designated as a molded product (Mb). ^{The brightness L *} of the surface of the scratched molded product (Mb) was measured by the SCE method using a spectrocolorimeter. ^{Let L *} measured in this way be "L ^* (mb)".

(Judgment of scratch resistance)
^{The determination index ΔL *} (mb-ma) for the conspicuousness of scratches on the molded product (Mb) was calculated from the following formula (3). The ^{larger the absolute value of ΔL *} (mb-ma), the more conspicuous the scratches are.
ΔL ^* (mb-ma) = L ^* (mb) -L ^* (ma) ・ ・ ・ (3)

When ^{the absolute value of ΔL *} (mb-ma) is 3.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When ^{the absolute value of ΔL *} (mb-ma) is more than 3.0 to 7.0 or less, the scratches are inconspicuous and the design of the molded product is not impaired.
When ^{the absolute value of ΔL *} (mb-ma) exceeds 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-shaped jig 10 having a hemispherical tip 11 was prepared, and the tip 11 was covered with a car wash towel 12 (Joyful Co., Ltd. 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. In, the molded product (Ma) was scratched by sliding it in the horizontal direction (in the figure, in the direction of the double-headed arrow) and reciprocating it 100 times. At that time, the load applied was 1 kg (9.8 N). A product (Mc) in which the molded product (Ma) was scratched was designated as a molded product (Mc). ^{The brightness L *} of the surface of the scratched molded product (Mc) was measured by the SCE method using a spectrocolorimeter. ^{Let L *} measured in this way be "L ^* (mc)".

(Judgment of scratch resistance)
^{The determination index ΔL *} (mc-ma) for the conspicuousness of scratches on the molded product (Mc) was calculated from the following formula (4). The ^{larger the absolute value of ΔL *} (mc-ma), the more conspicuous the scratches are.
ΔL ^* (mc-ma) = L ^* (mc) -L ^* (ma) ... (4)

When ^{the absolute value of ΔL *} (mc-ma) is 4.5 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 4.5 to 7.0 or less, the scratches are inconspicuous and the design of the molded product is not impaired.
When ^{the absolute value of ΔL *} (mc-ma) exceeds 7.0, scratches are conspicuous and the design of the molded product is impaired.

<Evaluation of antistatic property>
(Dirt chamber test)
A molded product (Ma) left at a temperature of 23 ° C. and a humidity of 65% for 24 hours was set in a dirt chamber test apparatus, and a test was conducted in which 3 g of carbon glass was blown for 5 minutes. The molded product (Ma) after the test was designated as a molded product (Md). This molded product (Md) was visually observed and evaluated according to the following evaluation criteria. If the evaluation of the dirt chamber test is Δ or higher, it is considered to have antistatic property.
◯: 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 is unevenly adhered to the entire surface.

<Evaluation of wipe 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-shaped jig 10 having a hemispherical tip 11 was prepared, and the tip 11 was covered with a car wash towel 12 (Joyful Co., Ltd. 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. In the above, the molded product (Me) was scratched by sliding it in the horizontal direction (in the direction of the double-headed arrow in the figure) and reciprocating it 100 times. At that time, the load applied was 1 kg (9.8 N). By washing off the carbon black adhering to the surface of the scratched molded product (Me) with a neutral surfactant (automotive detergent, manufactured by SOFT99 Corporation, "Car Shampoo") and drying it. A molded product (Mf) was obtained. ^{The brightness L *} of the surface of the molded product (Mf) was measured by the SCE method using a spectrocolorimeter. ^{Let L *} measured in this way be "L ^* (mf)".

(Judgment of wipe resistance)
The wiping scratch resistance determination index ΔL ^* (mf-ma) was calculated from the following formula (5). The ^{larger the absolute value of ΔL *} (mf-ma), the more conspicuous the scratches are.
ΔL ^* (mf-ma) = L ^* (mf) -L ^* (ma) ... (5)

When ^{the absolute value of ΔL *} (mf-ma) is 4.5 or less, 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, the scratches are inconspicuous and the design of the molded product is not impaired.
When ^{the absolute value of ΔL *} (mf-ma) exceeds 7.0, scratches are conspicuous and the design of the molded product is impaired.

