JP2014074141A - Thermoplastic resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition providing a molded article which has more improved shock resistance while maintaining excellent flame resistance.SOLUTION: A thermoplastic resin composition contains [A] a mixed graft resin which is a rubbery polymer reinforced graft resin in which a polymer containing a cyanated vinyl compound unit (gx) and an aromatic vinyl compound unit (gy) is grafted to a rubbery polymer, contains (A-1) a graft resin containing a copolymer comprising the structural unit (gx) of 5 mass% or more and smass% or less, (A-2) a graft resin containing a copolymer comprising the structural unit (gx) of over smass% and smass% or less, and (A-3) a graft resin containing a copolymer comprising the structural unit (gx) of over smass% and 60 mass% or less, and satisfies (s-s)≥3 (mass%), [B] a polycarbonate resin and [D] a flame retardant.

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 as follows.
1. [A] A rubbery polymer in which a copolymer containing a structural unit (gx) derived from a vinyl cyanide compound and a structural unit (gy) derived from an aromatic vinyl compound is grafted to the rubbery polymer. (A-1) a rubbery polymer reinforced graft resin comprising a copolymer containing the structural unit (gx) at 5% by mass or more and s ₁ % by mass or less, (A-2) ) A rubbery polymer reinforced graft resin comprising a copolymer containing the structural unit (gx) in an amount of more than s ₁ % by mass and s ₂ % by mass or less, and (A-3) the structural unit (gx), mixed graft resin comprising a rubbery polymer reinforced graft resin comprising a copolymer containing more than ₂ mass% and not more than 60 mass%, and (s ₂ −s ₁ ) ≧ 3 (mass%) When,
[B] polycarbonate resin;
[D] a flame retardant;
In a thermoplastic resin composition containing
The rubbery polymer reinforced graft resins (A-1), (A-2), and (A-3) are contained in amounts of 1 to 98.9 masses when the total content is 100 mass%. %, 1-90% by mass and 0.1-90% by mass,
The content of the flame retardant [D] is 1 to 35 parts by mass when the total of the mixed graft resin [A] and the polycarbonate resin [B] is 100 parts by mass. Resin composition.
2. s ₁ is 10 to 30 mass%, _{s 2} is the thermoplastic resin composition of claim 1 which is 15 to 45 mass%.
3. When the mixed graft resin [A] graft-polymerizes the polymerizable unsaturated monomer (am) containing the vinyl cyanide compound and the aromatic vinyl compound in the presence of the rubbery polymer, the cyanide is used. From 25 to 95:75 to 27 to 60:73 to 40, or from 27 to 60:73 to 40 to 5 to 25:95 to 75 by mass ratio of the vinyl compound and the aromatic vinyl compound. The thermoplastic resin composition according to the above 1 or 2, which is a resin obtained by graft polymerization while changing the charged amount.
4). Said 1 thru | or 3 whose content rate of said mixed graft resin [A] and said polycarbonate resin [B] is 3-80 mass% and 20-97 mass%, respectively, when these sum total is 100 mass%. The thermoplastic resin composition according to any one of the above.
5. The ratio of the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound contained in the mixed graft resin [A] is 100% by mass. The thermoplastic resin composition according to any one of 1 to 4 above, which is 5 to 60% by mass and 40 to 95% by mass, respectively.
6). Furthermore, [C] a structural unit derived from the vinyl cyanide compound obtained by polymerizing a polymerizable unsaturated monomer containing a vinyl cyanide compound and an aromatic vinyl compound in the absence of a rubbery polymer. The thermoplastic resin composition according to any one of 1 to 5 above, comprising (cx) and a copolymer containing a structural unit (cy) derived from the aromatic vinyl compound.
7). The copolymer [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% polymer comprising at _{r 2} wt% or less than the (C-2), made from the structural units (cx), a polymer beyond _{r 2} wt% comprising 60 wt% or less (C-3), And (r ₂ −r ₁ ) ≧ 3 (mass%),
The content ratios of the polymers (C-1), (C-2), and (C-3) are 1 to 89.9% by mass and 10 to 70%, respectively, when the total content is 100% by mass. 7. The thermoplastic resin composition as described in 6 above, wherein the thermoplastic resin composition is 10% by mass and 0.1-80% by mass.
8). The thermoplastic resin composition according to claim 6 or 7, wherein r2 is ₂₀ to 45 mass%.
9. The content ratio of the structural unit (cx) contained in the copolymer [C] is 5 to 60% by mass when the total of the structural units constituting the copolymer [C] is 100% by mass. The thermoplastic resin composition according to any one of 6 to 8 above.
10. r ₁ is 10 to 35 wt%, _{r 2} is 25 to 45 wt%,
When the content ratios of the polymers (C-1), (C-2), and (C-3) are 100% by mass, the total content is 35 to 89.5% by mass and 10 to 50%, respectively. The thermoplastic resin composition according to any one of 6 to 9 above, which is mass% and 0.5 to 50 mass%.
11. The content ratios of the mixed graft resin [A], the polycarbonate resin [B], and the copolymer [C] are 3 to 65% by mass, 20 to 90%, respectively, when the total content is 100% by mass. The thermoplastic resin composition according to any one of 6 to 10 above, wherein the thermoplastic resin composition is mass% and 2 to 60 mass%.
12 The thermoplastic resin composition according to any one of 1 to 11, wherein the flame retardant [D] is a halogen-based compound.
13. A molded article comprising the thermoplastic resin composition according to any one of 1 to 12 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] a rubbery polymer containing a structural unit (gx) derived from a vinyl cyanide compound and a structural unit (gy) derived from an aromatic vinyl compound. A mixed graft resin (hereinafter also referred to as “component [A]”) of three types of rubber polymer-reinforced graft resin grafted with a coalescence, and [B] polycarbonate resin (hereinafter referred to as “component [B]”). And [D] a flame retardant (hereinafter also referred to as “component [D]”). The component [A] comprises a rubbery polymer reinforced graft resin (A-1) comprising a copolymer containing the structural unit (gx) at 5% by mass or more and s ₁ % by mass or less, and the structural unit (gx). ), A rubbery polymer reinforced graft resin (A-2) comprising a copolymer containing more than s ₁ % by mass and s ₂ % by mass or less, and a structural unit (gx) exceeding s ₂ % by mass. Rubber-like polymer reinforced graft resin (A-3) comprising a copolymer contained at 60% by mass or less, and (s ₂ −s ₁ ) ≧ 3 (% by mass). Moreover, the content rate of the rubber-like polymer reinforcement | strengthening graft resin (A-1), (A-2), and (A-3) which comprises the said component [A] is when these sum is 100 mass%. 1-98.9% by mass, 1-90% by mass and 0.1-90% by mass, respectively, and the content of the component [D] is the sum of the components [A] and [B] being 100. When it is made into a mass part, it is 1-35 mass part.

