JP2016003284A - Thermoplastic resin composition and lamp housing for vehicle using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a thermoplastic resin composition which can obtain a molded article having good balance among impact resistance, heat resistance, surface smoothness, weather resistance and color development property; and a lamp housing for a vehicle using the same.SOLUTION: There is provided a thermoplastic resin composition which comprises a specific graft copolymer (A), a graft copolymer (B), a copolymer (C) and a copolymer (D), in which the mass ratio between the graft copolymer (A) and the graft copolymer (B) is 50:50 to 80:20, the total of the rubber content derived from the graft copolymer (A) and the graft copolymer (B) contained in the thermoplastic resin composition is 10 to 30 mass%, the amount of the structural unit derived from a conjugated diene-based rubber is less than 2 mass% and 10 to 30 pts.mass of the copolymer (C) is contained.

Description

  The present invention relates to a thermoplastic resin composition and a vehicle lamp housing using the same.

  Automotive lamps such as tail lamps and stop lamps are schematically composed of a lens such as polymethyl methacrylate (PMMA resin) or polycarbonate (PC resin), a lamp housing that supports the lens, and a lamp that is housed in the lamp housing. Has been. For the lamp housing, a rubber-reinforced styrene resin is often selected because it is lightweight and has high productivity.

As a typical rubber-reinforced styrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin) is known.
However, the ABS resin uses polybutadiene, which is a conjugated diene rubber, as a rubber component, and since it is easily decomposed by ultraviolet rays, there is a drawback that a molded product obtained from the ABS resin is inferior in weather resistance.
Therefore, an acrylate-styrene-acrylonitrile copolymer (ASA resin) containing an acrylic ester rubber as a rubber component is known as a resin having improved weather resistance of ABS resin. However, the molded product obtained from the ASA resin tended to be inferior in impact resistance and color developability as compared with the molded product obtained from the ABS resin.

  In general, a lamp housing for an automobile is often manufactured by performing secondary processing such as painting, plating, metal vapor deposition, etc. on the surface of a molded article of a thermoplastic resin in order to enhance its functionality and design. In recent years, from the viewpoint of low cost and productivity, a so-called “direct vapor deposition method” in which metal deposition is directly performed on the surface of a molded product is generally used as secondary processing. The appearance of the molded product obtained by this direct vapor deposition method is likely to vary depending on the smoothness of the molded product surface before vapor deposition. Control was one of the important issues.

  In addition to the above-described requirements for the smoothness of the surface of the molded product, in recent years, it is necessary as a lamp housing because of the complicated shape, thinning, weighing, and shortening of the molding cycle of lamp housing products for automobiles. There is a demand for a thermoplastic resin composition having high melt fluidity during molding while maintaining impact resistance and heat resistance.

Patent Document 1 describes a diene graft copolymer, an acrylic rubber graft copolymer, and an acrylonitrile-styrene copolymer as resins having excellent impact resistance, chemical resistance, molding processability, and molding appearance. A thermoplastic resin composition containing (AS resin) is disclosed.
Patent Document 2 discloses an acrylic rubber-based graft copolymer, an acrylic rubber and a polyorganosiloxane rubber as thermoplastic resin compositions having excellent impact resistance, heat resistance, molded appearance, and vibration weldability. A thermoplastic resin composition containing a graft copolymer composed of a composite rubber and a maleimide copolymer is disclosed.

JP-A-6-256619 JP 2012-25941 A

However, the molded product obtained from the thermoplastic resin composition described in Patent Document 1 can improve impact resistance, but has a high level of moldability, heat resistance, and surface required for recent lamp housings. It did not satisfy all of smoothness and weather resistance.
A molded product obtained from the thermoplastic resin composition described in Patent Document 2 can also be obtained with good surface smoothness, impact resistance, heat resistance, and weather resistance, but has a high level required for recent lamp housings. The molding processability of was not satisfied.

  INDUSTRIAL APPLICABILITY The present invention can obtain a molded article having a good balance of impact resistance, heat resistance, surface smoothness, weather resistance, and color developability and is excellent in molding processability, and uses the same. An object is to provide a lamp housing for a vehicle.

  As a result of intensive studies, the present inventors have solved the above problems by using a total of four types of copolymers, that is, two types of graft copolymers having a specific structure and two types of copolymers having a specific structure. The present inventors have found that this can be done and have completed the present invention.

That is, this invention includes the following aspects.
[1] A thermoplastic resin composition comprising the following graft copolymer (A), graft copolymer (B), copolymer (C), and copolymer (D), wherein the graft copolymer ( Graft copolymer (A) having a mass ratio of (A) to graft copolymer (B) ((A) :( B)) of 50:50 to 80:20 and contained in the thermoplastic resin composition And the total rubber content derived from the graft copolymer (B) is 10 to 30% by mass, the structural unit derived from the conjugated diene rubber is less than 2% by mass, and the copolymer (C) is 10 To 30 parts by mass (however, the total of the graft copolymer (A), the graft copolymer (B), the copolymer (C), and the copolymer (D) is 100 parts by mass). Plastic resin composition.
Graft copolymer (A): 0 to 20% by mass of polyorganosiloxane and 80 to 100% by mass of alkyl (meth) acrylate monomer (however, the total of polyorganosiloxane and alkyl (meth) acrylate monomer is 100) And an acrylic rubber polymer (rs) having a volume average particle diameter of 70 to 200 nm obtained by polymerizing the aromatic vinyl monomer and the vinyl cyanide monomer. An acrylic rubber graft copolymer obtained by graft polymerization of a monomer component containing at least one monomer selected from the body.
Graft copolymer (B): 0 to 30% by mass of conjugated diene rubbery polymer and 70 to 100% by mass of alkyl (meth) acrylate monomer (however, conjugated diene rubbery polymer and alkyl (meth)) Acrylic rubbery polymer (rl) having a volume average particle size of 300 to 600 nm obtained by polymerizing acrylate monomers to 100% by mass) is polymerized with an aromatic vinyl monomer. And an acrylic rubber graft copolymer obtained by graft polymerization of a monomer component containing at least one monomer selected from vinyl cyanide monomers.
Copolymer (C): N, N-dimethylformamide at 25 ° C. containing 10 to 65% by mass of maleimide monomer units in 100% by mass of all monomer units constituting copolymer (C) A copolymer having a reduced viscosity in a solution of 0.4 to 0.7 dl / g.
Copolymer (D): a monomer component containing at least one monomer selected from aromatic vinyl monomers and vinyl cyanide monomers (however, maleimide monomers are not included) A copolymer having a reduced viscosity of 0.4 to 0.7 dl / g in an N, N-dimethylformamide solution at 25 ° C.
[2] A vehicle lamp housing obtained by molding the thermoplastic resin composition according to [1].

  The thermoplastic resin composition of the present invention can provide a molded product having a good balance of impact resistance, heat resistance, surface smoothness, weather resistance, and color developability, and is excellent in molding processability.

Hereinafter, the present invention will be described in detail.
In the following description, the “molded product” is obtained by molding the thermoplastic resin composition of the present invention.

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention includes the following graft copolymer (A), graft copolymer (B), copolymer (C), and copolymer (D).

<Graft copolymer (A)>
The graft copolymer (A) was selected from an acrylic rubber polymer (rs) having a volume average particle diameter of 70 to 200 nm, from an aromatic vinyl monomer and a vinyl cyanide monomer. This is an acrylic rubber-based graft copolymer obtained by graft polymerization of a monomer component (f1) containing at least one monomer (hereinafter also referred to as “(f1) component”).

(Acrylic rubbery polymer (rs))
The acrylic rubbery polymer (rs) is obtained by polymerizing an alkyl (meth) acrylate monomer (e1) (hereinafter also referred to as “monomer (e1)”), or a polyorganosiloxane (s) ( Hereinafter, it is also obtained by polymerizing “(s) component”) and the monomer (e1). The acrylic rubbery polymer (rs) obtained by polymerizing the monomer (e1) is a (meth) acrylic acid ester rubber of polyalkyl (meth) acrylate obtained by polymerizing the monomer (e1). On the other hand, the acrylic rubbery polymer (rs) obtained by polymerizing the component (s) and the monomer (e1) is a composite rubber in which a polyalkyl (meth) acrylate and a component (s) are combined. .

The polymerization of the monomer (e1) and the polymerization of the component (s) and the monomer (e1) are performed by at least one of a crosslinking agent and a graft crossing agent (hereinafter collectively referred to as “component (e2)”). It is preferably carried out in the presence of When the polymerization is carried out in the presence of the component (e2), the color developability of the molded product is further improved.
When the polymerization of the monomer (e1) is performed in the presence of the component (e2), at least of the unit derived from the monomer (e1), the unit derived from the crosslinking agent, and the unit derived from the graft crossing agent A (meth) acrylic acid ester rubber of polyalkyl (meth) acrylate having one side is obtained. Further, when the polymerization of the component (s) and the monomer (e1) is performed in the presence of the component (e2), the unit derived from the monomer (e1), the unit derived from the crosslinking agent, and the graft crossing agent A composite rubber in which a polyalkyl (meth) acrylate having at least one of the units derived from and (s) component is combined is obtained.

As the monomer (e1), an alkyl (meth) acrylate containing one polymerizable unsaturated group is preferably used. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate And alkyl acrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Among these, n-butyl acrylate is preferable.
These monomers (e1) may be used individually by 1 type, and may use 2 or more types together.

The cross-linking agent is an alkyl (meth) acrylate containing two or more polymerizable unsaturated groups. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (Meth) acrylate, 1,4-butylene glycol di (meth) acrylate and the like can be mentioned.
The graft crossing agent is an alkyl (meth) acrylate containing two or more polymerizable unsaturated groups, and specific examples include allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate and the like.
These crosslinking agents and graft crossing agents may be used alone or in combination of two or more.