<Evaluation of durability of wipe resistance>
A molded product (Mf) left at a temperature of 23 ° C. and a humidity of 65% for 24 hours was set in a dirt chamber test apparatus, 3 g of carbon glass was blown for 5 minutes, and then the surface of the molded product was washed with 200 mL of water and dried. A molded product (Mg) was obtained.
As shown in FIG. 1, a rod-shaped jig 10 having a hemispherical tip 11 was prepared, and the tip 11 was covered with a car wash towel 12 (Joyful Co., Ltd. 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 (Mg) 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 (Mg) 13. In, the molded product (Mg) was scratched by sliding it in the horizontal direction (in the figure, in the direction of the double-headed arrow) and reciprocating it 100 times. At that time, the load applied was 1 kg (9.8 N). By washing off the carbon black adhering to the surface of the scratched molded product (Mg) with a neutral surfactant (automotive detergent, manufactured by SOFT99 Corporation, "Car Shampoo") and drying it. A molded product (Mh) was obtained. ^{The brightness L *} of the surface of the molded product (Mh) was measured by the SCE method using a spectrocolorimeter. ^{Let L *} measured in this way be "L ^* (mh)".

(Judgment of durability of wipe resistance)
^{The durability Δ (ΔL *} ) of the wipe resistance of the molded product was calculated from the following formulas (6) to (7). The larger the absolute value of Δ (ΔL ^* ), the lower the durability of wipe 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 21a 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) is placed on the test piece 21. The test piece 22 was reciprocated in the horizontal direction (in the direction of the bidirectional arrow in the figure). At this time, it was investigated whether or not a squeak noise was generated, and the evaluation was made according to the following criteria. △ The above is considered to have the effect of suppressing squeak noise.
⊚: No squeaking noise is generated with either 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 does not occur when the load is 500 g (4.9 N).
Δ: A small squeak noise is heard with either a load of 500 g (4.9 N) or 1 kg (9.8 N).
X: A squeak noise is generated at both a load of 500 g (4.9 N) and a load of 1 kg (9.8 N).

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

<Each ingredient>
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 acid 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 sufficiently replacing the stainless polymerization tank with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added to prepare ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _{1) to 8.0 mmol / L. .5} ) The hexane solution of 5) was continuously supplied in an amount of 5 L / h for 1 hour, and then _{the hexane solution of VO (OC 2} H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was 5 L / h. Hexane was continuously supplied in an amount of 5 L / h. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization tank so that the polymerization liquid in the polymerization tank was always 10 L. A bubbling tube was used to supply ethylene at an amount of 2000 L / h, propylene at an amount of 1000 L / h, and hydrogen at an amount of 8 L / h, and the polymerization reaction was carried out at 35 ° C.
The polymerization reaction was carried out under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (A-1). The obtained polymerization solution was decalcified with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1). Table 1 shows the properties of the ethylene / propylene copolymer (A-1) polymer.

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

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

<Cross-linked ethylene / α-olefin copolymer (C)>
(Preparation of crosslinked ethylene / α-olefin copolymer (C-1))
Ion-exchanged water was added to the aqueous dispersion of olefin resin (B-1) (100 parts as solid content) so that the solid content concentration became 35%, and 0.2 part of t-butylcumyl peroxide as an organic peroxide was added. One part of divinylbenzene was added as a polyfunctional compound, and the mixture was 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 size 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, both the crosslinked ethylene and α-olefin were prepared in the same manner as in the preparation of the crosslinked ethylene / α-olefin copolymer (C-1) except that the amount of t-butylcumylperoxide added was changed. Aqueous dispersions of polymers (C-2) to (C-5) were obtained. Table 3 shows the gel content and volume average particle size of the crosslinked ethylene / α-olefin copolymers (C-2) to (C-5).

