JP5828711B2 - Thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition that gives a molded article excellent in impact resistance.

Polypropylene resin has low specific gravity, excellent water resistance, hydrolysis resistance, chemical resistance, hinge characteristics and moldability, and is widely used as molding material for automobile parts, electrical parts, household goods, miscellaneous goods, etc. . However, there are problems in impact resistance, rigidity, heat resistance, appearance, molding shrinkage and paintability.
On the other hand, rubber-reinforced resins such as ABS resin obtained by graft polymerization of aromatic vinyl compound and vinyl cyanide compound to conjugated diene rubber are excellent in moldability, impact resistance, rigidity, appearance and paintability. It is used as a molding material for automobile parts, electrical products, building materials, household goods, sundries, etc. However, there is a problem that the specific gravity is high and there is a limit to the weight reduction as compared with the polypropylene resin.

  Therefore, development of a polymer alloy material that makes use of the respective characteristics by making a polypropylene alloy and a rubber reinforced resin into a polymer alloy has been studied. However, since the polypropylene resin and the rubber reinforced resin are poor in compatibility, it is difficult to form a polymer alloy and it is difficult to improve physical properties. Thereafter, for the purpose of polymer alloying of a polypropylene resin and a rubber reinforced resin, compounding agents including a compatibilizing agent have been studied (for example, see Patent Documents 1 to 3).

Patent Document 1 discloses a polypropylene resin composition containing a polypropylene resin, a rubber-containing graft copolymer, and a polypropylene resin graft copolymer.
Patent Document 2 discloses a rubber-reinforced resin obtained by polymerizing a monomer component containing an aromatic vinyl compound in the presence of a hydrogenated diene polymer obtained by hydrogenating a conjugated diene (co) polymer, A thermoplastic resin composition containing a polyolefin is disclosed.
Patent Document 3 discloses a copolymer obtained by polymerizing a monomer containing an aromatic vinyl compound and a vinylcyan compound in the presence of a conjugated diene rubber polymer having a gel content of 20 to 100% by mass. A resin or a composition of a copolymer resin and a vinyl monomer (co) polymer, wherein the content of the conjugated diene rubber polymer is 3 to 70% by mass. Resin composition, polyolefin resin, and hydrogenated conjugated diene polymer, hydrogenated conjugated diene polymer having a diene hydrogenation rate of 10 to 95% Is disclosed.

  In recent years, mechanical parts and sliding parts in automobiles and various machines including electronic devices are becoming lighter or thinner. For molded products containing resin materials used for their housings and parts. Therefore, the impact resistance superior to that of conventional products has been demanded.

JP 2008-7550 A JP-A-9-95588 JP 2004-210871 A

  An object of this invention is to provide the thermoplastic resin composition which gives the molded article excellent in impact resistance.

The present invention is as follows.
1. [A] A rubbery polymer reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, [B] an aromatic A polymer (B-1) comprising a structural unit (by) derived from a vinyl compound and comprising a structural unit (bx) derived from a vinyl cyanide compound in an amount of 0% by mass or more and ₁ % by mass or less; and the above structural unit (By), the polymer (B-2) containing the structural unit (bx) in an amount exceeding ₁ mass% and ₂ mass% or less, and the structural unit (by). bx) comprising a polymer (B-3) containing more than r ₂ % by mass and not more than 60% by mass, and (r ₂ -r ₁ ) ≧ 5 (% by mass), [C ] A propylene polymer containing a structural unit derived from propylene, and [D] aromatic A block copolymer (D-1) comprising a polymer block containing a structural unit derived from a nil compound and a polymer block containing a structural unit derived from a conjugated diene compound, and the block copolymer (D- 1) containing at least one selected from hydrogenated polymers (D-2) obtained by subjecting to a hydrogenation reaction, wherein r ₁ is 12 to 18% by mass in the above component [B] There, _{r 2} is from 18 to 25 mass%, constituting the component (B), the polymer (B-1), containing the polymer (B-2) and the polymer (B-3) The ratio is 10 to 90% by mass, 3 to 70% by mass, and 5 to 80% by mass, respectively, when the total is 100% by mass.
2 . The content of the structural unit (bx) contained in the component [B] is 5 to 40% by mass when the total of the structural units constituting the component [B] is 100% by mass. The thermoplastic resin composition as described.
3 . The content ratios of the component [A], the component [B], the component [C], and the component [D] are 3 to 70% by mass, 3. The thermoplastic resin composition according to 1 or 2 above, which is 85% by mass, 3-70% by mass, and 0.5-50% by mass.
4 . When the proportion 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 component [A] is 100% by mass. The thermoplastic resin composition according to any one of 1 to 3 above, which is 5 to 40% by mass and 60 to 95% by mass, respectively.
5 . When the content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) is 100% by mass, the content is 25 to 70% by mass, respectively. The thermoplastic resin composition according to any one of 1 to 4 above, which is 7 to 40% by mass and 15 to 60% by mass.
6 . A molded article comprising the thermoplastic resin composition according to any one of 1 to 5 above.

According to the thermoplastic resin composition of the present invention, a molded product having excellent impact resistance can be obtained. Therefore, the thermoplastic resin composition of the present invention is suitable for forming members such as vehicles, ships, OA equipment, home appliances, electric / electronic equipment, building materials, and daily goods, sports goods, stationery, and other molded articles. It is.
The thermoplastic resin composition of the present invention is a composition prepared by blending a predetermined resin with a recycled resin from a molded product containing an ABS resin or a recycled resin from a molded product containing a propylene-based polymer. It can be a thing. That is, a low-cost composition using raw material components excluding recycled resin can be obtained.

It is a schematic explanatory drawing which shows the relationship between the ratio (%) of a structural unit (bx), and the production amount of a component [B] about component [B] obtained by the power feed method.

