JP5679693B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame retardant polycarbonate resin composition. More specifically, the present invention relates to a flame retardant polycarbonate resin composition excellent in transparency, including a polycarbonate resin component containing a specific carbonate structural unit.

  Aromatic polycarbonate resins have been used in a wide range of fields because they have transparency, excellent heat resistance and strength, and have certain flame retardancy. However, in order to meet the increasing demand for flame retardancy of electronic / electrical equipment parts and OA-related parts in recent years and the demand for increased flame retardancy associated with the thinning of products, the flame retardancy of aromatic polycarbonate resin is Not enough. Furthermore, in recent years, there are many cases in which high flame retardancy is required to meet V-1 or V-0 in the UL standard (U.S. Underwriters Laboratory Standard) -94, and high flame retardancy has been imparted. PC materials have become very important.

  For the purpose of improving the flame retardancy of polycarbonate resin, halogenated flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomer have been used together with flame retardant aids such as antimony oxide from the viewpoint of flame retardant efficiency. For example, Patent Document 1 proposes a flame-retardant polycarbonate resin composition containing 1 to 20% by weight of a carbonate oligomer of brominated bisphenol A based on the polycarbonate resin. However, from the viewpoint of safety or impact on the environment at the time of disposal and incineration, a flame retardant method using a flame retardant containing no halogen is required from the market. A polycarbonate resin composition containing an organophosphorus flame retardant as a non-halogen flame retardant, especially an organophosphate ester compound, exhibits excellent flame retardancy, and also has a high fluidizing action as a plasticizer, and many methods Has been proposed and used. For example, Patent Document 2 proposes adding a phosphate ester to improve the flame retardancy of a polycarbonate-based resin. However, in order to improve the flame retardancy of these resin compositions, it is necessary to add a large amount of phosphoric ester, and as a result, there is a problem that the heat resistance and impact resistance of the resin molded product are lowered. It was. Further, there are cases where it is not preferable in the molding environment and appearance of the molded product, such as corrosion of the mold or roll during molding, generation of gas, and discoloration.

  In contrast, silicone flame retardants are used as flame retardants for polycarbonate resins in place of the conventional flame retardants. Patent Documents 3 and 4 disclose a flame retardant resin composition in which a specific silicone compound is added to a thermoplastic resin. However, the resin composition to which the silicone compound described in such a literature is added alone has generally not achieved a significant improvement in flame retardancy. Although there are cases where flame retardant performance is improved by the incorporation of high-concentration silicone compounds, such formulations may adversely affect plastics moldability, kneadability and other required properties, and are also disadvantageous in terms of cost. Therefore, it was not practical.

  One of the techniques for obtaining a high degree of flame retardancy is suppression of the resin dripping phenomenon in the combustion test. As a method therefor, there are a method using a resin having a branch unit as a base resin, a method of adding polytetrafluoroethylene having a fibril-forming ability (hereinafter sometimes abbreviated as fibrillated PTFE) as an anti-drip agent, and the like. Yes (see Patent Document 5, Patent Document 6, and Patent Document 7). Among them, the method using an aromatic polycarbonate resin having a branch unit as the base resin is sufficiently satisfactory in terms of both a drip prevention effect and a fluidity, although a drip improving effect is preferably observed in terms of excellent transparency. The current situation is that nothing has been obtained. Furthermore, there is a problem that the impact resistance, which is a characteristic of the polycarbonate resin, is significantly lowered. The method of adding fibrillated PTFE is easy to obtain a drip-preventing effect, and since there is little decrease in fluidity due to the addition of fibrillated PTFE, a material that requires high flame resistance (V-0, V-1 according to UL standards). This is a method that has been widely applied to materials having (1). However, there is a problem that the transparency characteristic of the polycarbonate resin is impaired.

  A flame retardant resin composition in which a polycarbonate-polydiorganosiloxane copolymer-containing resin is used as a polycarbonate resin and fibrillated PTFE is blended is also known (see Patent Document 8). Advanced flame retardant composition that achieves V-0 by UL standard because the oxygen index is improved by using polycarbonate-polydiorganosiloxane copolymer as a base resin, and the effect of preventing melt dripping by the addition of fibrillated PTFE. A thing is obtained. However, there is a problem that transparency is lowered.

Japanese Examined Patent Publication No. 47-44537 Japanese Examined Patent Publication No. 62-25706 Japanese Examined Patent Publication No. 62-60421 JP-A-5-86295 JP-A-11-323118 Japanese Patent No. 3129374 JP 2008-297424 A JP-A-8-81620

  In contrast to the current situation in which a polycarbonate resin composition excellent in transparency having both fluidity and flame retardancy is required as described above, the above prior art cannot be said to satisfy such a requirement. An object of the present invention is to provide a flame retardant polycarbonate resin composition satisfying such a requirement.

  As a result of intensive research aimed at achieving the above-mentioned object, the present inventors have found that a polycarbonate-polydiorganosiloxane copolymer (component A) containing a carbonate constituent unit containing a specific siloxane structure and an organic acid metal salt flame retardant The polycarbonate resin composition consisting of (Component B) was found to be excellent in the intended transparency and also excellent in flame retardancy, and reached the present invention.

［上記一般式〔１〕において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数３〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式〔２〕で表される基からなる群より選ばれる少なくとも一つの基である。

（上記一般式〔２〕においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数３〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１〜１０の整数、ｈは４〜７の整数である。）］ That is, according to the present invention, (1) (A) a polycarbonate polycarbonate resin having transparency comprising a carbonate structural unit represented by the following general formula [1] and a carbonate structural unit represented by the following general formula [3] For 100 parts by weight of combined (component A)

[In General Formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]. .

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

（上記一般式〔３〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１００未満の自然数である。Ｘは炭素原子数２〜８の二価脂肪族基である。）
（Ｂ）有機酸金属塩系難燃剤（Ｂ成分）０．０１〜０．２重量部を含有する難燃性ポリカーボネート樹脂組成物であって、且つＵＬ―９４に準じた難燃性評価がＶ−０であることを特徴とする難燃性ポリカーボネート樹脂組成物が提供される。

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number less than 100. X is a divalent aliphatic group having 2 to 8 carbon atoms.)
(B) A flame retardant polycarbonate resin composition containing 0.01 to 0.2 parts by weight of an organic acid metal salt flame retardant (component B), and the flame retardant evaluation according to UL-94 is V Provided is a flame retardant polycarbonate resin composition characterized by being −0.

