JP2010150301A - Aromatic vinyl graft copolymer for resin blend and thermoplastic resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber-reinforced resin that gives a resin blend excellent in thermal stability during the residence time in an extruder or a molding machine and excellent in appearance of a molded article and that can be produced in a simple and efficient manner. <P>SOLUTION: An aromatic vinyl graft copolymer for a resin blend is a graft copolymer (B1) produced by polymerizing (b) a vinyl monomer including an aromatic vinyl compound in the presence of (a) a rubbery polymer. The phosphorus content in the graft copolymer (B1) is 200-5,000 ppm or the sulfur content in the same is 1,000-5,000 ppm. The graft copolymer (B1) can be produced by performing emulsion polymerization to form a latex of the graft copolymer and solidifying the latex in the presence of an alkali metal salt of an oxoacid including a phosphorus atom and/or a sulfur atom (a phosphoric acid, a sulfonic acid or the like). A resin blend excellent in thermal stability and appearance of the molded article can be produced by blending the graft copolymer (B1) with other thermoplastic resins such as polycarbonate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aromatic vinyl-based graft copolymer for resin blends which gives a thermoplastic resin composition excellent in thermal stability and appearance of a molded article, and thermal stability containing the graft copolymer and a polycarbonate resin. The present invention relates to a thermoplastic resin composition having excellent properties and appearance of a molded product.

  Polycarbonate resin is excellent in heat resistance and impact resistance, so it is used in a wide range of fields such as automobile parts, electrical / electronic parts, precision machine parts, etc., but it is inferior in moldability and impact resistance at low temperatures. There are disadvantages. On the other hand, rubber reinforced resin represented by ABS resin is a material excellent in mechanical strength and moldability, but is used for materials such as automobile parts and OA parts that require heat resistance and high impact resistance. Has insufficient heat resistance and impact resistance, and uses are limited.

  As a method for compensating for these disadvantages, it is known to blend a polycarbonate resin and a rubber reinforced resin. By this method, the moldability and the impact resistance at low temperatures which were the disadvantages of the polycarbonate resin were improved, and the heat resistance and the impact resistance which were the disadvantages of the rubber reinforced resin were improved. As a result, a resin blend excellent in moldability, impact resistance, mechanical strength and heat resistance is obtained, and it is used as a housing material for OA equipment such as electrical products, computers and word processors, automotive components, furniture components such as office furniture. Widely used.

  However, a resin blend of polycarbonate and a rubber reinforced resin such as ABS resin is inferior in thermal stability during residence in a molding machine or an extruder, and has a drawback that impact resistance of a molded product is lowered when the residence time is long. is there. Therefore, in order to prevent this, it has been necessary to limit the extrusion conditions and molding conditions such as shortening the residence time in the molding machine and the extruder as much as possible and lowering the molding temperature.

  As a method for improving the thermal stability during residence of such a resin blend, a method of adding one or more acid compounds selected from inorganic acids, organic acids and organic acid anhydrides to the resin blend (see, for example, Patent Document 1) , A method of containing an organic phosphonic acid or a phosphoric acid ester metal salt in a resin blend (see, for example, Patent Document 2 and Patent Document 3), an organic phosphoric acid ester, an organic phosphorous acid ester, or a metal salt thereof and an organic carboxyl A method in which an acid or an organic carboxylic acid anhydride is used in combination with a resin blend (for example, see Patent Document 4) is disclosed.

  However, in recent years, the molding method has been made larger and thinner, the molding temperature is higher than before, the injection molding machine is also larger, and the molding conditions are becoming stricter with respect to the resin. It is becoming increasingly difficult to improve the thermal stability during residence.

  As a new solution, recently, a method for producing a resin blend using an ABS resin having a low alkali metal index, an alkaline earth metal index, and a chlorine content (see Patent Document 5), and coagulating a latex of a rubber-reinforced resin There has also been proposed a method of using an alkaline earth metal as a coagulant in the process, maintaining a pH during coagulation in a specific range, and producing a resin blend using the obtained rubber-reinforced resin (see Patent Document 6).

However, in the method described in Patent Document 5, although the thermal stability of the resin blend is improved, it is necessary to thoroughly wash the coagulated product in the process of coagulating the latex of the ABS resin produced by emulsion polymerization and taking out the resin. Therefore, a large amount of water is used, and not only water resources cannot be saved, but also the economic burden such as wastewater treatment is large. Moreover, even when a resin blend is produced using a rubber reinforced resin obtained by the method described in Patent Document 6, thermal stability may not be sufficiently improved.
JP 56-131657 A JP-A-55-123647 JP 54-40854 A JP-A-63-260948 Japanese Patent Laid-Open No. 6-263962 JP-A-9-100309

  An object of the present invention is to provide a rubber-reinforced resin that can provide a resin blend excellent in thermal stability at the time of residence and appearance of a molded product and can be easily and efficiently manufactured, a method for manufacturing the same, and the rubber-reinforced resin and polycarbonate resin. An object of the present invention is to provide a thermoplastic resin composition excellent in the thermal stability during residence and the appearance of a molded product.

  As a result of diligent research to achieve the above object, the inventors of the present invention have previously incorporated a latex of rubber-reinforced resin obtained by emulsion polymerization or the like with a coagulant and recovered it as a powder. By using a rubber-reinforced resin obtained by allowing an alkali metal salt of a specific oxo acid such as acid or sulfonic acid to exist, particularly a rubber-reinforced resin having a specific content of phosphorus or sulfur, The present inventors have found that a resin blend excellent in thermal stability during residence and appearance of a molded product can be obtained, and the present invention has been achieved.

  Thus, according to one aspect of the present invention, a graft copolymer (b) obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (a) ( An aromatic vinyl-based graft copolymer for resin blends which is B1) and has a phosphorus content of 200 to 5000 ppm or a sulfur content of 1000 to 5000 ppm in the graft copolymer (B1).

  According to another aspect of the present invention, the polycarbonate resin (A) is 35 to 90% by mass, the aromatic vinyl graft copolymer for resin blend (B1) is 10 to 65% by mass, and the vinyl monomer A thermoplastic resin composition comprising 0 to 55% by mass of the (co) polymer (B2) of the monomer (b) (provided that the total of the components (A), (B1) and (B2) is 100% by mass). The MFR value X (g / min) under the condition of a temperature of 260 ° C., a load of 5 kg, and a holding time of 5 minutes is 40 or less, and the MFR value Y (temperature of 260 ° C., load of 5 kg, holding time of 15 minutes is Y ( g / min) is 80 or less, and Y / X is 1.3 or less. A thermoplastic resin composition is provided.

  According to still another aspect of the present invention, a vinyl copolymer (b) containing an aromatic vinyl compound is emulsion-polymerized in the presence of the rubbery polymer (a) to produce a graft copolymer ( B1) latex is obtained, and the latex is coagulated and recovered using a coagulant in the presence of an alkali metal salt of an oxo acid composed of phosphorus atoms and / or sulfur atoms. A method for producing a graft copolymer for blending is provided.

  According to the present invention, when a latex of a rubber-reinforced resin is obtained by emulsion polymerization, and when the latex is coagulated and recovered using a coagulant, the coagulation is alkalinized with a specific oxo acid such as phosphoric acid or sulfonic acid. Since it was carried out in the presence of a metal salt and the rubber-reinforced resin was used as a component of the resin blend, a resin blend excellent in thermal stability during residence and appearance of the molded product, particularly in an extruder or molding machine Thus, a resin blend having a small change in fluidity (MFR) during residence and excellent appearance of a molded product is provided.

Hereinafter, the present invention will be described in detail.
The aromatic vinyl-based graft copolymer (B1) for resin blending of the present invention gives a thermoplastic resin composition excellent in thermal stability during residence and appearance of a molded product by blending with an arbitrary thermoplastic resin. Examples of such thermoplastic resins include polycarbonate resins, and polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate, and polylactic acid.

