JP2014051563A - Thermoplastic resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition providing a molded article maintaining excellent flame resistance and having further improved shock resistance.SOLUTION: The composition contains [A] a rubbery polymer reinforced graft resin, [B] a polycarbonate resin, [C] a polymer having a constitutional unit derived from a vinyl cyanide compound, cx and a constitutional unit derived from an aromatic vinyl compound, cy, and [D] a flame retardant, and the polymer [C] contains a polymer C1 containing the unit cx of 5% to r%, a polymer C2 containing the unit cx over r% to r% or less, and a polymer C3 containing the unit cx of over r% to 60% and r-r≥3, and the content ratio of polymers C1, C2 and C3 are 5 to 70%, 10 to 80% and 10 to 80%.

Description

  The present invention relates to a thermoplastic resin composition that provides a molded article having flame retardancy and excellent impact resistance.

A polymer alloy of a polycarbonate resin and a styrene resin such as ABS resin or AS resin is excellent in heat resistance and impact resistance. For example, in a vehicle field, an electric field, an electronic field, a communication field, an OA / home appliance field, etc. Widely used as a molding material for resin members and the like. When such a molding material is used for forming a housing, an enclosure, a frame, a chassis or the like related to a product that generates heat, flame resistance is required.
In recent years, in order to prove the safety of products, resin molded products used for OA equipment, home appliances, etc. have the highest flame retardant level based on the subject 94 of Underwriters Laboratories (UL), an American flame retardant standard. V-0 standard certification is required.

Conventionally, in order to impart flame retardancy, a halogen flame retardant or a non-halogen flame retardant has been added to a polymer alloy composed of a polycarbonate resin and a styrene resin. In the case of using a halogen flame retardant, a flame retardant aid mainly composed of a brominated flame retardant represented by tetrabromobisphenol A, its oligomer, a brominated epoxy oligomer, etc., and a metal oxide represented by antimony trioxide. Often used in combination with an agent.
Patent Document 1 includes (A) 1 to 97% by weight of a thermoplastic resin, (B) 1 to 97% by weight of polycarbonate, (C) 1 to 30% by weight of a flame retardant, and (D) 1 to 30% by weight of an inorganic filler. (However, a thermoplastic resin composition containing (A) + (B) + (C) + (D) = 100 wt%) is disclosed. As the flame retardant (C), an oligomer of tetrabromobisphenol A whose end is sealed with tribromophenol is used, and it is used in combination with antimony trioxide or triphenyl phosphate.

  As a non-halogen flame retardant, a phosphorus flame retardant is known. For example, Patent Document 2 discloses a condensation having a polystyrene resin, a polycarbonate resin, a resorcin structure and a 2,6-dialkylphenylene ether structure. A flame retardant resin composition containing a phosphorus compound and having a phosphorus content in the condensed phosphorus compound of 9% by weight or more is disclosed. Further, Patent Document 3 discloses (A) (a) an ethylene-propylene rubber polymer and / or a hydrogenated diene rubber polymer in the presence of (b) an aromatic vinyl compound and a vinyl cyanide compound. 10 to 40 parts by weight of a rubber-reinforced resin obtained by graft polymerization of a monomer component containing as a main component, and (B) 90 to 60 parts by weight of an aromatic polycarbonate having a weight average molecular weight of 16,000 to 30,000 (However, for (A) + (B) = 100 parts by weight) 100 parts by weight in total, (C) 8-25 parts by weight of the condensed phosphate ester, and (D) polytetrafluoroethylene 0.05- A flame retardant thermoplastic resin composition containing 10 parts by weight is disclosed.

  It is also known that the use of an aromatic substituted or unsubstituted phosphate ester as a phosphorus flame retardant can impart moderate flame retardancy and impact resistance to a polymer alloy of polycarbonate and styrene resin. It has been put to practical use as a molding material for equipment, OA equipment and the like.

JP-A-10-130485 Japanese Patent Laid-Open No. 10-168273 JP 2001-234052 A

Conventionally, when a thermoplastic resin composition containing an ABS resin and a polycarbonate resin and a thermoplastic resin composition containing a flame retardant is used, the desired effect can be obtained on the flammability, which is an indicator of flame retardancy. In terms of sex, further improvements have been demanded.
An object of the present invention is to provide a thermoplastic resin composition that provides a molded article having improved impact resistance while maintaining excellent flame retardancy.

The present invention is shown below.
1. [A] a rubbery polymer reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of a rubbery polymer;
[B] polycarbonate resin;
[C] a polymer comprising a structural unit (cx) derived from a vinyl cyanide compound and a structural unit (cy) derived from an aromatic vinyl compound;
[D] a flame retardant;
In a thermoplastic resin composition containing
The polymer [C] includes the polymer (C-1) containing the structural unit (cx) in an amount of 5% by mass or more and ₁ % by mass or less, and the structural unit (cx) in excess of ₁ % by mass. Te polymer comprising at _{r 2} mass% or less and (C-2), the structural unit (cx), becomes from a polymer containing 60 wt% or less beyond the _{r 2} wt% (C-3), and , (R ₂ −r ₁ ) ≧ 3 (mass%),
The content ratios of the polymers (C-1), (C-2) and (C-3) are 5 to 70% by mass and 10 to 80% by mass, respectively, when the total content is 100% by mass. And 10 to 80% by mass,
The rubbery polymer reinforced graft resin [A], the polycarbonate resin [B] and the polymer [C] are contained in an amount of 1 to 80% by mass, respectively, when the total content is 100% by mass, The content of the flame retardant [D] is 10 to 95% by mass and 1 to 70% by mass, and the rubber polymer reinforced graft resin [A], the polycarbonate resin [B], and the polymer [C]. 1 to 30 parts by mass when the total is 100 parts by mass.
2. _{2. The} thermoplastic resin composition according to 1 above, wherein r2 is 15 to 45% by mass.
3. The polymer [C] is a copolymer composed of a structural unit (cx) and a structural unit (cy), and the vinyl cyanide compound and the aromatic vinyl compound are contained in a mass ratio of 5 to 25:95 to The above 1 containing a polymer obtained by polymerization while changing the amount charged from 75 to 25 to 60:75 to 40, or from 25 to 60:75 to 40 to 5 to 25:95 to 75 Or the thermoplastic resin composition of 2.
4). The content ratio of the structural unit (cx) contained in the polymer [C] is 15 to 40% by mass when the total of the structural units constituting the polymer [C] is 100% by mass. The thermoplastic resin composition according to any one of 1 to 3.
5. The polymerizable unsaturated monomer used to form the rubber polymer reinforced graft resin [A] contains a vinyl cyanide compound and an aromatic vinyl compound, and is contained in the rubber polymer reinforced graft resin [A]. When the ratio of the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound is 100% by mass, the ratio is 5 to 40 respectively. The thermoplastic resin composition according to any one of the above 1 to 4, which is mass% and 60 to 95 mass%.
6). r ₁ is 10 to 30% by mass, r ₂ is 20 to 40% by mass,
When the content ratios of the polymers (C-1), (C-2), and (C-3) are 100% by mass of the total of these, 5-55% by mass, 20-70% by mass, respectively. And the thermoplastic resin composition according to any one of 1 to 5 above, which is 20 to 70% by mass.
7). The thermoplastic resin composition according to any one of 1 to 6, wherein the flame retardant [D] is a halogen compound.
8). A molded article comprising the thermoplastic resin composition according to any one of 1 to 7 above.

  According to the thermoplastic resin composition of the present invention, while maintaining excellent flame retardancy, a molded article having further excellent impact resistance as compared with conventional compositions is provided. Therefore, the thermoplastic resin composition of the present invention includes molded products of resin members, outdoor molded products, etc. in the electrical field, electronic field, communication field, OA / home appliance field, building material field, vehicle field, ship field, etc. It is suitable for forming molded articles such as daily miscellaneous goods, sports equipment and stationery.

The present invention will be described in detail below.
In this specification, “(meth) acryl” refers to acryl and methacryl, “(meth) acrylate” refers to acrylate and methacrylate, “(meth) acryloyl group” refers to acryloyl group or methacryloyl group, “Polymer” means homopolymers and copolymers.

The thermoplastic resin composition of the present invention comprises a rubbery polymer reinforced graft resin (hereinafter referred to as “component [A]) obtained by polymerizing a polymerizable unsaturated monomer in the presence of [A] a rubbery polymer. ], [B] polycarbonate resin (hereinafter also referred to as "component [B]"), [C] a structural unit derived from a vinyl cyanide compound (cx), and an aromatic vinyl compound. A polymer containing a structural unit (cy) derived from (hereinafter also referred to as “component [C]”) and [D] a flame retardant (hereinafter also referred to as “component [D]”). the polymer [C], the structural unit (cx), the polymer comprising at most 5 mass% or more _{r 1} wt% and (C-1), the structural unit (cx), and _{r 1} wt% Exceeding r ₂ mass% and containing the polymer (C-2) and the structural unit (cx) in excess of r ₂ mass% And (r ₂ -r ₁ ) ≧ 3 (mass%), and the polymers (C-1), (C-2) and ( The content ratio of C-3) is 5 to 70% by mass, 10 to 80% by mass and 10 to 80% by mass, respectively, when the total of these is 100% by mass. The content ratios of the resin [A], the polycarbonate resin [B], and the polymer [C] are 1 to 80% by mass, 10 to 95% by mass, and 1%, respectively, when the total of these is 100% by mass. The content of the flame retardant [D] is 100 parts by mass of the total of the rubbery polymer reinforced graft resin [A], the polycarbonate resin [B], and the polymer [C]. 1 to 30 parts by mass.