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 is a rubbery polymer obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of [A] a rubbery polymer. Combined reinforced graft resin, [B] A polymer containing a structural unit (by) derived from an aromatic vinyl compound and a structural unit (bx) derived from a vinyl cyanide compound in an amount of 0% by mass or more and r ₁ % by mass or less. (B-1), the polymer (B-2) containing the structural unit (by), and containing the structural unit (bx) in an amount exceeding ₁ mass% and ₂ mass% or less, and the structural unit. (By) and a polymer (B-3) containing the structural unit (bx) in an amount exceeding 60 mass% and exceeding ₂ mass%, and (r ₂ -r ₁ ) ≧ 5 ( Mass%) polymer, [C] propylene containing structural units derived from propylene A block copolymer (D-1) comprising a polymer and a polymer block containing a structural unit derived from a [D] aromatic vinyl compound and a structural unit derived from a conjugated diene compound; And at least one selected from hydrogenated polymers (D-2) obtained by subjecting the block copolymer (D-1) to a hydrogenation reaction, and in the above component [B] , _{r 1} is 12 to 18 wt%, _{r 2} is from 18 to 25 mass%, constituting the component (B), the polymer (B-1), the polymer (B-2) and The content ratio of the polymer (B-3) is 10 to 90% by mass, 3 to 70% by mass, and 5 to 80% by mass, respectively, when the total of these is 100% by mass. To do.

The component [A] is obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer (hereinafter referred to as “graft polymerization”). A rubbery polymer reinforced graft resin (hereinafter referred to as “graft resin”) contained in a resin composition (hereinafter referred to as “rubber reinforced resin”). This graft resin is a copolymer containing a structural unit derived from a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound, that is, a structural unit derived from an aromatic vinyl compound and a vinyl cyanide compound. A copolymer containing at least a structural unit derived from is a resin grafted to a rubbery polymer, and a polymerizable unsaturated monomer containing a rubbery polymer part and an aromatic vinyl compound and a vinyl cyanide compound And a copolymer part (graft part) containing a structural unit derived from the body.
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. The composition of the ungrafted polymer depends on the type of polymerizable unsaturated monomer used, and the ungrafted polymer is usually contained in the component [B] in the composition of the present invention.

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

  Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymers such as styrene; styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymers such as acrylonitrile / styrene / isoprene copolymers; natural rubber, etc. It is done. 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 an ethylene unit and an ethylene / α-olefin copolymer containing a unit composed of an α-olefin having 3 or more carbon atoms, a urethane rubber, an acrylic rubber, a silicone rubber, Examples thereof include a silicone-acrylic IPN rubber and a polymer obtained by hydrogenating a (co) polymer containing a unit composed of a conjugated diene compound. 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 component [A] is preferably a rubbery polymer reinforced graft resin obtained using a diene rubber as the rubbery polymer.

  The shape of the rubbery polymer used for forming the component [A] can be, for example, particulate (spherical or substantially spherical), linear, curved, or the like. When it is in the form of particles, the volume average particle diameter is preferably 50 to 2,000 nm, more preferably 80 to 1,000 nm, from the viewpoints of mechanical properties and molding processability. The volume average particle diameter can be measured by image analysis using an electron micrograph, a laser diffraction method, a light scattering method, or the like.

  The polymerizable unsaturated monomer includes an aromatic vinyl compound and a vinyl cyanide compound.

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

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

  As described above, since the rubber-reinforced resin obtained by graft polymerization usually contains an ungrafted polymer, the ungrafted polymer usually contains a structural unit (bx) derived from a vinyl cyanide compound and an aromatic. A structural unit (by) derived from a group vinyl compound is included.

  The lower limit of the total amount of the aromatic vinyl compound and the vinyl cyanide compound contained in the polymerizable unsaturated monomer is preferably 70% by mass, more preferably 80% by mass, and still more preferably 95% by mass. . The upper limit is usually 100% by mass. The ratio of the aromatic vinyl compound and the vinyl cyanide compound is 100% by mass from the viewpoint of molding processability, chemical resistance, impact resistance, rigidity, dimensional stability, molding appearance, etc. Respectively, Preferably they are 40-95 mass% and 5-60 mass%, More preferably, they are 50-90 mass% and 10-50 mass%, More preferably, they are 60-85 mass% and 15-40 mass%.

  The polymerizable unsaturated monomer may contain other vinyl monomers in addition to the aromatic vinyl compound and the vinyl cyanide compound.

  When the polymerizable unsaturated monomer contains another vinyl monomer, examples thereof include a (meth) acrylic acid ester compound, a maleimide compound, an unsaturated acid anhydride, a carboxyl group-containing unsaturated compound, Examples include hydroxyl group-containing unsaturated compounds (excluding (meth) acrylic acid ester compounds in which the ester moiety contains a hydroxyalkyl group), oxazoline group-containing unsaturated compounds, and the like.

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.

As the component [A], preferred graft resins are as follows.
(1) Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber. (2) In the presence of a diene rubber, Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester compound (3) In the presence of a diene rubber, an aromatic vinyl compound, Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising a vinyl cyanide compound and a maleimide compound

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  When the component [A] and the ungrafted polymer are separated from the rubber-reinforced resin containing the component [A] obtained as described above, for example, 10 g of the rubber-reinforced resin is added to 100 to 200 ml of acetone (rubber If the polymer is an acrylic rubber, use acetonitrile) and shake it at 25 ° C for 2 to 3 hours using a shaker etc. to separate the insoluble and soluble components produced. The method of recovery is applied. Acetone-soluble matter (acetonitrile-soluble matter) corresponds to an ungrafted polymer, and some of it is contained in component [B] depending on the amount of the polymerizable unsaturated monomer used.

  The graft ratio in the component [A] is preferably 20 to 120%, more preferably 30 to 100%, and still more preferably 35 from the viewpoints of moldability, impact resistance of the molded product, molded appearance, and the like. ~ 80%. 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 gram of rubber-reinforced resin obtained by graft polymerization in 20 ml of acetone (acetonitrile is used when the rubbery polymer is an acrylic rubber), and is shaken using a shaker. (Temperature 25 ° C., 2 hours), then centrifuge using a centrifuge (temperature 5 ° C., rotation speed 23,000 rpm, 1 hour) to separate the insoluble matter and the soluble matter. The mass (g) of the minute, and T is the mass (g) of the rubbery polymer contained in 1 gram of the rubber-reinforced resin. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

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

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

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

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

A preferred component [A] in the present invention is a graft resin obtained by polymerizing a polymerizable unsaturated monomer containing a vinyl cyanide compound and an aromatic vinyl compound in the presence of a rubbery polymer, When the ratio of the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound in the graft portion constituting this graft resin is 100% by mass in total. , Preferably 5 to 40 mass% and 60 to 95 mass%, more preferably 10 to 35 mass% and 65 to 90 mass%, respectively. By using the composition containing the component [A] in the above range, a molded product having an excellent balance between impact resistance and molded appearance can be obtained.
The content of the structural units (gx) and (gy) is calculated from the polymerization prescription and the polymerization conversion rate, the method of obtaining the infrared absorption spectrum (IR), the nuclear magnetic resonance spectrum, etc., and further the ozonolysis of the graft resin. Then, it can be obtained by a method used for CHN elemental analysis, liquid chromatographic analysis, or the like.

