JP6678449B2 - Thermoplastic resin composition for heat cycle injection molding, molded article, and method for producing molded article - Google Patents

Description

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

Improving the impact resistance of molded products not only expands the applications of molded products, but also makes it possible to cope with thinning and increasing the size of molded products, greatly increasing industrial utility. . Therefore, various methods have been proposed for improving the impact resistance of molded articles.
Among these methods, a method of increasing the impact resistance of a molded product while maintaining characteristics derived from the hard resin by using a resin material obtained by combining a rubbery polymer and a hard resin has already been industrialized. Examples of such resin materials include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene-α-olefin-styrene (AES) resin, polyorganosiloxane-acrylate-acrylonitrile-styrene (SAS) resin, and acrylonitrile- Styrene-acrylic acid ester (ASA) resin, or a thermoplastic resin composition in which these are further added to a hard resin are exemplified.
In recent years, in the field of vehicles and the like, the non-painting process in which the painting process is omitted has been advanced. In this case, since the molded product is directly assembled to the product, the molded product is required to have high designability. In order to improve the design property of a molded product, a molding method has been proposed in which a mold surface temperature is heated to a temperature equal to or higher than a thermal deformation temperature or a glass transition temperature of a thermoplastic resin composition during molding.

While maintaining the properties derived from the hard resin, a thermoplastic resin composition capable of obtaining a molded article with improved impact resistance, and a molding method for improving the design of the molded article, for example, the following Things have been suggested.
(1) A thermoplastic resin composition obtained by adding a SAS resin to a methacrylic ester resin as a hard resin (Patent Document 1).
(2) A thermoplastic resin composition obtained by adding an ABS resin to a methacrylic ester resin as a hard resin is subjected to heat cycle injection molding, and a mold surface temperature is heated to a temperature equal to or higher than a thermal deformation temperature of the thermoplastic resin composition during molding. Method (Patent Document 2).
(3) A thermoplastic resin composition obtained by adding a methacrylic acid ester resin, an AES resin and an acrylonitrile-styrene (AS) resin to a polycarbonate resin which is a hard resin is injection-molded. A method of heating the product to a temperature higher than the glass transition temperature (Patent Document 3).

However, in the thermoplastic resin composition of (1), it is necessary to add a large amount of the SAS resin in order to improve the impact resistance of the molded product, and in the obtained molded product, the surface derived from the methacrylic acid ester resin is required. The 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 the high heat resistance and weather resistance required in the field and the like.
The molded product obtained by the molding method of (3) has insufficient weather resistance because it uses a polycarbonate resin.

JP 08-283524 A JP 2005-220265 A JP 2012-131908 A

  The present invention relates to a thermoplastic resin composition which, when subjected to heat cycle injection molding, provides a molded article having excellent surface appearance, scratch resistance, impact resistance, color development, heat resistance, and heat aging resistance. Provided are a molded article and a method for producing the molded article.

The present invention includes the following aspects.
[1] A thermoplastic resin composition molded by a heat cycle injection molding method in which a cavity surface temperature of a mold is repeatedly increased and decreased by using an injection mold in which a cavity surface of the mold is alternately heated and cooled. ,
Poly (meth) acrylate having a unit derived from polyorganosiloxane (Aa) and (meth) acrylate, and / or one or both of a unit derived from a crosslinking agent and a unit derived from a graft crossing agent (Ab) 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 a composite rubbery polymer (A) comprising B)
(Meth) acrylic acid ester, a (meth) acrylic acid ester resin (C) obtained by polymerizing a vinyl monomer component (m2) containing 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 rubbery 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] Any of [1] to [3], further including 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 according to the above.
[5] A molded article 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] is molded using an injection molding die in which the cavity surface of the die is alternately heated and cooled. A method for producing a molded article, wherein a molded article is obtained by molding using a heat cycle injection molding method in which the cavity surface temperature is repeatedly increased and decreased.

  According to the present invention, when subjected to heat cycle injection molding, surface appearance, scratch resistance, impact resistance, color development, heat resistance, a thermoplastic resin composition from which a molded article excellent in heat aging resistance is obtained, And a method for producing a molded article using the same.

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

The following definitions of terms apply throughout the present specification and claims.
“(Meth) acrylic acid” means acrylic acid or methacrylic acid.
“Molded product” means a product obtained by molding a thermoplastic resin composition. The molded article of the thermoplastic resin composition for heat cycle injection molding means a product obtained by heat cycle injection molding the thermoplastic resin composition for heat cycle injection molding.
The term “scratch resistance” refers to the difficulty of scratching the surface of a molded article with a hard and sharp object such as a nail (scratch).
"Heat aging resistance" means that the color does not easily change before and after the molded article is left under high temperature conditions (the difference in color before and after being left is small).
“Surface appearance” means that the surface of the molded article is glossy and there is no uneven color at the weld portion.

"Thermoplastic 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. The thermoplastic resin composition of the present invention may contain, if necessary, a silicone oil (D), a styrene-based resin (E), a graft copolymer (I), and other heat-curable resins as long as the effects of the present invention are not impaired. It may contain a plastic resin and various additives.

The graft copolymer (B) is obtained by polymerizing the vinyl monomer component (m1) in the presence of the composite rubbery polymer (A).
The composite rubbery polymer (A) comprises a polyorganosiloxane (Aa) and a poly (meth) acrylate (Ab).
The (meth) acrylate resin (C) is obtained by polymerizing the vinyl monomer component (m2).

The styrene resin (E) is obtained by polymerizing a vinyl monomer component (m3).
The graft copolymer (I) is obtained by polymerizing a 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) to (I), (m1) to (m4), etc.) will be described.

<Polyorganosiloxane (Aa)>
The polyorganosiloxane (Aa) is not particularly limited, but is preferably a polyorganosiloxane having a vinyl polymerizable functional group, and contains a vinyl polymerizable functional group based on the total number of moles of all the constituent units constituting the polyorganosiloxane. Containing 0.3 to 3 mol% of siloxane units and 97 to 99.7 mol% of dimethylsiloxane units, and having three or more siloxane bonds based on the total number of moles of all silicon atoms in the polydimethylsiloxane. Polyorganosiloxanes having 1 mol% or less of atoms are more preferred.

  Examples of the dimethylsiloxane constituting the polyorganosiloxane (Aa) include a dimethylsiloxane-based cyclic body having three or more membered rings. Among them, a three-membered to seven-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. 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 through a siloxane bond, but in consideration of 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 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-based crosslinking agent include trifunctional or tetrafunctional silane-based crosslinking agents, such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The method for producing the polyorganosiloxane (Aa) is not limited. For example, it can be manufactured by the following method.
First, a siloxane-based crosslinking agent is added to a siloxane mixture composed of dimethylsiloxane and a siloxane containing a vinyl polymerizable functional group, if necessary, and then emulsified with an emulsifier and water to disperse the siloxane mixture in an aqueous medium. An aqueous dispersion of the siloxane mixture obtained is obtained. Next, the dispersed particles (siloxane mixture) in the aqueous siloxane mixture dispersion are micronized using a homomixer that micronizes particles by shearing force due to high-speed rotation, a homogenizer that micronizes by jet power from a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifying device such as a homogenizer since the distribution of the dispersed particles, and thus the particle size of the polyorganosiloxane (Aa), becomes small. Next, the aqueous dispersion of the siloxane mixture in which the dispersed particles have been made finer is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction liquid is cooled, and the polymerization is stopped by neutralizing with an alkaline substance such as caustic soda, caustic potash, and sodium carbonate to obtain 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 a “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; 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), and sodium polyoxyethylene nonylphenyl ether sulfate. Among them, sulfonic acid emulsifiers such as sodium alkylbenzenesulfonate and sodium alkylsulfonate are preferable. These emulsifiers are preferably used in an amount 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 acids, aliphatic substituted benzenesulfonic acids, and aliphatic substituted naphthalenesulfonic acids, 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 benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable because of excellent stabilizing effect of the aqueous dispersion of polyorganosiloxane (Aa). Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, it is possible to minimize the effect of the emulsifier used for the aqueous dispersion of the polyorganosiloxane (Aa) on the color development of the thermoplastic resin composition. Can be suppressed.

The volume average particle size of the polyorganosiloxane (Aa) in the aqueous dispersion is such that the molded article has more excellent color developability, the viscosity of the aqueous dispersion increases when the polyorganosiloxane (Aa) is produced, and the coagulum ( Coagulum) is preferably 0.01 to 0.09 μm, more preferably 0.02 to 0.08 μm, since generation of coagulum can be prevented.
The volume average particle diameter is a value measured by a laser diffraction / scattering method. Specifically, it is measured by the method described in 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 adopted.

<Poly (meth) acrylate (Ab)>
The poly (meth) acrylate (Ab) is a copolymer having a unit derived from a (meth) acrylate and one or both of a unit derived from a crosslinking agent and a unit derived from a graft crosslinking agent. It is.
In the poly (meth) acrylate (Ab), the (meth) acrylate corresponding to the crosslinking agent or the grafting agent is a crosslinking agent or a grafting agent, and does not correspond to the (meth) acrylate. Shall be.

  Examples of the (meth) acrylate include alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms; (meth) acrylates having an aromatic hydrocarbon group such as a phenyl group and a benzyl group, and the like. No. As the (meth) acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferred. The (meth) acrylate can be used alone or in combination of two or more.

Crosslinking agents and grafting agents respectively improve the impact resistance, color development and heat aging of the molded articles.
Examples of the crosslinking agent include dimethacrylate compounds, and specific examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.
Examples of the graft crossing agent include an allyl compound, specifically, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like.

  In the poly (meth) acrylate (Ab), the total amount of the units derived from the cross-linking agent and the units derived from the graft crossing agent is excellent in the impact resistance, color development, heat aging resistance of the molded product, and the graft copolymer. Since coagulum (coagulum) during the production of the coalesced (B) is reduced, 0.1 to 5% by mass of the total unit of 100% by mass of the poly (meth) acrylate (Ab) is reduced. Preferably, it is 0.2 to 3% by mass, more preferably 0.5 to 2% by mass.