One of the more preferable embodiments of the present invention is that (2) the viscosity average molecular weight of the component A is 1.6 × 10 ^{4 to} 3.0 × 10 ⁴ , and the structural viscosity index (N) is 1.60 to 2 The flame-retardant polycarbonate resin composition according to the above configuration (1), which is .50.
One of the more preferred embodiments of the present invention is an aggregated structure in which (3) A component is a polydiorganosiloxane domain dispersed in a polycarbonate part matrix composed of carbonate constituent units represented by the general formula [1]. The flame retardant polycarbonate resin composition according to the above constitution (1) or (2), wherein the polydiorganosiloxane domain has an average size of 5 to 40 nm and a normalized dispersion of 40% or less.
One of the more preferable embodiments of the present invention is as described in any one of the above structures (1) to (3), wherein (4) in the general formula [3], p + q is 30 to 60. It is a flame retardant polycarbonate resin composition.
One of the more preferable embodiments of the present invention is characterized in that the polydiorganosiloxane block represented by the general formula [3] is 2 to 20% by weight based on the total weight of the component (5) A. The flame-retardant polycarbonate resin composition according to any one of the above-described configurations (1) to (4).
One of the more preferable embodiments of the present invention is that (6) the component B is an alkali (earth) metal salt of a perfluoroalkyl sulfonate, an alkali (earth) metal salt of an aromatic sulfonate, and an aromatic imide. The flame retardancy according to any one of the above constitutions (1) to (5), wherein the flame retarder is one or more organic acid metal salt flame retardants selected from the group consisting of alkali (earth) metal salts It is a polycarbonate resin composition.
One of the more preferable embodiments of the present invention is that (7) a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less has a total light transmittance of 80% to 95%. The flame-retardant polycarbonate resin composition according to any one of the above-described configurations (1) to (6).
One of the more preferable embodiments of the present invention is (8) an injection-molded article comprising the flame-retardant polycarbonate resin composition according to any one of the above constitutions 1 to 7.
One of the more preferred embodiments of the present invention is (9) an extrusion-molded product comprising the flame-retardant polycarbonate resin composition according to any one of the above constitutions 1 to 7.

Hereinafter, the details of the present invention will be described.
<Component A: Polycarbonate copolymer>
The polycarbonate copolymer used as the component A of the present invention is, as described above, a transparency comprising a carbonate constituent unit represented by the general formula [1] and a carbonate constituent unit represented by the general formula [3]. A polycarbonate copolymer having In addition, having transparency here means that the total light transmittance of a 2 mm-thick plate is 80% or more.

  Examples of the dihydric phenol (I) for deriving the carbonate structural unit represented by the general formula [1] include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis ( 4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy) Phenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9 -Bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-di Droxy-3,3′-dimethyldiphenyl ether, 4,4′-sulfonyldiphenol, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 2,2′-dimethyl-4,4 '-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'- Sulfonyldiphenol, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} , 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6 Decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-biphenyl. (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

In the carbonate structural unit represented by the general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or carbon. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a hydrogen atom, carbon An alkyl group of 1 to 6 or a phenyl group is particularly preferable. R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom or 1 to 10 carbon atoms. An alkyl group, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate structural unit represented by the above formula [3], for example, a compound represented by the following general formula (I) is preferably used.

  The dihydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of. Of these, (2-allylphenol) -terminated polydiorganosiloxane, (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-) are particularly preferred. 4-Allylphenol) -terminated polydimethylsiloxane is preferred. In order to achieve a high degree of transparency, the degree of organosiloxane polymerization (p + q) of the dihydroxyaryl-terminated polydiorganosiloxane is suitably less than 100. The degree of diorganosiloxane polymerization (p + q) is preferably 5 to 70, more preferably 20 to 60, still more preferably 30 to 60, and particularly preferably 30 to 50. Above the lower limit of the preferable range, the impact resistance and flame retardancy are excellent, and below the upper limit of the preferable range, the transparency is excellent. A copolymer having the above lower limit or more has a high effect of modifying rheological properties due to the introduction of a polydiorganosiloxane moiety having a low cohesive force, and tends to increase the structural viscosity index. As a result, it is possible to obtain a highly flame-retardant resin molded article in which drip during combustion is suppressed while maintaining high fluidity during shear flow. Such a copolymer below the upper limit tends to reduce the average size and normalized dispersion of the polydiorganosiloxane domain. As a result, a resin molded product having excellent transparency can be obtained even under molding conditions where it stays in the cylinder for a long time at a high temperature. The number of moles per unit weight of the polydiorganosiloxane unit below the upper limit is increased, and the unit is easily incorporated into the polycarbonate evenly. When the degree of polymerization of the diorganosiloxane is large, the incorporation of polydiorganosiloxane units into the polycarbonate becomes uneven and the proportion of polydiorganosiloxane units in the polymer molecule increases. Polycarbonate is likely to occur, and the compatibility with each other tends to decrease. As a result, large polydiorganosiloxane domains are likely to occur. On the other hand, from the viewpoint of fluidity, impact resistance, and flame retardancy, it is advantageous that the polydiorganosiloxane domain is somewhat large, and therefore there is a preferred range of polymerization degree as described above. The polycarbonate copolymer used as the component A of the present invention comprises a continuous phase mainly composed of a carbonate constituent unit represented by the general formula [1] and a carbonate constituent unit represented by the general formula [3]. A sea-island type phase separation structure consisting of a dispersed phase as a main component is formed. In the present invention, the matrix refers to a continuous phase mainly composed of a carbonate structural unit represented by the general formula [1], and the polydiorganosiloxane domain refers to a carbonate represented by the general formula [3] dispersed in the matrix. A dispersed phase whose main component is a structural unit. As described above, the polydiorganosiloxane domain is not necessarily composed of a single component because the structure is formed by phase separation from the carbonate structural unit represented by the general formula [1] as a matrix.

The content of the polydiorganosiloxane component in the total weight of the polycarbonate copolymer used as the component A of the present invention is suitably 2 to 20% by weight. The polydiorganosiloxane component content is preferably 4 to 15% by weight, more preferably 4 to 12% by weight, and most preferably 6 to 12% by weight. Above the lower limit of the preferable range, the impact resistance and flame retardancy are excellent, and when it is lower than the upper limit of the preferable range, stable transparency that is hardly affected by the molding conditions is easily obtained. Such diorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement. In the present invention, the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the general formula [3] may be used alone or in combination of two or more. Further, carbonate structural units other than the above general formulas [1] and [3] can be used in combination within a range of 10% by weight or less with respect to the total weight of the component A within the range not hindering the present invention.

Next, the manufacturing method of a polycarbonate copolymer is demonstrated below.
By reaction of dihydric phenol (I) with a chloroformate-forming compound such as chloroformate of phosgene or dihydric phenol (I) in a mixture of an organic solvent insoluble in water and an aqueous alkali solution in advance. A mixed solution of a chloroformate compound of divalent phenol (I) and / or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group is prepared. As the chloroformate-forming compound, phosgene is preferred.

  In producing the chloroformate compound from the dihydric phenol (I), all the dihydric phenol (I) derived from the carbonate structural unit represented by the general formula [1] can be converted to the chloroformate compound at once. Alternatively, a part thereof may be added as a reaction raw material to a subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.

  The method for this chloroformate compound formation reaction is not particularly limited, but usually a method of carrying out in a solvent in the presence of an acid binder is preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them.

  The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using the phosgene which is a suitable chloroformate formation compound, the method of blowing gasified phosgene into a reaction system can be employ | adopted suitably.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Is used.

  The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, 2 equivalents or slightly more than 2 equivalents per mole of dihydric phenol (I) used for forming the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents). It is preferable to use an acid binder.

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used. In order to improve the transparency of the obtained polycarbonate-polydiorganosiloxane copolymer, it is effective to lower the solid content concentration. The concentration of the dihydric phenol (I) is preferably 400 g / L or less, more preferably 300 g / L or less, and still more preferably 250 g / L or less. The concentration of the dihydric phenol (I) is preferably as low as possible from the viewpoint of stable transparency, but the lower limit is preferably 100 g / L or more from the viewpoint of production efficiency.

