JP6116182B2 - Thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition excellent in translucency, impact resistance, heat resistance and fluidity, and a molded article using the same.

  For the so-called “illumination” that gives decoration such as lighting devices such as lamps and display devices such as switches, light sources such as lamps are combined with transparent or translucent molded products. Yes. As a forming material of a molded product, a molding material containing various thermoplastic resins is used.

  Polycarbonate resin has excellent transparency, heat resistance and mechanical properties, but is sensitive to notch sensitivity, and therefore has a characteristic that impact resistance is significantly lowered when a molded product is damaged. Moreover, although it is excellent in heat resistance, a molding temperature must be set high, and may be unsuitable for manufacturing a large-sized molded product.

  In addition, ABS resins such as acrylonitrile, butadiene, and styrene resins are molding materials that are extremely balanced in moldability, impact resistance, dimensional stability, etc., and are used in the fields of vehicles, home appliances, and office automation equipment. It is widely used for etc. However, since this ABS resin does not have sufficient heat resistance, there has been proposed a polymer alloy which is used in combination with a polycarbonate resin and has improved notched impact strength, molding processability and heat resistance. Such a polymer alloy is one of molding materials widely used in the vehicle field, the housing of OA equipment, and the like, but may be opaque and may not be illuminated.

However, Patent Document 1 discloses at least one selected from a transparent thermoplastic resin, a transparent mixture of thermoplastic resins, and a transparent mixture containing a thermoplastic resin and an oligomer or polymer additive, and transparent dispersion heat. A thermoplastic resin composition containing plastic resin particles is disclosed.
In Patent Document 2, [A] a vinyl monomer (b) containing an aromatic vinyl compound is polymerized in the presence of a rubbery polymer having a refractive index in the range of 1.520 to 1.580. A rubber reinforced copolymer resin (A1) obtained by the above, or a mixture of the rubber reinforced copolymer resin (A1) and a (co) polymer (A2) of the vinyl monomer (b). Thermoplastic characterized by containing 5-60 mass% of reinforced resin and 40-95 mass% of [B] polycarbonate resin (provided that the total of [A] and [B] is 100 mass%). A resin composition is disclosed.

JP-T-2004-521968 JP 2006-328355 A

In recent years, in the field of vehicles such as automobiles, a molding material excellent in translucency, impact resistance and heat resistance has been demanded to give a display according to the purpose, in particular, to a display device showing the operating state of the automobile. ing.
An object of the present invention is to provide a thermoplastic resin composition and a molded article which are made of a rubbery polymer reinforced graft resin and an aromatic polycarbonate resin as essential components and are translucent and excellent in impact resistance, heat resistance and fluidity. Is to provide.

The present invention is as follows.
1. [A] A rubbery polymer having a refractive index in the range of 1.520 to 1.580, a structural unit (gx) derived from a vinyl cyanide compound, a structural unit (gy) derived from an aromatic vinyl compound, and (A-1) a copolymer containing 5% by mass or more and s ₁ % by mass or less of the structural unit (gx). A rubbery polymer reinforced graft resin comprising (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; (A-3) and a rubbery polymer reinforced graft resin comprising a copolymer containing the structural unit (gx) in an amount exceeding ₂ mass% and not exceeding 60 mass%, and s ₁ is 10 to 30 Mass%, s ₂ is 15-45 mass%, and In the thermoplastic resin composition having a semi-transparency, comprising a mixed graft resin (s ₂ −s ₁ ) ≧ 3 (% by mass) and [B] a polycarbonate resin,
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 ratios of the mixed graft resin [A] and the polycarbonate resin [B] are 3 to 60% by mass and 40 to 97% by mass, respectively, when the total is 100% by mass. A thermoplastic resin composition.
2 . 2. The thermoplastic resin composition as described in 1 above, wherein the rubbery polymer is a styrene / butadiene copolymer.
3 . 3. The thermoplastic resin according to 2 above, wherein the content of styrene units constituting the styrene / butadiene copolymer is 10 to 80% by mass when the total of all monomer units is 100% by mass. Composition.
4 . 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 3 above, which is 5 to 60% by mass and 40 to 95% by mass, respectively.
5 . 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 4 above, comprising (cx) and a copolymer containing a structural unit (cy) derived from the aromatic vinyl compound.
6 . 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 70% by mass and 10 to 80% by mass, respectively, when the total content is 100% by mass. And the thermoplastic resin composition according to 5 above, which is 5 to 70% by mass.
7 . 7. The thermoplastic resin composition as described in 6 above, wherein r2 is ₂₀ to 45% by mass.
8 . 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 5 to 7 above.
9 . 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 content is 5 to 45% by mass and 30 to 65% by mass, respectively. And the thermoplastic resin composition according to any one of 6 to 8 , which is 15 to 55% by mass.
10 . The content ratios of the mixed graft resin [A], the polycarbonate resin [B], and the copolymer [C] are 1 to 59% by mass and 40 to 97%, respectively, when the total content is 100% by mass. The thermoplastic resin composition according to any one of 5 to 9 above, which is mass% and 1 to 59 mass%.
11 . A molded article comprising the thermoplastic resin composition according to any one of 1 to 10 above.