The component (s) is preferably a polyorganosiloxane containing a vinyl polymerizable functional group, more preferably a polyorganosiloxane having a vinyl polymerizable functional group-containing siloxane unit and a dimethylsiloxane unit, and among them, 3 or more A polyorganosiloxane having 1 mol% or less of silicon atoms having a siloxane bond with respect to all silicon atoms in the polydimethylsiloxane is particularly preferred. The proportion of the vinyl polymerizable functional group-containing siloxane unit is preferably 0.3 to 3 mol%, and the proportion of the dimethylsiloxane unit is 97 to 99.7 mol% (however, the vinyl polymerizable functional group-containing siloxane unit and the dimethylsiloxane unit are The total is 100 mol%).
The vinyl polymerizable functional group is not particularly limited as long as it can be cross-linked with polyalkyl (meth) acrylate, but considering the reactivity with polyalkyl (meth) acrylate, methacryl group, vinyl Group, aromatic alkenyl group, mercapto group, azo group and the like are preferable, and methacryl group is more preferable.

  The component (s) can be obtained, for example, by polymerizing a siloxane mixture containing a vinyl polymerizable functional group-containing siloxane, dimethylsiloxane, and, if necessary, a siloxane crosslinking agent. Although it does not restrict | limit especially as a method of superposition | polymerization, It is preferable to manufacture by emulsion polymerization. Specifically, it is preferable to produce by using an emulsifier and an acid catalyst, mixing a siloxane mixture in water using a homomixer or an ultrasonic mixer, and emulsifying and condensing.

The vinyl polymerizable functional group-containing siloxane contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane through a siloxane bond. Considering the reactivity with dimethylsiloxane, various alkoxysilane compounds containing vinyl polymerizable functional groups are preferred as the vinyl polymerizable functional group-containing siloxane. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane; p-vinylphenyldimethoxymethylsilane; γ-mercaptopropyldimethoxy And mercaptosiloxanes such as methylsilane and γ-mercaptopropyltrimethoxysilane. These vinyl polymerizable functional group-containing siloxanes may be used alone or in combination of two or more.
The content of the vinyl polymerizable functional group-containing siloxane in the siloxane mixture is preferably 0.3 to 3% by mass when the total with dimethylsiloxane is 100% by mass.

Examples of dimethylsiloxane include dimethylsiloxane-based cyclic bodies having 3 or more membered rings, and 3- to 7-membered dimethylsiloxane-based cyclic bodies are preferable. Specifically, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, etc. Is mentioned. These dimethylsiloxanes may be used alone or in combination of two or more.
The content of dimethylsiloxane in the siloxane mixture is preferably 97 to 99.7% by mass when the total with the vinyl polymerizable functional group-containing siloxane is 100% by mass.

Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents. Specific examples include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. These siloxane crosslinking agents may be used alone or in combination of two or more.
The content of the siloxane-based crosslinking agent in the siloxane mixture is preferably 0 to 3 parts by mass with respect to a total of 100 parts by mass of the vinyl polymerizable functional group-containing siloxane and dimethylsiloxane.

Examples of the emulsifier include alkylbenzenesulfonic acid, alkylsulfuric acid, and anionic surfactants such as sodium salt, potassium salt, and ammonium salt thereof. Specifically, dodecylbenzenesulfonic acid, octylbenzenesulfonic acid, octylsulfate, Examples include lauryl sulfate, sodium dodecylbenzenesulfonate, sodium octylbenzenesulfonate, sodium octyl sulfate, sodium lauryl sulfate, and the like. These emulsifiers may be used alone or in combination of two or more.
The blending amount of the emulsifier is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the vinyl polymerizable functional group-containing siloxane and dimethylsiloxane from the viewpoint of suppressing emulsion stability and coloring of the molded product.

Examples of the acid catalyst include organic acid catalysts such as sulfonic acids (eg, aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, aliphatic substituted naphthalene sulfonic acid, etc.); inorganic acids such as mineral acids (eg, sulfuric acid, hydrochloric acid, nitric acid, etc.) A catalyst etc. are mentioned. These acid catalysts may be used alone or in combination of two or more.
Among these, aliphatic substituted benzenesulfonic acid is preferable because it is excellent in the stabilizing action of the siloxane latex described later. The aliphatic substituent in the aliphatic substituted benzenesulfonic acid is preferably an alkyl group having 9 to 20 carbon atoms, and more preferably n-dodecylbenzenesulfonic acid having 12 carbon atoms.

The mixing of the acid catalyst may be performed at the timing when the siloxane mixture, the emulsifier and water are mixed, or may be made into a latex (siloxane latex) obtained by emulsifying the siloxane mixture with the emulsifier and water and then finely divided. Considering the ease of control of the particle size of the component (s), it is preferable to mix the siloxane latex and acid catalyst after the siloxane latex is made fine. In particular, it is preferable to drop the finely divided siloxane latex into the acid catalyst aqueous solution at a constant rate.
In addition, when mixing an acid catalyst at the timing which mixes a siloxane mixture, an emulsifier, and water, it is preferable to atomize after mixing these.

The volume average particle size of the component (s) is preferably from 30 to 100 nm, more preferably from 30 to 60 nm, from the viewpoint of improving the impact resistance, surface smoothness and color developability of the molded product.
The volume average particle diameter of the component (s) can be controlled by adjusting the composition of the siloxane mixture, the amount of acid catalyst used (the content of the acid catalyst in the acid catalyst aqueous solution), the polymerization temperature, and the like.
Here, the volume average particle diameter of the component (s) is a volume-based average particle diameter measured by a laser diffraction / light scattering method.

(Method for producing acrylic rubbery polymer (rs))
The acrylic rubbery polymer (rs) can be obtained, for example, by subjecting the monomer (e1) to a radical polymerization by allowing a normal radical polymerization initiator and an emulsifier to act. When radical polymerization is performed in the presence of the component (e2), the monomer (e1) and the component (e2) may be mixed and polymerized by acting a radical polymerization initiator and an emulsifier.

Further, when the acrylic rubbery polymer (rs) is produced by polymerizing the component (s) and the monomer (e1), the acrylic rubbery polymer (rs) is, for example, a latex of the component (s). It can be obtained by adding the monomer (e1) to the mixture and allowing a normal radical polymerization initiator and an emulsifier to act thereon for radical polymerization. When radical polymerization is performed in the presence of the component (e2), the monomer (e1) and the component (e2) are added to the latex of the component (s), and the polymerization is performed by acting a radical polymerization initiator and an emulsifier. That's fine.
The monomer (e1) or (e2) component can be added by adding the monomer (e1) or (e2) component to the (s) component latex at once, or simply adding it to the (s) component latex. Examples include a method of dropping the monomer (e1) or (e2) component at a constant rate. Considering the impact resistance of the molded product, a method of adding the monomer (e1) or (e2) component to the latex of the component (s) at a time is preferable.
In addition, when performing radical polymerization in the presence of the component (e2), the monomer (e1) and the component (e2) may be added individually, or after mixing them in advance to form a mixture, May be added to the latex of component (s) all at once or at a constant rate.

  Examples of the radical polymerization initiator used for radical polymerization include peroxides, azo initiators, redox initiators in which an oxidizing agent and a reducing agent are combined. Among these, redox initiators are preferable, and in particular, redox initiators in which ferrous sulfate, sodium pyrophosphate, glucose, and hydroperoxide are combined, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, and Rongalite. A redox initiator that is a combination of hydroperoxide and is preferred.

Although it does not restrict | limit especially as an emulsifier used for radical polymerization, since it is excellent in the stability of the latex at the time of superposition | polymerization and a polymerization rate can be raised, sodium sarcosinate, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, rosin acid soap, etc. Various carboxylates; anionic emulsifiers such as alkyl sulfates, sodium alkylbenzene sulfonates, sodium polyoxyethylene nonylphenyl ether sulfates, etc. are preferred, and these are used properly according to the purpose.
The total amount of the emulsifier used in the production of the component (s) is 0.2 to 10 parts by mass with respect to 100 parts by mass in total of the component (s) and the monomer (e1). The amount is preferable from the viewpoints of particle size control and impact resistance, surface smoothness, and color developability of the molded product.

The amount of the component (s) used is 0 to 20% by mass, and the amount of the monomer (e1) used is 80 to 100% by mass (however, the total of the component (s) and the monomer (e1) is 100% by mass. %)). When the amount of the component (s) used exceeds 20% by mass and the amount of the monomer (e1) used is less than 80% by mass, the surface smoothness and color developability of the molded product deteriorate.
Considering the surface smoothness and color developability of the molded product, the amount of component (s) used is preferably 0 to 15% by mass, and the amount of monomer (e1) used is preferably 85 to 100% by mass.

  Moreover, when superposing | polymerizing in presence of (e2) component, 0.1-4 mass parts is preferable with respect to 100 mass parts of monomers (e1), and the usage-amount of (e2) component is 0.4. -3 mass parts is more preferable.

The volume average particle diameter of the acrylic rubbery polymer (rs) is 70 to 200 nm. When the volume average particle size is less than 70 nm, the molding processability of the thermoplastic resin composition is lowered, and the impact resistance and surface smoothness of the molded product are lowered. On the other hand, when the volume average particle diameter exceeds 200 nm, the surface smoothness and color developability of the molded product are lowered. In consideration of the moldability of the thermoplastic resin composition and the balance of the impact resistance, surface smoothness and color developability of the molded product, the volume average particle diameter is preferably 90 to 160 nm.
Here, the volume average particle diameter of the acrylic rubbery polymer (rs) is a volume-based average particle diameter measured by a laser diffraction / light scattering method.

(Method for producing graft copolymer (A))
The graft copolymer (A) is obtained by graft polymerization of the component (f1) to the above acrylic rubbery polymer (rs).

The component (f1) is a monomer component including at least one monomer selected from an aromatic vinyl monomer and a vinyl cyanide monomer.
Examples of aromatic vinyl monomers include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pt-butyl styrene, halogenated styrene, vinyl toluene, and the like. Can be mentioned. Among these, styrene and α-methylstyrene are preferable.
Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile, fumaronitrile and the like. Among these, acrylonitrile is preferable.
Each of these aromatic vinyl monomers and vinyl cyanide monomers may be used alone or in combination of two or more.

The component (f1) may contain another vinyl monomer copolymerizable with at least one of an aromatic vinyl monomer and a vinyl cyanide monomer.
Examples of other vinyl monomers include alkyl (meth) acrylate monomers, maleimide monomers, amide monomers, etc. These other vinyl monomers are used alone. Or two or more of them may be used in combination.
Examples of the alkyl (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, phenyl (meth) acrylate, 4-t -Butylphenyl (meth) acrylate, (di) bromophenyl (meth) acrylate, chlorophenyl (meth) acrylate, etc. are mentioned.
Examples of the maleimide monomer include N-phenylmaleimide and N-cyclohexylmaleimide.
Examples of amide monomers include acrylamide and methacrylamide.

