JP2011116839A - Flame-retardant light-diffusive polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant light-diffusive polycarbonate resin composition that has excellent flame retardant characteristics while retaining high light transmittance and diffusibility. <P>SOLUTION: The flame-retardant light-diffusive polycarbonate resin composition includes, based on (A) 100 pts.wt. of an aromatic polycarbonate resin (component A) having branch structure with a proportion of the branch structure of 0.7-1.5 mol%, (B) 0.05-7.0 pts.wt. of a silicone compound (component B) having an aromatic group, (C) 0.005-1.0 pt.wt. of an organometallic salt compound (component C), and (D) 0.005-15.0 pts.wt. of a light diffusing agent (component D). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to a flame retardant light diffusing polycarbonate resin composition having excellent flame retardant properties while maintaining high light transmittance and diffusibility.

  Disperse organic and inorganic light diffusing agents in transparent resins such as aromatic polycarbonate resin, acrylic resin, and styrene resin for applications that require light diffusibility such as various lighting covers, display covers, automobile meters, and various nameplates. The material used is widely used. Among such transparent resins, aromatic polycarbonate resins are particularly widely used as resins having excellent mechanical properties, heat resistance, weather resistance, and high light transmittance. Examples of the light diffusing agent include organic particles having a crosslinked structure, and more specifically, crosslinked acrylic particles, crosslinked silicone particles, and crosslinked styrene particles. Further, inorganic particles such as inorganic particles such as calcium carbonate, barium sulfate, aluminum hydroxide, silicon dioxide, titanium oxide, and calcium fluoride, or short glass fibers can be used. In particular, organic particles are excellent in surface smoothness of molded products as compared with inorganic particles and can achieve a high appearance of molded products, and thus can be applied to a wide range of applications.

  In these applications, in recent years, it has been said that light diffusing polycarbonate resin has a high difficulty level of V-0 in UL Standard (Underwriters Laboratory Standards) -94, because fire igniting promotes the spread of fire in resin lighting covers. Flammability is starting to be demanded. Aromatic polycarbonate resin has excellent flame retardant properties compared to the flame retardant properties of transparent resins such as acrylic resin and styrene resin, but in order to obtain advanced flame retardant properties (V-0) It is necessary to prevent dripping of the resin (see Patent Documents 1 and 2). However, when polytetrafluoroethylene, a commonly known drip inhibitor, is added to the aromatic polycarbonate resin, the polytetrafluoroethylene and the aromatic polycarbonate resin are incompatible with each other, so that the total light transmission of the molded product is achieved. There is a problem that the rate decreases. Further, a resin composition comprising a polycarbonate having a branched structure and an organic metal salt (see Patent Document 3), and a resin composition comprising a polycarbonate having a branched structure, an organic metal salt and a specific siloxane compound (see Patent Documents 4 and 5). Are also specifically described. Although the composition which maintains the outstanding flame retardance and transparency by these is provided, the further flame retardance improvement is calculated | required by diversification of a polycarbonate use and the thinning of a product. Moreover, these do not describe optical characteristics representing total light transmittance and diffusibility, but only describe transparency. Various flame retardant polycarbonate resin compositions have been developed depending on the application, and the flame retardant level varies, but it is necessary to raise the flame retardant level of each material as much as possible, for example, in the electrical application With regard to the UL94 standard widely used as a flammability index, if the minimum thickness of a specimen that can achieve the flame retardance rank V-0 of the material can be reduced even by 0.1 mm, the use as a flame retardant material will be expanded and its effect Is very big. Also, if the amount of flame retardant used can be reduced even if the flame retardant level is the same, reducing the amount of gas generated during processing, improving workability, improving quality stability, and improving various physical properties. Connected. Therefore, the achievement of these issues is highly demanded.

JP 2009-108281 A JP 2006-143949 A Japanese Patent No. 3129374 Japanese Patent No. 3163596 JP 2007-31583 A

  An object of the present invention is to provide a flame retardant light diffusing polycarbonate resin composition having excellent flame retardant properties while maintaining high light transmittance and diffusibility.

  As a result of intensive research aimed at achieving the above object, the present inventors have achieved a desired high light transmission by combining a specific amount of a polycarbonate resin having a branched structure with a limited branching rate, a flame retardant, and a light diffusing agent. It has been found that a flame retardant light diffusing polycarbonate resin composition having excellent flame retardancy can be obtained while maintaining the rate and diffusivity, and has reached the present invention.

  That is, according to the present invention, (1) (A) 100 parts by weight of an aromatic polycarbonate resin (component A) having a branched structure with a branching ratio of 0.7 to 1.5 mol%, (B) aromatic group 0.05 to 7.0 parts by weight of a silicone compound (component B), (C) an organometallic salt compound (component C) 0.005 to 1.0 parts by weight, and (D) a light diffusing agent (component D) A flame retardant light diffusing polycarbonate resin composition comprising 0.005 to 15.0 parts by weight is provided.

Hereinafter, the present invention will be specifically described.
<A component: aromatic polycarbonate resin>
The aromatic polycarbonate resin having a branching ratio of 0.7 to 1.5 mol% used as the A component of the present invention is an aromatic polycarbonate resin having a branched structure (A-1 component) or directly with the A-1 component. If it is a mixture with a chain aromatic polycarbonate resin (A-2 component) and the branching ratio as a whole of the A component satisfies 0.7 to 1.5 mol%, the branching ratio is 0.7 to 1.5 mol. An aromatic polycarbonate resin having a branched structure outside the range of% may be included.

From the viewpoint of imparting more excellent flame retardancy, the A component preferably contains 20% to 100% by weight of the A-1 component, more preferably 70% to 100% by weight, more preferably 100% by weight. Is more preferable. The branching ratio as the whole component A is 0.7 to 1.5 mol%, preferably 0.7 to 1.3 mol%, more preferably 0.85 to 1.2 mol%. The branching rate is the number of moles of the structural unit derived from the branching agent to the total number of moles of the structural unit derived from the dihydric phenol used for the production included in the entire resin (the number of moles of the structural unit derived from the branching agent / derived from the dihydric phenol. The total number of moles of structural units × 100 (expressed in mol%)), and the branching ratio can be measured by ¹ H-NMR measurement.

  If the branching ratio is low, satisfactory branching characteristics cannot be obtained, the melt tension is too low, flame retardancy related to the composition, especially drip prevention, is difficult to be exhibited, and extrusion molding and blow molding are difficult. It is not preferable. On the other hand, if the branching ratio is high, the polymer is crosslinked, a gel is generated, and the impact resistance of the polymer is lowered. Further, if the branching rate is too high, the surface of the molded product is likely to be clouded, and there is a problem that the cylinder temperature must be increased or the injection speed must be adjusted more finely in order to eliminate this.

  When the branching rate of the A component of the present invention is Z mol% and the melt tension at 280 ° C. is Y, the relationship between Z and Y is 3.8Z−2.4 ≦ Y ≦ 3.8Z + 4.5. More preferably, it is 3.8Z-1.8 <= Y <= 3.8Z + 3.9. If Y <3.8Z-2.4, there is a problem that drip is likely to occur in the flame retardancy test and sufficient flame retardancy cannot be obtained, and the melt tension is too low to easily cause drawdown, Extrusion molding and blow molding may not be easily performed, which is not preferable. Further, if Y 1> 3.8Z + 4.5, the melt tension is too high, the fluidity is poor and the moldability is poor, and the surface state of the molded product is deteriorated. The melt tension can be measured as a tension generated at a temperature of 280 ° C., an extrusion temperature of 10 mm / min, a tensile speed of 157 mm / s, and an orifice L / D = 8 / 2.1.