  The structural unit (gx) contained in the component [A] and the structural unit (bx) contained in the component [B] may be the same as or different from each other. Moreover, the structural unit (gy) contained in the component [A] and the structural unit (by) contained in the component [B] may be the same or different.

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

  In the composition of the present invention, the content of the component [A] is preferably 3 to 70 masses when the total of the components [A], [B], [C] and [D] is 100 mass%. %, More preferably, it is 10-55 mass%, More preferably, it is 15-40 mass%. When the content of the component [A] is 3 to 70% by mass, a molded product having an excellent balance between impact resistance and molded appearance 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.

The component [B] contains a structural unit (by) derived from an aromatic vinyl compound, and a polymer (b) having a structural unit (bx) derived from a vinyl cyanide compound in an amount of 0% by mass to ₁ % by mass. B-1), a polymer (B-2) containing the structural unit (by) and containing the structural unit (bx) in an amount of more than r ₁ % by mass and ₂ % by mass or less, and the structural unit (B-2) by) and a polymer (B-3) containing the structural unit (bx) in an amount of more than r ₂ % by mass and 60% by mass or less. That is, both of the component [B] may include two types of copolymers including the structural units (bx) and (by), the structural unit (by), and the structural unit (bx). It consists of a (co) polymer. Each polymer may optionally further contain another structural unit (hereinafter also referred to as “structural unit (bz)”). In the component [B], r ₁ is 12 to 18% by mass, r ₂ is 18 to 25% by mass, and (r ₂ −r ₁ ) ≧ 5 (% by mass).
Moreover, the content rate of the said polymer (B-1), a polymer (B-2), and a polymer (B-3) is 10-90 mass%, respectively, when these sum is 100 mass%. 3 to 70% by mass and 5 to 80% by mass.

For the vinyl cyanide compound forming the structural unit (bx), the description of the vinyl cyanide compound contained in the polymerizable unsaturated monomer used for forming the component [A] is applied. The structural unit (bx) contained in the component [B] may be only one type or two or more types. As the vinyl cyanide compound, acrylonitrile is preferable.
The content of the structural unit (bx) contained in the component [B] is preferably 5 to 40% by mass, more preferably 7 to 7%, assuming that the total of the structural units constituting the component [B] is 100% by mass. It is 32 mass%, More preferably, it is 10-25 mass%. When the content of the structural unit (bx) is 5 to 40% by mass, a molded product having excellent molding processability (fluidity) of the composition can be obtained.

For the aromatic vinyl compound forming the structural unit (by), the description of the aromatic vinyl compound contained in the polymerizable unsaturated monomer used for forming the component [A] is applied. The structural unit (by) contained in the component [B] 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 (by) contained in the component [B] is preferably 60 to 95% by mass, more preferably 68 to 95% when the total of structural units constituting the component [B] is 100% by mass. It is 93 mass%, More preferably, it is 75-90 mass%. When the content of the structural unit (by) is 60 to 95% by mass, a molded product having excellent molding processability (fluidity) of the composition can be obtained.

Examples of the monomer forming the structural unit (bz) 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 [B] contains the structural unit (bz), the upper limit of the content is the sum of the structural units constituting the component [B], that is, the structural units (bx), (by) and (bz ) Is 100% by mass, preferably 30% by mass, more preferably 15% by mass.
In addition, this structural unit (bz) may be contained in all of a polymer (B-1), a polymer (B-2), and a polymer (B-3), and may be contained in one part. .

  The said component [B] consists of a polymer (B-1), a polymer (B-2), and a polymer (B-3), but the polymer (B-1) in the case of containing a structural unit (bx) In the polymer (B-2) and the polymer (B-3), the type of the structural unit (bx) may be the same or different. The type of the structural unit (by) may also be the same or different. The types in the case of including the structural unit (bz) may also be the same or different.

The polymer (B-1), the polymer (B-2) and the polymer (B-3) are polymers having different contents of the structural unit (bx), and the structural unit (bx) It is a polymer in which the content of is increased.
The component [B] is composed of the polymer (B-1), the polymer (B-2), and the polymer (B-3) having the above configuration, so that the component [B] is between the component [A] and the component [C]. Therefore, it is possible to efficiently produce a molded article having a high compatibility improvement effect and excellent impact resistance. In particular, when the component [B] composed of an aggregate of copolymers having a content ratio of the structural unit (bx) in the range of 5 to 40% by mass as described above is used, the above effect is remarkable.

The said polymer (B-1) is a polymer which contains a structural unit (bx) by 0 mass% or more and r ₁ mass% or less (r ₁ is 12-18 mass%) , and is illustrated below.
(1) (Co) polymer (B-1-1) comprising structural unit (by)
(2) Copolymer (B-1-2) comprising structural units (bx) and (by)
(3) Copolymer (B-1-3) comprising structural units (bx), (by) and (bz)
(4) Copolymer (B-1-4) comprising structural units (by) and (bz)
A polymer of these embodiments can be used in combination as a polymer (B-1). Further, for example, the polymer (B-1-2) or the polymer (B-1-3) is composed of two types of polymers, and 0 <r ₁₁ <r ₁₂ ≦ r ₁ In this case, a polymer (B-1) obtained by using a polymer containing ₁₁ mass% of the structural unit (bx) and a polymer containing ₁₂ mass% of the structural unit (bx) can be used. .
The polymer (B-1) is a polymer not containing the structural unit (bx), that is, a (co) polymer (B-1-1) or a copolymer (B-1-4). In the case where these polymers are included, copolymers containing structural units (bx) and (by), that is, the above-mentioned copolymers (B-1-2) and copolymers It is preferable that at least one of (B-1-3) is included. At this time, the content ratio of the copolymer containing the structural units (bx) and (by) is preferably 40% by mass or more, more preferably 50 to 95% by mass with respect to the polymer (B-1). More preferably, it is 55-90 mass%.
r ₁ is 12 to 18 mass%. When two or more kinds of polymers corresponding to the polymer (B-1) are contained, the value shown as “content of the structural unit (bx) contained in the polymer (B-1)” is included in each polymer. It is an average value calculated from the content of the structural unit (bx).