  Graft polymerization can be carried out in one stage or in multiple stages by adding the component (f1) to the latex of the acrylic rubbery polymer (rs) and allowing a normal radical polymerization initiator and an emulsifier to act.

The amount of the acrylic rubber polymer (rs) used is preferably 10 to 70% by mass, and the amount of the component (f1) used is 30 to 90% by mass (provided that the acrylic rubber polymer (rs) and (F1) The total amount with the component is preferably 100% by mass). If the amount of the acrylic rubber polymer (rs) and the component (f1) used is within the above range, the molding processability of the thermoplastic resin composition, the impact resistance of the molded product, and the surface smoothness are further improved. .
Considering the balance of the molding processability of the thermoplastic resin composition and the impact resistance and surface smoothness of the molded product, the amount of the acrylic rubber polymer (rs) used is more preferably 30 to 60% by mass, As for the usage-amount of f1) component, 40-70 mass% is more preferable.

  Further, the composition ratio of the component (f1) used for graft polymerization is not particularly limited, but from the viewpoint of balance of physical properties of the molded product, the ratio of the aromatic vinyl monomer is 5 to 95% by mass, and cyanation is performed. The proportion of vinyl monomer is 0 to 50% by mass, and the proportion of other vinyl monomers is 0 to 95% by mass (provided that the total of each monomer is 100% by mass). It is preferable.

Examples of the radical polymerization initiator and the emulsifier used for the graft polymerization include the radical polymerization initiator and the emulsifier exemplified above in the description of the method for producing the acrylic rubbery polymer (rs).
In the production of the graft copolymer (A), the emulsifier used for the production of the acrylic rubbery polymer (rs) can be used as it is, and it is not necessary to add the emulsifier again during the graft polymerization.
Further, when graft polymerization is performed, various known chain transfer agents (for example, mercaptan compounds, terpene compounds, α-methylstyrene diesters) are used to control the molecular weight and graft ratio of the obtained graft copolymer (A). A polymer, etc.) may be added.
The polymerization conditions are not particularly limited.

The graft copolymer (A) is usually obtained in a latex state. As a method of recovering the graft copolymer (A) from the latex of the graft copolymer (A), the latex is poured into hot water in which a coagulant is dissolved, and recovered by coagulating into a slurry state. A method (wet method); a method of spraying latex in a heated atmosphere to recover the graft copolymer semi-directly (spray dry method) and the like.
Examples of the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid; metal salts such as calcium chloride, calcium acetate and aluminum sulfate.

The graft ratio of the graft copolymer (A) is preferably 30 to 100% by mass. When the graft ratio of the graft copolymer (A) is within the above range, the molding processability of the thermoplastic resin composition, the impact resistance and the surface smoothness of the molded product are further improved.
Considering the balance of the moldability of the thermoplastic resin composition, the impact resistance of the molded article, and the surface smoothness, the graft ratio of the graft copolymer (A) is more preferably 40 to 100% by mass.

Here, the “graft ratio” of the graft copolymer (A) is the ratio of the component (f1) that is directly grafted to the rubber with respect to the acrylic rubbery polymer (rs).
The graft ratio of the graft copolymer (A) can be measured as follows.
1 g of the graft copolymer is added to 80 mL of acetone, heated to reflux at 65 to 70 ° C. for 3 hours, and the resulting suspension acetone solution is centrifuged at 14,000 rpm for 30 minutes in a centrifuge to precipitate. A component (acetone insoluble component) and an acetone solution (acetone soluble component) are separated. And the precipitation component (acetone insoluble component) is dried, the mass (Y (g)) is measured, and a graft ratio is computed by following formula (1). In formula (1), Y is the mass (g) of the acetone-insoluble component of the graft copolymer, X is the total mass (g) of the graft copolymer used to determine Y, and the rubber fraction is the graft copolymer. It is a content ratio in terms of solid content of the acrylic rubbery polymer of the polymer.
Graft ratio (mass%) = {(Y−X × rubber fraction) / X × rubber fraction} × 100 (1)

<Graft copolymer (B)>
The graft copolymer (B) was selected from an aromatic rubber-based polymer (rl) having a volume average particle diameter of 300 to 600 nm, from an aromatic vinyl monomer and a vinyl cyanide monomer. This is an acrylic rubber-based graft copolymer obtained by graft polymerization of a monomer component (f2) containing at least one monomer (hereinafter also referred to as “(f2) component”).

(Acrylic rubbery polymer (rl))
The acrylic rubbery polymer (rl) is obtained by polymerizing an alkyl (meth) acrylate monomer (e3) (hereinafter also referred to as “monomer (e3)”) or a conjugated diene rubbery polymer. It is obtained by polymerizing (g) (hereinafter also referred to as “component (g)”) and monomer (e3). The acrylic rubbery polymer (rl) obtained by polymerizing the monomer (e3) is a (meth) acrylic acid ester rubber of polyalkyl (meth) acrylate obtained by polymerizing the monomer (e3). On the other hand, the acrylic rubber polymer (rl) obtained by polymerizing the component (g) and the monomer (e3) is a composite rubber in which a polyalkyl (meth) acrylate and the component (g) are combined. .

The polymerization of the monomer (e3) and the polymerization of the component (g) and the monomer (e3) are preferably performed in the presence of the above-described component (e2). When the polymerization is carried out in the presence of the component (e2), the color developability of the molded product is further improved.
In the case where the monomer (e3) is polymerized in the presence of the component (e2), at least of the unit derived from the monomer (e3), the unit derived from the crosslinking agent, and the unit derived from the graft crossing agent. A (meth) acrylic acid ester rubber of polyalkyl (meth) acrylate having one side is obtained. Further, when the polymerization of the component (g) and the monomer (e3) is carried out in the presence of the component (e2), the unit derived from the monomer (e3), the unit derived from the crosslinking agent, and the graft crossing agent A composite rubber in which a polyalkyl (meth) acrylate having at least one of the units derived from and (g) component is combined is obtained.

  Examples of the monomer (e3) include the monomer (e1) exemplified above in the description of the graft copolymer (A).

Examples of the component (g) include polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and methyl methacrylate-butadiene rubber. Among these, polybutadiene rubber and styrene-butadiene rubber are preferable.
The component (g) is obtained by a known emulsion polymerization method using an emulsifier.

The volume average particle size of the component (g) is preferably 200 to 500 nm, and preferably 200 to 450 nm from the viewpoint of improving the molding processability of the thermoplastic resin composition and the impact resistance, surface smoothness and color developability of the molded product. More preferred.
The component (g) having a volume average particle size in the above range may be obtained by taking a long time by several stages of seed polymerization, but a conjugated diene system having a relatively small particle size of about 30 to 100 nm. It is preferable to use a rubber latex that is produced in advance and is enlarged to a target size by an enlargement operation. The method for the enlargement operation is not particularly limited, and examples thereof include a method by adding an acidic aqueous solution such as acetic acid and a method by adding an acid group-containing copolymer latex.
Here, the volume average particle diameter of the component (g) is a volume-based average particle diameter measured by a laser diffraction / light scattering method.

(Method for producing acrylic rubbery polymer (rl))
The acrylic rubbery polymer (rl) can be obtained, for example, by subjecting the monomer (e3) to an ordinary radical polymerization initiator and an emulsifier to cause radical polymerization. When the radical polymerization is performed in the presence of the component (e2), the monomer (e3) and the component (e2) may be mixed and polymerized by acting a radical polymerization initiator and an emulsifier.

When the acrylic rubbery polymer (rl) is produced by polymerizing the component (g) and the monomer (e3), the acrylic rubbery polymer (rl) is, for example, a latex of the component (g). It is obtained by adding the monomer (e3) to the mixture and allowing a normal radical polymerization initiator and an emulsifier to act thereon for radical polymerization. When radical polymerization is performed in the presence of the component (e2), the monomers (e3) and (e2) are added to the latex of the component (g), and the polymerization is performed by acting a radical polymerization initiator and an emulsifier. That's fine.
Examples of the method for adding the monomer (e3) and the component (e2) include the methods exemplified above in the method for producing the acrylic rubbery polymer (rs). In consideration of the impact resistance and weather resistance of the molded product, a method of adding the monomer (e3) or the (e2) component in a batch to the latex of the (g) component is preferable.
In addition, also when performing radical polymerization in presence of (e2) component, the method similar to an acrylic rubber-like polymer (rs) can be used.

  As the radical polymerization initiator used for radical polymerization, the radical polymerization initiators exemplified above in the method for producing an acrylic rubbery polymer (rs) can be used. Redox initiators that combine ferrous sulfate, sodium pyrophosphate, glucose, and hydroperoxide, and redox initiators that combine ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalite, and hydroperoxide. Is preferred.

As an emulsifier used for radical polymerization, the emulsifier previously illustrated in the manufacturing method of an acrylic rubber-like polymer (rs) can be used. Various carboxylic acid salts such as sodium sarcosine, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, and rosin acid soap; alkyl sulfate, alkylbenzene sulfonic acid Anionic emulsifiers such as sodium and sodium polyoxyethylene nonylphenyl ether sulfate are preferred, and these are used properly according to the purpose.
The amount of the emulsifier used is 0.2 to 10 parts by mass with respect to the total of 100 parts by mass of the component (g) and the monomer (e3) as the total of the emulsifier used for the production of the component (g) latex. Is preferable from the viewpoints of particle size control and impact resistance, weather resistance, surface smoothness, and color developability of the molded product.

The amount of component (g) used is 0 to 30% by mass, and the amount of monomer (e3) used is 70 to 100% by mass (provided that the total of component (g) and monomer (e3) is 100% by mass. %)). (G) When the usage-amount of a component exceeds 30 mass% and the usage-amount of a monomer (e3) will be less than 70 mass%, the surface smoothness and coloring property of a molded article will fall.
Considering the weather resistance of the molded product, the amount of component (g) used is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and the amount of monomer (e3) used is 80 to 100% by mass. Preferably, 90-100 mass% is more preferable.

  Moreover, when superposing | polymerizing in presence of (e2) component, 0.1-4 mass parts is preferable with respect to 100 mass parts of monomers (e3), and the usage-amount of (e2) component is 0.4. -3 mass parts is more preferable.