  In the present invention, the polycarbonate resin (A) is not particularly limited as long as it has a carbonate bond in the main chain, and examples thereof include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. These may be used alone or in combination of two or more. Among these, aromatic polycarbonate is most preferable from the viewpoint of impact resistance, heat resistance, and the like. These polycarbonate resins may be modified at the ends with R-CO- groups and R'-O-CO- groups (R and R 'each represents an organic group).

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

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

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

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

  The viscosity average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 40,000, more preferably 17,000 to 30,000, and particularly preferably 18,000 to 28,000. The higher the viscosity average molecular weight, the higher the impact resistance, while the fluidity is insufficient and the moldability tends to be inferior. In addition, as long as the viscosity average molecular weight as a whole falls in the above range, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed and used.

  Blending of the polycarbonate resin (A) in the thermoplastic resin composition of the present invention obtained by blending the aromatic vinyl-based graft copolymer (B1) and optionally the (co) polymer (B2) with the polycarbonate resin (A) The ratio is determined according to the required mechanical strength, rigidity, molding processability, and heat resistance, but is usually 35 to 90% by mass, preferably 35 to 80% by mass, more preferably 40 to 80% by mass. More preferably, it is 40 to 70% by mass (however, the sum of components (A), (B1) and (B2) is 100% by mass). If it is this range, it will become a composition excellent in various, such as moldability and heat resistance.

  The aromatic vinyl graft copolymer for resin blend in the present invention is a graft copolymer obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (a). It is a polymer (B1).

The rubbery polymer (a) is not particularly limited as long as the glass transition temperature (hereinafter referred to as “Tg”) is normal temperature or lower, but in order to make the mechanical strength of the resin blend sufficient, the above polymer is used. The Tg is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, and particularly preferably −20 ° C. or lower. If the Tg of the rubbery polymer is too high, the mechanical strength of the resulting resin blend will be reduced.
As the rubbery polymer (a), diene rubbers and hydrogenated products thereof, ethylene-α-olefin rubbers, acrylic rubbers, silicone rubbers, silicone / acrylic composite rubbers and the like can be used. Of these, diene rubbers and hydrogenated products thereof, acrylic rubbers, silicone rubbers, and silicone / acrylic composite rubbers are preferred from the viewpoint that they can be easily used in emulsion polymerization of the graft copolymer. In addition, these can be used individually or in combination of 2 or more types.

Examples of the diene rubber include a polymer obtained by polymerizing a monomer composed of a diene compound such as 1,3-butadiene and isoprene and optionally another compound copolymerizable therewith. Examples of the other copolymerizable compounds include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, and the like. A combination of more than one species can be used. Specific examples of the conjugated diene rubber include polybutadiene, butadiene / styrene random copolymer, butadiene / styrene block copolymer, butadiene / acrylonitrile copolymer, and the like. The diene rubber may be a hydrogenated product obtained by hydrogenating all or part of the carbon-carbon double bonds derived from the diene compound. The said diene rubber can be used individually or in combination of 2 or more types.

  As said acrylic rubber, the polymer obtained by superposing | polymerizing the monomer which consists of alkyl acrylate ester and the other compound copolymerizable with these as needed is mentioned. Examples of alkyl acrylate esters include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, acrylic acid 2 -Methylpentyl, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate and the like. Examples of the other copolymerizable compounds include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, and the like. The said compound which comprises a monomer can be used individually or in combination of 2 or more types.

  The diene rubber or acrylic rubber preferably contains a crosslinkable monomer as a constituent monomer as appropriate. Examples of the crosslinkable monomer include “polyfunctional vinyl compounds”. The polyfunctional vinyl compound is a compound having two or more vinyl groups in one molecule and different from the above “diene compound”, and has a function of crosslinking the rubbery polymer (a). It also serves as a reaction starting point during graft polymerization. In particular, it is suitably used when the rubbery polymer (a) is an acrylic rubber. Specific examples of these polyfunctional vinyl compounds include aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, acrylic acid esters of polyhydric alcohols such as (poly) ethylene glycol dimethacrylate and trimethylolpropane triacrylate, and the like. Examples include methacrylic acid esters, diallyl malate, diallyl fumarate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, and allyl methacrylate. These polyfunctional vinyl compounds can be used alone or in combination of two or more. The polyfunctional vinyl compound is not necessarily required when the rubbery polymer (a) is composed only of a diene rubber, but when an acrylic rubber is used, the rubbery polymer (a). It is preferably used in a blending ratio of 0.1 to 5% by mass with respect to 100% by mass of the total amount of monomers constituting the.

  When the amount of the polyfunctional vinyl compound used is too small, the degree of cross-linking of the resulting rubbery polymer (a) is lowered, and as a result, the rubber elasticity is reduced, so that the rubbery polymer (a) is used. When the resin blend containing the obtained graft copolymer (B1) is molded into a molded product, the rubber particles are remarkably deformed, resulting in a decrease in the mechanical strength of the molded product, and further anisotropy of the molded product. May cause it. Moreover, in the polymerization for obtaining the graft copolymer (B1), the reaction starting point is decreased, and grafting may be insufficient. On the other hand, if the amount of the polyfunctional vinyl compound used is too large, the degree of crosslinking of the rubber polymer (a) becomes too high, and the rubber elasticity may be lost and become hard. When such a hard rubbery polymer (a) is used, the mechanical strength of the molded product containing the finally obtained resin blend tends to decrease.

Examples of the silicone rubber include polyorganosiloxane rubber-like polymers obtained by a known polymerization method using organosiloxane as a raw material, and those obtained in a latex state by emulsion polymerization are preferred because of easy graft polymerization. The latex of the polyorganosiloxane rubber polymer can be obtained by a known method, for example, a method described in US Pat. No. 3,294,725. As a preferable method, it is produced by condensing organosiloxane with water using a homomixer or an ultrasonic mixer in the presence of a sulfonic acid emulsifier and a polymerization catalyst such as alkylbenzene sulfonic acid and alkyl sulfonic acid. can do. Specific examples of organosiloxanes include linear organosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane. Examples include organosiloxane and branched organosiloxane. These organosiloxanes can be used alone or in combination of two or more.
When producing the polyorganosiloxane, a graft crossing agent or a cross-linking agent may be co-condensed within a range that does not impair the intended performance of the present invention.

  As the graft crossing agent, for example, a compound having both an unsaturated group and an alkoxysilyl group can be used. By using this compound, a vinyl group, an allyl group, a methacryloyl group or the like can be introduced into the polyorganosiloxane. Specific examples of the graft crossing agent include p-vinylphenylmethyldimethoxysilane and p-vinylphenylethyldimethoxymethylsilane.

  Examples of the crosslinking agent capable of cocondensing polyorganosiloxane include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, tetraethoxysilane, 1,3-bis [2- (dimethoxymethylsilyl) And tetrafunctional cross-linking agents such as ethyl) benzene and 1,4-bis [2- (dimethoxymethylsilyl) ethyl] benzene. Moreover, you may use the crosslinking prepolymer polycondensed previously as these crosslinking agents.

  Further, the molecular chain terminal of the polyorganosiloxane may be blocked with, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, or a methyldiphenylsilyl group.

The silicone / acrylic composite rubber refers to a rubbery polymer containing a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber. A preferable silicone-acrylic composite rubber is a composite rubber having a structure in which a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber are intertwined with each other so that they cannot be separated. Examples of the polyorganosiloxane rubber include the polyorganosiloxane described for the silicone rubber. Examples of the polyalkyl (meth) acrylate rubber include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, and 4-hydroxybutyl acrylate. , Lauryl methacrylate, stearyl methacrylate and other alkyl (meth) acrylates (monomers) obtained by copolymerization, and if desired, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene; acrylonitrile And vinyl cyanide compounds such as methacrylonitrile; various vinyl monomers such as methacrylic acid-modified silicone and fluorine-containing vinyl compounds. Good.
Silicone / acrylic composite rubber can be produced, for example, by the method described in JP-A-4-239010, Japanese Patent No. 2137934, and the like. As such a silicone / acrylic composite rubber graft copolymer, for example, “Metablene SX-006 (trade name)” manufactured by Mitsubishi Rayon Co., Ltd. is commercially available.

