JP5379667B2 - Thermoplastic resin composition and molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in melt flowability and giving a molded article excellent in mechanical characteristics, heat resistance, flame retardancy and chemical resistance. <P>SOLUTION: This thermoplastic resin composition is provided by including a thermoplastic resin (A), a graft polymer (B) obtained by polymerizing a monomer component (b) containing phenyl (meth)acrylate (b1) which may have a substituent, in the presence of a rubber like polymer (br) containing a polyorganosiloxane-based rubber (bs), a flowability-improver (C) and a dripping inhibitor (D). <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  In the present invention, a thermoplastic resin composition containing a thermoplastic resin (A), a graft polymer (B), a fluidity improver (C), and an anti-dripping agent (D), and the thermoplastic resin composition are molded. The present invention relates to a molded article to be obtained.

Polycarbonate resins have excellent mechanical properties, heat resistance, flame retardancy, electrical properties, dimensional stability, etc., so OA equipment, information / communication equipment, electronic / electric equipment, home appliances, automotive components, Used in a wide range of fields such as building materials.
However, the polycarbonate resin has a problem that the molding process temperature is high and the melt fluidity is inferior. In recent years, since the thickness and weight of the molded body have been reduced for the purpose of cost reduction, it is necessary to obtain sufficient mechanical properties and flame retardancy even in the molded body having a reduced thickness and weight.

  In order to solve these problems, for example, Patent Document 1 proposes a thermoplastic resin composition in which a polycarbonate resin, a graft polymer, a fluidity improver, a dripping inhibitor and a flame retardant are blended.

JP 2006-257126 A

  However, in the method proposed in Patent Document 1, since the graft polymer obtained by grafting methyl methacrylate to the polyorganosiloxane rubber is blended, the mechanical properties and flame retardancy of the obtained molded product are not sufficient. .

  An object of the present invention is to provide a thermoplastic resin composition that provides a molded article having excellent melt fluidity and excellent mechanical properties, heat resistance, flame retardancy, and chemical resistance.

In the present invention, a phenyl (meth) acrylate (b1) which may have a substituent in the presence of a thermoplastic polymer (A) and a rubbery polymer (br) containing a polyorganosiloxane rubber (bs). It is a thermoplastic resin composition containing a graft polymer (B) obtained by polymerizing a monomer component (b) containing, a fluidity improver (C) and an anti-dripping agent (D).
Moreover, this invention is a molded object obtained by shape | molding this thermoplastic resin composition.

  The thermoplastic resin composition of the present invention is excellent in melt fluidity and gives a molded article excellent in mechanical properties, heat resistance, flame retardancy, and chemical resistance.

  The thermoplastic resin composition of the present invention contains a thermoplastic resin (A), a graft polymer (B), a fluidity improver (C), and an anti-dripping agent (D).

As the thermoplastic resin (A) of the present invention, known thermoplastic resins can be used, for example, olefinic resins such as polyethylene (PE) and polypropylene (PP); polystyrene (PS) and high impact polystyrene (HIPS). , Methacrylate / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SMA), acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / styrene / acrylate Styrenic resin (St resin) such as copolymer (ASA), acrylonitrile / ethylene / styrene copolymer (AES); Acrylic resin (Ac resin) such as polymethyl methacrylate (PMMA); Hard, semi-rigid , Soft polyvinyl chloride resin (PVC resin) Polycarbonate resins (PC resins), polyamide resins (PA resins), polyester resins (PEs resins) such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), (modified) polyphenylene ether resins (PPE) Resin), polyoxymethylene resin (POM resin), polysulfone resin (PSO resin), polyarylate resin (PAr resin), polyphenylene sulfide resin (PPS resin), thermoplastic polyurethane resin Engineering plastics such as (PU resin); styrene elastomer, olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, fluorine elastomer, 1,2- Thermoplastic elastomer (TPE) such as rebutadiene and trans-1,4-polyisoprene; PC resin such as PC / ABS / St resin resin alloy, PVC resin such as PVC / ABS / St resin alloy, PA / PA-based resin such as ABS / St-based resin alloy, PA-based resin such as PA / TPE, PA / PP / polyolefin-based resin alloy, PEs-based resin such as PBT / TPE / polyolefin-based resin alloy, PC such as PC / PBT -Based resin / PEs-based resin alloy, polyolefin-based resin / TPE, alloys between olefin-based resins such as PP / PE, PPE / HIPS, PPE / PBT, PPE-based resin alloys such as PPE / PA, PVC such as PVC / PMMA And polymer alloys such as Al resin / Ac resin alloy. These thermoplastic resins (A) may be used individually by 1 type, and may use 2 or more types together.
Among these thermoplastic resins, polycarbonate resin, polyamide resin, and the effect of improving the melt fluidity of the resulting thermoplastic resin composition, the mechanical properties of the resulting molded article, and the flame retardant improvement effect, Engineering plastics such as polyester resins such as polyethylene terephthalate and polybutylene terephthalate, (modified) polyphenylene ether resins, polyoxymethylene resins, polysulfone resins, polyarylate resins, polyphenylene sulfide resins and thermoplastic polyurethane resins The polycarbonate resin is more preferable.

  Examples of the polycarbonate-based resin include aromatic polycarbonate resins having a bisphenol A skeleton or a bisphenol TMC skeleton.

As a method for producing a polycarbonate-based resin, a known production method can be used. For example, a phosgene method in which a divalent phenol compound and phosgene are reacted, a transesterification in which a divalent phenol compound and a carbonate compound are reacted. Law.
Examples of the phosgene method include a method in which a divalent phenol compound such as 2,2-bis (4-hydroxyphenyl) propane is reacted by blowing phosgene in the presence of an alkaline aqueous solution and a solvent.
Examples of the transesterification method include a method in which a divalent phenol compound such as 2,2-bis (4-hydroxyphenyl) propane is reacted with a carbonate ester compound such as diphenyl carbonate in the presence of a catalyst.

  The viscosity-average molecular weight of the polycarbonate-based resin is preferably 10,000 to 40,000, and preferably 15,000 to 25,000 because the thermoplastic resin composition obtained has excellent melt fluidity. More preferred.

  The graft polymer (B) of the present invention is a phenyl (meth) acrylate (b1) which may have a substituent in the presence of a rubbery polymer (br) containing a polyorganosiloxane rubber (bs). Obtained by polymerizing the monomer component (b) containing

The rubbery polymer (br) includes a polyorganosiloxane rubber (bs).
The polyorganosiloxane rubber (bs) is obtained by polymerizing organosiloxane. Among the polyorganosiloxane rubbers, a polyorganosiloxane rubber having a vinyl polymerizable functional group is preferable from the viewpoint of imparting a graft active point.
The polyorganosiloxane rubber having a vinyl polymerizable functional group can be obtained by polymerizing dimethylsiloxane, a siloxane having a vinyl polymerizable functional group, and an organosiloxane containing a siloxane crosslinking agent.

Examples of dimethylsiloxane include a dimethylsiloxane-based cyclic body having three or more members. Among these dimethylsiloxanes, 3 to 7-membered dimethylsiloxane-based cyclics are preferable. For example, hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), Examples include dodecamethylcyclohexasiloxane (D6), and octamethylcyclotetrasiloxane (D4) is more preferable because of its excellent ability to control the particle size distribution of the resulting polyorganosiloxane rubber (bs). These dimethylsiloxanes may be used alone or in combination of two or more.
Here, the “3-membered dimethylsiloxane-based cyclic” refers to “dimethylsiloxane-based cyclic having three siloxane units (SiO)”, that is, “hexamethylcyclotrisiloxane (D3)”.

  The content of dimethylsiloxane is preferably 30 to 99% by mass, and preferably 50 to 98% by mass, because 100% by mass of the organosiloxane is excellent in mechanical properties and flame retardancy of the obtained molded product. Is more preferable.

The siloxane having a vinyl polymerizable functional group is a siloxane compound having a vinyl polymerizable functional group and capable of binding to dimethylsiloxane via a siloxane bond. Examples of the siloxane having a vinyl polymerizable functional group include β- (meth) acryloyloxyethyldimethoxymethylsilane, γ- (meth) acryloyloxypropyldimethoxymethylsilane, γ- (meth) acryloyloxypropylmethoxydimethylsilane, γ -(Meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylethoxydiethylsilane, γ- (meth) acryloyloxypropyldiethoxymethylsilane, δ- (meth) acryloyloxybutyldiethoxymethylsilane, etc. (Meth) acryloyloxysilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; vinylphenylsilane such as p-vinylphenyldimethoxymethylsilane; γ-mercaptopropyl Examples include mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These siloxanes having a vinyl polymerizable functional group may be used alone or in combination of two or more.
Among these siloxanes having a vinyl polymerizable functional group, (meth) acryloyloxysilane is preferable from the viewpoint of reactivity with dimethylsiloxane.

  The content of the siloxane having a vinyl polymerizable functional group is preferably 0.1 to 20% by mass, because 100% by mass of the organosiloxane is excellent in the mechanical properties of the obtained molded body. More preferably, it is 10 mass%.

  Examples of the siloxane-based crosslinking agent include trifunctional or tetrafunctional silane-based crosslinking agents, and examples include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. These siloxane crosslinking agents may be used alone or in combination of two or more.

  The content of the siloxane-based crosslinking agent is preferably 0.1 to 10% by mass, and preferably 1 to 5% by mass, because 100% by mass of the organosiloxane is excellent in mechanical properties and flame retardancy of the obtained molded product. % Is more preferable.

