JP2013010877A - Thermoplastic resin composition, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition providing a molded article excellent in the balance of impact resistance, areal impact resistance and appearance.SOLUTION: The composition contains [A] a graft resin obtained by polymerizing monomers containing an aromatic vinyl compound and a cyanated vinyl compound, [B] a copolymer containing a unit bx originated from a cyanated vinyl compound and a unit originated from an aromatic vinyl compound, and [C] a (co)polymer containing >97% of a unit c originated from an aromatic vinyl compound, wherein the component [B] is composed of a polymer B1 containing ≥3% and ≤r% of the unit bx, a polymer B2 containing >r% and ≤r% of the bx, and a polymer B3 containing >r% and ≤60% of the unit bx; r-r≥5; and the proportions of the polymer B1, the polymer B2 and the polymer B3 are 5 to 70%, 5 to 80% and 10 to 90%, respectively.

Description

  The present invention relates to a thermoplastic resin composition that gives a molded article having an excellent balance of impact resistance, surface impact resistance and molding appearance.

  Resin compositions containing polystyrene are used in the fields of food containers, stationery, miscellaneous goods and the like because they have excellent transparency and appearance and give molded articles with high tensile strength and rigidity. However, there is a drawback that the impact resistance is not sufficient. Therefore, uncrosslinked rubber polymer is dissolved in styrene monomer, bulk polymerization method in which styrene monomer is polymerized as it is, prepolymerization of styrene monomer is performed, then rubber polymer is blended and suspension polymerization is performed A resin composition comprising a resin (ABS resin) obtained by polymerizing styrene and acrylonitrile in the presence of impact-resistant polystyrene (HIPS), polybutadiene, etc. produced by a method such as bulk suspension polymerization However, it has come to be widely used for home appliances, OA equipment, machine parts and the like that require impact resistance (see, for example, Patent Documents 1 to 3).

In Patent Document 1, a soft component particle made of styrene-butadiene copolymer dispersed in this matrix having a polystyrene as a matrix has a single occlusion structure with a specific average particle diameter, and the occlusion rate and graft rate are A rubber-modified styrenic resin composition in a specific range, namely high impact polystyrene (HIPS) is disclosed.
In Patent Documents 2 and 3, a resin (ABS resin) obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer having a specific gel content and an average particle size; A resin composition containing polystyrene or high impact polystyrene (HIPS) is disclosed.

  In recent years, as electronic parts, mechanical parts, sliding parts, etc. in automobiles and various machines have become lighter or thinner, molded products containing resin materials used for their housings have dropped. However, it is required to have a high so-called practical impact strength, such as being not broken and having no cracks when subjected to an impact on the surface. This practical impact strength is known to have a high correlation with the surface impact strength (falling weight impact strength) measured by the falling weight test and low correlation with the Izod impact strength or Charpy impact strength. Yes. Therefore, even if the Izod impact strength and Charpy impact strength are improved, the practical impact strength may not be improved.

  Also, depending on the use of the molded product, surface gloss may be required with or without a colorant or the like, and resin alloys prepared by combining an ABS resin with an aromatic polyester resin or the like are widely used.

JP-A-5-320272 JP 2004-256744 A JP-A-2005-350542

  An object of the present invention is to provide a thermoplastic resin composition that gives a molded article having an excellent balance of impact resistance, surface impact resistance, and molding appearance property with glossiness as an index.

The present invention is as follows.
1. [A] a rubbery polymer reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer;
[B] a copolymer comprising a structural unit (bx) derived from a vinyl cyanide compound and a structural unit (by) derived from an aromatic vinyl compound;
[C] a (co) polymer containing a structural unit (c) derived from an aromatic vinyl compound;
In a thermoplastic resin composition containing
The component [B] contains the polymer (B-1) containing the structural unit (bx) at 3 mass% or more and ₁ mass% or less and the structural unit (bx) exceeding ₁ mass% r. a polymer (B-2) containing ₂ % by mass or less of r, and a polymer (B-3) containing the structural unit (bx) in excess of r ₂ % by mass and 60% by mass or less, and (R ₂ −r ₁ ) ≧ 5 (mass%),
The content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) is 5 to 70% by mass, respectively, when the total content is 100% by mass. 5 to 80 mass% and 10 to 90 mass%,
The said component [C] contains the said structural unit (c) exceeding 97 mass%, The thermoplastic resin composition characterized by the above-mentioned.
2. The thermoplastic resin composition according to claim 1 r ₂ is 15 to 45 mass%.
3. The component [B] is a copolymer comprising a structural unit (bx) and a structural unit (by), and the vinyl cyanide compound and the aromatic vinyl compound are mixed at a mass ratio of 3 to 10:97 to 90. From 15 to 60:85 to 40, or from 15 to 60:85 to 3 to 10:97 to 90, a copolymer obtained by polymerization while changing the charged amount is included. The thermoplastic resin composition according to 1 or 2.
4). The content ratio of the structural unit (bx) contained in the component [B] is 10 to 40% by mass when the total of the structural units constituting the component [B] is 100% by mass. The thermoplastic resin composition in any one of thru | or 3.
5. The content ratios of the component [A], the component [B], and the component [C] are 3 to 70% by mass, 5 to 80% by mass, and 3 to 3%, respectively, when the total content is 100% by mass. It is 90 mass%, The thermoplastic resin composition in any one of Claims 1 thru | or 4.
6). When the proportion of the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound contained in the component [A] is 100% by mass. The thermoplastic resin composition according to any one of claims 1 to 5, which is 5 to 40% by mass and 60 to 95% by mass, respectively.
7. r ₁ is 5 to 30% by mass, r ₂ is 15 to 40% by mass,
When the content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) is 100% by mass, the content is 10 to 60% by mass. The thermoplastic resin composition according to any one of claims 1 to 6, which is 10 to 50 mass% and 30 to 75 mass%.
8). The thermoplastic resin composition according to any one of claims 1 to 7, further comprising [D] a rubbery polymer reinforced graft resin obtained by polymerizing an aromatic vinyl compound in the presence of a rubbery polymer. object.
9. A molded article comprising the thermoplastic resin composition according to any one of 1 to 8 above.