<Composite rubber-like polymer (A)>
The composite rubbery polymer (A) is composed of a polyorganosiloxane (Aa) and a poly (meth) acrylate (Ab).
The composite rubbery polymer (A) typically has a structure in which a polyorganosiloxane (Aa) and a poly (meth) acrylate (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 rubber-like polymer (A) is preferably 1 to 20% by mass, and more preferably 3 to 20%, based on the total mass (100% by mass) of the composite rubber-like polymer (A). 18 mass% is more preferable. If the content of the polyorganosiloxane (Aa) is at least the lower limit of the above range, the impact resistance of the molded article will be more excellent, and if it is at most the upper limit of the above range, the impact resistance will be more excellent.

The method for producing the composite rubber-like polymer (A) is not particularly limited. For example, a method of hetero-aggregating or co-blowing an aqueous dispersion of a polyorganosiloxane (Aa) and an aqueous dispersion of a poly (meth) acrylate (Ab) separately prepared, an aqueous dispersion of a polyorganosiloxane (Aa) In one of the dispersion and the aqueous dispersion of the poly (meth) acrylic acid ester (Ab), a method of forming the other polymer to form a composite and the like can be given. By these methods, an aqueous dispersion of the composite rubbery polymer (A) is obtained.
Among the methods for producing the composite rubber-like polymer (A), among the above, the (meth) acrylic acid is used in an aqueous dispersion of the polyorganosiloxane (Aa) because the molded article has more excellent impact resistance and coloring properties. A method in which a monomer component containing an acid ester monomer and one or both of a crosslinking agent and a graft crosslinking agent is emulsion-polymerized is preferable. 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. By polymerization to a certain degree, an aqueous dispersion of the composite rubber-like polymer (A) is obtained.

Preferred 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, and palmitic acid, sodium lauryl sulfate, sodium N-lauroyl sarcosinate, alkenyl succinate. Acid dipotassium, sodium alkyl diphenyl ether disulfonate, sodium polyoxyethylene alkyl phenyl ether sulfate and the like.
As the emulsifier, an acid-type emulsifier having two or more functional groups in one molecule or a salt thereof is preferable because gas generation during molding of the thermoplastic resin composition can be further suppressed. Sodium diphenyl ether disulfonate is preferred.
Examples of the radical polymerization initiator include peroxides, azo initiators, and redox initiators obtained by combining an oxidizing agent and a reducing agent. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide is particularly preferable.

The volume average particle diameter of the composite rubbery polymer (A) dispersed in the aqueous dispersion is from 0.05 to 0.15 μm, preferably from 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 rubbery polymer (A) having a volume average particle diameter of 0.05 to 0.15 μm. The thermoplastic resin composition contains a composite rubber-like polymer (A) having a volume average particle diameter of 0.05 to 0.15 μm derived from the graft copolymer (B). It is a thing.
When the volume average particle diameter of the composite rubber-like polymer (A) is at least the lower limit of the above range, the impact resistance of the molded product is more excellent, and when it is at most the upper limit of the above range, the coloring property of the molded product, Excellent heat aging resistance and weather resistance.
The method for controlling the volume average particle diameter of the composite rubber-like polymer (A) is not particularly limited, and examples thereof include a method of adjusting the type or amount of the emulsifier.
The electron microscope shows that the average particle size of the composite rubber-like polymer (A) in the aqueous dispersion directly represents the volume average particle size of the composite rubber-like polymer (A) in the thermoplastic resin composition. 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, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith, as long as the effects of the present invention are not impaired. .

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinyl xylene, pt-butylstyrene, and ethylstyrene. Of these, styrene and α-methylstyrene are preferred. 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 methacrylates, acrylates, and maleimide-based compounds.
Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, and 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 include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and the like.
As the maleimide-based compound, for example, N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide N-substituted maleimide compounds such as N-tert-butylmaleimide, N-cyclohexylmaleimide, N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.) and N-aralkylmaleimide Is mentioned.
These can be used alone or in combination of two or more.

  The content of the aromatic vinyl compound in the vinyl monomer component (m1) is preferably from 65 to 82% by mass, and more preferably from 73 to 82% by mass, based on the total mass (100% by mass) of the vinyl monomer component (m1). 80 mass% is more preferable, and 75-80 mass% is still more preferable. When the content of the aromatic vinyl compound with respect to the total mass of the vinyl monomer component (m1) is within the above range, the molded product has more excellent coloration properties and impact resistance.

  The content of the vinyl cyanide compound in the vinyl monomer component (m1) is preferably from 18 to 35% by mass, and preferably from 20 to 20%, based on the total mass (100% by mass) of the vinyl monomer component (m1). 27 mass% is more preferable, and 20 to 25 mass% is still more preferable. If 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 molded product will have more excellent color development and impact resistance.

<Graft copolymer (B)>
The graft copolymer (B) is obtained by polymerizing the vinyl monomer component (m1) in the presence of the composite rubbery polymer (A).
The graft copolymer (B) is obtained by grafting a granular composite rubber-like polymer (A) having a volume average particle diameter of 0.05 to 0.15 μm to a vinyl monomer component (m1). It is presumed to be composed of a chain in which the core is composed of a composite rubber-like polymer (A) and an outer layer (shell) composed of a polymer of a vinyl monomer component (m1). Is done. However, since the core-shell type is not always completely obtained, it is obtained by polymerizing the vinyl monomer component (m1) in the presence of the composite rubbery polymer (A). It is more appropriate to stipulate:

The graft copolymer (B) is 10 to 80% by mass of the vinyl monomer component (m1) in the presence of 20 to 90% by mass of the composite rubbery polymer (A) (provided that the composite rubbery polymer ( A) and the total amount of the vinyl monomer component (m1) is 100% by mass.), And is preferably obtained by polymerization, and the composite rubber-like polymer (A) is 25 to 85% by mass. Is more preferably obtained by polymerizing 15 to 75% by mass of a vinyl monomer component (m1) in the presence of (A), and in the presence of 30 to 80% by mass of a composite rubber-like polymer (A). More preferably, it is obtained by polymerizing 20 to 70% by mass of a 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, (A total of the polymer of the copolymer (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 a polymer of the vinyl monomer component (m1), more preferably 30 to 80% by mass of the composite rubbery polymer (A) and a vinyl monomer 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 is used. The productivity of (B) is good, and the color development 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 the vinyl monomer component (m1) to the aqueous dispersion of the composite rubber-like polymer (A) and subjecting the vinyl monomer component (m1) to radical polymerization in the presence of an emulsifier. . Thereby, an aqueous dispersion of the graft copolymer (B) is obtained. At this time, various known chain transfer agents may be added to control the graft ratio and the molecular weight of the graft component.
The polymerization conditions for radical polymerization are not particularly limited, and include, for example, polymerization conditions at 60 to 90 ° C. for 1 to 4 hours.

  Examples of the radical polymerization initiator used in the radical polymerization include peroxides, azo initiators, and redox initiators obtained by combining an oxidizing agent and a reducing agent. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide is particularly preferable.

  Examples of the emulsifier include the emulsifier used in the production of the composite rubber-like polymer (A). The emulsifier contained in the composite rubber-like polymer (A) is used as it is, and it is not necessary to add an emulsifier during the polymerization of the vinyl monomer component (m1). An emulsifier may be added during the polymerization of (m1).

  As a method for recovering the graft copolymer (B) from the aqueous dispersion of the graft copolymer (B), (i) an aqueous dispersion of the graft copolymer (B) is dissolved in hot water in which a coagulant is dissolved. And a method of recovering by coagulating into a slurry state (wet method), (ii) semi-directly grafting by spraying an aqueous dispersion of the graft copolymer (B) in a heated atmosphere A method of recovering the copolymer (B) (spray dry method), and the like.

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

As a method for obtaining the graft copolymer (B) in the dry state from the graft copolymer (B) in the slurry state, the following (i-1) is used after the emulsifier residue remaining in the slurry is eluted into water by washing. ) Or (i-2).
(I-1) The slurry is dehydrated by a centrifugal dehydrator or a press dehydrator, and further dried by a flash dryer or the like.
(I-2) Dehydration and drying of the slurry are simultaneously performed by a compression dehydrator, an extruder, or the like.
After drying, the graft copolymer (B) is obtained in the form of powder or particles. Further, the graft copolymer (B) discharged from the compression dehydrator or the extruder can be directly sent to an extruder or a molding machine for producing a thermoplastic resin composition.

<Vinyl monomer component (m2)>
The vinyl monomer component (m2) contains at least a (meth) acrylate, a maleimide compound, and an aromatic vinyl compound as monomers.
As long as the effects of the present invention are not impaired, the vinyl-based monomer component (m2) may contain, in addition to the (meth) acrylate, the maleimide-based compound, and the aromatic vinyl compound, other monomer units copolymerizable therewith. It may further include a body.

  Examples of the (meth) acrylate include alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms; (meth) acrylates having an aromatic hydrocarbon group such as a phenyl group and a benzyl group, and the like. No. These can be used alone or in combination of two or more. As the (meth) acrylate, methyl methacrylate is preferred.

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

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinyl xylene, pt-butylstyrene, and ethylstyrene. Of these, styrene and α-methylstyrene are preferred. These can be used alone or in combination of two or more.

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

  The content of the (meth) acrylate in the vinyl monomer component (m2) is 55 to 93.5% by mass based on the total mass (100% by mass) of the vinyl monomer component (m2). Preferably, it is more preferably 60 to 84.5% by mass. If the content of the (meth) acrylate in the vinyl monomer component (m2) is within the above range, the impact resistance, the color development, the scratch resistance, the weather resistance, and the heat aging resistance of the molded product are reduced. Better.

  The content of the maleimide-based compound in the vinyl-based monomer component (m2) is 1 to 30% by mass relative to the total mass (100% by mass) of the vinyl-based monomer component (m2). % By mass is preferable, and 10 to 20% by mass is more preferable. If the content of the maleimide-based compound in the vinyl-based monomer component (m2) is at least the lower limit of the above range, the heat resistance and heat aging resistance of the molded article are more excellent, and at most the upper limit of the above range. In addition, the color development 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 relative to the total mass (100% by mass) of the vinyl monomer component (m2). 5.5 to 10% by mass is preferred. If the content of the aromatic vinyl compound in the vinyl monomer component (m2) is within the above range, the balance of the fluidity of the thermoplastic resin composition, the heat aging resistance of the molded article, the coloring property, and the weather resistance is obtained. Excellent.

<(Meth) acrylate resin (C)>
The (meth) acrylate resin (C) is obtained by polymerizing the vinyl monomer component (m2). That is, it is a polymer of the vinyl monomer component (m2) and contains at least a unit derived from a (meth) acrylate, a unit derived from a maleimide compound, and a unit derived from an aromatic vinyl compound. The content of the unit derived from the maleimide compound is 1 to 30% by mass based on the total mass (100% by mass) of all the units, and the content of the unit derived from the aromatic vinyl compound is It is 5.5 to 15% by mass relative to the total mass (100% by 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, and the like).