The component [A] is a resin composition (hereinafter referred to as “rubber reinforced resin”) obtained by polymerizing a polymerizable unsaturated monomer (hereinafter referred to as “graft polymerization”) in the presence of a rubbery polymer. The rubbery polymer reinforced graft resin (hereinafter referred to as “graft resin”). This graft resin is a resin in which a (co) polymer containing a structural unit derived from a polymerizable unsaturated monomer is grafted to a rubbery polymer. It consists of a (co) polymer part (graft part) containing structural units derived from monomers.
The rubber-reinforced resin obtained by graft polymerization is usually a (co) polymer not grafted to a rubbery polymer (hereinafter referred to as “ungrafted polymer”) in addition to the rubbery polymer-reinforced graft resin. .)including. The composition of the ungrafted polymer depends on the type of the polymerizable unsaturated monomer used, and the ungrafted polymer is usually contained in the component [C] in the composition of the present invention.

  The rubbery polymer may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C., but may be a diene polymer (hereinafter referred to as “diene rubber”). ) And a non-diene polymer (hereinafter referred to as “non-diene rubber”). Further, the rubbery polymer may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

  Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymer rubbers such as styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymer rubbers such as acrylonitrile / styrene / isoprene copolymers, natural rubber, etc. Is mentioned. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The diene rubber can be used singly or in combination of two or more.

  Examples of the non-diene rubber include ethylene units and ethylene / α-olefin copolymer rubbers including units composed of α-olefins having 3 or more carbon atoms; urethane rubbers; acrylic rubbers; silicone rubbers; Examples include silicone / acrylic IPN rubbers; polymers obtained by hydrogenating (co-) polymers containing units composed of conjugated diene compounds (however, the hydrogenation rate is 50% or more). The hydrogenated copolymer may be a block copolymer or a random copolymer. The non-diene rubber can be used alone or in combination of two or more. Of these, the molded article obtained is excellent in weather resistance, that is, since the change in color tone or mechanical strength is small, the ethylene / α-olefin copolymer rubber, the acrylic rubber, and the conjugated diene A polymer obtained by hydrogenating a (co) polymer containing units composed of a series compound is preferred.

  In the present invention, the component [A] preferably contains a rubbery polymer reinforced graft resin obtained by using a diene rubber as the rubbery polymer. It is also a preferred embodiment that a rubbery polymer reinforced graft resin obtained using a diene rubber is used in combination with a rubbery polymer reinforced graft resin obtained using a non-diene rubber.

  The polymerizable unsaturated monomer is preferably a vinyl monomer. As this vinyl monomer, aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic ester compound, maleimide compound, unsaturated acid anhydride, carboxyl group-containing unsaturated compound, hydroxyl group-containing unsaturated compound (However, the ester part excludes the (meth) acrylic acid ester compound containing a hydroxyalkyl group), an oxazoline group-containing unsaturated compound, and the like. Among these, it is preferable that an aromatic vinyl compound and a vinyl cyanide compound are included.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. However, it shall not have a substituent such as a functional group. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  As described above, since the rubber-reinforced resin obtained by graft polymerization usually contains an ungrafted polymer, when the polymerizable unsaturated monomer contains a vinyl cyanide compound, A polymer will contain the structural unit (cx) derived from a vinyl cyanide compound.

The (meth) acrylic acid ester compound is not particularly limited as long as it is a compound having a (meth) acryloyl group. However, carboxylic acids such as (meth) acrylic acid are not included. Examples thereof include compounds in which the ester moiety contains a hydrocarbon group, and compounds in which the ester moiety contains a hydroxyalkyl group. These compounds can be used alone or in combination of two or more.
Examples of the (meth) acrylic acid ester compound in which the ester portion contains a hydrocarbon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like.
Moreover, as a compound in which an ester part contains a hydroxyalkyl group, (meth) acrylic acid 2-hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3 -Hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, And compounds obtained by adding ε-caprolactone to 2-hydroxyethyl (meth) acrylate.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, and p-hydroxy-α-methyl. Styrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinyl Naphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol 3 Hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, and the like. These compounds can be used alone or in combination of two or more.

  In the present invention, as described above, the polymerizable unsaturated monomer preferably contains an aromatic vinyl compound and a vinyl cyanide compound. In this case, the lower limit of the total amount of the aromatic vinyl compound and the vinyl cyanide compound is preferably 70% by mass, more preferably 80% by mass, and still more preferably 95% by mass. The upper limit is usually 100% by mass. The ratio of aromatic vinyl compound and vinyl cyanide compound is 100% by mass when both are combined. Molding processability, chemical resistance, hydrolysis resistance, impact resistance, rigidity, dimensional stability, molded appearance From the viewpoint of properties, etc., preferably 40 to 95% by mass and 5 to 60% by mass, more preferably 50 to 90% by mass and 10 to 50% by mass, and still more preferably 60 to 85% by mass and 15 to 40% by mass, respectively. %.

As the component [A], preferred graft resins are as follows.
(1) Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber. (2) In the presence of a diene rubber, Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound (3) In the presence of a diene rubber, an aromatic vinyl compound, a vinyl cyanide compound And a graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising a (meth) acrylic acid ester compound. The graft resins shown in these embodiments (1) to (3) are the following (4) to (4) You may use together with the graft resin of (6).
(4) Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a non-diene rubber (5) In the presence of a non-diene rubber Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound (6) In the presence of a non-diene rubber, an aromatic vinyl compound, cyanide Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising a vinyl fluoride compound and a (meth) acrylic acid ester compound The above embodiment (1), (2) or (3), and the above embodiment (4), In the case of combining (5) or (6), an effect of improving the impact resistance can be obtained as compared with the case where the above aspect (4), (5) or (6) is used alone.

  The method for producing the component [A] is not particularly limited, and a known method can be applied. As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used.

  When the component [A] is produced, the polymerization may be started by supplying the polymerizable unsaturated monomers all at once in the reaction system in the presence of the total amount of the rubbery polymer. Alternatively, the polymerization may be performed while continuously feeding. Further, in the presence or absence of a part of the rubbery polymer, polymerization may be started by batch supply of polymerizable unsaturated monomers, or may be divided or continuously supplied. Good. At this time, the remainder of the rubbery polymer may be supplied in a batch, divided or continuously in the middle of the reaction.

  When performing emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.

  Examples of the polymerization initiator include organic peroxides, azo compounds, inorganic peroxides, and redox polymerization initiators.

  Examples of the organic peroxide include tert-butyl hydroperoxide, tert-amyl-tert-butyl peroxide, tert-butyl-tert-hexyl peroxide, tert-amyl-tert-hexyl peroxide, di (tert-hexyl). ) Peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydropa Oxide, 1,3-bis (tert-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butyl kumi Ruperoxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxylaurate, tert-butylperoxymonocarbonate, bis (tert-butylcyclohexyl) peroxy Examples include dicarbonate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, and the like.

  Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, and 2,2′-azobis (2-methylbutyronitrile). 2,2′-azobisdimethylvaleronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2′-azobis (2,4,4) 4-trimethylpentane), 2,2′-azobis (2-methylpropane), dimethyl 2,2′-azobis (2-methylpropionate) and the like.

Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, and ammonium persulfate.
Further, as a redox type polymerization initiator, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate and the like are used as reducing agents, potassium peroxodisulfate, hydrogen peroxide, cumene hydroperoxide, What used tert-butyl hydroperoxide etc. as the oxidizing agent can be used.

The usage-amount of the said polymerization initiator is 0.05-10 mass% normally with respect to the whole quantity of the said polymerizable unsaturated monomer.
The polymerization initiator can be supplied to the reaction system all at once or continuously.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more.

The amount of the chain transfer agent used is usually 0.01 to 5% by mass with respect to the total amount of the polymerizable unsaturated monomer.
The chain transfer agent can be supplied to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more.

  The usage-amount of the said emulsifier is 0.1-10 mass% normally with respect to the whole quantity of the said polymerizable unsaturated monomer.

  Emulsion polymerization can be carried out under known conditions depending on the type of polymerizable unsaturated monomer, polymerization initiator and the like. The latex obtained by this emulsion polymerization is usually subjected to coagulation of the resin component with a coagulant to form a powder or the like. Thereafter, it is purified by washing with water, etc., dried and collected. For coagulation, conventionally known coagulants are used, and inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used.

  When the component [A] is produced by solution polymerization, bulk polymerization, and bulk-suspension polymerization, a known method can be applied.

When the component [A] and the ungrafted polymer are separated from the rubber-reinforced resin containing the component [A] obtained as described above, for example, 10 g of the rubber-reinforced resin is added to 100 to 200 ml of acetone (rubber If the polymer is an acrylic rubber, use acetonitrile) and shake it at 25 ° C for 2 to 3 hours using a shaker etc. to separate the insoluble and soluble components produced. The method of recovery is applied. The acetone-soluble component (acetonitrile-soluble component) corresponds to the ungrafted polymer, and may correspond to the component [C] depending on the type and amount of the polymerizable unsaturated monomer used. .
When the polymerizable unsaturated monomer includes an aromatic vinyl compound and a vinyl cyanide compound, the ungrafted polymer is derived from a structural unit derived from the vinyl cyanide compound and the aromatic vinyl compound. It may contain a structural unit, and in this case, it corresponds to “component [C]” described later.
The ungrafted polymer is prepared by putting a rubber-reinforced resin into acetone (when the rubbery polymer is an acrylic rubber, acetonitrile is used) and shaking using a shaker (temperature 25 ° C., 2 It is a soluble content obtained by centrifugation (temperature 5 ° C., rotation speed 23,000 rpm, 1 hour) using a centrifuge.

  The graft ratio in the component [A] is preferably 20 to 230%, more preferably 30 to 200%, and still more preferably 50, from the viewpoints of moldability, impact resistance of the molded product, molded appearance, and the like. ~ 170%. If this graft ratio is too low, the impact resistance and molded appearance of the molded product may be lowered. On the other hand, if the graft ratio is too high, the moldability is not sufficient and the impact resistance may be lowered.