According to the thermoplastic resin composition of the present invention, it is possible to obtain a molded article that is excellent in fluidity, excellent in translucency without containing a light scattering material, and further excellent in impact resistance and heat resistance. .
The rubbery polymer forming the rubbery polymer reinforced graft resin [A] is a styrene / butadiene copolymer, and the content of styrene units constituting the styrene / butadiene copolymer is within a predetermined range. In some cases, it is particularly excellent in translucency, impact resistance and fluidity.
Therefore, the molded article containing the thermoplastic resin composition of the present invention is excellent in translucency, impact resistance and heat resistance, and easily transmits light to give decorativeness. For example, interior parts of vehicles such as automobiles It is suitable for.

The present invention will be described in detail below.
In the present invention, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acryl and methacryl. The “refractive index” is a value obtained by preparing a film having a thickness of 100 to 500 μm by press molding and measuring it at 25 ° C. with an Abbe refractometer. The value of the refractive index at 25 ° C. of each homopolymer containing 100% by mass of the combined structural unit can be used as the calculated value according to the content ratio of the structural unit. Furthermore, “translucent” means that the total light transmittance according to ASTM D1003 is 30 to 80%.

The thermoplastic resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) is obtained by adding [A] a rubbery polymer having a refractive index in the range of 1.520 to 1.580 to vinyl cyanide. A rubbery polymer reinforced graft resin in which a copolymer containing a structural unit (gx) derived from a compound and a structural unit (gy) derived from an aromatic vinyl compound is grafted, (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, and (A-2) s ₁ mass of the structural unit (gx). The rubbery polymer reinforced graft resin comprising a copolymer containing more than% and not more than ₂ % by mass, and (A-3) the structural unit (gx) in excess of ₂ % by mass and not more than 60% by mass. A rubbery polymer reinforced graft resin comprising a copolymer comprising, s ₁ is 10 to 30% by mass, s ₂ is 15 to 45% by mass and (s ₂ −s ₁ ) ≧ 3 (% by mass). And [B] polycarbonate resin (hereinafter also referred to as “component [B]”), and a thermoplastic resin composition having translucency, the rubber polymer reinforced graft The resin (A-1), (A-2) and (A-3) content ratios are 1 to 98.9% by mass and 1 to 90% by mass, respectively, when the total content is 100% by mass. And 0.1 to 90% by mass, and the content ratios of the component [A] and the component [B] are 3 to 60% by mass and 40 to 97%, respectively, when the total of these components is 100% by mass. It is characterized by mass%.

The rubbery polymer reinforced graft resin constituting the component [A] is generally a vinyl cyanide compound and an aromatic vinyl in the presence of a rubbery polymer having a refractive index in the range of 1.520 to 1.580. A composite resin contained in a resin composition (hereinafter referred to as “rubber-reinforced resin”) obtained by polymerizing a polymerizable unsaturated monomer (am) containing a compound (hereinafter referred to as “graft polymerization”). (Hereinafter also referred to as “graft resin”). 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. 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 may be a homopolymer or a copolymer, and examples thereof include a diene polymer and a non-diene polymer. These may be used alone or in combination. Further, the rubbery polymer may be a non-crosslinked polymer or a crosslinked polymer.
The refractive index of the rubbery polymer is usually determined by the type of polymer structural unit and its content.

Diene polymers include styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, styrene / butadiene copolymers such as acrylonitrile / styrene / butadiene copolymers; styrene / isoprene copolymers, styrene / butadiene copolymers, and the like. Examples include styrene / isoprene copolymers such as isoprene / styrene copolymers, acrylonitrile / styrene / isoprene copolymers; hydrides of the above (co) polymers, and the like.
Each of the above copolymers may be a block copolymer or a random copolymer.

  The refractive index of the rubber polymer is 1.520 to 1.580, preferably 1.522 to 1.575, more preferably 1.530 to 1.570, and still more preferably 1.535 to 1.565. Particularly preferably, it is in the range of 1.539 to 1.565. When the refractive index is too small, the molded product tends to be opaque. The rubbery polymer is preferably a styrene / butadiene copolymer and a styrene / isoprene copolymer, particularly preferably a styrene / butadiene copolymer, a styrene / butadiene / styrene copolymer, an acrylonitrile / styrene / A butadiene copolymer, a styrene / isoprene / styrene copolymer, an acrylonitrile / styrene / isoprene copolymer, and a hydride thereof (block, random or homo).