As a method for producing the (meth) acrylate 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 into a reactor, and heated. Then, the (meth) acrylate resin (C) is recovered by a precipitation method from the obtained aqueous dispersion containing the (meth) acrylate resin (C).
The polymerization conditions for emulsion polymerization are not particularly limited, and include, for example, polymerization conditions at 40 to 120 ° C. for 1 to 15 hours.
Examples of the emulsifier include ordinary emulsifiers for emulsion polymerization (eg, potassium rosinate, sodium alkylbenzenesulfonate).
Examples of the polymerization initiator include organic and inorganic peroxide-based initiators.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.
As the precipitation method, the same method as that for recovering the graft copolymer (B) from the aqueous dispersion can be employed.

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

The mass average molecular weight (Mw) of the (meth) acrylate resin (C) is preferably from 100,000 to 300,000, and more preferably from 120,000 to 220,000. When the mass average molecular weight of the (meth) acrylate resin (C) is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, the color development, the scratch resistance, and the heat aging resistance are reduced. Better.
The mass average molecular weight (Mw) of the (meth) acrylate resin (C) is a standard polystyrene (PS) converted value obtained by analyzing a solution dissolved in tetrahydrofuran (THF) by gel permeation chromatography (GPC). It is.
As the (meth) acrylate resin (C), one type may be used alone, or two or more types may be used in combination.

<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, and methyl hydrogen silicone oil.
The modified silicone oil is a silicone oil in which various organic groups are introduced into a part of a side chain in the polyorganosiloxane structure and / or one end of the polyorganosiloxane structure or both ends 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 methylchlorinated phenyl. 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, carbinol modified silicone oil, etc. .
As the silicone oil (D), one type may be used alone, or two or more types may be used in combination.

<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, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith, as long as the effects of the present invention are not impaired. .

Specific examples of the aromatic vinyl compound and the vinyl cyanide compound include those similar to the vinyl monomer component (m1). The same applies to preferred ones.
Examples of other monomers include methacrylates, acrylates, and maleimide-based compounds. Specific examples of these monomers include those similar to those exemplified 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 from 50 to 90% by mass, and preferably from 55 to 90% by mass, based on 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 obtained thermoplastic resin composition and the color development of the molded product are more excellent.

  The content of the vinyl cyanide compound in the vinyl monomer component (m3) is preferably from 10 to 50% by mass relative 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 molded article is more excellent in impact resistance and heat resistance.

<Styrene resin (E)>
The styrene resin (E) is obtained by polymerizing a vinyl monomer component (m3). That is, it is a polymer of the vinyl monomer component (m3) and contains 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, and the like). From the viewpoint of heat resistance of molded articles, suspension polymerization method and bulk polymerization method are used. preferable. At this time, various known chain transfer agents may be added.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.
The polymerization conditions are not particularly limited, and include, for example, polymerization conditions at 40 to 130 ° C. for 1 to 20 hours.

The weight average molecular weight (Mw) of the styrenic resin (E) is preferably from 70,000 to 200,000, and more preferably from 90,000 to 150,000. When the weight 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 standard polystyrene (PS) -converted value obtained by analyzing a solution dissolved in tetrahydrofuran (THF) by gel permeation chromatography (GPC).

<Ethylene / α-olefin copolymer (F)>
The ethylene / α-olefin copolymer (F) contains an ethylene unit and an α-olefin unit obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms by a known polymerization method. It is a copolymer.
The ethylene / α-olefin copolymer (F) may further include 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 more excellent.

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

  Examples of the non-conjugated diene include dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-cycloheptadiene, 5-cyclooctadiene and the like. Among them, dicyclopentadiene and / or 5-ethylidene-2-norbornene are preferable as the non-conjugated diene unit because the obtained molded product has more excellent impact resistance.

  The ethylene unit content of the ethylene / α-olefin copolymer (F) is from 45 to 45 when the total of all the constituent 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 content of the ethylene unit is within the above range, the impact resistance of the molded product is more excellent.

  The content of the total of the ethylene unit and the α-olefin unit is preferably from 90 to 100% by mass, when the total of all the constituent units constituting the ethylene / α-olefin copolymer (F) is 100% by mass. , 95 to 99% by mass. If the total content of the ethylene units and the α-olefin units 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 from 4 × 10 ^{4 to} 35 × 10 ^4, more preferably from 5 × 10 ⁴ to 10 × 10 ⁴ . When the mass average molecular weight (Mw) is 4 × 10 ⁴ or more, the molded article is more excellent in impact resistance and coloring. On the other hand, when 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 development of the molded product, and the impact resistance are further excellent.

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

  The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer (F) are values measured using gel permeation chromatography (GPC) and converted into 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 a Ziegler-Natta catalyst. Manufactured.

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

Examples of the polymerization method include a method in which ethylene and an α-olefin, or ethylene, an α-olefin, and a non-conjugated diene are copolymerized in a solvent in the presence of the catalyst (metallocene catalyst or Ziegler-Natta catalyst). Can be Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). One type of hydrocarbon solvent may be used alone, or two or more types may be used in combination. Further, α-olefin as a raw material may be used as a solvent.
At the time of polymerization, a molecular weight regulator such as hydrogen may be used.
The polymerization conditions are not particularly limited, and include, for example, polymerization conditions at 40 to 120 ° C. and 0.2 to 5 MPa for 1 to 10 hours.

  Ethylene and α-olefins can be obtained by changing the supply amounts of ethylene, α-olefin and non-conjugated diene, the type and amount of molecular weight regulator such as hydrogen, the type and amount of catalyst, the reaction temperature, the pressure and other reaction conditions. The ethylene unit content, the weight average molecular weight (Mw) and the 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 an ethylene / α-olefin copolymer (F) in an aqueous medium.
The aqueous olefin resin dispersion (G) may contain, as other components, an emulsifier, an acid-modified olefin polymer, and the like.

Examples of the emulsifier include known ones, for example, a long-chain alkyl carboxylate, a sulfosuccinic acid alkyl ester salt, and an alkylbenzene sulfonate.
The content of the emulsifier in the aqueous olefin resin dispersion (G) can suppress the thermal coloring of the thermoplastic resin composition obtained, and the ethylene / α-olefin copolymer dispersed in the aqueous olefin resin dispersion (G). The amount is preferably 1 to 8 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (F) from the viewpoint of easily controlling the particle size of the united product (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 (eg, polyethylene or polypropylene) with a compound having a functional group (eg, an unsaturated carboxylic acid compound). Can be Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic monoamide.
The content of the acid-modified olefin polymer in the aqueous olefin resin dispersion (G) is preferably from 1 to 40 parts by mass based on 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 excellent.

  The method for preparing the aqueous olefin resin 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 shear force is reduced. (G2) dissolving the ethylene / α-olefin copolymer (F) in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, or the like); And emulsifying the mixture, followed by sufficient stirring to distill off the hydrocarbon solvent. During the preparation of the aqueous olefin resin dispersion (G), an acid-modified olefin polymer, an emulsifier, or 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), a method in which the ethylene / α-olefin copolymer (F) and the acid-modified olefin polymer are mixed and kneaded, and in the method (g2), the ethylene / α-olefin A method of dissolving the copolymer (F) and the acid-modified olefin polymer in a hydrocarbon solvent may, for example, be mentioned.
The method of mixing 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 the step of melt-kneading the mixture.
The method for adding the emulsifier is not limited. For example, the same method as the method for adding the acid-modified olefin polymer can be used. In addition, in the method (g1) or (g2), a method in which an emulsifier is added to an aqueous medium, and in the method (g2), a method in which the emulsifier is dissolved in a hydrocarbon solvent may be used.

The volume average particle diameter of the ethylene / α-olefin copolymer (F) constituting the aqueous olefin resin dispersion (G) is preferably from 0.20 to 0.60 μm, from the viewpoint of excellent physical properties of the molded article. It is more preferably from 30 to 0.50 μm.
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. The thermoplastic resin composition is derived from the graft copolymer (I) and has an ethylene / α-olefin copolymer having a volume average particle diameter of 0.20 to 0.60 μm. It is preferable that it contains the coalescence (F).
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 diameter is 0.60 μm or less, the molded article is more excellent in impact resistance, color development, and heat aging resistance. When the average particle diameter of the ethylene / α-olefin copolymer (F) is 0.3 to 0.5 μm, the molded article is more excellent in impact resistance, color development, and heat aging resistance.
The volume average particle diameter of the ethylene / α-olefin copolymer (F) constituting the aqueous olefin resin dispersion (G) is the same as that of the ethylene / α-olefin copolymer (F) in the thermoplastic resin composition. Is confirmed by image analysis with an electron microscope.

As a method for controlling the volume average particle diameter of the ethylene / α-olefin copolymer (F) dispersed in the aqueous olefin resin dispersion (G), the type or amount of the emulsifier, the type of the acid-modified olefin polymer, Alternatively, a method of adjusting the content, the shearing force applied at the time of kneading, the temperature condition, and the like may be used.
The use amount of the emulsifier is preferably 1.0 to 10.0% by mass based on 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 based on the ethylene / α-olefin copolymer (F). As a temperature condition at the time of kneading, 100 to 300 ° C. is preferable.

<Crosslinked ethylene / α-olefin copolymer (H)>
The crosslinked ethylene / α-olefin copolymer (H) is an ethylene / α-olefin-based copolymer (F) or an ethylene / α-olefin-based copolymer (G) dispersed in an aqueous olefin resin dispersion (G). This is obtained by subjecting F) to a crosslinking treatment. By the cross-linking treatment, the balance between the impact resistance and the coloring properties of the molded product is further improved.

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 the coloring property of the molded article. , 60 to 75% by mass is particularly preferred.
The gel content in the present invention means that the crosslinked ethylene / α-olefin copolymer (H) is swollen with toluene, and is dried with respect to the crosslinked ethylene / α-olefin copolymer (H) before swelling. It is the ratio of the toluene insoluble matter. Specifically, it is determined by the method described in the examples.