The polyorganosiloxane rubber (bs) can be produced, for example, by adding an emulsifier and water to an organosiloxane and emulsifying it to prepare an organosiloxane latex, which is made into a fine particle by a shearing force by high-speed rotation, or a high pressure generator After making fine particles using a homogenizer that makes fine particles with the jet power generated by the polymerization, polymerization is performed at high temperature in the presence of an acid catalyst, and the acid is neutralized with an alkaline substance to obtain a latex of a polyorganosiloxane rubber (bs) A method is mentioned.
Among these production methods for polyorganosiloxane rubbers (bs), the resulting polyorganosiloxane rubbers (bs) have excellent ability to control the particle size distribution, so that the organosiloxane latex is made into fine particles using a homogenizer. The method is preferred.

Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts may be used individually by 1 type, and may use 2 or more types together.
Among these acid catalysts, the particle size distribution of the resulting polyorganosiloxane rubber (bs) is excellent in controllability and the appearance defect of the molded product due to the emulsifier of the polyorganosiloxane rubber (bs) is suppressed. From the viewpoint of excellent mechanical properties of the molded article, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid having no micelle forming ability are preferable.
Examples of the method of adding an acid catalyst include a method of mixing with an organosiloxane, an emulsifier and water to make fine particles, and a method of dropping the finely divided organosiloxane latex into an acid catalyst aqueous solution at a constant rate.
Among these methods of adding an acid catalyst, a method of mixing with an organosiloxane, an emulsifier, and water is preferable because of excellent controllability of the particle size distribution of the resulting polyorganosiloxane rubber (bs).

As an emulsifier used for polymerization of organosiloxane, an anionic emulsifier is preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium alkyl sulfate, and sodium polyoxyethylene nonylphenyl ether sulfate. These emulsifiers may be used individually by 1 type, and may use 2 or more types together.
Among these emulsifiers, sodium alkylbenzenesulfonate is preferred because the resulting molded article is excellent in heat resistance.

The polymerization temperature of the organosiloxane is preferably 50 to 95 ° C, more preferably 70 to 90 ° C.
The polymerization time of the organosiloxane is preferably 2 to 15 hours, preferably 5 to 10 hours, when an acid catalyst is added by using a method of mixing with an organosiloxane, an emulsifier and water to make fine particles. More preferred.

  As a method for stopping the polymerization of the organosiloxane, for example, after the reaction solution is cooled, the polyorganosiloxane rubber (bs) latex is neutralized with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like. Is mentioned.

The volume average particle size of the polyorganosiloxane rubber (bs) is preferably 10 to 800 nm, more preferably 20 to 600 nm.
When the volume average particle diameter of the polyorganosiloxane rubber (bs) is 10 nm or more, the resulting molded article has excellent mechanical properties. Further, when the volume average particle diameter of the polyorganosiloxane rubber (bs) is 800 nm or less, the obtained molded article is excellent in flame retardancy.
The volume average particle diameter in the present invention is measured with a capillary type particle size distribution analyzer.

The toluene-insoluble content of the polyorganosiloxane rubber (bs) is preferably 30% by mass or more, more preferably 50% by mass or more, in 100% by mass of the polyorganosiloxane rubber (bs). More preferably, it is at least mass%.
When the toluene-insoluble content of the polyorganosiloxane rubber (bs) is 30% by mass or more, the resulting molded article has excellent mechanical properties.
In addition, the toluene insoluble content of the polyorganosiloxane rubber (bs) is measured by the following method.
The polyorganosiloxane rubber (bs) is extracted from the polyorganosiloxane rubber (bs) latex using 2-propanol, dried at 25 ° C., and then the 2-propanol component is completely removed with a vacuum dryer. . After accurately weighing 0.5 g of the obtained polyorganosiloxane rubber (bs), it was immersed in 80 mL of toluene at 25 ° C. for 24 hours, centrifuged at 12,000 rpm for 60 minutes, and vacuum-dried at 50 ° C. for 24 hours, By accurately weighing the obtained solid content, the mass fraction of the polyorganosiloxane rubber (bs) toluene-insoluble component is calculated.
The toluene insoluble content of the polyorganosiloxane rubber (bs) can be controlled by adjusting the content of the siloxane crosslinking agent in the organosiloxane. The higher the content of the siloxane crosslinking agent in the organosiloxane, the higher the toluene-insoluble content of the polyorganosiloxane rubber (bs).

The rubber polymer (br) may contain other rubber in addition to the polyorganosiloxane rubber (bs) as long as the properties of the obtained thermoplastic resin composition are not impaired.
Examples of the other rubber include acrylic rubber (ba), diene rubber, and olefin rubber. These other rubbers may be used alone or in combination of two or more.
Among these other rubbers, acrylic rubber (ba) is preferred because the production process is simple and the molded article obtained has excellent mechanical properties.

  The acrylic rubber (ba) is obtained by polymerizing a monomer component containing an alkyl (meth) acrylate and, if necessary, a polyfunctional vinyl monomer.

Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and dodecyl methacrylate. Can be mentioned. These alkyl (meth) acrylates may be used individually by 1 type, and may use 2 or more types together.
Among these alkyl (meth) acrylates, n-butyl acrylate and 2-ethylhexyl (meth) acrylate are preferable because of excellent mechanical properties of the obtained molded body.

  The content of the alkyl (meth) acrylate is preferably 80 to 99.9% by mass in 100% by mass of the monomer component because it is excellent in the mechanical properties and flame retardancy of the resulting molded product. More preferably, it is -99 mass%.

Examples of the polyfunctional vinyl monomer include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and triallyl cyanurate. , Triallyl isocyanurate, diallyl phthalate, and divinylbenzene. These polyfunctional vinyl monomers may be used individually by 1 type, and may use 2 or more types together.
Among these polyfunctional vinyl monomers, allyl (meth) acrylate is preferable from the viewpoint of production cost.

  The content of the polyfunctional vinyl monomer is preferably 0.1 to 20% by mass, because the mechanical properties of the resulting molded article are excellent in 100% by mass of the monomer component. More preferably, it is mass%.

As a method for producing a composite rubber of a polyorganosiloxane rubber (bs) and an acrylic rubber (ba), for example, a simple process for obtaining an acrylic rubber (ba) in a latex of a polyorganosiloxane rubber (bs). The method of adding a monomer component and polymerizing is mentioned.
Examples of the method of adding the monomer component include a method of batch mixing with the latex of the polyorganosiloxane rubber (bs), and a method of dropping at a constant rate into the polyorganosiloxane rubber (bs) latex. .
Among the methods of adding these monomer components, a method of collectively mixing with the latex of the polyorganosiloxane rubber (bs) is preferable because the resulting molded article has excellent mechanical properties.
Examples of the polymerization initiator used for the polymerization of the monomer component include persulfates, organic peroxides, azo initiators, redox initiators combined with persulfates and reducing agents, organic peroxides and reductions. And redox initiators combined with agents. These polymerization initiators may be used alone or in combination of two or more.
Among these polymerization initiators, a redox initiator in which an organic peroxide and a reducing agent are combined is preferable because of excellent productivity.

The composition ratio of the rubber polymer (br) is 60 to 100% by mass of the polyorganosiloxane rubber (bs) and 0 to 40% by mass of other rubbers in the total 100% by mass of the rubber polymer (br). The polyorganosiloxane rubber (bs) is 80 to 100% by mass, and other rubbers are more preferably 0 to 20% by mass. The polyorganosiloxane rubber (bs) is 90 to 100% by mass, and other rubbers. More preferably, it is 0-10 mass%.
When the content of the polyorganosiloxane rubber (bs) is 60% by mass or more, the obtained molded article is excellent in flame retardancy.
When the content of other rubber is 40% by mass or less, the obtained molded article is excellent in flame retardancy.

The monomer component (b) contains phenyl (meth) acrylate (b1) which may have a substituent.
Examples of the optionally substituted phenyl (meth) acrylate (b1) include phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, monobromophenyl (meth) acrylate, dibromophenyl ( Examples include meth) acrylate, tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, and trichlorophenyl (meth) acrylate. The phenyl (meth) acrylate (b1) which may have these substituents may be used individually by 1 type, and may use 2 or more types together.
Among the phenyl (meth) acrylate (b1) which may have these substituents, phenyl (meth) acrylate is preferable, and phenyl methacrylate is more preferable because the molded article obtained is excellent in heat resistance.

  The content of phenyl (meth) acrylate (b1) which may have a substituent is excellent in mechanical properties and flame retardancy of the obtained molded product in 100% by mass of the monomer component (b). 10 to 100% by mass, and more preferably 30 to 100% by mass.

The monomer component (b) may contain a polyfunctional vinyl monomer (b2) as necessary in addition to the phenyl (meth) acrylate (b1) which may have a substituent.
Examples of the polyfunctional vinyl monomer (b2) include polyfunctional vinyl monomers exemplified as monomers for obtaining acrylic rubber. These polyfunctional vinyl monomers (b2) may be used individually by 1 type, and may use 2 or more types together.
Among these polyfunctional vinyl monomers (b2), allyl (meth) acrylate is preferable because it is excellent in mechanical properties and flame retardancy of the obtained molded product.

  As a content rate of a polyfunctional vinyl monomer (b2), it is 0-80 mass% from being excellent in the flame retardance of the molded object obtained in 100 mass% of monomer components (b). Preferably, it is 0 to 60% by mass.