  The molar ratio of the organic solvent insoluble in water is preferably 10 mol or more, more preferably 14 mol or more, per mol of dihydric phenol (I). By setting the molar ratio of the organic solvent to the dihydric phenol (I) within such a range, it becomes easier to control the average size and normalized dispersion of the polydiorganosiloxane domain to appropriate values. As a result, a polycarbonate-polydiorganosiloxane having a high total light transmittance and a low haze, even if it is a copolymer comprising a dihydroxyaryl-terminated polydiorganosiloxane (II) (p + q> 30) having a high siloxane polymerization degree A copolymer may be provided. Furthermore, such a copolymer has little influence on the transparency of molding conditions, and can stably give a molded product having high transparency.

The pressure in the formation reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, heat is generated with the reaction, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.
As the pH range in the formation reaction of the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

  In the production of the polycarbonate copolymer used as the component A of the present invention, a divalent phenol (I) chloroformate and a divalent phenol (I) carbonate oligomer having a terminal chloroformate group are thus prepared. After preparing the mixed solution of the chloroformate compound containing, the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the general formula [3] while stirring the mixed solution is prepared. Is added at a rate of 0.01 mol / min or less per 1 mol of the dihydric phenol (I) charged in the step, and the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound are subjected to interfacial polycondensation. Polycarbonate-polydiorganosiloxane copolymer Get the body. Although the present invention is not limited by any theory, the reason why the predetermined domain size and the normalized dispersion of the domain size can be reduced by such a method is presumed as follows.

  In the conventional method, since phosgene is reacted with a mixture of dihydric phenol (I) and dihydroxyaryl-terminated polydiorganosiloxane (II), dihydric phenol (I) and dihydroxyaryl-terminated polydiorganosiloxane (II) From these reactivity differences, a block copolymer having a long chain length composed of only one monomer is likely to be formed. Furthermore, a structure in which dihydroxyaryl-terminated polydiorganosiloxane (II) is bonded via a short-chain carbonate oligomer composed of dihydric phenol (I) is likely to be formed. On the other hand, in the process described above, the rapid increase of the dihydroxyaryl-terminated polydiorganosiloxane (II) concentration is suppressed, and as a result, the reaction between the monomer and the dihydric phenol (I) having a terminal chloroformate group with a carbonate oligomer. The amount of unreacted dihydroxyaryl-terminated polydiorganosiloxane (II) can be reduced. Such reduction eliminates the difference in reactivity between the dihydric phenol (I) and the dihydroxyaryl-terminated polydiorganosiloxane (II), and a long-chain block copolymer consisting of only one monomer, or a dihydroxyaryl-terminated polydiorganosiloxane. It is considered that the formation probability of a structure in which (II) is bonded through a short-chain carbonate oligomer composed of dihydric phenol (I) is lowered. Thereby, it is presumed that an aggregate structure having a small normalized dispersion of the polydiorganosiloxane domain size is formed, and a highly transparent and stable copolymer is obtained. When the addition rate of the above-mentioned dihydroxyaryl-terminated polydiorganosiloxane (II) is faster than 0.01 mol / min, the size of the polydiorganosiloxane domain dispersed therein in the molded article of the polycarbonate-polydiorganosiloxane copolymer obtained The normalized dispersion exceeds 40%, and the transparency tends to deteriorate. That is, good transparency cannot be obtained depending on molding processing conditions, or transparency tends to vary depending on the conditions. When the addition rate of the above-mentioned dihydroxyaryl-terminated polydiorganosiloxane (II) is slower than 0.0001 molar equivalent / min, it is not preferable in terms of production efficiency, and the polydiorganosiloxane component content of the resulting copolymer is reduced, This is not preferable because the molecular weight tends to vary. Accordingly, the lower limit of the addition rate of the dihydroxyaryl-terminated polydiorganosiloxane (II) is substantially 0.0001 molar equivalent / min. The addition rate of the dihydroxyaryl-terminated polydiorganosiloxane (II) is more preferably 0.005 mol / min or less, more preferably 0.005 mol / min or less per 1 mol of the dihydric phenol (I) charged in the preparation of the mixed solution. Is a rate of 0.0025 mol / min or less, and the lower limit is more preferably a rate of 0.0002 mol / min or more.

  Moreover, in order to improve uniform dispersibility, it is desirable that the dihydroxyaryl-terminated polydiorganosiloxane (II) is mixed with a solvent and put into a mixed solution containing a terminal chloroformate compound in a solution state. The concentration of the solution is desirably dilute within a range not inhibiting the reaction, preferably in the range of 0.2 to 0.01 mol / L, more preferably in the range of 0.1 to 0.02 mol / L. It is a range. Such a solvent is not particularly limited, but is preferably the same as the solvent used for the above-mentioned reaction for producing the chloroformate compound, and particularly preferably methylene chloride.

  In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Used. Specifically, when the dihydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction stage, It is preferable to use 2 equivalents or an excess of alkali with respect to the total number of moles of the monohydric phenol (I) and the dihydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

The interfacial polycondensation reaction between the dihydric phenol (I) oligomer and the dihydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.
In such a polycondensation reaction, a terminal terminator or a molecular weight regulator is usually used. Examples of the terminal terminator include compounds having a monohydric phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount of use is preferably in the range of 100 to 0.5 mol, more preferably 50 to 2 mol, with respect to 100 mol of all dihydric phenol compounds used, and it is natural that two or more compounds are used in combination. Is possible.

  In order to promote the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt can be added, and it is preferable to add it. Particularly preferably, triethylmine is used.

  The reaction time of such a polymerization reaction needs to be relatively long in order to improve transparency. The upper limit is preferably 30 minutes or longer, more preferably 50 minutes or longer, and the upper limit is preferably 2 hours or shorter, more preferably 1.5 hours or shorter from the viewpoint of production efficiency.

  The polycarbonate copolymer used as the component A of the present invention can be made into a branched polycarbonate copolymer by using a branching agent in combination with the above dihydric phenol compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

Even if the branched polycarbonate copolymer is produced by the interfacial polycondensation reaction after the completion of the production reaction, the branched solution may contain a branching agent in the mixed solution during the production reaction of the chloroformate compound. It may be a method in which an agent is added. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol% in the total amount of carbonate constituent units constituting the copolymer. Especially preferably, it is 0.05-1.0 mol%. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

  The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but can usually be suitably performed at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.

In some cases, the obtained polycarbonate copolymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η _SP / C] can also be obtained as a polycarbonate copolymer.
The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer having a desired purity (purity) by performing various post-treatments such as a known separation and purification method.

  The structural viscosity index is used as an index characterizing the melt flow characteristics of the polycarbonate resin, and is represented by the following formula (1).

  In the above formula (1), D is a shear rate (1 / sec), a is a constant, σ is a shear stress (Pa), and N is a structural viscosity index. This structural viscosity index is measured according to ISO11443. The structural viscosity index can be an index of resin fluidity in molding and can be an index of anti-drip ability during combustion. When N = 1, Newtonian fluidity is exhibited, and as N increases, non-Newtonian fluidity increases. When this structural viscosity index is high, the resin has a high viscosity in a molten state, so that the resin is difficult to dripping during combustion, and when the shear rate is high, the viscosity is lowered, and thus the molding processability is excellent. The polycarbonate copolymer used as the component A of the present invention preferably has a value of N of 1.60 to 2.50, more preferably 1.60 to 2.30, and even more preferably 1.65. 2.30. Copolymers with N of 1.60 or more exhibit excellent flame retardancy by suppressing dripping of fire types during combustion, and copolymers with N of 2.50 or less have low shear viscosity and excellent moldability. preferable.