The content of each unit of styrene and butadiene or isoprene in the styrene / butadiene copolymer and styrene / isoprene copolymer is not particularly limited.
The content of styrene units is preferably 10 to 80% by mass, more preferably 20 to 75% by mass, and still more preferably 25 to 65% by mass. When the content of the styrene unit is too large, impact resistance tends to decrease. On the other hand, when the content is too small, the molded product tends to be opaque.

  In the above styrene / butadiene copolymer and styrene / isoprene copolymer, the styrene unit content may be a copolymer of 10 to 30% by mass, exceeding 30% by mass and 80% by mass. The following copolymers can also be used. In the latter case, if it is preferably 33 to 70% by mass, more preferably 35 to 60% by mass, the composition of the present invention can be used to easily form a translucent molded article.

The gel content of the rubbery polymer is not particularly limited, but is usually 30 to 98%.
The volume average particle diameter of the rubbery polymer is preferably 80 to 15,000 nm, more preferably 100 to 15,000 nm, still more preferably 100 to 3,000 nm, still more preferably 200 to 2,000 nm, and particularly preferably. Is 500 to 2,000 nm. When the volume average particle diameter is outside the above range, impact resistance may not be sufficient. The volume average particle diameter can be measured by a laser diffraction / scattering method or the like.

  As long as the rubbery polymer has a volume average particle diameter within the above range, for example, JP-A-61-233010, JP-A-59-93701, JP-A-56-167704. What was enlarged by the well-known method described in etc. can also be used.

  The rubbery polymers reinforced graft resins (A-1), (A-2) and (A-3) constituting the component [A] may all be the same or different. Any two rubbery polymers may be the same.

  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.
(1) A structural unit (gx) derived from a vinyl cyanide compound and a structural unit derived from an aromatic vinyl compound (gx) and a rubbery polymer part comprising a styrene / butadiene copolymer or a styrene / isoprene copolymer ( (2) Graft resin formed with a graft portion made of gy) (2) A structural unit derived from a vinyl cyanide compound (gx) on a rubbery polymer portion made of a styrene / butadiene copolymer or a styrene / isoprene copolymer ), A graft resin in which a graft portion composed of a structural unit derived from an aromatic vinyl compound (gy) and a structural unit derived from a maleimide compound is formed. (3) Styrene / butadiene copolymer or styrene / isoprene copolymer In the rubbery polymer part made of coalescence, the structural unit (gx) derived from the vinyl cyanide compound, the aromatic vinyl compound Structural units (gy) and (meth) graft resin graft portion consisting of structural units derived from acrylic acid ester compound is formed to come

  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. And a method of separating and recovering the generated insoluble matter by shaking for 2 to 3 hours at 25 ° C. using a shaker or the like. The acetone-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.

  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 mixed graft resin in which the content (average value) of the structural unit (gx) is increased.
The component [A] is composed of the rubbery polymer reinforced graft resin (A-1), (A-2) and (A-3), so that the composition has excellent fluidity and impact resistance. A molded product 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 10 to 30 mass%, more preferably 15 to 30 wt%, more preferably 17 to 29% by weight, particularly preferably 22 to 28 wt%. 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 15 to 45% by mass, more preferably 20 to 42% by mass, still more preferably 22 to 40% by mass, still more preferably 25 to 35% by mass, and particularly preferably 27 to 33% by mass. When two or more types of copolymers having a structural unit (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.
Further, in the present invention, the relationship between s ₁ and s ₂ where the effect of the balance between the fluidity of the composition and the impact resistance of the resulting molded product 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 the composition containing the component [A] in the above range, a molded article having excellent fluidity and 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 the mixture of rubbery polymer reinforced graft resins (A-1), (A-2) and (A-3) obtained using a diene polymer as a rubbery polymer, these graft resins are used. A method for obtaining the ratio of the above 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 polymer. 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 10-95 mass%, 3-75 mass% and 0.5-75 mass%, more preferably 20 to 94% by mass, 5 to 60% by mass and 0.5 to 60% by mass, more preferably 30 to 92% by mass, 7 to 45% by mass and 1 to 45% by mass, particularly preferably 50 to 90% by mass, It is 10-30 mass% and 1-30 mass%.
In addition, the effect of the balance between the fluidity of the composition and the impact resistance of the molded article obtained is significant, s ₁ is 15 to 30% by mass, s ₂ is 22 to 40% by mass, When the content ratio of the rubbery polymer reinforced graft resin (A-1), (A-2) and (A-3) is 100% by mass of these, preferably 20 to 94% by mass, respectively. 5-60 mass% and 0.5-60 mass%, more preferably 30-92 mass%, 7-45 mass% and 1-45 mass%, still more preferably 50-90 mass%, 10-30 mass%. And a combination of 1 to 30% by 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 aromatic vinyl compound may be used. In a mass ratio, 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, while changing the charged amount, 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], it is possible to efficiently produce a molded article excellent in fluidity of the composition and excellent in impact resistance and heat resistance.