The monomer component (b) may include other monomers other than the optionally substituted phenyl (meth) acrylate (b1) and multifunctional vinyl monomer (b2). (B3) may be included.
Examples of the other monomer (b3) include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyl toluene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -(Meth) acrylates such as ethylhexyl (meth) acrylate and benzyl (meth) acrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; carboxyls such as itaconic acid, (meth) acrylic acid, fumaric acid and maleic acid And group-containing vinyl monomers. These other monomers (b3) may be used alone or in combination of two or more.
Among these other monomers (b3), methyl methacrylate and benzyl (meth) acrylate are preferable because the obtained molded article is excellent in mechanical properties.

As a content rate of another monomer (b3), it is preferable that it is 40 mass% or less in 100 mass% of monomer components (b), and it is more preferable that it is 10 mass% or less.
When the content of the other monomer (b3) is 40% by mass or less, the obtained molded article has excellent mechanical properties.

The monomer component (b) is polymerized in the presence of the rubbery polymer (br).
The method for polymerizing the monomer component (b) is not particularly limited, but a method of polymerizing in the presence of a latex containing the rubbery polymer (br) is preferable from the viewpoint of the production process.
The polymerization of the monomer component (b) may be batch polymerization or multistage polymerization.

The composition ratio of the rubber polymer (br) and the monomer component (b) in the polymerization of the monomer component (b) is 100 mass in total of the rubber polymer (br) and the monomer component (b). %, The rubbery polymer (br) is preferably 40 to 90% by mass, the monomer component (b) is preferably 10 to 60% by mass, the rubbery polymer (br) is 50 to 90% by mass, the monomer The component (b) is more preferably 10 to 50% by mass, the rubbery polymer (br) is preferably 70 to 90% by mass, and the monomer component (b) is further preferably 10 to 30% by mass.
When the content of the rubbery polymer (br) is 40% by mass or more, the obtained molded article is excellent in flame retardancy. Moreover, it is excellent in the mechanical characteristic of the molded object obtained as the content rate of a rubber-like polymer (br) is 90 mass% or less.
When the content of the monomer component (b) is 10% by mass or more, the resulting molded article has excellent mechanical properties. Moreover, it is excellent in the flame retardance of the molded object obtained as the content rate of a vinyl monomer (b) is 60 mass% or less.

  Examples of the polymerization initiator used for the polymerization of the monomer component (b) include those exemplified as the polymerization initiator used for the polymerization of the monomer component for obtaining the acrylic rubber (ba). These polymerization initiators may be used alone or in combination of two or more.

In the polymerization of the monomer component (b), an emulsifier may be used as necessary in order to stabilize the polymerization latex and control the particle diameter of the resulting graft polymer (B).
Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, and a nonionic emulsifier. Among these emulsifiers, anionic emulsifiers such as sulfonate emulsifiers, sulfate emulsifiers, and carboxylate emulsifiers are preferred, and the graft copolymer (B) is blended with the thermoplastic resin (A) having an ester bond. In this case, a sulfonate emulsifier is more preferable because hydrolysis of the thermoplastic resin (A) is suppressed.

In the polymerization of the vinyl monomer (b), in order to adjust the molecular weight or graft ratio of the vinyl monomer (b) unit of the obtained graft copolymer (B), a chain transfer agent is used as necessary. Also good.
Examples of the chain transfer agent include t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, and n-hexyl mercaptan.

As a method for recovering the graft polymer (B) from the latex of the graft polymer (B), a known recovery method can be used, and examples thereof include a coagulation method and a spray drying method.
Examples of the coagulant in the coagulation method include metal salts such as calcium chloride, calcium acetate, magnesium sulfate, and aluminum sulfate.
Among these coagulants, when blending the graft copolymer (B) with the thermoplastic resin (A) having an ester bond, the hydrolysis of the thermoplastic resin (A) is suppressed, so that calcium chloride, acetic acid is used. Calcium salts such as calcium are preferred.

  When the graft copolymer (B) is produced by the above method, a polymer (free polymer) of the vinyl monomer (b) that is not grafted on the rubbery polymer (br) may be produced. The graft copolymer (B) including such a free polymer is used.

As a volume average particle diameter of a graft polymer (B), it is preferable that it is 20-1000 nm, and it is more preferable that it is 50-800 nm.
When the volume average particle diameter of the graft polymer (B) is 20 nm or more, the resulting molded article has excellent mechanical properties. Moreover, it is excellent in the flame retardance of the molded object obtained as the volume average particle diameter of a graft polymer (B) is 1000 nm or less.

As a compounding quantity of a graft polymer (B), it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of thermoplastic resins (A), and it is more preferable that it is 1-5 mass parts.
When the blending amount of the graft polymer (B) is 0.1 parts by mass or more, the resulting molded article is excellent in mechanical properties and flame retardancy. Moreover, the original property of a thermoplastic resin (A) is not impaired as the compounding quantity of a graft polymer (B) is 10 mass parts or less.

As the fluidity improver (C) of the present invention, a known fluidity improver can be used. For example, a low-molecular acrylonitrile-styrene copolymer, polycaprolactone, aromatic vinyl monomer-phenyl (meth) acrylate. A copolymer and a low molecular polycarbonate are mentioned.
Among these fluidity improvers (C), when a polycarbonate resin is used as the thermoplastic resin (A), it is excellent in the effect of improving the melt fluidity of the resulting thermoplastic resin composition. A fluidity improver comprising a polymer (C1) obtained by polymerizing a monomer component comprising a body (c1) and optionally substituted phenyl (meth) acrylate (c2), an aromatic vinyl monomer It is obtained by polymerizing a monomer component including a monomer (c1), a phenyl (meth) acrylate (c2) which may have a substituent, and a vinyl monomer (c3) having a functional group (x). Compound (c4) having functional group (y) capable of reacting with polymer component (C2) and monomer component including phenyl (meth) acrylate (c2) which may have a substituent and functional group (x) Obtained by polymerization using Flow improver comprising a polymer (C3) is preferred.

  The polymer (C1) is obtained by polymerizing a monomer component containing an aromatic vinyl monomer (c1) and an optionally substituted phenyl (meth) acrylate (c2).

Examples of the aromatic vinyl monomer (c1) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, Examples include chlorostyrene, bromostyrene, vinyl toluene, vinyl naphthalene, and vinyl anthracene. These aromatic vinyl monomers (c1) may be used alone or in combination of two or more.
Among these aromatic vinyl monomers (c1), styrene, α-methylstyrene, and pt-butylstyrene are preferable because the production cost is low and the resulting molded article is excellent in heat resistance. α-methylstyrene is more preferable, and it is more preferable to use styrene and α-methylstyrene in combination.

The content of the aromatic vinyl monomer (c1) is preferably 0.5 to 99.5% by mass and more preferably 20 to 98% by mass in 100% by mass of the monomer component. 40 to 96 mass% is more preferable, and 60 to 93 mass% is particularly preferable.
When the content of the aromatic vinyl monomer (c1) is 0.5% by mass or more, the resulting thermoplastic resin composition has excellent melt fluidity, and the resulting molded article has excellent chemical resistance. Moreover, it is excellent in the mechanical characteristic of the molded object as the content rate of an aromatic vinyl monomer (c1) is 99.5 mass% or less.

  As a composition ratio in the case of using styrene and α-methylstyrene in combination as the aromatic vinyl monomer (c1), 60 to 90% by mass of styrene and α-methylstyrene in a total of 100% by mass of styrene and α-methylstyrene. It is preferably 10 to 40% by mass, more preferably 70 to 85% by mass of styrene and 15 to 30% by mass of α-methylstyrene.

Examples of the optionally substituted phenyl (meth) acrylate (c2) include those exemplified as the optionally substituted phenyl (meth) acrylate (b1). The phenyl (meth) acrylate (c2) which may have these substituents may be used individually by 1 type, and may use 2 or more types together.
Among these phenyl (meth) acrylates (c2) which may have a substituent, when a polycarbonate resin is used as the thermoplastic resin (A), the resulting molded article has high compatibility with the polycarbonate resin. Therefore, phenyl (meth) acrylate is preferable, and phenyl methacrylate is more preferable.

The content of phenyl (meth) acrylate (c2) which may have a substituent is preferably 0.5 to 99.5% by mass in 100% by mass of the monomer component, and 2 to 80%. More preferably, it is more preferably 4 to 60% by mass, and particularly preferably 7 to 40% by mass.
When the content of phenyl (meth) acrylate (c2) which may have a substituent is 0.5% by mass or more, the resulting molded article has excellent mechanical properties. Further, when the content of phenyl (meth) acrylate (c2) which may have a substituent is 99.5% by mass or less, the resulting thermoplastic resin composition is excellent in melt fluidity and obtained molding Excellent chemical resistance of the body.

In addition to the aromatic vinyl monomer (c1) and the optionally substituted phenyl (meth) acrylate (c2), the monomer component may contain other monomers (c5) as necessary. May be included.
Examples of the other monomer (c5) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate. , Isobornyl (meth) acrylate, (meth) acrylate such as t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc .; multifunctional such as allyl (meth) acrylate, 1,3-butylene di (meth) acrylate, divinylbenzene Vinyl benzoate; vinyl acetate; maleic anhydride; maleimide compounds such as N-phenylmaleimide and cyclohexylmaleimide; and ethylenically unsaturated monomers having a piperidyl group. These other monomers (c5) may be used individually by 1 type, and may use 2 or more types together.

As a content rate of another monomer (c5), it is preferable that it is 40 mass% or less in 100 mass% of monomer components, and it is more preferable that it is 10 mass% or less.
When the content of the other monomer (c5) is 40% by mass or less, the resulting thermoplastic resin composition has excellent melt fluidity and the resulting molded article has excellent chemical resistance.