The polymer (B-2) contains the structural unit (bx) in an amount exceeding ₁ mass% and ₂ mass% or less (r ₁ is 12 to 18 mass%, r ₂ is 18 to 25 mass%) . , A copolymer containing the structural units (bx) and (by), and may be a copolymer comprising the structural units (bx) and (by) as described above, or the structural units (bx), ( a copolymer comprising (by) and (bz) may be used. Moreover, as mentioned above, this polymer (B-2) can consist of at least 1 sort (s) of the polymer containing the predetermined amount of a structural unit (bx). For example, when it is composed of two types of copolymers and r ₁ <r ₂₁ <r ₂₂ ≦ r ₂ , a polymer containing ₂₁ % by mass of structural unit (bx) and structural unit (bx) And a polymer (B-2) consisting of a polymer containing ₂₂ mass% of r.
r ₂ is 18 to 25 mass%. When two or more kinds of polymers corresponding to the polymer (B-2) are contained, the value shown as “content of structural unit (bx) contained in polymer (B-2)” is included in each polymer. It is an average value calculated from the content of the structural unit (bx).
In the present invention, when r ₂ is 18 to 25 % by mass, in the composition of the present invention, in particular, the compatibility between the component [A] and the component [C] is improved. Excellent impact resistance.
In the present invention, the relationship between r ₁ and r _{2 at} which the effect of balance between impact resistance and molding appearance is significant is (r ₂ −r ₁ ) ≧ 5 (mass%), preferably (r ₂ −r ₁ ) ≧ 6 (mass%), more preferably (r ₂ −r ₁ ) ≧ 7 (mass%). However, usually (r ₂ −r ₁ ) ≦ 40 (mass%), preferably (r ₂ −r ₁ ) ≦ 33 (mass%), more preferably (r ₂ −r ₁ ) ≦ 25 (mass%). It is. When (r ₂ −r ₁ ) <5 (mass%), the effect of the present invention cannot be sufficiently obtained.

The polymer (B-3) is a polymer containing the structural unit (bx) in an amount exceeding 60% by mass (r ₂ is 18 to 25% by mass) exceeding r ₂ % by mass , and as described above. It may be a copolymer composed of the structural units (bx) and (by), or may be a copolymer composed of the structural units (bx), (by), and (bz). Moreover, as mentioned above, this polymer (B-3) can consist of at least 1 sort (s) of the polymer containing the predetermined amount of a structural unit (bx). For example, when it is composed of two types of copolymers and r ₂ <r ₃₁ <r ₃₂ ≦ 60, a polymer containing ₃₁ % by mass of structural unit (bx) and structural unit (bx) r A polymer containing ₃₂ % by mass and a polymer (B-3) comprising the same can be used.
When two or more types of polymers corresponding to the polymer (B-3) are contained, the value shown as “content of structural unit (bx) contained in polymer (B-3)” is included in each polymer. It is an average value calculated from the content of the structural unit (bx).

The content ratios of the polymer (B-1), the polymer (B-2) and the polymer (B-3) constituting the component [B] are as follows. Preferably 10 to 90 mass%, 3 to 70 mass% and 5 to 80 mass%, more preferably 20 to 80 mass%, 5 to 55 mass% and 10 to 70 mass%, still more preferably 25 to 70 mass%, They are 7-40 mass% and 15-60 mass%, Most preferably, they are 30-65 mass%, 8-30 mass%, and 25-50 mass%.
In addition, the effects of the fluidity of the composition and the balance between the impact resistance and the molded appearance of the molded product obtained are significant when r ₁ is 12 to 18 % by mass and r ₂ is 18 to 18 % by mass. When the total content of these polymers (B-1), polymers (B-2) and polymers (B-3) is 100% by mass, it is preferably 25 % by mass. Is 25 to 70 mass%, 7 to 40 mass% and 15 to 60 mass%, more preferably 30 to 65 mass%, 8 to 30 mass% and 25 to 50 mass%, still more preferably 32 to 65 mass%, 9 -25% by mass and 25-45% by mass, particularly preferably 40-65% by mass, 9-20% by mass and 25-40% by mass.

As described above, the content ratios of the polymer (B-1), the polymer (B-2), and the polymer (B-3) when r ₁ and r ₂ are determined are determined by liquid chromatography. be able to. For example, a copolymer containing a structural unit (bx) derived from a vinyl cyanide compound and a structural unit (by) derived from an aromatic vinyl compound was used using n-heptane, 1,2-dichloroethane, acetonitrile or the like. It can be used for gradient analysis.

Preferred embodiments of the component [B] in the present invention are shown below.
The polymer (B-1) preferably includes a copolymer composed of structural units (bx) and (by), and the copolymer is a (co) polymer composed of structural units (by), a structure. You may use together with the copolymer chosen from the copolymer which consists of unit (by) and (bz), the copolymer which consists of structural unit (bx), (by) and (bz), and. As the monomer for forming the structural unit (bz), maleimide compounds such as N-phenylmaleimide and (meth) acrylic acid ester compounds such as methyl methacrylate are preferable.
The polymer (B-2) preferably includes a copolymer composed of structural units (bx) and (by). The copolymer is composed of structural units (bx), (by), and (bz). You may use together with the copolymer which becomes. As the monomer for forming the structural unit (bz), maleimide compounds such as N-phenylmaleimide and (meth) acrylic acid ester compounds such as methyl methacrylate are preferable.
The polymer (B-3) preferably includes a copolymer composed of structural units (bx) and (by), and the copolymer includes structural units (bx), (by) and (bz). You may use together with the copolymer which consists of. As the monomer for forming the structural unit (bz), maleimide compounds such as N-phenylmaleimide and (meth) acrylic acid ester compounds such as methyl methacrylate are preferable.