  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 an 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 a polymerization initiator, a chain transfer agent, an emulsifier, a 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-mentioned components [A], [B] and [C], a molded article having excellent fluidity, impact resistance and heat resistance can be obtained more efficiently. Can be obtained.

  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 impact resistance and color tone 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 impact resistance and color tone 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 70% by mass, 10%, respectively, when the total of these is 100% by mass. -80 mass% and 5-70 mass%, more preferably 3-60 mass%, 20-70 mass% and 8-65 mass%, still more preferably 5-45 mass%, 30-65 mass% and 15-55. They are 7 mass%, Most preferably, they are 7-30 mass%, 40-60 mass%, and 25-45 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 that is highly effective, excellent in fluidity of the composition, excellent in impact resistance, heat resistance, and molded appearance 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]. The resulting molded article is excellent in impact resistance, heat resistance and molded appearance.
In the present invention, the relationship between r ₁ and r _{2 in} which the effect of the balance between the fluidity of the composition and the impact resistance of the resulting molded product 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.

Further, in the present invention, the effect of the balance between the fluidity of the composition and the impact resistance of the molded product to be obtained is 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 70% by mass, respectively. 10 to 80% by mass and 5 to 70% by mass, more preferably 3 to 60% by mass, 20 to 70% by mass and 8 to 65% by mass, still more preferably 5 to 45% by mass, 30 to 65% by mass and 15%. It is -55 mass%, Most preferably, it is 7-30 mass%, 40-60 mass%, and 25-45 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 article 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)], as above-mentioned, the measuring method with respect to the ungrafted polymer contained in the rubber reinforced resin obtained by graft polymerization is applicable.

  In this invention, when a resin component consists of component [A] and [B], these ratios are 3-60 mass% and 40-97 mass%, respectively when the sum total of both is 100 mass%. Preferably, they are 3-55 mass% and 45-97 mass%, More preferably, they are 4-45 mass% and 55-96 mass%, More preferably, they are 5-30 mass% and 70-95 mass%. When the proportions of the components [A] and [B] are in the above range, a molded product having excellent fluidity and excellent impact resistance and heat 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.

  In the present invention, when the resin component is composed of components [A], [B] and [C], these ratios are preferably 1 to 59 masses when the total of the three components is 100 mass%. %, 40 to 97% by mass and 1 to 59% by mass, more preferably 2 to 52% by mass, 45 to 95% by mass and 3 to 53% by mass, still more preferably 3 to 40% by mass, 50 to 90% by mass and It is 7-45 mass%, Most preferably, it is 5-30 mass%, 55-85 mass%, and 10-30 mass%. When the ratio of the above components [A], [B] and [C] is in the above range, a molded product having excellent fluidity and excellent impact resistance and heat resistance can be obtained. In addition, when there is too little content of the said component [A], it exists in the tendency for fluidity | liquidity to fall. When there is too little content of the said component [B], it exists in the tendency for impact resistance and heat resistance to fall. Moreover, when there is too little content of the said component [C], it exists in the tendency for fluidity | liquidity to fall.

  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 may further comprise a heat aging inhibitor, a filler, a weathering agent, a plasticizer, an antioxidant, an ultraviolet absorber, an antiaging agent, a flame retardant, a lubricant, and a weathering stability depending on the purpose and application. It contains an agent, light stabilizer, heat stabilizer, antistatic agent, water repellent agent, oil repellent agent, antifoaming agent, antibacterial agent, preservative, colorant (pigment, dye, etc.), release agent, etc. be able to. Each additive preferably has a particle size smaller than the wavelength of visible light in order to maintain translucency.

  Examples of the heat aging inhibitor include phenolic compounds, phosphorus-containing compounds, sulfur-containing compounds, and lactone-based compounds. These can be used alone or in combination of two or more.

  Examples of phenolic compounds include 2,6-di-tert-butylphenol derivatives, 2-methyl-6-tert-butylphenol derivatives, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-butylidene-bis (6-tert-butyl-m-cresol), pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol -Bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4, 6-di-tert-pentylphenyl acrylate, 2-tert-butyl-6- (3- ert- butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.