The viscosity average molecular weight of the component A of the present invention is preferably in the range of 10,000 to 50,000,
16,000 to 30,000 is more preferred, the range of 18,000 to 28,000 is even more preferred, and the range of 19,000 to 26,000 is most preferred. If the molecular weight exceeds 50,000, the melt tension may be too high and the moldability may be inferior. If the molecular weight is less than 10,000, the drip prevention effect when the molded piece is burned becomes insufficient. It may be difficult to exhibit excellent flame retardancy, or melt tension may be too low to make extrusion or blow molding difficult. In addition, the aromatic polycarbonate resin used as the component A of the present invention may be mixed with one or more aromatic polycarbonate resins having a branched structure so that the molecular weight satisfies the aforementioned preferable molecular weight range. . In this case, it is naturally possible to mix a polycarbonate resin having a branched structure whose viscosity average molecular weight is outside the above preferred molecular weight range. In addition, the viscosity average molecular weight as used in the field of this invention calculates | requires first using the Ostwald viscometer from the solution which melt | dissolved 0.7 g of polycarbonate resins in 20 ml of methylene chloride with the specific viscosity computed by following Formula,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  In the component A of the present invention, the total N (nitrogen) amount in the resin is preferably 0 to 7 ppm, more preferably 0 to 5 ppm. The total N (nitrogen) content in the resin can be measured using a TN-10 type trace nitrogen analyzer (chemiluminescence method) manufactured by Mitsubishi Chemical Corporation.

  The total Cl (chlorine) amount is preferably 0 to 200 ppm, more preferably 0 to 150 ppm. If the total N amount in the polycarbonate resin having a branched structure exceeds 7 ppm or the total Cl amount exceeds 200 ppm, the thermal stability is deteriorated, which is not preferable.

  The aromatic polycarbonate resin having a branched structure which is the A-1 component of the present invention is obtained by an interfacial polymerization reaction method performed in the presence of an organic solvent using a dihydric phenol, a branching agent, a monohydric phenol and phosgene.

  Representative examples of the dihydric phenol used to obtain the polycarbonate resin having a branched structure of the present invention are 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), hydroquinone, resorcinol, 4, 4′-biphenol, 1,1-bis (4hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1 -Bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2, 2-bis (4-hydroxyphenyl) pentane, 4,4 ′-(p-phenylenediisopropylidene) diphe 4,4 ′-(m-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxy Phenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide and the like. These may be used alone or in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is preferable.

  Representative examples of tri- or higher-valent phenols (branching agents) used in the present invention include 1,1,1-tris (4-hydroxyphenyl) ethane, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 2,6- Bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, tetra (4-hydroxyphenyl) methane, trisphenol, bis (2,4-dihydroxylphenyl) ketone, phloroglucin, phloroglucid, isantine bisphenol, Examples include 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, and pyromellitic acid. These may be used alone or in combination of two or more. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferable.

  The monohydric phenol (terminal terminator) used for the production of the polycarbonate resin having a branched structure which is the A-1 component of the present invention may have any structure and is not particularly limited. For example, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, 4-hydroxybenzophenone, phenol and the like can be mentioned. These may be used alone or in combination of two or more. Of these, p-tert-butylphenol is preferable.

  That is, the polycarbonate having a branched structure which is the A-1 component of the present invention is a structure in which the branched structure portion is derived from 1,1,1-tris (4-hydroxyphenyl) ethane, and the branched structure portion is excluded. The straight chain structure portion is preferably a structure derived from bisphenol A and the terminal is preferably a structure derived from p-tert-butylphenol.

  The branched polycarbonate resin of the present invention is preferably produced by the following method. That is, phosgene was blown into an alkaline aqueous solution in which a dihydric phenol compound and a branching agent were dissolved in the presence of an organic solvent to obtain a polycarbonate oligomer. It is the method characterized by making it superpose | polymerize.

  Further, as a reaction catalyst for promoting the reaction, for example, tertiary amine such as triethylamine, tributylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium A catalyst such as a compound can also be used. The reaction catalyst is preferably 0.002 mol% or less, more preferably 0.001 mol% or less, based on the dihydric phenol compound. In particular, the above reaction is preferably carried out without a catalyst. When it exceeds 0.002 mol%, the melt tension becomes too high with respect to the amount of the branching agent, or a gel is formed. In addition, the catalyst reacts with the chloroformate group to increase the number of thermally unstable urethane bonds, and the remaining catalyst increases the total N content in the branched polycarbonate resin, resulting in impact resistance and transparency. This is not preferable because the heat resistance is lowered. Therefore, it is particularly preferable to carry out the above reaction without a catalyst. At that time, the reaction temperature is usually preferably 0 to 40 ° C, more preferably 15 to 38 ° C. The reaction time is about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9.0 or more, more preferably 11.0 to 13.8.

  There is no particular limitation on the method of emulsifying the monohydric phenols after adding the above-mentioned interfacial polymerization reaction, but examples include a method of stirring with a stirrer or a method of adding an alkaline aqueous solution. There are simple stirring devices such as paddles, propellers, turbines or chi-type blades, high-speed stirrers such as homogenizers, mixers and homomixers, static mixers, colloid mills, orifice mixers, flow jet mixers, ultrasonic emulsifiers and the like. Of these, homomixers, static mixers and the like are preferably used in the polymerization without catalyst.

  Next, the branched polycarbonate resin organic solvent solution is washed, granulated, and dried to obtain the branched polycarbonate resin (powder) of the present invention. Further, the powder is melt extruded and pelletized to obtain the branched polycarbonate resin (pellet) of the present invention. Cleaning, granulation, drying and the like are not particularly limited, and known methods can be employed.

  In order to reduce the total Cl content in the polycarbonate resin having a branched structure, dichloromethane (methylene chloride), dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, used as a solvent during the reaction, It is necessary to remove chlorinated hydrocarbon solvents such as dichlorobenzene. For example, it is possible to sufficiently dry the polycarbonate resin powder and pellets having a branched structure.

  The aromatic polycarbonate having a branched structure of the present invention is preferably substantially free of halogen atoms. The phrase “substantially free of halogen atoms” means that the molecule does not contain halogen-substituted dihydric phenols, etc., and a trace amount of solvent (halogenated hydrocarbon) remaining in the above aromatic polycarbonate production method or carbonate precursor Not even the body.

  The linear aromatic polycarbonate resin that is component A-2 is usually obtained by reacting a dihydric phenol and a carbonate precursor by interfacial polycondensation or melt transesterification, as well as a carbonate prepolymer by solid-phase ester. It is obtained by polymerizing by an exchange method or polymerized by a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl). Phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) ), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3 -Isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4- Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4- Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4 -Hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis ( -Hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3- Bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ester, etc., and these can be used alone or in admixture of two or more.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) A homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene In particular, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl Copolymers of rucyclohexane and bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. Is done. Among these, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is more preferable.

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like. Of these, phosgene or diphenyl carbonate is industrially advantageous.

  In producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melt transesterification method, catalyst, terminal terminator, dihydric phenol antioxidant, etc., as necessary May be used. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more. In this polymerization reaction, a terminal stopper (monohydric phenol) is usually used. Monofunctional phenols can be used as such end terminators. Monofunctional phenols are generally used as end terminators for molecular weight control. Such monofunctional phenols are generally phenols or lower alkyl-substituted phenols represented by the following general formula (1). Monofunctional phenols can be indicated.

（式中、Ａは水素原子または炭素数１〜９の直鎖または分岐のアルキル基あるいはフェニル基置換アルキル基であり、ｒは１〜５、好ましくは１〜３の整数である。）

(In the formula, A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3.)

Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
In addition, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic polyester group as a substituent, or long chain alkyl carboxylic acid chlorides can also be shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

（式中、Ｘは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、ｎは１０〜５０の整数を示す。）

Wherein X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50.)

  As the substituted phenols of the general formula (2), those having n of 10 to 30, particularly 10 to 26 are preferable, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol.

