JP2011168682A - Process for producing polycarbonate resin composition and molded article obtained from the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing a polycarbonate resin composition having stable productivity upon production, excellent appearance without causing a surface defect such as a silver streak and stable flame retardancy, and to provide a molded article obtained by injection-molding the polycarbonate resin composition. <P>SOLUTION: In the process for producing the polycarbonate resin composition containing a polycarbonate resin, a titanium oxide additive having a surface treated with alumina and an organosiloxane, a flame retardant and a polytetrafluoroethylene as a flame retardant aid, a polytetrafluoroethylene whose crystal structure is a 13/6 helical structure is used when the polytetrafluoroethylene is blended in the polycarbonate resin. The molded article is obtained by injection-molding the resin composition obtained by the process. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a polycarbonate resin composition and a molded product comprising the same, and more specifically, there is no occurrence of surface defects such as silver streak, excellent appearance, excellent impact resistance, and high reflection. The present invention relates to a method for producing a heat-resistant and flame-retardant polycarbonate resin composition and a molded article obtained by molding the obtained polycarbonate resin composition.

  Polycarbonate resin is a general-purpose engineering plastic that has excellent transparency, mechanical strength, electrical properties, heat resistance, dimensional stability, etc., so electrical / electronic equipment parts, OA equipment, machine parts, vehicle parts, building parts, It is used in a wide range of fields such as various containers, leisure goods and miscellaneous goods.

  Among these fields of use, thin film transistors (TFT) and other information display devices such as computers and televisions, backlight reflectors for liquid crystal display devices, illuminated push switches and reflectors for photoelectric switches, etc. Display devices incorporating reflectors that require a high degree of light reflectance are becoming common.

  These light reflecting members that require a high degree of light reflectivity are resin molded bodies formed by molding a polycarbonate resin composition with a high content of fine particles such as titanium oxide in terms of light reflectivity, moldability, and impact strength. Is used.

  In addition, a light reflecting member made of a polycarbonate resin composition has a strong demand for flame retardancy, and a flame retardant by blending an aromatic polycarbonate resin with a halogen compound, a phosphorus compound, a siloxane compound, polytetrafluoroethylene, or the like. Many technologies have been proposed. Recently, in consideration of the environment, a flame retardant resin composition using another flame retardant without using a brominated flame retardant or a phosphorus flame retardant is also desired.

  Examples of flame retardant polycarbonates that have been used in combination with non-phosphorous flame retardants and titanium oxide include Patent Documents 1 and 2, all of which have to contain a flame retardant in order to increase combustibility. The combination caused poor appearance due to silver streaks.

  For example, Patent Document 1 discloses that a resin composition composed of a polycarbonate resin, a silicone-based flame retardant having a polyorganosiloxane polymer supported on silica, and polytetrafluoroethylene has a UL flame retardance of 1.5 mm and V-0. Are listed. However, since it causes poor appearance such as a flow mark at the time of molding with inorganic silica in the flame retardant and silver streak due to the removal of low-viscosity polydimethylsiloxane, it has sufficient performance especially for members that require designability. Is not good.

  Patent Document 2 describes a flame retardant resin composition obtained by adding titanium oxide to polytetrafluoroethylene, an organic metal salt, or a silicone compound to a polycarbonate resin. However, this composition has poor high temperature and residence stability and is significantly inferior in impact properties and appearance.

  Moreover, although patent documents 3-4 are mentioned as an example of the flame-retardant polycarbonate containing a titanium oxide, it cannot be said that all have sufficient performance.

  Patent Document 3 describes a resin composition obtained by adding (B) titanium oxide and (C) 1 to 8 parts by mass of an alkylbenzenesulfonic acid-based antistatic agent to (A) polycarbonate resin. However, since the amount of the alkali metal salt added is large, the molecular weight of the polycarbonate is greatly reduced at the time of molding, and the moldability and flame retardancy are lowered.

  Patent Document 4 describes a resin composition in which polytetrafluoroethylene, an organic metal salt, a silicone compound, and a specific titanium oxide are added to a polycarbonate resin. However, poor appearance such as silver streak depends largely on the state of secondary aggregation of titanium oxide, so satisfactory results cannot be obtained. In addition, poor appearance occurs due to the addition of the silicone compound.

  Regarding the surface treatment of titanium oxide, for example, Patent Document 5 describes the use of acicular titanium oxide obtained by treating polycarbonate resin with polyorganosiloxane. However, simply treating the surface of titanium oxide with polyorganosilane tends to cause appearance defects such as silver streak.

Japanese Patent No. 3124488 JP 2003-183491 A JP-A-11-181267 JP 2006-241262 A JP-A-8-59976

  Under such circumstances, there has been a strong demand for the development of a polycarbonate resin composition that is free from surface defects such as silver streak, has excellent appearance, has excellent impact resistance, and is highly reflective and flame retardant. .

  An object of the present invention is to produce a polycarbonate resin composition having no surface defects such as silver streak, excellent appearance, excellent impact resistance, and highly reflective and flame retardant, and the same. It is to provide a resin molded product, specifically, a light reflecting part.

  In order to solve the above problems, the inventors of the present invention have focused on polytetrafluoroethylene in a combination of titanium oxide that has been subjected to a specific surface treatment and polytetrafluoroethylene as a flame retardant aid. In production, by using polyfluoroethylene having a crystal structure of 13/6 helical structure, the productivity at the time of production is stabilized, and silver streaks caused by polytetrafluoroethylene aggregates in the molded product, etc. The present invention was completed by finding that a polycarbonate resin composition having no appearance of surface defects, excellent appearance, excellent impact resistance, high reflectivity, and stable high flame retardancy can be obtained. It came to do.

  That is, the first invention of the present invention is a polycarbonate resin composition containing a polycarbonate resin, a titanium oxide-based additive surface-treated with alumina and organosiloxane, a flame retardant, and polytetrafluoroethylene as a flame retardant aid) A method for producing a polycarbonate resin composition, wherein polytetrafluoroethylene having a crystal structure of 13/6 helical structure is used when blending polytetrafluoroethylene with a polycarbonate resin. .

Further, according to a second aspect of the present invention, in the first aspect, the polytetrafluoroethylene having a crystal structure of 13/6 helical structure is 60 to 95% by mass with a specific surface area of 0.01 to ⁵ mm ² / g. Is a method for producing a polycarbonate resin composition, comprising a step of mixing a master batch blended with a polycarbonate resin particle having a particle diameter of 180 to 1700 μm to obtain a polycarbonate resin composition.

  According to a third aspect of the present invention, there is provided the polycarbonate resin composition according to the first or second aspect, wherein the polytetrafluoroethylene has a crystal structure of 13/6 helical structure by adjusting the temperature. It is a manufacturing method of a thing.

  The fourth invention of the present invention is the method for producing a polycarbonate resin composition according to the third invention, wherein the polytetrafluoroethylene is maintained at a temperature of 19 ° C. or lower.

The fifth aspect of the present invention is the polytetrafluoroethylene having a crystal structure of 13/6 helical structure in any one of the first to fourth aspects, and a specific surface area of 0.01-5 mm ² / g. In forming a polycarbonate resin composition obtained by mixing a masterbatch blended with a polycarbonate resin powder having a particle size of 180 to 1700 μm having a particle size of 180 to 1700 μm, the crystal structure of polytetrafluoroethylene This is a method for producing a polycarbonate resin composition, characterized by forming a 15/7 helical structure.