The rubbery polymer reinforced graft resin constituting the component [A] generally contains a polymerizable unsaturated monomer (am) containing a vinyl cyanide compound and an aromatic vinyl compound in the presence of the rubbery polymer. It is a composite resin (hereinafter also referred to as “graft resin”) contained in a resin composition (hereinafter referred to as “rubber reinforced resin”) obtained by polymerization (hereinafter referred to as “graft polymerization”). This graft resin is a resin in which a copolymer containing structural units (gx) and (gy) derived from a polymerizable unsaturated monomer (am) is grafted to a rubbery polymer. A copolymer part (graft part) containing structural units (gx) and (gy) derived from a vinyl cyanide compound and an aromatic vinyl compound contained in the polymerized unsaturated monomer (am) It consists of. In addition to the structural units (gx) and (gy), the copolymer constituting the copolymer part (graft part) is further composed of other structural units (hereinafter also referred to as “structural units (gz)”). It may optionally be included. In this case, as a compound used for forming the structural unit (gz) (hereinafter, also referred to as “other vinyl monomer” that can be used as the polymerizable unsaturated monomer (am)), (meth) Acrylic ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds (excluding (meth) acrylic ester compounds in which the ester moiety contains a hydroxyalkyl group), Examples thereof include oxazoline group-containing unsaturated compounds. When the copolymer which comprises the said copolymer part (graft part) contains a structural unit (gz), the upper limit of the content is the sum total of a structural unit (gx), (gy), and (gz) 100. In the case of mass%, it is preferably 15 mass%, more preferably 10 mass%.
The component [A] is a mixture of three types of rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) each including the structural units (gx) and (gy). It is. These rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) contain structural units (gx) and (gy), but the component [A] is another vinyl. When the structural unit (gz) derived from the system monomer is included, the structural unit (gz) may be included in all graft resins, or included in only one or two of them. May be.
The rubber reinforced resin obtained by graft polymerization is usually a copolymer not grafted to the rubber polymer (hereinafter referred to as “ungrafted polymer”) in addition to the rubber polymer reinforced graft resin. including. Since the composition of the ungrafted polymer depends on the type of the polymerizable unsaturated monomer (am) used, the ungrafted polymer is the “component [C]” described later in the composition of the present invention. It may correspond to.

  The rubbery polymer used for forming the rubbery polymer reinforced graft resin may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C. A polymer (hereinafter referred to as “diene rubber”) and a non-diene polymer (hereinafter referred to as “non-diene rubber”) are preferable. 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. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more). The non-diene rubber can be used alone or in combination of two or more.

  In the present invention, the rubbery polymer reinforced graft resin is preferably a graft resin obtained using a diene rubber as the rubbery polymer.

  The polymerizable unsaturated monomer (am) used for forming the rubbery polymer reinforced graft resin includes a vinyl cyanide compound and an aromatic vinyl compound that form the structural units (gx) and (gy). This polymerizable unsaturated monomer (am) further forms a structural unit (gz), (meth) acrylic acid ester compound, maleimide compound, unsaturated acid anhydride, carboxyl group-containing unsaturated compound, hydroxyl group Other vinyl monomers such as a group-containing unsaturated compound (except for a (meth) acrylic acid ester compound in which the ester moiety contains a hydroxyalkyl group), an oxazoline group-containing unsaturated compound, and the like may also be included.

  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.

  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.

  The polymerizable unsaturated monomer (am) may be a monomer composed of a vinyl cyanide compound and an aromatic vinyl compound, or may be a vinyl cyanide compound, an aromatic vinyl compound and other vinyl monomers. The monomer which consists of may be sufficient. In the latter case, the lower limit of the total amount of the vinyl cyanide compound and the aromatic vinyl compound is preferably 70% by mass, more preferably 80% by mass, and still more preferably 95% by mass.

The (meth) acrylic acid ester compound is not particularly limited as long as it is a compound having a (meth) acryloyl group. However, carboxylic acid is 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.

  When the polymerizable unsaturated monomer (am) contains another vinyl monomer, the rubbery polymer reinforced graft resin has another vinyl monomer in the copolymer part (graft part). It has the structural unit (gz) derived from.

Preferred examples of the rubbery polymer reinforced graft resin are as follows. The three types of rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) constituting the component [A] may be the same type of graft resin or different from each other. It may be a graft resin.
(1) Graft resin in which a graft portion composed of a structural unit (gx) derived from a vinyl cyanide compound and a structural unit (gy) derived from an aromatic vinyl compound is formed on a rubbery polymer portion composed of a diene rubber. (2) From the structural unit (gx) derived from the vinyl cyanide compound, the structural unit (gy) derived from the aromatic vinyl compound, and the structural unit derived from the maleimide compound to the rubbery polymer portion comprising the diene rubber. (3) a structural unit derived from a vinyl cyanide compound (gx), a structural unit derived from an aromatic vinyl compound (gy), Graft resin in which a graft portion composed of a structural unit derived from a (meth) acrylate compound is formed

  The method for producing the rubber polymer reinforced graft resin can be a method including a step including emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, or a method including a polymerization step combining these.

  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 (am).
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 (am).
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 (am).

  Conditions such as reaction temperature during emulsion polymerization are not particularly limited. 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 isolating the rubbery polymer reinforced graft resin from the rubber reinforced resin containing the rubbery polymer reinforced graft resin obtained as described above, for example, 10 g of the rubber reinforced resin is added to 100 to 200 ml of acetone. (If the rubbery polymer is an acrylic rubber, use acetonitrile.) Using a shaker or the like, shake at 25 ° C. for 2 to 3 hours to separate and recover the insoluble matter produced. The method is applied. The acetone-soluble component (acetonitrile-soluble component) corresponds to the ungrafted polymer, and may correspond to the component [C] depending on the proportion of the polymerizable unsaturated monomer (am) used. is there.