The rubbery polymer (a) can be produced by other polymerization methods such as a solution polymerization method and a bulk polymerization method in addition to the emulsion polymerization method. However, it is preferable that the rubber polymer (a) is finally a dispersion liquid of latex or the like dispersed in an aqueous medium such as water. As a production method for obtaining such a dispersion, in addition to an emulsion polymerization method for directly obtaining a latex, an organic solvent system such as a solution polymerization method or a bulk polymerization method, or a polymer obtained in a bulk system can be dissolved. A method of dissolving and dissolving in a solvent and adding and dispersing in an aqueous medium together with a surfactant and re-emulsifying the same polymer by injecting the surfactant and the aqueous medium while kneading in a processing machine such as an extruder. Examples include emulsifying methods. However, the emulsion polymerization method is preferred.
When the rubbery polymer (a) is produced by an emulsion polymerization method, by appropriately selecting the production conditions such as the type / amount of the emulsifier, the type / amount of the initiator, the polymerization time, the polymerization temperature, the stirring conditions, The content and particle diameter can be easily adjusted. The volume average particle diameter of the rubber-like polymer particles (a) is not particularly limited, but is preferably 50 to 2000 nm, more preferably 65 to 1500 nm, and further preferably 80 to 1000 nm. When the volume average particle diameter is outside the above range, impact resistance may not be sufficient. The volume average particle diameter can be measured by a known method such as a laser diffraction / scattering method. Specifically, it can be measured by “Microtrack UPA150 type” manufactured by HONEYWELL, and all the particle sizes described in the present invention are the particle sizes obtained by this measuring method. The gel content of the rubbery polymer (a) is not particularly limited, but is usually 30 to 98%.

The rubbery polymer (a) may be enlarged rubber particles obtained by enlarging rubber particles having a small particle diameter by a known method as long as the volume average particle diameter is within the above range. Good. As a method for enlarging the particle size, a known method can be applied. For example, (i) an agglomerating agent such as an acid, salt, acid group-containing polymer latex or the like in an aqueous dispersion containing rubber particles having a small particle size. (Ii) applying a shearing force, (iii) freezing the aqueous dispersion, and then thawing. By these operations, the rubber particles are partially agglomerated to obtain a rubbery polymer (a) having an enlarged particle diameter. In the present invention, the method (i) is preferred.
Examples of the acid in the method (i) include acetic anhydride, acetic acid, nitric acid, phosphoric acid and the like. Examples of the salt include inorganic salts such as calcium chloride and magnesium sulfate. By using these, the aqueous dispersion containing rubber particles can be destabilized, and these particles can be partially agglomerated and enlarged. As the acid, it is particularly preferable to use acetic anhydride. In this case, rubber polymer particles having an arbitrary particle size can be obtained, and the particle size of the obtained composite rubber particles is stable over time. In addition, after forming the enlarged rubber particles, a method of neutralizing the dispersion is applied as necessary. When the rubbery polymer (a) of the present invention is enlarged rubber particles enlarged by the above-described method, the particle diameter after enlarged is preferably in the above range.
The rubbery polymer (a) of the present invention is a mixture of two or more rubbery polymers having different particle size distributions as long as the overall volume average particle size falls within the above range. It may be.

  The graft copolymer (B1) of the present invention is obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of the rubbery polymer (a). Obtained by emulsion polymerization. Here, as the vinyl monomer (b), one or more aromatic vinyl compounds or one or more aromatic vinyl compounds and one or more compounds copolymerizable with the aromatic vinyl compounds are used. Can be used in combination. Examples of the compound copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, and unsaturated compounds having other functional groups. These can be used alone or in combination of two or more.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, vinylnaphthalene, Monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, hydroxystyrene and the like. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.
Examples of (meth) acrylic acid ester compounds include acrylic acid esters such as cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate. , Isobutyl methacrylate, n-pentyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate Methacrylic acid esters such as cyclohexyl methacrylate, phenyl methacrylate and benzyl methacrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.

Examples of the maleimide compound include N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like. These can be used alone or in combination of two or more. Of these, N-phenylmaleimide is preferred.
Examples of the unsaturated compounds having other functional groups include ethylenically unsaturated compounds having one or more of a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an amide group, an epoxy group, an oxazoline group, and the like. It is done. Further, an ethylenically unsaturated compound having a group in which one of hydrogen atoms in an amino group is substituted with another atom or a functional group, such as an amide group, can also be used.
Examples of the unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These can be used alone or in combination of two or more.
Examples of the unsaturated compound having an acid anhydride group include maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used alone or in combination of two or more.
Examples of unsaturated compounds having a hydroxyl group include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy- Examples include 2-methyl-1-propene, 2-hydroxyethyl (meth) acrylate, and N- (4-hydroxyphenyl) maleimide. These can be used alone or in combination of two or more.

Examples of unsaturated compounds having an amino group include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, and (meth) acrylic acid 2 -Dimethylaminoethyl, phenylaminoethyl (meth) acrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, (meth) acrylamine, N-methylacrylamine and the like. These can be used alone or in combination of two or more.
Examples of the unsaturated compound having an amide group include (meth) acrylamide, N-methylacrylamide, N-methylmethacrylamide and the like. These can be used alone or in combination of two or more.
Examples of the unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. These can be used alone or in combination of two or more.
Examples of the unsaturated compound having an oxazoline group include vinyl oxazoline. These can be used alone or in combination of two or more.

  The ratio of the aromatic vinyl compound to the total amount of the vinyl monomer (b) in the graft copolymer (B1) of the present invention is preferably 1 to 99% by mass, more preferably 3 to 90% by mass, and still more preferably. Is 5 to 85% by mass. In addition, a graft copolymer (B1) can be used individually or in combination of 2 or more types.

As a method for producing the graft copolymer (B1), a method of radical polymerization of the vinyl monomer (b) in the presence of the rubber polymer (a) can be employed, and an emulsion polymerization method is usually employed. . The emulsion polymerization method can be carried out under known conditions according to a known method.
When the graft copolymer (B1) is produced by an emulsion polymerization method, in addition to the rubbery polymer (a), the vinyl monomer (b), water and an emulsifier, a polymerization initiator, a molecular weight regulator (chain transfer agent) ), An electrolyte or the like is used. The various compounds used in forming the polymer may be charged all at once into the reaction system during polymerization, or may be divided or continuously charged. Moreover, after adding a part, you may add the remainder continuously or intermittently.

  Examples of the emulsifier include alkali metal salts of higher fatty acids such as disproportionated rosin acid, oleic acid, lauric acid and stearic acid, alkali metal salts of sulfonic acids such as dodecylbenzenesulfonic acid, and dibasic alkalis such as alkenyl succinic acid. Anionic surfactants such as metal salts, nonionic surfactants such as polyethylene glycol alkyl ester type, alkyl ether type, alkylphenyl ether type, carboxylate, sulfate ester, sulfonate, phosphate ester salt as anion moiety And an amphoteric surfactant having an amine salt or a quaternary ammonium salt as the cation moiety. Examples of the amphoteric surfactant include betaines such as lauryl betaine and stearyl betaine, and aminotypes such as lauryl-β-alanine, stearyl-β-alanine, lauryl di (aminoethyl) glycine, and octidyl (aminoethyl) glycine. . Furthermore, a reactive emulsifier having a polymerizable unsaturated bond showing high reactivity such as a vinyl group, an acryloyl group, a methacryloyl group, an allyl group, an allyl ether group, or a propenyl group can also be used. These can be used alone or in combination of two or more.

  As the polymerization initiator, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate and the like conventionally used in producing this type of polymer, cumene hydroperoxide, diisopropylbenzene hydroperoxide, A redox polymerization initiator, benzoyl peroxide (a combination of organic hydroperoxides such as paramentane hydroperoxide, benzoyl peroxide, lauryl peroxide, etc., and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation ( BPO), lauroyl peroxide, tert-butyl peroxylaurate, peroxides such as tert-butyl peroxymonocarbonate, and azo polymerization initiators such as azobisisobutyronitrile. These can be used alone or in combination of two or more.