The volume average particle diameter of the acrylic rubbery polymer (rl) is 300 to 600 nm. When the volume average particle diameter is less than 300 nm, the molding processability of the thermoplastic resin composition is lowered, and the impact resistance of the molded product is lowered. On the other hand, when the volume average particle diameter exceeds 600 nm, the surface smoothness and color developability of the molded product are lowered. In consideration of the moldability of the thermoplastic resin composition and the balance of impact resistance, surface smoothness and color developability of the molded product, the volume average particle diameter is preferably 350 to 500 nm.
Here, the volume average particle diameter of the acrylic rubbery polymer (rl) is a volume-based average particle diameter measured by a laser diffraction / light scattering method.

(Method for producing graft copolymer (B))
The graft copolymer (B) is obtained by graft polymerization of the component (f2) to the above-mentioned acrylic rubbery polymer (rl).
The component (f2) is a monomer component containing at least one monomer selected from an aromatic vinyl monomer and a vinyl cyanide monomer. The component (f2) may contain another vinyl monomer copolymerizable with at least one of an aromatic vinyl monomer and a vinyl cyanide monomer.
Examples of the aromatic vinyl monomer, vinyl cyanide monomer, and other vinyl monomers include the aromatic vinyl monomers exemplified above in the description of the graft copolymer (A), cyan. Examples thereof include vinyl halide monomers and other vinyl monomers.

Graft polymerization can be carried out in one step or in multiple steps by adding the component (f2) to the latex of the acrylic rubbery polymer (rl) and allowing an ordinary radical polymerization initiator and emulsifier to act. The graft copolymer (B) is usually obtained in a latex state.
The method for recovering the graft copolymer (B) from the radical polymerization initiator and emulsifier and latex used in the graft polymerization is the same as the method for producing the graft copolymer (A).

The amount of the acrylic rubber polymer (rl) used is preferably 10 to 70% by mass, and the amount of the component (f2) used is 30 to 90% by mass (provided that the acrylic rubber polymer (rl) and (F2) The total amount with the component is preferably 100% by mass.). When the amount of the acrylic rubber polymer (rl) and the component (f2) used is within the above range, the molding processability of the thermoplastic resin composition, the impact resistance and the surface smoothness of the molded product are further improved. .
Considering the balance of the molding processability of the thermoplastic resin composition and the impact resistance and surface smoothness of the molded product, the amount of the acrylic rubber polymer (rl) used is more preferably 30 to 60% by mass, As for the usage-amount of f2) component, 40-70 mass% is more preferable.

  Further, the composition ratio of the component (f2) used for the graft polymerization is not particularly limited, but from the viewpoint of balance of physical properties of the molded product, the ratio of the aromatic vinyl monomer is 5 to 95% by mass, and cyanation is performed. The proportion of vinyl monomer is 0 to 50% by mass, and the proportion of other vinyl monomers is 0 to 95% by mass (provided that the total of each monomer is 100% by mass). It is preferable.

The graft ratio of the graft copolymer (B) is preferably 30 to 100% by mass. When the graft ratio of the graft copolymer (B) is within the above range, the molding processability of the thermoplastic resin composition, the impact resistance and the surface smoothness of the molded product are further improved.
Considering the balance between the moldability of the thermoplastic resin and the impact resistance and surface smoothness of the molded product, the graft ratio of the graft copolymer (B) is more preferably 30 to 80% by mass.
Here, the “graft ratio” of the graft copolymer (B) is the ratio of the component (f3) that is directly graft-bonded to the rubber with respect to the acrylic rubber polymer (rl). The graft ratio of the graft copolymer (B) is determined in the same manner as the graft ratio of the graft copolymer (A).

<Copolymer (C)>
The copolymer (C) is a copolymer containing a maleimide monomer unit.
Examples of the maleimide monomer constituting the copolymer (C) include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, Examples thereof include N-toluylmaleimide, N-xylylmaleimide, N-naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, N-orthomethoxyphenylmaleimide and the like. Among these, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, N-orthochlorophenylmaleimide, N-orthomethoxyphenylmaleimide are preferable, and N-cyclohexylmaleimide and N-phenylmaleimide are more preferable.
These maleimide monomers may be used alone or in combination of two or more.

The copolymer (C) is copolymerizable with at least one of an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, an aromatic vinyl monomer and a vinyl cyanide monomer. The vinyl monomer unit may be contained.
Examples of the aromatic vinyl monomer, vinyl cyanide monomer, and other vinyl monomers include the aromatic vinyl monomers exemplified above in the description of the graft copolymer (A), cyan. Examples thereof include vinyl halide monomers and other vinyl monomers.

The content of maleimide monomer units is 10 to 65% by mass in 100% by mass of all monomer units constituting the copolymer (C). When the content of the maleimide monomer unit is less than 10% by mass, the heat resistance of the copolymer (C) is lowered. Therefore, the molding processability of the thermoplastic resin composition and the heat resistance of the obtained molded product are reduced. Balance decreases. When the content of the maleimide monomer unit exceeds 65% by mass, the molding processability of the thermoplastic resin composition and the impact resistance, color development, and surface smoothness of the molded product are lowered.
In view of the moldability of the thermoplastic resin composition and the balance of impact resistance, heat resistance, color developability and surface smoothness of the molded product, the content of the maleimide monomer unit is preferably 25 to 60% by mass. .

When the copolymer (C) contains an aromatic vinyl monomer unit, the content thereof is 15 to 90% by mass in 100% by mass of all monomer units constituting the copolymer (C). Preferably, 20 to 77 mass% is more preferable. When the content of the aromatic vinyl monomer unit is within the above range, the molding processability of the thermoplastic resin composition and the heat resistance of the molded product are further improved.
Further, when the copolymer (C) contains a vinyl cyanide monomer unit, the content thereof is less than 30% by mass in 100% by mass of all the monomer units constituting the copolymer (C). Is preferable, and less than 20 mass% is more preferable. When the content of the vinyl cyanide monomer unit is within the above range, the molding processability of the thermoplastic resin composition, and the impact resistance and heat resistance of the molded product are further improved.

The reduced viscosity of the copolymer (C) in the N, N-dimethylformamide solution is 0.4 to 0.7 dl / g. When the reduced viscosity of the copolymer (C) is less than 0.4 dl / g, the impact resistance of the molded product is lowered, and when it exceeds 0.7 dl / g, the moldability of the thermoplastic resin composition is lowered.
The reduced viscosity here is a value obtained by dissolving 0.2 g of the copolymer (C) in 100 mL of N, N-dimethylformamide to obtain an N, N-dimethylformamide solution, and obtaining it with an Ubbelohde viscometer at 25 ° C. is there.

  The copolymer (C) is obtained by a known emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, or the like. Further, as the copolymer (C), those obtained by a technique obtained by combining these polymerization methods can be used, but those obtained by a solution polymerization method are preferably used.

<Copolymer (D)>
The copolymer (D) is a monomer component containing at least one monomer selected from an aromatic vinyl monomer and a vinyl cyanide monomer (however, a maleimide monomer is included) No.) is a copolymer obtained by polymerization. The monomer component constituting the copolymer (D) may contain another vinyl monomer copolymerizable with at least one of an aromatic vinyl monomer and a vinyl cyanide monomer. Good.
Examples of the aromatic vinyl monomer, vinyl cyanide monomer, and other vinyl monomers include the aromatic vinyl monomers exemplified above in the description of the graft copolymer (A), cyan. Vinylated monomers, and other vinyl monomers (excluding maleimide monomers).

  The composition of the copolymer (D) is not particularly limited, but from the viewpoint of the balance between the molding processability of the thermoplastic resin composition and the impact resistance, surface smoothness, and color developability of the molded product, the copolymer (D ) In 100% by mass of all monomer units, aromatic vinyl monomer units are 60 to 80% by mass, vinyl cyanide monomer units are 20 to 40% by mass, and other vinyl monomers It is preferable that a body unit is 0-20 mass%.

The reduced viscosity of the copolymer (D) in an N, N-dimethylformamide solution is 0.4 to 0.7 dl / g. When the reduced viscosity of the copolymer (D) is less than 0.4 dl / g, the impact resistance of the molded product is lowered, and when it exceeds 0.7 dl / g, the molding processability of the thermoplastic resin composition and the molded product are reduced. The surface smoothness is reduced.
The reduced viscosity here is a value obtained by dissolving 0.2 g of the copolymer (D) in 100 mL of N, N-dimethylformamide to form an N, N-dimethylformamide solution and obtaining it with an Ubbelohde viscometer at 25 ° C. is there.

  The copolymer (D) is obtained by a known emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method and the like. Further, as the copolymer (D), those obtained by a technique obtained by combining these polymerization methods can be used, but those obtained by a solution polymerization method are preferably used.

<Ratio>
The mass ratio ((A) :( B)) of the graft copolymer (A) and the graft copolymer (B) is 50:50 to 80:20. When the proportion of the graft copolymer (A) is too small (the proportion of the graft copolymer (B) is too large), the surface smoothness and color developability of the resulting molded product are lowered. On the other hand, when the proportion of the graft copolymer (A) is too large (the proportion of the graft copolymer (B) is too small), the molding processability of the resulting thermoplastic resin composition and the impact resistance of the molded product are low. descend.

  The total rubber content derived from the graft copolymer (A) and the graft copolymer (B) contained in the thermoplastic resin composition is 10 to 30% by mass. If the rubber content in the thermoplastic resin composition is less than 10% by mass, the impact resistance of the molded product is lowered, and if it exceeds 30% by mass, the molding processability of the resin composition, the heat resistance of the molded product, and the surface Smoothness and color developability deteriorate.

  Further, the structural unit derived from the conjugated diene rubber contained in the thermoplastic resin composition is less than 2% by mass. When the structural unit derived from the conjugated diene rubber is less than 2% by mass, the light resistance of the molded product is improved. The structural unit derived from the conjugated diene rubber is preferably less than 1% by mass.