The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the formula, S represents 1 g of rubber reinforced resin in 20 ml of acetone (when acetonitrile is used when the rubber polymer is acrylic rubber), and shaken using a shaker (temperature 25 ° C., 2 Time) and then using a centrifuge to centrifuge (temperature 5 ° C., rotation speed 23,000 rpm, 1 hour) to separate the insoluble matter and the soluble matter (g) Where T is the mass (g) of the rubbery polymer contained in 1 gram of rubber reinforced resin. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  The graft ratio is, for example, the type and amount of polymerization initiator used in the production of component [A], the type and amount of chain transfer agent, the supply method and supply time of the polymerizable unsaturated monomer, polymerization Temperature etc. can be adjusted by selecting suitably.

  The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component (or acetonitrile-soluble component) of the rubber-reinforced resin is preferably 0.2 to 0.00 from the viewpoint of molding processability and impact resistance. It is 9 dl / g, More preferably, it is 0.25-0.85 dl / g, More preferably, it is 0.3-0.8 dl / g.

Here, the intrinsic viscosity [η] can be obtained, for example, in the following manner.
When determining the graft ratio in the above component [A], the acetone-soluble component (or acetonitrile-soluble component) recovered after centrifugation is dissolved in methyl ethyl ketone, and five different concentrations are prepared. The intrinsic viscosity [η] is determined by measuring the reduced viscosity of each concentration at 30 ° C.

  The intrinsic viscosity [η] is used when producing the component [A], by adjusting the type and amount of polymerization initiator, chain transfer agent, emulsifier, solvent, etc., and further adjusting the polymerization time, polymerization temperature, etc. Can be controlled.

In the composition of the present invention, the component [A] may be included singly or in combination of two or more.
In the present invention, the structural unit (gx) derived from the vinyl cyanide compound and the fragrance in the graft part constituting the graft resin, which is a component [A] composed of one or more of the preferred graft resins exemplified above The proportion of the structural unit (gy) derived from the group vinyl compound is preferably 5 to 40% by mass and 60 to 95% by mass, more preferably 10 to 38% by mass, when the total of both is 100% by mass. % And 62-90% by mass, more preferably 10-35% by mass and 65-90% by mass, still more preferably 18-35% by mass and 65-82% by mass, particularly preferably 23-32% by mass and 68- By using a composition containing one or more of 77% by mass of a graft resin, a molded product having an excellent balance between impact resistance and heat resistance can be obtained. .
The content of the structural units (gx) and (gy) is calculated from the polymerization prescription and the polymerization conversion rate, the method of obtaining the infrared absorption spectrum (IR), the nuclear magnetic resonance spectrum, etc., and further the ozonolysis of the graft resin. Then, it can be obtained by a method used for CHN elemental analysis, liquid chromatographic analysis, or the like.

  The component [B] is not particularly limited as long as it is a polycarbonate resin having a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, and the like. In addition, this component [B] may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). Good.

  Examples of the aromatic polycarbonate include those obtained by melting a transesterification (transesterification reaction) of an aromatic dihydroxy compound and a carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, and pyridine and phosgene. What was obtained by the pyridine method using a reaction product etc. can be used.

  The aromatic dihydroxy compound may be any compound having two hydroxyl groups in the molecule, such as dihydroxybenzene such as hydroquinone and resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis ( -Hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-methyl) Phenyl) fluorene, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) diphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxy) Phenyl) ketone, bis (p-hydroxyphenyl) ether, bis (p-hydroxy) Phenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Examples thereof include bis (p-hydroxyphenyl) sulfoxide. These can be used alone or in combination of two or more.

  Of the aromatic hydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like. Of these, bisphenol A is particularly preferred.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

  The average molecular weight and molecular weight distribution of the component [B] are not particularly limited as long as the composition has moldability. The lower limit of the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 15,000 to 40,000, more preferably 16,000 to 30,000, still more preferably 17 , 8,000 to 28,000. As the weight average molecular weight increases, the notched impact strength increases. On the other hand, the fluidity is not sufficient and the moldability tends to be inferior.

  In the composition of the present invention, the component [B] may be included singly or in combination of two or more.

The component [C] is a copolymer including a structural unit (cx) derived from a vinyl cyanide compound and a structural unit (cy) derived from an aromatic vinyl compound, and further has another structural unit (hereinafter, (Also referred to as “structural unit (cz)”). This component [C] is a copolymer comprising three kinds of copolymers containing structural units (cx) and (cy), that is, a weight containing 5% by mass or more and ₁ % by mass or less of the above structural unit (cx). Polymer (C-1) composed of at least one kind of polymer and polymer composed of at least one kind of polymer containing the structural unit (cx) in excess of r ₁ % by mass and ₂ % by mass or less (C -2) and a polymer (C-3) composed of at least one polymer including the structural unit (cx) in an amount of more than r ₂ mass% and 60 mass% or less, and (r ₂ −r ₁ ) ≧ 3 (mass%). In addition, the content ratios of the polymers (C-1), (C-2), and (C-3) are 5 to 70% by mass and 10 to 80%, respectively, when the total of these is 100% by mass. Mass% and 10 to 80 mass%.

For the vinyl cyanide compound forming the structural unit (cx), the description of the vinyl cyanide compound that can be used as the polymerizable unsaturated monomer used for forming the component [A] is applied. The structural unit (cx) contained in the component [C] may be only one type or two or more types. As the vinyl cyanide compound, acrylonitrile is preferable.
The content of the structural unit (cx) contained in the component [C] is preferably 15 to 40% by mass, more preferably 18 to 20%, assuming that the total of the structural units constituting the component [C] is 100% by mass. It is 37 mass%, More preferably, it is 21-35 mass%. When the content of the structural unit (cx) is 15 to 40% by mass, a molded product having excellent moldability (fluidity) of the composition and excellent heat resistance can be obtained.

With respect to the aromatic vinyl compound that forms the structural unit (cy), the description of the aromatic vinyl compound that can be used as the polymerizable unsaturated monomer used in the formation of the component [A] is applied. The structural unit (cy) contained in the component [C] may be only one type or two or more types. As the aromatic vinyl compound, styrene and α-methylstyrene are preferable.
The content of the structural unit (cy) contained in the component [C] is preferably 60 to 85% by mass, more preferably 63 to 63% when the total of the structural units constituting the component [C] is 100% by mass. 82 mass%, more preferably 65-79 mass%. When the content of the structural unit (cy) is 60 to 85% by mass, a molded product having excellent molding processability (fluidity) of the composition and excellent heat resistance can be obtained.

Examples of the monomer that forms the structural unit (cz) include (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and oxazolines. And group-containing unsaturated compounds.
When the component [C] includes a structural unit (cz), the upper limit of the content is the sum of the structural units constituting the component [C], that is, the structural units (cx), (cy), and (cz). ) Is 100% by mass, preferably 30% by mass, more preferably 15% by mass.
In addition, this structural unit (cz) may be included in all of the polymers (C-1), (C-2), and (C-3), or may be included in part.

  Although the said component [C] consists of a polymer (C-1), (C-2), and (C-3), these polymers (C-1), (C-2), and (C-3) ), The type of the structural unit (cx) may be the same or different. The type of the structural unit (cy) may also be the same or different. The type of the structural unit (cz) may also be the same or different.

The polymers (C-1), (C-2) and (C-3) are copolymers having different structural unit (cx) contents, and the structural unit (cx) contents in turn. It is a copolymer with a large amount.
The component [C] is composed of the polymers (C-1), (C-2) and (C-3) having the above-described structure, thereby improving the compatibility between the components [A] and [B]. A molded product having a high effect and excellent balance between impact resistance and heat resistance can be efficiently produced. In particular, the use of the component [C] made of a copolymer aggregate in which the content of the structural unit (cx) is preferably in the range of 15 to 40% by mass as described above, the above effects are remarkable. .

The polymer (C-1) is a copolymer containing the structural unit (cx) at 5 mass% or more and r ₁ mass% or less, and is composed of the structural units (cx) and (cy) as described above. It may be a copolymer or a copolymer composed of structural units (cx), (cy), and (cz). Moreover, as mentioned above, this polymer (C-1) can consist of at least 1 type of the copolymer containing the predetermined amount of a structural unit (cx). For example, when it is composed of two kinds of copolymers and 5 ≦ r ₁₁ <r ₁₂ ≦ r ₁ , a copolymer containing ₁₁ mass% of structural units (cx) and structural units (cx) And a polymer (C-1) consisting of a copolymer containing ₁₂ % by mass of r.
r ₁ is preferably 10 to 30% by mass, more preferably 15 to 30% by mass, still more preferably 17 to 28% by mass, and particularly preferably 22 to 27% by mass. When the content of the structural unit (cx) is 2 or more types of copolymers having a content of 5% by mass or more and r ₁ % by mass or less, the “content of the structural unit (cx) contained in the polymer (C-1)” The value shown as is an average value calculated from the content of the structural unit (cx) contained in each copolymer.
The polymer (C-2) is a copolymer containing the structural units (cx) and (cy) containing the structural unit (cx) in an amount exceeding ₁ mass% and ₂ mass% or less. Thus, it may be a copolymer composed of structural units (cx) and (cy), or a copolymer composed of structural units (cx), (cy) and (cz). Moreover, as mentioned above, this polymer (C-2) can consist of at least 1 type of the copolymer containing the predetermined amount of a structural unit (cx). For example, when it is composed of two types of copolymers and r ₁ <r ₂₁ <r ₂₂ ≦ r ₂ , a copolymer containing ₂₁ mass% of structural units (cx) and structural units (cx ) And a copolymer (C-2) comprising ₂₂ % by mass of r.
r ₂ is preferably 15 to 45% by mass, more preferably 20 to 42% by mass, still more preferably 22 to 40% by mass, still more preferably 25 to 35% by mass, and particularly preferably 27 to 33% by mass. . When two or more types of copolymers having a structural unit (cx) content exceeding r ₁ % by mass and r ₂ % by mass or less are contained, “the structural unit (cx) contained in the polymer (C-2)” The value shown as “content” is an average value calculated from the content of the structural unit (cx) contained in each copolymer.
In the present invention, when r ₂ is 15 to 45% by mass, particularly in the composition of the present invention, the compatibility between the component [A] and the polymer (C-2) is improved. B] and the polymers (C-1) and (C-3) are also improved, resulting in excellent compatibility between the components [A] and [B]. The molded article has an excellent balance between impact resistance and heat resistance.
In the present invention, the relationship between r ₁ and r _{2 at} which the effect of balancing impact resistance and heat resistance becomes significant is (r ₂ −r ₁ ) ≧ 3 (mass%), preferably (r ₂ −r ₁ ) ≧ 4 (mass%), more preferably (r ₂ −r ₁ ) ≧ 4.5 (mass%). However, usually (r ₂ −r ₁ ) ≦ 10 (mass%), preferably (r ₂ −r ₁ ) ≦ 9 (mass%), more preferably (r ₂ −r ₁ ) ≦ 7 (mass%). It is. When (r ₂ −r ₁ ) <3 (mass%), the effect of the present invention cannot be sufficiently obtained.
The polymer (C-3) is a copolymer containing the structural unit (cx) in an amount exceeding ₂ mass% and not exceeding 60 mass%, and as described above, the structural units (cx) and (cy) It may be a copolymer consisting of or a copolymer consisting of structural units (cx), (cy) and (cz). Moreover, as mentioned above, this polymer (C-3) can consist of at least 1 type of the copolymer containing the predetermined amount of a structural unit (cx). For example, when it is composed of two types of copolymers and r ₂ <r ₃₁ <r ₃₂ ≦ 60, a copolymer containing ₃₁ % by mass of structural unit (cx) and structural unit (cx) And a polymer (C-3) composed of a copolymer containing ₃₂ % by mass of r.
When the content of the structural unit (cx) exceeds ₂ % by mass and contains 2 or more types of copolymers of 60% by mass or less, “content of structural unit (cx) contained in polymer (C-3)” The value shown as “amount” is an average value calculated from the content of the structural unit (cx) contained in each copolymer.