<Graft copolymer (D)>
(Preparation of Graft Copolymer (D-1))
The olefin resin aqueous dispersion (B-1) (70 parts as the solid content of the ethylene / propylene copolymer (A-1)) was placed in a stainless polymer tank equipped with a stirrer, and the olefin resin aqueous dispersion (B-1) was added. Ion-exchanged water was added to the mixture so that the solid content concentration was 30%, 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were charged, and the temperature was adjusted to 80 ° C. 23.4 parts of styrene, 6.6 parts of acrylonitrile and 0.6 parts of cumene hydroperoxide were continuously added for 150 minutes, and emulsion polymerization was carried out while keeping the polymerization temperature at 80 ° C., and the graft copolymer weight having an average particle size of 0.41 μm was performed. An aqueous dispersion containing the coalescence (D-1) was obtained. An antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1), the solid content is precipitated with sulfuric acid, and after the steps of washing, dehydration and drying, the powdery graft copolymer ( D-1) was obtained. The graft ratio of the graft copolymer (D-1) was measured and found to be 30%.
Further, in the examples described later, the average particle size 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))
The graft copolymers (D-2) to (D-5) are the same as those of the graft copolymer (D-1) except that the type of the olefin resin aqueous dispersion (B) is changed as shown in Table 4. ) Was obtained. 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 the aqueous dispersion of the olefin resin (B) was changed to the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C) as shown in Tables 4 to 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))
70 parts of ethylene / α-olefin copolymer (A-1) and 300 parts of toluene were charged in a stainless polymerization tank equipped with a stirrer, and the contents were stirred at 70 ° C. for 1 hour to uniformly dissolve them. After sufficient nitrogen substitution, 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 temperature was raised to 4 hours and the reaction was carried out for 4 hours. The internal temperature was raised to 120 ° C. and the reaction was carried out for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and the unreacted product and the solvent were distilled off by steam distillation. A twin-screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Corp.) was used at 220 ° C. in a vacuum of 93.325 kPa to substantially evaporate the volatile matter, pelletize it, and graft copolymer (D-11). ) Was obtained. The graft ratio of the graft copolymer (D-11) was measured and found to be 30%. Further, when the average particle size of the ethylene / α-olefin copolymer (A) in the thermoplastic resin composition was confirmed by an electron microscope, it was 0.4 μm.

(Preparation of Graft Copolymer (D-12))
As shown in Table 5, a graft copolymer (D-12) was obtained in the same manner as in the preparation of the graft copolymer (D-1) except that styrene and acrylonitrile were changed to styrene and methyl methacrylate. rice field. The graft ratio of the graft copolymer (D-12) is shown in Table 5.