  The crosslinking treatment of the ethylene / α-olefin copolymer (F) or the aqueous olefin resin dispersion (G) can be performed by a known method. Examples of the method of the crosslinking treatment include (a) a method of adding an organic peroxide and, if necessary, a polyfunctional compound to perform a crosslinking treatment, and (b) a method of performing a crosslinking treatment by ionizing radiation. The method (a) is preferred from the viewpoints of impact resistance and coloring of the molded product.

As the method (a), specifically, an organic peroxide and, if necessary, a polyfunctional compound are added to an ethylene / α-olefin copolymer (F) or an aqueous olefin resin dispersion (G). And heating.
For example, a crosslinked ethylene / α-olefin copolymer is obtained by adding an organic peroxide and, if necessary, a polyfunctional compound to the ethylene / α-olefin copolymer (F), kneading and pulverizing the mixture. The powder of (H) is obtained. If necessary, the pulverized product obtained by the pulverization may be subjected to a treatment such as classification. When an organic peroxide and, if necessary, a polyfunctional compound are added to the aqueous olefin resin dispersion (G) for 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 the organic peroxide and the polyfunctional compound, the heating temperature, the heating time, and the like.
The heating temperature depends on the type of the organic peroxide. The heating temperature is preferably from -5 ° C to + 30 ° C, which is the 10-hour half-life temperature of the organic peroxide.
The heating time is preferably 3 to 15 hours.

  The organic peroxide is for forming a crosslinked structure in the ethylene / α-olefin copolymer (F). Examples of the organic peroxide include a peroxyester compound, a peroxyketal compound, a dialkyl peroxide compound, and the like. One kind of the organic peroxide may be used alone, or two or more kinds may be used in combination.

As the organic peroxide, a dialkyl peroxide compound is particularly preferable because the gel content of the crosslinked ethylene / α-olefin copolymer (G) is 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, t-butyl Cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

  The amount of the organic peroxide added is such that the gel content of the crosslinked ethylene / α-olefin copolymer (H) can be easily adjusted to the range of 35 to 85% by mass. ) 0.1 to 5 parts by mass per 100 parts by mass is preferred.

The polyfunctional compound is used in combination with an organic peroxide as needed 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 methacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, and pentaerythritol tetraacrylate. And divinylbenzene is preferred because the gel content is easily adjusted. One of the polyfunctional compounds may be used alone, or two or more may be used in combination.

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

When the ethylene / α-olefin copolymer (F) is subjected to a crosslinking treatment to obtain a crosslinked ethylene / α-olefin copolymer (H), an acid-modified olefin polymer is added to the ethylene / α-olefin copolymer (F). 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 addition amount of the acid-modified olefin polymer is the same as the content of the acid-modified olefin polymer in the aqueous olefin resin dispersion (G), based on 100 parts by mass of the ethylene / α-olefin copolymer (F). 1 to 40 parts by mass is preferred.
The method for adding the acid-modified olefin polymer is not limited. After mixing the ethylene / α-olefin copolymer (F) and the acid-modified olefin polymer, a crosslinking treatment may be performed, or the ethylene / α-olefin copolymer (F) and the acid-modified olefin polymer may be mixed. They may be mixed after each crosslinking treatment.
The method of mixing the ethylene / α-olefin copolymer (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 such that the physical properties of the molded article are excellent. From this, 0.2 to 0.6 μm is preferable, and 0.3 to 0.5 μm is more preferable. When the volume average particle size 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 molded article is more excellent in impact resistance, color development, and heat aging resistance. When the crosslinked ethylene / α-olefin (H) has a volume average particle diameter of 0.3 μm to 0.5 μm, the molded article is more excellent in impact resistance, color development, and heat aging resistance.

In addition, the crosslinked ethylene / α-olefin copolymer (H) in the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (H) obtained by subjecting the aqueous olefin resin dispersion (G) to a crosslinking treatment 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 olefin resin dispersion (G), and the particle size Without the expansion of
In addition, the electron microscopy shows that the volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (H) in the aqueous dispersion indicates the volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (H). 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-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Styrene and α-methylstyrene are preferred from the viewpoints of fluidity, color development of molded articles, and impact resistance. One kind of the aromatic vinyl compound may be used alone, or two or more kinds may be used in combination.

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

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

  The content of the aromatic vinyl compound in the vinyl monomer component (m4) is preferably from 60 to 85% by mass, and more preferably from 62 to 85% by mass, based on the total mass (100% by mass) of the vinyl monomer component (m4). 80 mass% is more preferable. When the content of the aromatic vinyl compound is within the above-mentioned range, the color development and impact resistance of the molded product are further excellent.

  The content of the vinyl cyanide compound in the vinyl monomer component (m4) is preferably 15 to 40% by mass, and more preferably 20 to 40% based on the total mass (100% by mass) of the vinyl monomer component (m4). 38% by mass is more preferred. When the content of the vinyl cyanide compound is within the above range, the color development and impact resistance of the molded product are further improved.

<Graft copolymer (I)>
The graft copolymer (I) is obtained by polymerizing a vinyl monomer component (m4) in the presence of an olefin copolymer, and includes, for example, the following (α), (β), (Γ) and (δ).
(Α) A polymer obtained by polymerizing a vinyl monomer component (m4) in the presence of an ethylene / α-olefin copolymer (F).
(Β) A polymer obtained by polymerizing a vinyl monomer component (m4) in the presence of an aqueous olefin resin dispersion (G).
(Γ) Polymerization of vinyl monomer component (m4) in the presence of cross-linked ethylene / α-olefin copolymer (H) obtained by cross-linking ethylene / α-olefin copolymer (F) What was obtained.
(Δ) In the presence of an aqueous dispersion of a cross-linked ethylene / α-olefin copolymer (H) obtained by cross-linking an aqueous olefin resin dispersion (G), the vinyl monomer component (m4) Those obtained by polymerization.
The graft copolymer (I) is obtained by adding an olefin copolymer (ethylene / α-olefin copolymer (F), crosslinked ethylene / α-olefin copolymer (H), etc.) to a vinyl monomer component ( m4) to which a graft chain composed of a polymer is bonded, 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 completely core-shell type, it is defined as "obtained by polymerizing vinyl monomer component (m4) in the presence of olefin copolymer". It is more appropriate to do so.

The graft copolymer (I) is a vinyl monomer component (m4) 20 to 50 mass% (provided that the olefin copolymer and the vinyl monomer are present) in the presence of 50 to 80 mass% of the olefin copolymer. The total obtained with the monomer component (m4) is 100% by mass.).
That is, the graft copolymer (I) is composed of 50 to 80% by mass of the olefin-based copolymer and 20 to 50% by mass of the polymer of the vinyl-based monomer component (m4) (however, the olefin-based copolymer and the 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 from 50 to 80% by mass, the fluidity of the thermoplastic resin composition, the impact resistance of the molded product, and the balance of physical properties of the coloring properties are further improved.

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

  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, and the like).

As a method for producing the graft copolymer (I) by the emulsion polymerization method, for example, a mixture of a vinyl monomer component (m4) and an organic peroxide is mixed with an aqueous dispersion of an olefin copolymer (for example, (Aqueous dispersion of olefin resin (G) or aqueous dispersion of crosslinked ethylene / α-olefin copolymer (H)).
The organic peroxide is preferably used as a redox initiator obtained by combining an organic peroxide, a transition metal and a reducing agent.
At the time of polymerization, a chain transfer agent, an emulsifier, and the like may be used depending on the situation.

As a redox-based initiator, there is no need to set the polymerization reaction conditions to high temperatures, and it is possible to avoid deterioration of the olefin copolymer and the like, and to avoid a decrease in the impact resistance of the molded product. A combination of one iron-chelating agent-reducing agent is preferred.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide and the like.
The redox-based initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of the chain transfer agent include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allylsulfonic acid, methallylsulfonic acid, And the like, and α-methylstyrene dimer, and mercaptans are preferred from the viewpoint that the molecular weight can be easily adjusted. One type of the chain transfer agent may be used alone, or two or more types may be used in combination.
The method of adding the chain transfer agent may be any of batch, division, and continuous.
The amount of the chain transfer agent to be added is preferably 2.0 parts by mass or less based on 100 parts by mass of the vinyl monomer component (m4).

Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include a higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, a phosphate salt, a fatty acid salt, and an amino acid derivative salt.
Examples of the nonionic surfactant include the usual alkyl ester type, alkyl ether type, and alkyl phenyl ether type of polyethylene glycol.
Examples of the amphoteric surfactant include those having a carboxylate, a sulfate, a sulfonate, a phosphate and the like in the anion part, and an amine salt and a quaternary ammonium salt in the cation part.
The addition amount of the emulsifier is preferably 10 parts by mass or less based on 100 parts by mass of the vinyl monomer component (m4).
The polymerization conditions for emulsion polymerization are not particularly limited, and include, for example, 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 precipitant is added to the aqueous dispersion, and after heating and stirring, the precipitant is separated. And a precipitation method in which the precipitated graft copolymer (I) is washed with water, dehydrated, and dried.
Examples of the precipitant include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. As the precipitating agent, one type may be used alone, or two or more types may be used in combination.
If necessary, an antioxidant may be added to the aqueous dispersion containing the graft copolymer (I).

Examples of the method for producing the graft copolymer (I) by the solution polymerization method include, for example, an olefin-based copolymer (for example, an ethylene / α-olefin copolymer (F) or a 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 ordinary radical polymerization is used, for example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, halogenation such as dichloromethylene and carbon tetrachloride. Hydrocarbons and the like are used.
As a polymerization initiator in the solution polymerization, a general initiator is used, and for example, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, and hydroperoxide are used. Examples of the method for adding the polymerization initiator include a method of adding the polymerization initiator all at once and a method of continuously adding the polymerization initiator.
The polymerization conditions for the solution polymerization are not particularly limited, and include, for example, polymerization conditions at 50 to 90 ° C. for 1 to 10 hours.

<Other thermoplastic resins>
Examples of other thermoplastic resins include (meth) acrylate resins other than (meth) acrylate resin (C), polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polyvinyl chloride. , Polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester, polyethylene, polypropylene, polyamide (nylon), fluorine resin and the like. These may be used alone or in combination of two or more.

<Various additives>
Various additives include antioxidants, ultraviolet absorbers, lubricants, plasticizers, stabilizers, release agents, antistatic agents, processing aids, coloring agents (pigments, dyes, etc.), carbon fibers, glass fibers, Fillers such as lastonite, calcium carbonate, silica, etc., anti-drip agents, antibacterial agents, antifungal agents, coupling agents, paraffin oil and the like can be mentioned. These may be used alone or in combination of two or more.