  The graft ratio (average value) in the rubber polymer reinforced graft resin is preferably 20 to 230%, more preferably 30 to 30% from the viewpoints of molding processability, impact resistance of molded products, molded appearance, and the like. 150%, more preferably 35 to 100%. 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 rubbery polymer reinforced graft resin, the type and amount of chain transfer agent used, and the supply of polymerizable unsaturated monomer (am). The method, supply time, polymerization temperature, and the like can be adjusted by appropriately selecting.

In the present invention, the component [A] is a rubbery polymer reinforced graft resin (A-1) comprising at least one copolymer containing the structural unit (gx) at 5 mass% or more and s ₁ mass% or less. And a rubbery polymer reinforced graft resin (A-2) comprising at least one kind of a copolymer containing s ₁ % by mass and s ₂ % by mass or less of the structural unit (gx), and the structural unit (gx ) Is a mixed graft resin comprising a rubbery polymer reinforced graft resin (A-3) comprising at least one copolymer containing more than ₂ % by mass and not more than 60% by mass. The rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) are graft resins having different structural unit (gx) contents (average values), It is a graft resin in which the content (average value) of the structural unit (gx) is increased.
When the component [A] is composed of the rubbery polymer reinforced graft resin (A-1), (A-2) and (A-3), a molded article having excellent impact resistance can be obtained. In particular, when the component [A] composed of an aggregate of graft resins including a copolymer having a content (average value) of the structural unit (gx) of preferably in the range of 5 to 60% by mass is used, the above effect is obtained. Is remarkable.
In the rubbery polymer reinforced graft resin (A-1), (A-2) and (A-3), the type of the structural unit (gx) may be the same or different. The type of the structural unit (gy) may also be the same or different. The types of structural units (gz) may also be the same or different.

The copolymer constituting the copolymer part of the rubbery polymer reinforced graft resin (A-1) includes a structural unit (gx) in an amount of 5% by mass or more and s ₁ % by mass or less. It may be a copolymer consisting of structural units (gx) and (gy), or a copolymer consisting of structural units (gx), (gy) and (gz). Moreover, as mentioned above, the copolymer which comprises this copolymer part shall consist of at least 1 sort (s) of the copolymer containing the predetermined amount of a structural unit (gx). For example, when it is composed of two kinds of copolymers and 5 ≦ s ₁₁ <s ₁₂ ≦ s ₁ , a copolymer containing ₁₁ mass% of structural units (gx) and structural units (gx) And a graft resin containing a copolymer part composed of ₁₂ % by mass of s.
s ₁ is preferably 10 to 30% by mass, more preferably 15 to 30% by mass, still more preferably 17 to 29% by mass, and particularly preferably 22 to 28% by mass. When two or more types of copolymers having a structural unit (gx) content of 5% by mass or more and s ₁ % by mass or less are contained, “the copolymer part of the rubbery polymer reinforced graft resin (A-1) is constituted. The value shown as “content of structural unit (gx) contained in copolymer” is an average value calculated from the content of structural unit (gx) contained in each copolymer constituting the copolymer part. is there.
The copolymer constituting the copolymer part of the rubber-like polymer reinforced graft resin (A-2) includes a structural unit (gx) in an amount of more than s ₁ % by mass and s ₂ % by mass or less. A copolymer comprising (gx) and (gy), and may be a copolymer comprising the structural units (gx) and (gy) as described above, or the structural units (gx), (gy) and A copolymer comprising (gz) may be used. Moreover, as mentioned above, the copolymer which comprises this copolymer part shall consist of at least 1 sort (s) of the copolymer containing the predetermined amount of a structural unit (gx). For example, when it is composed of two kinds of copolymers and s ₁ <s ₂₁ <s ₂₂ ≦ s ₂ , a copolymer containing s ₂₁ mass% of structural units (gx) and structural units (gx ) And a graft resin containing a copolymer part composed of ₂₂ % by mass of s.
s ₂ is preferably 15 to 45 wt%, more preferably 20 to 42 wt%, more preferably 22 to 40 wt%, even more preferably 25 to 35% by weight, particularly preferably 27 to 33 wt% . When two or more types of copolymers having a structural unit (gx) content of more than s ₁ % by mass and s ₂ % by mass or less are contained, the “copolymer of rubbery polymer reinforced graft resin (A-2)” The value shown as “content of structural unit (gx) contained in copolymer constituting part” was calculated from the content of structural unit (gx) contained in each copolymer constituting copolymer part. Average value.
In the present invention, the relationship between s ₁ and s ₂ where the effect of impact resistance becomes significant is (s ₂ −s ₁ ) ≧ 3 (mass%), preferably (s ₂ −s ₁ ) ≧ 4 (mass%), more preferably (s ₂ -s ₁ ) ≧ 4.5 (mass%). However, usually (s ₂ −s ₁ ) ≦ 10 (mass%), preferably (s ₂ −s ₁ ) ≦ 9 (mass%), more preferably (s ₂ −s ₁ ) ≦ 7 (mass%). It is. When (s ₂ −s ₁ ) <3 (mass%), the effect of the present invention cannot be sufficiently obtained.
The copolymer constituting the copolymer part of the rubber polymer reinforced graft resin (A-3) has a structural unit (gx) of more than s ₂ % by mass and 60% by mass or less, preferably s ₂ A copolymer containing more than 60% by mass and not more than 60% by mass, and may be a copolymer composed of structural units (gx) and (gy) as described above, or may be a structural unit (gx), (gy ) And (gz). Moreover, as mentioned above, the copolymer which comprises this copolymer part shall consist of at least 1 sort (s) of the copolymer containing the predetermined amount of a structural unit (gx). For example, when it is composed of two kinds of copolymers and s ₂ <s ₃₁ <s ₃₂ ≦ 60, a copolymer containing s ₃₁ % by mass of a structural unit (gx) and a structural unit (gx) And a graft resin containing a copolymer part composed of ₃₂ % by mass of s.
When the content of the structural unit (gx) exceeds ₂ mass% and contains two or more polymers that are 60 mass% or less, “the copolymer part of the rubbery polymer reinforced graft resin (A-3) is included. The value shown as “content of structural unit (gx) contained in copolymer constituting” is an average value calculated from the content of structural unit (gx) contained in each copolymer constituting the copolymer part. It is.