(Preparation of Graft Copolymer (D-13))
150 parts of deionized water, 100 parts of butadiene monomer, 3.0 parts of hardened fatty acid potassium soap, 0.3 parts of sodium organic sulfonate, 0.2 parts of tarsaldodecyl mercaptan, 0 parts of potassium persulfate in a pressure-resistant container equipped with a stirrer. .3 parts and 0.14 parts of potassium hydroxide were charged, and the temperature was raised to 60 ° C. while stirring in a nitrogen atmosphere to start polymerization, and 0.1 part of potassium persulfate was dissolved when the polymerization rate was 65%. 5 parts of the deionized water was added to the pressure-resistant container to raise the polymerization temperature to 70 ° C., 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%. The rubber-like polymer latex (D-13-a) of the above was obtained.
200 parts of ion-exchanged water (including water in polybutadiene latex), 0.3 part of disproportionated potassium rosinate (solid content) in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer. , 0.01 part of ferrous sulfate heptahydrate, 0.2 part of sodium pyrophosphate, 0.5 part of crystalline glucose were charged, and after being completely dissolved, a rubbery polymer latex (D-13-a) was added. 50 parts of solid content was added and mixed.
The contents in the reactor were heated to 60 ° C. with stirring, and a vinyl monomer mixture (m1) of 39 parts of styrene and 11 parts of acrylonitrile was continuously added dropwise over 2 hours and supplied for graft polymerization. rice field. During that time, the jacket temperature was controlled so as to keep the temperature inside the reactor at 60 ° C. After completion of the dropping, the temperature was raised to 70 ° C. and kept for another 1 hour to complete the graft polymerization reaction. After cooling, an antioxidant (dilaurylthiodipropionate) was added to obtain a latex of a graft copolymer (D-13).
The obtained graft copolymer (D-13) latex was put into a 2.5% aqueous sulfuric acid solution (80 ° C.) in an amount of 1 time thereof with stirring, and further held at 90 ° C. for 5 minutes to solidify. A slurry of the graft copolymer (D-13) was obtained. Then, the slurry was washed with water and dehydrated twice, and 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 parts of the mixture was charged into the reactor. The inside of the reactor was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00026 parts of ferrous sulfate, 0.0008 parts of disodium ethylenediaminetetraacetate, 0.45 parts of longalit, and 10 parts of ion-exchanged water was added. The polymerization was started and the internal temperature was raised to 75 ° C. Further, this state was maintained for 1 hour to obtain a rubber-like polymer (D-14-a) having an average particle size of 0.096 μm.
A dispersion (solid content of 50 parts) of the rubbery polymer (D-14-a) was placed in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, and 0.15 parts of longalite was added. An aqueous solution consisting of 0.65 parts of dipotassium alkenyl succinate and 10 parts of ion-exchanged water is added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene, and 0.11 parts of t-butyl hydroperoxide. Was added dropwise over 1 hour and graft-polymerized. Five minutes after the completion of the dropping, an aqueous solution consisting of 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of longalit, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 was added. A mixed solution consisting of 2 parts, 18.8 parts of styrene, 0.19 parts of t-butylhydroperoxide, and 0.014 parts of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropping, the internal temperature was maintained at 75 ° C. for 10 minutes, and then cooled. An aqueous solution prepared by dissolving 0.2 parts of dipotassium acid in 5 parts of ion-exchanged water was added. Then, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and then 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-based mixture. To this, 300 parts of ion-exchanged water in which 0.67 parts of sodium dodecylbenzenesulfonate was dissolved was added, and the mixture was stirred with a homomixer at 10,000 rpm / 2 minutes, and then passed through a homogenizer once at a pressure of 30 MPa for stable premixing. An organosiloxane aqueous dispersion was obtained.
In addition, 2 parts of dodecylbenzene sulfonic 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 dodecylbenzene sulfonic acid. bottom. With this aqueous solution 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 to cool. This 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 aqueous dispersion of polyorganosiloxane (Ea) was dried at 170 ° C. for 30 minutes to determine the solid content concentration, which was 17.3%. The volume average particle size of the polyorganosiloxane (Ea) dispersed in the aqueous dispersion was 0.05 μm.

(Preparation of Graft Copolymer (F-1))
68.3 parts of an aqueous dispersion of polyorganosiloxane (Ea) and 0.75 parts of sodium polyoxyethylene alkyl phenyl ether sulfate were charged in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer. 203 parts of ion-exchanged water was added and mixed. Then, 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. By passing a nitrogen stream through this reactor, nitrogen was replaced in the atmosphere, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 parts of ferrous sulfate, 0.0003 parts of ethylenediaminetetraacetic acid disodium salt and 0.24 parts of longalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. Due to the polymerization of the acrylate component, the liquid temperature rose to 78 ° C. This state is maintained for 1 hour to complete the polymerization of the acrylate component, and the unit derived from polyorganosiloxane (Ea) and the (meth) acrylic acid ester-based monomer and the unit derived from the cross-linking agent and / or the graft cross-linking agent. An aqueous dispersion of a composite rubber-like polymer (E-1) composed of a poly (meth) acrylic acid ester containing and was obtained. The volume average particle size of the composite rubber-like polymer (E-1) dispersed in the aqueous dispersion was 0.096 μm.
After the liquid temperature inside the reactor was lowered to 60 ° C., an aqueous solution prepared by dissolving 0.4 part of Longarit in 10 parts of ion-exchanged water was added. Then, a mixed solution of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 parts of tertiary butyl hydroperoxide was added dropwise over about 1 hour for polymerization. After holding for 1 hour after the completion of the dropping, an aqueous solution prepared by dissolving 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of longalit in 10 parts of ion-exchanged water was added. Then, a mixed solution 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 the dropping, the mixture was cooled to obtain an aqueous dispersion of a graft copolymer (F-1) in which an acrylonitrile-styrene copolymer was grafted on the composite rubber-like polymer (E-1). .. Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a ratio of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (F-1) was gradually added dropwise to the calcium acetate aqueous solution to solidify it. The obtained coagulated product was separated, washed, and then 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-like polymer (E-1), the amount of emulsifier used, and the obtained composite rubber-like polymer (E-). The volume average particle diameter of 1) is shown.