  The sixth invention of the present invention is that in the fifth invention, polytetrafluoroethylene having a crystal structure of 13/6 helical structure is blended with the polycarbonate resin granules held at a temperature of 19 ° C. or lower. Is a method for producing a polycarbonate resin composition.

  According to a seventh aspect of the present invention, there is provided the polycarbonate resin composition according to the fifth or sixth aspect, wherein the obtained master batch is held at a temperature of 19 ° C. or lower and then mixed with the polycarbonate resin. It is a manufacturing method of a thing.

In addition, in an eighth aspect of the present invention, in the first aspect, the titanium oxide-based additive has a specific surface area of 0.01 to ⁵ mm ² / g and a particle size of 60 to 95 mass% of 180 to 1700 μm. It is a manufacturing method of the polycarbonate resin composition characterized by including the process of mixing the masterbatch mix | blended with the polycarbonate resin granular material which has.

  The ninth aspect of the present invention is the polycarbonate according to the first aspect, wherein the flame retardant is at least one selected from a condensed phosphate ester flame retardant or a metal salt flame retardant. It is a manufacturing method of a resin composition.

  The tenth invention of the present invention is the method for producing a polycarbonate resin composition according to the ninth invention, wherein the metal salt flame retardant is an alkali (earth) metal salt of an aromatic sulfonate. is there.

  The eleventh invention of the present invention is characterized in that, in the tenth invention, the alkali (earth) metal salt of an aromatic sulfonate is sodium paratoluenesulfonate and / or potassium paratoluenesulfonate. It is a manufacturing method of a polycarbonate resin composition.

The twelfth invention of the present invention is the metal salt flame retardant according to any one of the ninth to eleventh inventions, wherein the specific surface area is 0.01 to ⁵ mm ² / g and 60 to 95% by mass is 180%. It is a manufacturing method of the polycarbonate resin composition characterized by including the process of mixing the masterbatch mix | blended with the polycarbonate resin granular material which has a particle size of -1700 micrometers.

  The thirteenth aspect of the present invention is the polycarbonate resin composition according to the first aspect, wherein the content of the titanium oxide-based additive is 3 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is a manufacturing method of a thing.

  The fourteenth invention of the present invention is characterized in that, in the first invention, the content of polytetrafluoroethylene is 0.05 to 0.9 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is a manufacturing method of a polycarbonate resin composition.

  According to a fifteenth aspect of the present invention, in the ninth aspect, the polycarbonate is characterized in that the content of the condensed phosphate ester flame retardant is 2 to 25 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is a manufacturing method of a resin composition.

  In addition, in a sixteenth aspect of the present invention, in any of the ninth to twelfth aspects, the content of the metal salt flame retardant is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is a manufacturing method of the polycarbonate resin composition characterized by these.

  The seventeenth invention of the present invention is a molded product obtained by injection molding of the polycarbonate resin composition obtained by the production method of any one of the first to sixteenth inventions.

  According to the production method of the present invention, the titanium oxide-based additive surface-treated with alumina and organosiloxane, a flame retardant, and polytetrafluoroethylene as a flame retardant aid have a crystal structure of 13/6 helix. By using the polyfluoroethylene having a structure at the time of blending, the productivity at the time of production is stabilized, and the molded product has no appearance of surface defects such as silver streaks due to polytetrafluoroethylene aggregates, and the appearance In addition, it is possible to produce a polycarbonate resin composition having excellent properties, excellent impact resistance, and highly reflective and flame retardant.

[1. Overview]
The present invention is a method for producing a polycarbonate resin composition containing a polycarbonate resin, a titanium oxide-based additive surface-treated with alumina and organosiloxane, a flame retardant, and polytetrafluoroethylene as a flame retardant aid. In addition, when polytetrafluoroethylene is blended into the polycarbonate resin, polytetrafluoroethylene having a crystal structure of 13/6 helical structure is used.

[2. Polycarbonate resin]
The polycarbonate resin used in the present invention includes an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin, preferably an aromatic polycarbonate resin, specifically an aromatic dihydroxy. An optionally branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting the compound with phosgene or a diester of carbonic acid is used.

  The production method of the aromatic polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used. Further, when the melting method is used, a polycarbonate resin in which the amount of OH groups of terminal groups is adjusted can be used.

  As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, preferably bisphenol A. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  In order to obtain a branched aromatic polycarbonate resin, a part of the above-mentioned aromatic dihydroxy compound is mixed with the following branching agents, that is, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl). Heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1, Polyhydroxy compounds such as 3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxindole (= isa) Tin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. Dose, the aromatic dihydroxy compound is 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

  As the aromatic polycarbonate resin, among the above-mentioned, polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy Polycarbonate copolymers derived from the compounds are preferred. Further, it may be a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure. Furthermore, you may mix and use 2 or more types of the aromatic polycarbonate resin mentioned above.

  In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. For example, m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p- Long chain alkyl substituted phenols and the like.

  The molecular weight of the aromatic polycarbonate resin used in the present invention may be appropriately selected and determined depending on the use, but from the viewpoint of moldability, strength, etc., from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. The converted viscosity average molecular weight [Mv] is preferably 10,000 to 40,000, more preferably 10,000 to 30,000. As described above, when the viscosity average molecular weight is 10,000 or more, the mechanical strength tends to be further improved, and the viscosity average molecular weight is more preferable in the case where it is used for applications requiring high mechanical strength. On the other hand, by setting it as 40,000 or less, there exists a tendency to suppress and improve fluidity | liquidity fall more, and it is more preferable from a viewpoint of easy moldability.

  Among them, the viscosity average molecular weight is preferably 10,000 to 22,000, more preferably 12,000 to 22,000, and particularly preferably 14,000 to 20,000. Two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed. In this case, the viscosity average molecular weight of the mixture is preferably within the above range.

  In the present invention, the polycarbonate resin can be in the form of pellets, flakes, granules, etc., but when adjusting the master batch described later, It is particularly preferable to use one from the viewpoint of improving the dispersibility of the additive.

Specifically, the polycarbonate resin in the form of a granular material has 60 to 95% by mass of JIS.
The particle size distribution measured by a method according to K0069 (screening test method) is 180 to 1700 μm. The particle size distribution falling within this range is preferably 70% by mass or more, particularly preferably 80% by mass or more, preferably 92% by mass or less, and more preferably 90% by mass or less.

In addition, the polycarbonate resin in the form of a granular material preferably has a specific surface area determined by the BET multipoint method of 0.01 m ² / g or more, more preferably 0.1 m ² / g or more, and still more preferably. It is 0.5 m ² / g or more. Further, the upper limit of the specific surface area is preferably 5 mm ² / g or less, more preferably 3 mm ² / g or less, and still more preferably 2 mm ² / g or less.
When a polytetrafluoroethylene, a titanium oxide-based additive, a metal salt-based flame retardant, or the like is made into a master batch using a polycarbonate resin having such a particle size distribution and a specific surface area, it is particularly dispersible. An excellent polycarbonate resin composition of the present invention can be produced.

[3. Titanium oxide additive]
The titanium oxide-based additive in the present invention functions so as to improve the light-shielding property, whiteness, light reflection property and the like of a molded product obtained from the polycarbonate resin composition. The production method, crystal form, average particle size, and the like of titanium oxide used for the titanium oxide-based additive are not particularly limited. There are (1) the sulfuric acid method and (2) the chlorine method in the production method of titanium oxide. However, since titanium oxide produced by the sulfuric acid method tends to be inferior in whiteness of the composition to which this is added, the present invention In order to effectively achieve the above objective, those produced by the chlorine method are preferred.