The method for producing the polymer (B-1), polymer (B-2) and polymer (B-3) constituting the component [B] is not particularly limited, and the structure contained in each polymer. Examples include a method in which the monomer forming the unit is subjected to emulsion polymerization, solution polymerization, bulk polymerization, and the like. For example, the polymer (B-1), the polymer (B-2), and the polymer (B-3) are individually manufactured using the monomer, and then mixed to obtain the component [B]. Can be formed. Moreover, in one reaction system, after producing any 2 types of polymers, it can mix with another 1 type and can form component [B]. Further, three or more kinds of polymers may be produced in one reaction system.
Moreover, as mentioned above, the ungrafted polymer produced | generated when manufacturing the graft resin which is component [A] can be used as a part of component [B]. In this case, for example, the structure of the polymerizable unsaturated monomer used for the production of the graft resin includes the structures contained in the polymer (B-1), the polymer (B-2), and the polymer (B-3). It is selected so as to be included in the content ratio of the units, and three types of graft resins are produced, and all the polymers (B-1), polymers (B-2) and polymers (B) constituting the component [B] The method of producing | generating three types of ungrafted polymers corresponding to B-3) is mentioned.

  In one reaction system, two or three of the polymer (B-1), the polymer (B-2) and the polymer (B-3) containing the structural unit (bx) are used using a monomer. In the case of producing a seed polymer, there is a method of proceeding polymerization while changing the charged amount (feed amount, feed rate) of each monomer (vinyl cyanide compound, aromatic vinyl compound, etc.) to the reaction system. 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, By continuously supplying the vinyl cyanide compound to the reaction system continuously or intermittently, the content ratio of the structural unit (bx) is in a wide range of more than 0% by mass and less than 100% by mass. It can consist of aggregates. In the present invention, in the aggregate of copolymers obtained by this power feed method, the polymer (B-1), the polymer (B-2) and the polymer (B-3) are each predetermined. Since it can be contained in a proportion, it is suitable as a method for producing component [B].

In the present invention, a copolymer obtained by polymerization while changing the charged amounts of the vinyl cyanide compound and the aromatic vinyl compound from 0 to 10: 100 to 90 to 15 to 60:85 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 15-60: 85-40 to 0-10: 100-90. The copolymer is preferably part or all of the component [B]. By using the composition containing the copolymer obtained by this method, it is possible to efficiently produce a molded product having excellent fluidity of the composition and excellent balance between impact resistance and molded appearance.
FIG. 1 shows a copolymer obtained by polymerization while changing the charged amounts of a vinyl cyanide compound and an aromatic vinyl compound from 0 to 10: 100 to 90 to 15 to 60:85 to 40 by mass ratio. It is a graph which shows an example of distribution of (component [B]). Thus, in the power feed method, for example, the amount of polymer (B-1) produced is increased by changing the amount of monomer charged (feed amount, feed rate) during the reaction, etc. The production amount of the polymer (B-3) can be increased, or a copolymer for component [B] having a multi-modal distribution can be produced.

  The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component [B] is preferably 0.2 to 0.9 dl / g, more preferably 0, from the viewpoint of moldability and impact resistance of the molded product. .25 to 0.85 dl / g, more preferably 0.3 to 0.8 dl / g. In addition, when measuring the said intrinsic viscosity [(eta)], the measuring method with respect to the acetone soluble part (or acetonitrile soluble part) in the rubber reinforced resin containing the said component [A] is applicable.

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

  In the composition of the present invention, the content of the component [B] is preferably 5 to 85 mass when the total of the components [A], [B], [C] and [D] is 100 mass%. %, More preferably, it is 15-75 mass%, More preferably, it is 30-65 mass%. When the content of the component [B] is 5 to 85% by mass, a molded product having excellent fluidity of the composition and excellent balance between impact resistance and molded appearance can be obtained. In addition, when there is too little content of the said component [B], there exists a tendency for impact resistance to fall.

  The component [C] is a propylene polymer containing a structural unit derived from a propylene unit (hereinafter referred to as “structural unit (cx)”). As this component [C], a propylene homopolymer (polypropylene), a copolymer of propylene and ethylene, a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, propylene, and ethylene, And a copolymer with an α-olefin having 4 to 20 carbon atoms. The number of carbon atoms of the α-olefin is preferably 4 to 20, more preferably 4 to 10. Preferred α-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Examples include octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene, and 4-dimethyl-1-pentene.

  When the said component [C] is a copolymer, any of a random copolymer and a block copolymer may be sufficient. In the case of a block copolymer, a copolymer comprising a propylene polymer block and an ethylene polymer block; a copolymer comprising a propylene polymer block and an α-olefin (4 to 10 carbon atoms) polymer block A propylene polymer block, an ethylene / propylene random copolymer block, a propylene / α-olefin (4 to 10 carbon atoms) random copolymer block, and an ethylene / propylene / α-olefin (4 to 4 carbon atoms); 10) A copolymer comprising at least one selected from random copolymer blocks can also be used.

  When the component [C] is a copolymer, the lower limit of the content of the structural unit (cx) derived from the propylene unit is preferably 80% by mass, more preferably 85% by mass, and still more preferably 90% by mass. is there. Examples of the copolymer include a propylene / ethylene copolymer, a propylene / 1-butene copolymer, and a propylene / 1-butene / ethylene copolymer.

  As said component [C], a propylene homopolymer (polypropylene) and a block copolymer are preferable. These polymers may form a composite resin containing ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber or the like as a dispersed phase.

  The melt flow rate (hereinafter referred to as “MFR”) of the component [C] is preferably 0.1 to 200 g / 10 minutes, more preferably 1 to 150 g / 10 minutes, and still more preferably from the viewpoint of moldability. Is 2 to 100 g / 10 min. The MFR is measured under conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K7210.

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

  In the composition of the present invention, the content of the component [C] is preferably 3 to 70 masses when the total of the components [A], [B], [C] and [D] is 100 mass%. %, More preferably, it is 5-50 mass%, More preferably, it is 7-35 mass%. When the content of the component [C] is 3 to 70% by mass, a molded article having excellent fluidity of the composition and excellent balance between impact resistance and molded appearance can be obtained. In addition, when there is too little content of the said component [C], there exists a tendency for impact resistance to fall.

The component [D] includes a polymer block containing a structural unit derived from an aromatic vinyl compound (hereinafter referred to as “polymer block (dp1)”) and a polymer block containing a structural unit derived from a conjugated diene compound. (Hereinafter referred to as “polymer block (dp2)”), and water obtained by subjecting this block copolymer (D-1) to a hydrogenation reaction It is at least one selected from the addition polymer (D-2). That is, the component [D] may be either one of the block copolymer (D-1) or the hydrogenated polymer (D-2), or may be composed of both.
The content of the structural unit derived from the aromatic vinyl compound contained in the block copolymer (D-1) or hydrogenated polymer (D-2) is preferably from the viewpoint of impact resistance and low temperature characteristics. Is 10 to 70% by mass, more preferably 15 to 65% by mass, and particularly preferably 20 to 60% by mass.