Examples of phosphorus-containing compounds include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-tert-butylphenyl) phosphite, di Stearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2 -Methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-diphosphonite, sodium dihydrogen phosphate, phosphoric acid 1 Examples thereof include disodium hydrogen.
Examples of the sulfur compounds include 3,3′-thiobispropionic acid distearyl ester, 3,3′-thiobispropionic acid dimyristyl ester, 3,3′-thiobispropionic acid dioctadecyl ester, 3,3′- Thiobispropionic acid dilauryl ester, 3,3′-thiobispropionic acid didodecyl ester, 3,3′-thiobispropionic acid dioctadecyl ester, pentaerythrityl tetrakis (3-laurylthiopropionate), etc. Can be mentioned.
Examples of the lactone compound include 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one.

  When blending a heat aging inhibitor into the composition of the present invention, it is preferable to use a combination of a phenolic compound, a phosphorus-containing compound and a sulfur-containing compound. These blending ratios are not particularly limited. With this combination, for example, the tensile elongation can be maintained even when left for a long time at a high temperature of 50 ° C. to 80 ° C.

  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 weathering agent include phosphorus-containing compounds, benzotriazole compounds, triazine compounds, and benzophenone compounds. 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, lipid, ethylene bisstearylamide, hydrogenated castor oil, and the like. These can be used alone or in combination of two or more.

Examples of the antistatic agent include a low molecular weight antistatic agent and a high molecular weight antistatic agent. Moreover, these may be an ion conduction type or an electron conduction type.
The low molecular weight antistatic agent includes an anionic antistatic agent; a cationic antistatic agent; a nonionic antistatic agent; an amphoteric antistatic agent; a complex compound; a metal alkoxide such as alkoxysilane, alkoxytitanium, alkoxyzirconium, and the like. And derivatives thereof.
Examples of the polymer antistatic agent include a vinyl copolymer having a sulfonate in the molecule, an alkyl sulfonate, an alkyl benzene sulfonate, and betaine. Furthermore, polyether, polyamide elastomer, polyester elastomer, and the like can be used.

  The colorant may be a pigment or a dye. Examples of the pigment include carbon black and bengara.

The thermoplastic resin composition of the present invention comprises a rubber reinforced resin containing component [A], a component [B], and a component used as necessary by an extruder, a Banbury mixer, a kneader, a roll, a feeder ruder, etc. C] can be produced by kneading raw material components comprising a resin or additive for C]. The kneading temperature is usually 200 ° C to 280 ° C, preferably 210 ° C to 270 ° C. The method of using the raw material components is not particularly limited, and the respective components may be mixed and kneaded in a lump, or may be mixed and mixed in multiple stages.
A preferable production method is a method using an extruder, and it is particularly preferable to use a twin screw extruder.

The thermoplastic resin composition of the present invention has excellent compatibility between the components [A] and [B], and has a preferable MFR as follows. Further superior impact resistance and molding appearance can be obtained.
The MFR (ASTM D1238, temperature 240 ° C., load 10 kg) of the thermoplastic resin composition of the present invention is preferably 3 to 60 (g / 10 minutes), more preferably 5 to 45 (g / 10 minutes), still more preferably. Is 10 to 35 (g / 10 min).
The total light transmittance (ASTM D1003) of the thermoplastic resin composition of the present invention is 30 to 80%, more preferably 40 to 75%, still more preferably 45 to 70%, and particularly preferably 50 to 70%. Yes, excellent in translucency. If the total light transmittance is less than 30%, it is substantially opaque, so that it is difficult to obtain a molded article having high decorativeness utilizing the translucency.
Moreover, haze (ASTM D1003) becomes like this. Preferably it is 70 to 100%, More preferably, it is 80 to 97%, More preferably, it is 85 to 93%, and it is excellent in translucency.

By subjecting the thermoplastic resin composition of the present invention or the raw material components that will form its constituent components to known molding methods such as injection molding, sheet extrusion molding, profile extrusion molding, vacuum molding, and foam molding. It can be a molded product. That is, the molded article of the present invention contains the thermoplastic resin composition.
In the injection molding, in addition to a known molding method, a molded product can be obtained by gas assist molding, in-mold molding, two-color molding, thermo eject molding, sandwich molding, or the like.
In sheet extrusion molding, a smooth sheet, a sheet having an embossed pattern on the surface, and the like can be obtained.
In vacuum molding, straight molding, drape molding, plug assist molding, plug assist / reverse draw molding, air slip molding, snapback molding, reverse draw molding, air cushion molding, plug assist / air slip molding, free molding, matched mold molding A molded product can be obtained by plug ring molding, slip molding, contact heating molding, or the like.
In the case of forming a molded article, the composition of the present invention is usually processed after heating to 200 ° C. to 280 ° C., preferably 210 ° C. to 270 ° C. to prepare a melt.
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.
Moreover, you may give secondary processes, such as coating, sputtering, and welding, to various molded articles according to a use etc.