  Examples of the molecular weight regulator (chain transfer agent) include t-dodecyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert -Mercaptans such as tetradecyl mercaptan and thioglycolic acid, halogenated hydrocarbons such as chloroform and carbon tetrabromide, xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide, terpinolene, α-methylstyrene dimer, tetraethyl Examples include thiuram sulfide, acrolein, methacrolein, allyl alcohol, and 2-ethylhexyl thioglycol. These can be used alone or in combination of two or more.

  Examples of the electrolyte include potassium sulfate, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydrogen carbonate, sodium pyrophosphate, potassium phosphate, and the like. These can be used alone or in combination of two or more.

  The emulsion polymerization may be performed by a known method. For example, the polymerization temperature is preferably 40 to 90 ° C, more preferably 45 to 85 ° C.

  About each usage-amount of a rubber-like polymer (a) and a vinyl-type monomer (b), a vinyl-type monomer (b) is 25-230 normally with respect to 100 mass parts of rubber-like polymers (a). It is 40 mass parts, More preferably, it is 40-180 mass parts. If the content of the rubbery polymer (a) is too small, the impact resistance tends to be inferior. If it is too much, the moldability, the surface appearance of the molded product, etc. tend to be inferior.

The emulsion-polymerized latex is usually recovered as a graft copolymer (B1) powder by washing the powder obtained by coagulation with a coagulant and drying it.
The graft copolymer (B1) of the present invention having a phosphorus content of 200 to 5000 ppm or a sulfur content of 1000 to 5000 ppm is used for the coagulation of the latex with this coagulant to effect the oxoacid consisting of phosphorus atoms and / or sulfur atoms. It can manufacture suitably by performing in presence of the alkali metal salt of this.

The phosphorus content of the graft copolymer (B1) of the present invention is preferably 200 to 4000 ppm, more preferably 500 to 4000 ppm, and still more preferably 1000 to 3000 ppm. If the phosphorus content is less than 200 ppm, the effect of improving the thermal stability of the present invention cannot be sufficiently obtained, and if it exceeds 5000 ppm, the effect of improving the thermal stability of the present invention is saturated and the coagulation property of the latex is also deteriorated.
The sulfur content of the graft copolymer (B1) of the present invention is preferably 1000 to 4000 ppm, more preferably 1000 to 3000 ppm, and still more preferably 1200 to 2500 ppm. If the sulfur content is less than 1000 ppm, the thermal stability improving effect of the present invention cannot be sufficiently obtained, and if it exceeds 5000 ppm, the thermal stability improving effect of the present invention is saturated and the coagulation property of the latex is also deteriorated.
Moreover, a phosphorus atom and a sulfur atom may coexist, and even when coexisting, each content of phosphorus and sulfur in the present invention is the same as described above.

  The oxo acid refers to a compound in which a hydroxyl group and an oxo group are bonded to a specific atom and the hydroxyl group gives an acidic proton. Examples of the oxo acid composed of a phosphorus atom or a sulfur atom include phosphoric acid, phosphorous acid, sulfonic acid, sulfinic acid, sulfurous acid, and sulfuric acid. Examples of alkali metal salts of these oxo acids include sodium salts and potassium salts.

  In the present invention, it is preferable that the alkali metal salt of the oxo acid coexist in the polymer latex of the graft copolymer (B1) during coagulation, and the latex is coagulated using a known coagulant. By recovering as a powder, an aromatic vinyl-based graft copolymer for a resin blend that provides a thermoplastic resin composition excellent in the thermal stability and the appearance of a molded product, which is the object of the present invention, can be obtained.

  In the present invention, the alkali metal salt of the oxo acid is most preferably added after polymerization of the latex of the graft copolymer (B1). Or may be added during or after polymerization of the rubbery polymer (a).

The alkali metal salt of oxo acid in the present invention is particularly preferably an alkali metal salt of phosphoric acid or an alkali metal salt of sulfonic acid.
Examples of the alkali metal salt of phosphoric acid include tertiary potassium phosphate, tertiary sodium phosphate, secondary potassium phosphate, secondary sodium phosphate, primary potassium phosphate, primary sodium phosphate and the like. Tribasic potassium phosphate and trisodium phosphate are preferred.
As the alkali metal salt of sulfonic acid, sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate are preferable.

  As a preferable usage-amount of the said alkali metal salt, 0.1-5.0 mass parts is preferable with respect to 100 mass parts of latex solid content of a graft copolymer (B1), More preferably, it is 0.1-3.0 mass. Parts, even more preferably 0.1 to 2.0 parts by weight. If the amount used is less than 0.1 parts by mass, the thermoplastic resin composition obtained using the graft copolymer (B1) has insufficient thermal stability, and if it exceeds 5.0 parts by mass, the effect is saturated. In addition, the coagulation of the latex may be hindered, and the recovery of the graft copolymer (B1) as a powder may be hindered.

As the coagulant used in the present invention, an alkaline earth metal salt, particularly an inorganic salt of a divalent alkaline earth metal is preferably used. Examples of the inorganic salt of the divalent alkaline earth metal include magnesium sulfate, magnesium chloride, calcium sulfate, and calcium chloride. Among these, magnesium sulfate and calcium chloride are preferable from the viewpoint of industrial supply and economy, and magnesium sulfate is particularly preferable from the viewpoint of the thermal stability of the thermoplastic resin composition obtained in the present invention. Moreover, there is no restriction | limiting in particular about the addition amount at the time of coagulation | solidification, However, It is preferable that it is 1.0-10 mass parts with respect to 100 mass parts of latex solid content of a graft copolymer (B1). The graft copolymer (B1) of the present invention thus obtained usually contains magnesium or calcium derived from these preferred coagulants. The content of magnesium or calcium of the graft copolymer (B1) of the present invention is the sum of both, preferably 1500 ppm or more, more preferably 2000 ppm or more, even more preferably 2500 ppm or more, and even more. More preferably, it is 2800 ppm or more. When this content is less than 1500 ppm, the moldability according to the present invention becomes insufficient.
Moreover, there is no restriction | limiting in particular about solidification concentration of latex at the time of coagulation | solidification and coagulation | solidification, The conditions of a well-known range are applicable normally. That is, 60-100 degreeC is preferable about temperature, and it is preferable that it is the range of 5-40 mass% about solid content concentration.
In the case where the coagulant is an inorganic salt of a divalent alkaline earth metal, the substance expected to be produced in the reaction with the alkali metal salt of the oxo acid is an alkaline earth metal salt of the oxo acid. When the substance is recovered as the graft copolymer (B1) and then added in the subsequent granulation step, the effect of improving the thermal stability is insufficient. Graft copolymer (B1) having an extremely high thermal stability and an effect of improving the appearance of a molded product by coagulating and recovering it as a powder after coexisting with the latex of graft copolymer (B1). Is obtained.
If the thermal stability required for the present invention and the appearance of the molded product are not hindered, the alkali component or the acid component may be added after the solidification and neutralized after the solidification depending on the performance. .

  The graft copolymer (B1) obtained as described above is usually a grafted polymer obtained by grafting the (co) polymer of the vinyl monomer (b) onto the rubber polymer (a). In addition to being mainly contained, a (co) polymer of a vinyl monomer (b) not grafted to the rubbery polymer (a) or an ungrafted rubbery polymer (a) may be contained. .

The graft ratio of the graft copolymer (B1) (mass ratio of the vinyl monomer grafted to the rubber polymer) is preferably 10 to 200% by mass, more preferably 15 to 150% by mass, particularly preferably. 20 to 100% by mass. When the graft ratio is less than 10% by mass, the interfacial adhesive strength between the rubbery polymer (a) and the (co) polymer of the vinyl monomer (b) is inferior, so that the graft copolymer (B1) In some cases, the molded appearance, mechanical strength, etc. of the thermoplastic resin composition blended with the above-mentioned resin may decrease. On the other hand, if it exceeds 200% by mass, the impact resistance may not be sufficient, and the processability (fluidity) of the thermoplastic resin composition obtained using the present graft copolymer (B1) may be inferior. .
Here, said graft ratio is calculated | required by a following formula.
Graft ratio (mass%) = {(S−T) / T} × 100
In the above formula, S represents 1 g of the graft copolymer (B1) in 20 ml of acetone (acetonitrile when the rubbery polymer is an acrylic rubber), shaken with a shaker for 2 hours, and then centrifuged. Is the mass (g) of the insoluble matter obtained by centrifuging for 1 hour in a machine (rotation speed: 23,000 rpm) and separating the insoluble matter and the soluble matter, and T is the graft copolymer (B1) 1 It is the mass (g) of the rubbery polymer (a) contained in grams.