The content ratio of the polymers (C-1), (C-2) and (C-3) constituting the component [C] is preferably 5 to 5% when the total content thereof is 100% by mass. 70 mass%, 10-80 mass% and 10-80 mass%, more preferably 5-55 mass%, 20-70 mass% and 20-70 mass%, still more preferably 7-50 mass%, 25-50 mass% % And 30 to 65% by mass, particularly preferably 9 to 45% by mass, 30 to 50% by mass and 32 to 63% by mass.
In addition, r ₁ is 10 to 30% by mass and r ₁ is significant in improving the fluidity of the composition and the impact resistance of the obtained molded product while maintaining excellent flame retardancy. ₂ is 20 to 40% by mass, and the content ratios of the polymers (C-1), (C-2), and (C-3) are each preferably 100% by mass. Is 5 to 70 mass%, 10 to 80 mass% and 10 to 80 mass%, more preferably 5 to 55 mass%, 20 to 70 mass% and 20 to 70 mass%, still more preferably 7 to 50 mass%, 25 It is -50 mass% and 30-65 mass%, Most preferably, it is 9-45 mass%, 30-50 mass%, and 32-63 mass%.

When the mixture of the polymers (C-1), (C-2) and (C-3) is subjected to a liquid chromatography gradient analysis using n-heptane, 1,2-dichloroethane, acetonitrile or the like, a structure is obtained. units (cx) on the horizontal axis, it is possible to obtain a distribution of the amount of the copolymer containing a specific amount of structural units (cx) and the vertical axis, the polymer in the case of determining the r ₁ and r ₂ (C -1), the content ratio of (C-2) and (C-3) can be calculated | required.

The polymer (C-1) is preferably a copolymer composed of structural units (cx) and (cy), and the copolymer is composed of structural units (cx), (cy) and (cz). You may use together with the copolymer which becomes. As the monomer forming the structural unit (cz), maleimide compounds such as N-phenylmaleimide and (meth) acrylic acid ester compounds such as methyl methacrylate are preferable.
The polymer (C-2) is preferably a copolymer composed of structural units (cx) and (cy), and the copolymer is composed of structural units (cx), (cy) and (cz). You may use together with the copolymer which becomes. As the monomer forming the structural unit (cz), maleimide compounds such as N-phenylmaleimide and (meth) acrylic acid ester compounds such as methyl methacrylate are preferable.
The polymer (C-3) is preferably a copolymer composed of structural units (cx) and (cy), and the copolymer includes structural units (cx), (cy) and (cz). You may use together with the copolymer which consists of. As the monomer forming the structural unit (cz), maleimide compounds such as N-phenylmaleimide and (meth) acrylic acid ester compounds such as methyl methacrylate are preferable.

The method for producing the polymers (C-1), (C-2) and (C-3) constituting the component [C] is not particularly limited. Emulsion polymerization, solution polymerization, bulk polymerization and the like can be applied. At this time, the polymer to be mixed is preferably a polymer obtained by the same polymerization method, more preferably a preparation method or a solution polymerization in which latexes obtained by emulsion polymerization are mixed. It can be set as the preparation method which mixes the obtained polymerization solutions. Furthermore, after manufacturing the said polymers (C-1), (C-2), and (C-3) separately, a component [C] can be formed by mixing. Moreover, in one reaction system, after producing any 2 types of polymers, it can mix with another 1 type and can form component [C]. Furthermore, you may manufacture three types of polymers in one reaction system.
In addition, since the ungrafted polymer contained in the rubber reinforced resin used for forming the component [A] may be contained in the polymer (C-1), (C-2) or (C-3). The ungrafted polymer can be used as appropriate.

  In one reaction system, when producing two or three kinds of the polymers (C-1), (C-2) and (C-3), each monomer for the reaction system A method of proceeding polymerization while changing the charged amount (feed amount, feed rate) of the body (vinyl cyanide compound, aromatic vinyl compound, etc.) is applied. For example, a power feed method disclosed in JP-A-50-63085 can be applied. According to this power feed method, since a plurality of monomers can be sequentially polymerized at different ratios, while changing the charged amount (feed amount, feed rate) of all monomers, Containing a collection of copolymers in which the content ratio of the structural unit (cx) is in a wide range of 5 to 60% by mass by continuously or intermittently supplying the vinyl cyanide compound to the reaction system. It can be. In the present invention, the copolymer aggregate obtained by the power feed method includes the polymers (C-1), (C-2), and (C-3) at a predetermined ratio. Therefore, it is suitable as a copolymer for component [C].

  In the present invention, a copolymer obtained by polymerization while changing the charged amount of the vinyl cyanide compound and the aromatic vinyl compound from 5 to 25:95 to 75 to 25 to 60:75 to 40 by mass ratio. It is obtained by polymerizing the polymer and / or the charged amount of the vinyl cyanide compound and the aromatic vinyl compound while changing the mass ratio from 25-60: 75-40 to 5-25: 95-75. The copolymer is preferably part or all of the component [C]. In addition, changing the charge amount means increasing or decreasing the supply amount of the vinyl cyanide compound or the aromatic vinyl compound, and changing the use amount in the middle, 25:75 to 25:75 This method is not included. When a composition containing a copolymer obtained by the above power feed method is used, a molded product having excellent fluidity and a good balance between impact resistance and heat resistance can be efficiently produced.

  In addition, when a monomer (other monomer) other than the vinyl cyanide compound and the aromatic vinyl compound is used, the above-mentioned vinyl cyanide compound and (mixture of the aromatic vinyl compound and the other monomer) are charged. Copolymer obtained by polymerization while changing the mass ratio from 5 to 25:95 to 75 to 25 to 60:75 to 40, and / or the vinyl cyanide compound and (aromatic vinyl) A copolymer obtained by polymerizing the mixture of the mixture of the compound and other monomers) while changing the mass ratio from 25-60: 75-40 to 5-25: 95-75, It is preferable to use part or all of the component [C].

  The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component [C] is preferably 0.2 to 0.9 dl / g, more preferably 0, from the viewpoint of moldability and impact resistance of the molded product. .25 to 0.85 dl / g, more preferably 0.3 to 0.8 dl / g. In addition, when measuring the said intrinsic viscosity [(eta)], the measuring method with respect to the ungrafted polymer contained in the rubber reinforced resin obtained by graft polymerization as mentioned above can be applied.

  In the present invention, the content ratios of the components [A], [B] and [C], which are resin components, depend on the type of the component [D] described later in order to obtain the desired performance. When the component [D] is a halogen compound, the ratio of the components [A], [B], and [C] is 1 to 80 masses when the total of the three components is 100 mass%. %, 10 to 95% by mass and 1 to 70% by mass, preferably 3 to 65% by mass, 20 to 90% by mass and 2 to 60% by mass, more preferably 5 to 55% by mass and 30 to 80% by mass. And 5 to 50 mass%, more preferably 10 to 45 mass%, 40 to 70 mass%, and 10 to 40 mass%. By using the content ratios of the components [A], [B] and [C], a molded product having excellent impact resistance, heat resistance, fluidity and flame retardancy can be obtained.

  Moreover, when the said component [D] is a flame retardant (phosphorus compound etc.) except a halogen compound, when the sum total of the said 3 component shall be 100 mass%, component [A], [B] and [ C] is 1 to 80% by mass, 10 to 95% by mass and 1 to 70% by mass, respectively, preferably 1 to 60% by mass, 30 to 93% by mass and 1 to 50% by mass, and more preferably. Is 2-40% by mass, 50-92% by mass and 2-40% by mass, more preferably 3-20% by mass, 65-90% by mass and 3-25% by mass. By using the content ratios of the components [A], [B] and [C], a molded product having excellent impact resistance, heat resistance, fluidity and flame retardancy can be obtained.

The composition of the present invention may contain other polymers (other resins).
Examples of other polymers include polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyester resins, polyamide resins, and fluororesins.
When the composition of the present invention contains another polymer (other resin), the upper limit of the content is based on a total of 100 parts by mass of the above components [A], [B] and [C]. Preferably it is 30 mass parts, More preferably, it is 20 mass parts.

