JP2017114990A - Thermoplastic resin composition for heat cycle injection molding, molded product and method for producing molded product - Google Patents

Abstract

[PROBLEMS] To provide a thermoplastic resin composition capable of obtaining a molded article excellent in surface appearance, scratch resistance, impact resistance, color development, heat resistance, and heat aging resistance upon heat cycle injection molding, and the molded article. Provided.
It is obtained by polymerizing a vinyl monomer component (m1) in the presence of a composite rubber-like polymer (A) comprising a polyorganosiloxane (Aa) and a poly (meth) acrylic acid ester (Ab). In the composite rubber-like polymer (A), the graft copolymer (B) and the (meth) acrylate resin (C) obtained by polymerizing the vinyl monomer component (m2) The polyorganosiloxane (Aa) has a content of 1 to 20% by mass, the composite rubber-like polymer (A) has a volume average particle size of 0.05 to 0.15 μm, and a vinyl monomer component (m2 The thermoplastic resin composition for heat cycle injection molding in which the content of the maleimide compound is 1 to 30% by mass and the content of the aromatic vinyl compound is 5.5 to 15% by mass.
[Selection figure] None

Description

  The present invention relates to a thermoplastic resin composition for heat cycle injection molding, a molded article using the same, and a method for producing the molded article.

Improving the impact resistance of the molded product not only expands the applications of the molded product, but also makes it extremely useful for industrial applications, such as enabling the molded product to be made thinner and larger. . Therefore, various techniques have been proposed so far for improving the impact resistance of the molded product.
Among these techniques, a technique for 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-ethylene / α-olefin-styrene (AES) resin, polyorganosiloxane-acrylic ester-acrylonitrile-styrene (SAS) resin, acrylonitrile- Examples thereof include a styrene-acrylic acid ester (ASA) resin or a thermoplastic resin composition obtained by adding these to a hard resin.
In recent years, no-painting has been promoted in the vehicle field, etc., omitting the painting process. In this case, since the molded product is assembled to the product as it is, the molded product is required to have high designability. In order to improve the designability of a molded product, a molding method has been proposed in which the mold surface temperature is heated to a temperature equal to or higher than the heat distortion temperature of the thermoplastic resin composition or the glass transition temperature during molding.

As a thermoplastic resin composition capable of obtaining a molded article having improved impact resistance while maintaining the characteristics derived from the hard resin, and a molding method for improving the design of the molded article, for example, Things have been proposed.
(1) A thermoplastic resin composition obtained by adding a SAS resin to a methacrylic ester resin which is a hard resin (Patent Document 1).
(2) A thermoplastic resin composition obtained by adding an ABS resin to a methacrylic ester resin, which is a hard resin, is subjected to heat cycle injection molding, and the mold surface temperature is heated to a temperature higher than the thermal deformation temperature of the thermoplastic resin composition during molding. Method (Patent Document 2).
(3) A thermoplastic resin composition obtained by adding a methacrylic ester resin, an AES resin, and an acrylonitrile-styrene (AS) resin to a polycarbonate resin, which is a hard resin, is injection-molded, and the mold surface temperature is set during the molding. A method of heating above the glass transition temperature of an object (Patent Document 3).

However, in the thermoplastic resin composition (1), it is necessary to add a large amount of SAS resin in order to improve the impact resistance of the molded product. In the obtained molded product, the surface derived from the methacrylic ester resin Hardness (scratch resistance), heat resistance, and heat aging resistance are significantly reduced.
The molded product obtained by the molding method (2) has good design on the surface of the molded product, but does not use a heat-resistant component in the thermoplastic resin composition and uses an ABS resin. It does not have high heat resistance and weather resistance required in fields.
Since the molded product obtained by the molding method (3) uses a polycarbonate resin, the weather resistance is insufficient.

Japanese Patent Laid-Open No. 08-283524 JP 2005-220265 A JP 2012-131908 A

  The present invention relates to a thermoplastic resin composition capable of obtaining a molded product having excellent surface appearance, scratch resistance, impact resistance, color development, heat resistance, and heat aging resistance when heat cycle injection molding is used. And a method for producing the molded product.

The present invention includes the following aspects.
[1] A thermoplastic resin composition molded by a heat cycle injection molding method in which a mold cavity surface temperature is repeatedly raised and lowered using an injection mold in which mold cavity surfaces are alternately heated and cooled. ,
Poly (meth) acrylate ester having units derived from polyorganosiloxane (Aa) and (meth) acrylate, and one or both of a unit derived from a crosslinking agent and a unit derived from a graft crossing agent A graft copolymer obtained by polymerizing a vinyl monomer component (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the composite rubber-like polymer (A) comprising (Ab) ( B) and
A (meth) acrylic ester resin (C) obtained by polymerizing a vinyl monomer component (m2) containing a (meth) acrylic ester, a maleimide compound and an aromatic vinyl compound,
The content of the polyorganosiloxane (Aa) in the composite rubber-like polymer (A) (100% by mass) is 1 to 20% by mass,
The composite rubber-like polymer (A) has a volume average particle diameter of 0.05 to 0.15 μm,
The content of the maleimide compound in the vinyl monomer component (m2) (100% by mass) is 1 to 30% by mass, and the content of the aromatic vinyl compound is 5.5 to 15% by mass. A thermoplastic resin composition for heat cycle injection molding.
[2] The thermoplastic resin composition for heat cycle injection molding according to [1], further comprising a silicone oil (D).
[3] The thermoplastic resin composition for heat cycle injection molding according to [1] or [2], further comprising a styrene resin (E).
[4] In any one of [1] to [3], further comprising a graft copolymer (I) obtained by polymerizing a vinyl monomer component (m4) in the presence of an olefin copolymer The thermoplastic resin composition for heat cycle injection molding described.
[5] A molded product obtained by molding the thermoplastic resin composition for heat cycle injection molding according to any one of [1] to [4].
[6] The thermoplastic resin composition for heat cycle injection molding according to any one of [1] to [4], using an injection mold in which the cavity surface of the mold is alternately heated and cooled, A method for producing a molded product, wherein a molded product is obtained by molding by a heat cycle injection molding method in which the cavity surface temperature is repeatedly raised and lowered.

  According to the present invention, a thermoplastic resin composition capable of obtaining a molded article having excellent surface appearance, scratch resistance, impact resistance, color development, heat resistance, and heat aging resistance upon heat cycle injection molding, It is possible to provide a molded article and a method for producing the molded article using the.

It is a schematic perspective view of the molded article for scratch resistance and surface appearance evaluation produced in [Example].

The following definitions of terms apply throughout this specification and the claims.
“(Meth) acrylic acid” means acrylic acid or methacrylic acid.
“Molded product” means a product formed by molding a thermoplastic resin composition. The molded product of the thermoplastic resin composition for heat cycle injection molding means a product obtained by heat cycle injection molding of the thermoplastic resin composition for heat cycle injection molding.
“Scratch resistance” means the resistance to scratches (scratches) caused by scratching the surface of a molded article with a hard pointed object such as a nail.
“Heat aging resistance” means that the color hardly changes before and after the molded product is allowed to stand under a high temperature condition (the color difference between before and after standing is small).
“Surface appearance” means that the surface of the molded article is glossy and there is no uneven color in the welded portion.

"Thermoplastic resin composition for heat cycle injection molding"
The thermoplastic resin composition for heat cycle injection molding of the present invention (hereinafter also simply referred to as “thermoplastic resin composition”) comprises a graft copolymer (B) and a (meth) acrylate resin (C). Including. If necessary, the thermoplastic resin composition of the present invention can be used within the range that does not impair the effects of the present invention, such as silicone oil (D), styrene resin (E), graft copolymer (I), A plastic resin and various additives may be included.

The graft copolymer (B) is obtained by polymerizing the vinyl monomer component (m1) in the presence of the composite rubber-like polymer (A).
The composite rubbery polymer (A) is composed of a polyorganosiloxane (Aa) and a poly (meth) acrylic acid ester (Ab).
The (meth) acrylic ester resin (C) is obtained by polymerizing the vinyl monomer component (m2).

The styrene resin (E) is obtained by polymerizing the vinyl monomer component (m3).
The graft copolymer (I) is obtained by polymerizing the vinyl monomer component (m4) in the presence of an olefin copolymer.
The graft copolymer (I) is a vinyl-based copolymer in the presence of an ethylene / α-olefin copolymer (F), an aqueous olefin resin dispersion (G), or a crosslinked ethylene / α-olefin copolymer (H). It is preferably obtained by polymerizing the monomer component (m4).
Hereinafter, each component ((A)-(I), (m1)-(m4) etc.) is demonstrated.

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

  Examples of the dimethylsiloxane constituting the polyorganosiloxane (Aa) include a dimethylsiloxane-based cyclic body having three or more members. Among these, a 3-membered to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.

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

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

The manufacturing method of polyorganosiloxane (Aa) is not limited. For example, it can be produced by the following method.
First, if necessary, a siloxane-based crosslinking agent is added to a siloxane mixture composed of dimethylsiloxane and a siloxane containing a vinyl polymerizable functional group, and then emulsified with an emulsifier and water to disperse the siloxane mixture in an aqueous medium. A siloxane mixture aqueous dispersion is obtained. Subsequently, the dispersed particles (siloxane mixture) in the aqueous siloxane mixture dispersion are made into fine particles using a homomixer that makes fine particles by a shearing force by high-speed rotation, a homogenizer that makes fine particles by a jet output from a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifier such as a homogenizer because the particle size distribution of the dispersed particles, and thus the polyorganosiloxane (Aa), becomes small. Next, the siloxane mixture aqueous dispersion in which the dispersed particles are atomized is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction liquid is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash or sodium carbonate to stop the polymerization, thereby obtaining an aqueous dispersion in which polyorganosiloxane (Aa) is dispersed in an aqueous medium.
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; Alkyl ethers; and lactams such as N-methyl-2-pyrrolidone. In the present invention, it is preferable to use only water or a mixture of water and a water-miscible organic solvent as the aqueous medium.

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

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

The volume average particle diameter of the polyorganosiloxane (Aa) in the aqueous dispersion is such that the color development of the molded article is more excellent, the viscosity of the aqueous dispersion during the production of the polyorganosiloxane (Aa), and agglomerates ( (Coagulum) can be prevented, and is preferably 0.01 to 0.09 μm, more preferably 0.02 to 0.08 μm.
The volume average particle diameter is a value measured by a laser diffraction / scattering method. Specifically, it is measured by the method shown in the examples described later.
In addition, as a method of controlling the volume average particle diameter of the polyorganosiloxane (Aa), for example, a method described in JP-A-5-279434 can be employed.

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

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

Each of the crosslinking agent and the graft crossing agent improves the impact resistance, color developability and heat aging property of the molded product.
Examples of the crosslinking agent include dimethacrylate compounds, and specific examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and the like.
Examples of the grafting agent include allyl compounds, specifically, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like.

  In the poly (meth) acrylic acid ester (Ab), the total amount of the unit derived from the crosslinking agent and the unit derived from the graft crossing agent is excellent in impact resistance, color developability and heat aging resistance of the molded product, Since the coagulum (coagulum) at the time of production of the combined body (B) is reduced, 0.1 to 5% by mass is 100% by mass with respect to a total of 100% by mass of all units constituting the poly (meth) acrylic acid ester (Ab). Preferably, 0.2-3 mass% is more preferable, and 0.5-2 mass% is further more preferable.

<Composite rubbery polymer (A)>
The composite rubbery polymer (A) is composed of a polyorganosiloxane (Aa) and a poly (meth) acrylic acid ester (Ab).
The composite rubber-like polymer (A) typically has a structure in which a polyorganosiloxane (Aa) and a poly (meth) acrylic acid ester (Ab) are entangled with each other at a micro level or chemically bonded to each other. Guessed.

  The content of the polyorganosiloxane (Aa) in the composite rubbery polymer (A) is preferably 1 to 20% by mass relative to the total mass (100% by mass) of the composite rubbery polymer (A). 18 mass% is more preferable. If the content of the polyorganosiloxane (Aa) is not less than the lower limit of the above range, the impact resistance of the molded product is more excellent, and if it is not more than the upper limit of the above range, the impact resistance is more excellent.