  The crystal form of titanium oxide includes a rutile type and an anatase type, but a rutile type crystal form is preferred from the viewpoint of light resistance. The average particle size of the titanium oxide-based additive is usually 0.1 to 0.7 μm, preferably 0.1 to 0.4 μm. When the average particle diameter is less than 0.1 μm, the light shielding property of the molded product is poor, and when it exceeds 0.7 μm, the surface of the molded product is roughened or the mechanical strength of the molded product is lowered. In the present invention, two or more types of titanium oxides having different average particle diameters may be mixed and used.

  The titanium oxide-based additive is preferably pretreated with an alumina-based surface treatment agent before being surface-treated with an organosiloxane-based surface treatment agent described later. Alumina hydrate is preferably used as the alumina-based surface treatment agent. Furthermore, it may be pretreated with silicic acid hydrate together with alumina hydrate. The pretreatment method is not particularly limited, and any method can be used. The pretreatment with alumina hydrate and, if necessary, silicic acid hydrate is preferably carried out in the range of 1 to 15% by weight with respect to titanium oxide.

  Titanium oxide pretreated with alumina hydrate and, if necessary, silicic acid hydrate can further improve the thermal stability by surface treatment with an organosiloxane-based surface treatment agent. In addition, it improves the uniform dispersibility and the stability of the dispersed state in the polycarbonate resin composition. As the organosiloxane-based surface treatment agent, a polyorganohydrogensiloxane compound is preferable.

  There are (1) a wet method and (2) a dry method as surface treatment methods using an organosiloxane-based surface treatment agent of titanium oxide. In the wet method, a mixture of an organosiloxane-based surface treatment agent and a solvent is added with alumina hydrate, and if necessary, titanium oxide pretreated with silicic acid hydrate. Furthermore, it is a method of heat-processing at 100-300 degreeC after that. In the dry method, pretreated titanium oxide and polyorganohydrogensiloxanes are mixed with a Henschel mixer or the like in the same manner as described above, and an organic solution of polyorganohydrogensiloxanes is sprayed on the pretreated titanium oxide. And a method of heat-treating at 100 to 300 ° C. The amount of the siloxane-based surface treatment agent is not particularly limited, but in consideration of the reflectivity of titanium oxide, the moldability of the resin composition, etc., usually in the range of 1 to 5% by weight with respect to titanium oxide. is there.

  Content of a titanium oxide type additive is the range of 3-30 mass parts with respect to 100 mass parts of aromatic polycarbonate resin. When the compounding amount of the titanium oxide-based additive is less than 3 parts by mass, the light shielding properties and reflection characteristics of the molded product obtained from the resin composition become insufficient, and when it exceeds 30 parts by mass, the impact resistance of the resin composition Is insufficient. The preferred amount of the titanium oxide-based additive is preferably 5 parts by mass or more, particularly preferably 8 parts by mass or more, preferably 25 parts by mass or less, particularly preferably 20 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Or less. In addition, the mass of a titanium oxide type additive means the total mass also including these processing agents, when the surface treatment is carried out with an alumina hydrate, silicic acid hydrate, and an organosiloxane type surface treating agent.

[4. Polytetrafluoroethylene]
The polytetrafluoroethylene resin used as a flame retardant aid is a polymer or copolymer containing a tetrafluoroethylene structure, and specific examples include tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin Among them, tetrafluoroethylene resin is preferable.
Moreover, as polytetrafluoroethylene resin, what has fibril formation ability is preferable, and dripping prevention property at the time of combustion can be improved remarkably by having fibril formation ability.

  Polytetrafluoroethylene having fibril-forming ability is classified as “type 3” in the ASTM standard. Preferred examples of the polytetrafluoroethylene having fibril forming ability include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., and Polyflon F201L, FA500B and FA500C manufactured by Daikin Chemical Industries, Ltd. In addition, as an aqueous dispersion of polytetrafluoroethylene, Teflon (registered trademark) 31-JR manufactured by Mitsui / Dupont Fluorochemical Co., Ltd., Fullon D-1 manufactured by Daikin Chemical Industries, Ltd. And a polyfluoroethylene compound having a multilayer structure obtained by polymerizing the body. Any type can be used for the resin composition of the present invention. Moreover, these may be used individually by 1 type and may be used in mixture of 2 or more types.

The average particle size of polytetrafluoroethylene is preferably 200 μm or more, more preferably 300 μm or more, still more preferably 400 μm or more, and preferably 600 μm or less, as measured by a method in accordance with JIS K6892. More preferably, it is 550 micrometers or less, More preferably, it is 500 micrometers or less.
The bulk density of polytetrafluoroethylene is a bulk density measured by a method in accordance with JIS K6892, preferably 0.3 g / ml or more, more preferably 0.35 g / ml or more, and still more preferably 0.4 g / ml. ml, preferably 0.6 g / ml or less, more preferably 0.55 g / ml or less, still more preferably 0.5 g / ml or less.

In polytetrafluoroethylene, the tetrafluoroethylene chain is regularly connected, but the carbon main chain is twisted little by little to form a helical structure, and the helical structure changes depending on the temperature. It is a structure that returns to its original value even after 6 revolutions for every 13 pieces, but when it exceeds 19 ° C, the helical structure is unraveled a little and the 15/7 helical structure (even if it is made 7 revolutions for every 15 carbon atoms) Transition to the back structure).
When polytetrafluoroethylene has a 15/7 helical structure, it becomes viscous and dispersibility is lowered, which is likely to cause lumps and classification, and the flame retardancy improving effect tends to be reduced. Therefore, it is preferable that polytetrafluoroethylene is mixed with other components while maintaining a temperature of 19 ° C. or lower and having a 13/6 helical structure.
Specifically, polytetrafluoroethylene is stored at a temperature of 19 ° C. or lower, if necessary, refrigerated and preferably premixed with a part of the polycarbonate resin similarly stored at 19 ° C. or lower to form a master batch. In the same manner as described above, it is preferable to mix and melt-knead the remaining polycarbonate resin and other components.

In order to further improve the appearance of a molded article obtained by injection molding a resin composition containing polytetrafluoroethylene, polytetrafluoroethylene coated with an organic polymer can be used.
By using the organic polymer-coated polytetrafluoroethylene, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated polytetrafluoroethylene can be produced by various known methods. For example, (1) a polytetrafluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and coagulated or spray-dried. (2) In the presence of an aqueous dispersion of polytetrafluoroethylene particles, the monomer constituting the organic polymer is polymerized and then powdered by coagulation or spray drying. (3) A monomer having an ethylenically unsaturated bond is emulsion-polymerized in a dispersion obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles and an aqueous dispersion of organic polymer particles, and then solidified or sprayed. Examples thereof include a method of producing powder by drying.

  As the organic polymer-coated polytetrafluoroethylene, those in which the content ratio of polytetrafluoroethylene in the coated polytetrafluoroethylene is in the range of 40 to 95% by mass are preferable, among which 43 to 80% by mass, What becomes 45-70 mass%, especially 47-60 mass% is preferable. As the specific coated polytetrafluoroethylene of the present invention, for example, Metabrene A-3800, A-3700, KA-5503 manufactured by Mitsubishi Rayon Co., Ltd., Poly TS AD001 manufactured by PIC, or the like can be preferably used. .