In the composition of the present invention, the content of the rubbery polymer derived from the component [A] is preferably 3 to 35 mass with respect to the entire composition from the viewpoint of moldability and impact resistance of the molded product. %, More preferably 5 to 25% by mass.
When the component [A] is composed of a graft resin obtained by using a diene rubber and a graft resin obtained by using a non-diene rubber, the diene rubber and the non-diene The proportion of rubber is selected.
From the viewpoint of the balance between the mechanical strength and the appearance of the molded product, the ratio of the diene rubber and the non-diene rubber is preferably 40 to 95% by mass and 5%, respectively, when the total of both is 100% by mass. It is -60 mass%, More preferably, it is 50-90 mass% and 10-50 mass%.
Moreover, from the viewpoint of the balance between weather resistance and chemical resistance, when the total of both is 100% by mass, the proportions of diene rubber and non-diene rubber are preferably 5 to 60% by mass and 40 to 40%, respectively. It is 95 mass%, More preferably, it is 10-50 mass% and 50-90 mass%.

The composition of the present invention contains a flame retardant [D].
Examples of the component [D] include halogen compounds, phosphorus compounds, guanidine compounds, silicone compounds, and the like. These can be used alone or in combination of two or more.

As halogen compounds,
(D1) Brominated polyethylene, tetrabromoethane, tetrabromocyclooctane, hexabromocyclododecane, dibromoethyldibromocyclohexane, dibromodimethylhexane, 2- (bromomethyl) -2- (hydroxymethyl) -1,3-propanediol, Dibromoneopentyl glycol, tribromoneopentyl alcohol, pentaerythrityl tetrabromide, monobromodipentaerythritol, dibromodipentaerythritol, tribromodipentaerythritol, tetrabromodipentaerythritol, pentabromodipentaerythritol, hexabromodipentaerythritol Brominated aliphatic compounds such as hexabromotripentaerythritol, polybrominated pentaerythritol, or derivatives thereof, Bromine cycloaliphatic compound or a derivative thereof;
(D2) Tribromo of tetrabromobisphenol A, tetrabromobisphenol S, tetrabromobisphenol A-diallyl ether, tetrabromobisphenol A-dimethallyl ether, tetrabromobisphenol A-diglycidyl ether, tetrabromobisphenol A-diglycidyl ether Phenol adduct, tetrabromobisphenol A-bis (2-hydroxydiethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (2-bromoethyl ether), tetrabromo Bisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), tetra Romo bisphenol A- polycarbonate oligomer, tetrabromobisphenol A- diglycidyl ethers such as brominated bisphenol adduct epoxy oligomer, brominated bisphenols or derivatives thereof;
(D3) hexabromobenzene, pentabromotoluene, ethylenebispentabromodiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, bis (2,4,6-tribromophenoxy) ethane, tetrabromophthalic anhydride, octabromotrimethylphenylindane, Tribromophenyl allyl ether, 2,3-dibromopropyl pentabromophenyl ether, octabromo-1,1,3-trimethyl-1-phenylindane, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, ethane-1 , 2-bis (pentabromophenyl), bis (2,4,6-tribromophenoxy) ethane, ethylenebistetrabromophthalimide, polydibromophenylene Oxide, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, tris (2,3-dibromopropyl-1) isocyanurate, tris (tribromophenyl) cyanurate, atactic Brominated aromatic compounds or derivatives thereof, such as brominated polystyrene having a structure and brominated styrene-propylene copolymer having an atactic structure;
(D4) Pentabromobenzyl acrylate, atactic brominated styrene / methyl methacrylate copolymer, atactic brominated styrene / methyl methacrylate / glycidyl methacrylate copolymer, atactic brominated styrene / glycidyl methacrylate copolymer Brominated (meth) acrylic compounds such as polymers and polypentabromobenzyl acrylate;
(D5) Bromine atom and nitrogen atom-containing compounds such as ethylenebisdibromonorbornane dicarboximide and tris (2,3-dibromopropyl) isocyanurate;
(D6) Chlorine atom-containing compounds such as chlorinated paraffin, chlorinated naphthalene, perchloropentadecane, chlorinated aromatic compounds, and chlorinated alicyclic compounds;
(D7) Brominated inorganic compounds such as ammonium bromide.

〔式中、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ、互いに独立して、アリール基又はアラルキル基であり、Ｘはアリーレン基であり、ｊ、ｋ、ｌ及びｍは、それぞれ、互いに独立して、０又は１であり、Ｎは１〜５の整数である。〕 Examples of phosphorus compounds include phosphoric acid esters represented by the following general formula (I) and salts thereof, phosphorous acid esters represented by the following general formula (II) and salts thereof, and represented by the following general formula (III). Phosphonic acid esters and salts thereof, condensed phosphates represented by the following general formula (IV), phosphazene derivatives, and the like.
O = P (OR ¹ ) _s (OM ^{n +} _{1 / n} ) _3-s (I)
[In the formula, each R ¹ is independently a hydrocarbon group having 1 to 30 carbon atoms, and each M is independently a hydrogen atom, or Group 1A, Group 1B of the periodic table, It is a metal atom selected from Group 2A and Group 2B, s is 1, 2 or 3, and n is 1 or 2. ]
P (OR ¹ ) _t (OM ^{n +} _{1 / n} ) _3-t (II)
[In the formula, each R ¹ is independently a hydrocarbon group having 1 to 30 carbon atoms, and each M is independently a hydrogen atom, or Group 1A, Group 1B of the periodic table, It is a metal atom selected from Group 2A and Group 2B, t is 1, 2 or 3, and n is 1 or 2. ]
O = P (R ² ) (OM ^{n +} _{1 / n} ) ₂ (III)
[Wherein, R ² is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and each M is independently a hydrogen atom, or Group 1A, Group 1B of the periodic table, It is a metal atom selected from Group 2A and Group 2B, and n is 1 or 2. However, the case where all of R ² and M are hydrogen atoms is excluded. ]

[Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an aryl group or an aralkyl group, X is an arylene group, j, k, l and m are Independently of each other, it is 0 or 1, and N is an integer of 1 to 5. ]

In the phosphoric acid ester represented by the general formula (I), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, but may be an aliphatic hydrocarbon group (which may be linear or branched). , An alicyclic hydrocarbon group (which may have a substituent) and an aromatic hydrocarbon group (which may have a substituent), and a saturated type or an unsaturated type But you can. The number of carbon atoms is preferably 6 to 28, more preferably 10 to 24. In addition, when s = 2 or s = 3, a ring structure may be formed by two R ¹ .

The phosphoric acid ester represented by the general formula (I) is a monoester when s = 1, for example, methyl dihydrogen phosphate, ethyl dihydrogen phosphate, hexyl dihydrogen phosphate, octyl dihydrogen. Examples include phosphate, nonyl dihydrogen phosphate, decyl dihydrogen phosphate, dodecyl dihydrogen phosphate, octadecyl dihydrogen phosphate, nonylphenyl dihydrogen phosphate, and the like. When s = 2, it is a diester such as dimethyl phosphate, diethyl phosphate, dihexyl phosphate, dioctyl phosphate, di (2-ethylhexyl) phosphate, dinonyl phosphate, didecyl phosphate, didodecyl phosphate, ditetradecyl phosphate, diester Examples include octadecyl phosphate, diphenyl phosphate, dibenzyl phosphate and the like. It can also be a metal salt of each compound. Further, when s = 3, it is a triester, for example, trimethyl phosphate, triethyl phosphate, trihexyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, Examples include cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate and the like.
Furthermore, in the case of s = 2, to form a ring structure with ^{R 1} each other, sodium 2,2-methylenebis (4,6-di -tert- butylphenyl) phosphate, sodium 2,2'-methylenebis ( 4,6-di-tert-butylphenyl) phosphate, lithium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, sodium-2,2′-ethylidenebis (4,6-di) -Tert-butylphenyl) phosphate, lithium-2,2'-ethylidenebis (4,6-di-tert-butylphenyl) phosphate, and the like can also be used.

In the phosphite represented by the above general formula (II), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, but may be an aliphatic hydrocarbon group (straight or branched). ), An alicyclic hydrocarbon group (which may have a substituent) and an aromatic hydrocarbon group (which may have a substituent), and may be saturated or unsaturated. It may be a mold. The number of carbon atoms is preferably 6 to 28, more preferably 10 to 24.

  The phosphite ester represented by the general formula (II) is a monoester when t = 1, for example, methyl dihydrogen phosphite, ethyl dihydrogen phosphite, hexyl dihydrogen phosphite, Octyl dihydrogen phosphite, nonyl dihydrogen phosphite, decyl dihydrogen phosphite, dodecyl dihydrogen phosphite, octadecyl dihydrogen phosphite, hexacosyl dihydrogen phosphite, dodecyl phenyl dihydrogen phosphite Etc. When t = 2, it is a diester, for example, dimethyl hydrogen phosphite, diethyl hydrogen phosphite, dihexyl hydrogen phosphite, dioctyl hydrogen phosphite, di (2-ethylhexyl) hydrogen phosphite, dinonyl hydro Genphosphite, didecyl hydrogen phosphite, didodecyl hydrogen phosphite, ditetradecyl hydrogen phosphite, dioctadecyl hydrogen phosphite, octyl benzyl hydrogen phosphite, nonyl tridecyl hydrogen phosphite, butyl eico Examples thereof include silhydrogen phosphite, diphenyl hydrogen phosphite, dibenzyl hydrogen phosphite and the like. When t = 3, it is a triester, for example, trimethyl phosphite, triethyl phosphite, trihexyl phosphite, trioctyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tridodecyl phosphite Phyto, trioctadecyl phosphite, triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, diphenyl decyl Examples thereof include phosphite and phenyl didecyl phosphite. It can also be a metal salt of each compound.

In the phosphonate represented by the general formula (III), R ² is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. In the latter case, an aliphatic hydrocarbon group (straight chain) Or an alicyclic hydrocarbon group (which may have a substituent) and an aromatic hydrocarbon group (which may have a substituent). Also, it may be saturated or unsaturated. The number of carbon atoms is preferably 6 to 28, more preferably 10 to 24.