  The content of the copolymer (C) in the thermoplastic resin composition is 10 to 30 parts by mass (however, the graft copolymer (A), the graft copolymer (B), the copolymer (C), and The total of the copolymer (D) is 100 parts by mass). When the content of the copolymer (C) is less than 10 parts by mass, the heat resistance of the molded product is lowered, and when it exceeds 30 parts by mass, the molding processability of the thermoplastic resin composition is lowered. In consideration of the balance between the moldability of the thermoplastic resin composition and the heat resistance of the molded product, the content of the copolymer (C) is preferably 10 to 20 parts by mass.

  The content of the copolymer (D) in the thermoplastic resin composition is 30 to 70 parts by mass (provided that the graft copolymer (A), the graft copolymer (B), and the copolymer (C) And the total of the copolymer (D) is 100 parts by mass). When the content of the copolymer (D) is less than 30 parts by mass, the molding processability of the thermoplastic resin composition decreases, and when it exceeds 70 parts by mass, the heat resistance and impact resistance of the molded product decrease. Considering the moldability of the thermoplastic resin composition and the balance between the heat resistance and impact resistance of the molded product, the content of the copolymer (D) is more preferably 40 to 60 parts by mass.

<Other ingredients>
The thermoplastic resin composition of the present invention contains the above-described graft copolymer (A), graft copolymer (B), copolymer (C), and copolymer (D). The thermoplastic resin composition may be composed only of the graft copolymer (A), the graft copolymer (B), the copolymer (C), and the copolymer (D), but other thermoplastics. A resin (another thermoplastic resin (H)) may be contained. Moreover, the thermoplastic resin composition may contain an additive.

Other thermoplastic resins (H) include, for example, acrylonitrile-ethylene-propylene-diene-styrene copolymer (AES resin), polymethyl methacrylate, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin). ), Polyolefins such as polyvinyl chloride, polyethylene and polypropylene, styrene elastomers such as styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS), various olefins Elastomers, various polyester elastomers, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer, polyaceter Resins, modified polyphenylene ether (modified PPE resin), ethylene - vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyarylate, and the like liquid crystal polyester resin and a polyamide resin (nylon).
These other thermoplastic resins (H) may be used alone or in combination of two or more.

  Examples of the additives include various stabilizers such as antioxidants and light stabilizers, colorants such as dyes and pigments, lubricants, plasticizers, mold release agents, antistatic agents, and inorganic fillers.

  The thermoplastic resin composition includes a graft copolymer (A), a graft copolymer (B), a copolymer (C), a copolymer (D), and other thermoplastic resins (H) as necessary. And additives are mixed and dispersed with a V-type blender or Henschel mixer, and the resulting mixture is melt-kneaded using a melt-kneader such as a screw extruder, Banbury mixer, pressure kneader, or mixing roll. It is manufactured by. Moreover, you may pelletize a melt-kneaded material using a pelletizer etc. as needed.

<Effect>
The thermoplastic resin composition of the present invention described above includes two types of graft copolymers (A) and (B) having the specific structure described above, and two types of copolymers (C) having the specific structure described above. , (D), a molded article having a good balance of impact resistance, heat resistance, surface smoothness, weather resistance, and color developability can be obtained, and the molding processability is excellent.
The thermoplastic resin composition of the present invention is suitable as a material for a vehicle lamp housing.

"Molding"
The molded product obtained by the present invention is formed by molding the thermoplastic resin composition of the present invention by a known molding method, and has a balance of impact resistance, heat resistance, surface smoothness, weather resistance, and color developability. It is good.
Moreover, the molded product obtained by the present invention can form a metal film by direct vapor deposition without performing a special pretreatment such as an undercoat, and uses a number of processes, dedicated equipment, and a high-cost treatment agent. It can be easily obtained without it.
Examples of industrial applications of the molded article include vehicle parts, in particular, vehicle lamp housings such as head lamps and tail lamps, indicator lights and fog lamps, home appliance parts such as lighting equipment housings, OA equipment housings, interior members, and the like. Among these, a vehicle lamp housing is preferable because the effect of excellent brightness after direct vapor deposition in addition to molding processability, impact resistance, and heat resistance is particularly utilized.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example. In the following examples, “%” and “part” are based on mass unless otherwise specified.
Various measurements and evaluation methods in the following examples and comparative examples are as follows.

"Measurement / Evaluation"
<Measurement of volume average particle diameter>
Using a nanotrack particle size distribution meter ("UPA-EX150" manufactured by Nikkiso Co., Ltd.), using ion-exchanged water as a measurement solvent, polyorganosiloxane (s), conjugated diene rubber polymer (g), acrylic The volume-based average particle diameters of the rubber polymer (rs) and the acrylic rubber polymer (rl) were measured.

<Evaluation of molding processability>
The melt volume rate (MVR) of the thermoplastic resin composition was measured in accordance with ISO 1133 using a melt indexer (“F-F01” manufactured by Toyo Seiki Seisakusyo Co., Ltd.) under the conditions of 220 ° C. and 10 kg load. . A higher MVR value means higher fluidity and better molding processability.

<Evaluation of impact resistance>
In accordance with ISO 3167, a test piece was prepared from a pellet-shaped thermoplastic resin composition by an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). The Charpy impact strength of this test piece was measured in an atmosphere of 23 ° C. according to ISO 179.

<Evaluation of heat resistance>
In accordance with ISO 3167, a test piece was prepared from a pellet-shaped thermoplastic resin composition by an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). Based on ISO 75, the deflection temperature under load (HDT) of this test piece was measured using an HDT tester (“6A-2” manufactured by Toyo Seiki Seisakusyo Co., Ltd.), with a load of 1.80 MPa and a flat width (4 mm thickness). Measured under conditions. The higher the value of HDT, the better the heat resistance.

<Evaluation of surface smoothness>
From a pellet-shaped thermoplastic resin composition, using a 4 ounce injection molding machine (manufactured by Nippon Steel Co., Ltd.), a cylinder set temperature of 260 ° C., a mold temperature of 60 ° C., and an injection rate of 20 g / sec. A plate-shaped test piece having a thickness of 100 mm, a width of 100 mm, and a thickness of 2 mm was produced.
Next, a film thickness of 50 nm was formed on the obtained test piece with a vacuum deposition device (“VPC-1100” manufactured by ULVAC KIKOH Co., Ltd.) under the conditions of a degree of vacuum of 6.0 × 10 ⁻³ Pa and a film formation rate of 1 nm / second. An aluminum vapor deposition film was formed. Thus, about the molded article which performed direct vapor deposition, the diffuse reflectance was measured using the reflectance meter (The limited company Tokyo Denshoku make, "TR-1100AD"). The smaller the diffuse reflectance, the better the surface smoothness.

<Evaluation of color development>
From a pellet-shaped thermoplastic resin composition, using a 4 ounce injection molding machine (manufactured by Nippon Steel Co., Ltd.), a cylinder set temperature of 260 ° C., a mold temperature of 60 ° C., and an injection rate of 20 g / sec. A plate-shaped test piece having a thickness of 100 mm, a width of 100 mm, and a thickness of 2 mm was produced.
About the obtained test piece, the brightness (L ^* ) was measured by the SCE method using the spectrocolorimeter ("CM-508D" manufactured by Konica Minolta, Inc.). The lower L ^* is, the more black it is and the better the color development (pigment coloring).

<Evaluation of weather resistance>
From a pellet-shaped thermoplastic resin composition, using a 4 ounce injection molding machine (manufactured by Nippon Steel Co., Ltd.), a cylinder set temperature of 260 ° C., a mold temperature of 60 ° C., and an injection rate of 40 g / sec. A plate-shaped test piece having a thickness of 100 mm, a width of 100 mm, and a thickness of 2 mm was produced.
About the obtained test piece, using a Sunshine Super Long Life Weather Meter (manufactured by Suga Test Instruments Co., Ltd., “WEL-SUN-DCH type”) under the condition of 63 ° C. rain (60 minutes cycle rain 12 minutes) Exposure for 1000 hours. The degree of discoloration (ΔE) of the molded product before and after 1000 hours of exposure was measured with a spectrocolorimeter. A smaller value of ΔE means better weather resistance.

"Manufacture of polyorganosiloxane (s)"
<Production Example 1: Production of polyorganosiloxane (s-1)>
98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. Thereto, 0.67 part of sodium dodecylbenzenesulfonate, was added an aqueous solution of an ion exchange water 300 parts and stirred for 2 minutes at 10,000 rpm / min homomixer, a homogenizer at a pressure of 300 kg / cm ² 2 Through circulation, a stable premixed organosiloxane latex was obtained.
Separately, 10 parts of dodecylbenzenesulfonic acid and 90 parts of ion-exchanged water were put into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer, and a 10% aqueous solution of dodecylbenzenesulfonic acid ( Acid catalyst aqueous solution) was prepared.
While this acid catalyst aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 2 hours. After the completion of the addition, the temperature was maintained for 3 hours and then cooled to 40 ° C. or lower. Next, this reaction product was neutralized to pH 7.0 with a 10% aqueous sodium hydroxide solution to obtain a latex of polyorganosiloxane (s-1).
The obtained polyorganosiloxane (s-1) had a latex solid content of 18.2% and a volume average particle size of 40 nm.

“Production of Conjugated Diene Rubber Polymer (g)”
<Production Example 2: Production of small particle size conjugated diene rubber polymer (g-1)>
In a stainless steel autoclave with a stirrer and a thermometer, 145 parts of ion-exchanged water (hereinafter abbreviated as “water”), 1.0 part of disproportionated potassium rosinate, 1.0 part of potassium oleate, and Rongalite 0.4 Part, anhydrous sodium sulfate 0.1 part, t-dodecyl mercaptan 0.3 part, diisopropylbenzene hydroperoxide 0.5 part, 1,3-butadiene 26.2 parts, and styrene 1.4 parts. The temperature was raised until the internal temperature of the autoclave reached 50 ° C, and then an aqueous solution consisting of 0.5 parts of sodium pyrophosphate, 0.005 parts of ferrous sulfate heptahydrate and 5 parts of ion-exchanged water was added for polymerization. Started. At a polymerization temperature of 57 ° C., a mixture consisting of 68.6 parts of 1,3-butadiene and 3.6 parts of styrene was dropped by a pressure pump. Subsequently, when the polymerization conversion rate reached 40%, 0.3 part of n-dodecyl mercaptan was added and the polymerization was further continued. After 8 hours, the remaining 1,3-butadiene was removed to obtain a latex of a small particle size conjugated diene rubber polymer (g-1).
The obtained small particle size conjugated diene rubber polymer (g-1) had a latex solid content of 40.2%, a polymerization conversion rate of 97%, and a volume average particle size of 70 nm.