It does not restrict | limit especially as a manufacturing method of a composite rubber-like polymer (A). For example, a method of heteroaggregating or co-hygrolating an aqueous dispersion of polyorganosiloxane (Aa) and an aqueous dispersion of poly (meth) acrylic acid ester (Ab) separately produced, and an aqueous solution of polyorganosiloxane (Aa) In any one of the dispersion and the aqueous dispersion of poly (meth) acrylic acid ester (Ab), there is a method of forming the other polymer and making it composite. By these methods, an aqueous dispersion of the composite rubber-like polymer (A) is obtained.
As a method for producing the composite rubber-like polymer (A), among them, the impact resistance and color developability of the molded product are more excellent. Therefore, in the aqueous dispersion of polyorganosiloxane (Aa), (meth) acrylic is used. A method of emulsion polymerization of a monomer component containing an acid ester monomer and one or both of a crosslinking agent and a graft crossing agent is preferred. For example, an emulsifier and a monomer component are added to an aqueous dispersion of polyorganosiloxane (Aa) at room temperature, the temperature is raised to 40 to 80 ° C., and a radical polymerization initiator is added for 0.5 to 3 hours. An aqueous dispersion of the composite rubber-like polymer (A) is obtained by polymerizing to a certain extent.

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

The composite rubber-like polymer (A) dispersed in the aqueous dispersion has a volume average particle size of 0.05 to 0.15 μm, preferably 0.07 to 0.13 μm.
That is, the graft copolymer (B) is obtained by polymerizing the vinyl monomer component (m1) in the presence of the composite rubber-like polymer (A) having a volume average particle diameter of 0.05 to 0.15 μm. The thermoplastic resin composition obtained is derived from the graft copolymer (B) and contains a composite rubber-like polymer (A) having a volume average particle diameter of 0.05 to 0.15 μm. It is a waste.
When the volume average particle diameter of the composite rubber-like polymer (A) is not less than the lower limit of the above range, the impact resistance of the molded product is more excellent, and when it is not more than the upper limit of the above range, the color developability of the molded product, Excellent heat aging resistance and weather resistance.
Although it does not restrict | limit especially as a method of controlling the volume average particle diameter of a composite rubber-like polymer (A), The method etc. which adjust the kind or usage-amount of an emulsifier are mentioned.
Note that the average particle size of the composite rubber-like polymer (A) in the aqueous dispersion shows the volume average particle size of the composite rubber-like polymer (A) in the thermoplastic resin composition as it is. This is confirmed by image analysis.

<Vinyl monomer component (m1)>
The vinyl monomer component (m1) contains at least an aromatic vinyl compound and a vinyl cyanide compound as monomers.
The vinyl monomer component (m1) may further contain other monomers copolymerizable with these in addition to the aromatic vinyl compound and the vinyl cyanide compound as long as the effects of the present invention are not impaired. .

  Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Among these, styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more.

Examples of other monomers include methacrylic acid esters, acrylic acid esters, maleimide compounds, and the like.
Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, methacrylic acid. Examples include isoamyl, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and phenyl methacrylate.
Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate.
Examples of maleimide compounds include N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide). , N-tert-butylmaleimide, N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), N-substituted maleimide compounds such as N-aralkylmaleimide Is mentioned.
These can be used alone or in combination of two or more.

  65-82 mass% is preferable with respect to the total mass (100 mass%) of a vinyl-type monomer component (m1), and the content rate of the aromatic vinyl compound in a vinyl-type monomer component (m1) is 73- 80 mass% is more preferable, and 75-80 mass% is further more preferable. When the content of the aromatic vinyl compound relative to the total mass of the vinyl monomer component (m1) is within the above range, the color developability and impact resistance of the molded product are more excellent.

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

<Graft copolymer (B)>
The graft copolymer (B) is obtained by polymerizing the vinyl monomer component (m1) in the presence of the composite rubber-like polymer (A).
The graft copolymer (B) is a graft composed of a polymer of a vinyl monomer component (m1) on a granular composite rubber-like polymer (A) having a volume average particle diameter of 0.05 to 0.15 μm. Presumed to be composed of a core part composed of a composite rubber-like polymer (A) and an outer layer part (shell) composed of a polymer of the vinyl monomer component (m1). Is done. However, since it does not always have such a core-shell type, it is obtained by polymerizing the vinyl monomer component (m1) in the presence of the composite rubber-like polymer (A). It is more appropriate to define "

In the presence of 20 to 90% by mass of the composite rubbery polymer (A), the graft copolymer (B) is 10 to 80% by mass of the vinyl monomer component (m1) (however, the composite rubbery polymer ( The total of A) and the vinyl monomer component (m1) is 100% by mass.) And is preferably obtained by polymerizing 25 to 85% by mass of the composite rubber-like polymer (A). More preferably, it is obtained by polymerizing 15 to 75% by mass of the vinyl monomer component (m1) in the presence of 30% to 80% by mass of the composite rubber-like polymer (A). Furthermore, it is more preferable to be obtained by polymerizing 20 to 70% by mass of the vinyl monomer component (m1).
That is, the graft copolymer (B) is composed of 20 to 90% by mass of the composite rubbery polymer (A) and 10 to 80% by mass of the polymer of the vinyl monomer component (m1) (however, the composite rubbery heavy The total of the polymer (A) and the polymer of the vinyl monomer component (m1) is 100% by mass.), And the composite rubber-like polymer (A) is 25 to 85% by mass. And 15 to 75% by mass of the polymer of the vinyl monomer component (m1), more preferably 30 to 80% by mass of the composite rubber-like polymer (A), More preferably, it is composed of 20 to 70% by mass of the polymer of the body component (m1).
If the content of the composite rubber-like polymer (A) with respect to the total (100% by mass) of the composite rubber-like polymer (A) and the vinyl monomer component (m1) is within the above range, the graft copolymer The productivity of (B) is good, and the color developability and impact resistance of the molded product are more excellent.

The graft copolymer (B) is produced, for example, by emulsion polymerization. That is, it is produced by adding a vinyl monomer component (m1) to an aqueous dispersion of a composite rubber-like polymer (A) and radically polymerizing the vinyl monomer component (m1) in the presence of an emulsifier. . Thereby, the aqueous dispersion of a graft copolymer (B) is obtained. At this time, various known chain transfer agents may be added in order to control the graft ratio and the molecular weight of the graft component.
The polymerization conditions for radical polymerization are not particularly limited, and examples include polymerization conditions at 60 to 90 ° C. for 1 to 4 hours.

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

  As an emulsifier, the emulsifier used in the case of manufacture of a composite rubber-like polymer (A) is mentioned. The emulsifier contained in the composite rubber polymer (A) is used as it is, and it is not necessary to add an emulsifier when polymerizing the vinyl monomer component (m1). If necessary, the vinyl monomer component An emulsifier may be added during the polymerization of (m1).

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

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

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

<Vinyl monomer component (m2)>
The vinyl monomer component (m2) contains at least a (meth) acrylic acid ester, a maleimide compound and an aromatic vinyl compound as monomers.
The vinyl monomer component (m2) is within the range not impairing the effects of the present invention, in addition to the (meth) acrylic acid ester, the maleimide compound and the aromatic vinyl compound, and other monomers which can be copolymerized therewith. It may further include a body.

  Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group; (meth) acrylic acid esters having an aromatic hydrocarbon group such as a phenyl group and a benzyl group. Can be mentioned. These can be used alone or in combination of two or more. As the (meth) acrylic acid ester, methyl methacrylate is preferable.

Examples of maleimide compounds include N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide). , N-tert-butylmaleimide, N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.), N-substituted maleimide compounds such as N-aralkylmaleimide Is mentioned. These can be used alone or in combination of two or more.
The maleimide-based compound preferably contains at least one of N-cyclohexylmaleimide and N-phenylmaleimide from the viewpoint of more excellent color developability and weather resistance of the molded article, and includes both N-cyclohexylmaleimide and N-phenylmaleimide. It is particularly preferable to include it.

  Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Among these, styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

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

  The content of the (meth) acrylic acid ester in the vinyl monomer component (m2) is 55 to 93.5% by mass with respect to the total mass (100% by mass) of the vinyl monomer component (m2). 60-604.5 mass% is more preferable. If the content of the (meth) acrylic acid ester in the vinyl monomer component (m2) is within the above range, the molded product has impact resistance, color development, scratch resistance, weather resistance, and heat aging resistance. Better.

  The content of the maleimide compound in the vinyl monomer component (m2) is 1 to 30% by mass with respect to the total mass (100% by mass) of the vinyl monomer component (m2). % By mass is preferable, and 10 to 20% by mass is more preferable. If the content of the maleimide compound in the vinyl monomer component (m2) is not less than the lower limit of the above range, the heat resistance and heat aging resistance of the molded product are more excellent, and if not more than the upper limit of the above range. Further, the coloring property and weather resistance of the molded product are more excellent.

  The content of the aromatic vinyl compound in the vinyl monomer component (m2) is 5.5 to 15% by mass with respect to the total mass (100% by mass) of the vinyl monomer component (m2). 5.5-10 mass% is preferable. If the content of the aromatic vinyl compound in the vinyl monomer component (m2) is within the above range, the fluidity of the thermoplastic resin composition, the heat aging resistance of the molded product, the color developability, and the weather resistance are balanced. Excellent.

<(Meth) acrylic ester resin (C)>
The (meth) acrylic ester resin (C) can be obtained by polymerizing the vinyl monomer component (m2). That is, it is a polymer of the vinyl monomer component (m2), and includes at least a unit derived from a (meth) acrylic acid ester, a unit derived from a maleimide compound, and a unit derived from an aromatic vinyl compound. The content of units derived from maleimide compounds is 1 to 30% by mass relative to the total mass (100% by mass) of all units, and the content of units derived from aromatic vinyl compounds is It is 5.5-15 mass% with respect to the total mass (100 mass%).
The polymerization method of the vinyl monomer component (m2) is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, etc.).

As a method for producing the (meth) acrylic ester resin (C) by the emulsion polymerization method, for example, a vinyl monomer component (m2), an emulsifier, a polymerization initiator, and a chain transfer agent are charged in a reactor and heated. And a method of recovering the (meth) acrylic ester resin (C) from the aqueous dispersion containing the (meth) acrylic ester resin (C) obtained by a precipitation method.
The polymerization conditions for emulsion polymerization are not particularly limited, and examples include polymerization conditions at 40 to 120 ° C. for 1 to 15 hours.
Examples of the emulsifier include usual emulsion polymerization emulsifiers (potassium rosinate, sodium alkylbenzenesulfonate, etc.).
Examples of the polymerization initiator include organic and inorganic peroxide initiators.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.
As the precipitation method, a method similar to that used for recovering the graft copolymer (B) from the aqueous dispersion can be employed.

Examples of the method for producing the (meth) acrylic ester resin (C) by the suspension polymerization method include, for example, a vinyl monomer component (m2), a suspending agent, a suspending aid, and a polymerization initiator in the reactor. Examples include a method in which a chain transfer agent is charged, polymerized by heating, and the resulting slurry is dehydrated and dried to recover the (meth) acrylate resin (C).
The polymerization conditions for suspension polymerization are not particularly limited, and examples include polymerization conditions at 40 to 120 ° C. for 1 to 15 hours.
Examples of the suspending agent include tricalcium phosphite and polyvinyl alcohol.
Examples of the suspension aid include sodium alkylbenzene sulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.