  Further, as the substituted phenols of the general formula (3), those in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or phenol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. Is carried out by distilling the water. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an optionally substituted aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, alkali metal compounds such as potassium salt, calcium hydroxide, Alkaline earth metal compounds such as barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals, alkali metals And organic earth salts of alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds manganese compounds, H Emission compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. A catalyst may be used independently and may be used in combination of 2 or more type. The amount of these polymerization catalysts used is preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of dihydric phenol as a raw material. Chosen by

  In the polymerization reaction, in order to reduce phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis ( Compounds such as phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Of these, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate are preferable, and 2-methoxycarbonylphenyl phenyl carbonate is particularly preferably used.

  Furthermore, it is preferable to use a deactivator that neutralizes the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acid, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonate-2-phenyl-2-propyl, dodecylbenzenesulfonate-2-phenyl-2-butyl, octylsulfonate tetrabutylphospho Salts, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetradecylbenzenesulfonate tetra Octyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate Over DOO, decyl trimethyl ammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

  Among the quenching agents, those of phosphonium salt or ammonium salt type are preferred. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 with respect to the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

  The molecular weight of the A-2 component linear aromatic polycarbonate resin is not specified, but if the viscosity average molecular weight is less than 10,000, the high-temperature characteristics and the like deteriorate, and if it exceeds 50,000, the moldability seems to decrease. Therefore, the viscosity average molecular weight is preferably 10,000 to 50,000, more preferably 16,000 to 30,000, still more preferably 18,000 to 28,000, and most preferably 19,000. ~ 26,000. Further, two or more kinds of linear polycarbonate resins may be mixed. In this case, as long as the viscosity average molecular weight of the mixture obtained by mixing two or more kinds is in a preferable range, it is naturally possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range.

  In particular, a mixture with a polycarbonate resin having a viscosity average molecular weight exceeding 50,000 is preferable because it has a high anti-drip ability and exhibits the effect of the present invention more efficiently. More preferred is a mixture with a polycarbonate resin having a viscosity average molecular weight of 80,000 or more, and further preferred is a mixture with a polycarbonate resin having a viscosity average molecular weight of 100,000 or more. That is, those having a clear two-peak distribution by a method such as GPC (gel permeation chromatography) can be preferably used.

  The linear aromatic polycarbonate which is the component A-2 of the present invention is preferably the above aromatic polycarbonate resin and substantially free of halogen atoms. “Substantially free of halogen atoms” means that the molecule does not contain halogen-substituted dihydric phenols, etc., and includes trace amounts of chlorinated solvents, carbonate precursors, etc. remaining in the above aromatic polycarbonate production method. It is not something to do.

<B component: silicone compound>
The silicone compound used as component B of the present invention is a silicone compound having an aromatic group, and preferably has a viscosity at 25 ° C. of 300 cSt or less. As the viscosity increases, the transparency of the molded product decreases. Further, in order for the B component silicone compound to effectively exhibit a flame retardant effect, the dispersed state in the combustion process is important. Viscosity is an important factor that determines the dispersion state. This is because if the silicone compound is too volatile during the combustion process, that is, if the viscosity of the silicone compound is too low, the silicone remaining in the system at the time of combustion is dilute. It is thought that it becomes difficult to form a structure. From this viewpoint, the viscosity at 25 ° C. is more preferably 10 to 300 cSt, still more preferably 15 to 200 cSt, and most preferably 20 to 170 cSt.

  The aromatic group of the B component is bonded to the silicone atom, which improves compatibility with the polycarbonate resin and contributes to maintaining transparency, and is advantageous for forming a carbonized film during combustion. It also contributes to the development of flame retardant effect. When it does not have an aromatic group, it is difficult to obtain transparency of the molded product, and it is difficult to obtain high flame retardancy.

（式（４）中、Ｘはそれぞれ独立にＯＨ基、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基を示す。ｎは０〜５の整数を表わす。さらに式（４）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）
（３）平均重合度が３〜１５０
であるシリコーン化合物の中から選択される少なくとも一種以上のシリコーン化合物である。 The silicone compound of the present invention is preferably a silicone compound containing a Si-H group. In particular, a silicone compound containing a Si—H group and an aromatic group in the molecule,
(1) The amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g.
(2) The ratio (aromatic group amount) in which an aromatic group represented by the following general formula (4) is contained is 10 to 70% by weight, and

(In formula (4), each X independently represents an OH group or a hydrocarbon group having 1 to 20 carbon atoms which may have a heteroatom-containing functional group. N represents an integer of 0 to 5. (4) In the case where n is 2 or more, different types of X can be taken.
(3) Average polymerization degree is 3 to 150
And at least one silicone compound selected from silicone compounds.

  More preferably, the Si-H group-containing unit is selected from silicone compounds containing at least one constituent unit represented by the formula among the constituent units represented by the following general formulas (5) and (6). At least one silicone compound.

（式（５）および式（６）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基、または下記一般式（７）で示される化合物を示す。α１〜α３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（７）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In Formula (5) and Formula (6), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group, or the following general formula ( 7) wherein α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and the repeating unit in the case where m1 is 2 or more in formula (7) (Several different repeating units can be taken.)

（式（７）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基を示す。α４〜α８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（７）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (7), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms that may have a hetero atom-containing functional group. Α 4 to α 8 are each independently 0. Or represents 1. m2 represents 0 or an integer greater than or equal to 1. Further, in the formula (7), when m2 is 2 or more, the repeating unit may take a plurality of repeating units.

  More preferably, when M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit, the silicone compound is composed of MD units or MDT units.

Z ^{1 to} Z ^{8 of} the structural units represented by the general formulas (5), (6) and (7) above, and 1 to 1 carbon atoms which may have a hetero atom-containing functional group in X of the general formula (4) Examples of the hydrocarbon group 20 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a decyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group and an allyl group, and a phenyl group. , Aryl groups such as tolyl groups, and aralkyl groups, and these groups may include various functional groups such as epoxy groups, carboxyl groups, carboxylic anhydride groups, amino groups, and mercapto groups. Good. More preferably, it is a C1-C8 alkyl group, an alkenyl group, or an aryl group, and especially a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a propyl group, a vinyl group, or a phenyl group is preferable.

  Among the structural units represented by the general formulas (5) and (6), when the silicone compound includes at least one structural unit represented by the formula, when it has a plurality of repeating units of siloxane bonds, they are randomly shared. Any form of polymerization, block copolymerization and tapered copolymerization can be employed.

  In the present invention, it is preferable that the amount of Si—H in the silicone compound is in the range of 0.1 to 1.2 mol / 100 g for the silicone compound containing the preferred Si—H group as the B component. When the Si—H amount is in the range of 0.1 to 1.2 mol / 100 g, formation of a silicone structure is facilitated during combustion. More preferred is a silicone compound having a Si-H amount in the range of 0.1 to 1.0 mol / 100 g, most preferably in the range of 0.2 to 0.6 mol / 100 g. When the amount of Si—H is small, it is difficult to form a silicone structure, and when the amount of Si—H is large, the thermal stability of the composition is lowered. Here, the silicone structure refers to a network structure formed by a reaction between silicone compounds or a reaction between a resin and silicone.

The Si—H group amount referred to here means the number of moles of the Si—H structure contained per 100 g of the silicone compound. This is the volume of hydrogen gas generated per unit weight of the silicone compound by the alkali decomposition method. Can be determined by measuring. For example, when 122 ml of hydrogen gas is generated per 1 g of the silicone compound at 25 ° C., the Si—H amount is 0.5 mol / 100 g according to the following formula.
122 × 273 / (273 + 25) ÷ 22400 × 100≈0.5

  On the other hand, in the resin composition in which the silicone compound is blended with the aromatic polycarbonate resin (component A), in order to suppress the white turbidity of the molded product or the decrease in transparency due to the wet heat treatment, as described above, the dispersion state of the silicone compound is is important. When the silicone compound is unevenly distributed, the resin composition itself becomes cloudy, and further, peeling occurs on the surface of the molded product, or the silicone compound migrates during the wet heat treatment and is unevenly distributed to reduce transparency. This is because it is difficult to obtain a molded article having good properties. Important factors that determine the dispersion state include the amount of aromatic groups in the silicone compound and the average degree of polymerization. In particular, the average degree of polymerization is important in a transparent resin composition.