The mass average molecular weight of the polymer (C1) is preferably 5,000 to 150,000, more preferably 10,000 to 100,000, and 30,000 to 70,000. More preferred is 40,000 to 60,000.
When the mass average molecular weight of the polymer (C1) is 5,000 or more, the resulting molded article is excellent in mechanical properties and heat resistance. Moreover, it is excellent in the melt fluidity | liquidity of the thermoplastic resin composition obtained as the polymer (C1) mass average molecular weight is 150,000 or less.

  The molecular weight distribution (mass average molecular weight / number average molecular weight) of the polymer (C1) is preferably 5.0 or less, because it is excellent in melt fluidity of the resulting thermoplastic resin composition, and is 4.0 or less. Is more preferable, and it is still more preferable that it is 3.0 or less.

  The fluidity improver containing the polymer (C2) and the polymer (C3) comprises a thermoplastic resin (A), a graft polymer (B), a fluidity improver (C), and an anti-drip agent (D). When the product is melt kneaded, the functional group (x) of the polymer (C2) reacts with the functional group (y) of the polymer (C3), so that the fluidity improver becomes the thermoplastic resin (A). Exhibits phase separation behavior and exhibits an effect of improving melt fluidity.

  The polymer (C2) comprises an aromatic vinyl monomer (c1), an optionally substituted phenyl (meth) acrylate (c2), and a vinyl monomer (c3) having a functional group (x). It can be obtained by polymerizing the monomer component.

As an aromatic vinyl monomer (c1), the aromatic vinyl monomer (c1) illustrated as a monomer for obtaining a polymer (C1) is mentioned. These aromatic vinyl monomers (c1) may be used alone or in combination of two or more.
Among these aromatic vinyl monomers (c1), styrene, α-methylstyrene, and pt-butylstyrene are preferable because the production cost is low and the resulting molded article is excellent in heat resistance. α-methylstyrene is more preferred.

As a content rate of an aromatic vinyl monomer (c1), it is preferable that it is 0.5-99 mass% in 100 mass% of monomer components, and it is more preferable that it is 20-95 mass%. More preferably, it is -90 mass%.
When the content of the aromatic vinyl monomer (c1) is 0.5% by mass or more, the resulting thermoplastic resin composition has excellent melt fluidity, and the resulting molded article has excellent chemical resistance. Moreover, it is excellent in the mechanical characteristic of the molded object as the content rate of an aromatic vinyl monomer (c1) is 99.5 mass% or less.

Examples of the optionally substituted phenyl (meth) acrylate (c2) include those exemplified as the optionally substituted phenyl (meth) acrylate (b1). The phenyl (meth) acrylate (c2) which may have these substituents may be used individually by 1 type, and may use 2 or more types together.
Among these phenyl (meth) acrylates (c2) which may have a substituent, when a polycarbonate resin is used as the thermoplastic resin (A), the resulting molded article has high compatibility with the polycarbonate resin. Therefore, phenyl (meth) acrylate is preferable, and phenyl methacrylate is more preferable.

The content of phenyl (meth) acrylate (c2) which may have a substituent is preferably 0.5 to 99% by mass in 100% by mass of the monomer component, and 4.5 to 79%. More preferably, it is 0.5 mass%, and it is still more preferable that it is 9.5-59.5 mass%.
When the content of phenyl (meth) acrylate (c2) which may have a substituent is 0.5% by mass or more, the resulting molded article has excellent mechanical properties. Further, when the content of phenyl (meth) acrylate (c2) which may have a substituent is 99% by mass or less, the thermoplastic resin composition obtained has excellent melt fluidity, and the obtained molded article Excellent chemical resistance.

Examples of the functional group (x) include an epoxy group, a carboxyl group, a hydroxyl group, and an amino group.
Examples of the vinyl monomer (c3) having a functional group (x) include an epoxy group-containing vinyl monomer such as glycidyl (meth) acrylate; a carboxyl group-containing vinyl monomer such as (meth) acrylic acid; 2 -Hydroxyl group-containing vinyl monomers such as hydroxyethyl (meth) acrylate; and amino group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate.
Among these vinyl monomers (c3) having a functional group (x), when the compound is melt-kneaded, it has excellent reactivity with the functional group (y) of the polymer (C3). Epoxy group-containing vinyl monomers such as (meth) acrylate are preferred, and glycidyl (meth) acrylate is more preferred.

As a content rate of the vinyl monomer (c3) which has a functional group (x), it is preferable that it is 0.1-5 mass% in 100 mass% of monomer components, and is 0.5-2.5 mass. % Is more preferable.
When the content of the vinyl monomer (c3) having the functional group (x) is 0.5% by mass or more, the resulting molded article has excellent mechanical properties. Further, when the content of the vinyl monomer (c3) having a functional group (x) is 5% by mass or less, the resulting thermoplastic resin composition has excellent melt fluidity, and the resulting molded article has chemical resistance. Excellent.

The monomer component includes an aromatic vinyl monomer (c1), an optionally substituted phenyl (meth) acrylate (c2), and a vinyl monomer (c3) having a functional group (x). If necessary, other monomer (c5) may be contained.
Examples of the other monomer (c5) include the other monomer (c5) exemplified as the monomer for obtaining the polymer (C1). These other monomers (c5) may be used individually by 1 type, and may use 2 or more types together.

As a content rate of another monomer (c5), it is preferable that it is 40 mass% or less in 100 mass% of monomer components, and it is more preferable that it is 10 mass% or less.
When the content of the other monomer (c5) is 40% by mass or less, the resulting thermoplastic resin composition has excellent melt fluidity and the resulting molded article has excellent chemical resistance.

The polymer (C2) is preferably incompatible with the thermoplastic resin (A).
In the present specification, the compatibility of the polymer (C2) with the thermoplastic resin (A) is measured by the following method.
A molded product is obtained by injection molding a thermoplastic resin composition containing 95 parts by mass of the thermoplastic resin (A) and 5 parts by mass of the polymer (C2), and a photograph of the molded product is taken using a transmission electron microscope. The photograph is image-analyzed.
When the volume average domain diameter of the polymer (C2) dispersed in the thermoplastic resin (A) is confirmed as phase separation of 0.05 μm or more, the polymer (C2) is in comparison with the thermoplastic resin (A). Judged as incompatible. When the volume average domain diameter of the polymer (C2) dispersed in the thermoplastic resin (A) is not confirmed as phase separation of 0.05 μm or more, the polymer (C2) is in phase with the thermoplastic resin (A). Judged as melted.

As content of the functional group (x) which a polymer (C2) has, it is preferable that it is 0.01-0.2 mmol / g, and it is more preferable that it is 0.03-0.1 mmol / g.
When the content of the functional group (x) contained in the polymer (C2) is 0.01 mmol / g or more, the polymer (C3) has excellent reactivity with the functional group (y) contained in the polymer (C3). Excellent mechanical properties.
When the content of the functional group (x) of the polymer (C2) is 0.2 mmol / g or less, the resulting thermoplastic resin composition has excellent melt fluidity.

The mass average molecular weight of the polymer (C2) is preferably from 5,000 to 200,000, more preferably from 10,000 to 170,000, and from 15,000 to 150,000. More preferred is 30,000 to 120,000.
When the mass average molecular weight of the polymer (C2) is 5,000 or more, the resulting molded article is excellent in mechanical properties and heat resistance. Moreover, it is excellent in the melt fluidity | liquidity of the thermoplastic resin composition obtained as the polymer (C2) mass average molecular weight is 200,000 or less.

  The polymer (C3) is a compound (c4) having a functional group (y) capable of reacting with a monomer component containing a phenyl (meth) acrylate (c2) which may have a substituent and the functional group (x). ) To obtain a polymer.

Examples of the optionally substituted phenyl (meth) acrylate (c2) include those exemplified as the optionally substituted phenyl (meth) acrylate (b2). The phenyl (meth) acrylate (c2) which may have these substituents may be used individually by 1 type, and may use 2 or more types together.
Among these phenyl (meth) acrylates (c2) which may have a substituent, when a polycarbonate resin is used as the thermoplastic resin (A), the resulting molded article has high compatibility with the polycarbonate resin. Therefore, phenyl (meth) acrylate is preferable, and phenyl methacrylate is more preferable.

The content of phenyl (meth) acrylate (c2) which may have a substituent is preferably 0.5% by mass or more, and 25% by mass or more in 100% by mass of the monomer component. More preferably, it is more preferably 60% by mass or more.
When the content of phenyl (meth) acrylate (c2) which may have a substituent is 0.5% by mass or more, the resulting molded article has excellent mechanical properties.

The monomer component may contain other monomer (c6) as needed, in addition to phenyl (meth) acrylate (c2) which may have a substituent.
Examples of the other monomer (c6) include the aromatic vinyl monomer (c1) and the other monomer (c5) exemplified as the monomer for obtaining the polymer (C1). These other monomers (c6) may be used individually by 1 type, and may use 2 or more types together.
Among these other monomers (c6), methyl methacrylate and benzyl (meth) acrylate are preferable because the resulting molded article is excellent in mechanical properties.

As a content rate of another monomer (c6), it is preferable that it is 99.5 mass% or less in 100 mass% of monomer components, It is more preferable that it is 75 mass% or less, 40 mass% or less More preferably.
When the content of the other monomer (c6) is 99.5% by mass or less, the resulting thermoplastic resin composition has excellent melt fluidity and the resulting molded article has excellent chemical resistance.