<Methacrylic acid ester resin (G)>
(Preparation of methacrylic acid ester resin (G-1))
150 parts of ion-exchanged water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2'-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan in a stainless polymerization tank with a stirrer. , Calcium hydrooxyapatite 0.47 part and potassium alkenyl succinate 0.003 part were charged. The internal temperature of the polymerization tank was set to 75 ° C. and the reaction was carried out for 3 hours, and the temperature was raised to 90 ° C. and the reaction was carried out for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic acid ester resin (G-1). The refractive indexes of the monomer and methacrylic acid ester resin (G-1) used are shown in Table 7.

(Preparation of methacrylic acid ester resin (G-2))
150 parts of ion-exchanged water, 98 parts of methyl methacrylate, 2 parts of N-phenylmaleimide, 0.2 parts of 2,2'-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan in a stainless polymerization tank with a stirrer. A part, 0.7 part of polyvinyl alcohol was charged. The internal temperature of the polymerization tank was set to 75 ° C. and the reaction was carried out for 3 hours, and the temperature was raised to 90 ° C. and the reaction was carried out for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic acid ester resin (G-2). The refractive indexes of the monomer and methacrylic acid ester resin (G-2) used are shown in Table 7.

(Preparation of methacrylic acid ester resin (G-3))
150 parts of ion-exchanged water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 parts of 2,2'-azobis (isobutyronitrile), n-octyl in a stainless polymerization tank with a stirrer. 0.25 parts of mercaptan and 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set to 75 ° C. and the reaction was carried out for 3 hours, and the temperature was raised to 90 ° C. and the reaction was carried out for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic acid ester resin (G-3). The refractive indexes of the monomer and methacrylic acid ester resin (G-3) used are shown in Table 7.

(Preparation of methacrylic acid ester resin (G-4))
150 parts of ion-exchanged water, 56 parts of methyl methacrylate, 29 parts of N-phenylmaleimide, 15 parts of styrene, 0.2 parts of 2,2'-azobis (isobutyronitrile), n-octyl in a stainless polymerization tank with a stirrer. 0.25 parts of mercaptan and 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set to 75 ° C. and the reaction was carried out for 3 hours, and the temperature was raised to 90 ° C. and the reaction was carried out for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic acid ester resin (G-4). The refractive indexes of the monomer and methacrylic acid ester resin (G-4) used are shown in Table 7.

(Preparation of methacrylic acid ester resin (G-5))
150 parts of ion-exchanged water, 53 parts of methyl methacrylate, 31 parts of N-phenylmaleimide, 16 parts of styrene, 0.2 parts of 2,2'-azobis (isobutyronitrile), n-octyl in a stainless polymerization tank with a stirrer. 0.25 parts of mercaptan and 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set to 75 ° C. and the reaction was carried out for 3 hours, and the temperature was raised to 90 ° C. and the reaction was carried out for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic acid ester resin (G-5). The refractive indexes of the monomer and methacrylic acid ester resin (G-5) used are shown in Table 7.

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

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

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

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

[Comparative Examples 1 to 6]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the formulation was changed to that shown in Table 11.
The thermoplastic resin composition is pelletized, various molded products are molded, and impact resistance, heat resistance, color development, scratch resistance, scratch resistance, antistatic property, wiping scratch resistance, and wiping scratch durability. , The squeak noise suppression effect was evaluated. The results are shown in Table 11.

The molded products obtained from the thermoplastic resin compositions of Examples 1 to 26 have impact resistance, heat resistance, color development, scratch resistance, scratch resistance, antistatic properties, wipe resistance, and wipe resistance. It was excellent in sustainability and squeak noise suppression effect.
Therefore, when the thermoplastic resin composition of the present invention is used, impact resistance, heat resistance, color development, scratch resistance, scratch resistance, antistatic property, wiping scratch resistance, wiping scratch durability, and squeaking. It can be seen that a molded product having an excellent sound suppression effect can be obtained, and that it can be applied to applications such as vehicle interior / exterior parts, office equipment, home appliances, and building materials.