  From this viewpoint, the silicone compound of the present invention preferably has an aromatic group content of 10 to 70% by weight in the silicone compound. More preferred is a silicone compound having an aromatic group content in the range of 15 to 60% by weight, most preferably in the range of 25 to 55% by weight. If the amount of the aromatic group in the silicone compound is less than 10% by weight, the silicone compound is unevenly distributed, resulting in poor dispersion, and it may be difficult to obtain a molded article having good transparency. If the amount of the aromatic group is more than 70% by weight, the molecular rigidity of the silicone compound itself is increased, and therefore it is unevenly distributed and poorly dispersed, and it may be difficult to obtain a molded product with good transparency.

Here, the amount of the aromatic group means a ratio of the aromatic group represented by the general formula (4) described above in the silicone compound, and can be obtained by the following calculation formula.
Aromatic group amount = [A / M] x 100 (wt%)
Here, A and M in the above formula represent the following numerical values, respectively.
A = total molecular weight of aromatic group moieties represented by the general formula (4) contained in one molecule of the silicone compound M = molecular weight of the silicone compound

  Furthermore, the silicone compound used as the component B of the present invention preferably has a refractive index in the range of 1.40 to 1.60 at 25 ° C. More preferred is a silicone compound having a refractive index in the range of 1.42 to 1.59, and most preferred is a range of 1.44 to 1.59. When the refractive index is within the above range, the silicone compound is finely dispersed in the aromatic polycarbonate, thereby providing a resin composition with less white turbidity and good dyeability.

  Further, the silicone compound used as the component B of the present invention preferably has a volatilization amount of 18% or less by a heat loss method at 105 ° C./3 hours. More preferably, the silicone compound has a volatilization amount of 10% or less. When the volatilization amount is larger than 18%, there is a problem that the amount of the volatile matter from the resin increases when the resin composition of the present invention is extruded and pelletized, and more bubbles are generated in the molded product. There is a problem.

  The silicone compound used as the component B may be linear or branched as long as the above conditions are satisfied, and the Si—H group is a side chain in the molecular structure, It is possible to use various compounds possessed at any of terminal, branching points, or plural sites.

In general, the structure of a silicone compound containing a Si—H group in the molecule is constituted by arbitrarily combining the following four types of siloxane units.
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _{1/2 and} other monofunctional siloxane units D units: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. Unit T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 trifunctional siloxane units Q units etc: tetrafunctional siloxane represented by SiO ₂ Place

Specifically, the structure of the silicone compound containing a Si—H group used in the present invention is expressed as D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _{m D n T p, M m} D n Q q, M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .
(The coefficients m, n, p, q in the above formula are integers representing the degree of polymerization of each siloxane unit. Also, if any of m, n, p, q is a numerical value of 2 or more, the coefficient The siloxane units with can be two or more siloxane units having different hydrocarbon groups having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom-containing functional group.

Here, the sum of the coefficients in each characteristic formula is the average degree of polymerization of the silicone compound. In this invention, it is preferable to make this average degree of polymerization into the range of 3-150, More preferably, it is the range of 4-80, More preferably, it is the range of 5-60. When the degree of polymerization is less than 3, the volatility of the silicone compound itself is increased, so that there is a problem that the volatile content from the resin tends to increase during processing of the resin composition containing the silicone compound. If the degree of polymerization is greater than 150, the flame retardancy and transparency of the resin composition containing this silicone compound tends to be insufficient.
In addition, said silicone compound may be used independently, respectively and may be used in combination of 2 or more type.

  Such a silicone compound having a Si—H bond can be produced by a method known per se. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-product hydrochloric acid and low-boiling components. In addition, a silicone oil having a C1-C20 hydrocarbon group that may have an Si-H bond, an aromatic group represented by the general formula (4), or other heteroatom-containing functional group in the molecule, cyclic When using siloxane or alkoxysilane as a starting material, use an acid catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc., and optionally add water for hydrolysis to advance the polymerization reaction, The target silicone compound can be obtained by removing the acid catalyst and low-boiling components used in the same manner.

Further, a silicone compound containing a Si—H group is a siloxane unit represented by the following structural formula: M, M ^H , D, D ^H , D ^{φ 2} , T, T ^φ (where M: (CH ₃ ) ₃ SiO _{1 1 2} ^MH : H (CH ₃ ) ₂ SiO _1/2 D: (CH ₃ ) ₂ SiOD ^H : H (CH ₃ ) SiOD ^{φ 2} : (C ₆ H ₅ ) ₂ SiT: (CH ₃ ) SiO _3/2 T ^φ: _{(C 6} H ₅₎ has a _{SiO 3/2), m} the average number of the respective siloxane units having per molecule, _{respectively, m h, d, d h} , d p2, t, and _{t p} In this case, it is preferable to satisfy all of the following relational expressions.
2 ≦ m + m _h ≦ 40
0.35 ≦ d + d _h + d _p2 ≦ 148
0 ≦ t + t _p ≦ 38
0.35 ≦ m _h + d _h ≦ 110
Outside this range, it becomes difficult to simultaneously achieve good flame retardancy and excellent transparency in the resin composition of the present invention, and in some cases, it becomes difficult to produce a silicone compound containing a Si—H group.

  Content of the silicone compound used as B component of this invention is 0.05-7.0 weight part with respect to 100 weight part of aromatic polycarbonate resin (A component), Preferably it is 0.1-4. 0 parts by weight, more preferably 0.1 to 3.0 parts by weight, and most preferably 0.3 to 2.0 parts by weight. If the content is too large, there is a problem that the heat resistance of the resin is lowered or gas is easily generated during processing, and if it is too small, there is a problem that flame retardancy is not exhibited.

<C component: organometallic salt compound>
As the organometallic salt compound used as the component C of the present invention, various metal salts conventionally used for flame-retarding polycarbonate resins can be used, and in particular, alkali perfluoroalkyl sulfonate (soil) Alkali (earth) metal salt of organic sulfonic acid such as metal salt, alkali sulfonate alkali (earth) metal salt, alkali (earth) metal salt of aromatic imide, alkali of sulfate ester (earth) ) Metal salts and alkali (earth) metal salts of phosphoric acid partial esters. (Here, the notation of alkali (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). These are not only used alone but also used in combination of two or more. It is also possible to do. The metal constituting the organometallic salt compound is preferably an alkali metal or an alkaline earth metal, and more preferably an alkali metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium, and lithium, sodium, and potassium are particularly preferable.

Examples of the alkali (earth) metal salt of the organic sulfonic acid include an alkali (earth) metal salt of an aliphatic sulfonic acid and an alkali (earth) metal salt of an aromatic sulfonic acid.
Preferred examples of the alkali (earth) metal salt of the aliphatic sulfonic acid include an alkali (earth) metal salt of an alkyl sulfonate, and a part of the alkyl group of the alkali (earth) metal salt of the alkyl sulfonate is a fluorine atom. And alkali (earth) metal salts of sulfonates substituted with, and alkali (earth) metal salts of perfluoroalkyl sulfonates, and these can be used alone or in combination of two or more.

  Preferred examples of the alkali (earth) metal salt of alkyl sulfonate include methane sulfonate, ethane sulfonate, propane sulfonate, butane sulfonate, methyl butane sulfonate, hexane sulfonate, heptane sulfone. Examples thereof include acid salts and octane sulfonates, and these can be used alone or in combination of two or more. In addition, a metal salt in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

  On the other hand, preferred examples of alkali (earth) metal salts of perfluoroalkyl sulfonate include perfluoromethane sulfonate, perfluoroethane sulfonate, perfluoropropane sulfonate, perfluorobutane sulfonate, perfluoro Examples include methylbutane sulfonate, perfluorohexane sulfonate, perfluoroheptane sulfonate, and perfluorooctane sulfonate, and those having 1 to 8 carbon atoms are particularly preferable. These can be used alone or in combination of two or more.