  In the present invention, the content of polytetrafluoroethylene is 0.05 parts by mass or more, preferably 0.08 parts by mass, particularly preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin. 0.9 parts by mass or less, preferably 0.7 parts by mass or less, particularly preferably 0.5 parts by mass or less. In the case of coated polytetrafluoroethylene, the amount added corresponds to the amount of pure polytetrafluoroethylene. When the content of polytetrafluoroethylene is less than 0.05 parts by mass, the flame retardancy is not sufficient. On the other hand, when the content exceeds 0.9 parts by mass, the appearance of the molded product tends to deteriorate.

[5. Flame retardants]
Examples of the flame retardant used in the present invention include phosphorus flame retardants, metal salt flame retardants, and silicone flame retardants. Among them, phosphorus flame retardants and metal salt flame retardants are preferably used. . As the phosphorus-based flame retardant, a condensed phosphate ester-based flame retardant is preferable.
[5-1. Condensed phosphate ester flame retardant]

  Preferred examples of the condensed phosphate ester flame retardant in the present invention include phosphorus compounds represented by the following general formula (1).

（式中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、各々独立して、炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基、Ｘはアリーレン基を示し、ｐ、ｑ、ｒおよびｓは、０または１であり、ｋは１から５の整数である。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, X Represents an arylene group, p, q, r and s are 0 or 1, and k is an integer of 1 to 5.)

  In the condensed phosphate ester flame retardant represented by the general formula (1), k is 1 to 5, and k is an average value of a mixture of condensed phosphate esters having different k. X represents an arylene group, and is a divalent group derived from a dihydroxy compound such as resorcinol, hydroquinone, bisphenol A, and the like.

  Specific examples of the condensed phosphate ester flame retardant represented by the general formula (1) include, when resorcinol is used as a dihydroxy compound, phenyl resorcinol polyphosphate, cresyl resorcinol polyphosphate, phenyl cresyl resorcinol Polyphosphate, xylyl resorcin polyphosphate, phenyl-pt-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcin polyphosphate, phenyl isopropylphenyl diisopropylphenyl -Resorcinol polyphosphate etc. are mentioned preferably.

（式中、Ｒ_５、Ｒ_６及びＲ_７は、各々独立して、炭素数１〜６のアルキル基又はアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｈ、ｉ及びｊは、０又は１である。） As the condensed phosphate ester flame retardant, among the general formula (1), a phosphorus flame retardant represented by the following general formula (2) is particularly preferable from the viewpoint of thermal stability.

(Wherein R ₅ , R ₆ and R ₇ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, h, i and j are 0 or 1.)

  The condensed phosphate ester flame retardant represented by the general formula (2) can be produced from phosphorus oxychloride or the like by a known method. Specific examples of the condensed phosphate ester flame retardant represented by the general formula (2) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, and methylphosphonic acid diphenyl ester. Preferred examples thereof include phenylphosphonic acid diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate.

  The content of the condensed phosphate ester flame retardant is 2 parts by mass or more, preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 25 parts by mass or less, preferably 22 with respect to 100 parts by mass of the polycarbonate resin. .5 parts by weight or less, more preferably 20 parts by weight or less. When the blending amount of the phosphorus-based flame retardant is less than 2 parts by mass, the flame retardancy is insufficient, and when it exceeds 25 parts by mass, a remarkable decrease in heat resistance and mechanical properties are caused.

[5-2. Metal salt flame retardant]
Examples of the metal salt flame retardant used in the present invention include an organic metal salt compound and an inorganic metal salt compound, and an organic metal salt compound is preferable from the viewpoint of good dispersibility in an aromatic polycarbonate resin. .
Examples of the organic metal salt compound include organic sulfonic acid metal salts, organic sulfonamide metal salts, organic carboxylic acid metal salts, organic boric acid metal salts, and organic phosphoric acid metal salts. Among these, from the viewpoint of thermal stability when mixed with a polycarbonate resin, organic sulfonic acid metal salts, organic sulfonamide metal salts, and organic phosphoric acid metal salts are preferable, and organic sulfonic acid metal salts, particularly aromatic sulfonic acids, among others. Metal salts are particularly preferred.
The aromatic sulfonic acid metal salt is a metal salt that can be added to polycarbonate to improve flame retardancy. Of these, aromatic alkylsulfonic acid metal salts and derivatives thereof are preferably used.

  The metal of the aromatic sulfonic acid metal salt is preferably an alkali metal or an alkaline earth metal. Examples of the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium. Among them, as alkali metals, sodium and potassium are preferable, and as alkaline earth metals, magnesium, calcium and cesium are preferable from the viewpoint of compatibility with polycarbonate resin and imparting flame retardancy, and aromatic sulfonic acid metal salts are: It may be a mixture of two or more.

Examples of aromatic sulfonic acid metal salts include sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, sodium 4 / 4'-dibromodiphenyl-sulfone-3-sulfone, 4 / 4'-dibromodiphenyl. -Sulfone-3-sulfone potassium, 4-chloro-4'-nitrodiphenyl sulfone-3-sulfonic acid calcium, diphenyl sulfone-3.3'-disulfonic acid disodium, diphenyl sulfone-3.3'-disulfonic acid dipotassium It is done. Among them, examples of non-halogen aromatic sulfonic acid metal salts include sodium dodecylbenzene sulfonate and sodium styrene sulfonate. Among them, sodium paratoluene sulfonate or para Potassium toluenesulfonate is preferably used.
In addition, 1 type may be used for a metal salt type flame retardant, and it may use 2 or more types together by arbitrary combinations and a ratio.

  Content of a metal salt type flame retardant is 0.01-0.5 mass part with respect to 100 mass parts of polycarbonate resin compositions. Thus, the flame retardance of the aromatic polycarbonate resin composition of this invention can be improved by containing a metal salt type flame retardant.

  If the content of the metal salt flame retardant is less than 0.01 parts by mass, the resulting aromatic polycarbonate resin composition has insufficient flame retardancy, and conversely if it exceeds 0.5 parts by mass, the aromatic polycarbonate resin A decrease in thermal stability, a poor appearance of a molded product of the aromatic polycarbonate resin composition, and a decrease in mechanical strength occur. The lower limit of the content is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, particularly preferably 0.07 parts by mass or more, and the upper limit is preferably 0.4 parts by mass or less. Preferably it is 0.3 mass part or less, Most preferably, it is 0.2 mass part or less.

[5-3. Other flame retardants]
As the flame retardant, a silicone compound may be used. As the silicone compound, polyorganosiloxane having a linear or branched structure described in JP-A No. 2006-169451 is preferable. The organic group of the polyorganosiloxane is a hydrocarbon such as an alkyl group having 1 to 20 carbon atoms and a substituted alkyl group, or a vinyl and alkenyl group, a cycloalkyl group, and an aromatic hydrocarbon group such as phenyl or benzyl. It is chosen from among them.
The polydiorganosiloxane may not contain a functional group or may contain a functional group. In the case of a polydiorganosiloxane containing a functional group, the functional group is preferably a methacryl group, an alkoxy group or an epoxy group.

It is preferable that content of the silicone compound in the resin composition of this invention is 0.5-10 mass parts with respect to 100 mass parts of polycarbonate resin. It is preferable that the content of the silicone compound for the flame retardant is in the above range since flame retardancy is improved without impairing the transparency, the appearance of the molded product, the elastic modulus, and the like.
The silicone compound may be used in combination with the metal salt flame retardant.

[6. Other ingredients]
<Elastomer>
The polycarbonate resin composition of the present invention may contain an elastomer as another component. By containing the elastomer, the impact resistance of the polycarbonate resin composition can be improved.