Further, the acetone-soluble component of the graft copolymer (B1) (acetonitrile-soluble component when the rubbery polymer is an acrylic rubber), that is, not grafted to the rubbery polymer (a) (co) The intrinsic viscosity [η] of the polymer (measured in methyl ethyl ketone at 30 ° C.) is preferably 0.1 to 1.3 dl / g, more preferably 0.2 to 1.0 dl / g, particularly preferably 0.3. -0.7 dl / g. By setting it as this range, the thermoplastic resin composition obtained using this graft copolymer (B1) will be excellent in the physical property balance of moldability and impact resistance. Further, the polydispersity of the acetone-soluble matter, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC is preferably 1.3 to 5, More preferably, it is 1.5-4, More preferably, it is 1.5 or more and less than 3. If this Mw / Mn ratio is too large, the moldability tends to decrease.
The graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiator, chain transfer agent, emulsifier, solvent, etc. used in producing the graft copolymer (B1), and further the polymerization time, It can be easily controlled by selecting the polymerization temperature or the like.
When using a plurality of graft copolymers (B1), they may be mixed after isolation, but as another method, for example, a latex containing each resin is produced by emulsion polymerization and then mixed. Thereafter, it can be obtained by coagulation.

The compound constituting the vinyl monomer (b) preferably contains a vinyl cyanide compound, and is particularly preferably used in combination of the following (1) and (2). When a vinyl cyanide compound is used, the thermoplastic resin composition obtained according to the present invention tends to improve the impact resistance and chemical resistance.
(1) An aromatic vinyl compound and a vinyl cyanide compound.
(2) Aromatic vinyl compounds, vinyl cyanide compounds and other compounds.
Therefore, the graft copolymer (B1) of the present invention may be one or more graft copolymers obtained by using only an aromatic vinyl compound as the vinyl monomer (b). The monomer (b) may be one or more graft copolymers obtained using the monomer (1) above, and the vinyl monomer (b) (2) above may be used. One or more types of graft copolymers obtained using monomers may be used. Furthermore, these may be combined appropriately.
In the above (1), the amount of each of the aromatic vinyl compound and the vinyl cyanide compound used is preferably 60 to 95% by mass, respectively, when the total amount of the vinyl monomer (b) is 100% by mass. It is 5-40 mass%, More preferably, it is 65-90 mass% and 10-35 mass%, More preferably, it is 70-85 mass% and 15-30 mass%.
In the above (2), the use amount of the aromatic vinyl compound, the vinyl cyanide compound and other compounds is preferably 50 when the total amount of the vinyl monomer (b) is 100% by mass. -94 mass%, 5-40 mass% and 1-45 mass%, more preferably 30-85 mass%, 10-35 mass% and 5-40 mass%, still more preferably 45-80 mass%, 15-30 Mass% and 5 to 30 mass%.

In the present invention, the graft copolymer (B1) may be used by mixing with one or more kinds of (co) polymers (B2) of vinyl monomers as desired.
This (co) polymer (B2) can be produced by the same method as the graft copolymer (B1) except that the rubbery polymer (a) is not used. That is, the (co) polymer (B2) can be obtained by polymerizing the vinyl monomer (b) containing an aromatic vinyl compound in the absence of the rubbery polymer (a). As this vinyl-type monomer, the thing similar to what was illustrated as a vinyl-type monomer (b) used when manufacturing the graft copolymer (B1) of the said invention can be used. These can be used alone or in combination of two or more. The vinyl monomer may be the same component as the vinyl monomer used for forming the graft copolymer (B1), or may be a different component. When they are the same component, the amount of each compound used may be the same or different.

  The (co) polymer (B2) can be produced by a known method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, bulk-suspension (bulk-suspension) polymerization, and these polymerization methods. You may manufacture by the method of combining. The polymer may be catalytic polymerization using a polymerization initiator, or may be thermal polymerization without using a polymerization initiator. These polymerization methods may be combined. Here, these (co) polymers (B2) can be used alone or in combination of two or more.

When the (co) polymer (B2) is produced by solution polymerization, a solvent, a polymerization initiator, a chain transfer agent, or the like is usually used. Examples of the solvent include inert polymerization solvents used in known radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, and halogenated carbonization such as dichloromethylene and carbon tetrachloride. Hydrogen, acetonitrile, dimethylformamide, N-methylpyrrolidone and the like can be used.
Examples of the polymerization initiator include organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpinolene and the like.
Here, the solution polymerization can be performed under known conditions, but the polymerization temperature is preferably in the range of 80 to 180 ° C. The solution polymerization may be catalytic polymerization using a polymerization initiator, or may be thermal polymerization without using a polymerization initiator.
A known method can be applied to the production method by bulk polymerization and suspension polymerization. As the polymerization initiator, chain transfer agent and the like used in these methods, for example, the compounds exemplified in the solution polymerization can be used.

As a monomer which comprises the said (co) polymer (B2), the combination of following (3)-(6) is illustrated. In addition, the compound enumerated regarding the said graft copolymer (B1) can be applied to each monomer, and its preferable compound is also the same.
(3) Aromatic vinyl compounds.
(4) Aromatic vinyl compounds and vinyl cyanide compounds.
(5) Aromatic vinyl compounds, vinyl cyanide compounds and other compounds.
(6) Aromatic vinyl compounds and other compounds other than vinyl cyanide compounds.
These (co) polymers (B2) can be used alone or in combination of two or more.

In addition, the usage-amount according to the kind of vinyl-type monomer (b) is as follows.
In the above (4), the amount of each of the aromatic vinyl compound and vinyl cyanide compound used is preferably 60 to 95% by mass when the total amount of the vinyl monomer (b) is 100% by mass, respectively. It is 5-40 mass%, More preferably, it is 65-90 mass% and 10-35 mass%, More preferably, it is 70-85 mass% and 15-30 mass%.
In the above (5), the use amount of the aromatic vinyl compound, the vinyl cyanide compound and other compounds is preferably 35 to 94, respectively, when the total amount of the vinyl monomer (b) is 100% by mass. Mass%, 5-40 mass% and 1-30 mass%, more preferably 45-85 mass%, 10-35 mass% and 5-25 mass%, still more preferably 55-80 mass%, 15-30 mass% And 5 to 20% by mass.
In the above (6), the use amount of the aromatic vinyl compound and other compounds is preferably 65 to 95% by mass and 5 to 5%, respectively, when the total amount of the vinyl monomer (b) is 100% by mass. They are 35 mass%, More preferably, they are 70-90 mass% and 10-30 mass%, More preferably, they are 75-85 mass% and 15-25 mass%.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the (co) polymer (B2) is preferably 0.1 to 1.4 dl / g, more preferably 0.2 to 1.2 dl / g. Particularly preferred is 0.3 to 1.0 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent. The intrinsic viscosity [η] can be obtained by adjusting production conditions or mixing (co) polymers (B2) having different intrinsic viscosities [η] as in the case of the graft copolymer (B1). Can be controlled.

  Regardless of whether the graft copolymer (B1) is used in combination with the (co) polymer (B2), the content of the rubber polymer (a) in the thermoplastic resin composition of the present invention is The total is 100% by mass, preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass. If the content of the rubbery polymer (a) is too small, the impact resistance tends to be inferior. If it is too much, the moldability and heat resistance tend to be inferior.