  Of these, the alkali metal salt of perfluoroalkylsulfonic acid is most preferable. Among these alkali metals, rubidium and cesium are suitable when the demand for flame retardancy is higher, but these are not versatile and difficult to purify, resulting in disadvantages in terms of cost. There is. On the other hand, although it is advantageous in terms of cost, lithium and sodium may be disadvantageous in terms of flame retardancy. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Monomer or polymer aromatic sulfite alkali (earth) metal salts of aromatic sulfides are described in JP-A-50-98539, for example, disodium diphenyl sulfide-4,4′-disulfonate. And dipotassium diphenyl sulfide-4,4′-disulfonate.

  Examples of sulfonic acid alkali (earth) metal salts of aromatic carboxylic acids and esters are described in JP-A No. 50-98540, for example, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polyethylene terephthalate. And polysodium acid polysulfonate.

  Monomeric or polymeric aromatic ether sulfonate alkali (earth) metal salts are described in JP-A-50-98542, for example, 1-methoxynaphthalene-4-sulfonate calcium, 4- Disodium dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate, polysodium poly (1,3-phenylene oxide) polysulfonate, polysodium poly (1,4-phenylene oxide) polysulfonate And poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-butylphenylene oxide) lithium polysulfonate, and the like.

  Examples of alkali (earth) metal sulfonates of aromatic sulfonates are described in JP-A No. 50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

  Monomeric or polymeric aromatic (earth) metal sulfonates are described in JP-A No. 50-98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, Examples include dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, and calcium biphenyl-3,3′-disulfonate.

  Monomeric or polymeric aromatic sulfonesulfonic acid alkali (earth) metal salts are described in JP-A-52-54746, for example, sodium diphenylsulfone-3-sulfonate, diphenylsulfone-3- Examples include potassium sulfonate, dipotassium diphenyl-3,3′-disulfonate, dipotassium diphenylsulfone-3,4′-disulfonate, and the like.

  Examples of alkali sulfonate alkali (earth) metal salts of aromatic ketones are described in JP-A No. 50-98547, for example, α, α, α-trifluoroacetophenone-4-sulfonic acid sodium salt, benzophenone-3 , 3'-disulfonic acid dipotassium.

  Heterocyclic sulfonic acid alkali (earth) metal salts are described in JP-A-50-116542, for example, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate. Thiophene-2,5-disulfonate calcium, sodium benzothiophenesulfonate, and the like.

  Examples of the alkali (earth) metal sulfonate of aromatic sulfoxide are described in JP-A-52-54745, and examples thereof include potassium diphenyl sulfoxide-4-sulfonate.

  Examples of the condensate obtained by methylene bond of alkali (earth) metal salt of aromatic sulfonate include formalin condensate of sodium naphthalene sulfonate and formalin condensate of sodium anthracene sulfonate.

  Examples of the alkali (earth) metal salt of the sulfate ester include, in particular, alkali (earth) metal salts of sulfate esters of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid ester of palmitic acid monoglyceride, stearic acid monoglyceride sulfate and the like. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Specific examples of the alkali (earth) metal salt of the phosphoric acid partial ester include bis (2,6-dibromo-4-cumylphenyl) phosphoric acid, bis (4-cumylphenyl) phosphoric acid, and bis (2,4,6). Alkali (earth) such as bis (2,4-dibromophenyl) phosphoric acid, bis (4-bromophenyl) phosphoric acid, diphenylphosphoric acid, bis (4-tert-butylphenyl) phosphoric acid ) Metal salts can be mentioned.

  Examples of the alkali (earth) metal salt of the aromatic imide include saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonamide (in other words, di (p-toluenesulfone) imide), N- (N Examples include '-benzylaminocarbonyl) sulfanilimide, and alkali (earth) metal salts such as N- (phenylcarboxyl) sulfanilimide and bis (diphenylphosphoric acid) imide.

  Among these, preferable components are selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides. One or more kinds of compounds are exemplified, among which potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, disulfonate sulfonate of formula (8), di (p-toluenesulfone) imide One or more compounds selected from the group consisting of potassium salt and sodium salt of di (p-toluenesulfone) imide are more preferred. Most preferred is potassium perfluorobutane sulfonate.

[式中、ｎは０〜３を表し、ＭはＫあるいはＮａを表す。]

[Wherein n represents 0 to 3, and M represents K or Na. ]

  The amount of component C contained in the resin composition of the present invention is 0.005 to 1.0 parts by weight, preferably 0.006 to 0.00 parts per 100 parts by weight of the aromatic polycarbonate resin (component A). 3 parts by weight, more preferably 0.007 to 0.1 parts by weight, still more preferably 0.008 to 0.05 parts by weight, and most preferably 0.01 to 0.025 parts by weight. When the content of the component C is too large, not only the transparency that is a feature of the present invention is impaired, but also the resin is decomposed during molding and the flame retardancy is decreased. If the addition amount is too small, the flame retardancy becomes insufficient and the flame retardancy that is the object of the present invention is not exhibited.

<D component: Light diffusing agent>
The light diffusing agent used as the component D of the present invention may be any of organic fine particles typified by polymer fine particles and inorganic fine particles. The polymer fine particles are typically exemplified by organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Furthermore, other copolymerizable monomers other than such monomers can also be used. Examples of other organic crosslinked particles include silicone crosslinked particles typified by polyorganosilsesquioxane.

  Among the components D, polymer fine particles are preferable, and organic crosslinked particles can be preferably used. In such organic crosslinked particles, examples of monomers used as non-crosslinkable monomers include non-crosslinkable vinyl monomers such as acrylic monomers, styrene monomers, and acrylonitrile monomers, and olefin monomers. Acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and phenyl methacrylate alone or in combination. Can be used. Of these, methyl methacrylate is particularly preferable. As the styrenic monomer, styrene, α-methyl styrene, methyl styrene (vinyl toluene), alkyl styrene such as ethyl styrene, and halogenated styrene such as brominated styrene can be used, and styrene is particularly preferable. . As the acrylonitrile monomer, acrylonitrile and methacrylonitrile can be used. As the olefin monomer, ethylene, various norbornene-type compounds, and the like can be used. Furthermore, glycidyl methacrylate, N-methylmaleimide, maleic anhydride, etc. can be illustrated as another copolymerizable monomer. As a result, the organic crosslinked particles of the present invention may have units such as N-methylglutarimide. On the other hand, examples of the crosslinkable monomer for the non-crosslinkable vinyl monomer include divinylbenzene, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and propylene glycol. (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A di (meth) acrylate, dicyclopentanyl di (meth) acrylate , Dicyclopentenyl di (meth) acrylate, N-methylol (meth) acrylamide, and the like.

  The average particle size of the light diffusing agent used as the D component of the present invention is preferably 0.01 to 50 μm, more preferably 1 to 30 μm, and further preferably 2 to 30 μm. If the average particle size is less than 0.01 μm or exceeds 50 μm, the light diffusibility may be insufficient. The average particle size is represented by a 50% value (D50) of the cumulative distribution of particle sizes obtained by the laser diffraction / scattering method. The particle size distribution may be single or plural. That is, it is possible to combine two or more light diffusing agents having different average particle diameters. However, a more preferred light diffusing agent has a narrow particle size distribution. It is more preferable to have a distribution containing 70% by weight or more of the particles in the range of 2 μm before and after the average particle diameter. The shape of the light diffusing agent is preferably close to a sphere from the viewpoint of light diffusibility, and more preferably a shape close to a true sphere. Such a sphere includes an elliptical sphere.

  The refractive index of the light diffusing agent used as the D component of the present invention is usually preferably in the range of 1.30 to 1.80, more preferably 1.33 to 1.70, still more preferably 1.35 to 1.80. A range of 65. These exhibit a sufficient light diffusion function in a state where they are blended in the resin composition.