<Content of each component>
The content of the graft copolymer (B) is 100 mass in total of the graft copolymer (B), the (meth) acrylate resin (C), the styrene resin (E), and the graft copolymer (I). % Is preferably 18 to 80% by mass, more preferably 30 to 60% by mass. When the content of the graft copolymer (B) is within the above range, the balance between impact resistance and heat resistance of the molded product is more excellent.

  The content of the (meth) acrylic ester resin (C) is determined by the amount 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 100 mass% in total, and 40-70 mass% is more preferable. When the content of the (meth) acrylic acid ester resin (C) is within the above range, the molded product is more excellent in the balance of color development, heat resistance, and heat aging resistance.

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

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). On the other hand, 0 to 40% by mass is preferable, and 1 to 40% by mass is more preferable. When the content of the styrenic resin (E) is within the above range, the thermoplastic resin composition has excellent balance of fluidity, impact resistance of a molded product, color development, weather resistance, and heat aging resistance.
The content of the styrene resin (E) of 0% by mass indicates that the thermoplastic resin composition does not contain the styrene resin (E).

The content of the graft copolymer (I) is 100 mass in total of the graft copolymer (B), the (meth) acrylate resin (C), the styrene resin (E), and the graft copolymer (I). % Is preferably 0 to 15% by mass. When the content of the graft copolymer (I) is within the above range, excellent 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 obtained.
The content of the graft copolymer (I) of 0% by mass indicates that the thermoplastic resin composition does not contain the graft copolymer (I).

  Based on the total (100% by mass) of the composite rubbery polymer (A) and the olefin copolymer in the graft copolymer (I), the 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 from 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, and more preferably 68 to 99% by mass based on the total (100% by mass) of the olefin-based copolymer and the composite rubber-like polymer (A). 96 mass% is more preferable. When the ratio of the olefin-based 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 product is more excellent. When the proportion of the olefin-based copolymer is 15% by mass or less (the proportion of the composite rubber-like polymer (A) is 85% by mass or more), the molded product is more excellent in color development, heat aging resistance, and weather resistance.

  The total content (rubber content) of the composite rubbery polymer (A) and the olefin 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 coloring property, and the heat resistance are further excellent.

  The total content of the graft copolymer (B) and the graft copolymer (I) is such that the graft copolymer (B), the (meth) acrylate resin (C), the styrene resin (E), It is preferably from 10 to 60% by mass with respect to 100% by mass in total with the 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 coloring property, the heat resistance, etc. Is even better.

  The content of the graft copolymer (B) is preferably from 18 to 80% by mass, more preferably from 30 to 60% by mass, based on the total mass of the thermoplastic resin composition. 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.

The content of the (meth) acrylate resin (C) is preferably from 20 to 82% by mass, more preferably from 40 to 70% by mass, based on the total mass of the thermoplastic resin composition. When the content of the (meth) acrylic acid ester resin (C) is within the above range, the molded product is more excellent in the balance of color development, heat resistance, and heat aging resistance.
The content of the other (meth) acrylate resin is preferably 0 to 90% by mass, and more preferably 15 to 90% by mass, based on the total of the (meth) acrylate resin (C) and the other (meth) acrylate resin. 80 mass% is more preferable.

As a preferred embodiment of the thermoplastic resin composition of the present invention, it contains a graft copolymer (B) and a (meth) acrylate resin (C),
The content of the graft copolymer (B) is 18 to 80% by mass based on 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 the present embodiment, the content of the graft copolymer (B) is preferably 30 to 60% by mass, and the content of the (meth) acrylate resin (C) is preferably 40 to 70% by mass. .
In the present embodiment, the total content of the graft copolymer (B) and the (meth) acrylate resin (C) with respect to the total mass of the thermoplastic resin composition is preferably from 50 to 100% by mass.

As another preferred embodiment of the thermoplastic resin composition of the present invention, the composition comprises a graft copolymer (B), a (meth) acrylate resin (C), and a silicone oil (D),
The content of the graft copolymer (B) is 18 to 80% by mass based on the total of the graft copolymer (B) and the (meth) acrylate resin (C), and the (meth) acrylate resin (C ) 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 a total of 100 parts by mass of the graft copolymer (B) and the (meth) acrylate resin (C). Is mentioned.
In the present embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylate resin (C) is 40 to 70% by mass, and the silicone oil is used. The content of (D) is preferably 0.3 to 3 parts by mass.
In the present embodiment, the total content of the graft copolymer (B), the (meth) acrylate resin (C), and the silicone oil (D) is 50 to 100 mass with respect to the total mass of the thermoplastic resin composition. % Is preferred.

As another preferred embodiment of the thermoplastic resin composition of the present invention, a graft copolymer (B), a (meth) acrylate resin (C), a silicone oil (D), and a styrene resin (E) And
The content of the graft copolymer (B) is 18 to 60% by mass based on the total of the graft copolymer (B), the (meth) acrylate resin (C), and the styrene-based resin (E). ) The content of the acrylate resin (C) is 20 to 81% by mass, the content of the styrene resin (E) is 1 to 40% by mass,
The content of the silicone oil (D) is 0.1 to 5 parts by mass with respect to the total of 100 parts by mass of the graft copolymer (B), the (meth) acrylate resin (C), and the styrene-based resin (E). Is a thermoplastic resin composition.
In the present embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylate resin (C) is 20 to 69% by mass, and the styrene-based resin is used. 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 the present embodiment, the total content of the graft copolymer (B), the (meth) acrylate resin (C), the silicone oil (D), and the styrene-based resin (E) based on the total mass of the thermoplastic resin composition The amount is preferably from 70 to 100% by mass.

As another preferred embodiment of the thermoplastic resin composition of the present invention, it includes a graft copolymer (B), a (meth) acrylate resin (C), and a graft copolymer (I),
With respect to the total of the graft copolymer (B), the (meth) acrylate resin (C) and the graft copolymer (I), the content of the graft copolymer (B) is 18 to 60% by mass, A thermoplastic resin composition in which the content of the (meth) acrylate resin (C) is 20 to 81% by mass and the content of the graft copolymer (I) is 1 to 15% by mass.
In the present embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylate resin (C) is 30 to 69% by mass, and the content of the graft copolymer is 30 to 69% by mass. It is preferable that the content of the polymer (I) is 1 to 10% by mass.
In this embodiment, the total content of the graft copolymer (B), the (meth) acrylate resin (C) and the graft copolymer (I) with respect to the total mass of the thermoplastic resin composition is 50 to 50%. 100% by mass is preferred.

As another preferred embodiment of the thermoplastic resin composition of the present invention, a graft copolymer (B), a (meth) acrylate resin (C), a silicone oil (D), and a graft copolymer (I) ) And
With respect to the total of the graft copolymer (B), the (meth) acrylate resin (C) and the graft copolymer (I), the content of the graft copolymer (B) is 18 to 60% by mass, 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,
The content of the silicone oil (D) is 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the graft copolymer (B), the (meth) acrylate resin (C), and the graft copolymer (I). Part of the thermoplastic resin composition.
In the present embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylate resin (C) is 30 to 69% by mass, and the content of the graft copolymer is 30 to 69% by mass. It is preferable that the content of the polymer (I) is 1 to 10% by mass and the content of the silicone oil (D) is 0.3 to 3 parts by mass.
In this embodiment, the total of the graft copolymer (B), the (meth) acrylate 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 another preferred embodiment of the thermoplastic resin composition of the present invention, a graft copolymer (B), a (meth) acrylate resin (C), a silicone oil (D), and a styrene resin (E) And a graft copolymer (I),
The content of the graft copolymer (B) is based on the total of the graft copolymer (B), the (meth) acrylate resin (C), the styrene resin (E), and the graft copolymer (I). 18 to 60% by mass, the content of the (meth) acrylate resin (C) is 20 to 80% by mass, the content of the styrene resin (E) is 1 to 40% by mass, and the content of the graft copolymer (I) is The content is 1 to 10% by mass,
Silicone oil (D) content based on 100 parts by weight of the total of the graft copolymer (B), the (meth) acrylate resin (C), the styrene-based resin (E), and the graft copolymer (I) Is 0.1 to 5 parts by mass.
In the present embodiment, the content of the graft copolymer (B) is 30 to 60% by mass, the content of the (meth) acrylate resin (C) is 40 to 68% by mass, 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 the present embodiment, the graft copolymer (B), the (meth) acrylate resin (C), the silicone oil (D), the styrene resin (E), and the graft copolymer based on the total mass of the thermoplastic resin composition The total content with (I) is preferably from 90 to 100% by mass.

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

<Production method of thermoplastic resin composition>
The thermoplastic resin composition comprises a graft copolymer (B), a (meth) acrylate resin (C), and, if necessary, other components (silicone oil (D), styrene resin (E), It can be obtained by mixing the copolymer (I), another thermoplastic resin, and various additives.

<Use 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 increased and decreased by using an injection molding mold in which the cavity surface of the mold is alternately heated and cooled. Goods.
The heat cycle injection molding method will be described later in detail.

<Effects>
In the thermoplastic resin composition of the present invention described above, the unit derived from the polyorganosiloxane (Aa) and the unit derived from the (meth) acrylate, the unit derived from the crosslinking agent, and the unit derived from the graft crossing agent A vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a composite rubbery polymer (A) comprising a poly (meth) acrylate (Ab) having at least one of The graft copolymer (B) obtained by polymerizing the component (m1) is polymerized with a vinyl monomer component (m2) containing a (meth) acrylate, a maleimide compound and an aromatic vinyl compound. Containing the obtained (meth) acrylate resin (C), and containing the polyorganosiloxane (Aa) in the composite rubber-like polymer (A) (100% by mass). Is 1 to 20% by mass, the volume average particle diameter of the composite rubber-like polymer (A) is 0.05 μm to 0.15 μm, and the above-mentioned in the vinyl monomer component (m2) (100% by mass) Since the content of the maleimide-based 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 the scratch resistance when molded by the heat cycle injection molding method. A molded article having excellent scratch resistance, impact resistance, coloring, heat resistance, and heat aging resistance can be obtained. Further, the fluidity of the thermoplastic resin composition is also good.