  The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

  The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Ethylene-α olefins such as silicone rubber, butadiene-acrylic composite rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber System rubber, ethylene-acrylic rubber, fluorine rubber and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene -Butadiene rubber is preferred.

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same shall apply hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kaneace (registered trademark, the same applies hereinafter) M-511 "," Kaneace M-600 "," Kaneace M-400 "manufactured by Kaneka Corporation "Kane Ace M-580 , "Kane Ace MR-01", and the like.

  A preferable content of the elastomer is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin. When the amount is less than 0.1 parts by mass, the impact resistance improving effect by the elastomer is insufficient, and when the amount exceeds 10 parts by mass, the appearance defect or the heat resistance of the molded article formed from the polycarbonate resin composition is deteriorated. The lower limit of the content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and the upper limit of the content is preferably 7.5 parts by mass or less, more preferably 5 parts by mass or less. The amount is particularly preferably 4 parts by mass or less.

<Aromatic vinyl-diene-vinyl cyanide copolymer>
The polycarbonate resin composition of the present invention can contain an aromatic vinyl-diene-vinyl cyanide copolymer.
The copolymer comprises an aromatic vinyl monomer and a diene, a vinyl cyanide monomer, and other copolymerizable monomers as required.

  The diene is butadiene, isoprene or the like, preferably a prepolymerized diene rubber, such as polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, etc. These can be mentioned, and these can be used alone or in combination of two or more. Particularly preferably, polybutadiene rubber and / or styrene-butadiene copolymer rubber is used.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, vinyltoluene, and the like, and styrene and / or α-methylstyrene is particularly preferable.

The copolymer composition ratio is not particularly limited, but 10 to 70 parts by weight of a diene rubber is preferable with respect to 100 parts by weight of the copolymer from the viewpoint of molding processability and impact resistance of the obtained resin composition. Similarly, the amount of vinyl cyanide monomer is preferably 8 to 40 parts by weight. The aromatic vinyl monomer is preferably in the range of 20 to 80 parts by weight.
The method for producing the copolymer is not particularly limited, and known methods such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or bulk / suspension polymerization are used.

  The content of the aromatic vinyl-diene-vinyl cyanide copolymer is 5 to 30% by mass with respect to a total of 100% by mass of the polycarbonate resin and the aromatic vinyl-diene-vinyl cyanide copolymer. By containing the aromatic vinyl-diene-vinyl cyanide copolymer in this way, the impact resistance and fluidity of the polycarbonate resin composition of the present invention can be improved. A more preferable content is 7 to 25% by mass.

[7. Other additives]
The transparent polycarbonate resin composition of the present invention may contain one or more selected from various additives as long as the effects of the present invention are not impaired. Examples of such additives include phosphorus stabilizers, phenolic antioxidants, ultraviolet absorbers and mold release agents, fluorescent whitening agents, inorganic fillers, and additives selected from the group consisting of dyes and pigments. It is done.

<Phosphorus stabilizer>
It is preferable to add a phosphorus-based heat stabilizer such as a phosphite ester or a phosphate ester to the resin composition of the present invention in order to improve the thermal stability.

  Examples of phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl Phenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert) Butylphenyl) triesters of phosphorous acid such as octyl phosphite, diesters, monoesters, and the like.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, tetrakis (2,4-di-). tert-butylphenyl) -4,4-diphenylphosphonite and the like.

Among the above phosphorus-based heat stabilizers, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol phosphite and tris (2,4-di-tert-butylphenyl) phosphite are preferred. Among them, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite and Tris (2,4-di-t-butylphenyl) phosphite is particularly preferred.
In addition, a heat stabilizer may be used independently and may be used in combination of 2 or more type.

  The content of the phosphorus stabilizer in the resin composition of the present invention is preferably 0.005 to 0.2 parts by mass, and 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is more preferable. It is preferable for the content of the thermal stabilizer to be in the above-mentioned range since the thermal stability can be improved without causing hydrolysis or the like.

<Phenolic antioxidant>
It is preferable to add a phenolic antioxidant to the resin composition of the present invention.
More specifically, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, tetrakis [ Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-butylidenebis -(3-methyl-6-tert-butylphenyl), triethylene glycol-bis [3- (3-tert-butyl-hydroxy-5-methylphenyl) propionate], and 3,9-bis {2- [3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl Tetraoxaspiro [5,6] undecane. Among these, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane is preferable. These antioxidants may be used alone or in combination of two or more.

  It is preferable that content of the phenolic antioxidant in the resin composition of this invention is 0.02-0.5 mass part with respect to 100 mass parts of polycarbonate resin. This range is preferable because the antioxidant property can be improved without inhibiting the effects of the present invention.

<Ultraviolet absorber>
An ultraviolet absorber can be added to the resin composition of the present invention. Molded articles made of the resin composition of the present invention tend to be yellowish by ultraviolet rays when exposed to light such as sunlight or fluorescent lamps for a long time, but by adding an ultraviolet absorber, It can prevent or delay that a molded article becomes yellowish. Examples of the ultraviolet absorber include benzophenone, benzotriazole, phenyl salicylate, and hindered amine.

  Specific examples of benzophenone ultraviolet absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone. 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4 And '-tetrahydroxy-benzophenone.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1- Methyl-1-phenylmethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2,4-di-tert-butyl- 6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol, 2,2′-methylenebis [ 6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol] and the like.

Specific examples of the phenyl salicylate UV absorber include phenylsaltylate, 2,4-ditertiary-butylphenyl-3,5-ditertiary-butyl-4-hydroxybenzoate, and the like.
Specific examples of the hindered amine ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
An ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together.

  The content of the ultraviolet absorber in the resin composition of the present invention is preferably 0.001 to 1 part by mass, and 0.005 to 0.8 part by mass with respect to 100 parts by mass of the polycarbonate resin. More preferably, it is 0.01-0.5 mass part. When the content of the ultraviolet absorber is in the above range, the weather resistance can be improved without causing a decrease in emission color due to absorption of excitation light of the organic ultraviolet light-emitting phosphor and without causing bleed-out on the surface of the molded product. Therefore, it is preferable.

<Release agent>
The resin composition of the present invention preferably contains a release agent.
A preferable mold release agent is a compound selected from an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, and an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000. Among these, compounds selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters are preferably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. In the present specification, the term “aliphatic carboxylic acid” is used to include alicyclic carboxylic acids. Among the aliphatic carboxylic acids, mono- or dicarboxylic acids having 6 to 36 carbon atoms are preferable, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellic acid, and tetrariacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, or may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.
A mold release agent may be used individually by 1 type, and may use 2 or more types together.

  It is preferable that content of the mold release agent in this invention is 0.01-1 mass part with respect to 100 mass parts of polycarbonate resin. It is preferable for the content of the release agent to be in the above range since there is no decrease in hydrolysis resistance and a release effect can be obtained.

<Fluorescent brightener>
In the present invention, any conventionally known optical brightener may be used as long as the effects of the present invention are not impaired. There are various types of such fluorescent brighteners. Specific examples include coumarin derivatives, naphthotriazolyl stilbene derivatives, benzoxazole derivatives, oxazole derivatives, benzimidazole derivatives, and diaminostilbene-disulfonate derivatives. Can be mentioned. Moreover, as a commercial item, the brand name HAKKOL PSR (3-phenyl-7- (2H-naphtho (1.2-d) -triazol-2-yl) coumarin) from Hocoll Industries, and Hoechst AG, the brand name HOSTALUX KCB ( Benzoxazole derivatives), available from Sumitomo Chemical as trade name WHITEFLOUR PSN CONC (oxazole compounds).