The functional group (y) can react with the functional group (x).
As the functional group (y), when the functional group (x) is an epoxy group, examples thereof include a carboxyl group, a hydroxyl group, and a methylol group. Among these functional groups (y), a carboxyl group is preferred because of excellent reactivity with an epoxy group.
As a functional group (y), when a functional group (x) is a carboxyl group, a hydroxyl group and an isocyanate group are mentioned, for example.
As a functional group (y), when a functional group (x) is a hydroxyl group, an isocyanate group is mentioned, for example.
Examples of the functional group (y) include a carboxyl group when the functional group (x) is an amino group.

As the compound (c4) having a functional group (y) capable of reacting with the functional group (x), when the functional group (y) is a carboxyl group, for example, a carboxyl group-containing vinyl monomer such as (meth) acrylic acid Body; carboxyl group-containing chain transfer agent such as 3-mercaptopropionic acid; 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxyethyl) -2-methyl- And carboxyl group-containing polymerization initiators such as propionamidine]. The compound (c4) having a functional group (y) capable of reacting with these monomer components and the functional group (x) may be used alone or in combination of two or more.
Among these compounds (c4) having a functional group (y) capable of reacting with the monomer component and the functional group (x), a carboxyl group can be efficiently introduced into the terminal of the polymer (C3). A transfer agent and a carboxyl group-containing polymerization initiator are preferred.

The polymer (C3) is preferably compatible with the thermoplastic resin (A).
In addition, in this specification, the compatibility with respect to the thermoplastic resin (A) of a polymer (C3) is measured by the method similar to the measuring method of the compatibility of a polymer (C2).

As content of the functional group (y) which a polymer (C3) has, it is preferable that it is 0.02-0.5 mmol / g, and it is more preferable that it is 0.05-0.3 mmol / g.
When the content of the functional group (y) in the polymer (C3) is 0.02 mmol / g or more, the polymer (C2) has excellent reactivity with the functional group (x) in the polymer (C2), Excellent mechanical properties.
When the content of the functional group (y) in the polymer (C3) is 0.5 mmol / g or less, the resulting thermoplastic resin composition has excellent melt fluidity.

The mass average molecular weight of the polymer (C3) is preferably 5,000 to 200,000, and more preferably 10,000 to 120,000.
When the mass average molecular weight of the polymer (C3) is 5,000 or more, the resulting molded article is excellent in mechanical properties and heat resistance. Moreover, it is excellent in the melt fluidity | liquidity of the thermoplastic resin composition obtained as the mass mean molecular weight of a polymer (C3) is 200,000 or less.

As a composition ratio of the fluidity improver (C) containing the polymer (C2) and the polymer (C3), the polymer (C2) 0 in 100% by mass in total of the polymer (C2) and the polymer (C3). It is preferable that they are 0.5-99.5 mass%, a polymer (C3) 0.5-99.5 mass%, a polymer (C2) 30-70 mass%, a polymer (C3) 30-70 mass%. It is more preferable that
As the amount of the functional group in the fluidity improver (C) containing the polymer (C2) and the polymer (C3), the amount of the functional group (y) may be larger than the amount of the functional group (x). preferable.

As the fluidity improver (C) of the present invention, a fluidity improver containing a polymer (C1) and a fluidity improver containing a polymer (C2) and a polymer (C3) may be used in combination.
The composition ratio when the fluidity improver containing the polymer (C1) and the fluidity improver containing the polymer (C2) and the polymer (C3) are used in combination is the polymer (C1) and the polymer (C2). The polymer (C3) is preferably 10 to 80% by mass, the polymer (C2) 10 to 45% by mass, and the polymer (C3) 10 to 45% by mass in the total 100% by mass of the polymer (C3). .

Examples of the polymerization method for obtaining the polymer (C1), the polymer (C2), and the polymer (C3) include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method.
Among these polymerization methods, the suspension polymerization method and the emulsion polymerization method are preferable because the recovery method is easy.
In the case of the emulsion polymerization method, since salts remaining in the polymer may cause decomposition of the thermoplastic resin (A), a method of recovering the polymer by acid coagulation using a carboxylic acid emulsifier, a phosphate ester, etc. A method of recovering the polymer by salt coagulation with calcium acetate or the like using a nonionic anionic emulsifier is preferred.

  The polymerization initiator for obtaining the polymer (C1), the polymer (C2), and the polymer (C3) is exemplified as a polymerization initiator used for polymerization of monomer components for obtaining the acrylic rubber (ba). The thing which was done is mentioned. These polymerization initiators may be used alone or in combination of two or more.

  The mixing method of the fluidity improver (C) is not particularly limited, and the polymer (C1), the polymer (C2), and the polymer (C3) may be mixed, respectively. The blend (C3) may be blended and melt-kneaded and then mixed with the polymer (C1).

  The blending method of the fluidity improver (C) is not particularly limited, and the powder of the polymer (C1), the polymer (C2), and the polymer (C3) is made of a thermoplastic resin (A), a graft polymer ( B), which may be added to the anti-dripping agent (D), and after preparing a master batch of the thermoplastic resin (A) and the fluidity improver (C), the master batch is converted into the thermoplastic resin (A), graft You may mix | blend with a polymer (B) and a dripping inhibitor (D).

As a compounding quantity of a fluid improvement agent (C), it is preferable that it is 1-20 mass parts with respect to 100 mass parts of thermoplastic resins (A), It is more preferable that it is 3-15 mass parts, 5 More preferably, it is 10 mass parts.
It is excellent in the melt fluidity | liquidity of the thermoplastic resin composition obtained as the compounding quantity of a fluid improvement agent (C) is 1 mass part or more. Moreover, the original property of a thermoplastic resin (A) is not impaired as the compounding quantity of a fluid improvement agent (C) is 20 mass parts or less.

As the anti-drip agent (D) of the present invention, a known anti-drip agent can be used. For example, polytetrafluoroethylene such as “Polyflon FA-500” (trade name, manufactured by Daikin Industries, Ltd.); “BLENDEX” SAN-modified polytetrafluoroethylene such as “B449” (trade name, manufactured by GE Specialty Chemicals); “methabrene A-3000”, “methabrene A-3750”, “methabrene A-3800” (trade name, Mitsubishi Rayon Co., Ltd.) Acrylic-modified polytetrafluoroethylene such as One of these anti-dripping agents (D) may be used alone, or two or more thereof may be used in combination.
Among these anti-dripping agents, SAN-modified polytetrafluoroethylene and acrylic-modified polytetrafluoroethylene are excellent because of the excellent dispersibility of the anti-dripping agent in the resulting molded article and excellent mechanical properties, heat resistance, and flame retardancy. Are preferred, and acrylic-modified polytetrafluoroethylene is more preferred.

  As a method for producing SAN-modified polytetrafluoroethylene and acrylic-modified polytetrafluoroethylene, for example, a latex of polytetrafluoroethylene (D1) particles and a latex of polymer (D2) particles are mixed and obtained by coagulation or spray drying. Method: A method of polymerizing the monomer (d2) for constituting the polymer (D2) in the presence of latex of polytetrafluoroethylene (D1) particles, and obtaining it by coagulation or spray drying; polytetrafluoroethylene (D1) ) Polymerization of the monomer (d2) for constituting the polymer (D2) in the presence of a latex in which the latex of the particles and the latex of the polymer (D2) particles are mixed, and a method obtained by coagulation or spray drying. .

The particle diameter of the polytetrafluoroethylene (D1) particles is preferably 0.01 to 10 μm, and more preferably 0.05 to 1 μm.
When the particle diameter of the polytetrafluoroethylene (D1) particles is 0.01 μm or more, the resulting antidrip agent (D) is excellent in powder recoverability. Moreover, it is excellent in the dispersibility of the polytetrafluoroethylene (D1) in the molded object obtained as the particle diameter of a polytetrafluoroethylene (D1) particle | grain is 10 micrometers or less.

The polymer (D2) is obtained by polymerizing the monomer (d2).
As the monomer (d2), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate and other (meth) acrylates; aromatic such as styrene Vinyl monomer; vinyl cyanide monomers such as (meth) acrylonitrile. These monomers (d2) may be used individually by 1 type, and may use 2 or more types together.
Among these monomers, methyl methacrylate is preferable because it is excellent in dispersibility of polytetrafluoroethylene (D1) in the obtained molded article.

The content of polytetrafluoroethylene in the SAN-modified polytetrafluoroethylene and acrylic-modified polytetrafluoroethylene is preferably 10 to 80% by mass in 100% by mass of the anti-dripping agent (D). More preferably, it is mass%.
When the content of polytetrafluoroethylene in SAN-modified polytetrafluoroethylene and acrylic-modified polytetrafluoroethylene is 10% by mass or more, the resulting molded article is excellent in flame retardancy. When the content of polytetrafluoroethylene in SAN-modified polytetrafluoroethylene and acrylic-modified polytetrafluoroethylene is 80% by mass or less, the appearance of the resulting molded article is excellent.

As a compounding quantity of a dripping inhibitor (D), it is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of thermoplastic resins (A), and it is more preferable that it is 0.1-5 mass parts. Preferably, it is 0.3-2 mass parts.
When the blending amount of the anti-dripping agent (D) is 0.01 parts by mass or more, the obtained molded article is excellent in flame retardancy. Moreover, the original property of a thermoplastic resin (A) is not impaired as the compounding quantity of a dripping inhibitor (D) is 10 mass parts or less.