  The molded product of the present invention is suitable for lighting devices such as lamps, display devices such as switches, office equipment, home appliances, cases such as vehicle parts, housings, trays, disks, etc. by utilizing its excellent properties. is there.

  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. Evaluation method The measurement method of each evaluation item in the following Examples and Comparative Examples is shown below.
(1) Volume average particle diameter The volume average particle diameter of the dispersed particles (rubber polymer) in the latex used for the preparation of the rubber polymer reinforced graft resin is measured with a laser particle size analyzer (model “LPA-3100”, (Otsuka Electronics Co., Ltd.) and measured by the light scattering method and calculated by the cumulant method with 70 times integration. In addition, after producing the thermoplastic resin composition, the number average particle diameter of the rubber polymer reinforced graft resin contained in the composition is substantially the same as the volume average particle diameter of the rubber polymer before graft polymerization. Was confirmed with a transmission electron microscope.
(2) Graft rate Described in the text.
(3) Intrinsic viscosity [η]
The acetone-soluble component and the raw material [R] contained in the raw material [P] were each dissolved in methyl ethyl ketone, and the intrinsic viscosity [η] at 30 ° C. was measured using an Ubbelohde viscometer.

(4) Fluidity (MFR)
The melt flow rate (MFR) was measured at a temperature of 240 ° C. and a load of 10 kg in accordance with ASTM D1238.
(5) Izod impact strength Measured according to ASTM D256. The size of the test piece is 2.5 × 1/2 × ¼ inch and is notched.
(6) Total light transmittance Measured according to ASTM D1003. The thickness of the test piece is 2.5 mm.
(7) Thermal deformation temperature According to ASTM D648, the thermal deformation temperature (HDT) was measured at a load of 18.56 kg / cm ² . The thickness of the test piece is 1/2 inch.
(8) Haze Measured according to ASTM D1003. The thickness of the test piece is 2.5 mm.

2. Production Raw Materials The raw materials (resin component and polymer component) used for the production of the thermoplastic resin composition are as follows.
2-1. Raw material [P]
This raw material [P] is a rubber-reinforced aromatic vinyl resin obtained by the following Synthesis Examples 1 to 9, 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, a volume average particle size of 0.3 μm, and styrene 70 parts of latex containing 40 parts (see Table 1) of styrene / butadiene copolymer (hereinafter referred to as “SBR”) having a unit amount of 10%, 9.6 parts of styrene and acrylonitrile 5.4 parts 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, thereby obtaining a latex containing a rubber-reinforced aromatic vinyl resin P1.
Next, an aqueous sulfuric acid solution was added to the latex to coagulate and wash the resin component, and the rubber-reinforced aromatic vinyl resin P1 was recovered. The graft ratio of the graft resin (component [A]) contained in the rubber-reinforced aromatic vinyl resin P1 is 75%, and an ungrafted (co) polymer corresponding to the component [C] (hereinafter referred to as “acetone soluble component”). “)” Was 12.5%, and the intrinsic viscosity [η] of this acetone-soluble component (30 ° C. in methyl ethyl ketone) was 0.50 dl / g (see Table 1).

In Table 1, the calculated values of the refractive index of the rubbery polymer used are listed. The refractive index is based on the fact that the rubbery polymer consists of 10% styrene units and 90% butadiene units, and the refractive indexes of polystyrene and polybutadiene are 1.591 and 1.515, respectively. It calculated according to the following formula.
Refractive index = 1.591 x 0.1 + 1.515 x 0.9
= 1.523

Synthesis examples 2 and 3 (synthesis of raw materials P2 and P3)
The rubber-reinforced aromatic vinyl series is the same as in Synthesis Example 1 except that a styrene / butadiene copolymer (SBR) having a volume average particle diameter and a styrene unit amount shown in Table 1 is used as the rubber polymer. Resins P2 and P3 were obtained (see Table 1).
The graft ratio in the graft resin (component [A]) contained in the rubber-reinforced aromatic vinyl resin P2 according to Synthesis Example 2 is 50%, and an ungrafted (co) polymer corresponding to the component [C] (acetone soluble component) ) Was 25.0%, and the intrinsic viscosity [η] (30 ° C. in methyl ethyl ketone) of this acetone-soluble component was 0.50 dl / g (see Table 1).
The graft ratio of the graft resin (component [A]) contained in the rubber-reinforced aromatic vinyl resin P3 according to Synthesis Example 3 is 85%, and the ungrafted (co) polymer (acetone soluble component) corresponding to the component [C] ) Was 7.5%, and the intrinsic viscosity [η] (30 ° C. in methyl ethyl ketone) of this acetone-soluble component was 0.80 dl / g (see Table 1).