The mass average molecular weight (Mw) of the (meth) acrylic acid ester resin (C) is preferably 100,000 to 300,000, and more preferably 120,000 to 220,000. If the weight average molecular weight of the (meth) acrylic ester resin (C) is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, the coloring property, the scratch resistance, and the heat aging resistance Better.
The weight average molecular weight (Mw) of the (meth) acrylic ester resin (C) is a value in terms of standard polystyrene (PS) calculated by analyzing a solution dissolved in tetrahydrofuran (THF) by gel permeation chromatography (GPC). It is.
(Meth) acrylic acid ester resin (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Silicone oil (D)>
The silicone oil (D) is not particularly limited as long as it has a polyorganosiloxane structure. For example, it may be an unmodified silicone oil or a modified silicone oil.
Examples of the unmodified silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, and the like.
The modified silicone oil is a silicone oil in which various organic groups are introduced into a part of the side chain in the polyorganosiloxane structure and / or one terminal part of the polyorganosiloxane structure, or both terminal parts of the polyorganosiloxane structure. . Examples of the modified silicone oil include amino-modified silicone oil, alkyl-modified silicone oil, polyether-modified silicone oil, fluorine-modified silicone oil, higher alkoxy-modified silicone oil, higher fatty acid-modified silicone oil, methylstyryl-modified silicone oil, and methyl chlorinated phenyl. Examples include silicone oil, methyl hydrogen silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, acrylic acid-modified silicone oil, methacrylic acid-modified silicone oil, mercapto-modified silicone oil, phenol-modified silicone oil, and carbinol-modified silicone oil. .
A silicone oil (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Vinyl monomer component (m3)>
The vinyl monomer component (m3) contains at least an aromatic vinyl compound and a vinyl cyanide compound as monomers.
The vinyl monomer component (m3) may further contain other monomers copolymerizable with these in addition to the aromatic vinyl compound and the vinyl cyanide compound as long as the effects of the present invention are not impaired. .

Specific examples of the aromatic vinyl compound and the vinyl cyanide compound are the same as those exemplified for the vinyl monomer component (m1). The preferable ones are also the same.
Examples of other monomers include methacrylic acid esters, acrylic acid esters, maleimide compounds, and the like. Specific examples of these monomers are the same as those mentioned for the vinyl monomer component (m1). Other monomers can be used alone or in combination of two or more.

  The content of the aromatic vinyl compound in the vinyl monomer component (m3) is preferably 50 to 90% by mass with respect to the total mass (100% by mass) of the vinyl monomer component (m3). 80 mass% is more preferable. When the content of the aromatic vinyl compound in the vinyl monomer component (m3) is within the above range, the fluidity of the resulting thermoplastic resin composition and the color developability of the molded product are more excellent.

  The content of the vinyl cyanide compound in the vinyl monomer component (m3) is preferably 10 to 50% by mass with respect to the total mass (100% by mass) of the vinyl monomer component (m3). 45 mass% is more preferable. When the content of the vinyl cyanide compound in the vinyl monomer component (m3) is within the above range, the impact resistance and heat resistance of the molded product are more excellent.

<Styrene resin (E)>
The styrene resin (E) is obtained by polymerizing the vinyl monomer component (m3). That is, it is a polymer of the vinyl monomer component (m3) and includes at least a unit derived from an aromatic vinyl compound and a unit derived from a vinyl cyanide compound.
The polymerization method of the vinyl monomer component (m3) is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, etc.). preferable. At this time, various known chain transfer agents may be added.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.
Polymerization conditions are not particularly limited, and examples include polymerization conditions at 40 to 130 ° C. for 1 to 20 hours.

The mass average molecular weight (Mw) of the styrene resin (E) is preferably 70,000 to 200,000, more preferably 90,000 to 150,000. When the mass average molecular weight of the styrene resin (E) is within the above range, the fluidity of the thermoplastic resin composition and the impact resistance of the molded product are more excellent.
The mass average molecular weight of the styrene-based resin (E) is a value in terms of standard polystyrene (PS) calculated by analyzing a solution dissolved in tetrahydrofuran (THF) by gel permeation chromatography (GPC).

<Ethylene / α-olefin copolymer (F)>
The ethylene / α-olefin copolymer (F) includes an ethylene unit and an α-olefin unit obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms by a known polymerization method. It is a copolymer.
The ethylene / α-olefin copolymer (F) may further contain a non-conjugated diene unit. When the ethylene / α-olefin copolymer (F) contains a non-conjugated diene unit, the impact resistance of the molded product is further improved.

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

  Non-conjugated dienes include dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-cycloheptadiene, 1, 5-cyclooctadiene etc. are mentioned. Among these, dicyclopentadiene and / or 5-ethylidene-2-norbornene is preferable as the non-conjugated diene unit because the resulting molded article has more excellent impact resistance.

  The ethylene unit content of the ethylene / α-olefin copolymer (F) is 45 to 45% when the total of all the structural units constituting the ethylene / α-olefin copolymer (F) is 100% by mass. 80 mass% is preferable and 50-75 mass% is more preferable. When the ethylene unit content is within the above range, the impact resistance of the molded product is more excellent.

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

The mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (F) is preferably 4 × 10 ^{4 to} 35 × 10 ^{4, and} more preferably 5 × 10 ⁴ to 10 × 10 ⁴ . When the mass average molecular weight (Mw) is 4 × 10 ⁴ or more, the impact resistance and color developability of the molded product are more excellent. On the other hand, if the mass average molecular weight (Mw) is 35 × 10 ⁴ or less, the fluidity of the thermoplastic resin composition is more excellent. When the mass average molecular weight (Mw) is 5 × 10 ⁴ to 10 × 10 ⁴ , the fluidity of the thermoplastic resin composition, the color developability of the molded product, and the impact resistance are further improved.

  The molecular weight distribution (Mw / number average molecular weight (Mn)) of the ethylene / α-olefin copolymer (F) is preferably from 1.0 to 5.0, more preferably from 3.1 to 4.0. When the molecular weight distribution (Mw / Mn) is 5.0 or less, the impact resistance of the molded product is more excellent. When the molecular weight distribution (Mw / Mn) is 3.1 to 4.0, the fluidity of the thermoplastic resin composition and the impact resistance of the molded product are further improved.

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

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

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

Examples of the polymerization method include a method in which ethylene and α-olefin, or ethylene, α-olefin, and non-conjugated diene are copolymerized in a solvent in the presence of the catalyst (metallocene catalyst or Ziegler-Natta catalyst). It is done. Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may use the raw material alpha olefin as a solvent.
In the polymerization, a molecular weight regulator such as hydrogen may be used.
Polymerization conditions are not particularly limited, and examples include polymerization conditions of 40 to 120 ° C. and 0.2 to 5 MPa for 1 to 10 hours.

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

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

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

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

  The preparation method of the olefin resin aqueous dispersion (G) is not limited. As the preparation method, for example, (g1) the ethylene / α-olefin copolymer (F) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.), and the mechanical shearing force is increased. (G2) The ethylene / α-olefin copolymer (F) is dissolved in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.), and then added to an aqueous medium. And then emulsifying and emulsifying the mixture, followed by sufficient stirring to distill off the hydrocarbon solvent. In preparing the aqueous olefin resin dispersion (G), an acid-modified olefin polymer, an emulsifier, and the like may be added as other components.

The method for adding the acid-modified olefin polymer is not limited. For example, in the method (g1), the ethylene / α-olefin copolymer (F) and the acid-modified olefin polymer are mixed and melt-kneaded, and in the method (g2), the ethylene / α-olefin is mixed. Examples thereof include a method of dissolving the copolymer (F) and the acid-modified olefin polymer in a hydrocarbon solvent.
The mixing method of the ethylene / α-olefin copolymer (F) and the acid-modified olefin polymer is not limited. Examples of the mixing method include a melt kneading method using a kneader, a Banbury mixer, a multi-screw extruder and the like. In this case, the step of mixing the ethylene / α-olefin copolymer (F) and the acid-modified olefin polymer may also serve as a step of melt-kneading the mixture.
The method for adding the emulsifier is not limited. For example, the method similar to the addition method of an acid-modified olefin polymer is mentioned. Examples of the method (g1) or (g2) include a method of adding an emulsifier to an aqueous medium, and a method of dissolving the emulsifier in a hydrocarbon solvent in the method (g2).

The volume average particle diameter of the ethylene / α-olefin copolymer (F) constituting the aqueous olefin resin dispersion (G) is preferably 0.20 to 0.60 μm in view of excellent physical properties of the molded product. 30-0.50 micrometer is more preferable.
That is, the graft copolymer (I) polymerizes the vinyl monomer component (m1) in the presence of the ethylene / α-olefin copolymer (F) having a volume average particle diameter of 0.20 to 0.60 μm. Ethylene / α-olefin copolymer having a volume average particle diameter of 0.20 to 0.60 μm derived from the graft copolymer (I). It is preferable that a combination (F) is included.
When the volume average particle diameter is 0.20 μm or more, the impact resistance of the molded product is more excellent. When the volume average particle size is 0.60 μm or less, the impact resistance, color developability, and heat aging resistance of the molded product are more excellent. When the average particle diameter of the ethylene / α-olefin copolymer (F) is 0.3 to 0.5 μm, the impact resistance, color developability, and heat aging resistance of the molded product are further improved.
The volume average particle diameter of the ethylene / α-olefin copolymer (F) constituting the olefin resin aqueous dispersion (G) is the same as that of the ethylene / α-olefin copolymer (F) in the thermoplastic resin composition. It is confirmed by image analysis with an electron microscope that the volume average particle diameter is shown.

The method for controlling the volume average particle size of the ethylene / α-olefin copolymer (F) dispersed in the aqueous olefin resin dispersion (G) includes the type or amount of emulsifier, the type of acid-modified olefin polymer. Or the method of adjusting content, the shear force added at the time of kneading | mixing, temperature conditions, etc. is mentioned.
The amount of the emulsifier used is preferably 1.0 to 10.0% by mass with respect to 100% by mass of the ethylene / α-olefin copolymer (F). The amount of the acid-modified olefin polymer used is preferably 5.0 to 30.0% by mass relative to the ethylene / α-olefin copolymer (F). As temperature conditions at the time of kneading | mixing, 100-300 degreeC is preferable.

<Crosslinked ethylene / α-olefin copolymer (H)>
The crosslinked ethylene / α-olefin copolymer (H) is an ethylene / α-olefin copolymer (F) dispersed in an ethylene / α-olefin copolymer (F) or an aqueous olefin resin dispersion (G) ( F) was obtained by crosslinking treatment. Crosslinking treatment further improves the balance between impact resistance and color development of the molded product.

The gel content of the crosslinked ethylene / α-olefin copolymer (H) is preferably from 35 to 85% by mass, more preferably from 45 to 80% by mass, from the viewpoint of the balance between the impact resistance and color developability of the molded product. 60 to 75% by mass is particularly preferable.
The gel content in the present invention means that the crosslinked ethylene / α-olefin copolymer (H) is swollen with toluene, and the crosslinked ethylene / α-olefin copolymer (H) before swelling is dried. This is the proportion of toluene insoluble matter. In detail, it calculates | requires by the method as described in an Example.

  The crosslinking treatment of the ethylene / α-olefin copolymer (F) or the aqueous olefin resin dispersion (G) can be carried out by a known method. Examples of the crosslinking treatment method include (a) a method in which an organic peroxide and, if necessary, a polyfunctional compound are added to carry out a crosslinking treatment, and (b) a method in which a crosslinking treatment is performed with ionizing radiation. The method (a) is preferred from the viewpoint of impact resistance and color development of the molded product.

Specifically, as the method of (a), an ethylene / α-olefin copolymer (F) or an aqueous olefin resin dispersion (G) is mixed with an organic peroxide and, if necessary, a polyfunctional compound. The method of adding and heating is mentioned.
For example, when an organic peroxide and, if necessary, a polyfunctional compound are added to the ethylene / α-olefin copolymer (F), melt-kneaded, and pulverized, a crosslinked ethylene / α-olefin copolymer is obtained. A powder of (H) is obtained. If necessary, the pulverized product obtained by pulverization may be subjected to a treatment such as classification. When an organic peroxide and, if necessary, a polyfunctional compound are added to the olefin resin aqueous dispersion (G) and subjected to crosslinking treatment, an aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (H) is obtained. can get.
The gel content of the crosslinked ethylene / α-olefin copolymer (H) can be adjusted by adjusting the addition amount of organic peroxide and polyfunctional compound, heating temperature, heating time and the like.
The heating temperature varies depending on the type of organic peroxide. The heating temperature is preferably −5 ° C. to + 30 ° C., which is the 10-hour half-life temperature of the organic peroxide.
The heating time is preferably 3 to 15 hours.