In the present invention, the preferred component [A] includes the total amount of structural units (gx) derived from the vinyl cyanide compound and the structural units (gy) derived from the aromatic vinyl compound in the graft portion constituting each graft resin. The ratio of the total amount is preferably 5 to 60% by mass and 40 to 95% by mass, more preferably 10 to 45% by mass and 55 to 90% by mass, respectively, when the total of both is 100% by mass. More preferably, it is a mixed graft resin of 15 to 40% by mass and 60 to 85% by mass. By using a composition containing the component [A] in the above range, a molded article having excellent impact resistance can be obtained.
The distribution of all structural units (gx) contained in the rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) constituting the component [A] is ozonolysis. And by a method combining liquid chromatography.
Hereinafter, from a mixture of rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) obtained using a diene rubber as a rubbery polymer, A method for obtaining the ratio will be described.
To a container containing about 0.4 g of the above mixture, 20 ml of ethyl acetate and 20 ml of methanol are added and stirred. Next, with the container immersed in dry ice / ethanol and cooled, ozone gas is passed through the container to decompose the diene rubber. The end of the decomposition reaction can be judged by blue coloration due to excess ozone in the liquid in the container. Thereafter, nitrogen gas is supplied at room temperature until the blue color in the liquid in the container disappears. Next, the vessel is immersed in ice water, 0.5 g of sodium borohydride is added and stirred for 1 hour, and acetic acid is added dropwise. Since bubbles are generated by the dropwise addition of acetic acid, acetic acid is added until the generation of bubbles is completed (about 2 mL). Then, after adding 20 ml of methanol and stirring for 1 hour, it concentrates to about 5 ml under reduced pressure. The obtained concentrated solution is dissolved in 100 ml of methyl ethyl ketone, and filtered using a fluororesin filter having a pore diameter of 1 μm, and the precipitate is collected. When this precipitate is dried and then weighed, the total mass of each graft portion (copolymer portion) in the rubbery polymer reinforced graft resin (A-1), (A-2) and (A-3) is obtained. .
Next, when the precipitate is subjected to a gradient analysis of liquid chromatography using n-heptane, 1,2-dichloroethane, acetonitrile or the like, the structural unit (gx) is a specific amount of structural unit (gx) with the structural unit (gx) as the horizontal axis. It is possible to obtain a distribution in which the vertical axis represents the amount of a copolymer containing a copolymer (copolymer constituting the graft portion).

The rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) constituting the component [A] are contained in a proportion of 100% by mass, respectively. 1-98.9 mass%, 1-90 mass% and 0.1-90 mass%, preferably 5-90 mass%, 2-70 mass% and 0.5-80 mass%, more preferably 25-80 mass%, 4-55 mass% and 3-65 mass%, more preferably 35-70 mass%, 6-40 mass% and 5-40 mass%, particularly preferably 55-65 mass%, 8- 35 mass% and 8-25 mass%.
Moreover, the fluidity of the composition and the impact resistance effect of the obtained molded product become prominent because s ₁ is 15 to 30% by mass and s ₂ is 22 to 40% by mass. When the content ratio of the rubber-like polymer-reinforced graft resin (A-1), (A-2) and (A-3) is 100% by mass of these, preferably 2 to 90% by mass, respectively. 5-60 mass% and 1-80 mass%, more preferably 30-70 mass%, 15-40 mass% and 7-40 mass%, still more preferably 57-61 mass%, 19-32 mass% and 9 It is a combination of ˜23 mass%.

  The component [A] is obtained by mixing a rubber reinforced resin containing a graft resin corresponding to the rubbery polymer reinforced graft resin (A-1), (A-2) or (A-3). In the graft polymerization of a polymerizable unsaturated monomer (am) containing a vinyl cyanide compound and an aromatic vinyl compound in the presence of a rubbery polymer, the vinyl cyanide compound and the above aromatic vinyl are used. While changing the charge amount of the compound from 5 to 25:95 to 75 to 27 to 60:73 to 40 or from 27 to 60:73 to 40 to 5 to 25:95 to 75 by mass ratio It may be obtained by graft polymerization. The rubbery polymer reinforced graft resin contained in the rubber reinforced resin obtained by the latter method is a resin mixture in which the structure (type and ratio) of the graft part with respect to the rubbery polymer part is different. By using such a resin mixture as a raw material for component [A], a molded product having excellent fluidity and impact resistance of the composition can be efficiently produced.

  In the case where the polymerizable unsaturated monomer (am) further contains another vinyl monomer in addition to the vinyl cyanide compound and aromatic vinyl compound, the vinyl cyanide compound and (aromatic vinyl compound) And a mixture of other vinyl monomers), a copolymer obtained by polymerization while changing the mass ratio from 5 to 25:95 to 75 to 27 to 60:73 to 40, and / Or charge amount of the above-mentioned vinyl cyanide compound and (mixture of aromatic vinyl compound and other vinyl monomer) from 27-60: 73-40 to 5-25: 95-75 in mass ratio A rubber-reinforced resin obtained by polymerization while changing is preferably used as a raw material for the component [A].

As described above, the rubber-reinforced resin obtained by graft polymerization usually contains an ungrafted polymer. And since the said polymerizable unsaturated monomer (am) contains an aromatic vinyl compound and a vinyl cyanide compound, this ungrafted polymer is a structural unit (henceforth "structural unit" derived from a vinyl cyanide compound). And (cx) ") and a structural unit derived from an aromatic vinyl compound (hereinafter referred to as" structural unit (cy) "). It corresponds to.
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 intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the ungrafted polymer is preferably 0.2 to 0.9 dl / g, more preferably 0.25 to 0.5 from the viewpoint of moldability and impact resistance. 0.85 dl / g, more preferably 0.3 to 0.8 dl / g.

  Here, the intrinsic viscosity [η] is obtained by dissolving ungrafted polymer in methyl ethyl ketone, preparing five different concentrations, and measuring the reduced viscosity at each concentration at 30 ° C. using an Ubbelohde viscosity tube. Can be sought.

  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.

  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 composition of the present invention may further contain another polymer (other resin).
Other polymers include (co) polymers (aromatic vinyl (co) polymers, acrylic (co) polymers) containing structural units derived from vinyl monomers having a different structure from the component [A]. Coalesce, polyvinyl chloride resin, polyvinylidene chloride resin, fluororesin, etc.), polyolefin resin, polyester resin, polyamide resin and the like.
When the composition of the present invention contains another polymer (other resin), the upper limit of the content is preferably 20 masses with respect to a total of 100 mass parts of the components [A] and [B]. Part, more preferably 10 parts by weight.