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

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

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

The thermoplastic resin composition of the present invention is a rubbery polymer obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of [A] a rubbery polymer. Copolymer reinforced graft resin, [B] copolymer containing structural unit (bx) derived from vinyl cyanide compound, and structural unit (by) derived from aromatic vinyl compound, and [C] aromatic vinyl compound (Co) polymer containing the structural unit (c) derived from the above, and the component [B] contains the structural unit (bx) in an amount of 3% by mass or more and ₁ % by mass or less of r ( B-1) and, the structural units (bx), the polymer comprising at _{r 2} mass% or less beyond the _{r 1} wt% and (B-2), the structural unit (bx), the _{r 2} wt% And a polymer (B-3) contained in an amount of 60% by mass or less, and (r ₂ -r ₁ ) ≧ 5 (mass%), and the content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) is, when these totals are 100 mass%, They are respectively 5-70 mass%, 5-80 mass%, and 10-90 mass%, The said component [C] contains the said structural unit (c) exceeding 97 mass%, It is characterized by the above-mentioned.

The component [A] is obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer (hereinafter referred to as “graft polymerization”). A rubbery polymer reinforced graft resin (hereinafter referred to as “graft resin”) contained in a resin composition (hereinafter referred to as “rubber reinforced resin”). This graft resin is a copolymer containing a structural unit derived from a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound, that is, a structural unit derived from an aromatic vinyl compound and a vinyl cyanide compound. A copolymer containing at least a structural unit derived from is a resin grafted to a rubbery polymer, and a polymerizable unsaturated monomer containing a rubbery polymer part and an aromatic vinyl compound and a vinyl cyanide compound And a copolymer part (graft part) containing a structural unit derived from the body.
The rubber reinforced resin obtained by graft polymerization is usually a copolymer not grafted to the rubber polymer (hereinafter referred to as “ungrafted polymer”) in addition to the rubber polymer reinforced graft resin. including. The composition of this ungrafted polymer depends on the type of polymerizable unsaturated monomer used. Usually, the ungrafted polymer is the component [B] and / or component [C] in the composition of the present invention. include.

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

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

  Examples of the non-diene rubber include an ethylene unit and an ethylene / α-olefin copolymer containing a unit composed of an α-olefin having 3 or more carbon atoms, a urethane rubber, an acrylic rubber, a silicone rubber, Examples thereof include a silicone-acrylic IPN rubber and a polymer obtained by hydrogenating a (co) polymer containing a unit composed of a conjugated diene compound. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more). The non-diene rubber can be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The graft ratio in the component [A] is preferably 20 to 120%, more preferably 30 to 100%, and still more preferably 35 from the viewpoints of moldability, impact resistance of the molded product, molded appearance, and the like. ~ 80%. If this graft ratio is too low, the impact resistance and molded appearance of the molded product may be lowered. On the other hand, if the graft ratio is too high, the moldability is not sufficient and the impact resistance may be lowered.

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

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

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

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

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

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

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

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

  In the composition of the present invention, the content of the component [A] is preferably 3 to 70% by mass, more preferably 100% by mass when the total of the components [A], [B] and [C] is 100% by mass. Is 10 to 55 mass%, more preferably 15 to 40 mass%. When the content of the component [A] is 3 to 70% by mass, a molded product having an excellent balance of impact resistance, surface impact resistance, and molded appearance can be obtained. In addition, when there is too little content of said component [A], there exists a tendency for impact resistance and surface impact resistance to fall.

The component [B] is a copolymer including a structural unit (bx) derived from a vinyl cyanide compound and a structural unit (by) derived from an aromatic vinyl compound, and further has another structural unit (hereinafter, "Also referred to as" structural unit (bz) "). This component [B] is a copolymer comprising three kinds of copolymers containing structural units (bx) and (by), that is, a weight containing 3% by mass or more and r ₁ % by mass or less of the structural unit (bx). A polymer (B-1) composed of at least one kind of a polymer and a polymer (B1) composed of at least one kind of polymer containing the structural unit (bx) in an amount exceeding ₁ mass% and ₂ mass% or less. -2) and a polymer (B-3) composed of at least one polymer including the structural unit (bx) in an amount of more than r ₂ mass% and 60 mass% or less, and (r ₂ −r ₁ ) ≧ 5 (mass%). Moreover, the content rate of the said polymer (B-1), a polymer (B-2), and a polymer (B-3) is 5-70 mass%, respectively, when these sum total is 100 mass%. 5 to 80% by mass and 10 to 90% by mass.

For the vinyl cyanide compound forming the structural unit (bx), the description of the vinyl cyanide compound contained in the polymerizable unsaturated monomer used for forming the component [A] is applied. The structural unit (bx) contained in the component [B] may be only one type or two or more types. As the vinyl cyanide compound, acrylonitrile is preferable.
The content of the structural unit (bx) contained in the component [B] is preferably 10 to 40% by mass, more preferably 12 to 12%, assuming that the total of the structural units constituting the component [B] is 100% by mass. It is 35 mass%, More preferably, it is 15-32 mass%. When the content of the structural unit (bx) is 10 to 40% by mass, a molded product having excellent molding processability (fluidity) of the composition can be obtained.

For the aromatic vinyl compound forming the structural unit (by), the description of the aromatic vinyl compound contained in the polymerizable unsaturated monomer used for forming the component [A] is applied. The structural unit (by) contained in the component [B] may be only one type or two or more types. As the aromatic vinyl compound, styrene and α-methylstyrene are preferable.
The content of the structural unit (by) contained in the component [B] is preferably 60 to 90% by mass and more preferably 65 to 90% by mass when the total of the structural units constituting the component [B] is 100% by mass. It is 88 mass%, More preferably, it is 68-85 mass%. When the content of the structural unit (by) is 60 to 90% by mass, a molded product having excellent molding processability (fluidity) of the composition can be obtained.