Usually, the higher the viscosity average molecular weight (Mv) of the resin, the higher the structural viscosity index, but the aromatic polycarbonate resin is not preferable because the fluidity decreases as the viscosity average molecular weight increases. The viscosity average molecular weight of the polycarbonate copolymer used as the component A of the present invention is preferably 1.6 × 10 ^{4 to} 3.0 × 10 ⁴ , more preferably 1.6 × 10 ^{4 to} 2.5 × 10 6. ⁴ and more preferably 1.7 × 10 ^{4 to} 2.4 × 10 ⁴ . If it is above the lower limit of this preferred range, practical mechanical strength can be obtained in many fields, and if it is below this upper limit, the shear viscosity at a high shear rate is low, which is suitable for various molding methods, particularly injection molding. is there.

In addition, calculation of the viscosity average molecular weight of the polycarbonate copolymer used as A component of this invention is performed in the following way. First, the specific viscosity (η _SP ) calculated by the following formula was determined using an Ostwald viscometer from a solution in which 0.7 g of a polycarbonate copolymer was dissolved in 100 ml of methylene chloride at 20 ° C.,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η] ^{2 c} (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

  The polycarbonate copolymer used as the component A of the present invention has excellent flame retardancy while maintaining good shear fluidity, and has both good moldability and dripping prevention effect due to an increase in melt viscosity. It is characteristic in that it is compatible with difficult properties. This surprising feature is that the polycarbonate copolymer has a high structural viscosity index and is comparable in viscosity at high shear rates to that at low shear rates compared to polycarbonate homopolymers of equivalent viscosity average molecular weight. This is thought to be due to a high phenomenon. The shear rate dependence of the melt viscosity varies greatly depending on the polymerization degree and content of the polydiorganosiloxane component constituting the polycarbonate copolymer, and also the method for producing the copolymer. The present invention has good moldability and melt viscosity. This is extremely useful in that the range in which the effect of preventing dripping due to the increase in the size is compatible is specified.

  The average size of the polydiorganosiloxane domain contained in the polycarbonate copolymer used as the component A of the present invention is suitably in the range of 5 to 40 nm. The lower limit of the average size is preferably 6 nm, and the upper limit of the average size is preferably 20 nm, more preferably 15 nm, and particularly preferably 12 nm. If it is less than the lower limit of this suitable range, impact resistance and flame retardancy will not be sufficiently exhibited, and if it exceeds the upper limit of such suitable range, transparency will not be stably exhibited. Furthermore, even if the average size of the polydiorganosiloxane domain is in a suitable range, if the normalized dispersion exceeds 40%, good and stable transparency cannot be exhibited, which is not preferable. The normalized dispersion of the polydiorganosiloxane domain size is preferably 40% or less, more preferably 30% or less, and still more preferably 20% or less. The lower limit of such normalized dispersion is practically preferably 5% or more, more preferably 10% or more. By having such an appropriate average domain size and its normalized dispersion, a molded article excellent in both transparency, impact resistance, and flame retardancy is provided.

  The average domain size and normalized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer molded article comprising the polycarbonate copolymer used as the component A in the present invention is determined by the small angle X-ray scattering method (Small Angle X-ray Scattering). : SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region where the scattering angle (2θ) is less than 10 °. In this small-angle X-ray scattering method, if there is a region of about 1 to 100 nm in which the electron density is different in a substance, the X-ray diffuse scattering is measured by the difference in the electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of an aggregated structure in which polydiorganosiloxane domains are dispersed in the matrix of the polycarbonate copolymer used as the component A of the present invention, X-ray diffuse scattering occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there is a particle size, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, is accurate, simple, and reproducible. It can be measured well.

  The average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of the particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size with the average domain size, and is represented by the following formula (2).

In the above formula (2), [delta] is the standard deviation of the polydiorganosiloxane domain size, D _AV is the average domain size.

  The terms “average domain size” and “normalized dispersion” used in connection with the present invention are the three-stage plate (width 50 mm, length 90 mm, thickness 3.0 mm from the gate side (length 20 mm) produced by injection molding. ), 2.0 mm (length 45 mm), 1.0 mm (length 25 mm)), a measurement value obtained by measuring a thickness of 1.0 mm by a small angle X-ray scattering method is shown.

<B component: organic acid metal salt flame retardant>
As the organic acid metal salt flame retardant used as the component B of the present invention, various metal salts conventionally used for flame-retarding polycarbonate resins can be used. Examples include (earth) metal salts, alkali (earth) metal salts of aromatic imides, alkali (earth) metal salts of sulfate esters, and alkali (earth) metal salts of phosphoric acid partial esters ( Here, the notation of alkali (earth) metal salt is used in the meaning including both alkali metal salt and alkaline earth metal salt). Among them, one or more 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 organic alkali (earth) metal salt is preferably used, and the alkali (earth) metal salt of perfluoroalkylsulfonic acid is more preferable. These may be used alone or in combination of two or more.

  Preferred examples of alkali (earth) metal salts of perfluoroalkyl sulfonate include perfluoromethane sulfonate, perfluoroethane sulfonate, perfluoropropane sulfonate, perfluorobutane sulfonate, and perfluoromethylbutane. Examples thereof include sulfonate, perfluorohexanesulfonate, perfluoroheptanesulfonate, and perfluorooctanesulfonate, and those having 1 to 8 carbon atoms are particularly preferable. Among these, perfluoroalkylsulfonic acid alkali metal salts are preferable. As the alkali metal salt used in the alkali metal perfluoroalkyl sulfonate, rubidium and cesium are suitable when the demand for flame retardancy is higher, but these are not versatile and difficult to purify. As a result, it may be disadvantageous in terms of cost. 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. Among these, potassium perfluorobutanesulfonate and cesium perfluorobutanesulfonate are particularly preferable.

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, Mention may be made of 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,
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 alkali (earth) metal salts of aromatic imides include saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonamide (in other words, di (p-toluenesulfone) imide), N- (N ′ -Benzylaminocarbonyl) sulfanilimide, and alkali (earth) metal salts such as N- (phenylcarboxyl) sulfanilimide and bis (diphenylphosphoric acid) imide.

  Examples of alkali (earth) metal salts of sulfates include alkali (earth) metal salts of sulfates of monovalent and / or polyhydric alcohols, and such monovalent and / or polyhydric alcohols. Examples of sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, and lauric acid monoglyceride sulfate. Examples thereof include an ester, a sulfate ester of palmitic acid monoglyceride, and a sulfate ester of stearic acid monoglyceride. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Specific examples of alkali (earth) metal salts of phosphoric acid partial esters include bis (2,6-dibromo-4-cumylphenyl) phosphoric acid, bis (4-cumylphenyl) phosphoric acid, and bis (2,4,6- Alkali (earth) such as tribromophenyl) phosphate bis (2,4-dibromophenyl) phosphate, bis (4-bromophenyl) phosphate, diphenylphosphate, bis (4-tert-butylphenyl) phosphate Mention may be made of metal salts.

  The amount of the B component contained in the resin composition of the present invention is 0.01 to 0.2 parts by weight, preferably 0.01 to 0.18 parts by weight with respect to 100 parts by weight of the A component. More preferably, it is 0.01-0.15 weight part, More preferably, it is 0.03-0.15 weight part. If the content of the component B is too large, not only the transparency, which is a feature of the present invention, is impaired, but also in some cases, 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.