  A preferable content of the fluorescent brightening agent is 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin. If the content is less than 0.005 parts by mass, the whitening effect is small, and if it exceeds 0.1 parts by mass, the yellowing tends to be strong. The content of the fluorescent brightener is more preferably 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

<Inorganic filler>
The polycarbonate resin in the present invention can contain an inorganic filler for the purpose of improving strength and rigidity. The shape of the inorganic filler is arbitrary such as a needle shape, a plate shape, a granular shape or an amorphous shape. Specific examples of inorganic fillers include glass fillers such as glass fibers (chopped strands), glass short fibers (milled fibers), glass flakes, and glass beads; carbon fibers such as carbon fibers, carbon short fibers, carbon nanotubes, and graphite. Fillers: Whiskers such as potassium titanate and aluminum borate; Silicate compounds such as talc, mica, wollastonite, kaolinite, zonotolite, sepiolite, attabargite, montmorillonite, bentonite, smectite; silica, alumina, calcium carbonate, etc. It is done. Among these, talc, mica, wollastonite, and kaolinite are preferable for the purpose of obtaining good surface design. Two or more of these may be used in combination.

  Content of an inorganic filler is 1-60 mass parts with respect to 100 mass parts of polycarbonate resins. When the content of the inorganic filler is less than 1 part by mass, the reinforcing effect may not be sufficient. Moreover, when it exceeds 60 mass parts, an external appearance and impact resistance may be inferior, and fluidity | liquidity may not be enough. The content of the inorganic filler is preferably 3 to 50 parts by mass, particularly preferably 5 to 30 parts by mass.

From the viewpoint of thermal stability when the inorganic filler is contained in the resin composition, a granular material obtained by granulating an average particle diameter of 0.01 to 100 μm with a binder is preferable. The average particle diameter is more preferably 0.05 to 50 μm, and further preferably 0.1 to 25 μm. If the average particle size is too small, the reinforcing effect tends to be insufficient. Conversely, if the average particle size is too large, the product appearance tends to be adversely affected, and the impact resistance may be insufficient. The most preferable average particle diameter of the inorganic filler is 0.2 to 15 μm, particularly 0.3 to 10 μm. Note the average particle size of the inorganic filler in the present invention refers to a D ₅₀ measured by a liquid phase precipitation method using X-ray transmission. As an apparatus capable of performing such measurement, a Sedigraph particle size analyzer (“Model 5100” manufactured by Micromeritics Instruments) can be mentioned.

  Examples of the inorganic filler that is a raw material for the granular inorganic filler include silicate compounds such as wollastonite, talc, mica, zonotlite, sepiolite, attabargite, and kaolinite; complex oxides such as potassium titanate, alumina oxide, and zinc oxide; Carbonate compounds such as calcium carbonate; sulfate compounds such as barium sulfate and calcium sulfate; carbon-based fillers such as graphite; silica; glass-based fillers such as glass flakes and glass beads; aluminum borate and the like. May be used alone or in combination of two or more.

<Dye and pigment>
The polycarbonate resin composition of the present invention may contain a dye / pigment. Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes, and the content of the dye / pigment in the present invention is less than 3 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

  Examples of inorganic pigments include carbon black; sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron brown. , Titanium Cobalt Green, Cobalt Green, Cobalt Blue, Oxide Pigment such as Copper-Chromium Black, Copper-Iron Black, Chromic Acid Pigment such as Yellow Lead and Molybdate Orange; Ferrocyan Pigment such as Bitumen Etc.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

  Of these, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

<Other additives>
In the resin composition of the present invention, an antistatic agent, an antifogging agent, a lubricant / antiblocking agent, a fluidity improving agent, a plasticizer, a dispersant, an antibacterial agent can be used as long as the purpose of the present invention is not impaired. An agent can be contained. These may be used alone or in combination of two or more.

[8. Production method]
The polycarbonate resin composition of the present invention is produced by mixing and melting and kneading each component constituting the polycarbonate resin composition. As the method, a method applied to a conventionally known thermoplastic resin composition can be applied. Examples thereof include a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw or twin-screw extruder, a kneader, and the like. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[8.1 Masterbatch]
<Polycarbonate-polytetrafluoroethylene masterbatch>
The polycarbonate resin composition of the present invention may use a production method in which polycarbonate, the titanium oxide-based additive, the flame retardant, and polytetrafluoroethylene as a flame retardant aid and other necessary components are blended together. However, after obtaining a masterbatch described below, a production method in which the masterbatch is melt-kneaded with the polycarbonate resin composition is preferable.
Specifically, in order to improve the dispersibility of polytetrafluoroethylene in the resin composition and in the molded product, the polycarbonate resin composition of the present invention contains polytetrafluoroethylene having a crystal structure of 13/6 helical structure. By blending into a polycarbonate resin in the form of a granule having a specific surface area of 0.01 to 5 mm ² / g and a particle size of 60 to 95% by mass of 180 to 1700 μm, a larger amount of polytetrafluoro than the final blending amount is obtained. It is preferable to obtain a polycarbonate resin composition by obtaining a polycarbonate-polytetrafluoroethylene masterbatch containing ethylene and then melt-kneading the masterbatch with a required amount of polycarbonate resin in the form of pellets or granules.

Since polytetrafluoroethylene has a crystal structure of 13/6 helix at 19 ° C. or lower, specifically, by adding polytetrafluoroethylene held at a temperature of 19 ° C. or lower to a polycarbonate resin, A tetrafluoroethylene masterbatch can be obtained.
At this time, it is preferable to use a polycarbonate resin held at a temperature of 19 ° C. or less for the polycarbonate resin, more preferably the atmospheric temperature at the time of mixing is 19 ° C. or less, and further, the polycarbonate-polytetra after blending. It is particularly preferred to keep the fluoroethylene masterbatch at 19 ° C. or lower.

  Examples of the method for producing the polycarbonate-polytetrafluoroethylene master batch include a method of mixing using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, and the like, and the use of a drum tumbler is preferred. The blending amount of polytetrafluoroethylene in the polycarbonate-polytetrafluoroethylene masterbatch is preferably 20 to 120 parts by mass, more preferably 25 to 100 parts by mass with respect to 100 parts by mass of the polycarbonate resin. By melting and kneading such a polycarbonate-polytetrafluoroethylene master batch at the time of production, the appearance of the molded product becomes better.

<Polycarbonate-titanium oxide additive masterbatch>
The polycarbonate resin composition of the present invention has a specific surface area of 0.01 to ⁵ mm ² / g for improving the dispersibility of the titanium oxide additive in the resin composition and in the molded product. And a polycarbonate-titanium oxide-based additive containing a larger amount of titanium oxide-based additive than the final blended amount by blending with a polycarbonate resin in the form of a granule having a particle diameter of 180 to 1700 μm with 60 to 95% by mass After obtaining the master batch, it is preferable to melt-knead the master batch with a necessary amount of the polycarbonate resin in the form of pellets or granules and other desired components to obtain a polycarbonate resin composition.

  Examples of the method for producing the polycarbonate-titanium oxide additive master batch include a method of mixing using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, and the like, and the use of a Henschel mixer is preferred. The compounding amount of the titanium oxide-based additive in the polycarbonate-titanium oxide-based additive master batch is preferably 20 to 100 parts by mass, more preferably 25 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate resin. . By melting and kneading such a polycarbonate-titanium oxide additive master batch at the time of production, the appearance of the molded product becomes better.