Examples of the monomer forming the structural unit (bz) include (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and oxazolines. And group-containing unsaturated compounds.
When the component [B] contains the structural unit (bz), the upper limit of the content is the sum of the structural units constituting the component [B], that is, the structural units (bx), (by) and (bz ) Is 100% by mass, preferably 30% by mass, more preferably 15% by mass.
In addition, this structural unit (bz) may be contained in all of a polymer (B-1), a polymer (B-2), and a polymer (B-3), and may be contained in one part. .

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

The polymer (B-1), the polymer (B-2) and the polymer (B-3) are polymers having different contents of the structural unit (bx), and the structural unit (bx) It is a polymer in which the content of is increased.
The component [B] is composed of the polymer (B-1), the polymer (B-2), and the polymer (B-3) having the above configuration, so that the component [B] is between the component [A] and the component [C]. Therefore, it is possible to efficiently produce a molded article having a good balance of impact resistance, surface impact resistance and molding appearance. In particular, when the component [B] made of a copolymer aggregate having a structural unit (bx) content in the range of 10 to 40% by mass as described above is used, the above effect is remarkable.

The polymer (B-1) is a polymer containing the structural unit (bx) at 3% by mass or more and r ₁ % by mass or less, and as described above, the polymer (Bx) is composed of the structural units (bx) and (by). It may be a polymer or a copolymer composed of structural units (bx), (by), and (bz). Moreover, as mentioned above, this polymer (B-1) can consist of at least 1 sort (s) of the polymer containing the predetermined amount of a structural unit (bx). For example, when it is composed of two types of copolymers and 3 ≦ r ₁₁ <r ₁₂ ≦ r ₁ , a polymer containing ₁₁ % by mass of structural units (bx) and a structural unit (bx) and a polymer (B-1) composed of a polymer containing ₁₂ % by mass of r.
r ₁ is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, still more preferably 10 to 20% by mass, and particularly preferably 12 to 18% by mass. When the content of the structural unit (bx) is 2 or more kinds of polymers having a content of 3% by mass or more and r ₁ % by mass or less, the “content of the structural unit (bx) contained in the polymer (B-1)” The value shown is an average value calculated from the content of the structural unit (bx) contained in each polymer.
The polymer (B-2) is a copolymer containing the structural units (bx) and (by) containing the structural unit (bx) in an amount exceeding ₁ mass% and ₂ mass% or less. Thus, it may be a copolymer composed of structural units (bx) and (by), or a copolymer composed of structural units (bx), (by) and (bz). Moreover, as mentioned above, this polymer (B-2) can consist of at least 1 sort (s) of the polymer containing the predetermined amount of a structural unit (bx). For example, when it is composed of two types of copolymers and r ₁ <r ₂₁ <r ₂₂ ≦ r ₂ , a polymer containing ₂₁ % by mass of structural unit (bx) and structural unit (bx) And a polymer (B-2) consisting of a polymer containing ₂₂ mass% of r.
r ₂ is preferably 15 to 45% by mass, more preferably 16 to 40% by mass, still more preferably 17 to 35% by mass, still more preferably 18 to 28% by mass, and particularly preferably 18 to 25% by mass. . When the content of the structural unit (bx) comprises r ₂ mass% or less is a polymer of two or more than ₁ wt% r, "containing the polymer (B-2) to include structural units (bx) The value shown as “amount” is an average value calculated from the content of the structural unit (bx) contained in each polymer.
In the present invention, when r ₂ is 15 to 45% by mass, in the composition of the present invention, in particular, the compatibility between the component [A] and the component [C] is improved. Excellent balance of impact resistance, surface impact resistance and molding appearance.
In the present invention, the relationship between r ₁ and r ₂ where the effect of balance of impact resistance, surface impact resistance and molding appearance is significant is (r ₂ −r ₁ ) ≧ 5 (mass%). Preferably, (r ₂ −r ₁ ) ≧ 6 (mass%), more preferably (r ₂ −r ₁ ) ≧ 7 (mass%). However, usually (r ₂ −r ₁ ) ≦ 40 (mass%), preferably (r ₂ −r ₁ ) ≦ 33 (mass%), more preferably (r ₂ −r ₁ ) ≦ 25 (mass%). It is. When (r ₂ −r ₁ ) <5 (mass%), the effect of the present invention cannot be sufficiently obtained.
The polymer (B-3) is a polymer containing the structural unit (bx) in an amount exceeding 60% by mass and exceeding ₂ % by mass, and as described above, from the structural units (bx) and (by). The copolymer which consists of structural unit (bx), (by) and (bz) may be sufficient. Moreover, as mentioned above, this polymer (B-3) can consist of at least 1 sort (s) of the polymer containing the predetermined amount of a structural unit (bx). For example, when it is composed of two types of copolymers and r ₂ <r ₃₁ <r ₃₂ ≦ 60, a polymer containing ₃₁ % by mass of structural unit (bx) and structural unit (bx) r A polymer containing ₃₂ % by mass and a polymer (B-3) comprising the same can be used.
When the content of the structural unit (bx) exceeds ₂ % by mass and contains 2 or more types of polymers of 60% by mass or less, “content of the structural unit (bx) contained in the polymer (B-3)” The value shown as “is an average value calculated from the content of the structural unit (bx) contained in each polymer.

The content ratios of the polymer (B-1), the polymer (B-2) and the polymer (B-3) constituting the component [B] are as follows. Preferably 5 to 70 mass%, 5 to 80 mass% and 10 to 90 mass%, more preferably 7 to 70 mass%, 7 to 65 mass% and 20 to 80 mass%, still more preferably 10 to 60 mass%, They are 10-50 mass% and 30-75 mass%, Most preferably, they are 12-50 mass%, 12-35 mass%, and 40-70 mass%.
In addition, the effect of the balance between the fluidity of the composition and the impact resistance, surface impact resistance and molding appearance of the molded product obtained is significant, r ₁ is 5 to 30% by mass, r ₂ is 15 to 40 wt%, the polymer (B-1), if the content of the polymer (B-2) and polymer (B-3) is, that these total is 100 mass% Respectively, preferably 10 to 60% by mass, 10 to 50% by mass and 30 to 75% by mass, more preferably 12 to 50% by mass, 12 to 35% by mass and 40 to 70% by mass, and still more preferably 14 to They are 45 mass%, 14-32 mass%, and 42-68 mass%, Most preferably, they are 16-43 mass%, 16-30 mass%, and 44-65 mass%.