<Other ingredients>
On the other hand, the resin composition of the present invention may contain other resins and fillers as long as the transparency is not impaired. However, many of the other resins and fillers impair the transparency. Therefore, the selection of the type and quantity should take that point into consideration.

  Unless the transparency is impaired, the resin composition of the present invention is blended with a thermoplastic resin other than the component A in order to improve the mechanical properties, chemical properties or electrical properties of the molded product. be able to. The blending amount of the other thermoplastic resin varies depending on the type and purpose, but is usually preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight per 100 parts by weight of component A.

  Other thermoplastic resins include, for example, polycarbonate resins other than component A, polyethylene resins, polypropylene resins, polyalkyl methacrylate resins, and other general-purpose plastics, polyphenylene ether resins, polyacetal resins, polyamide resins, cyclic polyolefin resins, Engineering plastics represented by polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), so-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylenesulfide Can be mentioned. Furthermore, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

  In the resin composition of the present invention, additives known per se can be blended in a small proportion for imparting various functions and improving properties to the molded product. These additives are used in usual amounts as long as the object of the present invention is not impaired. Such additives include heat stabilizers, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents (PTFE particles, etc.), colorants (pigments such as carbon black and titanium oxide, dyes), light diffusion. Agents (acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterials Agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers or photochromic agents.

In order to improve the thermal stability, antioxidant property, light stability (ultraviolet light stability) and releasability of the resin composition of the present invention, the additives used for these improvements in the aromatic polycarbonate resin are as follows. Advantageously used. Hereinafter, these additives will be specifically described.
The resin composition of this invention can mix | blend a phosphorus containing stabilizer as a heat stabilizer. As the phosphorus-containing stabilizer, any of phosphite compounds, phosphonite compounds, and phosphate compounds can be used.

  Various phosphite compounds can be used. Specific examples include phosphite compounds represented by the following general formula [4], phosphite compounds represented by the following general formula [5], and phosphite compounds represented by the following general formula [6].

［式中Ｒ^５は、水素原子または炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルカリール基、炭素数７〜３０のアラルキル基、またはこれらのハロ、アルキルチオ（アルキル基は炭素数１〜３０）またはヒドロキシ置換基を示し、３個のＲ^５は互いに同一または互いに異なるのいずれの場合も選択でき、また２価フェノール類から誘導されることにより環状構造も選択できる。］

[Wherein R ⁵ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio thereof (an alkyl group). Represents 1 to 30 carbon atoms) or a hydroxy substituent, and three R ^{5 s} can be selected from the same or different from each other, and a cyclic structure can be selected by being derived from dihydric phenols. ]

［式中Ｒ^６、Ｒ^７はそれぞれ水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。なお、シクロアルキル基およびアリール基は、アルキル基で置換されていないもの、またはアルキル基で置換されているもののいずれも選択できる。］

[Wherein R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group, a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group or those substituted with an alkyl group. ]

［式中Ｒ^８、Ｒ^９は炭素数１２〜１５のアルキル基である。なお、Ｒ^８およびＲ^９は互いに同一または互いに異なるのいずれの場合も選択できる。］で表わされるホスファイト化合物を挙げることができる。

[Wherein R ⁸ and R ⁹ are alkyl groups having 12 to 15 carbon atoms. Note that R ⁸ and R ⁹ can be selected to be the same or different from each other. The phosphite compound represented by this can be mentioned.

  Examples of the phosphonite compound include a phosphonite compound represented by the following general formula [7] and a phosphonite compound represented by the following general formula [8].

［式中、Ａｒ^１、Ａｒ^２は炭素数６〜２０のアリール基ないしアルキルアリール基、または炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示し、４つのＡｒ^１は互いに同一、または互いに異なるいずれも選択できる。または２つのＡｒ^２は互いに同一、または互いに異なるいずれも選択できる。］

[In the ^formula, Ar 1, Ar ² represents a 2- (4-oxyphenyl) propyl-substituted aryl group of the aryl group or alkyl aryl group having 6 to 20 carbon atoms, or 15-25 carbon atoms, the four Ar ¹ Either the same or different from each other can be selected. Alternatively, ^two Ar ² can be selected to be the same or different from each other. ]

  Preferable specific examples of the phosphite compound represented by the above general formula [4] include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenylmono (Tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite are mentioned.

  Preferred specific examples of the phosphite compound represented by the above general formula [5] include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc., preferably distearyl pentaerythritol diphosphite, Examples thereof include bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

  Preferable specific examples of the phosphite compound represented by the general formula [6] include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

  Preferable specific examples of the phosphonite compound represented by the general formula [7] include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di -N-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert) -Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propyl) Phenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4′-biphe Range phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphospho And nitrite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, and the like. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and tetrakis (2 , 4-Di-tert-butylphenyl) -biphenylenediphosphonite is more preferred. The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically tetrakis (2,4-di-tert-butylphenyl) -4,4. '-Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -3,3' -It is possible to use one or two or more of biphenylene diphosphonites in combination, but a mixture of these three is preferable.

  Preferable specific examples of the phosphonite compound represented by the general formula [8] include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n -Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3 -Phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-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) Nyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, and bis (2,4-di-tert-butylphenyl) -phenyl-phenyl Phosphonite is more preferred. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- One or two of phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite can be used in combination. It is a mixture. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, and more preferably in the range of 5: 2 to 3.

On the other hand, as phosphate compounds, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate, and trimethyl phosphate is preferable.
Among the above phosphorus-containing heat stabilizers, more preferred compounds include compounds represented by the following general formulas [9] and [10].

（式〔９〕中、Ｒ^１０およびＲ^１１は、それぞれ独立して炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示す。）

(In the formula [9], R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

（式〔１０〕中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１８、Ｒ^１９およびＲ^２０はそれぞれ独立して水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示し、Ｒ^１６は水素原子または炭素原子数１〜４のアルキル基を示し、およびＲ^１７は水素原子またはメチル基を示す。）

(In the formula [10], R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group. A group or an aralkyl group, R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁷ represents a hydrogen atom or a methyl group.)

In the formula [9], R ¹⁰ and R ¹¹ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound represented by the formula [9] include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl). Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) Examples thereof include phosphite, and tris (2,6-di-tert-butylphenyl) phosphite is particularly preferable.

  Specifically, the compound represented by the formula [10] is a phosphite derived from 2,2′-methylenebis (4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, 2 2,2'-methylenebis (4,6-di-tert-butylphenol) and phosphites derived from phenol, especially from 2,2'-methylenebis (4,6-di-tert-butylphenol) and phenol. Derived phosphites are preferred.

  In addition, the phosphorus compound of Formula [10] can be manufactured by a well-known method. For example, there is a method of reacting a bisphenol compound represented by the following general formula [11] with phosphorus trichloride to obtain a corresponding phosphoric chloride, and then reacting it with a phenol represented by the following general formula [12]. .

（式〔１１〕中、Ｒ^２１、Ｒ^２２、Ｒ^２３、およびＲ^２４はそれぞれ水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示し、Ｒ^２５は水素原子または炭素原子数１〜４のアルキル基を示し、およびＲ^２６は水素原子またはメチル基を示す。）

(In the formula [11], R ²¹ , R ²² , R ²³ and R ²⁴ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ²⁵ represents hydrogen. And represents an atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁶ represents a hydrogen atom or a methyl group.)