The block copolymer (D-1) is a copolymer containing polymer blocks (dp1) and (dp2) obtained by the method described later, and is a polymer that is not hydrogenated. That is, all the structural units derived from the conjugated diene compound are in a form having a double bond.
The polymer block (dp1) constituting the block copolymer (D-1) may be a polymer block consisting only of a structural unit derived from an aromatic vinyl compound, or a structure derived from an aromatic vinyl compound. The polymer block which consists of a unit and the structural unit derived from other polymerizable unsaturated monomers, such as a conjugated diene compound, may be sufficient. The content of the structural unit derived from the aromatic vinyl compound contained in the polymer block (dp1) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass. It is.
The polymer block (dp2) constituting the block copolymer (D-1) may be a polymer block consisting only of a structural unit derived from a conjugated diene compound, or a structure derived from a conjugated diene compound. The polymer block which consists of a unit and the structural unit derived from other polymerizable unsaturated monomers, such as an aromatic vinyl compound, may be sufficient. The content of the structural unit derived from the conjugated diene compound contained in the polymer block (dp2) is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. is there.

  For the aromatic vinyl compound used for forming the polymer block (dp1) and the like, the description of the aromatic vinyl compound contained in the polymerizable unsaturated monomer used for forming the component [A] is applied. . This aromatic vinyl compound may be used alone or in combination of two or more.

  Examples of the conjugated diene compound used for forming the polymer block (dp2) and the like include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1 , 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, chloroprene and the like. This conjugated diene compound may be used alone or in combination of two or more.

Examples of the structure of the block copolymer (D-1) include (RS) _m , (RS) _m R, (SR) _m S, and (RS) _m. X, (S—R) _m X, (R—S—R) _m X, (S—R—S) _m X, etc. It may be branched.
“R” indicates a polymer block (dp1), “S” indicates a polymer block (dp2), and m is an integer of 1 or more. When a plurality of polymer blocks R or S are contained in one molecule, all Rs may be the same, some Rs may be the same, or all Rs may be different. . The same applies to S.

  The block copolymer (D-1) includes styrene / butadiene block copolymer, styrene / isoprene block copolymer, styrene / butadiene / styrene block copolymer (SBS), styrene / isoprene / styrene block copolymer. Examples include coalescence (SIS).

Next, the hydrogenated polymer (D-2) is a polymer block (dp2) in the block copolymer (D-1) as a result of subjecting the block copolymer (D-1) to a hydrogenation reaction. In the polymer block (dp1), a part or all of the double bond derived from the conjugated diene compound is lost, and the polymer block (dp1) contains a double bond derived from the conjugated diene compound. ), Part or all of the double bond derived from the conjugated diene compound has disappeared.
The hydrogenation rate by the hydrogenation reaction is preferably 80% or more, more preferably 90% or more, from the viewpoint of thermal stability and durability of the obtained molded product.

  The block copolymer (D-2) includes styrene / butadiene block copolymer, styrene / isoprene block copolymer, styrene / butadiene / styrene block copolymer (SBS), and styrene / isoprene / styrene block. Examples thereof include a partially hydrogenated product or a completely hydrogenated product of a copolymer (SIS). Examples of the hydrogenated product include styrene / ethylene butylene / ethylene block copolymer (SEBC), styrene / ethylene butylene / styrene block copolymer (SEBS), styrene / butadiene / butylene / styrene block copolymer (SBBS), Examples include styrene / ethylene propylene block copolymer (SEP), styrene / ethylene propylene / styrene block copolymer (SEPS), styrene / ethylene, ethylene propylene / styrene block copolymer (SEEPS), and the like.

  The weight average molecular weight in terms of standard polystyrene of the block copolymer (D-1) or hydrogenated polymer (D-2) is preferably 50,000 to 700, from the viewpoint of mechanical strength and moldability. 000, more preferably 70,000 to 650,000, particularly preferably 100,000 to 600,000. This weight average molecular weight can be obtained by gel permeation chromatography (GPC).

  Said block copolymer (D-1) or hydrogenated polymer (D-2) can be manufactured using a living polymerization method, a coupling reaction, a hydrogenation reaction in the presence of a catalyst, and the like.

  Commercially available products used for the above component [D] include “DYNARON” series products manufactured by JSR, “TR” series products manufactured by JSR, “Tough Tech” series products manufactured by Asahi Kasei Chemicals, and “Septon” manufactured by Kuraray. Series products, "Esporex SB" series products manufactured by Sumitomo Chemical Co., Ltd., "A" series or "G" series products manufactured by Clayton, and the like.

  In the composition of the present invention, the content of the component [D] is preferably 0.5 to 0.5% when the total of the components [A], [B], [C] and [D] is 100% by mass. 50 mass%, More preferably, it is 1-40 mass%, More preferably, it is 2-30 mass%. When the content of the component [D] is 0.5 to 50% by mass, a molded article having excellent impact resistance can be obtained.

The composition of the present invention may contain other polymers (other resins).
Examples of other polymers include polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyester resins, polyamide resins, and fluororesins. Another polymer may be contained independently and may be contained in 2 or more types of combinations.
When the composition of the present invention contains another polymer (other resin), the content thereof is based on a total of 100 parts by mass of the above components [A], [B], [C] and [D]. The amount is preferably 2 to 30 parts by mass, more preferably 5 to 20 parts by mass.

  In the composition of the present invention, the total content of the rubbery polymer derived from the component [A] is preferably 5 to the entire composition from the viewpoint of molding processability and impact resistance of the molded product. It is 40 mass%, More preferably, it is 8-30 mass%.

  The composition of the present invention may further comprise fillers, plasticizers, antioxidants, ultraviolet absorbers, anti-aging agents, flame retardants, lubricants, weathering stabilizers, light stabilizers, heat stabilizers, depending on the purpose and application. Agent, antistatic agent, water repellent agent, oil repellent agent, antifoaming agent, antibacterial agent, preservative, colorant (pigment, dye, etc.), fluorescent brightener, conductivity enhancer, etc. it can.

  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 flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.

  Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, tripentyl phosphate Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, modified compounds thereof, condensed phosphate ester compounds, phosphorus Phosphorus flame retardants such as phosphazene derivatives containing elements and nitrogen elements; polytetrafluoroethylene, guanidine salts, silicone compounds, phosphazene compounds, and the like.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, and zinc stannate.
Examples of the reactive flame retardant include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl poly). Acrylate), chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether, and the like.