  The composition of the present invention preferably contains an aromatic vinyl-based (co) polymer as the other polymer, and in the absence of a rubbery polymer, the polymerizability contains a vinyl cyanide compound and an aromatic vinyl compound. A copolymer (hereinafter, “component”) obtained by polymerizing an unsaturated monomer and containing a structural unit (cx) derived from a vinyl cyanide compound and a structural unit (cy) derived from an aromatic vinyl compound. [C] ") is particularly preferable. When the composition of the present invention contains the above components [A], [B] and [C], brittle fracture is suppressed by a drop weight impact test at a low temperature of 0 ° C. or lower, for example, −30 ° C., It is possible to more efficiently obtain a molded article that is easily ductile fracture and excellent in chemical resistance.

  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)”).

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 5 to 60% by mass, more preferably 5 to 5%, assuming that the total of structural units constituting the component [C] is 100% by mass. It is 50 mass%, More preferably, it is 10-50 mass%. When the content of the structural unit (cx) is 5 to 60% by mass, a molded product having excellent molding processability (fluidity) of the composition and excellent chemical resistance and paintability 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 40 to 95% by mass, more preferably 50 to 50% when the total of the structural units constituting the component [C] is 100% by mass. It is 95 mass%, More preferably, it is 50-90 mass%. When the content of the structural unit (cy) is 40 to 95% by mass, a molded product having excellent molding processability (fluidity) of the composition and excellent chemical resistance and paintability 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 preferably 15% by mass, more preferably 12% by mass.

  The component [C] is preferably a copolymer comprising the structural units (cx) and (cy), and the copolymer comprising the structural units (cx) and (cy) and the structural units (cx), ( It may be a combination with a copolymer comprising (cy) and (cz).

When the component [C] is a copolymer composed of structural units (cx) and (cy), a mixture of three kinds of copolymers having different content ratios of the structural units (cx) and (cy) to each other, The polymer (C-1) comprising at least one copolymer comprising 5% by mass or more and ₁ % by mass or less of the structural unit (cx) and the structural unit (cx) exceeding ₁ % by mass of r A copolymer (C-2) comprising at least one copolymer containing at least ₂ % by mass of r and a copolymer containing at least 60% by mass of r ₂ % by mass and structural unit (cx). It is preferably a mixture comprising at least one polymer (C-3) and having (r ₂ -r ₁ ) ≧ 3 (mass%). The content ratios of the polymers (C-1), (C-2) and (C-3) are preferably 1 to 89.9% by mass, respectively, when the total of these is 100% by mass. 10 to 70% by mass and 0.1 to 80% by mass, more preferably 10 to 89.9% by mass, 10 to 60% by mass and 0.1 to 70% by mass, still more preferably 35 to 89.5% by mass. 10 to 50% by mass and 0.5 to 50% by mass, particularly preferably 50 to 89.5% by mass, 10 to 40% by mass and 0.5 to 30% by mass.

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. In 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. In addition, this structural unit (cz) may be included in all of the polymers (C-1), (C-2) and (C-3), or included in any one or two of them. Also good.
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 impact 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 5 to 60% by mass, as described above, makes the above effect 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 35% by mass, more preferably 12 to 35% by mass, still more preferably 15 to 35% by mass, and particularly preferably 17 to 35% 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 20 to 45 wt%, more preferably 22 to 45 wt%, more preferably 25 to 45 wt%. 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 ₂₀ to 45% by mass, in the composition of the present invention, the compatibility between the component [A] and the polymer (C-2) is particularly improved. B] and the polymers (C-1) and (C-3) are also improved, resulting in excellent compatibility between the components [A] and [B]. Excellent impact resistance in molded products.
Further, in the present invention, the relationship between r ₁ and r ₂ where the impact resistance effect 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.

In the present invention, the effects of the fluidity of the composition and the impact resistance of the molded product obtained are significant when r ₁ is 10 to 35% by mass and r ₂ is ₂₀ to 45% by mass. When the total content of these polymers (C-1), (C-2) and (C-3) is 100% by mass, preferably 1 to 89.9% by mass. %, 10 to 70% by weight and 0.1 to 80% by weight, more preferably 10 to 89.9% by weight, 10 to 60% by weight and 0.1 to 70% by weight, still more preferably 35 to 89.5% by weight. %, 10 to 50% by mass and 0.5 to 50% by mass, particularly preferably 50 to 89.5% by mass, 10 to 40% by mass and 0.5 to 30% by 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. A distribution can be obtained in which the horizontal axis is the unit (cx) and the vertical axis is the amount of the copolymer containing a specific amount of the structural unit (cx).

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.

In the case of producing the polymers (C-1), (C-2) and (C-3), for example, 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. Further, the above polymers (C-1), (C-2) and (C-3) may be produced individually and then mixed. Moreover, after manufacturing any two types of polymers in one reaction system, you may mix with another 1 type. 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 of the structural unit (cx) is in a wide range of 0 to 70% 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 method for producing 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 27 to 60:73 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 27-60: 73-40 to 5-25: 95-75. The copolymer is preferably part or all of the component [C]. By using a composition containing a copolymer obtained by this method, a molded product having excellent fluidity and impact 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 5-25: 95-75 to 27-60: 73-40, 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 27-60: 73-40 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 mixture of the polymers (C-1), (C-2) and (C-3) is from the viewpoint of molding processability and impact resistance of the molded product. , Preferably 0.2 to 0.9 dl / g, more preferably 0.25 to 0.85 dl / g, still 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, when the resin component is composed of components [A] and [B], the content ratio of the components [A] and [B], which are resin components, is the component [ D]. When the component [D] is a halogen compound, when the total of the two components is 100% by mass, the ratio of the components [A] and [B] is when the total of both is 100% by mass. Respectively, preferably 3 to 80% by mass and 20 to 97% by mass, more preferably 10 to 70% by mass and 30 to 90% by mass, still more preferably 20 to 60% by mass and 40 to 80% by mass, particularly preferably. Are 30-45 mass% and 55-70 mass%. When the proportions of the components [A] and [B] are in the above range, a molded article having excellent impact resistance can be obtained. In addition, when there is too little content of the said component [A], there exists a tendency for impact resistance to fall.