  The content of the component D in the present invention is 0.005 to 15.0 parts by weight, preferably 0.05 to 10.0 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin (component A). Preferably it is 0.05-3.0 weight part. If the D component is less than 0.005 parts by weight, the light diffusibility is insufficient, and if it exceeds 15.0 parts by weight, the light transmittance decreases.

<E component: UV absorber>
The E component of the present invention is an ultraviolet absorber added for the purpose of imparting light resistance. As the ultraviolet absorber, in the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2- Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4 ′ -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4- Hydroxy-2-methoxyphenyl) Examples include methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  In the benzotriazole series, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomer copolymerizable with the monomer And 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer and 2-hydroxyphenyl-2H-benzotriazole skeleton A polymer having

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one) And 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one) and the like.

  In the case of cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like.

  Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The

  Among them, benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable in terms of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 part by weight, most preferably 100 parts by weight of component A. Is 0.05 to 0.5 parts by weight.

<F component: fluorescent whitening agent>
The fluorescent whitening agent that is the F component of the present invention is not particularly limited as long as it is used for improving the color tone of a resin or the like to white or bluish white. For example, stilbene, benzimidazole, benzoxazole, Naphthalimide type, rhodamine type, coumarin type, oxazine type compound and the like can be mentioned. Specifically, CI Fluorescent Brightener 219: 1, Eastman Chemical OB-1 manufactured by Eastman Chemical Co., etc. can be used. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part. The content of the fluorescent brightening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the component A. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

<Other ingredients>
(I) Phosphorus stabilizer It is preferable that the flame retardant polycarbonate resin composition of the present invention is blended with a phosphorus stabilizer to the extent that does not promote hydrolyzability. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, an alkyl phosphate compound typified by trimethyl phosphate is preferably blended. A combination of such an alkyl phosphate compound and a phosphite compound and / or phosphonite compound is also a preferred embodiment.

(II) Hindered phenol stabilizer The flame retardant polycarbonate resin composition of the present invention may further contain a hindered phenol stabilizer. Such blending exhibits an effect of suppressing, for example, hue deterioration during molding and hue deterioration during long-term use. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4′-methylene bis (2,6- Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′- Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Nbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di- tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Anurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di-tert -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types.

  The content of the phosphorus stabilizer and the hindered phenol stabilizer is preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, more preferably 100 parts by weight of component A. Preferably it is 0.01-0.3 weight part.

(III) Thermal stabilizer other than the above The flame retardant polycarbonate resin composition of the present invention may contain a thermal stabilizer other than the phosphorus stabilizer and the hindered phenol stabilizer. Preferable examples of such other heat stabilizers include lactone stabilizers represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Is done. Details of such a stabilizer are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the component A.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A.

(IV) Anti-drip agent The resin composition of the present invention is excellent in anti-drip property, but a normal anti-drip agent can be used in combination to further reinforce such performance. The amount is preferably 0.3 parts by weight or less, more preferably 0.1 parts by weight or less, still more preferably 0.08 parts by weight or less, and most preferably 0.05 parts by weight or less with respect to 100 parts by weight of component A. Examples of such an anti-drip agent include a fluorine-containing polymer having a fibril forming ability. Polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is particularly preferable. The term “transparency” does not impair transparency, for example, to use PTFE in an amount that does not exceed 5% of the haze of a 2 mm thick plate. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is preferably 1 million to 10 million, and more preferably 2 million to 9 million, in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and transparency. . As commercial products of PTFE in a mixed form, “METABRENE A3000” (trade name), “METABBRENE A3700” (trade name), “METABBRENE A3750” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “SN3307” manufactured by Shine Polymer (Trade name), “SN3305” (trade name) manufactured by Shine Polymer, and the like.

(V) Others In addition to the above, the flame-retardant polycarbonate resin composition of the present invention contains other thermoplastic resins and additives known per se for imparting various functions to the molded product and improving properties. A small proportion can be blended. These additives are used in usual amounts as long as the object of the present invention is not impaired.
Examples of such additives include colorants (for example, pigments and dyes such as carbon black and titanium oxide), fluorescent dyes, light stabilizers (typified by hindered amine compounds), and inorganic phosphors (for example, aluminate as a base crystal). Phosphors), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (eg fine particle titanium oxide, fine particle zinc oxide), mold release agents, flow modifiers, radical generators, infrared rays Examples include absorbents (heat ray absorbents) and photochromic agents.

  Other thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (non-crystalline) And so-called super engineering plastics such as engineering plastics typified by polyarylate and liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. . Furthermore, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

<About production of resin composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, A component, B component, C component, D component and optionally E component, F component, and other components can be sufficiently obtained using premixing means such as V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. After mixing, if necessary, granulate with an extrusion granulator or briquetting machine, then melt and knead with a melt kneader typified by a vent type twin screw ruder, and pelletize with a device such as a pelletizer. A method is mentioned. As another method, A component, B component, C component, D component and optionally E component, F component, and other components are each independently fed to a melt kneader represented by a vent type twin screw rudder, A component And a method in which a part of other components is premixed and then supplied to the melt-kneader independently of the remaining components, the component B is diluted and mixed with water or an organic solvent, and then supplied to the melt-kneader, or such a diluted mixture There is also a method of premixing with other components and then feeding to a melt-kneader. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

<Manufacture of molded products>
The resin composition of this invention can manufacture various products by usually injection-molding this pellet and obtaining a molded article. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerlessness can be used. Also in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra-molding) Including those using critical fluids), rapid heating / cooling mold forming, heat insulating mold forming and in-mold remelt molding, and combinations of these, etc. can be used.

  Furthermore, various surface treatments can be performed on the molded product formed from the resin composition. Surface treatment includes decorative coating, hard coat, water / oil repellent coat, hydrophilic coat, UV absorbing coat, infrared absorbing coat, electromagnetic wave absorbing coat, heat generating coat, antistatic coat, antistatic coating, conductive coating, and meta coating. Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed. In particular, a transparent sheet coated with a transparent conductive layer is preferred.

  The polycarbonate resin composition of the present invention is a resin composition in which a silicone compound having an aromatic group, an organometallic salt compound, and a light diffusing agent are blended with an aromatic polycarbonate resin having a branched structure with a limited branching rate. Flame retardant light diffusion with improved flame retardancy while maintaining high light transmittance and diffusivity by limiting the amount of organic alkali (earth) metal salt to a narrow range It is a conductive polycarbonate resin composition.

  The polycarbonate resin composition of the present invention can impart a high degree of flame retardancy without using a brominated flame retardant or a phosphorus flame retardant, which is considered to have a high environmental load, and has a high light transmittance. It is extremely useful for various industrial uses, such as being suitable as a light guide plate, a surface light emitting structure, and a diffusion plate, and its industrial effect is extremely great.

It is the schematic which shows the measuring method of the dispersion degree in this invention.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
The following items were evaluated.

(I) Flame retardancy The pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours in a hot air circulation dryer, and the cylinder temperature was 320 using an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at 0 ° C. and a mold temperature of 80 ° C. The vertical combustion test of UL standard 94 was conducted at thicknesses of 2.2 mm and 1.5 mm, and the grade was evaluated. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated.