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

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

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

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

In the present invention, a copolymer obtained by polymerization while changing the charged amount of the vinyl cyanide compound and the aromatic vinyl compound from 3 to 10:97 to 90 to 15 to 60:85 to 40 by mass ratio. It is obtained by polymerizing the polymer and / or the charged amount of the vinyl cyanide compound and the aromatic vinyl compound while changing the mass ratio from 15-60: 85-40 to 3-10: 97-90. The copolymer is preferably part or all of the component [B]. By using the composition containing the copolymer obtained by this method, the flowability of the composition is excellent, and a molded product having an excellent balance of impact resistance, surface impact resistance and molding appearance is efficiently produced. can do.
FIG. 1 shows a copolymer obtained by polymerization while changing the charged amounts of a vinyl cyanide compound and an aromatic vinyl compound from 3 to 10:97 to 90 to 15 to 60:85 to 40 by mass ratio. It is a graph which shows an example of distribution of (component [B]). Thus, in the power feed method, for example, the amount of polymer (B-1) produced is increased by changing the amount of monomer charged (feed amount, feed rate) during the reaction, etc. The production amount of the polymer (B-3) can be increased, or a copolymer for component [B] having a multi-modal distribution can be produced.

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

  The structural unit (by) contained in the component [B] and the structural unit (c) contained in the component [C] may be the same as or different from each other.

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

  In the composition of the present invention, the content of the component [B] is preferably 5 to 80% by mass, more preferably 100% by mass when the total of the components [A], [B] and [C] is 100% by mass. Is 10 to 65% by mass, more preferably 15 to 60% by mass. When the content of the component [B] is 5 to 80% by mass, a molded article having excellent fluidity of the composition and excellent balance of impact resistance, surface impact resistance and molding appearance can be obtained. . In addition, when there is too little content of the said component [B], there exists a tendency for surface impact resistance to fall.

  The component [C] is a (co) polymer containing a structural unit (c) derived from an aromatic vinyl compound, and is a component containing more than 97% by mass of the structural unit (c).

  The aromatic vinyl compound used for forming the component [C] is preferably a monocyclic compound such as styrene; p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethyl. Hydrogen atoms bonded to the aromatic ring constituting styrene, such as styrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-tert-butylstyrene, Alkyl styrene substituted with 1-20 alkyl groups; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluoro Halogenated styrene such as styrene, o-fluorostyrene, o-methyl-p-fluorostyrene; p-chloroethylene Halogen-substituted alkyl styrene such as styrene, m-chloroethyl styrene, o-chloroethyl styrene; p-trimethylsilyl styrene, m-trimethylsilyl styrene, o-trimethylsilyl styrene, p-triethylsilyl styrene, m-triethylsilyl styrene, o-triethyl Alkylsilyl styrene such as silyl styrene and p-dimethyl tert-butyl silyl styrene; phenyl group-containing silyl styrene such as p-dimethylphenyl silyl styrene, p-methyldiphenyl silyl styrene and p-triphenyl silyl styrene; p-dimethyl chloro Halogen-containing compounds such as silyl styrene, p-methyldichlorosilyl styrene, p-trichlorosilyl styrene, p-dimethylbromosilyl styrene, p-dimethyl iodosilyl styrene Rusuchiren; silyl group-containing silylstyrene such as p- trimethylsilyl dimethylsilyl styrene. Of these, styrene is particularly preferred.

  The component [C] is a (co) polymer obtained by using a polymerizable unsaturated monomer containing an aromatic vinyl compound, for example, a polymerizable unsaturated monomer consisting only of an aromatic vinyl compound. (Co) polymers comprising one or more of structural units (c), and copolymers obtained by using aromatic vinyl compounds and other vinyl monomers. A polymer is mentioned. In the case of the latter copolymer, examples of other vinyl monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, and the like. When combining, the structural unit derived from the vinyl cyanide compound has a content of less than 3% by mass or a content of more than 60% by mass.

  The component [C] is preferably polystyrene. The structure of polystyrene is any of atactic in which styrene units are randomly arranged, syndiotactic in which styrene units are regularly arranged alternately, and isotactic in which styrene units are regularly arranged in one direction. There may be.

  The weight average molecular weight of the component [C] is preferably 20,000 to 700,000, more preferably 30,000 to 500,000, and particularly preferably 40,000 to 400,000 from the viewpoint of fluidity. . This weight average molecular weight can be obtained by gel permeation chromatography (GPC).

The production method of the component [C] can be conventionally known solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like.
Further, as described above, a copolymer having a content of a structural unit derived from a vinyl cyanide compound, which is produced when the component [B] is produced by the power feed method, and this content Can be used as a part of the component [C].

  Content of the structural unit (c) contained in the said component [C] is more than 97 mass%, Preferably it is 98-100 mass%, More preferably, it is 99-100 mass%.

  The melt flow rate (temperature: 200 ° C., load: 5 kg) of the component [C] is preferably 0.5 to 80 g / 10 minutes, more preferably 1 to 50 g / 10 minutes, from the viewpoint of molding processability and molding appearance. Particularly preferably, it is 2 to 30 g / 10 minutes.

  In the composition of the present invention, the component [C] may be contained alone or in a combination of two or more.

  In the composition of the present invention, the content of the component [C] is preferably 3 to 90% by mass, more preferably 100% by mass when the total of the components [A], [B] and [C] is 100% by mass. Is 5 to 60% by mass, more preferably 10 to 55% by mass. When the content of the component [C] is 3 to 90% by mass, a molded product having excellent fluidity of the composition and excellent balance of impact resistance, surface impact resistance and molding appearance can be obtained. . In addition, when there is too little content of the said component [C], there exists a tendency for fluidity | liquidity to fall.