（式〔１２〕中、Ｒ^２７、Ｒ^２８、およびＲ^２９はそれぞれ水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示す。）

(In the formula [12], R ²⁷ , R ²⁸ and R ²⁹ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

  Specific examples of the compound of the general formula [11] include 2,2′-methylenebisphenol, 2,2′-methylenebis (4-methylphenol), 2,2′-methylenebis (6-methylphenol), 2, 2'-methylenebis (4,6-dimethylphenol), 2,2'-ethylidenebisphenol, 2,2'-ethylidenebis (4-methylphenol), 2,2'-isopropylidenebisphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2, 2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dihydroxy-3,3'-di α-methylcyclohexyl) -5,5′-dimethylphenylmethane, 2,2′-methylenebis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-) tert-butylphenol), 2,2-butylidene-bis (4-methyl-6-tert-butylphenol), and the like, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert- Butylphenol) and 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol) are preferred.

  On the other hand, specific examples of the compound of the general formula [12] include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tert- Butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6 Examples include tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, and 2,6-di-tert-butyl-4-s-butylphenol. And compounds having two or more alkyl substituents are preferred.

  Examples of the antioxidant that can be added to the resin composition of the present invention include phenolic antioxidants. The phenolic antioxidant can suppress discoloration when exposed to heat and exhibits a certain degree of effect on improving flame retardancy. Various types of such phenolic antioxidants can be used.

  Specific examples of such phenolic antioxidants include, for example, 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'-methylenebis (4-ethyl-6-tert- Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-me Renbis (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) fe Ru] 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), 2,4-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) isocyanurate, 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, tetrakis [methylene-3 -(3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane can be mentioned and can be preferably used.

  More preferably, 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, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Further, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate is preferable.

  Also, a sulfur-containing antioxidant can be used as the antioxidant. It is particularly suitable when the resin composition is used for rotational molding or compression molding. Specific examples of such sulfur-containing antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate. , Distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4 -(3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. be able to. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.

The phosphorus-containing heat stabilizer, phenolic antioxidant, and sulfur-containing antioxidant listed above can be used alone or in combination of two or more.
The proportion of these stabilizers in the composition is 0.0001 to 1 part by weight of the phosphorus-containing stabilizer, phenol-based antioxidant, or sulfur-containing antioxidant per 100 parts by weight of component A, respectively. preferable. More preferably, it is 0.0005-0.5 weight part, More preferably, it is 0.001-0.2 weight part.

  A release agent can be blended in the resin composition of the present invention as necessary. In the present invention, since it has flame retardancy by containing B component, it is possible to achieve good flame retardancy even when a release agent that usually has an adverse effect on flame retardancy is blended. Can do. As such a release agent, those known per se can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-alkene polymer may be used. These may be modified with a functional group-containing compound such as acid modification), silicone compounds (Other than the component C of the present invention. Examples include linear or cyclic polydimethylsiloxane oil and polymethylphenyl silicone oil. These are also modified with functional group-containing compounds such as acid modification. ), Fluorine compounds (fluorine oil typified by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, and fluorine oil can be mentioned. Preferable mold release agents include saturated fatty acid esters. For example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, and lower fatty acid esters such as stearic acid stearate. , Higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The content of the release agent is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of component A.

  Since the resin composition of the present invention is often used for a housing of OA equipment or the like, it is preferable that the resin composition contains an ultraviolet absorber. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy. -4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2 '-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis ( 5-benzoyl-4-hydroxy 2-methoxyphenyl) benzophenone ultraviolet absorbers typified by methane and the like.

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, and 2- (2′-hydroxy). -5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'- Di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α'-dimethylbenzyl) phenylbenzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetraphthal Ruimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2- Yl) phenol], methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-benzotriazole ultraviolet rays typified by condensation products with polyethylene glycol An absorbent can be mentioned.

  Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol, 2- (4,6-bis- (2,4 There may be mentioned hydroxyphenyltriazine compounds such as -dimethylphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol.

A light stabilizer can also be mix | blended with the resin composition of this invention. Examples of such light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butyl malonate, 1,2,3,4-butane Condensation product of carboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid and 1,2,2,6,6-pentamethyl- A condensate of 4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1, , 2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, poly {[ 6-morpholino-s-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4, 8,10-tetraoxaspiro [5,5 Undecane) condensate with diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) ) Amino] -chloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β , Β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol, polymethylpropyl 3-oxy- [4- ( 2,2,6,6-tetramethyl) piperidinyl] siloxane, hindered amines.
The contents of the ultraviolet absorber and the light stabilizer are each preferably 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, per 100 parts by weight of component A.

  In addition, a blueing agent can be blended in the resin composition of the present invention in order to counteract the yellowishness based on the ultraviolet absorber and the like. Any bluing agent can be used without any problem as long as it is usually used for polycarbonate resin. In general, anthraquinone dyes are preferred because they are readily available. Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No. (Color Index No.) 60725; Trade names “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Violet 31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No. 60725; trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA. No. 61500; trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation, generic name Solvent Violet 36 [CA. No. 68210; Trade name: “Macrolex Violet 3R” manufactured by Bayer, Inc., generic name: Solvent Blue 97 [trade name: “Macrolex Blue RR” manufactured by Bayer, Inc.], and generic name: Solvent Blue 45 [CA. No. 61110; trade name “Terrazol Blue RLS” manufactured by Sand Corp.] and the like, and Macrolex Blue RR, Macrolex Violet B and Terrazol Blue RLS are particularly preferable. The content of the bluing agent is preferably 0.000005 to 0.0010 parts by weight, more preferably 0.00001 to 0.0001 parts by weight per 100 parts by weight of component A.

  The resin composition of the present invention is excellent in anti-drip properties, but a normal anti-drip agent can be used in combination to further reinforce such performance. However, in the resin composition of the present invention, the blending amount is suitably 0.5 parts by weight or less, preferably 0.3 parts by weight or less, based on 100 parts by weight of component A so as not to impair such transparency. More preferred is less than or equal to parts by weight, and even more preferred is less than or equal to 0.1 parts by weight. 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” as used herein means, for example, that PTFE is used in such an amount that the total light transmittance of a 2 mm-thick plate does not fall below 80%. 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 1 million to 10 million, 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. . Commercially available products of PTFE in a mixed form include “METABRENE A3000” (trade name), “METABBRENE A3700” (trade name), “METABRENE A3750” (trade name), Shinpoly SN3307 (trade name), and Mitsubishi Rayon Co., Ltd. Examples thereof include “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

<About production of resin composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, component A, component B and optionally other components are mixed thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and then an extrusion granulator as necessary. And granulating with a briquetting machine or the like, and then melt-kneading with a melt-kneader typified by a vent-type biaxial ruder and pelletizing with a device such as a pelletizer. Alternatively, the A component, the B component and optionally other components are each independently fed to a melt kneader represented by a vented twin-screw rudder, and after pre-mixing part of the A component and other components , A method of supplying 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 the diluted mixture is premixed with other components and then melt kneaded. The method of supplying to a machine is also mentioned. 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.