  Moreover, when the said component [D] is a flame retardant except a halogen compound (phosphorus compound etc.), when the sum total of the said 2 component shall be 100 mass%, the ratio of component [A] and [B] Are preferably 3 to 80% by mass and 20 to 97% by mass, more preferably 4 to 50% by mass and 50 to 96% by mass, and still more preferably 5 to 100% by mass when the total of both is 100% by mass. They are 35 mass% and 65-95 mass%, Most preferably, it is 5-15 mass% and 85-95 mass%. When the ratio of the components [A] and [B] is in the above range, a molded product having excellent impact resistance, heat resistance, fluidity and flame retardancy can be obtained.

  In the present invention, when the resin component is composed of the components [A], [B] and [C], the content ratios of the components [A], [B] and [C] which are resin components are intended. In order to obtain performance, it depends on the type of component [D] described later. 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%. When the proportions of the above components [A], [B] and [C] are in the above range, a molded product excellent in impact resistance, chemical 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. When the proportions of the above components [A], [B] and [C] are in the above range, a molded product excellent in impact resistance, chemical resistance, heat resistance, fluidity and flame retardancy can be obtained.

  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 molding processability and impact resistance of the molded product. %, More preferably 5 to 25% by 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.

Although content of the said component [D] is suitably selected according to the kind, when the sum total of the said component [A] and [B] is 100 mass parts, it is 1-35 mass parts.
When the component [D] is a halogen compound, the content thereof is preferably 5 to 30 parts by mass, more preferably 10 to 10 parts when the total of the components [A] and [B] is 100 parts by mass. 25 parts by mass.
Further, when the component [D] is a flame retardant excluding a halogen compound (phosphorus compound, etc.), the content is preferably when the total of the components [A] and [B] is 100 parts by mass. Is 7-30 parts by mass, more preferably 12-25 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.
By blending a fibrous filler such as glass fiber or carbon fiber, a highly rigid material can be obtained. A flame retardant material can be obtained by blending a flame retardant, a flame retardant aid, and the like. A matte material can be obtained by blending rubber particles and a functional group-containing polymer. Furthermore, a semi-transparent, high appearance material can be obtained by using a rubbery polymer having a refractive index adjusted.

  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.

  When the composition of the present invention contains the components [A], [B] and [C], in particular, excellent compatibility between the components [A] and [B], and in the obtained molded product, It is possible to obtain weld strength and surface impact resistance that are much better than before. In addition, the molded products obtained are required to have an excellent balance of impact resistance, heat resistance and surface impact resistance, such as members of vehicles, ships, electronic devices, home appliances, building materials, daily goods, sports equipment. Suitable for stationery and the like.

  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 manufacturing a molded article using the above molding apparatus, the molding temperature and mold temperature are determined depending on the type of the raw material for component [A] and the raw material for component [B], or the raw material component used (other polymer). Selection), etc., as appropriate.
For example, when the raw material for component [A] contains a rubbery polymer reinforced graft resin using a diene rubber, the cylinder temperature during molding is usually 230 ° C to 280 ° C. 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 8, 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, 92 parts of ion-exchanged water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 70 parts of latex containing 40 parts, 9.6 parts of styrene and 5.4 parts of acrylonitrile were accommodated and heated with stirring. When the internal temperature reached 38 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.004 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.066 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 60 minutes, 21.6 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 36 parts of styrene, 9 parts of acrylonitrile, 0.12 part of tert-dodecyl mercaptan and 0.11 part of cumene hydroperoxide, Added continuously over 3 hours. Thereafter, 0.1 part of cumene hydroperoxide was added, and the polymerization was continued for another hour to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product, and the resin component was coagulated and washed with water to obtain a rubber-reinforced aromatic vinyl resin (P1). The graft ratio of this resin is 76%, the content of ungrafted (co) polymer (hereinafter referred to as “acetone-soluble matter”) is 30%, and the intrinsic viscosity [η] ( 30 ° C. in methyl ethyl ketone) was 0.36 dl / g.

Synthesis Example 2 (Synthesis of raw material P2)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion-exchanged water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 70 parts of latex containing 40 parts, 10.95 parts of styrene and 4.05 parts of acrylonitrile were accommodated and heated with stirring. When the internal temperature reached 38 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.004 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.066 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 60 minutes, 21.6 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 36 parts of styrene, 9 parts of acrylonitrile, 0.12 part of tert-dodecyl mercaptan and 0.11 part of cumene hydroperoxide, Added continuously over 3 hours. Thereafter, 0.1 part of cumene hydroperoxide was added, and the polymerization was continued for another hour to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product, and the resin component was coagulated and washed with water to obtain a rubber-reinforced aromatic vinyl resin (P2). The graft ratio of this resin is 74%, and the content of ungrafted (co) polymer (acetone soluble component) is 30%. The intrinsic viscosity [η] of this acetone soluble component (30 ° C. in methyl ethyl ketone) Was 0.35 dl / g.

Synthesis example 3 (synthesis of raw material P3)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion-exchanged water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 70 parts of latex containing 40 parts, 8.25 parts of styrene and 6.75 parts of acrylonitrile were placed and heated with stirring. When the internal temperature reached 38 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.004 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.066 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 60 minutes, 21.6 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 36 parts of styrene, 9 parts of acrylonitrile, 0.12 part of tert-dodecyl mercaptan and 0.11 part of cumene hydroperoxide, Added continuously over 3 hours. Thereafter, 0.1 part of cumene hydroperoxide was added, and the polymerization was continued for another hour to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product, and the resin component was coagulated and washed with water to obtain a rubber-reinforced aromatic vinyl resin (P3). The graft ratio of this resin is 83%, and the content of ungrafted (co) polymer (acetone soluble component) is 27%. The intrinsic viscosity [η] of this acetone soluble component (in methyl ethyl ketone, 30 ° C.) Was 0.37 dl / g.

Synthesis Example 4 (Synthesis of raw material P4)
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 parts of salt and 0.03 parts of sodium dithionite were added. As a monomer, 5 parts of n-butyl acrylate was added, and the temperature was increased while stirring. Polymerization was started by adding 0.12 part of potassium persulfate at an internal temperature of 75 ° C.
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 continued for another hour. Cooled to ° C. Thereafter, 33 parts of ion-exchanged water, 0.8 part of potassium rosinate, 0.07 part of tert-butyl hydroperoxide were added, 0.4 part of sodium pyrophosphate, and ferrous sulfate heptahydrate 0.01. Part, a solution prepared by dissolving 0.3 part of glucose in 15 parts of ion-exchanged water, 9.6 parts of styrene, and 5.4 parts of acrylonitrile were added, and the temperature was raised to 75 ° C. After polymerization for 60 minutes, 28 parts of styrene, 7 parts of acrylonitrile, 0.1 part of tert-dodecyl mercaptan and 0.2 part of tert-butyl hydroperoxide were continuously added over 4 hours, and polymerization was further performed for 1 hour. Continued.
Coagulation with an aqueous magnesium sulfate solution, washing with water, and drying were performed to obtain a rubber-reinforced aromatic vinyl resin (P4). The graft ratio of this resin is 42%, the content of ungrafted (co) polymer (acetone soluble component) is 29%, and the intrinsic viscosity [η] of acetone soluble component is 0.45 dl / g. there were.