The composition of the present invention may contain other polymers (other resins).
Other polymers include a rubbery polymer reinforced graft resin (hereinafter referred to as “rubbery polymer reinforced graft resin [D]”) obtained by polymerizing an aromatic vinyl compound in the presence of a rubbery polymer. For example, "graft resin [D]" or "component [D]"), polyolefin resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyester resin, polyamide resin, fluorine resin, and the like. Another polymer may be contained independently and may be contained in 2 or more types of combinations. In this invention, it is preferable that component [D] is included.
When the composition of the present invention contains another polymer (other resin), the content is preferably 100 parts by mass in total of the above components [A], [B] and [C]. It is 1-30 mass parts, More preferably, it is 5-20 mass parts.

In addition, the rubbery polymer reinforced graft resin [D] contains, similarly to the component [A], a structural unit (c) derived from an aromatic vinyl compound contained in a resin composition obtained by graft polymerization. The at least (co) polymer is a resin grafted to the rubbery polymer, and comprises a rubbery polymer part and a (co) polymer part (graft part) containing the structural unit (c). Even when this graft resin [D] is produced, a (co) polymer composed of one or more structural units (c) which is not grafted to the rubbery polymer is formed. The (co) polymer is included in component [C].
The said component [D] may be used independently and may be used in combination of 2 or more type.

The rubbery polymer used for forming the component [D] includes homopolymers such as polybutadiene, polyisoprene and polychloroprene, styrene / butadiene series such as styrene / butadiene copolymer and styrene / butadiene / styrene copolymer. Copolymers, styrene / isoprene copolymers, styrene / isoprene copolymers such as styrene / isoprene / styrene copolymers, diene rubbers such as natural rubber, and ethylene units and α having 3 or more carbon atoms -Non-diene rubbers such as ethylene / α-olefin copolymers containing units consisting of olefins. Of these, diene rubber is preferable, and polybutadiene (low cis type polybutadiene, high cis type polybutadiene, etc.), styrene / butadiene copolymer and the like are particularly preferable.
In addition, the shape of the rubbery polymer can be, for example, particulate (spherical or substantially spherical), linear, curved, or the like. When it is in the form of particles, the volume average particle diameter is preferably 200 to 5,000 nm, more preferably 500 to 4,000 nm, from the viewpoints of mechanical properties and molding processability. The volume average particle diameter can be measured by image analysis using an electron micrograph, a laser diffraction method, a light scattering method, or the like.

  The component [D] is preferably a graft resin obtained by polymerizing styrene in the presence of polybutadiene.

  The production method of the component [D] can be the same as that of the component [A], but preferred polymerization methods are bulk polymerization, solution polymerization, emulsion polymerization, precipitation polymerization, bulk suspension polymerization and the like. . The component [D] obtained by these methods is contained in, for example, a rubber-reinforced resin known as “impact-resistant polystyrene (HIPS)”.

  In the composition of the present invention, the content of the component [D] is preferably 1 to 30 parts by mass, more preferably 100 parts by mass when the sum of the components [A], [B] and [C] is 100 parts by mass. Is 5 to 20 parts by mass, more preferably 7 to 15 parts by mass. When the content of the component [C] is 1 to 30 parts by mass, a molded article having excellent fluidity of the composition and excellent balance of impact resistance, surface impact resistance and molding appearance can be obtained. .

  In the composition of the present invention, the total content of the rubbery polymer derived from the component [A] or both of the components [A] and [D] is determined by the molding processability and the impact resistance of the molded product. From the viewpoint, it is preferably 3 to 35% by mass, more preferably 5 to 25% by mass with respect to the entire composition.

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

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

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

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

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

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

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

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

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

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

  The composition of the present invention can be obtained by a method using a kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, and (two) rolls. In kneading, the raw material components may be kneaded in a lump or may be kneaded while being divided and blended. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. The kneading temperature is preferably 150 ° C to 250 ° C, more preferably 180 ° C to 220 ° C.

  Since the composition of the present invention contains the components [A], [B] and [C], it has much more excellent impact resistance and surface impact resistance than conventional ones, and has excellent surface gloss. A molded product can be obtained. Therefore, the composition of the present invention is required to have a balance of impact resistance, surface impact resistance and molded appearance, such as components for vehicles, ships, electronic devices, home appliances, building materials, daily goods, sporting goods. Suitable for forming stationery and the like.

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

When a molded product is produced using the molding apparatus, the molding temperature and mold temperature are determined depending on the types of the components [A], [B] and [C], or the raw material components used (other polymers). Selection), etc., as appropriate.
For example, when the said component [A] contains the rubbery polymer reinforcement | strengthening graft resin which uses a diene rubber, the cylinder temperature at the time of shaping | molding is 150 degreeC-250 degreeC normally. The mold temperature is usually 20 ° C to 90 ° C.
In any of the above cases, when the molded product is large, the cylinder temperature is generally set higher than the above temperature.

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

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

1. Production Raw Materials The raw materials (resin component and polymer component) used for the production of the thermoplastic resin composition are as follows. The measurement of the graft ratio, intrinsic viscosity [η], etc. was performed according to the method described above.
1-1. Raw material [P]
This raw material [P] is a rubber reinforced resin obtained by the following Synthesis Examples 1 and 2, both of which are a rubber polymer reinforced graft resin [A] and an ungrafted (co) polymer. (May contain component [B]).