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

  The composition of the present invention can be obtained by a method using a kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, and (two) rolls. In kneading, the raw material components may be kneaded in a lump or may be kneaded while being divided and blended. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. The kneading temperature is preferably 160 ° C to 250 ° C, more preferably 170 ° C to 220 ° C.

  Since the composition of the present invention contains the components [A], [B], [C] and [D], it is possible to obtain a molded article having much higher impact resistance than conventional ones. Therefore, the composition of the present invention is suitable for forming members such as vehicles, ships, electronic devices, home appliances, and building materials, daily miscellaneous goods, sports equipment, stationery, and the like that require impact resistance.

  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 types of the above components [A], [B], [C] and [D], or the raw material components used (others). The polymer is appropriately selected depending on the type of the polymer.
For example, when the said component [A] contains the rubbery polymer reinforcement | strengthening graft resin which uses a diene rubber, the cylinder temperature at the time of shaping | molding is 160 degreeC-250 degreeC normally. The mold temperature is usually 30 ° C to 70 ° 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 resin obtained by Synthesis Example 1 below, and includes a component [A] that is a rubbery polymer-reinforced graft resin and an ungrafted (co) polymer (component [B]. In some cases, a part of the resin is included.

Synthesis Example 1 (Synthesis of raw material P1)
In a glass flask equipped with a stirrer, in a nitrogen stream, 61 parts of ion exchange water, 0.20 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, a polybutadiene rubber having a volume average particle diameter of 300 nm (gel content 80 %) 97 parts of a latex containing 55.5 parts, 6.5 parts of a latex containing 4.5 parts of a styrene-butadiene copolymer rubber (styrene unit amount 30%) having a volume average particle diameter of 600 nm, 7 parts of styrene and acrylonitrile 3 The portion was accommodated and heated with stirring. When the internal temperature reached 43 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.04 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.055 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 50 minutes, 0.07 part of sodium pyrophosphate, 0.01 part of ferrous sulfate heptahydrate and 0.08 part of glucose were dissolved in 8 parts of ion-exchanged water, 22 parts of styrene, acrylonitrile. 8 parts, 0.54 parts tert-dodecyl mercaptan and 0.22 parts cumene hydroperoxide were continuously added over 110 minutes. Thereafter, 0.09 part of cumene hydroperoxide was further added, and then polymerization was 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 resin (P1). The graft ratio in the graft resin (component [A]) contained in this resin (P1) is 34%. In the graft part, the structural unit derived from the vinyl cyanide compound (gx) and the structural unit derived from the aromatic vinyl compound ( The ratio of gy) is 30% and 70% when the total of both is 100%, and the content of ungrafted (co) polymer (hereinafter referred to as “acetone-soluble matter”) is 20. The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component was 0.25 dl / g.

1-2. Raw material [Q]
This raw material [Q] is an acrylonitrile / styrene copolymer obtained by the following Synthesis Examples 2 and 3 or a commercially available product, or a mixture of plural kinds thereof.

Synthesis Example 2 (Synthesis of raw material Q1)
In this synthesis example, a first monomer comprising 0.1 part of diisopropylbenzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan, 48.5 parts of styrene and 1.5 parts of acrylonitrile (at the start of synthesis, the first supply) And a second monomer comprising a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.1 part tert-dodecyl mercaptan, 37.5 parts styrene and 12.5 parts acrylonitrile (at the start of synthesis, Polymerization was performed in the following manner to obtain a raw material Q1.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Next, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material Q1. In addition, the acrylonitrile unit amount with respect to the whole raw material Q1 is 18.6%.
This raw material Q1 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.40 dl / g.

Synthesis example 3 (synthesis of raw material Q2)
A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, the first reactor was charged with a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 40 parts of toluene, and 0.14 part of tert-dodecyl mercaptan as a molecular weight regulator. And a solution prepared by dissolving 0.07 part of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, in 5 parts of toluene, are continuously supplied. Polymerization was carried out at 0 ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the styrene / acrylonitrile copolymer. This styrene / acrylonitrile copolymer was used as the raw material Q2. In addition, the acrylonitrile unit amount with respect to the whole raw material Q2 is 27.3%.
This raw material Q2 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.51 dl / g.

  Further, as a raw material Q3, polystyrene “GPPS 679” (trade name) manufactured by PS Japan Co., Ltd. was used. The melt flow rate according to ISO 1133 (temperature 200 ° C., load 5 kg) is 18 g / 10 minutes, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) is 0.37 dl / g.

1-3. Raw material [R]
As the raw material R1, polypropylene “Novatech PP BC6C” (trade name) manufactured by Nippon Polypro Co., Ltd. was used. The melt flow rate (temperature 230 ° C., load 2.16 kg) according to JIS K7210 is 2.5 g / 10 minutes.

1-4. Raw material [S]
As the raw material S1, SEBC “DYNARON 4600C” (trade name) manufactured by JSR Corporation was used. The styrene content is 20%, and the melt flow rate (temperature 230 ° C., load 21.2 N) according to JIS K7210 is 5.5 g / 10 min.
As the raw material S2, SEBS “Tuftec H1041” (trade name) manufactured by Asahi Kasei Chemicals Corporation was used. The styrene content is 32%, and the melt flow rate (temperature 230 ° C., load 2.16 kg) according to ISO 1133 is 5.0 g / 10 min.
Further, as a raw material S3, a styrene / butadiene thermoplastic elastomer “TR2000” (trade name) manufactured by JSR Corporation was used. The styrene content is 40%, and the melt flow rate (temperature 200 ° C., load 5 kg) according to JIS K7210 is 13 g / 10 min.

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1-3 and Comparative Examples 1-9
A thermoplastic resin composition was obtained using the raw materials [P], [Q], [R] and [S] in the proportions shown in Tables 1 to 3. In evaluating the composition, a composition for evaluating physical properties containing an additive (antioxidant) corresponding to the evaluation item was prepared in advance and used.
The raw material [P] may be a mixture of the component [A] and the component [B] according to the present invention depending on the synthesis method. Therefore, using the graft ratio in the raw material [P], the composition soluble in acetone, etc., the total amount of the raw materials [P], [Q], [R] and [S] used, that is, the component [ The content ratio of the polymer corresponding to the component [B] with respect to the total amount (100% by mass) of A], [B], [C] and [D] is calculated, and the components [A], [C] and [C] D] and the content ratio are shown in the “Configuration” column of each table. Then, the component [B], select a polymer (B-1), since it is constituted by a polymer (B-2) and polymer _{(B-3), r 1} = 15 and _r 2 = 20 Then, each ratio when these totals were taken as 100% was analyzed by the following method. The content of the structural unit (bx) contained in the component [B] is shown in the “Configuration” column of each table.