  Examples of the phosphonic acid ester represented by the above general formula (III) include dimethyl phosphonate, diethyl phosphonate, dibutyl phosphonate, dihexyl phosphonate, dioctyl phosphonate, didecyl phosphonate, didodecyl phosphonate, dioctadecyl phosphonate, and phosphone. Examples include diphenyl acid, ditolyl phosphonate, dimethyl methyl phosphonate, diethyl ethyl phosphonate, diisopropyl methyl phosphonate, dioctyl phenyl phosphonate, and diphenyl methyl phosphonate. It can also be a metal salt of each compound.

In the condensed phosphate compound represented by the general formula (IV), R ⁴ , R ⁵ , R ⁶ and R ⁷ are aryl groups or aralkyl groups, preferably cresyl groups, phenyl groups, xylenyl groups, propyls. A phenyl group and a butylphenyl group; X is an arylene group, preferably a hydrocarbon group derived from resorcinol, hydroquinone or bisphenol A.

  Examples of the phosphazene derivatives include cyclic phosphazene compounds (cyclophosphazene compounds), chain phosphazene compounds, and crosslinked phenoxyphosphazene compounds.

  In addition, aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based compound, molybdenum-based compound, zinc stannate, and the like can be used.

Content of the said component [D] is suitably selected according to the kind, but when the sum total of the said component [A], [B] and [C] is 100 mass parts, it is 1-30 mass parts It is.
When the component [D] is a halogen compound, the content is preferably 4 to 20 parts by mass when the total of the above components [A], [B] and [C] is 100 parts by mass. Preferably it is 8-15 mass parts.
Further, when the component [D] is a flame retardant excluding the halogen compound (phosphorus compound, etc.), the content thereof is 100 parts by mass of the total of the components [A], [B] and [C]. In the case, it is preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass.

In addition, when making a thermoplastic resin composition contain component [D], it is preferable to use a flame retardant adjuvant. As this flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples include ammonium polyphosphate, tin oxide, polytetrafluoroethylene, and the like. These may be used alone or in combination of two or more.
By using polytetrafluoroethylene, dripping during combustion can be prevented. A preferred number average molecular weight for sufficiently obtaining this action is 1,000,000 or more. In order to maintain impact resistance, the average particle size is preferably 600 μm or less, more preferably 400 μm or less.

  The composition of the present invention may further comprise a filler, a plasticizer, an antioxidant, an ultraviolet absorber, an anti-aging agent, a lubricant, a weathering stabilizer, a light stabilizer, a heat stabilizer, a charge, depending on the purpose and application. It may contain an inhibitor, a water repellent, an oil repellent, an antifoaming agent, an antibacterial agent, an antiseptic, a colorant (pigment, dye, etc.), a fluorescent whitening agent, a conductivity imparting agent and the like.

  Examples of the filler include heavy calcium carbonate, colloidal calcium carbonate, light calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, magnesium hydroxide, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, Ground silica, fused silica, kaolin, diatomaceous earth, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloon, shirasu balloon, saran Examples include balloons and phenol balloons. These can be used alone or in combination of two or more.

  Examples of the plasticizer include phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, aliphatic monobasic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, polyhydric alcohol ester, epoxy plasticizer, high Examples include molecular plasticizers and chlorinated paraffins. These can be used alone or in combination of two or more.

  Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds. These can be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and triazine compounds. These can be used alone or in combination of two or more.

  Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiols. Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphoric compounds, and the like. These can be used alone or in combination of two or more.

  Examples of the lubricant include wax, silicone, and lipid. These can be used alone or in combination of two or more.

  The molded product of the present invention comprises the above thermoplastic resin composition of the present invention, or the raw material components that will form its constituent components, an injection molding device, a sheet extrusion molding device, a profile extrusion molding device, a hollow molding device, It can be manufactured by processing with a known molding apparatus such as a compression molding apparatus, a vacuum molding apparatus, a foam molding apparatus, a blow molding apparatus, an injection compression molding apparatus, a gas assist molding apparatus, or a water assist molding apparatus. That is, the molded article of the present invention contains the thermoplastic resin composition of the present invention.

When a molded product is produced using the molding apparatus, the molding temperature and mold temperature are determined depending on the types of the components [A], [B] and [C], or the raw material components used (other polymers). Selection), etc., as appropriate.
For example, when the said component [A] contains the rubber-like polymer reinforcement | strengthening graft resin which uses a diene rubber, the cylinder temperature at the time of shaping | molding is 230 degreeC-280 degreeC normally. The mold temperature is usually 20 ° C to 90 ° C.
In any of the above cases, when the molded product is large, the cylinder temperature is generally set higher than the above temperature.

  The molded product of the present invention may be provided with a through hole, a groove, a concave portion, a convex portion, and the like at an arbitrary position according to the purpose and application.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Production Raw Materials The raw materials (resin component and polymer component) used for the production of the thermoplastic resin composition are as follows. The measurement of the graft ratio, intrinsic viscosity [η], etc. was performed according to the method described above.
1-1. Raw material [P]
This raw material [P] is a rubber-reinforced aromatic vinyl resin obtained by the following Synthesis Examples 1 to 3, and includes a rubbery polymer-reinforced graft resin [A] and an ungrafted (co) polymer (heavy In some cases, it may contain a coalescence [C].

Synthesis Example 1 (Synthesis of raw material P1)
In a glass flask equipped with a stirrer, in a nitrogen stream, 42 parts of ion-exchanged water, 0.35 part of potassium rosinate, 0.2 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 80 parts of latex containing 32 parts, 19 parts of latex containing 8 parts of styrene / butadiene copolymer rubber (styrene unit amount 30%) having an average particle size of 600 nm, 14 parts of styrene and 6 parts of acrylonitrile are accommodated and stirred. The temperature rose. When the internal temperature reached 40 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.3 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization.
After polymerizing for 30 minutes, 45 parts of ion-exchanged water, 0.7 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.13 part of tert-dodecyl mercaptan and 0.1 part of cumene hydroperoxide were added for 3 hours. Over time. Thereafter, the polymerization was further continued for 1 hour, and 0.2 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to the reaction system to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and wash it with water. Thereafter, it was washed and neutralized with an aqueous potassium hydroxide solution, further washed with water and then dried to obtain a rubber-reinforced aromatic vinyl resin P1. Graft ratio in the graft resin (component [A]) contained in this resin P1 is 55%, and in the graft part, a structural unit derived from a vinyl cyanide compound (gx) and a structural unit derived from an aromatic vinyl compound (gy) When the total of both is 100%, the ratio is 26% and 74%, and the content of the ungrafted (co) polymer (hereinafter referred to as “acetone-soluble matter”) is 38%. The intrinsic viscosity [η] of this acetone-soluble component (in methyl ethyl ketone, 30 ° C.) was 0.45 dl / g.

Synthesis Example 2 (Synthesis of raw material P2)
In a glass flask equipped with a stirrer, 85 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 0.45 parts of sodium bicarbonate, 0.15 parts of sodium carbonate, sodium naphthalenesulfonate formalin condensation in a nitrogen stream 0.5 part salt and 0.03 part sodium dithionite were added. As a monomer, 5 parts of n-butyl acrylate was added, and the temperature was increased while stirring. When the internal temperature reached 75 ° C., 0.12 part of potassium persulfate was added to initiate polymerization. After polymerization for 60 minutes, 0.06 part of potassium persulfate, 44.5 parts of n-butyl acrylate and 0.5 part of allyl methacrylate were continuously added over 3 hours, and the polymerization was further continued for 1 hour. Thereafter, it is cooled to 65 ° C., 33 parts of ion-exchanged water, 0.8 part of potassium rosinate and 0.07 part of tert-butyl hydroperoxide are added, 0.4 parts of sodium pyrophosphate, and 7 water of ferrous sulfate. A solution obtained by dissolving 0.01 part of Japanese product and 0.3 part of glucose in 15 parts of ion-exchanged water, 10.95 parts of styrene, and 4.05 parts of acrylonitrile were added, and the temperature was raised to 75 ° C. After polymerizing for 60 minutes, 25.55 parts of styrene, 9.45 parts of acrylonitrile, 0.1 part of tert-dodecyl mercaptan and 0.2 part of tert-butyl hydroperoxide were continuously added over 4 hours. The polymerization was continued for 1 hour. After coagulation with a magnesium sulfate solution, washing with water, and drying, a rubber-reinforced aromatic vinyl resin P2 was obtained. Graft ratio in the graft resin (component [A]) contained in the resin P2 is 40%, and in the graft part, a structural unit derived from a vinyl cyanide compound (gx) and a structural unit derived from an aromatic vinyl compound (gy) When the sum of the two is 100%, the ratio is 25% and 75%, and the content of the ungrafted (co) polymer (acetone soluble component) is 30%. The intrinsic viscosity [η] of minutes (in methyl ethyl ketone, 30 ° C.) was 0.43 dl / g.

Synthesis example 3 (synthesis of raw material P3)
A 20-liter stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, and the like is placed on an ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Mooney viscosity (ML _{1 + 4).} , 100 ° C.) = 20) 25 parts, 10.95 parts of styrene, 4.05 parts of acrylonitrile, 0.5 part of tert-dodecyl mercaptan and 110 parts of toluene were heated and heated. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.09 part of tert-butyl peroxyisopropyl monocarbonate was added, and the temperature was further increased. While maintaining the internal temperature at 100 ° C., the polymerization was started at a stirring rotation speed of 100 rpm. After polymerization for 60 minutes, 43.8 parts of styrene, 16.2 parts of acrylonitrile and 0.36 parts of tert-butylperoxyisopropyl monocarbonate were continuously added over 3 hours. After 4 hours from the start of polymerization, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion rate was 97%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Subsequently, the reaction liquid was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. Thereafter, the volatile matter was substantially degassed using an extruder with a 40 mmφ vent (cylinder temperature 220 ° C., vacuum degree 760 mmHg) and pelletized to obtain a rubber-reinforced aromatic vinyl resin P3. The graft ratio of the graft resin (component [A]) contained in this resin P3 is 46%, and the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound in the graft part. When the sum of the two is 100%, the ratio is 24% and 76%, and the content of the ungrafted (co) polymer (acetone soluble component) is 64%. The intrinsic viscosity [η] of min (in methyl ethyl ketone, 30 ° C.) was 0.45 dl / g.