"Production of acid group-containing copolymer (i)"
<Production Example 3: Production of acid group-containing copolymer (i-1)>
In a reactor equipped with a reagent injector, a condenser, a jacket heater and a stirrer, 2.2 parts of potassium oleate, 2.5 parts of sodium dioctylsulfosuccinate, 0.3 part of Rongalite, ferrous sulfate heptahydrate 0.003 part of Japanese product, 0.009 part of disodium ethylenediaminetetraacetate, and 200 parts of ion-exchanged water were charged under a nitrogen stream. The temperature of the reactor was raised to 65 ° C. while stirring, and then a mixture consisting of 81.5 parts of n-butyl acrylate, 18.5 parts of methacrylate and 0.5 parts of cumene hydroperoxide was added for 2 hours. The polymerization was continued at the same temperature for 2 hours even after the addition was completed, and an acid group-containing copolymer (i-1) latex was obtained.
The polymerization conversion rate of the obtained acid group-containing copolymer (i-1) was 98%, and the volume average particle diameter was 150 nm.

<Production Example 4: Production of acid group-containing copolymer (i-2)>
Polymerization was conducted in the same manner as in Production Example 3 except that potassium oleate was changed to 3.2 parts, sodium dioctylsulfosuccinate 3.0 parts, n-butyl acrylate 88.5 parts, and methacrylate 11.5 parts. The latex of the acid group containing copolymer (i-2) whose volume average particle diameter is 60 nm was manufactured.

"Production of graft copolymer (A)"
<Production Example 5: Production of graft copolymer (A-1)>
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 295 parts of ion exchange water, 0.3 part of dipotassium alkenyl succinate, 50 parts of n-butyl acrylate, 1.5 parts of allyl methacrylate, 0.05 parts of 1,3-butylene glycol dimethacrylate and 0.04 part of t-butyl hydroperoxide were charged with stirring, and the inside of the reactor was purged with nitrogen, and then the contents were heated. At an internal temperature of 55 ° C., an aqueous solution consisting of 0.18 parts of Rongalite, 0.00009 parts of ferrous sulfate heptahydrate, 0.00027 parts of ethylenediaminetetraacetate, and 8 parts of ion-exchanged water was added to conduct polymerization. Started. After the polymerization exotherm was confirmed, the jacket temperature was set to 75 ° C., and the polymerization was continued until the polymerization exotherm was not confirmed, and was further maintained for 1 hour to obtain a latex of an acrylic rubber polymer (rs-1).
The polymerization conversion rate of the obtained acrylic rubbery polymer (rs-1) was 99%, and the volume average particle diameter was 155 nm.

Subsequently, 0.001 part of ferrous sulfate heptahydrate, 0.003 part of disodium ethylenediaminetetraacetate, 0.3 part of Rongalite, 10 parts of ionic water are added to the latex of the acrylic rubbery polymer (rs-1). An aqueous solution consisting of was added. Subsequently, a mixed liquid composed of 15 parts of acrylonitrile, 35 parts of styrene, and 0.26 part of t-butyl hydroperoxide was dropped over 100 minutes to be polymerized. After completion of dropping, after maintaining the temperature at 75 ° C. for 30 minutes, 0.05 part of cumene hydroperoxide was added, and after maintaining the temperature at 75 ° C. for 30 minutes, the mixture was cooled, and the graft copolymer (A -1) latex was obtained.
Subsequently, 100 parts of a 0.6% sulfuric acid aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (A-1) was gradually dropped into the solution to be solidified. Then, the precipitate was separated, dehydrated, washed, and dried to obtain a graft copolymer (A-1). The composition of the graft copolymer (A-1) is shown in Table 1.

<Production Example 6: Production of graft copolymer (A-2)>
1.75 parts of latex of polyorganosiloxane (s-1) produced in Production Example 1 in terms of solid content, ion exchange in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer 295 parts of water, 0.6 part of dipotassium alkenyl succinate, 48.25 parts of n-butyl acrylate, 0.5 part of allyl methacrylate, 0.1 part of 1,3-butylene glycol dimethacrylate, t-butyl hydroperoxide 04 parts were charged with stirring, and the inside of the reactor was purged with nitrogen, and then the contents were heated. At an internal temperature of 60 ° C., an aqueous solution comprising Rongalite 0.18 parts, ferrous sulfate heptahydrate 0.00009 parts, ethylenediaminetetraacetic acid disodium 0.00027 parts, and ion-exchanged water 8 parts was added to polymerize. Started. After the polymerization exotherm was confirmed, the jacket temperature was set to 75 ° C., and the polymerization was continued until the polymerization exotherm was not confirmed, and was further maintained for 1 hour to obtain an acrylic rubbery polymer containing polyorganosiloxane.
The polymerization conversion rate after 1 hour of the obtained acrylic rubbery polymer was 99%, and the volume average particle diameter was 135 nm.
Subsequently, 0.6 parts of sodium pyrophosphate was added at a liquid temperature of 70 ° C. inside the reactor, and after maintaining for 5 minutes, the latex of the acid group-containing copolymer (i-2) produced in Production Example 4 was solidified. 0.6 parts in terms of minutes were added, and stirring was continued for 30 minutes to carry out an enlargement treatment to obtain an enlarged latex of an acrylic rubber polymer (rs-2).
The resulting acrylic rubbery polymer (rs-2) had a volume average particle size of 155 nm.

Subsequently, 0.001 part of ferrous sulfate heptahydrate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.3 part of Rongalite, 10 parts of ion-exchanged water are added to the latex of the acrylic rubbery polymer (rs-2). An aqueous solution consisting of parts was added. Subsequently, a mixed liquid composed of 10 parts of acrylonitrile, 30 parts of styrene, and 0.18 part of t-butyl hydroperoxide was dropped over 80 minutes for polymerization. After completion of dropping, the mixture is kept at a temperature of 75 ° C. for 30 minutes, and then a mixture comprising 2.5 parts of acrylonitrile, 7.5 parts of styrene, 0.05 part of t-butyl hydroperoxide, and 0.02 part of n-octyl mercaptan. Was added dropwise over 20 minutes to polymerize. After completion of dropping, after maintaining the temperature at 75 ° C. for 30 minutes, 0.05 part of cumene hydroperoxide was added, and after maintaining the temperature at 75 ° C. for 30 minutes, the mixture was cooled, and the graft copolymer (A -2) latex was obtained.
Subsequently, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (A-2) was gradually dropped into the solution to be solidified. Then, the precipitate was separated, dehydrated, washed and then dried to obtain a graft copolymer (A-2). The composition of the graft copolymer (A-2) is shown in Table 1.

<Production Example 7: Production of graft copolymer (A-3)>
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, 7 parts of latex of polyorganosiloxane (s-1) produced in Production Example 1 in terms of solid content, ion-exchanged water 295 Parts, 0.1 parts of dipotassium alkenyl succinate, 43 parts of n-butyl acrylate, 0.3 parts of allyl methacrylate, 0.1 part of 1,3-butylene glycol dimethacrylate, 0.04 part of t-butyl hydroperoxide The contents were heated up after charging under nitrogen substitution in the reactor. At an internal temperature of 60 ° C., an aqueous solution comprising Rongalite 0.18 parts, ferrous sulfate heptahydrate 0.00009 parts, ethylenediaminetetraacetic acid disodium 0.00027 parts, and ion-exchanged water 8 parts was added to polymerize. Started. After the polymerization exotherm was confirmed, the jacket temperature was set to 75 ° C., and the polymerization was continued until the polymerization exotherm was not confirmed, and was further maintained for 1 hour, and the acrylic rubbery polymer (rs-3) containing polyorganosiloxane was retained. Latex was obtained.
The polymerization conversion rate after 1 hour of the obtained acrylic rubbery polymer (rs-3) was 99%, and the volume average particle diameter was 100 nm.

Subsequently, to the latex of the acrylic rubbery polymer (rs-3), 0.001 part of ferrous sulfate heptahydrate, 0.003 part of disodium ethylenediaminetetraacetate, 0.3 part of Rongalite, 10 parts of ionic water An aqueous solution consisting of was added. After the liquid temperature inside the reactor dropped to 70 ° C., it comprised 0.001 part of ferrous sulfate heptahydrate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.3 part of Rongalite, and 10 parts of ion-exchanged water. Additional aqueous solution was added. Subsequently, a mixed liquid composed of 2.5 parts of acrylonitrile, 7.5 parts of styrene, and 0.045 part of t-butyl hydroperoxide was dropped over 20 minutes to be polymerized. After completion of the dropwise addition, the temperature was maintained at 70 ° C. for 30 minutes, and then a mixture comprising 10 parts of acrylonitrile, 30 parts of styrene and 0.18 part of t-butyl hydroperoxide was dropped over 80 minutes and polymerized. After completion of dropping, after maintaining the temperature at 75 ° C. for 30 minutes, 0.05 part of cumene hydroperoxide was added, and after maintaining the temperature at 75 ° C. for 30 minutes, the mixture was cooled, and the graft copolymer (A -3) latex was obtained.
Next, 150 parts of a 1.5% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (A-3) was gradually dropped into the mixture to solidify. Then, the precipitate was separated, dehydrated, washed and then dried to obtain a graft copolymer (A-3). The composition of the graft copolymer (A-3) is shown in Table 1.

<Production Example 8: Production of graft copolymer (A-4)>
Polymerization was carried out in the same manner as in Production Example 5 except that 0.3 part of dipotassium alkenyl succinate was changed to 5 parts of sodium dodecylbenzenesulfonate, and an acrylic rubbery polymer (rs- The latex of 4) was obtained.
A graft copolymer (A-4) was obtained in the same manner as in Production Example 5 except that the latex of the obtained acrylic rubbery polymer (rs-4) was used. The composition of the graft copolymer (A-4) is shown in Table 1.