<Composition analysis of polymers (B-1), (B-2) and (B-3) in component [B]>
10 mg of a component (mixture of ungrafted polymer) excluding the graft resin contained in the thermoplastic resin composition was put into 10 ml of a mixture of acetonitrile and 1,2-dichloroethane (volume ratio 6: 4). Shake at 25 ° C. for 2-3 hours. Thereafter, insoluble matters (contaminants) were removed, and the soluble matters were subjected to liquid chromatography. Super system controller “SC8020” (model name) manufactured by Tosoh Corporation, online degasser “SD8022” (model name) manufactured by Tosoh Corporation, multi-pump “CCPMII” (model name) manufactured by Tosoh Corporation, UV detector “UV-8020” manufactured by Tosoh Corporation ”(Model name), Tosoh Corporation column“ TSK Silica-60 ”(model name), and Tosoh Corporation column oven“ CO-8020 ”(model name), using a liquid chromatograph apparatus, n-heptane The sample was developed with a mobile phase gradient from 1,2-dichloroethane mixture (volume ratio 7: 3) to acetonitrile / 1,2-dichloroethane mixture (volume ratio 6: 4), and the wavelength was measured with a UV detector. From the absorption value at 260 nm, the distribution of the composition of the polymers (B-1), (B-2) and (B-3) corresponding to the component [B] was measured. 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 the raw materials [P], [Q], [R] and [S] to the Henschel mixer, a total of 100 parts of these was added to tris (2,4-di-tert-butyl) as an antioxidant. Phenyl) phosphite (trade name “ADK STAB 2112”, manufactured by ADEKA) and pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (product) 0.2 parts of the name “Adeka Stub AO-60” (manufactured by ADEKA) 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 setting temperature at the time of melt-kneading was 170 degreeC-220 degreeC.
Then, after sufficiently drying the above pellets, the evaluation item was evaluated using an injection molding machine “EC60” (model name) manufactured by Toshiba Machine Co., Ltd. with a cylinder set temperature of 170 ° C. to 220 ° C. and a mold temperature of 50 ° C. A suitable test piece was prepared and subjected to evaluation.
(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) Tensile properties Tensile strength and elongation were measured according to JIS K 6251. The units are “MPa” and “%”, respectively.
(3) Bending properties The bending strength and bending modulus were measured according to ISO 178. The units are “MPa” and “MPa”, respectively.
(4) Rockwell hardness Measured according to ISO 2039.
(5) Heat distortion temperature It measured according to ASTM D648.
(6) Fluidity Using the above pellets, the melt flow rate was measured at a temperature of 220 ° C. and a load of 98 N according to ISO 1133. The unit is “g / 10 minutes”.

From Tables 1 to 3, the following is clear. That is, Comparative Examples 1, 4 and 7 are inferior in impact resistance because they do not contain the polymers (B-1) and (B-2) constituting the component [B] according to the present invention. Since Comparative Examples 2, 3, 5, 6, 8, and 9 do not contain the polymer (B-2) constituting the component [B] according to the present invention, the impact resistance is inferior.
On the other hand, in Examples 1-3 which are the compositions of this invention, it is clear that it is excellent in impact resistance.

Since the thermoplastic resin composition of the present invention gives a molded article excellent in impact resistance, for example, members such as vehicles, ships, OA equipment, home appliances, electrical / electronic equipment, building materials, and daily goods Suitable for the formation of sporting goods, stationery, etc.
The thermoplastic resin composition of the present invention is a composition prepared by blending a predetermined resin with a recycled resin from a molded product containing an ABS resin or a recycled resin from a molded product containing a propylene-based polymer. It can be a thing. That is, a low-cost composition using raw material components excluding recycled resin can be obtained, and the obtained molded product has excellent performance, so that the industrial utility value is extremely high.

Claims (6)

[A] a rubbery polymer reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer;
[B] A polymer (B-1) containing a structural unit (by) derived from an aromatic vinyl compound and containing a structural unit (bx) derived from a vinyl cyanide compound in an amount of 0% by mass to ₁ % by mass. And a polymer (B-2) containing the structural unit (by) and containing the structural unit (bx) in an amount of more than r ₁ % by mass and ₂ % by mass or less, and the structural unit (by). And a polymer (B-3) containing the structural unit (bx) in an amount exceeding 60 mass% and exceeding ₂ mass%, and (r ₂ −r ₁ ) ≧ 5 (mass%). Polymer,
[C] a propylene-based polymer containing a structural unit derived from propylene, and
[D] a block copolymer (D-1) comprising a polymer block containing a structural unit derived from an aromatic vinyl compound, and a polymer block containing a structural unit derived from a conjugated diene compound, and the block copolymer At least one selected from hydrogenated polymers (D-2) obtained by subjecting the polymer (D-1) to a hydrogenation reaction,
Containing
In the component [B], _{r 1} is 12 to 18 wt%, _{r 2} is from 18 to 25 wt%,
The content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) constituting the component [B] is 100% by mass. And 10 to 90% by mass, 3 to 70% by mass, and 5 to 80% by mass, respectively. Content of the structural units (bx) contained in the component [B], claim 1 when the sum of the structural units constituting the component (B) is 100 mass%, 5 to 40 wt% The thermoplastic resin composition described in 1. The content ratios of the component [A], the component [B], the component [C], and the component [D] are 3 to 70% by mass, It is 85 mass%, 3-70 mass%, and 0.5-50 mass%, The thermoplastic resin composition of Claim 1 or 2 . When the proportion 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 component [A] is 100% by mass. The thermoplastic resin composition according to any one of claims 1 to 3 , which is 5 to 40% by mass and 60 to 95% by mass, respectively. When the content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) is 100% by mass, the content is 25 to 70% by mass, respectively. The thermoplastic resin composition according to any one of claims 1 to 4 , which is 7 to 40% by mass and 15 to 60% by mass. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 5 .

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