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

As the organic peroxide, a dialkyl peroxide compound is particularly preferable because the gel content of the crosslinked ethylene / α-olefin copolymer (G) can be easily adjusted.
Specific examples of the dialkyl peroxide compound include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butyl. Examples include cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

  The addition amount of the organic peroxide is such that the gel content of the crosslinked ethylene / α-olefin copolymer (H) can be easily adjusted to a range of 35 to 85% by mass, so that the ethylene / α-olefin copolymer (F ) 0.1 to 5 parts by mass is preferable with respect to 100 parts by mass.

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

  The addition amount of the polyfunctional compound is such that the gel content of the crosslinked ethylene / α-olefin copolymer (H) can be easily adjusted to 35 to 85% by mass, so that the ethylene / α-olefin copolymer (F) 100 is added. 1-5 mass parts is preferable with respect to a mass part.

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

  The volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (H) or the volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (H) in the aqueous dispersion is excellent in the physical properties of the molded product. Therefore, 0.2 to 0.6 μm is preferable, and 0.3 to 0.5 μm is more preferable. When the volume average particle diameter is 0.2 μm or more, the impact resistance of the molded product is more excellent. When the volume average particle diameter is 0.6 μm or less, the impact resistance, color developability, and heat aging resistance of the molded product are more excellent. When the volume average particle diameter of the crosslinked ethylene / α-olefin (H) is 0.3 μm to 0.5 μm, the impact resistance, color developability, and heat aging resistance of the molded product are further improved.

In addition, the crosslinked ethylene / α-olefin copolymer (H) in the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (H) obtained by crosslinking the aqueous dispersion of the olefin resin (G) with an organic peroxide. The volume average particle diameter does not change with respect to the volume average particle diameter of the ethylene / α-olefin copolymer (F) in the aqueous olefin resin dispersion (G). That is, the crosslinking reaction of the ethylene / α-olefin copolymer (F) proceeds on the surface or inside of the particles of the ethylene / α-olefin copolymer (F) in the aqueous dispersion of olefin resin (G), and the particle diameter Without the expansion of.
The volume average particle size in the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (H) indicates the volume average particle size of the crosslinked ethylene / α-olefin copolymer (H). This is confirmed by image analysis.

<Vinyl monomer component (m4)>
The vinyl monomer component (m4) contains at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and other vinyl monomers as monomers.
The vinyl monomer component (m4) preferably contains an aromatic vinyl compound and a vinyl cyanide compound.

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

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

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

  The content of the aromatic vinyl compound in the vinyl monomer component (m4) is preferably 60 to 85% by mass with respect to the total mass (100% by mass) of the vinyl monomer component (m4), and 62 to 80 mass% is more preferable. When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

  The content of the vinyl cyanide compound in the vinyl monomer component (m4) is preferably 15 to 40% by mass with respect to the total mass (100% by mass) of the vinyl monomer component (m4). 38 mass% is more preferable. When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

<Graft copolymer (I)>
The graft copolymer (I) is obtained by polymerizing the vinyl monomer component (m4) in the presence of the olefin copolymer, and includes, for example, the following (α), (β), (Γ) and (δ) may be mentioned.
(Α) A product obtained by polymerizing the vinyl monomer component (m4) in the presence of the ethylene / α-olefin copolymer (F).
(Β) A product obtained by polymerizing the vinyl monomer component (m4) in the presence of the aqueous olefin resin dispersion (G).
(Γ) A vinyl monomer component (m4) is polymerized in the presence of the crosslinked ethylene / α-olefin copolymer (H) obtained by crosslinking the ethylene / α-olefin copolymer (F). Obtained.
(Δ) In the presence of the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (H) obtained by crosslinking the aqueous olefin resin dispersion (G), the vinyl monomer component (m4) is added. Obtained by polymerization.
The graft copolymer (I) is prepared by adding an olefin copolymer (ethylene / α-olefin copolymer (F), crosslinked ethylene / α-olefin copolymer (H), etc.) to a vinyl monomer component ( m4) a graft chain composed of a polymer, and a core part composed of a granular olefin copolymer and an outer layer part (shell part) composed of a polymer of a vinyl monomer component (m4). ). However, since it is not always such a core-shell type, it is defined as “obtained by polymerizing a vinyl monomer component (m4) in the presence of an olefin copolymer”. It is more appropriate to do.

The graft copolymer (I) is a vinyl monomer component (m4) 20 to 50% by mass in the presence of 50 to 80% by mass of the olefin copolymer (provided that the olefin copolymer and vinyl monomer The total obtained with the monomer component (m4) is 100% by mass).
That is, the graft copolymer (I) contains 50 to 80% by mass of an olefin copolymer and 20 to 50% by mass of a polymer of a vinyl monomer component (m4) (however, the olefin copolymer and vinyl). The total amount of the system monomer component (m4) and the polymer is 100% by mass.).
When the content ratio of the olefin copolymer is 50 to 80% by mass, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, and the physical property balance of color development properties are further improved.

The graft ratio of the graft copolymer (I) is preferably 20 to 100% by mass from the viewpoint of the balance between the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, and the color developability.
The graft ratio of the graft copolymer (I) is a value measured by the method described in Examples below.

  Examples of the polymerization method of the vinyl monomer component (m4) include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.).

As the method for producing the graft copolymer (I) by the emulsion polymerization method, for example, a mixture of an organic peroxide and a vinyl monomer component (m4) is used as an aqueous dispersion of an olefin copolymer (for example, Examples thereof include a method of continuously adding to an aqueous dispersion of an olefin resin (G) or an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (H)).
The organic peroxide is preferably used as a redox initiator that combines an organic peroxide, a transition metal, and a reducing agent.
In the polymerization, a chain transfer agent, an emulsifier or the like may be used depending on the situation.

The redox initiator does not require the polymerization reaction conditions to be at a high temperature, avoids deterioration of the olefin copolymer, etc., and avoids reduction in impact resistance of the molded product. A combination of a ferrous iron-chelating agent-reducing agent is preferred.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, and t-butyl hydroperoxide.
The redox initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of chain transfer agents include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allylsulfonic acid, methallylsulfonic acid, these Sodium salts, etc.), α-methylstyrene dimers, and the like, and mercaptans are preferred from the viewpoint of easy adjustment of the molecular weight. A chain transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
The addition amount of the chain transfer agent is preferably 2.0 parts by mass or less with respect to 100 parts by mass of the vinyl monomer component (m4).

Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, and amino acid derivative salts.
Examples of nonionic surfactants include ordinary polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types.
Examples of the amphoteric surfactant include those having a carboxylate salt, sulfate ester salt, sulfonate salt, phosphate ester salt and the like in the anion portion and amine salts and quaternary ammonium salts in the cation portion.
The addition amount of the emulsifier is preferably 10 parts by mass or less with respect to 100 parts by mass of the vinyl monomer component (m4).
The polymerization conditions for emulsion polymerization are not particularly limited, and examples include polymerization conditions at 50 to 90 ° C. for 1 to 10 hours.

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

Examples of the method for producing the graft copolymer (I) by the solution polymerization method include olefin copolymers (for example, ethylene / α-olefin copolymer (F) or crosslinked ethylene / α-olefin copolymer (H)). ) Is dissolved in a solvent, and a polymerization initiator and a vinyl monomer component (m4) are added.
As the solvent, an inert polymerization solvent used in usual radical polymerization is used. For example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, halogenated compounds such as dichloromethylene and carbon tetrachloride. A hydrocarbon or the like is used.
As the polymerization initiator in the solution polymerization, a general initiator is used, and for example, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide are used. Moreover, as the addition method of a polymerization initiator, the method of adding collectively or the method of adding continuously is mentioned.
The polymerization conditions for solution polymerization are not particularly limited, and examples include polymerization conditions at 50 to 90 ° C. for 1 to 10 hours.

<Other thermoplastic resins>
Other thermoplastic resins include, for example, (meth) acrylic ester resins other than (meth) acrylic ester resin (C), polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride , Polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester, polyethylene, polypropylene, polyamide (nylon), fluororesin and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

<Various additives>
Various additives include antioxidants, UV absorbers, lubricants, plasticizers, stabilizers, release agents, antistatic agents, processing aids, colorants (pigments, dyes, etc.), carbon fibers, glass fibers, Examples thereof include fillers such as lastite, calcium carbonate and silica, antidrip agents, antibacterial agents, antifungal agents, coupling agents, and paraffin oil. These may be used individually by 1 type and may be used in combination of 2 or more type.

<Content of each component>
The content of the graft copolymer (B) is 100 mass in total of the graft copolymer (B), the (meth) acrylic ester resin (C), the styrene resin (E), and the graft copolymer (I). 18-80 mass% is preferable with respect to%, and 30-60 mass% is more preferable. If the content of the graft copolymer (B) is within the above range, the balance of impact resistance and heat resistance of the molded product is more excellent.

  The content of the (meth) acrylic ester resin (C) is that of the graft copolymer (B), the (meth) acrylic ester resin (C), the styrene resin (E), and the graft copolymer (I). 20-82 mass% is preferable with respect to a total of 100 mass%, and 40-70 mass% is more preferable. If content of (meth) acrylic ester resin (C) is in the said range, the balance of the color development property, heat resistance, and heat aging resistance of a molded article will be more excellent.

  The content of the silicone oil (D) is 100 parts by mass in total of the graft copolymer (B), the (meth) acrylate resin (C), the styrene resin (E), and the graft copolymer (I). 0.1-5 mass parts is preferable, and 0.3-3 mass parts is more preferable. When the content of the silicone oil (D) is within the above range, the impact resistance, color developability, and heat aging resistance of the molded product are more excellent.

The content of the styrene resin (E) is 100% by mass in total of the graft copolymer (B), the (meth) acrylate resin (C), the styrene resin (E), and the graft copolymer (I). 0-40 mass% is preferable with respect to 1-40 mass%. When the content of the styrenic resin (E) is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the molded article, the color development, the weather resistance, and the heat aging resistance are excellent.
The content of the styrenic resin (E) of 0% by mass indicates that the thermoplastic resin composition does not contain the styrenic resin (E).

The content of the graft copolymer (I) is 100 mass in total of the graft copolymer (B), the (meth) acrylic ester resin (C), the styrene resin (E), and the graft copolymer (I). 0-15 mass% is preferable with respect to%. When the content of the graft copolymer (I) is within the above range, the balance of physical properties such as fluidity of the thermoplastic resin composition, impact resistance of the molded article, color development, heat resistance, and heat aging resistance is excellent.
The content of the graft copolymer (I) being 0% by mass indicates that the thermoplastic resin composition does not contain the graft copolymer (I).

  For the total (100% by mass) of the composite rubber-like polymer (A) and the olefin copolymer in the graft copolymer (I), an olefin copolymer (ethylene / α-olefin copolymer ( F), the proportion of the ethylene / α-olefin copolymer (F) and the crosslinked ethylene / α-olefin copolymer (H) in the aqueous olefin resin dispersion (G) is preferably 1 to 45% by mass, 4-32 mass% is more preferable. That is, the ratio of the composite rubber-like polymer (A) is preferably 55 to 99% by mass with respect to the total (100% by mass) of the olefin copolymer and the composite rubber-like polymer (A), and 68 to 96 mass% is more preferable. If the ratio of the olefin copolymer is 1% by mass or more (the ratio of the composite rubber-like polymer (A) is 99% by mass or less), the durability of the impact resistance of the molded article is more excellent. When the ratio of the olefin copolymer is 15% by mass or less (the ratio of the composite rubber-like polymer (A) is 85% by mass or more), the color developability, heat aging resistance, and weather resistance of the molded product are further improved.

  The total content (rubber content) of the composite rubber-like polymer (A) and the olefin-based copolymer in the graft copolymer (I) is 5 to 30 with respect to 100% by mass of the thermoplastic resin composition. % By mass is preferable, and 10 to 25% by mass is more preferable. When the rubber content is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, the color development, and the heat resistance are further improved.