In the thermoplastic resin composition of the present invention, the molded product (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 preferably 5 to 20 kJ / m ² . More preferably, there is. When the Charpy impact strength is equal to or higher than the lower limit, the impact resistance is sufficiently excellent, and when the Charpy impact strength is equal to or lower than the upper limit, the balance of other properties is good.
The “molded product (Ma2)” is obtained by melting and kneading the thermoplastic resin composition with a twin-screw extruder, and using an injection molding machine equipped with an injection molding die in which the cavity surface of the die is alternately heated and cooled. Heat cycle injection molding was performed under the conditions of 260 ° C., a mold temperature of 110 ° C. when the resin was filled in the mold, and a mold temperature of 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. Things.
"Charpy impact strength" is a value measured by performing a Charpy impact test on the molded article (Ma2) in accordance with ISO 179-1: 2000 under conditions of notch and 23 ° C.

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

In the thermoplastic resin composition of the present invention, the lightness L ^{* of} a molded article (Ma1) formed from the thermoplastic resin composition of the present invention is preferably 7.0 or less, and preferably 3.0 to 7.0. More preferred. When the lightness L ^* is equal to or less than the upper limit, the color developability is sufficiently excellent.
The “molded article (Ma1)” is obtained by adding a thermoplastic resin composition to a resin component (graft copolymer (B), (meth) acrylate resin (C), styrene resin (E), graft copolymer ( Injection in which 0.8 parts of carbon black is melt-kneaded in a twin-screw extruder with respect to 100 parts of the total amount of (I) and the other thermoplastic resin), and the cavity surface of the mold is heated and cooled alternately. Heat cycle injection molding is performed by an injection molding machine equipped with a molding die under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 110 ° C. when the resin is filled in the mold, and a mold temperature of 40 ° C. when cooling. It is what it was.
"Lightness L ^* " is a value measured by the SCE method for the molded article (Ma1). A detailed method of 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) of the molded article (Ma1) formed from the thermoplastic resin composition of the present invention before and after the weather resistance test is preferably 3.0 or less, and 1 More preferably, it is 0.0-3.0. When ΔE is equal to or less than the upper limit, weatherability is sufficiently excellent, and when ΔE is equal to or greater than the lower limit, the balance of other characteristics is good.
The “weather resistance test” is a test in which the molded article (Ma1) is treated for 1000 hours under the 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.
The “degree of discoloration (ΔE)” is a value measured by the SCE method using a spectrophotometer.

In the thermoplastic resin composition of the present invention, the degree of discoloration (ΔE) of the molded article (Ma1) formed from the thermoplastic resin composition of the present invention before and after the heat aging test is preferably 3.4 or less, More preferably, it is 0.5 to 3.4. When ΔE is equal to or less than the upper limit, the heat aging resistance is sufficiently excellent, and when ΔE is equal to or more than the lower limit, the balance of other properties is good.
The “heat aging resistance test” is a test in which a molded article (Ma1) is treated using a thermostat at a temperature of 90 ° C. and a humidity of 30% for 500 hours. The degree of discoloration (ΔE) is as described above.

The thermoplastic resin composition of the present invention has a molded product (Ma1) formed from the thermoplastic resin composition of the present invention, in which the difference in lightness L ^* (mb-ma) before and after the pencil hardness test is less than 3.0. Is preferable, and it is more preferable that it is 1.0 or more and less than 3.0. When the absolute value of L ^* (mb-ma) is equal to or less than the upper limit, the scratch resistance is sufficiently excellent, and when the absolute value is equal to or greater than the lower limit, 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 article (Mb)" was pressed with a pencil having a hardness of 3H against the surface of the molded article (Ma1) using a pencil hardness tester with a load of 7.35 N (750 g). Is moved about 5 cm to scratch the surface of the molded article (Ma1) with a pencil.

"Molding"
The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention.
As described above, a heat cycle injection molding method is used as the method for producing the molded article of the present invention, that is, the method for molding 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 a mold using an injection mold in which a 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 heat distortion temperature (HDT) of the thermoplastic resin composition, and then the heat is applied. The thermoplastic resin composition is injected, the temperature of the cavity surface of the mold is lowered, and the thermoplastic resin composition is cooled to obtain a molded product. The molded product is taken out of the mold. Thereafter, the cavity surface temperature of the mold is raised again to a temperature equal to or higher than the thermal deformation temperature of the thermoplastic resin composition, and the above series of steps (injection of the thermoplastic resin composition, cooling, removal of the molded product) are performed. repeat.
As a more specific condition of the heat cycle injection molding method, injection is performed at a resin temperature of (T + 120 ° C.) to (T + 200 ° C.) with respect to a heat distortion temperature (HDT) T ° C. of the thermoplastic resin composition, and a mold is formed. temperature _{T a} ° C. is a (T + 5 ℃) ~ ( T + 50 ℃), the temperature _{T B} ° C. during cooling and (T-10 ℃) ~ ( T-50 ℃), the T _a -T B = 15~100 ℃ It is preferable to employ conditions. Further, the cycle of this heat cycle is preferably the same as the cycle of general injection molding or within + 10% of the cycle of general injection molding.
The heat distortion temperature is another name for the deflection temperature under load, and is measured by the above-described measurement method.
As a method of heating the cavity surface temperature of the mold to a temperature equal to or higher than the thermal deformation temperature of the thermoplastic resin composition, a hot water cooling water switching system, a steam heating system, a heating oil system, a mold surface heat insulation system, and the like can be mentioned. 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, coloring, 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 more excellent scratch resistance and excellent surface appearance.

Hereinafter, specific examples will be described. However, the present invention is not limited to these examples. Examples 19 and 24 described below are reference examples.
“%” Described below means “% by mass”, and “parts” means “parts by mass”.
Various measurement and evaluation methods in the following examples and comparative examples are as follows.

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

<Method for measuring mass average molecular weight of (meth) acrylate 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 using tetrahydrofuran (THF: 40 ° C.) as a solvent. .

<Method for measuring mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of ethylene / α-olefin copolymer (F)>
Using GPC (GPC: “GPC / V2000” manufactured by Waters, column: “Shodex AT-G + AT-806MS” manufactured by Showa Denko KK), and using o-dichlorobenzene (145 ° C.) as a solvent, a mass average molecular weight in terms of polystyrene. (Mw), number average molecular weight and molecular weight (Mn) were measured, and the molecular weight distribution (Mw / Mn) was calculated.

<Method for measuring gel content of crosslinked ethylene / α-olefin copolymer (H)>
Aqueous or solvent dispersion of the crosslinked ethylene / α-olefin copolymer (H) is coagulated with dilute sulfuric acid, washed with water and dried, and 0.5 g of a coagulated powder sample [h1] is obtained. And then filtered through a 200 mesh wire gauze, and the residue was dried. The mass of the dried product [h2] was measured, and from the following formula (1), the crosslinked ethylene / α-olefin copolymer was obtained. The gel content of (H) was determined.
Gel content (%) = Amount of dry substance [h2] (g) / mass of coagulated powder sample [h1] (g) × 100 (1)

<Method for measuring graft ratio of graft copolymer (I)>
1 g of the graft copolymer (I) was added to 80 mL of acetone, and the mixture was refluxed by heating at 65 to 70 ° C. for 3 hours. And centrifuged at 14,000 rpm for 30 minutes to separate a precipitate component (acetone-insoluble component) and an acetone solution (acetone-soluble component). Then, the precipitated component (acetone-insoluble component) was dried, its mass (Y (g)) was measured, and the graft ratio was calculated from the following equation (2). In the 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 for obtaining Y. The rubber fraction is the solid content of the olefin copolymer of the graft copolymer (I).
Graft rate (%) = {(YX × Rubber fraction) / X × Rubber fraction} × 100 (2)

<Melting and kneading 1>
Example and Comparative Example A mixture obtained by mixing the graft copolymer (B), the (meth) acrylate resin (C), and the like according to the formulation of each was mixed with a twin-screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.). )), Melt-kneading was performed at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition (1). Furthermore, after melt-kneading, pelletization was performed using a pelletizer (“SH-type pelletizer” manufactured by Soken Co.).

<Melting and kneading 2>
A mixture obtained by mixing the graft copolymer (B), the (meth) acrylate resin (C), and the like according to the respective formulations of the Examples and Comparative Examples, and 0 to 100 parts of the total amount of the resin components in the mixture. .8 parts of carbon black ("966" manufactured by Mitsubishi Chemical Corporation) and mixed with a twin screw extruder ("PCM30" manufactured by Ikegai Co., Ltd.) with a vacuum vent of 30 mmφ, cylinder temperature 200-260 ° C, 93.325 kPa Melt kneading was performed in a vacuum to obtain a thermoplastic resin composition (2). Furthermore, after melt-kneading, pelletization was performed using a pelletizer (“SH-type pelletizer” manufactured by Soken Co.).

<Measurement of melt volume rate (MVR)>
For the thermoplastic resin composition (1), the MVR at 230 ° C. was measured under a load of 98 N (10 kg) according to ISO 1133: 1997. The MVR is a measure of the fluidity of the thermoplastic resin composition.

<Molding method A: Heat cycle injection molding>
(1. Molding of molded article (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 in the following procedure. did. The molded article 1 has a plate shape of 60 mm in length × 90 mm in width × 10 mm in thickness, and has a rectangular opening (25 mm × 30 mm in width) 2 in the center and an upper surface in the upper left corner in the figure (product). A rectangular opening 3 (25 mm long × 30 mm wide) and a circular opening 4 (diameter 10 mm) as viewed from above are formed in the lower left corner of the figure, respectively, through the molded article 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 positions on each of four sides surrounding the opening 2.
The pellets of the thermoplastic resin composition (2) obtained by melt-kneading are molded into “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. And heat cycle injection molding at a cylinder temperature (resin temperature at the time of injection) of 260 ° C, a mold temperature of 110 ° C during filling of the resin into the mold, and a mold temperature of 40 ° C during cooling. The process was performed to obtain a molded product (Ma1).

(2. Molding of molded article (Ma2))
As a molded product (molded product (Ma2)) for evaluation of impact resistance and heat resistance, a plate-shaped molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was formed in the following procedure.
The pellets of the thermoplastic resin composition (1) obtained by melt-kneading are mixed with pellets of Toshiba Machine Co., Ltd. "IS55FP-1.5A molding machine" equipped with "High-speed heat cycle molding unit" manufactured by Ono Sangyo Co., Ltd. Heat cycle injection molding was carried out under the conditions of a cylinder temperature (resin temperature at the time of injection) of 260 ° C., a mold temperature of 110 ° C. at the time of filling the resin into the mold, and a mold temperature of 40 ° C. at the time of cooling. To obtain a molded product (Ma2).