On the other hand, in Comparative Examples 1 to 5 in which the graft copolymer (D) containing no ethylene / α-olefin copolymer was used, and in Comparative Example 6 in which the antistatic agent (H) was not blended, the molded product was used. Impact resistance, scratch resistance, antistatic property, wipe resistance, durability of wipe resistance, and squeak noise suppression effect were low.

The molded product using the thermoplastic resin composition of the present invention is useful as vehicle interior / exterior parts, office equipment, home appliances, building materials 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-based monomer containing at least one vinyl-based 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. The graft copolymer (D) obtained by polymerizing the body mixture (m1) and
Methacrylic obtained by polymerizing a vinyl-based monomer mixture (m3) composed of a methacrylic acid ester and at least one vinyl-based monomer selected from a maleimide-based compound, an aromatic vinyl compound, and an acrylic acid ester. Acid ester resin (G) and
It consists of an antistatic agent (H), or the graft copolymer (D), the methacrylic acid ester resin (G), the antistatic agent (H), an antioxidant, a lubricant, a processing aid, a pigment, and a dye. , A thermoplastic resin composition comprising at least one additive selected from the group consisting of fillers, silicone oils and paraffin oils.
The antistatic agent (H) is a block copolymer having one or both of a polyolefin-based block and a polyamide-based block, and a hydrophilic block.
The content of the graft copolymer (D) is 14 to 40% by mass with respect to the total mass of the graft copolymer (D) and the methacrylic acid ester resin (G).
The content of the methacrylic acid ester resin (G) is 86 to 60% by mass with respect to the total mass of the graft copolymer (D) and the methacrylic acid ester resin (G).
The content of the antistatic agent (H) is 4 to 22 parts by mass with respect to 100 parts by mass in total of the graft copolymer (D) and the methacrylic acid ester resin (G).
Thermoplastic resin composition. A vinyl-based monomer containing at least one vinyl-based 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. The graft copolymer (D) obtained by polymerizing the body mixture (m1) and
A poly (meth) acrylic acid ester (Eb) containing a polyorganosiloxane (Ea) and one or both of a unit derived from a (meth) acrylic acid ester, a unit derived from a cross-linking agent, and a unit derived from a graft crossover agent. Vinyl containing at least one vinyl-based monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters in the presence of the composite rubbery polymer (E) composed of The graft copolymer (F) obtained by polymerizing the system monomer mixture (m2) and
Methacrylic obtained by polymerizing a vinyl-based monomer mixture (m3) composed of a methacrylic acid ester and at least one vinyl-based monomer selected from a maleimide-based compound, an aromatic vinyl compound, and an acrylic acid ester. Acid ester resin (G) and
The graft copolymer (D), the graft copolymer (F), the methacrylic acid ester resin (G), the antistatic agent (H), and the antioxidant, which are composed of an antistatic agent (H). A thermoplastic resin composition comprising at least one additive selected from the group consisting of lubricants, processing aids, pigments, dyes, fillers, silicone oils and paraffin oils.
The antistatic agent (H) is a block copolymer having one or both of a polyolefin-based block and a polyamide-based block, and a hydrophilic block.
The total content of the graft copolymer (D) and the graft copolymer (F) is the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester resin (G). ), Which is 14 to 40% by mass.
The ethylene / α-olefin copolymer with respect to the total mass of the ethylene / α-olefin copolymer contained in the graft copolymer (D) and the composite rubber-like polymer (E) contained in the graft copolymer (F). The proportion of the olefin copolymer is 1 to 85% by mass, and the proportion of the composite rubber-like polymer (E) is 15 to 99% by mass.
The content of the methacrylic acid ester resin (G) is 86 to 60 mass with respect to the total mass of the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester resin (G). % And
The content of the antistatic agent (H) is 4 to 22 with respect to 100 parts by mass in total of the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester resin (G). It is a mass part,