Synthesis Example 5 (Synthesis of raw material P5)
A 20 liter stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc., was charged with ethylene / α-olefin rubber (ethylene / propylene = 78/22 (%), Mooney viscosity (ML _{1 + 4).} , 100 ° C.) 20 parts, ethylene / propylene copolymer) 25 parts, 9.6 parts of styrene, 5.4 parts of acrylonitrile, 0.5 part of tert-dodecyl mercaptan, 110 parts of toluene, and the internal temperature is 75 ° C. The autoclave contents were stirred for 1 hour to obtain a homogeneous solution. Thereafter, 0.09 part of tert-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. After polymerization for 60 minutes, 48 parts of styrene, 12 parts of acrylonitrile, and 0.36 part of tert-butylperoxyisopropyl monocarbonate were continuously added over 3 hours. From 4 hours after the start of the polymerization reaction, 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 reaction. The polymerization conversion rate was 97%. Thereafter, the internal temperature was cooled to 100 ° C., 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave, Unreacted substances and solvent are distilled off by distillation, and volatiles are substantially degassed using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), pelletized, rubber-reinforced aromatic vinyl system Resin (P5) was obtained. The graft ratio of this resin is 50%, the content of ungrafted (co) polymer (acetone solubles) is 63%, and the intrinsic viscosity [η] of acetone solubles is 0.47 dl / g. there were.

Synthesis Example 6 (Synthesis of raw material P6)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion-exchanged water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 70 parts of latex containing 40 parts, 8.25 parts of styrene and 6.75 parts of acrylonitrile were placed and heated with stirring. When the internal temperature reached 38 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.004 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.066 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 60 minutes, 21.6 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 24.75 parts of styrene, 20.25 parts of acrylonitrile, 0.13 parts of tert-dodecyl mercaptan and 0. 3 cumene hydroperoxide. 1 part was added continuously over 3 hours. Thereafter, the polymerization was further continued for 1 hour 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 (P6). The graft ratio of this resin is 80%, and the content of ungrafted (co) polymer (acetone soluble component) is 28%. The intrinsic viscosity [η] of this acetone soluble component (30 ° C. in methyl ethyl ketone) Was 0.40 dl / g.

Synthesis Example 7 (synthesis of raw material P7)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion-exchanged water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 70 parts of latex containing 40 parts, 9.6 parts of styrene and 5.4 parts of acrylonitrile were accommodated and heated with stirring. When the internal temperature reached 38 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.004 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.066 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 60 minutes, 21.6 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 28.8 parts of styrene, 16.2 parts of acrylonitrile, 0.12 part of tert-dodecyl mercaptan and 0. 0 cumene hydroperoxide. 11 parts were added continuously over 3 hours. Thereafter, 0.1 part of cumene hydroperoxide was added, and the polymerization was continued for another hour to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product, and the resin component was coagulated and washed with water to obtain a rubber-reinforced aromatic vinyl resin (P7). The graft ratio of this resin is 73%, and the content of the ungrafted (co) polymer (acetone soluble component) is 31%. The intrinsic viscosity [η] of this acetone soluble component (30 ° C. in methyl ethyl ketone) Was 0.38 dl / g.

Synthesis Example 8 (synthesis of raw material P8)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion-exchanged water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 70 parts of latex containing 40 parts, 12 parts of styrene and 3 parts of acrylonitrile were accommodated and heated with stirring. When the internal temperature reached 38 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.004 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.066 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 60 minutes, 21.6 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 36 parts of styrene, 9 parts of acrylonitrile, 0.12 part of tert-dodecyl mercaptan and 0.11 part of cumene hydroperoxide, Added continuously over 3 hours. Thereafter, 0.1 part of cumene hydroperoxide was added, and the polymerization was continued for another hour to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product, and the resin component was coagulated and washed with water to obtain a rubber-reinforced aromatic vinyl resin (P8). The graft ratio of this resin is 59%, and the content of ungrafted (co) polymer (acetone soluble component) is 36%. The intrinsic viscosity [η] of this acetone soluble component (in methyl ethyl ketone, 30 ° C.) Was 0.32 dl / g.

The raw material [P] includes a part or all of the graft resins (A-1), (A-2) and (A-3) constituting the component [A] according to the present invention, depending on the synthesis method. There is a case. Therefore, s ₁ = 28 and s ₂ = 33 are selected, and when the total of the graft resins (A-1), (A-2) and (A-3) is 100%, the respective proportions are determined by ozonolysis and Table 1 shows the values obtained by a method combined with liquid chromatography (described above).
Furthermore, the raw material [P] may be a mixture comprising the component [A] and the component [C] according to the present invention depending on the synthesis method. Therefore, using the graft ratio in the raw material [P], the acetone-soluble composition, etc., the content of the polymer corresponding to the component [C] with respect to the total amount of the components [A] and [C] of the present invention is determined. The calculated values are shown in Table 1 together with the ratio of the component [A]. Then, the component [C], the polymer (C-1), as to be constituted by (C-2) and _(C-3), select r 1 = 28 and _r 2 = 33, these Each ratio when the total was taken as 100% was analyzed by the following method. Moreover, it showed in Table 1 about content of the structural unit (cx) contained in component [C].

<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 in Synthesis Example 9 below was used.

Synthesis Example 9 (synthesis of raw material R1)
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 76 parts of styrene, 24 parts of acrylonitrile and 25 parts of toluene, and 0.40 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 carried out at 140 ° C. for 2 hours, and the polymerization conversion after 2 hours was 83%.
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 the raw material R1.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this raw material R1 was 0.42 dl / g.
For this raw material R1, as in the case of the acetone-soluble component of the raw material [P], the composition analysis of the polymers (C-1), (C-2) and (C-3) (r ₁ = 28 And r ₂ = 33) to obtain 78%, 22% and 0%, respectively.