  The proportion of the component (B1) contained in the thermoplastic resin composition of the present invention is determined according to the required mechanical strength, rigidity, molding processability, and heat resistance. The blending ratio of the component (B1) in the thermoplastic resin composition of the present invention is 10 to 65% by mass, preferably 20 to 65, as the total of 100% by mass of the components (A), (B1) and (B2). It is 20 mass%, More preferably, it is 20-60 mass%, More preferably, it is 30-60 mass%. If it is this range, it will become a composition excellent in various, such as moldability and heat resistance. If the content of this component (B1) is less than 10% by mass, the moldability tends to be inferior, and if it exceeds 65% by mass, the heat resistance and the like tend to be inferior.

  The proportion of the component (B2) contained in the thermoplastic resin composition of the present invention is determined according to the required mechanical strength, rigidity, molding processability, and heat resistance. The blending ratio of the component (B2) in the thermoplastic resin composition of the present invention is 0 to 55% by mass, preferably 0 to 50% as the total of 100% by mass of the components (A), (B1) and (B2). It is 0 mass%, More preferably, it is 0-45 mass%, More preferably, it is 0-30 mass%. If it is this range, it will become a composition excellent in various, such as moldability and heat resistance. When the content of this component (B2) exceeds 55% by mass, impact resistance and the like tend to be inferior.

  Since the thermoplastic resin composition of the present invention contains the component (B1) having a phosphorus content of 200 to 5000 ppm or a sulfur content of 1000 to 5000 ppm in the above blending amount, the temperature is 260 ° C. and the load is 5 kg. The MFR value X (g / min) under the condition of holding time 5 minutes is 40 or less, the MFR value Y (g / min) under the condition of temperature 260 ° C., load 5 kg, holding time 15 minutes is 80 or less. In addition, Y / X is 1.3 or less, the rate of change in fluidity is low during residence, the thermal stability is excellent, and the appearance of the molded product is also excellent. The MFR value Y (g / min) is preferably 65 or less, and Y / X is preferably 1.2 or less. Such characteristics are characteristics that cannot be obtained even when a phosphorus compound or a sulfur compound is added when the components of the thermoplastic resin composition are mixed, as shown in Examples and Comparative Examples described later.

  The thermoplastic resin composition of the present invention is a flame retardant, an antioxidant, an anti-aging agent, an ultraviolet absorber, a plasticizer, a lubricant, an antistatic agent, a colorant, and a light stabilizer as long as the object of the present invention is not impaired. Further, various additives such as a heat stabilizer, a compatibilizer, an antibacterial agent, a filler, a reinforcing agent, and a metal powder may be contained.

As the flame retardant, an organic flame retardant, an inorganic flame retardant, a reaction flame retardant, or the like can be used. Examples of organic flame retardants include halogen flame retardants such as brominated bisphenol epoxy resins, phosphate esters such as trimethyl phosphate and triethyl phosphate, compounds obtained by modifying them with various substituents, condensed phosphate ester compounds, phosphorus Examples include phosphorus-based flame retardants such as phosphazene derivatives containing elements and nitrogen elements, and polytetrafluoroethylene. These can be used alone or in combination of two or more.
Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, silicone-based compounds, and phosphazene-based compounds. These can be used alone or in combination of two or more.
Examples of the reaction flame retardant include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, and tribromophenol. These can be used alone or in combination of two or more.
In addition, when mix | blending a flame retardant, you may use a flame retardant adjuvant together. Examples of the flame retardant aid include antimony compounds such as antimony trioxide, zinc borate, hydrated alumina, zirconium oxide, and ammonium polyphosphate. These can be used alone or in combination of two or more.

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
Examples of the anti-aging agent include monophenol-based, bis-, tris-, polyphenol-based, thiobisphenol-based, hindered phenol-based, and phosphite-based compounds. These can be used alone or in combination of two or more.
Examples of the ultraviolet absorber include benzophenone series, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
As the lubricant, fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, aliphatic alcohol , Polyhydric alcohol, polyglycol, polyglycerol, silicone and the like. These can be used alone or in combination of two or more.
As an antistatic agent, an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, an amphoteric antistatic agent, a complex compound, an antistatic plasticizer, etc., alone or in combination of two or more. Can be used.
Examples of the colorant include organic dyes, inorganic pigments, organic pigments, and carbon black. These can be used alone or in combination of two or more.

  The thermoplastic resin composition of the present invention is obtained by kneading raw material components using an extruder such as a single screw extruder or a twin screw extruder, a known kneader such as a Banbury mixer, a pressure kneader, or a two roll. Obtainable. The kneading may be performed by supplying raw material components all at once or by a multistage addition method.

  The thermoplastic resin composition of the present invention comprises an injection molding method, a sheet extrusion molding method, a vacuum molding method, a profile extrusion molding method, a compression molding method, a hollow molding method, a differential pressure molding method, a blow molding method, a foam molding method, a gas OA / home appliances, electrical / electronic field, sundries field, sanitary field, vehicle, etc., which are made into molded products of a predetermined shape such as film and sheet by various known molding methods such as injection molding method. It can be used for various parts such as uses, furniture fields such as chassis and office furniture, and housing materials. In addition, the obtained molded product can be subjected to laser marking such as black color development, white color development, and multicolor by irradiating the surface with laser.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. Parts and% are based on mass. Moreover, the evaluation method used in the Example is shown below.
(1) Weight average particle diameter of polymer particles The volume average particle diameter of the polymer particles in the rubber-like polymer latex was measured at room temperature using “Microtrack UPA150 type” manufactured by HONEYWELL. The unit is nm.
(2) pH during coagulation of polymer latex
The pH at the time of coagulation of the graft copolymer was determined by measuring the pH of the supernatant liquid at the time of coagulation using a general pH measuring device and based on the following criteria.
I: pH is less than 3.
II: The pH is 3 or more and less than 7.
III: pH is 7 or more and less than 11.
IV: pH is 11 or more.
(3) Metal content in the graft copolymer The metal content in the graft copolymer was determined by using the powder after solidification and drying of the component (B1) as a measurement sample. The relative content was measured by the fundamental parameter method using “PRO” (trade name).
(4) Appearance of molded product Using an electric injection molding machine “Erject NEX30” (trade name) manufactured by Nissei Plastic Industry Co., Ltd., a flat molded product of 80 mm × 55 mm × 2.4 mm was obtained by injection molding. . The molded product was provided with a side gate of 4 mm × 1 mm at the center of one side of 55 mm, the resin temperature at the time of molding was 240 ° C., and the mold temperature was 60 ° C.
The appearance of the obtained molded product was visually observed and evaluated according to the following criteria.
○: Defects are not observed in appearance.
X: Defects such as flow mark, foaming, jetting and silver are observed.
(5) Thermal Stability Index Using a thermoplastic resin composition pellet dehumidified and dried at 80 ° C. for 2 hours with a melt flow rate measuring device “Semi-Auto Indexer 3A” (trade name) manufactured by Toyo Seiki Co., Ltd., a temperature of 260 ° C. , Weight 5kg, MFR (melt flow rate) value (X g / min) under the condition of 5 minutes holding time (preheating time) in the measurement barrel, temperature 260 ° C, weight 5kg, holding time 15 minutes The lower MFR (melt flow rate) value (Y g / min) was measured. It can be judged that the greater the change in Y with respect to X, the poorer the thermal stability of the composition. Further, the ratio of change in MFR value (degree of MFR change) was calculated from the values of X and Y according to the following equation.
MFR change = Y / X
It can be judged that the thermal stability of the composition is good even if the MFR change degree is closer to 1, even if the MFR stays at a higher temperature.

Production Example 1-1 (Production of rubber-like polymer latex a-1)
After replacing the inside of a pressure vessel with a capacity of 10 L equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device, etc. with nitrogen, 100 parts water, 100 parts 1,3-butadiene, t-dodecyl mercaptan 0 0.3 part, potassium persulfate 0.3 part, higher fatty acid sodium soap 0.5 part, disproportionated potassium rosinate 1.5 part, β-naphthalenesulfonic acid formalin condensate sodium salt 0.15 part, electrolyte 1 part of sodium hydrogen carbonate was added and reacted at 50 to 70 ° C. for 40 hours with stirring, followed by cooling to terminate the reaction, thereby obtaining a diene rubbery polymer latex (a-1). At this time, the polymerization addition rate was 95%, the volume average particle diameter was 300 nm, and the gel content was 80% using toluene as a solvent and immersed in 30 ° C. for 48 hours and then filtered through a 100 mesh wire net. It was.