"Production of graft copolymer (B)"
<Production Example 9: Production of graft copolymer (B-1)>
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, the latex of the small particle size conjugated diene rubber polymer (g-1) prepared in Production Example 2 is 10 in terms of solid content. Part of the latex of the acid group-containing copolymer (i-1) produced in Production Example 3 was added at room temperature while stirring at 2.1 parts in terms of solid content, and further stirred for 30 minutes. An enlarged conjugated diene rubbery polymer having a diameter of 400 nm was obtained.
Next, 0.3 parts of dipotassium alkenyl succinate and 175 parts of ion-exchanged water (including the water in the enlarged conjugated diene rubber polymer latex) were charged into the reactor, and n-butyl was stirred under stirring. A mixture of 40 parts of acrylate, 0.16 part of allyl methacrylate, 0.08 part of 1,3-butylene glycol dimethacrylate and 0.1 part of t-butyl hydroperoxide was charged with stirring, and the inside of the reactor was purged with nitrogen. After that, the contents were heated. When the internal liquid temperature reaches 50 ° C., an aqueous solution comprising ferrous sulfate heptahydrate 0.00015 parts, disodium ethylenediaminetetraacetate 0.00045 parts, Rongalite 0.24 parts, and ion-exchanged water 5 parts Then, the internal temperature was raised to 75 ° C. to initiate radical polymerization. This state was maintained for 1 hour to complete the polymerization of the n-butyl acrylate component, and an acrylic rubbery polymer (rl-1) latex containing a conjugated diene rubbery polymer was obtained.
The resulting acrylic rubbery polymer (rl-1) had a volume average particle size of 380 nm.

Subsequently, an aqueous solution consisting of 0.15 parts of Rongalite, 0.65 parts of dipotassium alkenyl succinate and 10 parts of ion-exchanged water was added to the latex of the acrylic rubbery polymer (rl-1), and then acrylonitrile 6.3. A mixture of 18.7 parts of styrene, 18.7 parts of styrene and 0.11 part of t-butyl hydroperoxide was added dropwise over 1 hour for polymerization. 5 minutes after the completion of the dropwise addition, an aqueous solution consisting of 0.001 part of ferrous sulfate heptahydrate, 0.003 part of disodium ethylenediaminetetraacetate, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, A mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene, 0.19 part of t-butyl hydroperoxide, and 0.014 part of n-octyl mercaptan was added dropwise over 1 hour for polymerization. After completion of the dropping, the temperature is kept at 75 ° C. for 10 minutes and then cooled. When the internal temperature reaches 60 ° C., 0.2 part of an antioxidant (“ANTAGE W500” manufactured by Kawaguchi Chemical Industry Co., Ltd.) A dispersion composed of 0.2 parts of dipotassium alkenyl succinate and 5 parts of ion-exchanged water was added to obtain a latex of the graft copolymer (B-1).
Next, 100 parts of a 0.6% sulfuric acid aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (B-1) was gradually dropped into the solution and solidified. Then, the precipitate was separated, dehydrated, washed and dried to obtain a graft copolymer (B-1). The composition of the graft copolymer (B-1) is shown in Table 1.

<Production Example 10: Production of graft copolymer (B-2)>
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 230 parts of ion exchange water, 0.5 part of dipotassium alkenyl succinate, 40 parts of n-butyl acrylate, 0.24 part of allyl methacrylate, After 0.2 parts of triallyl isocyanurate and 0.1 part of t-butyl hydroperoxide were charged with stirring, and the inside of the reactor was purged with nitrogen, the contents were heated. At an internal temperature of 55 ° C., an aqueous solution consisting of 0.15 parts Rongalite, 0.00005 parts ferrous sulfate heptahydrate, 0.00015 parts disodium ethylenediaminetetraacetate, and 5 parts ion-exchanged water was added to polymerize. Started. After the polymerization exotherm was confirmed, the jacket temperature was set to 75 ° C., and the polymerization was continued until the polymerization exotherm was not confirmed, and was further maintained for 1 hour to obtain a rubber polymer having a volume average particle diameter of 100 nm.
0.5 parts of sodium pyrophosphate was added to the resulting rubbery polymer, and the jacket temperature was controlled so that the internal temperature became 70 ° C. Then, 1.5 parts of latex of the acid group-containing copolymer (i-1) produced in Production Example 3 was added at a solid temperature of 70 ° C., and the internal temperature was maintained at 70 ° C. for 30 minutes. Stirring and enlarged latex of acrylic rubber polymer was obtained.
The resulting enlarged acrylic rubbery polymer had a volume average particle size of 420 nm.

Subsequently, at an internal temperature of 70 ° C., the latex of the acrylic rubber-like polymer enlarged, 0.015 parts of Rongalite, 0.001 part of ferrous sulfate heptahydrate, 0.003 parts of disodium ethylenediaminetetraacetate Then, an aqueous solution consisting of 40 parts of ion-exchanged water is added, and then mixed with 10 parts of n-butyl acrylate, 0.06 part of allyl methacrylate, 0.05 part of triallyl isocyanurate, and 0.01 part of t-butyl hydroperoxide. The solution was added dropwise over 1 hour. After completion of the dropping, the temperature was maintained at 70 ° C. for 1 hour, followed by cooling to obtain an acrylic rubber polymer (rl-2) latex having a solid content of 18% and a volume average particle diameter of 450 nm. .
Next, a mixture of 15 parts of acrylonitrile, 35 parts of styrene, and 0.5 parts of t-butyl hydroperoxide was added dropwise to the latex of the acrylic rubbery polymer (rl-2) over 100 minutes up to 80 ° C. The temperature rose. After completion of the dropwise addition, the temperature of 80 ° C. was maintained for 30 minutes and then cooled to obtain a latex of graft copolymer (B-2).
Next, 100 parts of a 1.5% sulfuric acid aqueous solution was heated to 80 ° C., and 100 parts of the latex of the graft copolymer (B-2) was gradually dropped into the mixture to solidify. Then, the precipitate was separated, dehydrated, washed and dried to obtain a graft copolymer (B-2). The composition of the graft copolymer (B-2) is shown in Table 1.

<Production Example 11: Production of graft copolymer (B-3)>
In Production Example 10, polymerization was carried out in the same manner except that dipotassium alkenyl succinate was changed to 0.8 part and the latex of the acid group-containing copolymer (i-1) was changed to 0.4 part in terms of solid content. An acrylic rubbery polymer (rl-3) latex was obtained. The resulting acrylic rubbery polymer (rl-3) had a volume average particle size of 260 nm.
A graft copolymer (B-3) was obtained in the same manner as in Production Example 10 except that the latex of the obtained acrylic rubbery polymer (rl-3) was used. The composition of the graft copolymer (B-3) is shown in Table 1.

<Production Example 12: Production of graft copolymer (B-4)>
In Production Example 10, the procedure was the same except that 1.2 parts of dipotassium alkenyl succinate, 1 part of sodium pyrophosphate and 2 parts of latex of the acid group-containing copolymer (i-1) were converted to 2 parts in terms of solid content. Polymerization was performed to obtain an enlarged latex of an acrylic rubber polymer (rl-4). The resulting acrylic rubbery polymer (rl-4) had a volume average particle size of 700 nm.
A graft copolymer (B-4) was obtained in the same manner as in Production Example 10 except that the latex of the resulting acrylic rubbery polymer (rl-4) was used. The composition of the graft copolymer (B-4) is shown in Table 1.

<Production Example 13: Production of graft copolymer (B-5)>
In Production Example 9, the latex of the small particle size conjugated diene rubber polymer (g-1) is 20 parts in terms of solid content, and the latex of the acid group-containing copolymer (i-1) is 3. Polymerization was carried out in the same manner except that the content was changed to 0 part to obtain an acrylic rubber polymer (rl-5) latex containing a conjugated diene rubber polymer. The resulting acrylic rubbery polymer (rl-5) had a volume average particle size of 380 nm.
A graft copolymer (B-5) was obtained in the same manner as in Production Example 9, except that the latex of the resulting acrylic rubbery polymer (rl-5) was used. The composition of the graft copolymer (B-5) is shown in Table 1.

  “S-1” in Table 1 is the polyorganosiloxane (s-1) produced in Production Example 1, “n-BA” is n-butyl acrylate, “AN” is acrylonitrile, “ “St” is styrene.

"Production of copolymer (C)"
<Production Example 14: Production of copolymer (C-1)>
A copolymer (C-1) comprising 15% acrylonitrile monomer units, 55% styrene monomer units, and 30% N-phenylmaleimide monomer units was obtained by known continuous solution polymerization. The reduced viscosity of this copolymer (C-1) in an N, N-dimethylformamide solution at 25 ° C. was 0.61 dl / g. Table 2 shows the composition of the copolymer (C-1).

<Copolymer (C-2)>
“DENKA IP MS-NI” (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. was used as the copolymer (C-2).
The copolymer (C-2) consists of 52% N-phenylmaleimide monomer units and 48% styrene monomer units, and the reduced viscosity in an N, N-dimethylformamide solution at 25 ° C. is 0.42 dl / g. The composition of the copolymer (C-2) is shown in Table 2.

<Production Example 15: Production of copolymer (C-3)>
A copolymer (C-3) composed of 20% acrylonitrile monomer units, 58% styrene monomer units, and 22% N-phenylmaleimide monomer units was obtained by known continuous solution polymerization. The reduced viscosity of this copolymer (C-3) in an N, N-dimethylformamide solution at 25 ° C. was 0.64 dl / g. The composition of the copolymer (C-3) is shown in Table 2.

<Production Example 16: Production of copolymer (C-4)>
By known continuous solution polymerization, it is composed of 28% acrylonitrile monomer units, 24.5% styrene monomer units, 11% α-methylstyrene monomer units, and 36.5% N-phenylmaleimide monomer units. A copolymer (C-4) was obtained. The reduced viscosity of this copolymer (C-4) in an N, N-dimethylformamide solution at 25 ° C. was 0.47 dl / g. The composition of the copolymer (C-4) is shown in Table 2.

<Production Example 17: Production of copolymer (C-5)>
A copolymer (C-5) comprising 15% acrylonitrile monomer units, 55% styrene monomer units, and 30% N-phenylmaleimide monomer units was obtained by known continuous solution polymerization. The reduced viscosity of this copolymer (C-5) in an N, N-dimethylformamide solution at 25 ° C. was 0.21 dl / g. The composition of the copolymer (C-5) is shown in Table 2.