  The resin composition of the present invention gives a molded article excellent in transparency. The total light transmittance of a molded product having a thickness of 2 mm and having a calculated average roughness (Ra) of 0.03 μm or less molded using the resin composition of the present invention is preferably 80% to 95%, more preferably. 82 to 95%, more preferably 84 to 95%, and most preferably 84 to 90%. Thus, the transparent resin composition of the present invention is suitable for obtaining a molded article excellent in transparency. The transparent resin composition of the present invention can be advantageously used for various molded products that require transparency and high flame retardancy. Furthermore, since the transparent resin composition of the present invention is excellent in transparency, it is possible to obtain a molded product having excellent transparency and vivid colors by blending pigments and dyes.

  Moreover, the resin composition of this invention can also be used in the form of various profile extrusion molded products, a sheet | seat, a film, etc. by extrusion molding by the outstanding melt tension. For forming sheets and films, an inflation method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be formed into a molded product by rotational molding without melt-kneading.

  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 flame retardant polycarbonate resin composition of the present invention is a thick molded article in a resin composition in which an organic acid metal salt flame retardant is blended with a polycarbonate copolymer containing a specific carbonate constituent unit containing a polydiorganosiloxane unit. These technologies have excellent flame retardancy while maintaining transparency, and these technologies are not present in conventional flame retarding technologies. The polycarbonate resin composition of the present invention can impart a high level of flame retardancy without using a brominated flame retardant or a phosphorus flame retardant, which is considered to have a high environmental load, and even in a thin part of a molded product. Since the transparency is maintained even in the thick part, it is extremely useful for various industrial uses such as the OA equipment field and the electric / electronic equipment field, and the industrial effect exerted by it is extremely large.

  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 described more specifically with reference to examples and comparative examples. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. The evaluation was performed according to the following method.

1. Evaluation of polycarbonate-polyorganosiloxane copolymer (1) Viscosity average molecular weight (Mv)
Using a Ostwald viscometer, a specific viscosity (η _SP ) calculated by the following formula was determined from a solution obtained by dissolving a polycarbonate-polydiorganosiloxane copolymer in 100 ml of methylene chloride at 20 ° C.,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

(2) Polydiorganosiloxane component content Using JNM-AL400 manufactured by JEOL Ltd., the ¹ H-NMR spectrum of the polycarbonate-polydiorganosiloxane copolymer was measured, and the integration of the peak derived from dihydric phenol (I) was performed. The ratio was calculated by comparing the integral ratio of the peak derived from the dihydroxyaryl-terminated polydiorganosiloxane (II).
Polyorganosiloxane component content (wt%) = [A / (A + B)] × 100
A: [Integral ratio of ¹ H peak of dihydroxyaryl-terminated polydiorganosiloxane (II)] × [Molecular weight of polydiorganosiloxane moiety]
B: [Integral ratio of ¹ H peak of dihydric phenol (I)] × [Molecular weight of dihydric phenol]

(3) Structural viscosity index (N)
The polycarbonate-polydiorganosiloxane copolymer powder was kneaded at a temperature of 260 ° C. by a bent type twin screw extruder (manufactured by Technobel Co., Ltd., KZW15-25MG) and pelletized. The obtained pellets were dried with hot air at 120 ° C. for 5 hours, and then a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used in accordance with ISO11443 (JIS K 7199). Co., Ltd. Capillary model EF (diameter: 1.0 mm, length: 10.0 mm, L / D: 10), furnace temperature of 300 ° C., shear rate D (60.8-6080 sec ⁻¹ ) The structural viscosity index N was determined from the slope of the regression line obtained by plotting each value on a log-log graph.

(4) Average size of polydiorganosiloxane domain and standardized dispersion Polycarbonate-polydiorganosiloxane copolymer powder was kneaded at a temperature of 260 ° C. with a vented twin screw extruder (Technobel Co., Ltd., KZW15-25MG). And pelletized. The obtained pellets were dried with hot air at 120 ° C. for 5 hours, and then the width was measured at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U / SMIV]. A three-stage plate having a length of 50 mm, a length of 90 mm, and a thickness of 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm) from the gate side was molded. Using this three-stage plate, the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain at the intersection of 5 mm from the end of 1.0 mm thickness and 5 mm from the side were measured using an X-ray diffractometer ( It measured using Rigaku Corporation RINT-TTRII. The X-ray source was a CuKα characteristic X-ray (wavelength 0.1541841 nm), a tube voltage of 50 kV, and a tube current of 300 mA. The small angle scattering optical system was Slit: 1st 0.03 mm, HS 10 mm, SS 0.2 mm, and RS 0.1 mm. The measurement was performed by an asymmetric scanning method (2θ scanning) with an FT of 0.01 ° step, 4 sec / step, and a scanning range of 0.06-3 °. For the analysis of curve fitting, small angle scattering analysis software NANO-Solver (Ver. 3.3) manufactured by Rigaku Corporation was used. The analysis is an aggregate structure in which spherical domains of polydiorganosiloxane are dispersed in a polycarbonate polymer matrix, and assuming that there is a variation in particle size distribution, the density of the polycarbonate matrix is 1.2 g / cm ³ and the polydiorganosiloxane domain is The density was 1.1 g / cm ^3, and an isolated particle model that did not consider the interparticle interaction (interparticle interference) was used.

(5) Total light transmittance The polycarbonate-polydiorganosiloxane copolymer powder was kneaded at a temperature of 260 ° C. using a bent type twin screw extruder (manufactured by Technobel Co., Ltd., KZW15-25MG) and pelletized. The obtained pellets were dried with hot air at 120 ° C. for 5 hours, and then the width was measured at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U / SMIV]. A three-stage plate having a length of 50 mm, a length of 90 mm, and a thickness of 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm) from the gate side was molded. The total light transmittance at a thickness of 2.0 mm of the three-stage plate was measured using Haze Meter NDH 2000 manufactured by Nippon Denka Kogyo Co., Ltd. according to ASTM D1003.

2. Evaluation of Resin Composition (1) Transparency Pellets obtained from each composition of the examples were dried with a hot air circulation dryer at 120 ° C. for 5 hours, and an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U S-M IV] at a molding temperature of 280 ° C. and a mold temperature of 80 ° C., the width is 50 mm, the length is 90 mm, and the thickness is 3.0 mm (length 20 mm) and 2.0 mm (length 45 mm) from the gate side. A three-stage plate having a thickness of 1.0 mm (length: 25 mm) was formed. Using this three-stage plate, the total light transmittance at a thickness of 2.0 mm was measured by ASTM D1003. A sample having a total light transmittance of 80% or more was rated as ○, and a sample having less than 80% was rated as ×.

(2) Flame retardance The pellets obtained from each composition of the examples were dried in a hot air circulation dryer at 120 ° C. for 5 hours, and the cylinder temperature was 280 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 3.2 mm and 1.6 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.

[Examples 1 to 4 and Comparative Examples 1 to 4]
The resin composition which consists of a mixture ratio of Table 2 was created in the following ways. The description will be made according to the symbols in the following table. Each component in the ratio of Table 2 was weighed and uniformly mixed using a tumbler, and the mixture was put into an extruder to prepare a resin composition. 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 the cylinder temperature and the die temperature of 260 to 280 ° C. and the vent suction of 3000 Pa, cooled in a water bath, then cut into a strand by a pelletizer and pelletized. The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours, and each measurement sample was prepared under the above conditions. The raw materials used in Table 2 are as follows.

(A component)
PC-1: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 1.
PC-2: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 2.
PC-3: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 3.
PC-4: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 4.
PC-5: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 5.