The raw materials P1 to P3 obtained by the synthesis examples 1 to 3 are a mixture composed of the component [A] and the component [C] according to the present invention. Since component [C] is composed of the polymers (C-1), (C-2) and (C-3), r ₁ = 25 and r ₂ = 30 are selected, and the sum of these is 100 Each ratio in the case of% was analyzed by the following method and shown in Table 1. Further, the content of the structural unit (cx) contained in the component [C] is also shown in Table 1.

<Composition analysis of polymers (C-1), (C-2) and (C-3)>
Acetone-soluble 10 mg of raw material [P] is added to 10 ml of a mixture of acetonitrile and 1,2-dichloroethane (volume ratio 6: 4), and shaken at 25 ° C. for 2 to 3 hours with a shaker. It was. Thereafter, insoluble matters (contaminants) were removed, and the soluble matters were subjected to liquid chromatography. The apparatus was a super system controller “SC8020” (model name) manufactured by Tosoh Corporation, and “TSK Silica-60” (trade name) manufactured by Tosoh Corporation was used as a column. The sample was developed with a mobile phase having a gradient from an n-heptane / 1,2-dichloroethane mixture (volume ratio 7: 3) to an acetonitrile / 1,2-dichloroethane mixture (volume ratio 6: 4). The distribution of the composition was measured from the absorption value at a wavelength of 260 nm with a detector. The column temperature is 35 ° C. The determination of the polymer composition and distribution in the sample was made by preparing a calibration curve in advance using a styrene / acrylonitrile copolymer containing a structural unit of known type and content.

1-2. Raw material [Q]
The following commercially available products were used.
As the raw material Q1, polycarbonate “NOVAREX 7022PJ” (trade name) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used. The MFR (temperature 240 ° C., load 10 kg) is 9 g / 10 minutes.

1-3. Raw material [R]
The copolymer obtained by the following synthesis examples 4-13 was used.

Synthesis Example 4 (Synthesis of raw material R1)
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., 0.2 parts of diisopropylbenzene hydroperoxide, 0.26 parts of tert-dodecyl mercaptan, 73 parts of styrene and 27 parts of acrylonitrile were added to the reaction system. It dripped continuously over time and superposition | polymerization was performed. At the same time as the completion of the dropping, the polymerization was completed to obtain latex (L5-1).
On the other hand, in a glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate and 0.5 part of sodium hydrogen carbonate were placed in a nitrogen stream, and the temperature was raised while stirring. did. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., a mixture of 0.2 part of diisopropylbenzene hydroperoxide, 0.26 part of tert-dodecyl mercaptan, 20 parts of styrene and 80 parts of acrylonitrile was added to the reaction system. It dripped over 3 hours and superposed | polymerized. Polymerization was completed at the same time as the dropping was completed to obtain latex (L5-2).
Next, the latex (L5-1) and (L5-2) obtained above were mixed so that the content ratio (mass ratio) of the polymer was 50:50. And the polymer was solidified and washed with water using the magnesium sulfate solution. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R1. In the raw material R1, the polymer corresponding to the component [C] is a polymer contained in the latexes (L5-1) and (L5-2) obtained above.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R1 was 0.51 dl / g.

Synthesis Example 5 (Synthesis of raw material R2)
In this synthesis example, a first monomer consisting of a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.13 part tert-dodecyl mercaptan, 36.5 parts styrene and 13.5 parts acrylonitrile (at the start of synthesis, 1 source) and a second monomer consisting of a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.13 part tert-dodecyl mercaptan, 40 parts styrene and 10 parts acrylonitrile. The raw material R2 was obtained by polymerization in the following manner.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R2.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R2 was 0.51 dl / g.

Synthesis Example 6 (synthesis of raw material R3)
In this synthesis example, a first monomer composed of a mixture of 0.1 part of diisopropylbenzene hydroperoxide, 0.10 part of tert-dodecyl mercaptan, 36.5 parts of styrene and 13.5 parts of acrylonitrile (at the start of synthesis, 1 source) and a second monomer consisting of a mixture of 0.1 parts diisopropylbenzene hydroperoxide, 0.10 parts tert-dodecyl mercaptan, 40 parts styrene and 10 parts acrylonitrile. The raw material R3 was obtained by performing polymerization in the following manner.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R3.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R3 was 0.60 dl / g.

Synthesis Example 7 (Synthesis of raw material R4)
In this synthesis example, a first monomer composed of a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.2 part tert-dodecyl mercaptan, 36.5 parts styrene and 13.5 parts acrylonitrile (at the start of synthesis, 2nd monomer (starting synthesis) consisting of a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.2 part tert-dodecyl mercaptan, 38.5 parts styrene and 11.5 parts acrylonitrile In some cases, polymerization was carried out in the following manner to obtain a raw material R4.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R4.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R4 was 0.41 dl / g.

Synthesis Example 8 (Synthesis of raw material R5)
In this synthesis example, a first monomer composed of a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.2 part tert-dodecyl mercaptan, 36.5 parts styrene and 13.5 parts acrylonitrile (at the start of synthesis, 2nd monomer (starting synthesis) consisting of a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.2 part tert-dodecyl mercaptan, 41.5 parts styrene and 8.5 parts acrylonitrile In some cases, polymerization was performed in the following manner to obtain a raw material R5.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R5.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R5 was 0.40 dl / g.

Synthesis Example 9 (synthesis of raw material R6)
In this synthesis example, a first monomer composed of a mixture of 76.5 parts of styrene, 0.15 parts of diisopropylbenzene hydroperoxide, and 0.20 parts of tert-dodecyl mercaptan (accommodated in the first supply source at the start of synthesis) A second monomer consisting of a mixture of 23.5 parts of acrylonitrile, 0.05 part of diisopropylbenzene hydroperoxide and 0.06 part of tert-dodecyl mercaptan (contained in the second supply source at the start of synthesis), And polymerization was performed in the following manner to obtain a raw material R6.
To a glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate and 0.5 part of sodium bicarbonate were added in a nitrogen stream, and the temperature was raised while stirring. When the internal temperature reached 45 ° C., 0.062 part of ethylenediaminetetraacetic acid / tetrasodium dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.124 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., monomers were continuously supplied from the first and second supply sources to the reaction system, and polymerization was carried out over 3 hours. The total amount of monomers to be supplied is sequentially constant (100 parts), and the amount of monomers supplied from each supply source is determined as follows: First supply source: second supply source = 73:27, and at the end of supply (after 3 hours), the first supply source: second supply source = 80: 20.
Simultaneously with the completion of the monomer supply (after the completion of the three-hour supply), the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R6.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R6 was 0.51 dl / g.

Synthesis Example 10 (Synthesis of raw material R7)
In this synthesis example, a first monomer composed of a mixture of 0.1 part of diisopropylbenzene hydroperoxide, 0.2 part of tert-dodecyl mercaptan, 36.5 parts of styrene and 13.5 parts of acrylonitrile (at the start of synthesis, 1 monomer) and a second monomer comprising a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.2 part tert-dodecyl mercaptan, 30 parts styrene and 20 parts acrylonitrile. The raw material R7 was obtained by polymerizing in the following manner.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R7.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R7 was 0.41 dl / g.

Synthesis Example 11 (synthesis of raw material R8)
In this synthesis example, a first monomer composed of a mixture of 0.2 parts of diisopropylbenzene hydroperoxide, 0.23 parts of tert-dodecyl mercaptan, 83 parts of styrene and 17 parts of acrylonitrile (at the start of synthesis, the first source Polymerization was performed in the following manner to obtain a raw material R8.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R8.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R8 was 0.59 dl / g.

Synthesis Example 12 (synthesis of raw material R9)
A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, the first reactor was charged with a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and 0.15 part of tert-dodecyl mercaptan as a molecular weight regulator. And a solution in which 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, is dissolved in 5 parts of toluene, are continuously supplied. Polymerization was carried out at 0 ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the styrene / acrylonitrile copolymer. This styrene / acrylonitrile copolymer was used as raw material R9.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this raw material R9 was 0.51 dl / g.

Synthesis Example 13 (synthesis of raw material R10)
In this synthesis example, a first monomer composed of a mixture of 0.2 parts of diisopropylbenzene hydroperoxide, 0.23 parts of tert-dodecyl mercaptan, 60 parts of styrene and 40 parts of acrylonitrile is used as a first source at the start of synthesis. Polymerization was performed in the following manner to obtain a raw material R10.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material R10.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material R10 was 0.51 dl / g.

The raw materials (R1) to (R10) obtained in the synthesis examples 4 to 13 are composed of a plurality of copolymers. As follows, when r ₁ = 25 and r ₂ = 30 are selected, and the total of the polymers (C-1), (C-2) and (C-3) according to the present invention is 100% Each ratio was analyzed by the following method and shown in Table 2. Further, the content of the structural unit (cx) contained in the raw material [R] is also shown in Table 2.

<Composition analysis of polymers (C-1), (C-2) and (C-3)>
10 mg of raw material [R] was put into 10 ml of a mixture of acetonitrile and 1,2-dichloroethane (volume ratio 6: 4), and shaken at 25 ° C. for 2 to 3 hours with a shaker. Thereafter, insoluble matters (contaminants) were removed, and the soluble matters were subjected to liquid chromatography. The apparatus was a super system controller “SC8020” (model name) manufactured by Tosoh Corporation, and “TSK Silica-60” (trade name) manufactured by Tosoh Corporation was used as a column. The sample was developed with a mobile phase having a gradient from an n-heptane / 1,2-dichloroethane mixture (volume ratio 7: 3) to an acetonitrile / 1,2-dichloroethane mixture (volume ratio 6: 4). The distribution of the composition was measured from the absorption value at a wavelength of 260 nm with a detector. The column temperature is 35 ° C. The determination of the polymer composition and distribution in the sample was made by preparing a calibration curve in advance using a styrene / acrylonitrile copolymer containing a structural unit of known type and content.