Production Example 1-2 (Production of rubber polymer latex a-2)
After replacing the reactor used in Production Example 1-1 with nitrogen, 180 parts of water, 90 parts of 1,3-butadiene, 10 parts of styrene, 0.3 part of t-dodecyl mercaptan, 0.3 part of potassium persulfate, 3 parts of higher fatty acid sodium soap, 0.1 part of disproportionated potassium rosinate, 0.05 part of sodium salt of β-naphthalenesulfonic acid formalin condensate, 1 part of sodium pyrophosphate as an electrolyte, and 50 ~ After reacting at 70 ° C. for 20 hours, the reaction was terminated by cooling to obtain a diene rubbery polymer latex (a-2). At this time, the polymerization addition rate was 95%, the volume average particle diameter was 90 nm, and the gel content was 90%.

Production Example 1-3 (Production of rubber-like polymer latex a-3)
A monomer mixture (I) was prepared by mixing 99 parts of n-butyl acrylate and 1 part of allyl methacrylate. In addition, an aqueous solution (hereinafter referred to as “RED aqueous solution-1”) in which 0.02 part of disodium ethylenediaminetetraacetate, 0.8 part of sodium formaldehydesulfoxylate and 0.005 part of ferrous sulfate are dissolved in 20 parts of water. Were abbreviated as). Furthermore, an aqueous solution (hereinafter abbreviated as “OXI aqueous solution-1”) in which 0.04 part of potassium alkenyl succinate and 0.05 part of cumene hydroperoxide were dissolved in 20 parts of water was prepared. Next, 140 parts of water and 2 parts of potassium alkenyl succinate were charged into a 10 L glass reactor equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device, and the like while stirring under a nitrogen stream. The internal temperature was raised to 60 ° C. When the temperature reached 60 ° C., the entire amount of the RED aqueous solution-1 was charged. Immediately thereafter, the monomer mixture (I) and the OXI aqueous solution-1 were continuously added over 5 hours to initiate polymerization. The internal temperature of the reactor was kept at 60 ° C. After the addition of the monomer mixture (I) and OXI aqueous solution-1 was completed, the polymerization reaction was terminated by maintaining the internal temperature of the reactor at 60 ° C. for another hour, and the acrylic rubbery polymer latex (a -3) was obtained. At this time, the polymerization conversion was 98%, the volume average particle size was 100 nm, and the gel content was 85%.

Production Example 1-4 (Production of Rubber Polymer Latex a-4 by Enlargement of Particle Size of Polymer Latex)
The reactor used in Production Example 1-3 was charged with 100 parts of the rubber polymer latex a-2 in terms of solid content, and the internal temperature was raised to 40 ° C. while stirring. When the internal temperature reached 40 ° C., a suspension obtained by dispersing 2 parts of acetic anhydride in 40 parts of water with a homogenizer was charged into the reactor, and stirring was stopped while maintaining the internal temperature of the reactor at 40 ° C. The particle size was enlarged. After 10 minutes of particle size enlargement treatment, an aqueous solution in which 1.5 parts of potassium hydroxide is dissolved in 28.5 parts of water, and a sodium salt of β-naphthalenesulfonic acid formalin condensate in 22.5 parts of water. An aqueous solution in which 5 parts had been dissolved was added and stirred to complete the enlargement treatment to obtain a rubbery polymer latex (a-4). The resulting rubbery polymer particles had a volume average particle size of 650 nm.

Production Example 2-1 (Production of Graft Copolymer Latex B1-1)
A monomer mixture (II) was prepared by mixing 75 parts of styrene, 25 parts of acrylonitrile and 0.3 part of t-dodecyl mercaptan. Further, an aqueous solution (hereinafter abbreviated as “RED aqueous solution-2”) in which 0.5 parts of sodium pyrophosphate, 0.75 parts of dextrose and 0.01 parts of ferrous sulfate are dissolved in 20 parts of water is prepared. did. Furthermore, an aqueous solution (hereinafter abbreviated as “OXI aqueous solution-2”) in which 0.1 part of potassium alkenyl succinate and 0.3 part of cumene hydroperoxide were dissolved in 30 parts of water was prepared. The glass reactor used in Production Example 1-3 was charged with 100 parts of the rubber polymer latex (a-1) in terms of solid content, and the internal temperature was raised to 40 ° C. while stirring in a nitrogen stream. Warm up. When the temperature reached 40 ° C., 85% by mass of RED aqueous solution-2 was added to the reactor. Immediately thereafter, 85% by mass of the monomer mixture (II) and the OXI-2 aqueous solution were continuously added over 5 hours to proceed the polymerization reaction. The internal temperature was raised to 60 ° C. from the start of polymerization, and then maintained at this temperature. Five hours after the start of the polymerization, the remaining 15% by mass of the RED aqueous solution-2 and the remaining 15% by mass of the OXI aqueous solution-2 were added to the reactor and kept at the same temperature for 1 hour. Polymerization was terminated later to obtain a graft copolymer latex B1-1.

Production Example 2-2 (Production of Graft Copolymer Latex B1-2)
76 parts of styrene and 24 parts of acrylonitrile were mixed to prepare a monomer mixture (III). Further, an aqueous solution (hereinafter abbreviated as “RED aqueous solution-3”) in which 0.3 part of sodium formaldehyde sulfoxylate was dissolved in 10 parts of water was prepared. Further, an aqueous solution (hereinafter abbreviated as “OXI aqueous solution-3”) in which 0.5 part of t-butyl hydroperoxide was dissolved in 50 parts of water was prepared. In the glass reactor used in Production Example 1-3, 100 parts of the rubbery polymer latex (a-3) and 1 part of potassium alkenyl succinate were charged in terms of solid content, while stirring under a nitrogen stream, The internal temperature was raised to 50 ° C. When the temperature reached 50 ° C., 85% by mass of RED aqueous solution-3 was added to the reactor. Immediately thereafter, the monomer mixture (II) and an OXI-3 aqueous solution corresponding to 85% by mass were continuously added over 5 hours to proceed the polymerization reaction. The internal temperature was raised to 60 ° C. from the start of polymerization, and then maintained at this temperature. Five hours after the start of the polymerization, the remaining 15% by mass of the RED aqueous solution-3 and the remaining 15% by mass of the OXI aqueous solution-2 were added to the reactor and kept at the same temperature for 1 hour. The polymerization was terminated later to obtain a graft copolymer latex B1-2.

Production Example 2-3 (Production of Graft Copolymer Latex B1-3)
As rubber-like polymer latex, except that 75 parts of latex (a-1) of Production Example 1-1 was used in terms of solid content and 25 parts of latex (a-4) of Production Example 1-4 was used in terms of solid content. Polymerization was carried out in the same manner as in Production Example 1-1 to obtain a graft copolymer latex B1-3.

Production Example 2-4 (Production of rubber-reinforced copolymer resin polymer latex B1-4)
Polymerization was carried out in the same manner as in Production Example 2-2 except that potassium lauryl sulfonate was used in place of potassium alkenyl succinate in Production Example 2-2, to obtain a graft copolymer latex B1-4. It was.