Thermoplastic resin composition. The thermoplastic resin composition according to claim 1 or 2, wherein the ethylene / α-olefin copolymer is a crosslinked ethylene / α-olefin copolymer (C). A molded product using the thermoplastic resin composition according to any one of claims 1 to 3. A vinyl-based monomer containing at least one vinyl-based 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 step of polymerizing the body mixture (m1) to obtain a graft copolymer (D), and
A step of polymerizing a vinyl-based monomer mixture (m3) containing a methacrylic acid ester to obtain a methacrylic acid ester resin (G), and
The graft copolymer (D), the thermoplastic ester resin (G), and the antistatic agent (H) are mixed, or the graft copolymer (D) and the thermoplastic ester resin (G) are mixed. ), The antistatic agent (H), and at least one additive selected from the group consisting of antioxidants, lubricants, processing aids, pigments, dyes, fillers, silicone oils and paraffin oils. A method for producing a thermoplastic resin composition, which comprises a step of obtaining a thermoplastic resin composition.
The antistatic agent (H) is a block copolymer having one or both of a polyolefin-based block and a polyamide-based block, and a hydrophilic block.
The content of the graft copolymer (D) is 14 to 40% by mass with respect to the total mass of the graft copolymer (D) and the methacrylic acid ester resin (G).
The content of the methacrylic acid ester resin (G) is 86 to 60% by mass with respect to the total mass of the graft copolymer (D) and the methacrylic acid ester resin (G).
The content of the antistatic agent (H) is 4 to 22 parts by mass with respect to 100 parts by mass in total of the graft copolymer (D) and the methacrylic acid ester resin (G).
A method for producing a thermoplastic resin composition. A vinyl-based monomer containing at least one vinyl-based 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 step of polymerizing the body mixture (m1) to obtain a graft copolymer (D), and
A poly (meth) acrylic acid ester (Eb) containing a polyorganosiloxane (Ea) and one or both of a unit derived from a (meth) acrylic acid ester, a unit derived from a cross-linking agent, and a unit derived from a graft crossover agent. Vinyl containing at least one vinyl-based monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid esters in the presence of the composite rubbery polymer (E) composed of A step of polymerizing the system monomer mixture (m2) to obtain a graft copolymer (F), and
A step of polymerizing a vinyl-based monomer mixture (m3) containing a methacrylic acid ester to obtain a methacrylic acid ester resin (G), and
The graft copolymer (D), the graft copolymer (F), the thermoplastic ester resin (G), and the antistatic agent (H) are mixed, or the graft copolymer (D). ), The graft copolymer (F), the methacrylic acid ester resin (G), the antioxidant (H), antioxidants, lubricants, processing aids, pigments, dyes, fillers, silicones. A method for producing a thermoplastic resin composition, which comprises a step of mixing at least one additive selected from the group consisting of oil and paraffin oil to obtain a thermoplastic resin composition.
The antistatic agent (H) is a block copolymer having one or both of a polyolefin-based block and a polyamide-based block, and a hydrophilic block.
The total content of the graft copolymer (D) and the graft copolymer (F) is the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester resin (G). ), Which is 14 to 40% by mass.
The ethylene / α-olefin copolymer with respect to the total mass of the ethylene / α-olefin copolymer contained in the graft copolymer (D) and the composite rubber-like polymer (E) contained in the graft copolymer (F). The proportion of the olefin copolymer is 1 to 85% by mass, and the proportion of the composite rubber-like polymer (E) is 15 to 99% by mass.
The content of the methacrylic acid ester resin (G) is 86 to 60 mass with respect to the total mass of the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester resin (G). % And
The content of the antistatic agent (H) is 4 to 22 with respect to 100 parts by mass in total of the graft copolymer (D), the graft copolymer (F), and the methacrylic acid ester resin (G). It is a mass part,
A method for producing a thermoplastic resin composition. The method for producing a thermoplastic resin composition according to claim 5 or 6, wherein the ethylene / α-olefin copolymer is a crosslinked ethylene / α-olefin copolymer (C).

Images