As the flame retardant (E) of the present invention, known flame retardants can be used. For example, halogen compounds such as halogenated bisphenol A, halogenated polycarbonate oligomers, brominated epoxy compounds, and flame retardant aids such as antimony oxide. A flame retardant composed of a combination of: an organic salt flame retardant; a phosphoric flame retardant such as an aromatic phosphate ester flame retardant, a halogenated aromatic phosphate ester type flame retardant; a metal salt of aromatic sulfonic acid; Examples include sulfonic acid-based flame retardants such as metal salts of fluoroalkanesulfonic acid; silicone-based flame retardants such as branched-type phenyl silicone compounds and organopolysiloxanes such as phenyl silicone resins.
Among these flame retardants (E), sulfonic acid flame retardants such as aromatic sulfonic acid metal salts and perfluoroalkane sulfonic acid metal salts are preferred because the molded article obtained is excellent in flame retardancy.

Examples of the metal species of the sulfonic acid-based flame retardant include alkali metals such as sodium and potassium, and alkaline earth metals such as calcium.
Specific examples of the sulfonic acid flame retardant include potassium salt of 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide, potassium diphenylsulfone-3-sulfonate, diphenylsulfone-3-3 ′. -Potassium disulfonate, sodium paratoluenesulfonate, potassium perfluorobutanesulfonate.

As a compounding quantity of a flame retardant (E), it is preferable that it is 0.01-20 mass parts with respect to 100 mass parts of thermoplastic resins (A), and it is more preferable that it is 0.1-10 mass parts. .
When the blending amount of the flame retardant (E) is 0.01 parts by mass or more, the obtained molded article is excellent in flame retardancy. Moreover, the original property of a thermoplastic resin (A) is not impaired as the compounding quantity of a flame retardant (E) is 20 mass parts or less.

  The thermoplastic resin composition of the present invention may contain various additives such as an antioxidant and an ultraviolet absorber as necessary.

The thermoplastic resin composition of the present invention comprises a thermoplastic resin (A), a graft polymer (B), a fluidity improver (C), an anti-drip agent (D), and, if necessary, a flame retardant (E), It can prepare by mix | blending various additives and melt-kneading with well-known kneading machines, such as a roll, a Banbury mixer, a single screw extruder, a twin screw extruder. These can be operated batchwise or continuously, and the mixing order of each component is not particularly limited.
The thermoplastic resin composition of the present invention is preferably in the form of pellets.

The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention.
As the molding method, a known molding method can be used, and examples thereof include calendar molding, extrusion molding, extrusion blow molding, and injection molding.

  Since the molded article of the present invention is excellent in mechanical properties, heat resistance, flame retardancy, and chemical resistance, such as OA equipment, information / communication equipment, electronic / electric equipment, home appliances, automotive members, building materials, etc. Can be used in a wide range of fields.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”, respectively.

(1) Solid content The polymerization rate of the obtained polymer was measured by the following procedures.
1) Measure the mass (x) g of the aluminum pan.
2) About 1 g of polymer is taken in an aluminum dish and the mass (y) g is measured.
3) Place the aluminum dish containing the polymer in a dryer and heat at 180 ° C. for 45 minutes.
4) The aluminum dish containing the polymer is taken out of the dryer, cooled to 25 ° C. in a desiccator, and the mass (z) g is measured.
5) The solid content of the polymer is calculated according to the following formula.
Solid content [%] = (z−x) / (y−x) × 100

(2) Volume average particle diameter The volume average particle diameter of the obtained polyorganosiloxane rubber was measured using a laser diffraction / scattering particle size distribution measuring device (model name “LA-910”, manufactured by Horiba, Ltd.). It was measured.

(3) Toluene-insoluble matter From the obtained polyorganosiloxane rubber latex, the polyorganosiloxane rubber component was extracted using 2-propanol and dried at 25 ° C, and then the 2-propanol component was removed using a vacuum dryer. Completely removed.
After 0.5 g of the obtained polyorganosiloxane rubber was precisely weighed, it was immersed in 80 mL of toluene at 25 ° C. for 24 hours, centrifuged at 12,000 rpm for 60 minutes, and vacuum dried at 50 ° C. for 24 hours. The mass fraction of toluene-insoluble matter was calculated by precisely weighing the solid content.

(4) Mass average molecular weight, number average molecular weight The mass average molecular weight and the average molecular weight of the obtained polymer were determined from a standard polystyrene calibration curve using gel permeation chromatography. The measurement conditions are as shown below.
Apparatus: Model name “HLC-8220 GPC” (manufactured by Tosoh Corporation)
Column: Trade name “TSK-GEL SUPER HZM-N” (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C
Eluent: Chloroform Eluent speed: 0.6 ml / min Detector: RI

(5) Polymerization rate The polymerization rate of the obtained polymer was measured by the following procedures.
1) Measure the mass (x) g of the aluminum pan.
2) About 1 g of polymer is taken in an aluminum dish and the mass (y) g is measured.
3) Place the aluminum dish containing the polymer in a dryer and heat at 180 ° C. for 45 minutes.
4) The aluminum dish containing the polymer is taken out of the dryer, cooled to 25 ° C. in a desiccator, and the mass (z) g is measured.
5) The solid content of the polymer is calculated according to the following formula.
Solid content [%] = (z−x) / (y−x) × 100
6) Divide the calculated solid content by the theoretical solid content calculated from the charge to calculate the polymerization rate of the polymer.

(6) Epoxy group amount The epoxy group amount of the obtained polymer (C2) was measured by the following procedures.
1) Measurement of blank 1-1) Collect 10 ml of the following solution A with a whole pipette and put into a 100 ml Erlenmeyer flask with a stopper.
Solution A: 0.1N hydrochloric acid (tetrahydrofuran / ethanol = 1/1 (mass ratio)) solution 1-2) The collected solution A is titrated with the following solution B using phenolphthalein as an indicator. The point where the slight red color lasts for 30 seconds is taken as the end point of the titration, and the titration amount of the solution B at this time is (x) ml.
Solution B: 0.1N potassium hydroxide (alcoholic) solution 2) Measurement of polymer (C2) 2-1) Polymer (C2) in a range of 4 to 7 g (z) in a 100 ml conical stoppered flask ) Take g. 30 ml of tetrahydrofuran is added thereto to dissolve the polymer (C2).
2-2) 10 ml of the solution A is collected with a whole pipette and added to the Erlenmeyer flask containing the polymer (C2) solution.
2-3) A condensing tube is attached to the Erlenmeyer flask and heated at 60 ° C. for 5 minutes.
2-4) After cooling the Erlenmeyer flask, titrate with solution B using phenolphthalein as an indicator. The point at which the slight red color lasted for 30 seconds is taken as the end point of the titration, and the titration amount of the solution B at this time is (y) ml.
2-5) The epoxy group amount of the polymer (C2) is calculated by the following formula. F in the following formula represents the titer [mmol / l] of the solution B.
Epoxy group amount [mmol / g] = f × 0.1 × ((xy) / 1000) / z × 1000

(7) Amount of carboxyl group The amount of carboxyl group of the obtained polymer (C3) was measured by the following procedure.
1) Into a 200 ml Erlenmeyer flask with a stopper, take (x) g of the polymer (C3) in the range of 12 to 15 g. To this, 100 ml of tetrahydrofuran is added to dissolve the polymer (C3).
2) The solution of the polymer (C3) is titrated with the above solution B using phenolphthalein as an indicator. The point at which the slight red color lasted for 30 seconds is taken as the end point of the titration, and the titration amount of the solution B at this time is (y) ml.
3) The carboxyl group amount of the polymer (C3) is calculated by the following formula. F in the following formula represents the titer [mmol / l] of the solution B.
Amount of carboxyl group [mmol / g] = f × 0.1 × (y / 1000) / xx1000

(8) Compatibility 5 parts of the polymer is blended with 95 parts of the thermoplastic resin (A), and the molding temperature is 280 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.). A molded body having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm was produced under the condition of a mold temperature of 80 ° C.
A thin piece was cut out from the center of the obtained molded body with a frozen microtome, and the thin piece was dyed with ruthenium tetroxide or osmium tetroxide to obtain a sample. As the staining agent, an optimum one was selected according to the type of functional group contained in the polymer.
The obtained sample is photographed using a transmission electron microscope (model name “H-7600”, manufactured by Hitachi High-Technologies Corporation) and dispersed in the thermoplastic resin (A). The volume average domain diameter of the polymer was measured.
When the volume average domain diameter of the polymer was confirmed as phase separation of 0.05 μm or more, the polymer was judged to be incompatible with the thermoplastic resin (A). When the volume average domain diameter of the polymer dispersed in the thermoplastic resin (A) was not confirmed as phase separation of 0.05 μm or more, the polymer was judged to be compatible with the thermoplastic resin (A).

(9) Spiral flow length (melt flowability)
Using the injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.), the spiral flow length of the obtained thermoplastic resin composition was measured at a molding temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure. Under the condition of 50 MPa, the obtained molded body was measured with a width of 15 mm and a thickness of 2 mm.

(10) Charpy impact strength (mechanical properties)
The Charpy impact strength of the resulting molded body (length 80 mm x width 10 mm x thickness 4 mm, with notch) was measured using a Charpy impact tester (model name "Digital Impact Tester", manufactured by Toyo Seiki Seisakusho Co., Ltd.). In accordance with ISO-179-1, the measurement was performed at measurement temperatures of 23 ° C and -30 ° C.

(11) Deflection temperature under load (heat resistance)
The obtained molded body (length 80 mm × width 10 mm × thickness 4 mm) was subjected to an annealing treatment at 120 ° C. for 2 hours, and conformed to ISO 75-2, according to an HDT / VICAT testing machine (model name “No. ”, Manufactured by Yasuda Seiki Co., Ltd.), the deflection temperature under load was measured under the condition of a load of 1.82 MPa.