Synthesis Example 4 (Synthesis of raw material P4)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion exchange water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, a volume average particle size of 0.3 μm and a styrene unit 70 parts of latex containing 40 parts of SBR (see Table 1) having an amount of 45%, 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, thereby obtaining a latex containing a rubber-reinforced aromatic vinyl resin P4.
Next, a sulfuric acid aqueous solution was added to the latex to coagulate and wash the resin component, and the rubber-reinforced aromatic vinyl resin P4 was recovered. Graft ratio in the graft resin (component [A]) contained in the rubber-reinforced aromatic vinyl resin P4 is 85%, and contains an ungrafted (co) polymer (acetone soluble component) corresponding to the component [C]. The rate was 7.5%, and the inherent viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component was 0.80 dl / g (see Table 1).

Synthesis Example 5 (Synthesis of raw material P5)
The rubber-reinforced aromatic vinyl series is the same as in Synthesis Example 1 except that a styrene / butadiene copolymer (SBR) having a volume average particle diameter and a styrene unit amount shown in Table 1 is used as the rubber polymer. Resin P5 was obtained (see Table 1).
Graft ratio in graft resin (component [A]) contained in rubber-reinforced aromatic vinyl resin P5 is 50%, content of ungrafted (co) polymer (acetone soluble component) corresponding to component [C] Was 25.0%, and the intrinsic viscosity [η] of this acetone-soluble component (in methyl ethyl ketone, 30 ° C.) was 0.50 dl / g (see Table 1).

Synthesis Example 6 (Synthesis of raw material P6)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion exchange water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, a volume average particle size of 0.3 μm and a styrene unit 70 parts of latex containing 40 parts of SBR (see Table 1) having an amount of 35%, 8.25 parts of styrene, and 6.75 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, 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, and a latex containing a rubber-reinforced aromatic vinyl resin P6 was obtained.
Graft ratio in graft resin (component [A]) contained in rubber-reinforced aromatic vinyl resin P6 is 50%, content of ungrafted (co) polymer (acetone soluble component) corresponding to component [C] Was 25.0%, and the intrinsic viscosity [η] of this acetone-soluble component (in methyl ethyl ketone, 30 ° C.) was 0.50 dl / g (see Table 1).

Synthesis Example 7 (synthesis of raw material P7)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion exchange water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, a volume average particle size of 0.3 μm and a styrene unit 70 parts of a latex containing 40 parts of SBR having an amount of 35% (see Table 1), 9.6 parts of styrene, and 5.4 parts of acrylonitrile were placed and heated while 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 polymerization was continued for another hour to complete the polymerization, and a latex containing a rubber-reinforced aromatic vinyl resin P7 was obtained.
Next, an aqueous sulfuric acid solution was added to the latex to coagulate and wash the resin component, and the rubber-reinforced aromatic vinyl resin P7 was recovered.
Graft ratio in the graft resin (component [A]) contained in this rubber-reinforced aromatic vinyl resin P7 is 50%, and contains an ungrafted (co) polymer (acetone soluble component) corresponding to component [C] The rate was 25%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component was 0.50 dl / g (see Table 1).

Synthesis Example 8 (synthesis of raw material P8)
In a glass flask equipped with a stirrer, in a nitrogen stream, 92 parts of ion exchange water, 0.3 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, a volume average particle size of 0.3 μm and a styrene unit 70 parts of a latex containing 40 parts of SBR (see Table 1) having an amount of 35%, 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 polymerization was continued for another hour to complete the polymerization, and a latex containing a rubber-reinforced aromatic vinyl resin P8 was obtained.
Next, an aqueous sulfuric acid solution was added to the latex to coagulate and wash the resin component, and the rubber-reinforced aromatic vinyl resin P8 was recovered.
Graft ratio in the graft resin (component [A]) contained in this rubber-reinforced aromatic vinyl resin P8 is 50%, and contains an ungrafted (co) polymer (acetone soluble component) corresponding to component [C] The rate was 25%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component was 0.50 dl / g (see Table 1).

Synthesis Example 9 (synthesis of raw material P9)
A rubber-reinforced copolymer resin is prepared in the same manner as in Synthesis Example 1 except that polybutadiene having a volume average particle diameter shown in Table 1 (hereinafter, polybutadiene is referred to as “BR”) is used as the rubber polymer. P9 was obtained (see Table 1).
The graft ratio in the graft resin (component [A]) contained in the rubber-reinforced aromatic vinyl resin P9 is 75%, and the content of the ungrafted (co) polymer (acetone soluble component) corresponding to the component [C]. The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component was 0.44 dl / g (see Table 1).

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.

2-2. 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.

2-3. Raw material [R]
The copolymer obtained by the following synthesis example 10 was used.