(Ii) Optical characteristics (1) Total light transmittance: Pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours with a hot air circulation dryer, and then an injection molding machine [Toshiba Machine Co., Ltd. IS150EN -5Y], a flat plate test piece having a cylinder temperature of 330 ° C., a mold temperature of 80 ° C. and a side of 150 mm and a thickness of 2 mm was molded, and the haze meter HR-100 manufactured by Murakami Color Research Laboratory Co., Ltd. was used. The transmittance in the thickness direction was measured according to JIS-K 7136.
(2) Diffuse light transmittance: Using a haze meter HR-100 manufactured by Murakami Color Research Laboratory Co., Ltd., the diffuse light transmittance in the thickness direction of the flat test piece having a side of 150 mm and a thickness of 2 mm was measured according to JIS. Measured according to -K 7136.
(3) Diffusivity: The diffusivity of the flat test piece having a side of 150 mm and a thickness of 2 mm was measured using a variable angle photometer manufactured by Nippon Color Research Laboratory Co., Ltd. The measurement method in that case is shown in FIG. Note that the diffusivity is the angle of γ when the amount of transmitted light is 50 when the amount of transmitted light is 100 when γ = 0 degrees when a light beam is vertically applied to the specimen surface in FIG. .
(4) Surface luminous property: A flat test piece having a side of 150 mm and a thickness of 4 mm molded under the same conditions is superimposed on the upper part of a white reflector having a side of 150 mm and a thickness of 2 mm and a reflectance of 90%. A cold-cathode tube having a diameter of 3 mm and a length of 170 mm was placed on the test piece, and the luminescent property of the test piece was visually confirmed. Judgment is indicated by ◯ for a light emitting surface, Δ for a slightly darker object, and × for a darker object.

(Iii) Appearance: The surface appearance of a three-stage plate having 1 mm thickness, 2 mm thickness, and 3 mm thickness molded under the same conditions was visually confirmed. Judgment is indicated by ○ for objects with gloss on the surface and × for objects without gloss.

[Examples 1 to 29 and Comparative Examples 1 to 9]
The resin composition which consists of a mixture ratio of Table 1-Table 3 was created in the following ways. The description will be made according to the symbols in the following table. Each component of the ratio of the table | surface was measured, it mixed uniformly using the tumbler, this mixture was thrown into the extruder, and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration is the first stage kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. The strand was extruded under the conditions of cylinder temperature and die temperature of 290 ° C. and vent suction of 3000 Pa, cooled in a water bath, then strand-cut with a pelletizer and pelletized. Using the above-described method, the obtained pellets were molded into test pieces for flame retardancy evaluation and transparency evaluation. The raw materials used in Tables 1 to 3 are as follows.

(A component)
(A-1 component)
PC-B15H: Aromatic polycarbonate resin having a branched structure (branching rate 1.52 mol%, molecular weight 24,800)
(Manufacturing method of PC-B15H)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2340 parts of ion-exchanged water, 947 parts of a 25% aqueous sodium hydroxide solution, and 0.7 parts of hydrosulfite, and 710 parts of bisphenol A was dissolved with stirring (bisphenol A solution). ) After that, 2299 parts of methylene chloride, 112 parts of 48.5% sodium hydroxide aqueous solution, aqueous solution of 1,1,1-tris (4-hydroxyphenyl) ethane dissolved in 25% concentration in 14% sodium hydroxide aqueous solution 61.0 parts (1.60 mol%) was added, and phosgene was reacted by blowing 357 parts of phosgene over 15 minutes at 15 to 25 ° C. After completion of phosgenation, 245 parts of 11% strength p-tert-butylphenol in methylene chloride and 88 parts of 48.5% aqueous sodium hydroxide solution were added, stirring was stopped, and after standing for 10 minutes, stirring was performed. After 5 minutes of emulsification, a high emulsification dope was obtained by processing with a homomixer (Special Machine Industries Co., Ltd.) at a rotation speed of 1200 rpm and a bath frequency of 35 times. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization. After completion of the reaction, 5728 parts of methylene chloride was added for dilution, the methylene chloride phase was separated from the reaction mixture, 5000 parts of ion-exchanged water was added to the separated methylene chloride phase and mixed with stirring, and the stirring was stopped. The phase and the organic phase were separated. Next, water washing was repeated until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water to obtain a purified polycarbonate resin solution. Next, methylene chloride was evaporated at a liquid temperature of 75 ° C. with a 1000 L kneader in which 100 L of ion-exchanged water was added to the purified polycarbonate resin solution to obtain a granular material. 25 parts of the granular material and 75 parts of water were put into a hot water treatment tank equipped with a stirrer and stirred and mixed at a water temperature of 95 ° C. for 30 minutes. Subsequently, the mixture of the granular material and water was separated by a centrifugal separator to obtain a granular material containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, this granular material was continuously supplied at 50 kg / hr (in terms of polycarbonate resin) to a SUS316L conductive heat receiving groove type biaxial stirring continuous dryer controlled at 140 ° C., and the condition of an average drying time of 3 hours And dried to obtain a polycarbonate resin particle having a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 24,800 and a branching ratio of 1.52 mol%.

PC-B14H: Aromatic polycarbonate resin having a branched structure (branch rate 1.46 mol%, molecular weight 24,900)
(Manufacturing method of PC-B14H)
357 parts of phosgene, 59.5 parts (1.56 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane is dissolved at a concentration of 25% in a 14% aqueous sodium hydroxide solution, an 11% concentration A polycarbonate resin particle having a branched structure was obtained in the same manner as in the method for producing PC-B15H, except that 243 parts of p-tert-butylphenol in methylene chloride was used. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 24,900 and a branching ratio of 1.46 mol%.

PC-B14L: Aromatic polycarbonate resin having a branched structure (branch rate 1.46 mol%, molecular weight 20,100)
(Manufacturing method of PC-B14L)
359 parts of phosgene, 59.8 parts (1.57 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane in a 14% strength aqueous sodium hydroxide solution at a 25% concentration, 11% strength A polycarbonate resin granule having a branched structure was obtained in the same manner as in the production method of PC-B15H, except that it was changed to 280 parts of a methylene chloride solution of p-tert-butylphenol. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 20,100 and a branching ratio of 1.46 mol%.

PC-B12L: aromatic polycarbonate resin having a branched structure (branching rate: 1.27 mol%, molecular weight: 20,200)
(Manufacturing method of PC-B12L)
358 parts of phosgene, 53.3 parts (1.40 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane is dissolved at a concentration of 25% in a 14% aqueous sodium hydroxide solution, an 11% concentration A polycarbonate resin particle having a branched structure was obtained in the same manner as in the method for producing PC-B15H except that 276 parts of a methylene chloride solution of p-tert-butylphenol was used. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 20,200 and a branching rate of 1.27 mol%.

PC-B9H: Aromatic polycarbonate resin having a branched structure (branching rate 0.96 mol%, molecular weight 25,100)
(Manufacturing method of PC-B9H)
354 parts of phosgene, 38.1 parts (1.00 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane is dissolved at a concentration of 25% in a 14% aqueous sodium hydroxide solution, an 11% concentration A polycarbonate resin particle having a branched structure was obtained in the same manner as in the method for producing PC-B15H, except that it was changed to 219 parts of a methylene chloride solution of p-tert-butylphenol. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25,100 and a branching ratio of 0.96 mol%.

PC-B9L: Aromatic polycarbonate resin having a branched structure (branching rate 0.91 mol%, molecular weight 20,100)
(Manufacturing method of PC-B9L)
355 parts of phosgene, 38.1 parts (1.00 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane in a 14% strength aqueous sodium hydroxide solution at a 25% concentration, 11% strength A polycarbonate resin particle having a branched structure was obtained in the same manner as in the method for producing PC-B15H, except that 262 parts of p-tert-butylphenol in methylene chloride was changed. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 20,100 and a branching ratio of 0.91 mol%.

PC-B7H: Aromatic polycarbonate resin having a branched structure (branch rate 0.72 mol%, molecular weight 25,000)
(Manufacturing method of PC-B7H)
352 parts of phosgene, 29.0 parts (0.76 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane at a 25% concentration in an aqueous 14% sodium hydroxide solution, an 11% concentration A polycarbonate resin powder having a branched structure was obtained in the same manner as in the method for producing PC-B15H, except that 207 parts of p-tert-butylphenol in methylene chloride was used. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25,000 and a branching rate of 0.72 mol%.