  The total content of graft copolymer (B) and graft copolymer (I) is as follows: graft copolymer (B), (meth) acrylic ester resin (C), styrenic resin (E) and graft 10-60 mass% is preferable with respect to a total of 100 mass% with copolymer (I). If the total content of the graft copolymer (B) and the graft copolymer (I) is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, the color development, the heat resistance, etc. The physical property balance is even better.

  18-80 mass% is preferable with respect to the total mass of a thermoplastic resin composition, and, as for content of a graft copolymer (B), 30-60 mass% is more preferable. When the content of the graft copolymer (B) is within the above range, the balance of scratch resistance, impact resistance, and heat resistance of the molded product is more excellent.

20-82 mass% is preferable with respect to the total mass of a thermoplastic resin composition, and, as for content of (meth) acrylic acid ester resin (C), 40-70 mass% is more preferable. If content of (meth) acrylic ester resin (C) is in the said range, the balance of the color development property, heat resistance, and heat aging resistance of a molded article will be more excellent.
The content of the other (meth) acrylic ester resin is preferably 0 to 90% by mass with respect to the total of the (meth) acrylic ester resin (C) and the other (meth) acrylic ester resin. 80 mass% is more preferable.

As a preferred embodiment of the thermoplastic resin composition of the present invention, it includes a graft copolymer (B) and a (meth) acrylic ester resin (C),
The content of the graft copolymer (B) is 18 to 80% by mass with respect to the total of the graft copolymer (B) and the (meth) acrylate resin (C), and the (meth) acrylate resin (C ) Is a thermoplastic resin composition having a content of 20 to 82% by mass.
In this embodiment, it is preferable that content of the said graft copolymer (B) is 30-60 mass%, and content of the said (meth) acrylic ester resin (C) is 40-70 mass%. .
In the present embodiment, the total content of the graft copolymer (B) and the (meth) acrylic ester resin (C) with respect to the total mass of the thermoplastic resin composition is preferably 50 to 100% by mass.

Other preferred embodiments of the thermoplastic resin composition of the present invention include a graft copolymer (B), a (meth) acrylic ester resin (C), and a silicone oil (D).
The content of the graft copolymer (B) is 18 to 80% by mass with respect to the total of the graft copolymer (B) and the (meth) acrylate resin (C), and the (meth) acrylate resin (C ) Content is 20 to 82% by mass,
A thermoplastic resin composition having a silicone oil (D) content of 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the graft copolymer (B) and the (meth) acrylic ester resin (C). Is mentioned.
In this embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylic ester resin (C) is 40 to 70% by mass, and the silicone oil The content of (D) is preferably 0.3 to 3 parts by mass.
In this embodiment, the total content of the graft copolymer (B), the (meth) acrylic ester resin (C), and the silicone oil (D) with respect to the total mass of the thermoplastic resin composition is 50 to 100 mass. % Is preferred.

As other preferable embodiments of the thermoplastic resin composition of the present invention, a graft copolymer (B), a (meth) acrylic ester resin (C), a silicone oil (D), and a styrenic resin (E) Including
The content of the graft copolymer (B) is 18 to 60% by mass with respect to the total of the graft copolymer (B), the (meth) acrylic ester resin (C), and the styrene resin (E). ) The content of acrylic ester resin (C) is 20 to 81 mass%, the content of styrene resin (E) is 1 to 40 mass%,
The silicone oil (D) content is 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the graft copolymer (B), the (meth) acrylic ester resin (C), and the styrene resin (E). The thermoplastic resin composition which is is mentioned.
In this embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylic ester resin (C) is 20 to 69% by mass, and the styrenic It is preferable that the content of the resin (E) is 1 to 30% by mass and the content of the silicone oil (D) is 0.3 to 3 parts by mass.
In this embodiment, the total content of the graft copolymer (B), the (meth) acrylic ester resin (C), the silicone oil (D), and the styrenic resin (E) with respect to the total mass of the thermoplastic resin composition. The amount is preferably 70 to 100% by mass.

Other preferred embodiments of the thermoplastic resin composition of the present invention include a graft copolymer (B), a (meth) acrylate resin (C), and a graft copolymer (I),
The content of the graft copolymer (B) is 18 to 60% by mass with respect to the total of the graft copolymer (B), the (meth) acrylic ester resin (C) and the graft copolymer (I). A thermoplastic resin composition in which the content of the (meth) acrylic ester resin (C) is 20 to 81% by mass and the content of the graft copolymer (I) is 1 to 15% by mass.
In this embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylic ester resin (C) is 30 to 69% by mass, The content of the polymer (I) is preferably 1 to 10% by mass.
In this embodiment, the total content of the graft copolymer (B), the (meth) acrylic ester resin (C), and the graft copolymer (I) with respect to the total mass of the thermoplastic resin composition is 50 to 100 mass% is preferable.

As another preferable embodiment of the thermoplastic resin composition of the present invention, a graft copolymer (B), a (meth) acrylic ester resin (C), a silicone oil (D), and a graft copolymer (I ) And
The content of the graft copolymer (B) is 18 to 60% by mass with respect to the total of the graft copolymer (B), the (meth) acrylic ester resin (C) and the graft copolymer (I). The content of the (meth) acrylate resin (C) is 20 to 81% by mass, the content of the graft copolymer (I) is 1 to 15% by mass,
Content of silicone oil (D) is 0.1-5 mass with respect to a total of 100 mass parts of graft copolymer (B), (meth) acrylic ester resin (C), and graft copolymer (I). Part of the thermoplastic resin composition.
In this embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylic ester resin (C) is 30 to 69% by mass, The content of the polymer (I) is preferably 1 to 10% by mass, and the content of the silicone oil (D) is preferably 0.3 to 3 parts by mass.
In this embodiment, the total of the graft copolymer (B), the (meth) acrylic ester resin (C), the silicone oil (D), and the graft copolymer (I) with respect to the total mass of the thermoplastic resin composition. The content is preferably 50 to 100% by mass.

As other preferable embodiments of the thermoplastic resin composition of the present invention, a graft copolymer (B), a (meth) acrylic ester resin (C), a silicone oil (D), and a styrenic resin (E) And graft copolymer (I),
Graft copolymer (B), (meth) acrylic acid ester resin (C), styrenic resin (E) and graft copolymer (I) have a total content of graft copolymer (B). 18-60 mass%, content of (meth) acrylic ester resin (C) is 20-80 mass%, content of styrene resin (E) is 1-40 mass%, graft copolymer (I) Content is 1-10 mass%,
Content of silicone oil (D) with respect to a total of 100 parts by mass of graft copolymer (B), (meth) acrylic ester resin (C), styrene resin (E) and graft copolymer (I) May be 0.1 to 5 parts by mass of a thermoplastic resin composition.
In this embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylic ester resin (C) is 40 to 68% by mass, and the styrenic The content of the resin (E) is 1 to 40% by mass, the content of the graft copolymer (I) is 1 to 10% by mass, and the content of the silicone oil (D) is 0.3 to 3% by mass. Part.
In this embodiment, the graft copolymer (B), the (meth) acrylic ester resin (C), the silicone oil (D), the styrene resin (E), and the graft copolymer with respect to the total mass of the thermoplastic resin composition. The total content of (I) is preferably 90 to 100% by mass.

  In each of the above embodiments, a part of the (meth) acrylic ester resin (C) may be replaced with another (meth) acrylic ester resin. The content of the other (meth) acrylic ester resin is preferably 0 to 90% by mass with respect to the total of the (meth) acrylic ester resin (C) and the other (meth) acrylic ester resin. 80 mass% is more preferable.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition comprises a graft copolymer (B), a (meth) acrylic ester resin (C), and other components (silicone oil (D), styrenic resin (E), graft as required. It can be obtained by mixing copolymer (I), other thermoplastic resin, and various additives.

<Uses of thermoplastic resin composition>
The thermoplastic resin composition of the present invention is molded by a heat cycle injection molding method in which the cavity surface temperature of the mold is repeatedly raised and lowered using an injection mold in which the cavity surface of the mold is alternately heated and cooled. It is considered a product.
The heat cycle injection molding method will be described in detail later.

<Effect>
In the thermoplastic resin composition of the present invention described above, units derived from polyorganosiloxane (Aa) and (meth) acrylic acid ester, units derived from a crosslinking agent, and units derived from a graft crossing agent A vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a composite rubber-like polymer (A) comprising a poly (meth) acrylic acid ester (Ab) having either or both of A graft copolymer (B) obtained by polymerizing the component (m1) and a vinyl monomer component (m2) containing a (meth) acrylic acid ester, a maleimide compound and an aromatic vinyl compound are polymerized. (Meth) acrylic acid ester resin (C) obtained, and inclusion of polyorganosiloxane (Aa) in composite rubber-like polymer (A) (100% by mass) Of the composite rubber-like polymer (A) is 0.05 μm to 0.15 μm, and the vinyl monomer component (m2) (100% by mass) Since the content of the maleimide compound is 1 to 30% by mass and the content of the aromatic vinyl compound is 5.5 to 15% by mass, the surface appearance and scratch resistance when molded by the heat cycle injection molding method A molded article having excellent scratch resistance, impact resistance, color development, heat resistance, and heat aging resistance can be obtained. Moreover, the fluidity of the thermoplastic resin composition is also good.

In the thermoplastic resin composition of the present invention, the molded article (Ma2) formed from the thermoplastic resin composition of the present invention preferably has a Charpy impact strength of 5 kJ / m ² or more, and is 5 to 20 kJ / m ² . More preferably. If the Charpy impact strength is not less than the lower limit, the impact resistance is sufficiently excellent, and if it is not more than the upper limit, the balance of other characteristics is good.
“Molded product (Ma2)” is an injection molding machine equipped with an injection mold in which a thermoplastic resin composition is melt-kneaded with a twin-screw extruder and the cavity surface of the mold is alternately heated and cooled. Heat cycle injection molding was performed under the conditions of 260 ° C., mold temperature 110 ° C. during resin filling into the mold, and mold temperature 40 ° C. during cooling to obtain a molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. Is.
The “Charpy impact strength” is a value measured by conducting a Charpy impact test on the molded product (Ma2) according to ISO 179-1: 2000 under notched conditions at 23 ° C.

In the thermoplastic resin composition of the present invention, the deflection temperature under load of the molded article (Ma2) formed from the thermoplastic resin composition of the present invention is preferably 80 ° C. or higher, more preferably 80 to 115 ° C. preferable. If the deflection temperature under load is equal to or higher than the lower limit value, the heat resistance is sufficiently excellent, and if it is equal to or lower than the upper limit value, the balance of other characteristics is good.
The “deflection temperature under load” is a value measured by the flat-wise method for the molded product (Ma2) in accordance with ISO 75-1: 2004 according to 1.83 MPa, 4 mm.

In the thermoplastic resin composition of the present invention, the lightness L ^{* of} the molded article (Ma1) formed from the thermoplastic resin composition of the present invention is preferably 7.0 or less, and 3.0 to 7.0 is preferable. More preferred. If the lightness L ^* is not more than the above upper limit value, the color developability is sufficiently excellent, and if it is not less than the above lower limit value, the balance of other characteristics is good.
“Molded product (Ma1)” is a thermoplastic resin composition obtained by converting a resin component (graft copolymer (B), (meth) acrylate resin (C), styrenic resin (E), graft copolymer ( I) Injection in which the mold cavity surface is alternately heated and cooled by melt-kneading with a twin-screw extruder in a state containing 0.8 parts of carbon black with respect to 100 parts of the total amount of other thermoplastic resins) In an injection molding machine equipped with a molding die, heat cycle injection molding is performed under conditions of a cylinder temperature of 260 ° C., a mold temperature of 110 ° C. when filling the mold with resin, and a mold temperature of 40 ° C. during cooling. It is what.
“Lightness L ^* ” is a value measured by the SCE method for the molded product (Ma1). A detailed method for measuring the lightness (L ^* ) by the SCE method will be described in Examples described later.

In the thermoplastic resin composition of the present invention, the degree of discoloration (ΔE) before and after the weather resistance test of the molded article (Ma1) formed from the thermoplastic resin composition of the present invention is preferably 3.0 or less. More preferably, it is 0.0-3.0. If ΔE is not more than the upper limit value, the weather resistance is sufficiently excellent, and if it is not less than the lower limit value, the balance of other characteristics is good.
The “weather resistance test” is a test in which the molded product (Ma1) is treated for 1000 hours using a sunshine weather meter at a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall 12 minutes).
The “degree of color change (ΔE)” is a value measured by the SCE method using a spectrocolorimeter.