<Molding method B: General molding (injection molding that does not raise or lower the cavity surface temperature of the mold)>
(1. Molding of molded article (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.
The pellets of the thermoplastic resin composition (2) obtained by melt-kneading are charged into “IS55FP-1.5A molding machine” manufactured by Toshiba Machine Co., Ltd., and the cylinder temperature is 200 to 270 ° C. and the mold temperature is 60 ° C. Injection molding was performed under the conditions to obtain a molded product (Ma3).

(2. Molding of molded article (Ma4))
As a molded product (molded product (Ma4)) for evaluation of impact resistance and heat resistance, a plate-shaped molded product having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was formed in 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., and the cylinder temperature is 200 to 270 ° C. and the mold temperature is 60 ° C. Injection molding was performed under the conditions to obtain a molded product (Ma4).

<Evaluation of impact resistance: Charpy impact test>
For the molded article (Ma2) or (Ma4), a Charpy impact test (with a notch) was performed at 23 ° C. according to ISO 179-1: 2000, and the Charpy impact strength was measured.

<Evaluation of heat resistance>
With respect to the molded article (Ma2) or (Ma4), the deflection temperature under load (° C.) was measured by a flatwise method at 1.83 MPa and 4 mm in accordance with ISO 75-1: 2004.

<Evaluation of color development>
For the molded article (Ma1) or (Ma3), the lightness L ^* was measured by an SCE method using a spectrophotometer (“CM-3500d” manufactured by Konica Minolta Optics). L ^* measured in this manner is referred to as “L ^* (ma)”. The lower the L ^* , the blacker the color and the better the color developability.

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

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

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

<Evaluation of scratch resistance>
Using a pencil hardness tester, a pencil having a hardness of 3H is pressed against the surface of the molded product (Ma1) or (Ma3) with a load of 7.35 N (750 g). By moving about 5 cm, the surface of the molded article (Ma1) or (Ma3) was scratched with a pencil, and the molded article (Ma1) or (Ma3) was scratched. The lightness L ^* of the surface of the damaged molded article (Mb) was measured by an SCE method using a spectrophotometer. L ^* measured in this manner is referred to as “L ^* (mb)”.

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

<Evaluation of surface appearance>
The surface of the molded article (Ma1) or (Ma3) was visually observed, and judged based on the following criteria.
: The surface is glossy and there is no unevenness in the color of the weld.
Δ: There is surface gloss, but there is slight color unevenness in the welded part.
×: There is no surface gloss, and there is uneven color in the weld portion.

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

<Graft copolymer (B) and its comparative 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, 300 parts of ion-exchanged water in which 8 parts of sodium dodecylbenzenesulfonate were dissolved was added, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes. 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 pipe, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. While the aqueous solution was heated to 85 ° C., the premixed aqueous organosiloxane dispersion was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour, and the mixture was cooled. The reaction solution was allowed to stand at room temperature for 48 hours, and then neutralized with an aqueous sodium hydroxide solution to obtain an aqueous dispersion of polyorganosiloxane (Aa1).
A part of the aqueous polyorganosiloxane (Aa1) dispersion was dried at 170 ° C. for 30 minutes to obtain a solid concentration of 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 part of sodium dodecylbenzenesulfonate was dissolved. After stirring with a homomixer at 10,000 rpm for 2 minutes, the mixture was passed through a homogenizer once at a pressure of 30 MPa to obtain a stable premix. 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 pipe, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. While the aqueous solution was heated to 85 ° C., the premixed aqueous organosiloxane dispersion was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour, and the mixture was cooled. The reaction solution was allowed to stand at room temperature for 48 hours, and then neutralized with an aqueous sodium hydroxide solution to obtain an aqueous dispersion of polyorganosiloxane (Aa2).
A part of the aqueous polyorganosiloxane (Aa2) 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 Rubbery Polymer (A-1))
In a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 68.3 parts of an aqueous dispersion of polyorganosiloxane (Aa1) and 0.94 parts of an emulsifier (sodium polyoxyethylene alkylphenyl ether sulfate) And 203 parts of ion-exchanged water were 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 replaced 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. due to the polymerization of the (meth) acrylate component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylate component, thereby obtaining 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 size 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 in the preparation of the composite rubber-like polymer (A-1) except that the amount (part) of the emulsifier was changed. Obtained. Table 1 shows the volume average particle diameter of the composite rubbery polymer (A-2) dispersed in the aqueous dispersion.

(Preparation of Composite Rubbery Polymer (A-3))
In a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 68.3 parts of an aqueous dispersion of polyorganosiloxane (Aa2) and 0.85 parts of an emulsifier (sodium polyoxyethylene alkylphenyl ether sulfate) And 203 parts of ion-exchanged water were 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 replaced 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. due to the polymerization of the (meth) acrylate component. This state was maintained for 1 hour to complete the polymerization of the (meth) acrylate 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 size 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 rubbery polymers (A-4) to (A-7) were prepared in the same manner as in the preparation of the composite rubbery polymer (A-3) except that the amount (part) of the emulsifier was changed. )) Was obtained. Table 1 shows the volume average particle diameter of the composite rubbery 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. The inside of the reactor was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00026 part of ferrous sulfate, 0.0008 part of disodium ethylenediaminetetraacetate, 0.45 part of Rongalite, and 10 parts of ion-exchanged water was added. The polymerization was started, and the internal temperature was raised to 75 ° C. This state was further maintained for 1 hour to obtain an aqueous dispersion of the composite rubber-like polymer (A-8). The volume average particle size of the composite rubber-like polymer (A-8) dispersed in the aqueous dispersion was 0.096 μm. Table 2 shows the volume average particle size 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) to n-butyl acrylate and the amount (part) of emulsifier were changed, the same procedure as in the preparation of the composite rubbery polymer (A-3) was performed. Thus, aqueous dispersions of the composite rubbery polymers (A-9) to (A-13) were obtained. Table 2 shows the volume average particle diameter of the composite rubbery 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) was placed in a reactor equipped with a reagent injection container, a cooling pipe, 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. Then, a mixed solution of 7.5 parts of acrylonitrile, 22.5 parts of styrene and 0.18 part of tertiary butyl hydroperoxide was dropped and polymerized for about 1 hour. After holding for 1 hour after the completion of the dropping, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of disodium ethylenediaminetetraacetate and 0.25 part of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Next, a mixed solution of 5 parts of acrylonitrile, 15 parts of styrene and 0.1 part of tertiary butyl hydroperoxide was dropped and polymerized for about 40 minutes. After holding for 1 hour after the completion of the dropwise addition, the mixture was cooled to obtain an aqueous dispersion of a graft copolymer (B-1) in which an acrylonitrile-styrene copolymer was grafted on the composite rubbery 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 the aqueous dispersion of the graft copolymer (B-1) was gradually dropped into the aqueous calcium acetate solution to coagulate it. The obtained coagulated 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 in the preparation of the graft copolymer (B-1) except that the type of the aqueous dispersion of the composite rubbery 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) was placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, and a stirrer. After adjusting the temperature to 60 ° C., an aqueous solution consisting of 0.15 part of Rongalite, 0.65 part of dipotassium alkenylsuccinate and 10 parts of ion-exchanged water was added, and then 6.3 parts of acrylonitrile, 18.7 parts of styrene, A mixed solution consisting of 0.11 part of t-butyl hydroperoxide and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour to effect graft polymerization. Five minutes after the completion of the dropwise addition, an aqueous solution consisting of 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.15 part of Rongalit, and 5 parts of ion-exchanged water was added, and then acrylonitrile 6 .2 parts, styrene 18.8 parts, t-butyl hydroperoxide 0.19 parts and n-octyl mercaptan 0.014 parts were dropped over 1 hour to carry out graft polymerization. After dropping, the internal temperature was maintained at 75 ° C. for 10 minutes, and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of an antioxidant (Antage W500, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) and alkenyl succinate 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 in the preparation of the graft copolymer (B-1) except that the type of the aqueous dispersion of the composite rubbery polymer (A) was changed. 9) to (B-13) were obtained.

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

(Preparation of (meth) acrylate resin (C-2))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged water, 98 parts of methyl methacrylate, 2 parts of N-phenylmaleimide, 0.2 parts of 2,2′-azobis (isobutyronitrile), 0.25 of n-octylmercaptan Parts and 0.7 part of polyvinyl alcohol. The internal temperature of the polymerization tank was set to 75 ° C., and the reaction was performed for 3 hours. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylate resin (C-2). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylate resin (C-2).

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

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

(Preparation of (meth) acrylate resin (C-5))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged water, 53 parts of methyl methacrylate, 31 parts of N-phenylmaleimide, 16 parts of styrene, 0.2 parts of 2,2′-azobis (isobutyronitrile), n-octyl 0.25 parts of mercaptan and 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set to 75 ° C., and the reaction was performed for 3 hours. The content was extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylate resin (C-5). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylate resin (C-5).

(Preparation of (meth) acrylate 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 steel polymerization tank equipped with a stirrer .2 parts, n-octyl mercaptan 0.19 parts, and polyvinyl alcohol 0.7 parts. The internal temperature of the polymerization tank was set to 75 ° C., and the reaction was performed for 3 hours. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery (meth) acrylate resin (C-6). Table 5 shows the mass average molecular weight (Mw) of the (meth) acrylate resin (C-6).