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 1-18 and Comparative Examples 1-6
Thermoplastic resin compositions were obtained using the raw materials [P], [Q], [R] and [S] in the proportions shown in Tables 2 to 8. In evaluating the composition, a physical property evaluation composition containing an additive corresponding to the evaluation item was prepared in advance and used.
The raw material [P] may be a mixture comprising the component [A] and the component [C] according to the present invention, depending on the synthesis method. Therefore, a polymer corresponding to the component [C] with respect to the total amount of the components [A], [B] and [C] of the present invention, using the graft ratio in the raw material [P], the composition soluble in acetone, and the like. The content ratio was calculated and the value is 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 = 28 and _r 2 = 33, 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) 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 135 V, 16 A, 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.
(5) 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.

  From the results in Tables 2 to 5, the following is clear. The comparative example 1 is an example which does not contain the graft resins (A-1) and (A-2) constituting the component [A] according to the present invention, and the impact resistance was insufficient. The comparative example 2 is an example which does not contain the graft resin (A-1) constituting the component [A] according to the present invention, and the impact resistance was insufficient. The comparative example 3 is an example which does not contain the graft resins (A-2) and (A-3) constituting the component [A] according to the present invention, and the impact resistance was insufficient. On the other hand, in Examples 1 to 11, flammability (V-0) was obtained, and improved impact resistance was obtained.

  From the results of Tables 6 to 8, the following is clear. The comparative example 4 is an example which does not contain the graft resins (A-1) and (A-2) constituting the component [A] according to the present invention, and the impact resistance was insufficient. The comparative example 5 is an example which does not contain the graft resin (A-1) constituting the component [A] according to the present invention, and has insufficient impact resistance. The comparative example 6 is an example which does not contain the graft resins (A-2) and (A-3) constituting the component [A] according to the present invention, and the impact resistance was insufficient. On the other hand, in Examples 12 to 16, 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 (13)

[A] A rubbery polymer in which a copolymer containing a structural unit (gx) derived from a vinyl cyanide compound and a structural unit (gy) derived from an aromatic vinyl compound is grafted to the rubbery polymer. (A-1) a rubbery polymer reinforced graft resin comprising a copolymer containing the structural unit (gx) at 5% by mass or more and s ₁ % by mass or less, (A-2) ) A rubbery polymer reinforced graft resin comprising a copolymer containing the structural unit (gx) in an amount of more than s ₁ % by mass and s ₂ % by mass or less, and (A-3) the structural unit (gx), mixed graft resin comprising a rubbery polymer reinforced graft resin comprising a copolymer containing more than ₂ mass% and not more than 60 mass%, and (s ₂ −s ₁ ) ≧ 3 (mass%) When,
[B] polycarbonate resin;
[D] a flame retardant;
In a thermoplastic resin composition containing
The rubbery polymer reinforced graft resins (A-1), (A-2), and (A-3) are contained in amounts of 1 to 98.9 masses when the total content is 100 mass%. %, 1-90% by mass and 0.1-90% by mass,
The content of the flame retardant [D] is 1 to 35 parts by mass when the total of the mixed graft resin [A] and the polycarbonate resin [B] is 100 parts by mass. Resin composition. s ₁ is 10 to 30 mass%, the thermoplastic resin composition of claim 1 _{s 2} is 15 to 45 mass%.   When the mixed graft resin [A] graft-polymerizes the polymerizable unsaturated monomer (am) containing the vinyl cyanide compound and the aromatic vinyl compound in the presence of the rubbery polymer, the cyanide is used. From 25 to 95:75 to 27 to 60:73 to 40, or from 27 to 60:73 to 40 to 5 to 25:95 to 75 by mass ratio of the vinyl compound and the aromatic vinyl compound. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a resin obtained by graft polymerization while changing a charged amount.   The content ratios of the mixed graft resin [A] and the polycarbonate resin [B] are 3 to 80% by mass and 20 to 97% by mass, respectively, when the total content is 100% by mass. The thermoplastic resin composition according to any one of 3.   The ratio of the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound contained in the mixed graft resin [A] is 100% by mass. The thermoplastic resin composition according to any one of claims 1 to 4, which is 5 to 60% by mass and 40 to 95% by mass, respectively.   Furthermore, [C] a structural unit derived from the vinyl cyanide compound obtained by polymerizing a polymerizable unsaturated monomer containing a vinyl cyanide compound and an aromatic vinyl compound in the absence of a rubbery polymer. The thermoplastic resin composition according to any one of claims 1 to 5, comprising a copolymer containing (cx) and a structural unit (cy) derived from the aromatic vinyl compound. The copolymer [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% polymer comprising at _{r 2} wt% or less than the (C-2), made from the structural units (cx), a polymer beyond _{r 2} wt% comprising 60 wt% or less (C-3), And (r ₂ −r ₁ ) ≧ 3 (mass%),
The content ratios of the polymers (C-1), (C-2), and (C-3) are 1 to 89.9% by mass and 10 to 70%, respectively, when the total content is 100% by mass. The thermoplastic resin composition according to claim 6, wherein the thermoplastic resin composition is mass% and 0.1 to 80 mass%. The thermoplastic resin composition according to claim 6 or 7, wherein r2 is ₂₀ to 45 mass%.   The content ratio of the structural unit (cx) contained in the copolymer [C] is 5 to 60% by mass when the total of the structural units constituting the copolymer [C] is 100% by mass. The thermoplastic resin composition according to any one of claims 6 to 8. r ₁ is 10 to 35 wt%, _{r 2} is 25 to 45 wt%,
When the content ratios of the polymers (C-1), (C-2), and (C-3) are 100% by mass, the total content is 35 to 89.5% by mass and 10 to 50%, respectively. The thermoplastic resin composition according to any one of claims 6 to 9, wherein the thermoplastic resin composition is 0.5% by mass and 0.5-50% by mass.   The content ratios of the mixed graft resin [A], the polycarbonate resin [B], and the copolymer [C] are 3 to 65% by mass, 20 to 90%, respectively, when the total content is 100% by mass. The thermoplastic resin composition according to any one of claims 6 to 10, wherein the thermoplastic resin composition has a mass% of 2 to 60 mass%.   The thermoplastic resin composition according to any one of claims 1 to 11, 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 12.