In the thermoplastic resin composition of the present invention, the degree of discoloration (ΔE) before and after the heat aging resistance test of the molded article (Ma1) formed from the thermoplastic resin composition of the present invention is preferably 3.4 or less, More preferably, it is 0.5 to 3.4. If ΔE is not more than the upper limit value, the heat aging resistance is sufficiently excellent, and if it is not less than the lower limit value, the balance of other characteristics is good.
The “heat aging resistance test” is a test in which the molded article (Ma1) is treated for 500 hours using a thermostat at a temperature of 90 ° C. and a humidity of 30%. The degree of color change (ΔE) is as described above.

In the thermoplastic resin composition of the present invention, the absolute value of the lightness difference L ^* (mb-ma) before and after the pencil hardness test of the molded article (Ma1) formed from the thermoplastic resin composition of the present invention is less than 3.0. It is preferable that it is 1.0 or more and less than 3.0. If the absolute value of L ^* (mb-ma) is not more than the above upper limit value, scratch resistance is sufficiently excellent, and if it is not less than the above lower limit value, the balance of other characteristics is good.
“L ^* (mb−ma)” is a value calculated from the following equation (3).
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)
“L ^* (ma)” is the lightness L ^* of the molded product (Ma1). “L ^* (mb)” is the lightness L ^* of the molded product (Mb). The lightness L ^* is as described above.
“Molded product (Mb)” is a pencil hardness tester, and a 3H hardness pencil is pressed against the surface of the molded product (Ma1) under a load of 7.35 N (750 g), and the molded product (Ma1) is in that state. The surface of the molded product (Ma1) is scratched with a pencil by moving about 5 cm.

"Molding"
The molded article of the present invention is formed by molding the thermoplastic resin composition of the present invention.
As described above, the heat cycle injection molding method is used as the method for producing the molded article of the present invention, that is, the molding method of the thermoplastic resin composition of the present invention.

In the heat cycle injection molding method, a thermoplastic resin composition is molded by repeatedly raising and lowering the cavity surface temperature of the mold using an injection mold in which the cavity surface of the mold is alternately heated and cooled. In the heat cycle injection molding method, before the thermoplastic resin composition is injected into a mold, the cavity surface temperature of the mold is raised to a temperature equal to or higher than the thermal deformation temperature (HDT) of the thermoplastic resin composition, The plastic resin composition is injected, the cavity surface temperature of the mold is lowered, the thermoplastic resin composition is cooled to obtain a molded product, and the molded product is taken out from the mold. Thereafter, the cavity surface temperature of the mold is again raised to a temperature equal to or higher than the thermal deformation temperature of the thermoplastic resin composition, and the above-described series of steps (injection of thermoplastic resin composition, cooling, removal of molded product) is performed. repeat.
More specific conditions of the heat cycle injection molding method include injection at a resin temperature of (T + 120 ° C.) to (T + 200 ° C.) with respect to the thermal deformation temperature (HDT) T ° C. of the thermoplastic resin composition, and a mold. The temperature T _A ° C is (T + 5 ° C.) to (T + 50 ° C.), the cooling temperature T _B ° C is (T−10 ° C.) to (T−50 ° C.), and T _A −T _B = 15 to 100 ° C. It is preferable to adopt conditions. The cycle of the heat cycle is preferably the same as the cycle of general injection molding or within the cycle of general injection molding + 10%.
Thermal deformation temperature is another name for deflection temperature under load, and is measured by the above-described measuring method.
Examples of the method of heating the mold cavity surface temperature above the heat distortion temperature of the thermoplastic resin composition include a hot water / cold water switching method, a steam heating method, a heating oil method, a mold surface heat insulation method, etc. It is not limited.

  In the molded article of the present invention described above, since the thermoplastic resin composition of the present invention is used, it is excellent in scratch resistance, impact resistance, color development, heat resistance, weather resistance, and heat aging resistance. . Further, since the thermoplastic resin composition is molded by the heat cycle injection molding method, the molded article has better scratch resistance and excellent surface appearance.

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

<Measurement method of average particle diameter>
The volume average particle diameter (μm) was measured using Microtrac (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.) using pure water as a measurement solvent.

<Method for measuring mass average molecular weight of (meth) acrylic ester resin (C) and styrene resin (E)>
Using GPC (GPC: “HLC8220” manufactured by Tosoh Corporation, column: “TSK GEL SuperHZM-H” manufactured by Tosoh Corporation), the mass average molecular weight (Mw) in terms of polystyrene was measured as a solvent of tetrahydrofuran (THF: 40 ° C.). .

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

<Method for measuring gel content of crosslinked ethylene / α-olefin copolymer (H)>
An aqueous or solvent dispersion of the crosslinked ethylene / α-olefin copolymer (H) is coagulated with dilute sulfuric acid, washed with water and dried to obtain 0.5 g of a coagulated powder sample [h1], 200 mL of 110 ° C. toluene. It was immersed in 5 hours, then filtered through a 200 mesh wire net, the residue was dried, the mass of the dried product [h2] was measured, and from the following formula (1), a crosslinked ethylene / α-olefin copolymer The gel content of (H) was determined.
Gel content rate (%) = dry substance amount [h2] (g) / coagulated powder sample mass [h1] (g) × 100 (1)

<Method for measuring graft ratio of graft copolymer (I)>
1 g of the graft copolymer (I) is added to 80 mL of acetone and heated to reflux at 65 to 70 ° C. for 3 hours. The resulting suspension acetone solution is added to a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.). The mixture was centrifuged at 14,000 rpm for 30 minutes to separate a precipitation component (acetone insoluble component) and an acetone solution (acetone soluble component). And the precipitation component (acetone insoluble component) was dried, the mass (Y (g)) was measured, and the graft ratio was computed from following formula (2). In Formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (I), and X is the total mass (g) of the graft copolymer (I) used when Y is determined. The rubber fraction is the solid content of the olefin copolymer of the graft copolymer (I).
Graft rate (%) = {(Y-X × rubber fraction) / X × rubber fraction} × 100 (2)

<Melt-kneading 1>
A mixture obtained by mixing the graft copolymer (B), the (meth) acrylic ester resin (C) and the like in accordance with the formulation of each of the examples and comparative examples was used as a twin screw extruder with a 30 mmφ vacuum vent ("PCM30" manufactured by Ikegai Co., Ltd.). )) Was melt kneaded at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition (1). Further, after melt-kneading, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Melting and kneading 2>
According to the formulation of each of the examples and comparative examples, the mixture obtained by mixing the graft copolymer (B), the (meth) acrylic ester resin (C) and the like, and 0 in the total amount of the resin component in the mixture is 100 parts. 8 parts of carbon black (“# 966” manufactured by Mitsubishi Chemical Co., Ltd.) was mixed, and the cylinder temperature was 200 to 260 ° C. and 93.325 kPa in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.). Melt kneading was performed under vacuum to obtain a thermoplastic resin composition (2). Further, after melt-kneading, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Measurement of melt volume rate (MVR)>
About the thermoplastic resin composition (1), according to ISO 1133: 1997, MVR in 230 degreeC was measured with the load of 98 N (10 kg). In addition, MVR becomes a standard of the fluidity | liquidity of a thermoplastic resin composition.

<Molding method A: heat cycle injection molding>
(1. Molding of molded product (Ma1))
As a molded product (molded product (Ma1)) for evaluation of color development, weather resistance, heat aging resistance, scratch resistance and surface appearance, a four-point gate molded product 1 as shown in FIG. 1 is molded by the following procedure. did. The molded product 1 is a plate having a length of 60 mm × width of 90 mm × thickness of 10 mm, an opening 2 having a rectangular shape (25 mm in length × 30 mm in width) in the center, and an upper surface in the upper left corner in the figure (product). A rectangular opening 3 (length: 25 mm × width: 30 mm), and a circular opening 4 (diameter: 10 mm) as viewed from above are formed in the lower left corner of the figure so as to penetrate the molded product 1. On one surface of the molded article 1, gates 2 </ b> A extending in the center direction of the opening 2 are formed at four locations on each of the four sides surrounding the opening 2.
“IS55FP-1.5A molding machine manufactured by Toshiba Machine Co., Ltd.” equipped with “high-speed heat cycle molding unit” manufactured by Ono Sangyo Co., Ltd. was obtained by pelletizing the thermoplastic resin composition (2) obtained by melt-kneading. , And the cylinder temperature (resin temperature during injection) is 260 ° C, the mold temperature when filling the mold with resin is 110 ° C, and the mold temperature during cooling is 40 ° C. It implemented and obtained the molded article (Ma1).

(2. Molding of molded product (Ma2))
As a molded product for evaluation of impact resistance and heat resistance (molded product (Ma2)), a plate-shaped molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was molded according to the following procedure.
“IS55FP-1.5A molding machine” manufactured by Toshiba Machine Co., Ltd., equipped with a “high-speed heat cycle molding unit” manufactured by Ono Sangyo Co., Ltd. was obtained by pelletizing the thermoplastic resin composition (1) obtained by melt kneading. The heat cycle injection molding was carried out under the conditions of cylinder temperature (resin temperature during injection) 260 ° C, mold temperature when filling resin into the mold was 110 ° C, and mold temperature during cooling was 40 ° C. A molded product (Ma2) was obtained.

<Molding method B: General molding (injection molding that does not raise or lower the cavity surface temperature of the mold)>
(1. Molding of molded product (Ma3))
As a molded product (molded product (Ma3)) for evaluation of color development, weather resistance, heat aging resistance, scratch resistance and surface appearance, a four-point gate molded product 1 as shown in FIG. Molded with
The pellets of the thermoplastic resin composition (2) obtained by melt-kneading are put into an “IS55FP-1.5A molding machine” manufactured by Toshiba Machine Co., Ltd. Injection molding was performed under conditions to obtain a molded product (Ma3).

(2. Molding of molded product (Ma4))
As a molded product for evaluation of impact resistance and heat resistance (molded product (Ma4)), a plate-shaped molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was molded according to the following procedure.
The pellets of the thermoplastic resin composition (1) obtained by melt-kneading are put into an “IS55FP-1.5A molding machine” manufactured by Toshiba Machine Co., Ltd., with a cylinder temperature of 200-270 ° C. and a mold temperature of 60 ° C. Injection molding was performed under conditions to obtain a molded product (Ma4).

<Evaluation of impact resistance: Charpy impact test>
The molded product (Ma2) or (Ma4) was subjected to a Charpy impact test (notched) at 23 ° C. in accordance with ISO 179-1: 2000, and the Charpy impact strength was measured.

<Evaluation of heat resistance>
With respect to the molded product (Ma2) or (Ma4), the deflection temperature under load (° C.) was measured by the flatwise method in accordance with ISO 75-1: 2004 according to 1.83 MPa.

<Evaluation of color development>
For the molded product (Ma1) or (Ma3), the lightness L ^* was measured by the SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). The L ^* measured in this way is referred to as “L ^* (ma)”. The lower L ^* was, the more black the color was determined.

In this specification, “lightness (L ^* )” means a lightness value (L ^* ) among color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729: 2004. .
The “SCE method” means a method of measuring a color by using a spectrocolorimeter compliant with JIS Z 8722: 2009 and removing specularly reflected light with an optical trap.

<Evaluation of weather resistance>
The molded product (Ma1) or (Ma3) was treated for 1000 hours under conditions of a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall of 12 minutes) using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). Then, the degree of color change (ΔE) before and after the treatment was measured and evaluated by the SCE method using a spectrocolorimeter. The smaller the ΔE, the better the weather resistance.

<Evaluation of heat aging resistance>
The molded product (Ma1) or (Ma3) was treated for 500 hours under the conditions of a temperature of 90 ° C. and a humidity of 30% using a thermostat (manufactured by ESPEC Corporation). Then, the degree of color change (ΔE) before and after the treatment was measured and evaluated by the SCE method using a spectrocolorimeter. The smaller the ΔE, the better the heat aging property.