PC-B7L: Aromatic polycarbonate resin having a branched structure (branch rate 0.74 mol%, molecular weight 20,100)
(Manufacturing method of PC-B7L)
354 parts of phosgene, 30.5 parts (0.80 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane in a 14% strength aqueous sodium hydroxide solution at a 25% concentration, 11% concentration A polycarbonate resin particle having a branched structure was obtained in the same manner as in the method for producing PC-B15H, except that it was changed to 253 parts of p-tert-butylphenol in methylene chloride. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 20,100 and a branching ratio of 0.74 mol%.

PC-B6H: Aromatic polycarbonate resin having a branched structure (branching rate 0.67 mol%, molecular weight 25,100)
(Manufacturing method of PC-B6H)
352 parts of phosgene, 27.1 parts (0.71 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane is dissolved at a concentration of 25% in an aqueous 14% sodium hydroxide solution, an 11% concentration Except for changing to 205 parts of p-tert-butylphenol in methylene chloride, the same procedure as for PC-B15H was carried out to obtain a polycarbonate resin granule having a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25,100 and a branching rate of 0.67 mol%.

(A-2 component)
PC-L1: Linear polycarbonate resin (polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. Such a polycarbonate resin is produced without using an amine catalyst and is an aromatic polycarbonate resin. The ratio of the terminal hydroxyl group in the terminal was 10 mol%, and the viscosity average molecular weight was 25,500.)

(B component)
B-1: Silicone compound containing Si—H group and aromatic group (production of B-1)
A 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 301.9 g of water and 150 g of toluene, and cooled to an internal temperature of 5 ° C. A mixture of trimethylchlorosilane (21.7 g), methyldichlorosilane (23.0 g), dimethyldichlorosilane (12.9) and diphenyldichlorosilane (76.0) was charged into the dropping funnel and dropped into the flask over 2 hours while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged for 4 hours with stirring at an internal temperature of 20 ° C., then left to stand to remove the separated hydrochloric acid aqueous layer, added with 10% aqueous sodium carbonate solution, stirred for 5 minutes and then left to stand. The separated aqueous layer was removed. Then, it wash | cleaned 3 times with ion-exchange water, and it confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling substances, and then insoluble materials were removed by filtration to obtain a silicone compound B-1. This silicone compound B-1 had an Si—H group content of 0.21 mol / 100 g, an aromatic group content of 49% by weight, and an average degree of polymerization of 8.0.

B-2: Silicone compound containing Si—H group and aromatic group (production of B-2)
In a 1 L flask equipped with a stirrer, a cooling device and a thermometer, 100.7 g of 1,1,3,3-tetramethyldisiloxane, 60.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclo 129.8 g of tetrasiloxane, 143.8 g of octaphenylcyclotetrasiloxane, and 99.1 g of phenyltrimethoxysilane were charged, and 25.0 g of concentrated sulfuric acid was added with further stirring. After cooling to an internal temperature of 10 ° C., 13.8 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. This toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound B-2. This silicone compound B-2 was a silicone compound having a Si—H group content of 0.50 mol / 100 g, an aromatic group content of 30 wt%, and an average degree of polymerization of 10.95.

B-3: Silicone compound containing Si—H group and aromatic group (production of B-3)
In a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, 16.2 g of hexamethyldisiloxane, 61.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 103.8 g of octamethylcyclotetrasiloxane, and diphenyl 391.0 g of dimethoxysilane was charged, and 25.0 g of concentrated sulfuric acid was added with further stirring. After cooling to an internal temperature of 10 ° C., 29.4 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. This toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound B-3. This silicone compound B-3 was a silicone compound having an Si—H group amount of 0.20 mol / 100 g, an aromatic group amount of 50 wt%, and an average degree of polymerization of 42.0.

<Indication formula of each silicone compound>
B-1: M ₂ ^DH ₂ D ₁ D ^φ2 _{3
^{B-2: M H 3 D}} H 2 D 3.5 D φ2 1.45 T φ 1
B-3: M ₂ ^DH ₁₀ D ₁₄ D ^φ2 ₁₆
Each symbol in the above formula represents the following siloxane units, and the coefficient (subscript) of each symbol represents the number of siloxane units (degree of polymerization) in one molecule.
M: (CH ₃ ) ₃ SiO _1/2
M ^H : H (CH ₃ ) ₂ SiO _1/2
D: (CH ₃ ) ₂ SiO
_{^{D H: H (CH 3)}} SiO
D ^φ2 : (C ₆ H ₅ ) ₂ SiO
^Tφ : (C ₆ H ₅ ) SiO _3/2

(C component)
C-1: Perfluorobutanesulfonic acid potassium salt (Megafac F-114P, manufactured by Dainippon Ink, Inc.)
C-2: Sodium perfluorobutanesulfonate (Megafac F-114S, manufactured by Dainippon Ink, Inc.)

(D component)
D-1: Beaded cross-linked silicone (Momentive Performance Materials Japan GK Co., Ltd .: Tospearl 120 (trade name), average particle size 2 μm)
D-2: Beaded crosslinked silicone (Momentive Performance Materials Japan GK Co., Ltd .: Tospearl 145 (trade name), average particle size 5 μm)
D-3: Bead-like crosslinked acrylic particles (manufactured by Sekisui Plastics Co., Ltd .: MBX-5 (trade name), average particle diameter 5 μm)
D-4: Beaded crosslinked acrylic particles (manufactured by Sekisui Plastics Co., Ltd .: MBX-30 (trade name), average particle size 30 μm)
D-5: Calcium carbonate (Cypro Kasei Co., Ltd. product: Cypron A (trade name), average particle size 10 μm)

(E component)
E-1: Benzotriazole ultraviolet absorber (Kemipro Kasei Kogyo Co., Ltd .: Chemisorb 79)

(F component)
F-1: Fluorescent whitening agent (manufactured by Hakkol Chemical Co., Ltd .: Hakkol PSR)

(Other ingredients)
PEPQ: Tetrakis (di-t-butylphenyl) -biphenylenediphosphonite (manufactured by Clariant Japan: Sandstab P-EPQ (trade name))
IRX: Hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
L1: Saturated fatty acid ester release agent (Riken Vitamin Co., Ltd .: Riquemar SL900)
SN-3305: Anti-drip agent (manufactured by Shine Polymer: SN3305)

A Flat specimen B Light source γ Diffuse light angle

Claims (8)

  (A) 100 parts by weight of an aromatic polycarbonate resin (component A) having a branched structure with a branching ratio of 0.7 to 1.5 mol%, (B) a silicone compound having an aromatic group (component B) 0.05 -7.0 parts by weight, (C) organometallic salt compound (component C) 0.005-1.0 parts by weight, and (D) light diffusing agent (component D) 0.005-15.0 parts by weight Flame retardant light diffusing polycarbonate resin composition.   The flame retardant light diffusing polycarbonate resin composition according to claim 1, wherein the B component is a silicone compound containing a Si—H group in the molecule.   1 type in which C component is selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides The flame retardant light diffusing polycarbonate resin composition according to claim 1, wherein the flame retardant light diffusing polycarbonate resin composition is an organic alkali (earth) metal salt.   The flame retardant light diffusing polycarbonate resin composition according to any one of claims 1 to 3, wherein the component D is polymer fine particles.   The flame retardant light diffusion according to any one of claims 1 to 4, comprising 0.01 to 3 parts by weight of (E) ultraviolet absorber (E component) with respect to 100 parts by weight of component A. Polycarbonate resin composition.   The difficulty according to any one of claims 1 to 5, comprising 0.001 to 0.1 parts by weight of (F) a fluorescent whitening agent (F component) with respect to 100 parts by weight of the A component. A light diffusing polycarbonate resin composition.   The flame-retardant light-diffusing polycarbonate resin composition according to any one of claims 1 to 6, wherein a flame-retardant level V-0 of UL94 standard is achieved in a molded product having a thickness of 1.5 mm.   The molded article formed from the flame-retardant light diffusable aromatic polycarbonate resin composition of any one of Claims 1-7.

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