(12) UL94V test (flame retardant)
The obtained molded body (3.2 mm combustion rod) was subjected to UL-94V test, the combustion time and the number of dripping were measured, and UL determination was performed.
The burning time here means an average value of the flaming burning times of the five molded bodies.
The number of dripping referred to here is the number of moldings in which dropping was observed among the five molded bodies by the first flame contact and the molding in which dropping was observed among the five molded bodies by the second flame contact. Indicates the total number of bodies.
The UL judgment here is based on the judgment standard of the UL-94V test. In addition, the thing which does not correspond to any of "V-0", "V-1", and "V-2" was set to "Fail".

(13) Cantilever test (chemical resistance)
The obtained molded body (length 150 mm × width 25 mm × thickness 2 mm) was annealed at 120 ° C. for 4 hours, and the chemical resistance was measured by the following procedure under the conditions of a temperature of 23 ° C. and a humidity of 50% RH. did.
1) The molded body is supported at two points: an end of the molded body and a position (fulcrum) of about 30 mm from the end. The molded body is supported from above at the end, and the molded body is supported from below at the fulcrum. At this time, the end portion and the fulcrum are in contact with the molded body at a line perpendicular to the length direction of the molded body (not in contact with the surface), and the molded body is kept horizontal.
2) Put a specified load on the other end of the molded body. The stress applied to the compact is 20 MPa, and the load is obtained by the following calculation.
Stress [MPa] = 6 LW / bh ²
L: Distance from fulcrum to load [m]
W: Load [N]
b: Width of molded product [m]
h: Thickness of the molded product [m]
3) Place a 10 mm square filter paper on the upper surface of the fulcrum of the compact (the surface opposite to the fulcrum) to contain gasoline (so that gasoline does not flow out of the filter paper). Since gasoline volatilizes, it is replenished regularly.
4) Measure the time [seconds] from when gasoline is included in the filter paper to when the molded body breaks with a stopwatch.

[Production Example 1] Production of graft polymer (B-1) 96 parts of octamethylcyclotetrasiloxane, 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane, and 2 parts of tetraethoxysilane were mixed to obtain 100 parts of organosiloxane. It was.
To the resulting organosiloxane, 150 parts of deionized water in which 1 part of sodium dodecylbenzenesulfonate was dissolved was added and stirred at 10,000 rpm for 5 minutes with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa. A siloxane latex was obtained.
Subsequently, the obtained siloxane latex was put into a separable flask equipped with a condenser, a thermometer, and a stirrer, and a mixture of 0.2 part of sulfuric acid and 49.8 parts of deionized water was added dropwise over 3 minutes. . Then, after heating to 80 degreeC and hold | maintaining for 7 hours, superposition | polymerization was advanced, it cooled to 25 degreeC, hold | maintained for 6 hours, and neutralized with sodium hydroxide aqueous solution, and polyorganosiloxane type rubber latex was obtained. The resulting polyorganosiloxane rubber latex had a solid content of 29.8%, the resulting polyorganosiloxane rubber had a volume average particle size of 435 nm, and a toluene insoluble content of 30% or more.
A separable flask equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirring device was charged with 266.7 parts (80 parts in terms of solid content) of the obtained polyorganosiloxane rubber latex and 10 parts of deionized water. Thereafter, a mixed solution of 5 parts of allyl methacrylate and 0.11 part of cumene hydroperoxide was added.
The flask is purged with nitrogen through a stream of nitrogen, heated while stirring, and when the liquid temperature reaches 50 ° C., the following reducing agent aqueous solution is added to start the first stage polymerization, and the liquid temperature is increased to 70 ° C. C. for 1 hour.
Reducing agent aqueous solution:
Ferrous sulfate 0.0001 parts Ethylenediaminetetraacetic acid disodium salt 0.0003 parts Rongalite 0.3 parts Deionized water 5 parts Then, the following monomer mixture was added dropwise over 15 minutes.
Monomer mixture:
Phenyl methacrylate 15.0 parts n-octyl mercaptan 0.45 parts t-butyl hydroperoxide 0.3 parts After completion of dropping, the liquid temperature is maintained at 70 ° C. for 1 hour to perform the second stage polymerization, and graft copolymerization Combined (B-1) latex was obtained.
500 parts of an aqueous solution in which 5 parts of calcium acetate are dissolved is heated to 70 ° C. with stirring, and 301 parts of the graft polymer (B-1) latex is gradually dropped into the aqueous solution to solidify, separated, washed with water, and then dried. Thus, a powder of the graft polymer (B-1) was obtained.

[Production Example 2] Production of graft polymer (B-2) A polyorganosiloxane rubber latex 266. obtained in Production Example 1 was placed in a separable flask equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirring device. After adding 7 parts (80 parts in terms of solid content) and 10 parts of deionized water, a mixed solution of 5 parts of allyl methacrylate and 0.11 part of cumene hydroperoxide was added.
The flask is purged with nitrogen through a stream of nitrogen, heated while stirring, and when the liquid temperature reaches 50 ° C., the following reducing agent aqueous solution is added to start the first stage polymerization, and the liquid temperature is increased to 70 ° C. C. for 1 hour.
Reducing agent aqueous solution:
Ferrous sulfate 0.0001 parts Ethylenediaminetetraacetic acid disodium salt 0.0003 parts Rongalite 0.3 parts Deionized water 5 parts Then, the following monomer mixture was added dropwise over 15 minutes.
Monomer mixture:
Methyl methacrylate 13.5 parts n-Butyl acrylate 1.5 parts t-Butyl hydroperoxide 0.3 parts After completion of dropping, the liquid temperature is maintained at 70 ° C. for 1 hour to carry out the second stage polymerization, and graft copolymerization Combined (B-2) latex was obtained.
500 parts of an aqueous solution in which 5 parts of calcium acetate are dissolved is heated to 70 ° C. with stirring, and 301 parts of the graft polymer (B-2) latex is gradually dropped into the aqueous solution to solidify, separated, washed with water, and then dried. Thus, a powder of the graft polymer (B-2) was obtained.

[Production Example 3] Production of graft polymer (B-3) 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of organosiloxane.
To the resulting organosiloxane, 200 parts of deionized water in which 1 part of sodium dodecylbenzenesulfonate was dissolved was added and stirred at 10,000 rpm for 5 minutes with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa. A siloxane latex was obtained.
Next, 10 parts of dodecylbenzenesulfonic acid and 90 parts of deionized water are put into a separable flask equipped with a condenser, a thermometer and a stirrer, heated to 85 ° C., and the resulting siloxane latex is taken over 2 hours. It was dripped. Thereafter, the polymerization was allowed to proceed at 85 ° C. for 3 hours, then cooled to 25 ° C., held for 6 hours, and neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane rubber latex. The resulting polyorganosiloxane rubber latex had a solid content of 18.9%, the obtained polyorganosiloxane rubber had a volume average particle size of 70 nm, and the toluene insoluble content was less than 30%.
423.3 parts (80 parts in terms of solid content) of the obtained polyorganosiloxane rubber latex and 10 parts of deionized water were charged into a separable flask equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device. Thereafter, a mixed solution of 5 parts of allyl methacrylate and 0.11 part of cumene hydroperoxide was added.
The flask is purged with nitrogen through a stream of nitrogen, heated while stirring, and when the liquid temperature reaches 50 ° C., the following reducing agent aqueous solution is added to start the first stage polymerization, and the liquid temperature is increased to 70 ° C. C. for 1 hour.
Reducing agent aqueous solution:
Ferrous sulfate 0.0001 parts Ethylenediaminetetraacetic acid disodium salt 0.0003 parts Rongalite 0.3 parts Deionized water 5 parts Then, the following monomer mixture was added dropwise over 15 minutes.
Monomer mixture:
Methyl methacrylate 13.5 parts n-butyl acrylate 1.5 parts n-octyl mercaptan 0.45 parts t-butyl hydroperoxide 0.3 parts After the completion of dropping, the liquid temperature is maintained at 70 ° C. for 1 hour, and the second stage The graft polymer (B-3) latex was obtained.
After heating 500 parts of an aqueous solution containing 5 parts of calcium acetate to 70 ° C. with stirring, 458.2 parts of the graft polymer (B-3) latex was gradually dropped into the aqueous solution to solidify, separated, washed with water, Drying gave a powder of the graft polymer (B-3).

[Production Example 4] Production of polymer (C1-1) In a separable flask equipped with a thermometer, a nitrogen introduction tube, a cooling tube, and a stirring device, the following emulsifier mixture was added and stirred, The temperature was heated to 60 ° C.
Emulsifier mixture:
Phosphanol RS-610Na (manufactured by Kao Corporation) 1.0 part Deionized water 293 parts Next, the following reducing agent mixture was put into a separable flask.
Reducing agent mixture:
Ferrous sulfate 0.0001 parts Ethylenediaminetetraacetic acid disodium salt 0.0003 parts Rongalite 0.3 parts Deionized water 5 parts The following monomer mixture is dropped into a separable flask over 180 minutes, and then for 60 minutes. The polymerization was completed by stirring to obtain a polymer (C1-1) latex.
Monomer mixture:
Styrene 87.5 parts Phenyl methacrylate 12.5 parts n-octyl mercaptan 0.5 parts t-butyl hydroperoxide 0.2 parts 625 parts of an aqueous solution in which 5 parts of calcium acetate had been dissolved was heated to 83 ° C and stirred. The obtained polymer (C1-1) latex was gradually added dropwise thereto. Next, the temperature was raised to 91 ° C. and held for 5 minutes to coagulate the latex. The coagulated product was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (C1-1).
The polymerization rate of the polymer (C1-1) was 95%, the mass average molecular weight was 49000, and the number average molecular weight was 22000. When compatibility was confirmed using a polycarbonate resin (trade name “Panlite L-1225WS”, manufactured by Teijin Chemicals Ltd.) as the thermoplastic resin (A), the volume average domain diameter of the polymer (C1-1) was It was 0.4 μm and was incompatible with the polycarbonate resin.