<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 (Ma1) or (Ma3) under a load of 7.35 N (750 g), and the molded product (Ma1) or (Ma3) is pressed in this state. By moving about 5 cm, the surface of the molded product (Ma1) or (Ma3) was scratched with a pencil, and the molded product (Ma1) or (Ma3) was scratched. The brightness L ^* of the surface of the scratched molded article (Mb) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mb)”.

(Determination of scratch resistance)
A determination index ΔL ^* (mb−ma) for the visibility of scratches on the molded article (Mb) was calculated from the following formula (3). As the absolute value of ΔL ^* (mb−ma) is larger, the scratches are more conspicuous.
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)
When the absolute value of ΔL ^* (mb−ma) is 3.0 or less, the scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 3.0 to 7.0 or less, scratches are hardly noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

<Evaluation of surface appearance>
The surface of the molded product (Ma1) or (Ma3) was visually observed and judged according to the following criteria.
○: There is surface gloss and there is no uneven color in the weld.
Δ: There is surface gloss, but there is some uneven color at the weld.
X: No surface gloss and uneven color in the weld.

≪Each ingredient≫
In the following examples, the following composite rubber-like polymer (A), graft copolymer (B), (meth) acrylic ester resin (C), silicone oil (D), styrene resin (E), graft copolymer Polymer (I) was used.

<Graft copolymer (B) and its comparison product>
(Production of polyorganosiloxane (Aa1))
96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 2 parts of tetraethoxysilane were mixed to obtain 100 parts of a siloxane-based mixture. To this was added 300 parts of ion-exchanged water in which 8 parts of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred at 10000 rpm / 2 minutes with a homomixer, and then passed once through a homogenizer at a pressure of 30 MPa to provide stable premixed organosiloxane. An aqueous dispersion was obtained.
2 parts of dodecylbenzenesulfonic acid and 98 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. 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, followed by cooling. The reaction solution was allowed to stand at room temperature for 48 hours and then neutralized with an aqueous sodium hydroxide solution to obtain an aqueous dispersion of polyorganosiloxane (Aa1).
A part of the aqueous polyorganosiloxane (Aa1) dispersion was dried at 170 ° C. for 30 minutes and the solid content concentration was determined to be 17.3%. The volume average particle diameter of the polyorganosiloxane (Aa1) dispersed in the aqueous dispersion was 0.034 μm.

(Production of polyorganosiloxane (Aa2))
96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane and 2 parts of tetraethoxysilane were mixed to obtain 100 parts of a siloxane-based mixture. To this was added 300 parts of ion-exchanged water in which 0.67 parts of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred at 10000 rpm for 2 minutes with a homomixer. An aqueous organosiloxane dispersion was obtained.
2 parts of dodecylbenzenesulfonic acid and 98 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. 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, followed by cooling. The reaction solution was allowed to stand at room temperature for 48 hours and then neutralized with an aqueous sodium hydroxide solution to obtain an aqueous dispersion of polyorganosiloxane (Aa2).
A part of the polyorganosiloxane (Aa2) aqueous dispersion was dried at 170 ° C. for 30 minutes to obtain a solid content concentration of 17.3%. The volume average particle diameter of the polyorganosiloxane (Aa2) dispersed in the aqueous dispersion was 0.05 μm.

(Preparation of composite rubber-like polymer (A-1))
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 68.3 parts of an aqueous dispersion of polyorganosiloxane (Aa1) and 0.94 part of emulsifier (sodium polyoxyethylene alkylphenyl ether sulfate) Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 61.8 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added ( The mass ratio of polyorganosiloxane (Aa1) / n-butyl acrylate is 16/84). The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylic acid ester component to obtain an aqueous dispersion of the composite rubber-like polymer (A-1). The volume average particle diameter of the composite rubber-like polymer (A-1) dispersed in the aqueous dispersion was 0.041 μm. Table 1 shows the volume average particle diameter of the composite rubber-like polymer (A-1).

(Preparation of composite rubbery polymer (A-2))
As shown in Table 1, an aqueous dispersion of the composite rubber-like polymer (A-2) was prepared in the same manner as the preparation of the composite rubber-like polymer (A-1) except that the amount of emulsifier (parts) was changed. Obtained. Table 1 shows the volume average particle diameter of the composite rubber-like polymer (A-2) dispersed in the aqueous dispersion.

(Preparation of composite rubber-like polymer (A-3))
In a reactor equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 68.3 parts of an aqueous dispersion of polyorganosiloxane (Aa2), 0.85 part of emulsifier (sodium polyoxyethylene alkylphenyl ether sulfate) Was added, and 203 parts of ion-exchanged water was added and mixed. Thereafter, a mixture consisting of 61.8 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added ( The mass ratio of polyorganosiloxane (Aa2) / n-butyl acrylate is 16/84). The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water. An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylic acid ester component to obtain an aqueous dispersion of the composite rubber-like polymer (A-3). The volume average particle diameter of the composite rubber-like polymer (A-3) dispersed in the aqueous dispersion was 0.071 μm. Table 1 shows the volume average particle diameter of the composite rubber-like polymer (A-3).

(Preparation of composite rubbery polymers (A-4) to (A-7))
As shown in Table 1, the composite rubber-like polymers (A-4) to (A-7) were prepared in the same manner as the preparation of the composite rubber-like polymer (A-3) except that the amount (parts) of the emulsifier was changed. ) Was obtained. Table 1 shows the volume average particle diameters of the composite rubber-like polymers (A-4) to (A-7) dispersed in the aqueous dispersion.

(Preparation of composite rubbery polymer (A-8))
0.7 parts of dipotassium alkenyl succinate, 175 parts of ion-exchanged water, 100 parts of n-butyl acrylate, 0.26 parts of allyl methacrylate, 0.14 parts of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.2 part of the mixture was charged to the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00026 parts of ferrous sulfate, 0.0008 parts of disodium ethylenediaminetetraacetate, 0.45 parts of Rongalite, and 10 parts of ion-exchanged water was added. Polymerization was started and the internal temperature was raised to 75 ° C. Further, this state was maintained for 1 hour to obtain an aqueous dispersion of a composite rubber-like polymer (A-8). The volume average particle diameter of the composite rubber-like polymer (A-8) dispersed in the aqueous dispersion was 0.096 μm. Table 2 shows the volume average particle diameter of the composite rubber-like polymer (A-8).

(Preparation of composite rubbery polymers (A-9) to (A-13))
As shown in Table 2, except that the mass ratio of polyorganosiloxane (Aa2) and n-butyl acrylate and the amount of emulsifier (parts) were changed, it was the same as the preparation of the composite rubber-like polymer (A-3). An aqueous dispersion of composite rubber-like polymers (A-9) to (A-13) was obtained. Table 2 shows the volume average particle diameters of the composite rubber-like polymers (A-9) to (A-13) dispersed in the aqueous dispersion.

(Preparation of graft copolymer (B-1))
An aqueous dispersion (50 parts as a solid content) of the composite rubber-like polymer (A-1) is placed in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer. After the temperature was adjusted to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion-exchanged water was added. Next, a mixed liquid of 7.5 parts of acrylonitrile, 22.5 parts of styrene and 0.18 part of tertiary butyl hydroperoxide was dropped over about 1 hour to polymerize. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Subsequently, a mixed solution of 5 parts of acrylonitrile, 15 parts of styrene and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was held for 1 hour and then cooled to obtain an aqueous dispersion of a graft copolymer (B-1) obtained by grafting an acrylonitrile-styrene copolymer onto the composite rubber-like polymer (A-1). .
Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of an aqueous dispersion of the graft copolymer (B-1) was gradually dropped into the calcium acetate aqueous solution to be solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (B-1). Table 3 shows the use ratio of the composite rubber-like polymer (A-1), styrene and acrylonitrile.

(Preparation of graft copolymers (B-2) to (B-7))
As shown in Table 3, the graft copolymer (B-) was prepared in the same manner as the preparation of the graft copolymer (B-1) except that the type of the aqueous dispersion of the composite rubber-like polymer (A) was changed. 2) to (B-7) were obtained.

(Preparation of graft copolymer (B-8))
An aqueous dispersion (50 parts as a solid content) of the composite rubber-like polymer (A-8) is placed in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer. After bringing the temperature to 60 ° C., an aqueous solution consisting of 0.15 parts Rongalite, 0.65 parts dipotassium alkenyl succinate and 10 parts ion-exchanged water was added, then 6.3 parts acrylonitrile, 18.7 parts styrene, Then, a mixed solution consisting of 0.11 part of t-butyl hydroperoxide was dropped over 1 hour to cause graft polymerization. Five minutes after the completion of the dropping, an aqueous solution comprising 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 A mixture of .2 parts, 18.8 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for graft polymerization. After completion of the dropwise addition, the internal temperature was kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of antioxidant (Yantomi Pharmaceutical Co., Ltd., Antage W500) and alkenyl succinic acid were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (B-8). Table 4 shows the use ratio of the composite rubber-like polymer (A-8), styrene, and acrylonitrile.

(Preparation of graft copolymers (B-9) to (B-13))
As shown in Table 4, the graft copolymer (B-) was prepared in the same manner as the preparation of the graft copolymer (B-1) except that the type of the aqueous dispersion of the composite rubber-like polymer (A) was changed. 9) to (B-13) were obtained.

<(Meth) acrylic ester resin (C) and its comparison product>
(Preparation of (meth) acrylic ester resin (C-1))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan , 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylic ester resin (C-1). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylic acid ester resin (C-1).

(Preparation of (meth) acrylic ester resin (C-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 98 parts of methyl methacrylate, 2 parts of N-phenylmaleimide, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 of n-octyl mercaptan Part, 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylic ester resin (C-2). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylic acid ester resin (C-2).

(Preparation of (meth) acrylic ester resin (C-3))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylic ester resin (C-3). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylic ester resin (C-3).

(Preparation of (meth) acrylic ester resin (C-4))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 56 parts of methyl methacrylate, 29 parts of N-phenylmaleimide, 15 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylic ester resin (C-4). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylic acid ester resin (C-4).

(Preparation of (meth) acrylic ester resin (C-5))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 53 parts of methyl methacrylate, 31 parts of N-phenylmaleimide, 16 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered (meth) acrylic ester resin (C-5). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylic ester resin (C-5).

(Preparation of (meth) acrylic ester resin (C-6))
150 parts of ion-exchanged water, 82 parts of methyl methacrylate, 6 parts of N-phenylmaleimide, 6 parts of N-cyclohexylmaleimide, 6 parts of styrene, 2,2′-azobis (isobutyronitrile) 0 in a stainless polymerization tank equipped with a stirrer .2 parts, 0.19 parts of n-octyl mercaptan, and 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylic ester resin (C-6). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylic acid ester resin (C-6).

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

<Styrene resin (E)>
(Preparation of styrene resin (E-1))
In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, t -0.35 part of dodecyl mercaptan was charged and reacted at an initial temperature of 60 ° C for 5 hours. The temperature was raised to 120 ° C. and reacted for 4 hours. The contents were taken out to obtain a styrene resin (E-1). Table 6 shows the mass average molecular weight (Mw) of the styrene resin (E-1).

(Preparation of styrene resin (E-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 10 parts of methyl methacrylate, 22 parts of acrylonitrile, 68 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0 .25 parts, calcium hydroxyapatite 0.47 part, and potassium alkenyl succinate 0.003 part were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator and dehydrated, and dried to obtain a styrene resin (E-2). Table 6 shows the mass average molecular weight (Mw) of the styrene resin (E-2).

(Preparation of styrene resin (E-3))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 30 parts of N-phenylmaleimide, 15 parts of acrylonitrile, 55 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0.25 part, 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator and dehydrated, and dried to obtain a styrene resin (E-3). Table 6 shows the mass average molecular weight (Mw) of the styrene resin (E-3).