Synthesis Example 10 (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 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and 0.15 part of tert-dodecyl mercaptan as a molecular weight regulator. And a solution in which 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, is dissolved in 5 parts of toluene, are continuously supplied. Polymerization was carried out at 0 ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the styrene / acrylonitrile copolymer. This styrene / acrylonitrile copolymer was used as the raw material R1.
The intrinsic viscosity [η] of this raw material R1 (in methyl ethyl ketone, 30 ° C.) was 0.51 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 8%, 52% and 40%, respectively.

3. Production and Evaluation of Thermoplastic Resin Composition Examples 1-7 and Comparative Examples 1-6
Raw materials [P], [Q] and [R] were charged into a Henschel mixer at the ratios shown in Tables 2 to 5 and mixed. Then, it melt-kneaded using the twin-screw extruder (cylinder setting temperature: 240 degreeC), and obtained the pellet (thermoplastic resin composition).
Next, the pellets were sufficiently dried using a dehumidifying dryer, and an evaluation test piece was obtained using an injection molding machine (cylinder setting temperature: 250 ° C., mold temperature: 60 ° C.). Various evaluations were performed using this test piece, and the results are shown in each table.
In addition, since the raw materials [P] and [R] are used in combination in the production of the composition, the composition [A] of the present invention, using the graft ratio in the raw material [P], the composition soluble in acetone, etc. The content ratio of the polymer corresponding to the component [C] with respect to the total amount of [B] and [C] was calculated, and the value is shown in each table. 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 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.

From Tables 2 to 5, the following is clear. That is, Comparative Examples 1 and 2 are examples not containing the graft resin (A-1) constituting the component [A] according to the present invention, and the impact resistance and translucency were 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 translucency was insufficient. In Comparative Example 4, since the rubbery polymer used for forming the component [A] was a polybutadiene rubber, the translucency was insufficient. The comparative example 5 is an example which consists only of component [B], and fluidity | liquidity and translucency were inadequate. Comparative Example 6 is an example in which the content of component [B] is too small outside the scope of the present invention, and the heat resistance was insufficient.
On the other hand, in Examples 1 to 7 which are compositions having the constitution of the present invention, it is clear that they are excellent in translucency, impact resistance, heat resistance and fluidity.

  Since the thermoplastic resin composition of the present invention is excellent in translucency, impact resistance, heat resistance and fluidity, it is a lighting device such as a lamp, a display device such as a switch, OA equipment, home appliances, and vehicle parts. Suitable for housings, trays, disks, etc.

Claims (11)

[A] A rubbery polymer having a refractive index in the range of 1.520 to 1.580, a structural unit (gx) derived from a vinyl cyanide compound, a structural unit (gy) derived from an aromatic vinyl compound, and (A-1) a copolymer containing 5% by mass or more and s ₁ % by mass or less of the structural unit (gx). A rubbery polymer reinforced graft resin comprising (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; (A-3) and a rubbery polymer reinforced graft resin comprising a copolymer containing the structural unit (gx) in an amount exceeding ₂ mass% and not exceeding 60 mass%, and s ₁ is 10 to 30 Mass%, s ₂ is 15-45 mass%, and In the thermoplastic resin composition having a semi-transparency, comprising a mixed graft resin (s ₂ −s ₁ ) ≧ 3 (% by mass) and [B] a polycarbonate resin,
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 ratios of the mixed graft resin [A] and the polycarbonate resin [B] are 3 to 60% by mass and 40 to 97% by mass, respectively, when the total is 100% by mass. A thermoplastic resin composition.   The thermoplastic resin composition according to claim 1, wherein the rubbery polymer is a styrene / butadiene copolymer. The thermoplastic resin according to claim 2 , wherein the content of styrene units constituting the styrene / butadiene copolymer is 10 to 80% by mass when the total of all monomer units is 100% by mass. Resin composition. 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 3 , wherein the thermoplastic resin composition is 5 to 60 mass% and 40 to 95 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 4 , 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 70% by mass and 10 to 80% by mass, respectively, when the total content is 100% by mass. The thermoplastic resin composition according to claim 5 , wherein the thermoplastic resin composition is 5 to 70% by mass. The thermoplastic resin composition according to claim 6 , 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 5 to 7 . 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 content is 5 to 45% by mass and 30 to 65% by mass, respectively. The thermoplastic resin composition according to any one of claims 6 to 8 , wherein the thermoplastic resin composition is 15 to 55 mass%. The content ratios of the mixed graft resin [A], the polycarbonate resin [B], and the copolymer [C] are 1 to 59% by mass and 40 to 97%, respectively, when the total content is 100% by mass. The thermoplastic resin composition according to any one of claims 5 to 9 , wherein the thermoplastic resin composition is 1% by mass and 1 to 59% by mass. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 10 .