In the composition of the present invention, (A) polycarbonate resin “Novalex 7022PJ” (trade name) (viscosity average molecular weight 22,000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used as the other compounding agent.
(B2) Copolymer Resin of Vinyl Monomer AS resin “Sunrex SAN-C” (trade name) manufactured by Techno Polymer Co., Ltd. was used.
(C) Antioxidant C-1: Tris (2,4-di-t-butylphenyl) phosphite “JP-650” (trade name) manufactured by Johoku Chemical Industry Co., Ltd. was used.
C-2: 2 [1- (2hydroxy-3,5-di-t-pentylphenyl) -ethyl] -4,6-di-t-pentylphenyl acrylate “Sumilyzer GS” (trade name, manufactured by Sumitomo Chemical Co., Ltd.) ) Was used.
(D) Other compounding agents D-1: phosphoric acid.
D-2: Benzenephosphonic acid.
D-3: Magnesium salt of octadecyl phosphate.
D-4: A mixture of the following organic carboxylic acid compounds.
Trimellitic anhydride 5% by mass, Norbornene 2,3-dicarboxylic acid 5% by mass, Styrene / maleic anhydride 10% by mass, Monoisopropyl acid phosphate, 2,2-methylenebis [4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] 40% by mass, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Carboxylate 40% by mass

"Example 1"
To 100 parts of the solid content of the graft copolymer latex (B1-1), an aqueous solution in which 1.0 part of trisodium phosphate was dissolved in 10 parts of water was added and mixed with stirring for 10 minutes. This mixed latex is added to an aqueous solution (maintained at 85 ° C.) in which 2 parts of magnesium sulfate is added to 100 parts of a solid content of the graft copolymer latex separately prepared and then coagulated. Drying gave a white powder. During this coagulation, the supernatant was sampled and the pH was measured. In addition, the amount of metal contained in the powder was measured with a fluorescent X-ray spectrometer. The thermal stability of the composition was evaluated by mixing the resin powder and various materials with a Henschel mixer for 3 minutes and then pelletizing with an extruder set at 240 ° C. The evaluation results are shown in Table 1 together with the mixing ratio of the composition materials and the analysis results.

"Examples 2 to 6"
The same procedure as in Example 1 except that the type of graft copolymer latex, the type and amount or content of alkali metal salt, the type and amount of coagulant, and the composition ratio of the composition were changed to those shown in Table 1. Went. The results are shown in Table 1.

“Comparative Example 1”
The same operation as in Example 1 was performed except that tribasic sodium phosphate was not added. The results are shown in Table 2.
“Comparative Example 2”
The same operation as in Example 3 was performed except that tribasic sodium phosphate was not added. The results are shown in Table 2.
“Comparative Example 3”
The same operation as in Example 1 was performed except that the amount of the alkali metal salt of oxo acid was outside the scope of the present invention. The results are shown in Table 2.
"Comparative Examples 4-7"
The same operation as in Example 1 or 2 was performed, except that trisodium phosphate was not added and the component (D) shown in Table 2 was added. The results are shown in Table 2.
"Comparative Example 8"
The operation was performed in the same manner as in Example 1 except that 7.0 parts of tribasic sodium phosphate was added. However, the solidification property was poor and powder could not be obtained.

  From Table 1, the graft copolymer of the present invention was recovered by coagulation in the presence of an alkali metal salt of an oxo acid composed of phosphorus atoms and / or sulfur atoms, and the phosphorus content was 200 ppm or more, or The sulfur content is 1000 ppm or more, and the composition using the sulfur content has an MFR value X (g / min) of 40 minutes or less and a MFR value Y (g / min) of 15 minutes. Is 80 or less, Y / X is 1.3 or less, it can be seen that the thermal stability is excellent and the appearance of the molded product is also excellent.

On the other hand, Table 2 shows the following. Comparative Example 1 is an example in which the graft copolymer was recovered by coagulating the latex using magnesium sulfate as a coagulant in the absence of the alkali metal salt of the oxo acid. The sulfur content was lower than the range of the present invention, and the composition using the sulfur was inferior in the appearance of the molded product.
Comparative Example 2 is an example in which the graft copolymer was recovered by coagulating the latex using calcium chloride as a coagulant in the absence of the alkali metal salt of the oxo acid. The sulfur content was lower than the range of the present invention, and the composition using it was inferior in thermal stability.
Comparative Example 3 is an example in which the addition amount of the alkali metal salt of oxo acid is too small, but the content of phosphorus and sulfur in the graft copolymer is lower than the range of the present invention, and the composition using the same is The heat stability was inferior.
Comparative Examples 4 to 7 are examples in which the latex was coagulated in the absence of the alkali metal salt of the oxo acid to recover the graft copolymer, and then phosphorus or a sulfur-containing compound was added. The composition was inferior in thermal stability or appearance of the molded product.
In Comparative Example 8, the amount of tribasic sodium phosphate added was too large, and as described above, the coagulation property was poor and a powder could not be obtained.

  The aromatic vinyl-based graft copolymer of the present invention is blended with other thermoplastic resins such as polycarbonate to provide a resin blend excellent in thermal stability during residence in a molding machine or an extruder and appearance of a molded product. It is useful for manufacturing and can be used as a molding material in various fields.

Claims (13)

  A graft copolymer (B1) obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (a), wherein the graft copolymer ( An aromatic vinyl-based graft copolymer for resin blends having a phosphorus content of 200 to 5000 ppm or a sulfur content of 1000 to 5000 ppm in B1).   The aromatic vinyl graft copolymer according to claim 1, wherein the content of magnesium or calcium in the graft copolymer (B1) is 1500 ppm or more.   The graft copolymer (B1) is polymerized by an emulsion polymerization method, and the resulting latex of the copolymer is used in the presence of an alkali metal salt of an oxo acid composed of phosphorus atoms and / or sulfur atoms using a coagulant. The aromatic vinyl-based graft copolymer according to claim 1 or 2, wherein the aromatic vinyl-based graft copolymer is recovered by solidification.   The aromatic vinyl-type graft copolymer of Claim 3 whose compounding quantity of the alkali metal salt of the said oxo acid with respect to 100 mass parts of solids of the said latex is 0.1-5.0 mass parts.   An alkali metal salt of an oxo acid composed of the phosphorus atom is composed of tribasic potassium phosphate, tribasic sodium phosphate, dibasic potassium phosphate, dibasic sodium phosphate, primary potassium phosphate, and monobasic sodium phosphate. The aromatic vinyl-based graft copolymer according to claim 3, which is one or more selected.   The alkali metal salt of the oxo acid comprising the sulfur atom is at least one selected from potassium dodecyl sulfonate, sodium dodecyl sulfonate, potassium dodecyl benzene sulfonate, and sodium dodecyl benzene sulfonate. Aromatic vinyl-based graft copolymer.   Polycarbonate resin (A) 35-90 mass%, aromatic vinyl-type graft copolymer (B1) 10-65 mass% of any one of Claims 1 thru | or 7, and vinyl-type monomer (b ) (Co) polymer (B2) 0 to 55% by mass (provided that the total of components (A), (B1) and (B2) is 100% by mass), and has a temperature of 260 MFR value X (g / min) under the condition of ℃, load 5 kg, holding time 5 minutes is 40 or less, MFR value Y (g / min) under the condition of temperature 260 ° C, load 5 kg, holding time 15 minutes Is 80 or less, and Y / X is 1.3 or less, The thermoplastic resin composition characterized by the above-mentioned.   The thermoplastic resin composition according to claim 7, wherein the content of magnesium or calcium in the aromatic vinyl-based graft copolymer (B1) is 1500 ppm or more.   In the presence of the rubbery polymer (a), the vinyl monomer (b) containing the aromatic vinyl compound is emulsion-polymerized to obtain a latex of the graft copolymer (B1). A method for producing a graft copolymer for a resin blend, characterized by coagulating and recovering using a coagulant in the presence of an alkali metal salt of an oxo acid composed of atoms and / or sulfur atoms.   When solidifying, the alkali metal salt of the oxo acid is an amount sufficient for the phosphorus content in the recovered graft copolymer (B1) to be 200 to 5000 ppm, or the sulfur content to be 1000 to 5000 ppm. The production method according to claim 9, wherein the production method exists.   The manufacturing method of Claim 10 whose compounding quantity of the alkali metal salt of the said oxo acid with respect to 100 mass parts of solids of the said latex is 0.1-5.0 mass parts.   An alkali metal salt of an oxo acid composed of the phosphorus atom is composed of tribasic potassium phosphate, tribasic sodium phosphate, dibasic potassium phosphate, dibasic sodium phosphate, primary potassium phosphate, and monobasic sodium phosphate. The production method according to claim 9, which is one or more selected.   The alkali metal salt of an oxo acid composed of a sulfur atom is at least one selected from potassium dodecyl sulfonate, sodium dodecyl sulfonate, potassium dodecyl benzene sulfonate, and sodium dodecyl benzene sulfonate. Production method.