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

Synthesis Example 2 (Synthesis of raw material P2)
In a glass flask equipped with a stirrer, in a nitrogen stream, 61 parts of ion exchange water, 0.20 part of potassium rosinate, 0.18 part of tert-dodecyl mercaptan, a polybutadiene rubber having a volume average particle diameter of 300 nm (gel content 80 %) 97 parts of latex containing 55.5 parts, 6.5 parts of latex containing 4.5 parts of styrene-butadiene copolymer rubber (styrene unit amount 30%) having a volume average particle diameter of 600 nm, 9.5 parts of styrene, and Acrylonitrile 0.5 part was accommodated and it heated up, stirring. When the internal temperature reached 43 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.04 parts of ferrous sulfate heptahydrate and 0.25 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.055 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 50 minutes, a solution in which 0.07 part of sodium pyrophosphate, 0.01 part of ferrous sulfate heptahydrate and 0.08 part of glucose was dissolved in 8 parts of ion-exchanged water, 28.5 parts of styrene Acrylonitrile (1.5 parts), tert-dodecyl mercaptan (0.54 parts) and cumene hydroperoxide (0.22 parts) were continuously added over 110 minutes. Thereafter, 0.09 part of cumene hydroperoxide was further added, and then polymerization was continued for 1 hour to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and wash it with water. Thereafter, it was washed and neutralized with an aqueous potassium hydroxide solution, further washed with water, and dried to obtain a rubber-reinforced resin (P2). The graft ratio in the graft resin (component [A]) contained in this resin (P2) is 32%, and the structural unit (gx) derived from the vinyl cyanide compound and the structural unit derived from the aromatic vinyl compound ( The proportion of gy) is 5% and 95% when the total of both is 100%, and the content of ungrafted (co) polymer (acetone soluble component) is 21%. The intrinsic viscosity [η] of soluble component (in methyl ethyl ketone, 30 ° C.) was 0.21 dl / g.

1-2. Raw material [Q]
This raw material [Q] is an acrylonitrile / styrene copolymer obtained by the following Synthesis Examples 3 to 9, or a mixture of plural kinds thereof.

Synthesis Example 3 (Synthesis of raw material Q1)
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., 0.2 part of diisopropylbenzene hydroperoxide, 0.2 part of tert-dodecyl mercaptan, 95 parts of styrene and 5 parts of acrylonitrile were added to the reaction system for 3 hours. The solution was continuously dropped and polymerized. At the same time as the completion of the dropping, the polymerization was completed to obtain latex (L-1).
On the other hand, in a glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate and 0.5 part of sodium hydrogen carbonate were placed in a nitrogen stream, and the temperature was raised while stirring. did. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., 0.2 parts of diisopropylbenzene hydroperoxide, 0.2 parts of tert-dodecyl mercaptan, 87.5 parts of styrene and 12.5 acrylonitrile were added. Part of the mixture was added dropwise over 3 hours to conduct polymerization. The polymerization was completed simultaneously with the completion of the dropwise addition to obtain latex (L-2).
In a separate glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium bicarbonate were placed in a nitrogen stream, and the temperature was raised while stirring. did. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., a mixture of 0.2 part of diisopropylbenzene hydroperoxide, 0.2 part of tert-dodecyl mercaptan, 75 parts of styrene and 25 parts of acrylonitrile was added to the reaction system. It dripped over 3 hours and superposed | polymerized. At the same time as the completion of the dropping, the polymerization was completed to obtain a latex (L-3).
Next, the latexes (L-1), (L-2), and (L-3) obtained above were mixed so that the polymer content ratio was 33:34:33. And the polymer was solidified and washed with water using the magnesium sulfate solution. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material Q1. In the raw material Q1, the polymer corresponding to the component [B] is a polymer contained in the latexes (L-1), (L-2), and (L-3) obtained above. The amount of acrylonitrile unit with respect to the whole of Q1 is 18.6%.
This raw material Q1 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.51 dl / g.

Synthesis Example 4 (Synthesis of raw material Q2)
In this synthesis example, a first monomer composed of a mixture of 75 parts of styrene, 0.15 part of diisopropylbenzene hydroperoxide and 0.15 part of tert-dodecyl mercaptan (contained in the first supply source at the start of synthesis), A second monomer (accommodated in a second source at the start of synthesis) composed of a mixture of 25 parts of acrylonitrile, 0.05 part of diisopropylbenzene hydroperoxide and 0.05 part of tert-dodecyl mercaptan, and the following: Polymerization was carried out in the manner described above to obtain a raw material Q2.
To a glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate and 0.5 part of sodium bicarbonate were added in a nitrogen stream, and the temperature was raised while stirring. When the internal temperature reached 45 ° C., 0.062 part of ethylenediaminetetraacetic acid / tetrasodium dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.124 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., polymerization was carried out while continuously supplying monomers from the first and second supply sources to the reaction system over 3 hours. The total amount of monomers to be supplied is successively constant (100 parts), and the monomer supply amount (mass ratio) from each supply source is set to the first monomer: The second monomer was 91: 9, and the first monomer: second monomer = 0: 100 at the end of supply (after 3 hours).
Simultaneously with the completion of the monomer supply (after the completion of the three-hour supply), the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Next, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material Q2. In addition, the acrylonitrile unit amount with respect to the whole raw material Q2 is 18.6%.
This raw material Q2 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.51 dl / g.

Synthesis Example 5 (Synthesis of raw material Q3)
In this synthesis example, a first monomer comprising 0.1 part of diisopropylbenzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan, 48.5 parts of styrene and 1.5 parts of acrylonitrile (at the start of synthesis, the first supply) And a second monomer comprising a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.1 part tert-dodecyl mercaptan, 37.5 parts styrene and 12.5 parts acrylonitrile (at the start of synthesis, Polymerization was performed in the following manner to obtain a raw material Q3.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Next, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material Q3. In addition, the acrylonitrile unit amount with respect to the whole raw material Q3 is 18.6%.
This raw material Q3 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.40 dl / g.

Synthesis Example 6 (synthesis of raw material Q4)
In this synthesis example, a first monomer comprising 0.1 part of diisopropylbenzene hydroperoxide, 0.10 part of tert-dodecyl mercaptan, 24.25 parts of styrene and 0.75 part of acrylonitrile (the first supply at the start of synthesis) Source) and a second monomer consisting of a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.10 part tert-dodecyl mercaptan, 56.25 parts styrene and 18.75 parts acrylonitrile (at the start of synthesis, Polymerization was performed in the following manner using a second supply source) to obtain a raw material Q4.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 25 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Next, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material Q4. In addition, the acrylonitrile unit amount with respect to the whole raw material Q4 is 22.8%.
This raw material Q4 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.51 dl / g.