<Production Example 18: Production of copolymer (C-6)>
A copolymer (C-6) comprising 15% acrylonitrile monomer units, 55% styrene monomer units, and 30% N-phenylmaleimide monomer units was obtained by known continuous solution polymerization. The reduced viscosity of this copolymer (C-6) in an N, N-dimethylformamide solution at 25 ° C. was 0.82 dl / g. The composition of the copolymer (C-6) is shown in Table 2.

<Production Example 19: Production of copolymer (C-7)>
A copolymer (C-7) composed of 28.6% styrene monomer units and 71.4% N-phenylmaleimide monomer units was obtained by known continuous solution polymerization. The reduced viscosity of this copolymer (C-7) in an N, N-dimethylformamide solution at 25 ° C. was 0.55 dl / g. Table 2 shows the composition of the copolymer (C-7).

  In Table 2, “AN” is acrylonitrile and “St” is styrene.

"Production of copolymer (D)"
<Production Example 20: Production of copolymer (D-1)>
25 parts of acrylonitrile and 75 parts of styrene were polymerized by known suspension polymerization to obtain a copolymer (D-1). The reduced viscosity of this copolymer (D-1) in an N, N-dimethylformamide solution at 25 ° C. was 0.49 dl / g. Table 3 shows the composition of the copolymer (D-1).

<Production Example 21: Production of copolymer (D-2)>
28 parts of acrylonitrile and 72 parts of styrene were polymerized by known suspension polymerization to obtain a copolymer (D-2). The reduced viscosity of this copolymer (D-2) in an N, N-dimethylformamide solution at 25 ° C. was 0.62 dl / g. The composition of the copolymer (D-2) is shown in Table 3.

<Production Example 22: Production of copolymer (D-3)>
25 parts of acrylonitrile and 75 parts of styrene were polymerized by known suspension polymerization to obtain a copolymer (D-3). The reduced viscosity of this copolymer (D-3) in an N, N-dimethylformamide solution at 25 ° C. was 0.35 dl / g. Table 3 shows the composition of the copolymer (D-3).

<Production Example 23: Production of copolymer (D-4)>
29 parts of acrylonitrile and 71 parts of styrene were polymerized by known suspension polymerization to obtain a copolymer (D-4). The reduced viscosity of this copolymer (D-4) in an N, N-dimethylformamide solution at 25 ° C. was 0.88 dl / g. The composition of the copolymer (D-4) is shown in Table 3.

  In Table 3, “AN” is acrylonitrile and “St” is styrene.

"Examples 1-16, Comparative Examples 1-16"
The types and amounts of graft copolymers (A), graft copolymers (B), copolymers (C), and copolymers (D) shown in Tables 4-7, and 0.8 parts ethylene bisstearylamide And 0.2 part of silicone oil SH200 (manufactured by Toray Dow Corning Co., Ltd.), 0.2 part of ADK STAB AO-60 (manufactured by ADEKA Corporation), and 0.4 part of ADK STAB LA-57 (manufactured by ADEKA Corporation) And 0.8 part of carbon black were mixed using a Henschel mixer. Thermoplastic resin obtained by melt-kneading the obtained mixture at 240 ° C. using a screw type extruder (manufactured by Nippon Steel Co., Ltd., “TEX-30α type twin screw extruder”) and then pelletizing with a pelletizer A composition was obtained.
Molding processability was evaluated for the obtained thermoplastic resin composition. Moreover, a test piece was produced using the obtained thermoplastic resin composition, and impact resistance, heat resistance, surface smoothness, color developability, and weather resistance were evaluated. These results are shown in Tables 4-7.

“(A) :( B)” in Tables 4 to 7 is a mass ratio of the amounts of the graft copolymer (A) and the graft copolymer (B) used in the thermoplastic resin composition.
The “volume average particle diameter of (rs)” is the volume-based average particle diameter of the acrylic rubbery polymer (rs) used for the production of the graft copolymer (A). The “volume average particle diameter of (rl)” is the volume-based average particle diameter of the acrylic rubbery polymer (rl) used for the production of the graft copolymer (B).
"Rubber content in the resin composition" is the total amount (% by mass) of the rubber content derived from the graft copolymer (A) and the graft copolymer (B) contained in the thermoplastic resin composition. .
The “diene-derived component in the resin composition” is the content (% by mass) of the structural unit derived from the conjugated diene rubber contained in the thermoplastic resin composition.

  As shown in Tables 4 to 7, the thermoplastic resin compositions obtained in each Example were excellent in moldability. In addition, from each thermoplastic resin composition, a molded article having a good balance of impact resistance, heat resistance, surface smoothness, color development, and weather resistance was obtained.

On the other hand, as shown in Tables 4 to 7, in the case of each comparative example, the results were inferior to any of the items of molding processability, impact resistance, heat resistance, surface smoothness, color developability, and weather resistance.
Specifically, in the case of Comparative Example 1, since the volume average particle diameter of the acrylic rubbery copolymer (rs) was 50 nm, the results were inferior in molding processability, impact resistance and surface smoothness.
In the case of Comparative Example 2, the volume average particle diameter of the acrylic rubbery copolymer (rl) was 260 nm, which was inferior in molding processability and impact resistance.
In the case of Comparative Example 3, since the volume average particle diameter of the acrylic rubbery copolymer (rl) was 700 nm, the results were inferior in surface smoothness and color developability.
In the case of Comparative Example 4, since the mass ratio of the graft copolymer (A): the graft copolymer (B) was 100: 0, the results were inferior in molding processability and impact resistance.
In Comparative Examples 5 and 6, since the mass ratio of graft copolymer (A): graft copolymer (B) was 25:75 or 0: 100, the results were inferior in surface smoothness and color developability. It was.
In the case of Comparative Example 7, since the content of the copolymer (C) was 0 part by mass, the result was inferior in heat resistance.
In the case of the comparative example 8, since content of the copolymer (C) was 35 mass parts, it was a result inferior to moldability.
In the case of Comparative Example 9, since the reduced viscosity of the copolymer (C) was 0.21 dl / g, the result was inferior in impact resistance.
In the case of Comparative Example 10, since the reduced viscosity of the copolymer (C) was 0.82 dl / g, the result was inferior in molding processability.
In the case of Comparative Example 11, since the ratio of the maleimide monomer unit in the copolymer (C) was 71.4% by mass, the molding processability, impact resistance, surface smoothness and color developability were poor. there were.
In the case of Comparative Example 12, since the ratio of the rubber content derived from the graft copolymer (A) and the graft copolymer (B) contained in the thermoplastic resin composition was 5% by mass, the impact resistance was poor. It was a result.
In the case of Comparative Example 13, since the proportion of the rubber content derived from the graft copolymer (A) and the graft copolymer (B) contained in the thermoplastic resin composition was 40% by mass, molding processability and heat resistance The results were inferior to the colorability and color development. Moreover, the diffuse reflectance was very large. This is considered to be due to the poor transferability because the surface smoothness of the molded product is low and the fluidity of the thermoplastic resin composition is low.
In the case of Comparative Example 14, since the content of the structural unit derived from the conjugated diene rubber contained in the thermoplastic resin composition was 3% by mass, the weather resistance was poor.
In the case of Comparative Example 15, since the reduced viscosity of the copolymer (D) was 0.35 dl / g, the result was inferior in impact resistance.
In the case of Comparative Example 16, since the reduced viscosity of the copolymer (D) was 0.88 dl / g, the results were inferior in molding processability and surface smoothness.

  According to the present invention, it is possible to obtain a molded article having a good balance of impact resistance, heat resistance, surface smoothness, weather resistance, and color developability, and to provide a thermoplastic resin composition excellent in molding processability. In particular, the balance of molding processability, impact resistance, heat resistance, and color developability is at a very high level that cannot be obtained with conventional thermoplastic resin compositions and molded articles obtained by molding the thermoplastic resin compositions. The utility value as various industrial materials such as exterior parts, OA equipment, electrical / electronic equipment, etc. is high. In addition, the thermoplastic resin composition of the present invention is suitable as a material for a lamp housing that is required to be complicated in shape, thinned, and measured in recent years.

Claims (2)

A thermoplastic resin composition comprising the following graft copolymer (A), graft copolymer (B), copolymer (C), and copolymer (D),
The mass ratio ((A) :( B)) of the graft copolymer (A) and the graft copolymer (B) is 50:50 to 80:20,
The total rubber content derived from the graft copolymer (A) and the graft copolymer (B) contained in the thermoplastic resin composition is 10 to 30% by mass, and the structural unit derived from the conjugated diene rubber is Less than 2% by weight,
And 10-30 mass parts of copolymer (C) (however, the total of graft copolymer (A), graft copolymer (B), copolymer (C), and copolymer (D)) 100 parts by mass.) A thermoplastic resin composition.
Graft copolymer (A): 0 to 20% by mass of polyorganosiloxane and 80 to 100% by mass of alkyl (meth) acrylate monomer (however, the total of polyorganosiloxane and alkyl (meth) acrylate monomer is 100) And an acrylic rubber polymer (rs) having a volume average particle diameter of 70 to 200 nm obtained by polymerizing the aromatic vinyl monomer and the vinyl cyanide monomer. An acrylic rubber graft copolymer obtained by graft polymerization of a monomer component containing at least one monomer selected from the body.
Graft copolymer (B): 0 to 30% by mass of conjugated diene rubbery polymer and 70 to 100% by mass of alkyl (meth) acrylate monomer (however, conjugated diene rubbery polymer and alkyl (meth)) Acrylic rubbery polymer (rl) having a volume average particle size of 300 to 600 nm obtained by polymerizing acrylate monomers to 100% by mass) is polymerized with an aromatic vinyl monomer. And an acrylic rubber graft copolymer obtained by graft polymerization of a monomer component containing at least one monomer selected from vinyl cyanide monomers.
Copolymer (C): N, N-dimethylformamide at 25 ° C. containing 10 to 65% by mass of maleimide monomer units in 100% by mass of all monomer units constituting copolymer (C) A copolymer having a reduced viscosity in a solution of 0.4 to 0.7 dl / g.
Copolymer (D): a monomer component containing at least one monomer selected from aromatic vinyl monomers and vinyl cyanide monomers (however, maleimide monomers are not included) A copolymer having a reduced viscosity of 0.4 to 0.7 dl / g in an N, N-dimethylformamide solution at 25 ° C.   A lamp housing for a vehicle obtained by molding the thermoplastic resin composition according to claim 1.