<Ethylene / α-olefin copolymer (F)>
(Preparation of ethylene / propylene copolymer (F-1))
After fully substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ prepared to 8.0 mmol / L was added. ₅ ) a hexane solution of 5 L / h continuously for 1 hour, and then a VOCl ₃ hexane solution adjusted to 0.8 mmol / L as a catalyst in an amount of 5 L / h and 5 L of hexane. / H continuously. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene is supplied in an amount of 2300 L / h, propylene is supplied in an amount of 600 L / h, hydrogen is supplied in an amount of 400 L / h, and 5-ethylidene-2-norbornene is supplied in an amount of 100 L / h at the same time. The polymerization reaction was conducted at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (F-1). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (F-1). Table 7 shows the polymer properties (mass average molecular weight and molecular weight distribution) of the ethylene / propylene copolymer (F-1).

(Preparation of ethylene / propylene copolymers (F-2) to (F-4))
As shown in Table 7, except that the amount of hydrogen supply was changed, the ethylene / propylene copolymers (F-2) to (F-4) were prepared in the same manner as the preparation of the ethylene / propylene copolymers (F-1). ) Table 7 shows the polymer properties of the ethylene / propylene copolymers (F-2) to (F-4).

<Olefin resin aqueous dispersion (G)>
(Preparation of aqueous dispersion of olefin resin (G-1))
100 parts of ethylene / propylene copolymer (F-1) and maleic anhydride-modified polyethylene (Mitsui Chemicals, “Mitsui High Wax 2203A”, mass average molecular weight: 2,700, acid value: 30 parts of 30 mg / g) and 5 parts of potassium oleate (manufactured by Kao Corporation, “KS Soap”) were mixed as an emulsifier.
This mixture is supplied at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40), and water is supplied from a supply port provided in a vent portion of the twin screw extruder. While continuously supplying an aqueous solution obtained by mixing 0.5 part of potassium oxide and 2.4 parts of ion-exchanged water, it was heated to 220 ° C., melt-kneaded and extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the twin screw extruder and cooled to 90 ° C. Then, the solid discharged from the tip of the twin screw extruder is poured into warm water at 80 ° C., continuously dispersed, diluted to a solid content concentration of around 40% by mass, and an aqueous olefin resin dispersion (G -1) was obtained. Table 8 shows the volume average particle diameter of the ethylene / α-olefin copolymer (F) dispersed in the aqueous olefin resin dispersion (G-1).

(Preparation of aqueous olefin resin dispersions (G-2) to (G-4))
As shown in Table 8, the ethylene / α-olefin copolymer (F) is changed from the ethylene / propylene copolymer (F-1) to the ethylene / propylene copolymers (F-2) to (A-4). Except having changed, it carried out similarly to preparation of olefin resin aqueous dispersion (G-1), and obtained olefin resin aqueous dispersion (G-2)-(G-4).
Table 8 shows the volume average particle diameter of the ethylene / α-olefin copolymer (F) dispersed in each of the olefin resin aqueous dispersions (G-2) to (G-4).

<Crosslinked ethylene / α-olefin copolymer (H)>
(Preparation of crosslinked ethylene / α-olefin copolymer (H-1))
Ion exchange water was added to the olefin resin aqueous dispersion (G-1) (100 parts as a solid content) to a solid content concentration of 35%, and 1.2 parts of t-butylcumyl peroxide as an organic peroxide, As a polyfunctional compound, 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (H-1). Table 9 shows the gel content and volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (H-1).

(Preparation of crosslinked ethylene / α-olefin copolymers (H-2) to (H-4))
As shown in Table 9, except that the type of the olefin resin aqueous dispersion (G) and the amount of t-butylcumyl peroxide added were changed, the same as the preparation of the crosslinked ethylene / α-olefin copolymer (H-1). Thus, crosslinked ethylene / α-olefin copolymers (H-2) to (H-4) were obtained. Table 9 shows the gel content and volume average particle diameter of the crosslinked ethylene / α-olefin copolymers (H-2) to (H-4).

(Preparation of cross-linked ethylene / α-olefin copolymer (H-5))
With respect to 100 parts of the ethylene / α-olefin copolymer (F-2), 1.0 part of α, α′-bis (t-butylperoxy) diisopropylbenzene and 1.0 part of divinylbenzene are used as the organic peroxide. Are mixed and melt-kneaded at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (“Ikegai Co., Ltd.,“ PCM-30 ”), and then finely pulverized to form crosslinked ethylene. -The alpha-olefin copolymer (H-5) was obtained. Table 9 shows the gel content and volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (H-5).

<Graft copolymer (I)>
(Preparation of graft copolymer (I-1))
In a stainless steel polymerization tank equipped with a stirrer, a crosslinked ethylene / α-olefin copolymer (H-1) (70 parts as a solid content of the ethylene / propylene copolymer (F-1)) is placed, and the crosslinked ethylene / α-olefin is added. Add ion-exchanged water to the copolymer (H-1) so that the solid concentration is 30%, and charge 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose, The temperature was 80 ° C. 19.8 parts of styrene, 10.2 parts of acrylonitrile and 0.6 parts of cumene hydroperoxide are continuously added for 150 minutes, emulsion polymerization is carried out while maintaining the polymerization temperature at 80 ° C., and graft copolymer weight having an average particle size of 0.41 μm An aqueous dispersion containing the union (I-1) was obtained.
An antioxidant is added to the aqueous dispersion containing the graft copolymer (I-1), solids are precipitated with sulfuric acid, and after washing, dehydration and drying steps, the powdered graft copolymer ( I-1) was obtained. When the graft ratio of the graft copolymer (I-1) was measured, it was 30%. In addition, after dyeing a thermoplastic resin composition prepared by melt-kneading the graft copolymer (I-1) and the styrene resin (E-1) at a ratio of 20% by mass to 80% by mass with ruthenium, A thin piece was prepared and the volume average particle diameter of the ethylene / α-olefin copolymer (F) in the thermoplastic resin composition was confirmed by an electron microscope and found to be 0.41 μm.

(Preparation of graft copolymers (I-2) to (I-4))
As shown in Table 10, the graft copolymer (I-2) was prepared in the same manner as in the preparation of the graft copolymer (I-1) except that the type of the crosslinked ethylene / α-olefin copolymer (H) was changed. ) To (I-4) were obtained. Table 10 shows the graft ratios of the graft copolymers (I-2) to (I-4).

(Preparation of graft copolymer (I-5))
In a stainless steel polymerization tank equipped with a stirrer, 70 parts of a crosslinked ethylene / α-olefin copolymer (H-5) and 300 parts of toluene were charged, and the contents were stirred and stirred uniformly at 70 ° C. for 1 hour. After sufficient nitrogen substitution, 19.8 parts of styrene, 10.2 parts of acrylonitrile, 0.24 parts of t-dodecyl mercaptan and 0.22 parts of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was 110 ° C. The mixture was heated up to react for 4 hours. The internal temperature was raised to 120 ° C. and reacted for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.), pelletized, and graft copolymer (I-5 ) When the graft ratio of the graft copolymer (I-5) was measured, it was 30%. In addition, after dyeing the thermoplastic resin composition prepared by melt-kneading the graft copolymer (I-5) and the styrene resin (E-1) at a ratio of 20% by mass to 80% by mass with ruthenium, A thin piece was prepared, and the volume average particle diameter of the ethylene / α-olefin copolymer (F) in the thermoplastic resin composition was confirmed by an electron microscope and found to be 0.40 μm.

(Preparation of graft copolymer (I-6))
As shown in Table 10, except that the cross-linked ethylene / α-olefin copolymer (H-1) was changed to an aqueous olefin resin dispersion (G-2), it was the same as the preparation of the graft copolymer (I-1). Thus, a graft copolymer (I-6) was obtained. Table 10 shows the graft ratio of the graft copolymer (I-6).

[Example 1]
40 parts of graft copolymer (B-2), 60 parts of (meth) acrylic ester resin (C-3) and 0.3 part of silicone oil (D-1) are mixed and biaxial extrusion with 30 mmφ vacuum vent A thermoplastic resin composition was prepared by melting and kneading at 240 ° C. and 93.325 kPa vacuum using a machine (“PCM30” manufactured by Ikegai Co., Ltd.). Table 11 shows the MVR of the thermoplastic resin composition.
The obtained thermoplastic resin composition was pelletized and various molded products were molded, and impact resistance, heat resistance, color development, weather resistance, heat aging resistance, scratch resistance, and surface appearance were evaluated. The results are shown in Table 11.

[Examples 2-35]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the formulation was changed to the formulation shown in Tables 11 to 14, and MVR was measured.
The thermoplastic resin composition was pelletized, and various molded articles were molded, and impact resistance, heat resistance, color development, weather resistance, heat aging resistance, scratch resistance, and surface appearance were evaluated. The results are shown in Tables 11-14.

[Comparative Examples 1 to 12]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the formulation was changed to the formulation shown in Tables 15 to 16, and MVR was measured.
The thermoplastic resin composition was pelletized, and various molded articles were molded, and impact resistance, heat resistance, color development, weather resistance, heat aging resistance, scratch resistance, and surface appearance were evaluated. The results are shown in Tables 15-16.

The thermoplastic resin compositions of Examples 1 to 35 were excellent in fluidity. In addition, the molded articles of Examples 1 to 35 were excellent in impact resistance, heat resistance, color development, weather resistance, heat aging resistance, scratch resistance, and surface appearance. In particular, in Examples 27 to 35, the scratch resistance was further excellent.
On the other hand, for the molded products of Comparative Examples 1 to 12, any one or more of impact resistance, heat resistance, color development, weather resistance, heat aging resistance, scratch resistance, and surface appearance was insufficient. . In particular, the thermoplastic resin composition is the same as in Examples 3 and 28, but the surface appearance and scratch resistance of the molded articles of Comparative Examples 10 and 11 in which molding was performed by general molding instead of heat cycle injection molding. Was inferior.

  Therefore, the thermoplastic resin composition of the present invention has excellent fluidity, and when the thermoplastic resin composition of the present invention is heat cycle injection molded, the surface appearance, scratch resistance, impact resistance, color developability It was confirmed that a molded product excellent in heat resistance and heat aging resistance was obtained.

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

1 Four-point gate molded product 2, 3, 4 Opening 2A Gate

Claims (6)

A thermoplastic resin composition molded by a heat cycle injection molding method in which the cavity surface temperature of the mold is repeatedly raised and lowered using an injection mold in which the cavity surface of the mold is alternately heated and cooled,
Poly (meth) acrylate ester having units derived from polyorganosiloxane (Aa) and (meth) acrylate, and one or both of a unit derived from a crosslinking agent and a unit derived from a graft crossing agent A graft copolymer obtained by polymerizing a vinyl monomer component (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the composite rubber-like polymer (A) comprising (Ab) ( B) and
A (meth) acrylic ester resin (C) obtained by polymerizing a vinyl monomer component (m2) containing a (meth) acrylic ester, a maleimide compound and an aromatic vinyl compound,
The content of the polyorganosiloxane (Aa) in the composite rubber-like polymer (A) (100% by mass) is 1 to 20% by mass,
The composite rubber-like polymer (A) has a volume average particle diameter of 0.05 to 0.15 μm,
The content of the maleimide compound in the vinyl monomer component (m2) (100% by mass) is 1 to 30% by mass, and the content of the aromatic vinyl compound is 5.5 to 15% by mass. A thermoplastic resin composition for heat cycle injection molding.   The thermoplastic resin composition for heat cycle injection molding according to claim 1, further comprising silicone oil (D).   The thermoplastic resin composition for heat cycle injection molding according to claim 1 or 2, further comprising a styrene resin (E).   The heat according to any one of claims 1 to 3, further comprising a graft copolymer (I) obtained by polymerizing the vinyl monomer component (m4) in the presence of an olefin copolymer. Thermoplastic resin composition for cycle injection molding.   The molded article formed by shape | molding the thermoplastic resin composition for heat cycle injection molding as described in any one of Claims 1-4.   The thermoplastic resin composition for heat cycle injection molding according to any one of claims 1 to 4, wherein the mold cavity surface is used by using an injection mold in which the mold cavity surface is alternately heated and cooled. A method for producing a molded product, wherein a molded product is obtained by molding by a heat cycle injection molding method in which the temperature is repeatedly raised and lowered.

Images