Synthesis Example 7 (synthesis of raw material Q5)
In this synthesis example, a first monomer consisting of a mixture of 0.2 parts of diisopropylbenzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan, 95 parts of styrene and 5 parts of acrylonitrile (at the start of synthesis, the first source Polymerization was performed in the following manner to obtain a raw material Q5.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Next, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material Q5. In addition, the acrylonitrile unit amount with respect to the whole raw material Q5 is 6.0%.
This raw material Q5 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.53 dl / g.

Synthesis Example 8 (synthesis of raw material Q6)
In this synthesis example, a first monomer composed of a mixture of 0.2 parts of diisopropylbenzene hydroperoxide, 0.23 parts of tert-dodecyl mercaptan, 83 parts of styrene and 17 parts of acrylonitrile (at the start of synthesis, the first source Polymerization was performed in the following manner to obtain raw material Q6.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of styrene / acrylonitrile copolymers having different compositions.
Next, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material Q6. In addition, the acrylonitrile unit amount with respect to the whole raw material Q6 is 20.4%.
This raw material Q6 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.59 dl / g.

Synthesis Example 9 (synthesis of raw material Q7)
A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, the first reactor was charged with a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 40 parts of toluene, and 0.14 part of tert-dodecyl mercaptan as a molecular weight regulator. And a solution prepared by dissolving 0.07 part of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, in 5 parts of toluene, are continuously supplied. Polymerization was carried out at 0 ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the styrene / acrylonitrile copolymer. This styrene / acrylonitrile copolymer was used as the raw material Q7. In addition, the acrylonitrile unit amount with respect to the whole raw material Q7 is 27.3%.
This raw material Q7 had an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.51 dl / g.

1-3. Raw material [R]
The following commercially available products were used.
Polystyrene “GPPS 679” (trade name) manufactured by PS Japan Co., Ltd. was used as the raw material R1. The melt flow rate (temperature 200 ° C., load 5 kg) is 18 g / 10 min.
As the raw material R2, impact-resistant polystyrene “HIPS 475D” (trade name) manufactured by PS Japan was used. The melt flow rate (temperature 200 ° C., load 5 kg) is 2 g / 10 min. The rubbery polymer contained in this product is polybutadiene rubber, and the proportions of graft resin and ungrafted component (polystyrene) are 73% and 27%, respectively.

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1-9 and Comparative Examples 1-14
Thermoplastic resin compositions were obtained using the raw materials [P], [Q] and [R] in the proportions shown in Tables 1 to 5. In evaluating the composition, a composition for evaluating physical properties containing an additive (antioxidant) corresponding to the evaluation item was prepared in advance and used.
The raw material [P] may be a mixture of the component [A] and the component [B] according to the present invention depending on the synthesis method. Therefore, a polymer corresponding to the component [B] with respect to the total amount of the components [A], [B] and [C] of the present invention using the graft ratio in the raw material [P], the composition of the acetone soluble component, and the like. The content ratio was calculated and the value is shown in each table. Then, the component [B], select a polymer (B-1), since it is constituted by a polymer (B-2) and polymer _{(B-3), r 1} = 15 and _r 2 = 20 Then, each ratio when these totals were taken as 100% was analyzed by the following method. Moreover, it showed to each table | surface about content of the structural unit (bx) contained in component [B].

<Composition analysis of polymers (B-1), (B-2) and (B-3) in component [B]>
10 mg of a component (mixture of ungrafted polymer) excluding the graft resin contained in the thermoplastic resin composition was put into 10 ml of a mixture of acetonitrile and 1,2-dichloroethane (volume ratio 6: 4). Shake at 25 ° C. for 2-3 hours. Thereafter, insoluble matters (contaminants) were removed, and the soluble matters were subjected to liquid chromatography. Super system controller “SC8020” (model name) manufactured by Tosoh Corporation, online degasser “SD8022” (model name) manufactured by Tosoh Corporation, multi-pump “CCPMII” (model name) manufactured by Tosoh Corporation, UV detector “UV-8020” manufactured by Tosoh Corporation ”(Model name), Tosoh Corporation column“ TSK Silica-60 ”(model name), and Tosoh Corporation column oven“ CO-8020 ”(model name), using a liquid chromatograph apparatus, n-heptane The sample was developed with a mobile phase gradient from 1,2-dichloroethane mixture (volume ratio 7: 3) to acetonitrile / 1,2-dichloroethane mixture (volume ratio 6: 4), and the wavelength was measured with a UV detector. From the absorption value at 260 nm, the distribution of the composition of the polymers (B-1), (B-2) and (B-3) corresponding to the component [B] was measured. The column temperature is 35 ° C. The determination of the polymer composition and distribution in the sample was made by preparing a calibration curve in advance using a styrene / acrylonitrile copolymer containing a structural unit of known type and content.

<Composition for evaluating physical properties>
After supplying a predetermined amount of raw materials [P], [Q] and [R] to a Henschel mixer, tris (2,4-di-tert-butylphenyl) as an antioxidant is added to 100 parts in total. ) Phosphite (trade name “Adeka Stub 2112”, manufactured by ADEKA) 0.2 parts and pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name) 0.2 part of “ADK STAB AO-60” (manufactured by ADEKA) was added and mixed at 25 ° C. Next, this mixture was supplied to a twin-screw extruder “BT40” (model name) manufactured by Plastic Engineering Laboratory Co., Ltd. and melt-kneaded to obtain pellets (physical property evaluation composition). In addition, the cylinder setting temperature at the time of melt-kneading was 180 degreeC-220 degreeC.
Then, after sufficiently drying the above pellets, the evaluation items were evaluated using an injection molding machine “EC60” (model name) manufactured by Toshiba Machine Co., Ltd. with a cylinder set temperature of 180 ° C. to 220 ° C. and a mold temperature of 50 ° C. A suitable test piece was prepared and subjected to evaluation.
(1) Impact resistance In accordance with ISO 179, Charpy impact strength was measured at a temperature of 23 ° C. The unit is “kJ / m ² ”.
(2) Surface impact resistance A test piece having a size of 80 mm × 55 mm × 2.4 mm was set on a high-speed impact tester “HITS-P10” (model name) manufactured by Shimadzu Corporation, and a falling weight test (weight Punch tip diameter: 12.7 mm, cradle hole diameter: 43 mm, test speed: 6.7 m / sec, test temperature: 23 ° C.). The test was performed 4 times and the average value of the fracture energy was calculated. The unit is “J”.