Production Example 1: Method for producing PC-1 In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21915 parts of ion-exchanged water and 3675 parts of a 48.5% aqueous sodium hydroxide solution are placed and expressed by the above formula [1]. After dissolving 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 7.6 parts of hydrosulfite as the dihydroxy compound (I) constituting the carbonate structural unit, 14565 parts of methylene chloride ( 14 mol) was added to 1 mol of the dihydroxy compound (I), and 1900 parts of phosgene was blown in for 60 minutes at 22-30 ° C. with stirring. Add a solution of 4131% sodium hydroxide solution 1131 parts and p-tert-butylphenol 108 parts in 800 parts methylene chloride and stir the dihydroxyaryl terminal constituting the carbonate structural unit represented by the general formula [3] with stirring. A solution obtained by dissolving 430 parts of a polydiorganosiloxane compound (X-22-1821, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula [13] as polydiorganosiloxane (II) in 1600 parts of methylene chloride Polydiorganosiloxane (II) was added at a rate of 0.0008 mol / min per 1 mol of dihydric phenol (I) to obtain an emulsified state, and then vigorously stirred again. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued for 1 hour at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated with stirring to obtain a polycarbonate-polydiorganosiloxane copolymer powder. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer.

  The resulting polycarbonate-polydiorganosiloxane copolymer was measured for viscosity average molecular weight, polydiorganosiloxane component content, structural viscosity index, polydiorganosiloxane domain average size and normalized dispersion, and total light transmittance. The measurement results are shown in Table 1.

Production Example 2: Method for producing PC-2 In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 13980 parts of ion-exchanged water and 2956 parts of a 48.5% aqueous sodium hydroxide solution are placed and represented by the formula [1]. After dissolving 3369 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 6.8 parts of hydrosulfite as dihydric phenol (I), 11420 parts of methylene chloride was added, and the mixture was stirred for 22-30. At 700C, 1700 parts of phosgene was blown in for 70 minutes. A solution prepared by dissolving 431 parts of 48.5% aqueous sodium hydroxide solution, 11420 parts of methylene chloride and 85 parts of p-tert-butylphenol in 800 parts of methylene chloride was added, and the dihydric phenol represented by the formula [3] ( II) As a solution obtained by dissolving 373 parts of the polydiorganosiloxane compound (X-22-1821, manufactured by Shin-Etsu Chemical Co., Ltd.) in 1600 parts of methylene chloride, dihydroxyaryl-terminated polydiorganosiloxane (II) is dihydric phenol (I). After adding at a rate of 0.0008 mol / min per 1 mol, the mixture is stirred at a rotational speed of 8000 rpm for 2 minutes with a SL-type homomixer to obtain a highly emulsified state, and then left standing without stirring. The polymerization reaction was carried out by maintaining at ± 1 ° C for 2 hours (medium chloride per mole of bisphenol A). Ren 18 mol). After completion of the reaction, methylene chloride was added to dilute the organic phase to a polycarbonate-polyorganosiloxane copolymer concentration of 12% by weight, and the aqueous phase was separated and removed, followed by thorough washing. Next, this resin solution was put into a kneader filled with warm water, and methylene chloride was evaporated while stirring to obtain a polycarbonate-polydimethylsiloxane copolymer powder. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer. The obtained polycarbonate-polydiorganosiloxane copolymer was analyzed in the same manner as in Production Example 1. The measurement results are shown in Table 1.

Production Example 3: Production Method of PC-3 A polycarbonate-polydimethylsiloxane copolymer powder was obtained in the same manner as in Production Example 1 except that 77 parts of p-tert-butylphenol was used. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer. The obtained polycarbonate-polydiorganosiloxane copolymer was analyzed in the same manner as in Production Example 1. The measurement results are shown in Table 1.

Production Example 4: Method for producing PC-4 3897 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 204 parts of a polydiorganosiloxane compound (X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd.) A polycarbonate-polydimethylsiloxane copolymer powder was obtained in the same manner as in Production Example 1 except that it was dissolved in 800 parts of methylene chloride. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer. The obtained polycarbonate-polydiorganosiloxane copolymer was analyzed in the same manner as in Production Example 1. The measurement results are shown in Table 1.

Production Example 5: Production Method of PC-5 A solution of 430 parts of a polydiorganosiloxane compound (X-22-1821, manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in 1600 parts of methylene chloride was used as a dihydroxyaryl-terminated polydiorganosiloxane (II). Was added at a rate of 0.5 mol / min per mole of dihydric phenol (I) to obtain an emulsified state, 4.3 parts of triethylamine was added, and stirring was continued for 0.5 hours at a temperature of 26 to 31 ° C. Except for the above, a polycarbonate-polydimethylsiloxane copolymer powder was obtained in the same manner as in Production Example 1. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer. The obtained polycarbonate-polydiorganosiloxane copolymer was analyzed in the same manner as in Production Example 1. The measurement results are shown in Table 1.

(B component)
B-1: Perfluorobutanesulfonic acid potassium salt (Megafac F-114P manufactured by Dainippon Ink, Inc.)
B-2: Sodium perfluorobutanesulfonic acid salt (Megafac F-114S, manufactured by Dainippon Ink Co., Ltd.)
(Other ingredients)
C-1: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by Ciba Specialty Chemicals)
C-2: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals)
C-3: 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5,5] undecane (Sumitizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.)

  The flame retardant polycarbonate resin composition obtained in the present invention exhibits a high degree of flame retardancy and gives a sheet-shaped molded article having good transparency. Is possible. As specific examples, it can be widely used in the field of optical parts, electrical / electronic devices, and automobiles.

Claims (7)

(A) To 100 parts by weight of a transparent polycarbonate copolymer (component A) composed of a carbonate structural unit represented by the following general formula [1] and a carbonate structural unit represented by the following general formula [3]:

[In General Formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]. .

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number less than 100. X is a divalent aliphatic group having 2 to 8 carbon atoms.)
(B) One or more flame retardants (component B) 0.01 to 0.00 selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates and alkali (earth) metal aromatic sulfonates. A flame retardant polycarbonate resin composition containing 2 parts by weight, wherein the A component is an agglomerated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate part matrix composed of a carbonate constituent unit represented by the general formula [1] The polydiorganosiloxane domain has an average size of 5 to 15 nm, a normalized dispersion of 40% or less, and a flame retardancy evaluation according to UL-94 of V-0. Flammable polycarbonate resin composition. The viscosity-average molecular weight of the A component is ^{1.6 × 10 4 ~3.0 × 10 4} , structural viscosity index (N) of claim 1, which is a 1.60 to 2.50 Flame retardant polycarbonate resin composition.   In the said General formula [3], p + q is 30-60, The flame-retardant polycarbonate resin composition of Claim 1 or 2 characterized by the above-mentioned.   The difficulty according to any one of claims 1 to 3, wherein the polydiorganosiloxane block represented by the general formula [3] is 2 to 20 wt% based on the total weight of the component A. Flammable polycarbonate resin composition.   5. The smooth light flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less, wherein the total light transmittance is 80% to 95%. 5. Flame retardant polycarbonate resin composition.   An injection-molded article comprising the flame-retardant polycarbonate resin composition according to any one of claims 1 to 5.   The extrusion molded product which consists of a flame-retardant polycarbonate resin composition as described in any one of Claims 1-5.