<Polycarbonate-metal salt flame retardant master batch>
The polycarbonate resin composition of the present invention improves the dispersibility of the metal salt flame retardant in the resin composition and the molded article, and as a result, in order to obtain stable flammability, the metal salt flame retardant is used with a specific surface area. Is contained in a polycarbonate resin in the form of a granule having a particle size of 0.01 to 5 mm ² / g and 60 to 95% by mass of 180 to 1700 μm, so that a larger amount of metal salt flame retardant than the final compounding amount is added. A production method for obtaining a polycarbonate resin composition by melt-kneading the master batch with a polycarbonate resin after obtaining the contained polycarbonate-metal salt flame retardant master batch is suitably used.

  Examples of the method for producing the polycarbonate-metal salt flame retardant masterbatch include a method of mixing using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, etc., but it is preferable to use a Henschel mixer. The compounding amount of the metal salt flame retardant in the polycarbonate-metal salt flame retardant master batch is 0.5 parts by mass or more, preferably 0.8 parts by mass or more, more preferably 1 mass, per 100 parts by mass of the polycarbonate resin. Part or more, 5 parts by weight or less, preferably 4 parts by weight or less, more preferably 3 parts by weight or less.

  The polycarbonate-metal salt flame retardant master batch is melt-kneaded together with the polycarbonate-polytetrafluoroethylene master batch and / or the polycarbonate-titanium oxide additive master batch to improve the appearance of the molded product. In addition, variations in combustibility can be suppressed.

[9. Molding method]
The polycarbonate resin composition of the present invention can be used as a molding material for various molded products. In this case, an injection molding method is suitably applied as the applicable molding method. The injection molding method used here was an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold. A wide range of injection methods including molding methods, foam molding (including supercritical fluid) methods, insert molding methods, IMC (in-mold coating molding) molding methods, and the like.

[10. Polycarbonate resin molded body]
The molded product of the present invention is formed by molding the above-described polycarbonate resin composition of the present invention, and is excellent in light resistance, light shielding properties, light reflectivity, hue, flame retardancy, molding stability, and polycarbonate. Since the impact resistance, heat resistance, dimensional stability, appearance characteristics, etc. inherent to the resin are maintained at the same time, taking advantage of these features, a light reflector for backlight of a liquid crystal display device, a light reflection frame or light It can be used widely as a light reflecting member for lighting devices such as reflective sheets, electrical / electronic devices, advertising lamps, and automotive equipment such as automotive meter panels, especially its excellent flame retardancy and light reflectivity. From the viewpoint of impact resistance, it is useful for light reflectors for liquid crystal backlights and reflector frame parts.

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples and comparative examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
The measurement / evaluation methods and materials used in Examples and Comparative Examples are as follows.

1. Measurement / Evaluation Method [Flame Retardancy Evaluation]
The flame retardancy of the polycarbonate resin composition of the present invention was evaluated by conditioning a test piece for UL test obtained by the method described below for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. It was performed in accordance with UL94 test (combustion test of plastic materials for parts of equipment) defined by LS Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied. In addition, in the postscript Table 3 which shows an evaluation result, it describes with "flame retardance".

[Appearance of molded product]
The molded product appearance evaluation of the present invention is performed by counting the number of silver streaks on the surface of five flat plate plates obtained by the method described below, obtaining an average value per sheet, and the following five stages A to E: Classification and evaluation.
A: Silver streak number 0-2 B: Silver streak number 3-5 C: Silver streak number 6-8 D: Silver streak number 9-11 E: Silver streak number 12 or more

2. Materials used [Aromatic polycarbonate resin (A)]
(A1) Poly-4,4-isopropylidene diphenyl carbonate:
Product name “Iupilon (registered trademark) S-3000F” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 21,000, polycarbonate resin in the form of granular material, specific surface area 1.24 mm ² / g, particle size of 180-1700 μm Is 83 mass%
(A2) Poly-4,4-isopropylidene diphenyl carbonate:
Product name “Iupilon (registered trademark) S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 21,000, polycarbonate resin in pellet shape, specific surface area 0.003 mm ² / g, particle size of 180-1700 μm is 1 Less than mass% (substantially 0 mass%)

[Titanium oxide additive (B)]
Product name “Kronos 2233” manufactured by Kronos
(Average particle size: 0.20 μm)

[Flame Retardant (C)]
(C1) Condensed phosphate ester flame retardant:
Resorcinol bis-2,6-xylenyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd., trade name “PX-200”
(C2) Metal salt flame retardant-1: Sodium paratoluenesulfonate, manufactured by Cambridge International, trade name “Chemguard-NATS”
(C3) Metal salt flame retardant-2: potassium paratoluenesulfonate, manufactured by Cambridge International, trade name “Chemguard-PABS”

[Polytetrafluoroethylene (D)]
PTFE-1 and PTFE-2 in which the following polytetrafluoroethylene having fibril-forming ability was held under either of the following conditions (1) or (2) were used.
Product name “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemicals, Inc.
Average particle size 470 μm, bulk density 0.47 g / ml
Condition (1): held at a temperature of 19 ° C. or less (PTFE-1)
(The crystal structure is a 13/6 helical structure)
Condition (2): held at a temperature exceeding 19 ° C. (PTFE-2)
(The crystal structure is a 15/7 helical structure)

[Polycarbonate-polytetrafluoroethylene masterbatch (E) (hereinafter referred to as PC-PTFE masterbatch)]
(E1) PC-PTFE masterbatch-1: A masterbatch blended under any of the following conditions (a) to (d) was used.
Condition (a): 60% by mass of the above granular material-shaped polycarbonate resin (A1) held at a temperature exceeding 19 ° C. and 40% by mass of polytetrafluoroethylene (PTFE-1) held at a temperature of 19 ° C. or less. Blended for 5 minutes with a tumbler mixer Condition (b): 60% by mass of the above polycarbonate resin (A1) in the form of a granular material held at a temperature of 19 ° C. or less and polytetrafluoro held at a temperature of 19 ° C. or less A blend of 40% by mass of ethylene (PTFE-1) with a tumbler mixer in an atmosphere of 19 ° C. or less for 5 minutes Condition (c): An atmosphere of 19 ° C. or less obtained by blending under the above condition (b) Condition (d): 60% by mass of the above granular material-shaped polycarbonate resin (A1) held at a temperature exceeding 19 ° C. and exceeding 19 ° C. Blended with polytetrafluoroethylene (PTFE-2) 40% by mass with a tumbler mixer for 5 minutes (E2) PC-PTFE masterbatch-2: Use a masterbatch blended under the following conditions (e) did.
Condition (e): 80% by mass of the above granular material-shaped polycarbonate resin (A1) held at a temperature exceeding 19 ° C. and 20% by mass of polytetrafluoroethylene (PTFE-1) held at a temperature of 19 ° C. or less. Blended for 5 minutes with a tumbler mixer

[Polycarbonate-TiO ₂ masterbatch (F)]
(F1) PC-TiO ₂ Masterbatch-1: 70% by mass of powdery polycarbonate resin (A1) and 30% by mass of titanium oxide-based additive (B) blended for 1 minute using a Henschel mixer (F2) PC-TiO ₂ masterbatch-2: 80% by mass of powdery polycarbonate resin (A1) and 20% by mass of titanium oxide-based additive (B) blended in a Henschel mixer for 1 minute