(3) Molding appearance The molding appearance was evaluated by the glossiness of the test piece. According to JIS Z8741, the glossiness was measured at a light incident angle of 60 degrees. The measuring device is a digital gloss meter “GH-26D” (model name) manufactured by Murakami Color Research Laboratory. The unit is “%”.
(4) Fluidity Using the above pellets, the melt flow rate was measured at a temperature of 220 ° C. and a load of 98 N according to ISO 1133. The unit is “g / 10 minutes”.

From Tables 3 to 5, the following is clear. That is, Comparative Examples 1 to 3 do not include the polymer (B-1) constituting the component [B] according to the present invention, and the content ratio of the polymer (B-2) and the polymer (B-3) is Since they are all outside the scope of the present invention, they are inferior in impact resistance and surface impact resistance. Since Comparative Example 4 does not include the polymer (B-1) constituting the component [B] according to the present invention, it is inferior in impact resistance and surface impact resistance. Since Comparative Example 5 does not include the polymer (B-1) constituting the component [B] according to the present invention, it is inferior in impact resistance and surface impact resistance. Since Comparative Examples 6-8 do not include the polymers (B-2) and (B-3) constituting the component [B] according to the present invention, they are inferior in impact resistance and surface impact resistance. Since Comparative Example 9 does not contain the polymers (B-2) and (B-3), it is inferior in impact resistance and surface impact resistance. Since Comparative Example 10 does not contain the polymers (B-1) and (B-2), it is inferior in impact resistance and surface impact resistance.
Since the content rate of the polymer (B-1) which comprises the component [B] which concerns on this invention is outside the range of this invention, the comparative example 11 is inferior to impact resistance and surface impact resistance. Since the content rate of the polymer (B-2) which comprises the component [B] which concerns on this invention is outside the range of this invention, the comparative example 12 is inferior to impact resistance and surface impact resistance. Since the content rate of the polymer (B-1) which comprises the component [B] which concerns on this invention is outside the range of this invention, the comparative example 13 is inferior to impact resistance and surface impact resistance. Comparative Example 14 is an example not containing the components [A] and [B] according to the present invention, and is inferior in impact resistance, surface impact resistance, and molded appearance.
On the other hand, from Tables 1 and 2, it is clear that Examples 1 to 9 which are the compositions of the present invention are excellent in the balance of impact resistance, surface impact resistance and molding appearance.

Since the thermoplastic resin composition of the present invention provides a molded product having a good balance of impact resistance, surface impact resistance and molded appearance, for example, vehicles, ships, OA equipment, home appliances, electrical equipment / electronics It is suitable for forming members such as equipment and building materials, daily miscellaneous goods, sports equipment, stationery, and the like, and particularly suitable for forming a molded product having excellent surface gloss.
The thermoplastic resin composition of the present invention can be a composition prepared by blending a predetermined resin with a recycled resin from a molded product containing polystyrene, impact-resistant polystyrene or ABS resin. That is, a low-cost composition using raw material components excluding recycled resin can be obtained, and the obtained molded product has excellent performance, so that the industrial utility value is extremely high.

Claims (9)

[A] a rubbery polymer reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer;
[B] a copolymer comprising a structural unit (bx) derived from a vinyl cyanide compound and a structural unit (by) derived from an aromatic vinyl compound;
[C] a (co) polymer containing a structural unit (c) derived from an aromatic vinyl compound;
In a thermoplastic resin composition containing
The component [B] contains the polymer (B-1) containing the structural unit (bx) at 3 mass% or more and ₁ mass% or less and the structural unit (bx) exceeding ₁ mass% r. a polymer (B-2) containing ₂ % by mass or less of r, and a polymer (B-3) containing the structural unit (bx) in excess of r ₂ % by mass and 60% by mass or less, and (R ₂ −r ₁ ) ≧ 5 (mass%),
The content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) is 5 to 70% by mass, respectively, when the total content is 100% by mass. 5 to 80 mass% and 10 to 90 mass%,
The said component [C] contains the said structural unit (c) exceeding 97 mass%, The thermoplastic resin composition characterized by the above-mentioned. The thermoplastic resin composition according to claim 1 r ₂ is 15 to 45 mass%.   The component [B] is a copolymer comprising a structural unit (bx) and a structural unit (by), and the vinyl cyanide compound and the aromatic vinyl compound are mixed at a mass ratio of 3 to 10:97 to 90. From 15 to 60:85 to 40, or from 15 to 60:85 to 3 to 10:97 to 90, a copolymer obtained by polymerization while changing the charged amount is included. The thermoplastic resin composition according to 1 or 2.   The content ratio of the structural unit (bx) contained in the component [B] is 10 to 40% by mass when the total of the structural units constituting the component [B] is 100% by mass. The thermoplastic resin composition in any one of thru | or 3.   The content ratio of the component [A], the component [B], and the component [C] is 3 to 70% by mass, 5 to 80% by mass, It is 90 mass%, The thermoplastic resin composition in any one of Claims 1 thru | or 4.   When the proportion of the structural unit (gx) derived from the vinyl cyanide compound and the structural unit (gy) derived from the aromatic vinyl compound contained in the component [A] is 100% by mass. The thermoplastic resin composition according to any one of claims 1 to 5, which is 5 to 40% by mass and 60 to 95% by mass, respectively. r ₁ is 5 to 30% by mass, r ₂ is 15 to 40% by mass,
When the content ratio of the polymer (B-1), the polymer (B-2), and the polymer (B-3) is 100% by mass, the content is 10 to 60% by mass. The thermoplastic resin composition according to any one of claims 1 to 6, which is 10 to 50 mass% and 30 to 75 mass%.   The thermoplastic resin composition according to any one of claims 1 to 7, further comprising [D] a rubbery polymer reinforced graft resin obtained by polymerizing an aromatic vinyl compound in the presence of a rubbery polymer. object.   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 8.

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