[Production Example 5] Production of polymer (C1-2) The following emulsifier mixture was charged into a separable flask equipped with a thermometer, a nitrogen introduction tube, a cooling tube and a stirrer, and stirred in a nitrogen atmosphere. The temperature was heated to 60 ° C.
Emulsifier mixture:
Phosphanol RS-610Na (manufactured by Kao Corporation) 1.0 part Deionized water 293 parts Next, the following reducing agent mixture was put into a separable flask.
Reducing agent mixture:
Ferrous sulfate 0.0001 parts Ethylenediaminetetraacetic acid disodium salt 0.0003 parts Rongalite 0.3 parts Deionized water 5 parts The following monomer mixture is dropped into a separable flask over 180 minutes, and then for 60 minutes. The polymerization was terminated by stirring to obtain a polymer (C1-2) latex.
Monomer mixture:
Styrene 62.5 parts α-methylstyrene 22.5 parts Phenyl methacrylate 14.3 parts Methyl methacrylate 0.7 parts n-octyl mercaptan 0.5 parts t-butyl hydroperoxide 0.2 parts Calcium acetate 5 parts were dissolved 625 parts of the aqueous solution was heated to 83 ° C. and stirred. The obtained polymer (C1-2) latex was gradually added dropwise thereto. Next, the temperature was raised to 91 ° C. and held for 5 minutes to coagulate the latex. The coagulated product was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (C1-2).
The polymerization rate of the polymer (C1-2) was 95%, the mass average molecular weight was 52,000, and the number average molecular weight was 23000. When the compatibility was confirmed using a polycarbonate resin (trade name “Panlite L-1225WS”, manufactured by Teijin Chemicals Ltd.) as the thermoplastic resin (A), the volume average domain diameter of the polymer (C1-2) was It was 0.4 μm and was incompatible with the polycarbonate resin.

[Production Example 6] Production of polymer (C2-1) Production of polymer (C2-1) The following emulsifier mixture was charged into a separable flask equipped with a thermometer, a nitrogen introduction tube, a cooling tube and a stirring device. The inner temperature was heated to 60 ° C. under a nitrogen atmosphere.
Emulsifier mixture:
Phosphanol RS-610Na (manufactured by Kao Corporation) 1.0 part Deionized water 293 parts Next, the following reducing agent mixture was put into a separable flask.
Reducing agent mixture:
Ferrous sulfate 0.0001 parts Ethylenediaminetetraacetic acid disodium salt 0.0003 parts Rongalite 0.3 parts Deionized water 5 parts The following monomer mixture is dropped into a separable flask over 180 minutes, and then for 60 minutes. The polymerization was terminated by stirring to obtain a polymer (C2-1) latex.
Monomer mixture:
Styrene 60.0 parts α-Methylstyrene 22.5 parts Phenyl methacrylate 15.7 parts Methyl methacrylate 0.8 parts Glycidyl methacrylate 1.0 parts n-octyl mercaptan 0.5 parts t-butyl hydroperoxide 0.2 parts Acetic acid 625 parts of an aqueous solution in which 5 parts of calcium had been dissolved was heated to 83 ° C. and stirred. The obtained polymer (C2-1) latex was gradually added dropwise thereto. Next, the temperature was raised to 91 ° C. and held for 5 minutes to coagulate the latex. The coagulated product was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (C2-1).
The polymerization rate of the polymer (C2-1) was 95%, the mass average molecular weight was 52,000, the number average molecular weight was 23000, and the epoxy group amount was 0.04 mmol / g. When compatibility was confirmed using a polycarbonate resin (trade name “Panlite L-1225WS”, manufactured by Teijin Chemicals Ltd.) as the thermoplastic resin (A), the volume average domain diameter of the polymer (C2-1) was It was 0.4 μm and was incompatible with the polycarbonate resin.

[Production Example 7] Production of polymer (C3-1) A polymer (C3-1) was obtained in the same manner as in Production Example 5 except that the monomer mixture was changed to the following composition.
Monomer mixture:
Phenyl methacrylate 75.0 parts Benzyl methacrylate 25.0 parts 3-Mercaptopropionic acid 3.0 parts t-Butyl hydroperoxide 0.2 parts The polymerization rate of the polymer (C3-1) is 99%, and the mass average molecular weight is 14000. The number average molecular weight was 2000, and the carboxyl group amount was 0.2 mmol / g. When compatibility was confirmed using a polycarbonate resin (trade name “Panlite L-1225WS”, manufactured by Teijin Chemicals Ltd.) as the thermoplastic resin (A), the domain of the polymer (C3-1) could not be confirmed. It was compatible with polycarbonate resin.

[Examples 1-7, Comparative Examples 1-6]
A thermoplastic resin (A), a graft polymer (B), a fluidity improver (C), an anti-dripping agent (D), and a flame retardant (E) are mixed at a ratio shown in Table 1, and a twin-screw extruder ( Extrusion molding was performed at a kneading temperature of 270 ° C. using a model name “TEM-35” (manufactured by Toshiba Machine Co., Ltd.) to obtain pellets of a thermoplastic resin composition.
The obtained thermoplastic resin composition was injection molded at a molding temperature of 280 ° C. using an injection molding machine (model name “IS-100”, manufactured by Toshiba Machine Co., Ltd.) to obtain a molded body.

  Table 1 shows the melt flowability of the obtained thermoplastic resin composition, the mechanical properties, heat resistance, flame retardancy, and chemical resistance of the obtained molded article.

The abbreviations in Table 1 are shown below.
(A-1): Aromatic polycarbonate resin (trade name “Panlite L-1225WS”, manufactured by Teijin Chemicals Ltd.)
(B-1): Graft polymer obtained in Production Example 1 (B-2): Graft polymer obtained in Production Example 2 (B-3): Graft polymer obtained in Production Example 3 (C1) -1): Polymer obtained in Production Example 4 (C1-2): Polymer obtained in Production Example 5 (C2-1): Polymer obtained in Production Example 6 (C3-1): Production Polymer (D-1) obtained in Example 7: Polytetrafluoroethylene (trade name “Fluon CD123”, manufactured by Asahi ICI Fluoropolymers, average molecular weight 12 million)
(D-2): Acrylic-modified polytetrafluoroethylene (trade name “Metabrene A-3800”, manufactured by Mitsubishi Rayon Co., Ltd.)
(D-3): Acrylic-modified polytetrafluoroethylene (trade name “METABBRENE A-3750”, manufactured by Mitsubishi Rayon Co., Ltd.)
(E-1): Potassium perfluorobutanesulfonate (trade name “Megafac F-114”, manufactured by Dainippon Ink & Chemicals, Inc.)

As is apparent from Table 1, the thermoplastic resin composition of the present invention was excellent in melt fluidity and excellent in mechanical properties, heat resistance, flame retardancy, and chemical resistance of the resulting molded article.
On the other hand, the thermoplastic resin composition of Comparative Example 1 containing no graft polymer (B), fluidity improver (C), and anti-dripping agent (D) is inferior in melt fluidity, and mechanical properties of the resulting molded article Inferior in flame resistance and chemical resistance. The thermoplastic resin composition of Comparative Example 2 that does not contain the graft polymer (B) of the present invention was inferior in mechanical properties and flame retardancy of the molded article obtained. Thermoplastic resin compositions of Comparative Examples 3 to 6 in which a graft polymer (B) obtained by polymerizing a monomer component not containing phenyl (meth) acrylate (b1) which may have a substituent is blended The product was inferior in mechanical properties and flame retardancy of the resulting molded article.

  The thermoplastic resin composition of the present invention is excellent in melt fluidity, and is excellent in mechanical properties, heat resistance, flame retardancy, and chemical resistance of the obtained molded product. Therefore, the OA equipment, information / communication equipment, electronic / electricity, etc. It can be used in a wide range of fields such as equipment, home appliances, automobile members, and building materials.

Claims (6)

  In the presence of an aromatic polycarbonate resin (A) and a rubbery polymer (br) containing a polyorganosiloxane rubber (bs), a simple substance containing phenyl (meth) acrylate (b1) which may have a substituent. A thermoplastic resin composition comprising a graft polymer (B) obtained by polymerizing a monomer component (b), a fluidity improver (C), and an anti-drip agent (D).   Polymer obtained by polymerizing monomer component containing fluidity improver (C) containing aromatic vinyl monomer (c1) and optionally substituted phenyl (meth) acrylate (c2) The thermoplastic resin composition according to claim 1, comprising (C1). The fluidity improver (C) is an aromatic vinyl monomer (c1), an optionally substituted phenyl (meth) acrylate (c2), and a vinyl monomer (c3) having a functional group (x). And a monomer component containing phenyl (meth) acrylate (c2) which may have a substituent and a functional group (x) obtained by polymerizing a monomer component containing The thermoplastic resin composition of Claim 1 or 2 containing the polymer (C3) obtained by superposing | polymerizing using the compound (c4) which has a functional group (y) which can be performed. The thermoplastic resin composition according to any one of claims 1 to 3 , wherein the dripping inhibitor (D) is acrylic-modified polytetrafluoroethylene. Furthermore, the thermoplastic resin composition of any one of Claims 1-4 containing a flame retardant (E). The molded object obtained by shape | molding the thermoplastic resin composition of any one of Claims 1-5.