[Polycarbonate-Metal Salt Masterbatch (G)]
(G1) PC-metal salt masterbatch-1: 99% by mass of powdery polycarbonate resin (A1) and 1% by mass of metal salt flame retardant (C2) blended with a Henschel mixer for 1 minute (G2) PC-metal salt masterbatch-2: 99% by mass of powdery polycarbonate resin (A1) and 1% by mass of metal salt flame retardant (C3) blended for 1 minute using a Henschel mixer

[Phosphorus stabilizer (H)]
Tris (2,4-di-tert-butylphenyl) phosphite:
Product name “ADK STAB 2112” manufactured by ADEKA

(Examples 1-27, Comparative Examples 1-4)
(A) to (H) After using the materials shown in Tables 2 to 4 as ingredients and blending each component in the proportions (all mass%) shown in Tables 2 to 4, and mixing for 20 minutes in a tumbler Supplied to a Nippon Steel Works twin screw extruder (TEX30HSST) equipped with 1 vent, kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C., and melted extruded in a strand shape The resin composition was quenched in a water tank and pelletized using a pelletizer to obtain a polycarbonate resin composition pellet.

  Next, after drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, the cylinder temperature is 280 ° C. and the mold temperature is 80 ° C. The plate-shaped test piece (150 mm × 100 mm × 3 mm thickness) was molded by injection molding under the following conditions.

Similarly, after the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, the cylinder temperature was 280 ° C. and the mold temperature was 80 ° C. The test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 2 mm was molded under the conditions described above.
The evaluation results are shown in Tables 2 to 4.

It can be seen that the resin compositions described in the examples have better productivity at the time of melt-kneading and better appearance of the molded product than the comparative examples. Moreover, the resin composition using the polycarbonate resin-TiO ₂ masterbatch had a smaller number of silver streaks than the example in which the masterbatch was not used, and the appearance of the molded product was good.

  Although the combustibility (2 mm thickness) of the resin compositions of Examples 1 to 27 and Comparative Examples 1 to 4 were all V-0, Example 17 using a polycarbonate resin-metal salt masterbatch therein. -21, Example 23, and Example 25 had little combustible variation. It can be seen that the effect of increasing the dispersibility of the flame retardant appears.

  On the other hand, the resin composition of Comparative Example 4 uses a polycarbonate resin-polytetrafluoroethylene masterbatch. However, since polytetrafluoroethylene held at a temperature exceeding 19 ° C. was used, it was V-0 at a thickness of 2 mm. However, the flammability variation was large compared to the examples. The production stability was better than those of Comparative Examples 1 to 3.

  According to the production method of the present invention, a titanium oxide-based flame retardant surface-treated with alumina and organosiloxane, and a polytetrafluoroethylene which is a flame retardant aid, have a polycrystal having a 13/6 helical structure. By using fluoroethylene at the time of blending, the productivity at the time of production is stable, and there is no occurrence of surface defects such as silver streaks due to polytetrafluoroethylene aggregates in the molded product, and the appearance is excellent. Further, it is possible to produce a highly reflective and flame retardant polycarbonate resin composition having excellent impact resistance, so that a light reflecting plate, a light reflecting frame or a light reflecting sheet for a backlight of a liquid crystal display device It can be widely used as a light reflecting member for lighting equipment such as electric / electronic equipment, advertising lights, and automotive equipment such as automotive meter panels. , Industrial applicability is very high.

Claims (17)

  A method for producing a polycarbonate resin composition comprising a polycarbonate resin, a titanium oxide-based additive surface-treated with alumina and an organosiloxane, a flame retardant, and polytetrafluoroethylene as a flame retardant aid, comprising: A method for producing a polycarbonate resin composition, wherein polytetrafluoroethylene having a crystal structure of 13/6 helical structure is used when blending polytetrafluoroethylene. Polytetrafluoroethylene having a crystal structure of 13/6 helical structure was blended with a polycarbonate resin granule having a specific surface area of 0.01 to ⁵ mm ² / g and a particle size of 60 to 95% by mass of 180 to 1700 μm. The method for producing a polycarbonate resin composition according to claim 1, further comprising a step of mixing the master batch to obtain a polycarbonate resin composition.   The process for producing a polycarbonate resin composition according to claim 1 or 2, wherein the crystal structure of polytetrafluoroethylene is changed to a 13/6 helical structure by adjusting the temperature.   The method for producing a polycarbonate resin composition according to claim 3, wherein the polytetrafluoroethylene is maintained at a temperature of 19 ° C or lower. Polytetrafluoroethylene having a crystal structure of 13/6 helical structure) is blended with a polycarbonate resin particle having a specific surface area of 0.01 to ⁵ mm ² / g and a particle size of 60 to 95% by mass of 180 to 1700 μm. When molding the polycarbonate resin composition obtained by mixing the masterbatch, the crystal structure of polytetrafluoroethylene is molded into a 15/7 helical structure, and molded according to any one of claims 1 to 4. 2. A method for producing a polycarbonate resin composition according to item 1.   6. The polycarbonate resin composition according to claim 5, wherein polytetrafluoroethylene having a crystal structure of 13/6 helical structure is blended with the polycarbonate resin particles held at a temperature of 19 ° C. or lower. Method.   The method for producing a polycarbonate resin composition according to claim 5 or 6, wherein the obtained master batch is held at a temperature of 19 ° C or lower and then mixed with the polycarbonate resin. Including a step of mixing a master batch in which a titanium oxide-based additive is blended with a polycarbonate resin particle having a specific surface area of 0.01 to ⁵ mm ² / g and a particle size of 60 to 95% by mass of 180 to 1700 μm. The manufacturing method of the polycarbonate resin composition of Claim 1 characterized by the above-mentioned.   The method for producing a polycarbonate resin composition according to claim 1, wherein the flame retardant is at least one selected from a condensed phosphate ester flame retardant or a metal salt flame retardant.   The method for producing a polycarbonate resin composition according to claim 9, wherein the metal salt flame retardant is an alkali (earth) metal salt of an aromatic sulfonate.   The method for producing a polycarbonate resin composition according to claim 10, wherein the alkali (earth) metal salt of an aromatic sulfonate is sodium paratoluenesulfonate and / or potassium paratoluenesulfonate. Including a step of mixing a masterbatch in which a metal salt flame retardant is blended with a polycarbonate resin granule having a specific surface area of 0.01 to ⁵ mm ² / g and a particle size of 60 to 95% by mass of 180 to 1700 μm. The manufacturing method of the polycarbonate resin composition of any one of Claims 9-11 characterized by the above-mentioned.   Content of a titanium oxide type additive is 3-30 mass parts with respect to 100 mass parts of polycarbonate resins, The manufacturing method of the polycarbonate resin composition of Claim 1 characterized by the above-mentioned.   2. The method for producing a polycarbonate resin composition according to claim 1, wherein the content of polytetrafluoroethylene is 0.05 to 0.9 parts by mass with respect to 100 parts by mass of the polycarbonate resin.   The method for producing a polycarbonate resin composition according to claim 9, wherein the content of the condensed phosphate ester flame retardant is 2 to 25 parts by mass with respect to 100 parts by mass of the polycarbonate resin.   13. The polycarbonate resin composition according to claim 9, wherein the content of the metal salt flame retardant is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Manufacturing method.   The molded article obtained by injection-molding the polycarbonate resin composition obtained by the manufacturing method of any one of Claims 1-16.