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

<Styrene resin (E)>
(Preparation of styrene resin (E-1))
120 parts of ion-exchanged water, 0.1 part of polyvinyl alcohol, 0.3 parts of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, 75 parts of t -0.35 parts of dodecyl mercaptan was charged and reacted at an initial temperature of 60 ° C for 5 hours. The temperature was raised to 120 ° C., and the reaction was performed for 4 hours. The contents were taken out to obtain a styrene 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 steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged water, 10 parts of methyl methacrylate, 22 parts of acrylonitrile, 68 parts of styrene, 0.2 parts of 2,2′-azobis (isobutyronitrile), 0.2 parts of n-octyl mercaptan 0 .25 parts, 0.47 parts of calcium hydroxyapatite, and 0.003 parts of potassium alkenyl succinate were charged, the internal temperature was raised to 75 ° C., and the mixture was reacted for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, washed and dehydrated by a centrifugal dehydrator repeatedly, and dried to obtain a styrene 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 steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged water, 30 parts of N-phenylmaleimide, 15 parts of acrylonitrile, 55 parts of styrene, 0.2 parts of 2,2′-azobis (isobutyronitrile), 0.2 parts of n-octyl mercaptan 0.25 parts, 0.47 parts of calcium hydroxyapatite and 0.003 parts of potassium alkenyl succinate were charged, the internal temperature was raised to 75 ° C., and the mixture was reacted for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, and washing and dehydration with a centrifugal dehydrator were repeated 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 sufficiently replacing the 20 L stainless steel polymerization tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ adjusted to 8.0 mmol / L was added. _.5 ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VOCl ₃ adjusted to 0.8 mmol / L as a catalyst was added at a rate of 5 L / h and 5 L of hexane. / H continuously. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization tank so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene 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. Then, the polymerization reaction was carried out at 35 ° C.
A polymerization reaction was carried out under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (F-1). The resulting polymerization solution was decalcified with hydrochloric acid, then poured into methanol to precipitate, and then dried to obtain an ethylene / propylene copolymer (F-1). Table 7 shows the polymer properties (weight average molecular weight and molecular weight distribution) of the ethylene / propylene copolymer (F-1).

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

<Olefin resin aqueous dispersion (G)>
(Preparation of olefin resin aqueous dispersion (G-1))
100 parts of ethylene / propylene copolymer (F-1) and maleic anhydride-modified polyethylene (“Mitsui High Wax 2203A”, manufactured by Mitsui Chemicals, Inc., acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 20 parts of 30 mg / g) and 5 parts of potassium oleate ("KS Soap", manufactured by Kao Corporation) as an emulsifier were mixed.
This mixture was supplied at 4 kg / h from a hopper of a twin-screw extruder (manufactured by Ikegai Co., Ltd., "PCM30", L / D = 40), and water was supplied from a supply port provided at a vent portion of the twin-screw extruder. While continuously supplying an aqueous solution in which 0.5 part of potassium oxide and 2.4 parts of ion-exchanged water were mixed, the mixture was heated to 220 ° C., melt-kneaded, and extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of a twin-screw extruder, and cooled to 90 ° C. Then, the solid discharged from the tip of the twin-screw extruder is poured into warm water at 80 ° C., continuously dispersed, diluted to a solid content concentration of about 40% by mass, and an aqueous olefin resin dispersion (G -1) was obtained. Table 8 shows the volume average particle diameter of the ethylene / α-olefin copolymer (F) dispersed in the olefin resin aqueous 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) was converted from the ethylene / propylene copolymer (F-1) to the ethylene / propylene copolymers (F-2) to (A-4). Except for the change, aqueous olefin resin dispersions (G-2) to (G-4) were obtained in the same manner as in the preparation of the aqueous olefin resin dispersion (G-1).
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-exchanged water was added to the aqueous olefin resin dispersion (G-1) (100 parts as a solid content) so that the solid content concentration became 35%, and 1.2 parts of t-butylcumyl peroxide was used as an organic peroxide. One part of divinylbenzene was added as a polyfunctional compound and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (H-1). Table 9 shows the gel content and the 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 were changed, the same as in 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 the volume average particle diameter of the crosslinked ethylene / α-olefin copolymers (H-2) to (H-4).

(Preparation of crosslinked ethylene / α-olefin copolymer (H-5))
For 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 were used as organic peroxides. Is melt-kneaded at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (manufactured by Ikegai Co., Ltd., “PCM-30”), and then finely ground to obtain a crosslinked ethylene. -The alpha-olefin copolymer (H-5) was obtained. Table 9 shows the gel content and the volume average particle size of the crosslinked ethylene / α-olefin copolymer (H-5).

<Graft copolymer (I)>
(Preparation of Graft Copolymer (I-1))
A crosslinked ethylene / α-olefin copolymer (H-1) (70 parts as a solid content of the ethylene / propylene copolymer (F-1)) is put into a stainless steel polymerization tank equipped with a stirrer, and the crosslinked ethylene / α-olefin is added. Ion-exchanged water was added to the copolymer (H-1) so that the solid content became 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were charged, The temperature was 80 ° C. 19.8 parts of styrene, 10.2 parts of acrylonitrile and 0.6 part of cumene hydroperoxide were continuously added for 150 minutes, emulsion polymerization was carried out at a polymerization temperature of 80 ° C., and graft copolymer having an average particle diameter of 0.41 μm was obtained. An aqueous dispersion containing the coalescence (I-1) was obtained.
An antioxidant is added to the aqueous dispersion containing the graft copolymer (I-1), the solid content is precipitated with sulfuric acid, and the powdery graft copolymer ( I-1) was obtained. When the graft ratio of the graft copolymer (I-1) was measured, it was 30%. After dyeing a thermoplastic resin composition prepared by melt-kneading the graft copolymer (I-1) and the styrene-based resin (E-1) at a ratio of 20% by mass and 80% by mass with ruthenium, When a slice 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, it was 0.41 μm.

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

(Preparation of graft copolymer (I-5))
70 parts of a crosslinked ethylene / α-olefin copolymer (H-5) and 300 parts of toluene were charged into a stainless steel polymerization tank equipped with a stirrer, and the contents were uniformly stirred at 70 ° C. for 1 hour. After sufficiently purging with nitrogen, 19.8 parts of styrene, 10.2 parts of acrylonitrile, 0.24 part of t-dodecylmercaptan, and 0.22 part of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was reduced to 110 ° C. The reaction was allowed to react for 4 hours. The internal temperature was raised to 120 ° C., and the reaction was performed for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C, and 0.2 parts of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile components are substantially devolatilized at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a vacuum vent of 30 mmφ (manufactured by Ikegai Co., Ltd., “PCM30”), pelletized, and graft copolymer (I-5) ) Got. When the graft ratio of the graft copolymer (I-5) was measured, it was 30%. In addition, a thermoplastic resin composition prepared by melt-kneading the graft copolymer (I-5) and the styrene-based resin (E-1) at a ratio of 20% by mass and 80% by mass is dyed with ruthenium, and then, is super When a slice 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, it was 0.40 μm.

(Preparation of graft copolymer (I-6))
As shown in Table 10, except that the crosslinked ethylene / α-olefin copolymer (H-1) was changed to the olefin resin aqueous dispersion (G-2), 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 the graft copolymer (B-2), 60 parts of the (meth) acrylate resin (C-3) and 0.3 part of the silicone oil (D-1) are mixed, and twin screw extrusion with a 30 mmφ vacuum vent is performed. The mixture was melt-kneaded at 240 ° C. and a vacuum of 93.325 kPa using a machine (“PCM30” manufactured by Ikegai Co., Ltd.) to prepare a thermoplastic resin composition. Table 11 shows the MVR of the thermoplastic resin composition.
The obtained thermoplastic resin composition was pelletized, various molded articles were molded, and impact resistance, heat resistance, color development, weather resistance, heat aging resistance, scratch resistance, and surface appearance were evaluated. Table 11 shows the results.

[Examples 2 to 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 the MVR was measured.
The thermoplastic resin composition was pelletized, various molded articles were molded, and the 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 to 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 and 16, and the MVR was measured.
The thermoplastic resin composition was pelletized, and various molded articles were molded, and the 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 and 16.

The thermoplastic resin compositions of Examples 1 to 35 were excellent in fluidity. Further, the molded products of Examples 1 to 35 were excellent in impact resistance, heat resistance, coloring, weather resistance, heat aging resistance, scratch resistance, and surface appearance. In particular, regarding Examples 27 to 35, the scratch resistance was further excellent.
On the other hand, with respect to the molded products of Comparative Examples 1 to 12, one or more of the properties of impact resistance, heat resistance, color development, weather resistance, heat aging resistance, scratch resistance, and surface appearance were insufficient. . In particular, the thermoplastic resin composition is the same as in Examples 3 and 28, but the molded articles of Comparative Examples 10 and 11, in which molding was performed by general molding instead of heat cycle injection molding, had surface appearance and scratch resistance. 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 subjected to heat cycle injection molding, the surface appearance, scratch resistance, impact resistance, and color development It was confirmed that a molded article having excellent heat resistance and heat aging resistance was obtained.

  Molded articles using the thermoplastic resin composition of the present invention are useful as vehicle interior and exterior parts, office equipment, home appliances, building materials, and the like.

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

Claims (6)

Using an injection mold in which the cavity surface of the mold is alternately heated and cooled, a thermoplastic resin composition molded by a heat cycle injection molding method in which the cavity surface temperature of the mold is repeatedly increased and decreased,
Poly (meth) acrylate having a unit derived from polyorganosiloxane (Aa) and (meth) acrylate, and / or one or both of a unit derived from a crosslinking agent and a unit derived from a graft crossing agent (Ab) 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 a composite rubbery polymer (A) comprising B)
(Meth) acrylic ester resin (C) obtained by polymerizing a vinyl monomer component (m2) containing (meth) acrylic ester, maleimide compound and aromatic vinyl compound;
A graft copolymer (I) obtained by polymerizing a vinyl monomer component (m4) in the presence of an olefin copolymer ,
The content of the polyorganosiloxane (Aa) in the composite rubber-like polymer (A) (100% by mass) is 1 to 20% by mass,
The composite rubbery 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. Using an injection mold in which the cavity surface of the mold is alternately heated and cooled, a thermoplastic resin composition molded by a heat cycle injection molding method in which the cavity surface temperature of the mold is repeatedly increased and decreased,
Poly (meth) acrylate having a unit derived from polyorganosiloxane (Aa) and (meth) acrylate, and / or one or both of a unit derived from a crosslinking agent and a unit derived from a graft crossing agent (Ab) 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 a composite rubbery polymer (A) comprising B)
(Meth) acrylic ester resin (C) obtained by polymerizing a vinyl monomer component (m2) containing (meth) acrylic ester, maleimide compound and aromatic vinyl compound;
And silicone oil (D),
The content of the polyorganosiloxane (Aa) in the composite rubber-like polymer (A) (100% by mass) is 1 to 20% by mass,
The composite rubbery 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 a silicone oil (D). The thermoplastic resin composition for heat cycle injection molding according to any one of claims 1 to 3 , further comprising a styrene resin (E).   A molded article obtained by molding the thermoplastic resin composition for heat cycle injection molding according to any one of claims 1 to 4.   The cavity surface of a mold using the thermoplastic resin composition for heat cycle injection molding according to any one of claims 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 article, wherein a molded article is obtained by molding by a heat cycle injection molding method in which the temperature is repeatedly increased and decreased.

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