1-4. Raw material [S]
(1) Raw material S1 (flame retardant)
Brominated modified epoxy resin (tribromophenol-2,2-bis (dibromo-4-hydroxyphenyl) propane-2,2-bis [dibromo-4- (2,3-epoxypropoxy) phenyl] propane heavy by DIC Adduct) “Plasarm ECX-30” (trade name) was used.
(2) Raw material S2 (flame retardant aid)
Antimony trioxide manufactured by Nippon Seiko Co., Ltd. was used.
(3) Raw material S3 (flame retardant)
1,3-phenylene-bis (dixylenyl) phosphate “PX-200” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd. was used.
(4) Raw material S4 (flame retardant aid)
A polytetrafluoroethylene “Polyflon FA500C” (trade name) manufactured by Daikin Industries, Ltd. was used.

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1-27 and Comparative Examples 1-14
A thermoplastic resin composition was obtained using the raw materials [P], [Q], [R] and [S] in the proportions shown in Tables 3 to 13. In evaluating the composition, a physical property evaluation composition containing an additive corresponding to the evaluation item was prepared in advance and used.
As mentioned above, since the raw material [P] is a mixture comprising the component [A] and the component [C] according to the present invention, the graft ratio in the raw material [P], the composition soluble in acetone, etc. Was used to calculate the content of the polymer corresponding to component [C] with respect to the total amount of components [A], [B] and [C] of the present invention, and the values are shown in each table. Then, the component [C], the polymer (C-1), since it is constituted by (C-2) and _(C-3), select r 1 = 25 and _r 2 = 30, these Each ratio when the total was taken as 100% was analyzed by the following method. Moreover, it showed to each table | surface about content of the structural unit (cx) contained in component [C].

<Composition analysis of polymers (C-1), (C-2) and (C-3)>
10 mg of the component [C] contained in the thermoplastic resin composition was put into 10 ml of a mixture of acetonitrile and 1,2-dichloroethane (volume ratio 6: 4), and shaken at 25 ° C. for 2 to 3 hours using a shaker. I went. Thereafter, insoluble matters (contaminants) were removed, and the soluble matters were subjected to liquid chromatography. The apparatus was a super system controller “SC8020” (model name) manufactured by Tosoh Corporation, and “TSK Silica-60” (trade name) manufactured by Tosoh Corporation was used as a column. The sample was developed with a mobile phase having a gradient from an n-heptane / 1,2-dichloroethane mixture (volume ratio 7: 3) to an acetonitrile / 1,2-dichloroethane mixture (volume ratio 6: 4). The distribution of the composition was measured from the absorption value at a wavelength of 260 nm with a detector. The column temperature is 35 ° C. The determination of the polymer composition and distribution in the sample was made by preparing a calibration curve in advance using a styrene / acrylonitrile copolymer containing a structural unit of known type and content.

<Composition for evaluating physical properties>
After supplying a predetermined amount of raw materials [P], [Q], [R] and [S] to the Henschel mixer, 100 parts of these were added to Tris (2,4-di-) as an antioxidant. tert-butylphenyl) phosphite (trade name “ADK STAB 2112”, manufactured by ADEKA) and 2 [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl as a stabilizer ] -4,6-di-tert-pentylphenyl acrylate (trade name “Sumilyzer GS (F)”, manufactured by Sumitomo Chemical Co., Ltd.) 0.2 part was added and mixed at 25 ° C. Next, this mixture was supplied to a twin-screw extruder “BT40” (model name) manufactured by Plastic Engineering Laboratory Co., Ltd. and melt-kneaded to obtain pellets (physical property evaluation composition). In addition, the cylinder preset temperature in the case of melt-kneading was 240 degreeC-260 degreeC.
Thereafter, after sufficiently drying the pellets, an injection molding machine “EC60” (model name) or “J35AD” (model name) manufactured by Toshiba Machine Co., Ltd. with a cylinder set temperature of 240 ° C. to 260 ° C. and a mold temperature of 60 ° C. Name) was used to prepare a test piece suitable for the evaluation item.
(1) Impact resistance In accordance with ISO 179, Charpy impact strength was measured at a temperature of 23 ° C. The unit is “kJ / m ² ”.
(2) Heat resistance According to ISO 75, the deflection temperature under load was measured at a bending stress of 1.8 MPa. The unit is “° C.”.
(3) Fluidity In accordance with ISO 1133, the melt flow rate was measured at a temperature of 240 ° C. and a load of 98N. The unit is “g / 10 minutes”.

(4) Flammability The test piece produced by injection molding according to Subject 94 of Underwriters Laboratories (UL) was subjected to a vertical combustion test. When the raw materials S1 and S2 are used as the raw material [S], the size of the test piece is 127 mm × 12.7 mm × 1.5 mm, and when the raw materials S3 and S4 are used, the size of the test piece is 127 mm. X12.7 mm x 1.2 mm.
(5) Weather resistance Using the UV long life fade meter “FAL-5H • B” (model name) manufactured by Suga Test Instruments Co., Ltd., the same test piece used for the evaluation of the impact resistance was 135V, 16A, temperature. It was exposed to light at 63 ° C. and no rain for 100 hours, the discolored state of the surface of the test piece was visually observed, and the weather resistance was determined according to the following criteria.
○: No discoloration was observed.
Δ: Slight discoloration was observed.
X: Discoloration was clearly recognized.

From the results of Tables 3 to 8, the following is clear. In Comparative Examples 1 and 3, the proportions of the polymers (C-1) and (C-3) constituting the component [C] were outside the scope of the present invention, and the impact resistance was insufficient. In Comparative Examples 2, 4 to 7, the proportion of the polymer (C-1) constituting the component [C] is an example outside the range of the present invention, and the impact resistance was insufficient. On the other hand, in Examples 1 to 17, flammability (V-0) was obtained, and further improved impact resistance was obtained.
Moreover, the following is clear from the results of Tables 9 to 13. In Comparative Examples 8 and 10, the proportions of the polymers (C-1) and (C-3) constituting the component [C] were outside the scope of the present invention, and the impact resistance was insufficient. In Comparative Examples 9, 11 to 14, the ratio of the polymer (C-1) constituting the component [C] was an example outside the scope of the present invention, and the impact resistance was insufficient. On the other hand, in Examples 18 to 27, flammability (V-0) was obtained, and further improved impact resistance was obtained.

  Since the thermoplastic resin composition of the present invention provides a flame-retardant molded article excellent in impact resistance, it is used in the electrical field, electronic field, communication field, OA / home appliance field, building material field, vehicle field, ship field, etc. It is suitable for forming molded articles such as molded articles for resin members, molded articles for cold districts, molded articles for outdoor use, daily goods, sports goods, stationery, and the like.

Claims (8)

[A] a rubbery polymer reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of a rubbery polymer;
[B] polycarbonate resin;
[C] a polymer comprising a structural unit (cx) derived from a vinyl cyanide compound and a structural unit (cy) derived from an aromatic vinyl compound;
[D] a flame retardant;
In a thermoplastic resin composition containing
The polymer [C] includes the polymer (C-1) containing the structural unit (cx) in an amount of 5% by mass or more and ₁ % by mass or less, and the structural unit (cx) in excess of ₁ % by mass. Te polymer comprising at _{r 2} mass% or less and (C-2), the structural unit (cx), becomes from a polymer containing 60 wt% or less beyond the _{r 2} wt% (C-3), and , (R ₂ −r ₁ ) ≧ 3 (mass%),
The content ratios of the polymers (C-1), (C-2) and (C-3) are 5 to 70% by mass and 10 to 80% by mass, respectively, when the total content is 100% by mass. And 10 to 80% by mass,
The rubbery polymer reinforced graft resin [A], the polycarbonate resin [B] and the polymer [C] are contained in an amount of 1 to 80% by mass, respectively, when the total content is 100% by mass, The content of the flame retardant [D] is 10 to 95% by mass and 1 to 70% by mass, and the rubber polymer reinforced graft resin [A], the polycarbonate resin [B], and the polymer [C]. 1 to 30 parts by mass when the total is 100 parts by mass. The thermoplastic resin composition according to claim 1 r ₂ is 15 to 45 mass%.   The polymer [C] is a copolymer composed of a structural unit (cx) and a structural unit (cy), and the vinyl cyanide compound and the aromatic vinyl compound are contained in a mass ratio of 5 to 25:95 to The polymer obtained by superposing | polymerizing, changing a preparation amount from 75 to 25-60: 75-40 or from 25-60: 75-40 to 5-25: 95-75. The thermoplastic resin composition according to 1 or 2.   The content ratio of the structural unit (cx) contained in the polymer [C] is 15 to 40% by mass when the total of the structural units constituting the polymer [C] is 100% by mass. Item 4. The thermoplastic resin composition according to any one of Items 1 to 3.   The polymerizable unsaturated monomer used to form the rubber polymer reinforced graft resin [A] contains a vinyl cyanide compound and an aromatic vinyl compound, and is contained in the rubber polymer reinforced graft resin [A]. When the ratio of the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound is 100% by mass, the ratio is 5 to 40 respectively. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin composition is mass% and 60 to 95 mass%. r ₁ is 10 to 30% by mass, r ₂ is 20 to 40% by mass,
When the content ratios of the polymers (C-1), (C-2), and (C-3) are 100% by mass of the total of these, 5-55% by mass, 20-70% by mass, respectively. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin composition is 20 to 70% by mass.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the flame retardant [D] is a halogen-based compound.   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7.