JP5451505B2 - 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.

  The polycarbonate resin is a polymer in which an aromatic or aliphatic dioxy compound is linked by a carbonic acid ester, and among them, a polycarbonate resin (hereinafter referred to as “PC”) obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A). -A ") is used in many fields because it has excellent transparency, heat resistance, and mechanical properties such as impact resistance. In particular, applications that require transparency such as optical lenses and optical recording media are widely used by taking advantage of the high light transmittance of polycarbonate resin and the excellent transparency represented by extremely low haze. In recent years, from the viewpoint of reducing environmental impact and design, there has been an increasing demand for transparency of polycarbonate even in fields that did not require transparency so far, such as OA equipment, electrical / electronic equipment field, automobile field, and building field. ing. Among these fields of use, there are fields that require a high degree of flame retardancy, mainly in the fields of OA equipment and electrical / electronic equipment. The polycarbonate resin is a resin having a high oxygen index among various thermoplastic resins and generally having a self-extinguishing property. However, in order to satisfy safety requirements in OA equipment, electrical / electronic equipment fields, and other various uses, there is a strong demand for resin compositions with further improved flame retardancy. In addition, there is a demand for thinning the material, and it has become necessary to increase the flame retardancy without impairing transparency.

  In order to increase the flame retardancy of polycarbonate, it is necessary to suppress dripping during combustion. As a method for suppressing dripping during combustion, a method of adding polytetrafluoroethylene is generally known. For example, a technique for preventing dripping during combustion by mixing an organic alkali metal salt or alkaline earth metal salt with an aromatic polycarbonate and further adding polytetrafluoroethylene is disclosed. When ethylene is blended with an aromatic polycarbonate resin, the transparency of the molded product is lowered because polytetrafluoroethylene and the aromatic polycarbonate resin are incompatible. (See Patent Document 1) As a method for preventing dripping during combustion without using polytetrafluoroethylene, a technique of adding a carbon nanotube and a specific silicone resin to a polycarbonate resin has been disclosed. The transparency of can't be maintained. (Refer to Patent Document 2) As described in these reports, in order to improve the flame retardancy of polycarbonate resin, a method of adding a flame retardant has been usually used, but the transparency inherent in polycarbonate is not impaired. In order to improve the flame retardancy, there is a limit in the conventional method, and studies have been made to impart flame retardancy to the polycarbonate resin itself which is the main resin. A flame retardant polycarbonate resin composition having transparency has been reported by using a branched polycarbonate as a main resin and adding an organic alkali metal salt. However, flame retardancy at a high level was insufficient. In addition, it is a resin composition consisting of branched polycarbonate, aromatic sulfonic acid metal salt, halogenated organophosphate, phenyl group-containing polysiloxane, and polyarylene sulfide, and is thinned while maintaining the original transparency of the polycarbonate resin. However, a flame-retardant polycarbonate resin composition having a high flame retardancy that does not show a dripping phenomenon (hereinafter referred to as “drip”) even when burned has been reported. (See Patent Document 4) However, at present, a high degree of flame retardancy with a thin wall may be required. Generally, the thinner the wall, the more easily the entire molded product is softened during combustion, and drip is more likely to occur during combustion. Such a phenomenon occurs extremely sensitively to the thickness of the molded product, and even if the thickness difference is about 0.1 mm, there may be a difference in the presence or absence of drip. Furthermore, with the diversification of uses of polycarbonate and the thinning of products, the flame retardant level of materials has become very important. That is, if the flame retardancy of the material is improved even slightly, the application of the material is greatly expanded, and the product design can be widened. For example, regarding the UL94 standard widely used as a flame retardant index of materials in electrical applications, the minimum thickness of a test piece that can achieve the flame retardant rank V-0 by improving the flame retardant property of the material is reduced even by 0.1 mm. If it can, it will add a great deal of value to the material. On the other hand, a polycarbonate copolymer containing a carbonate structural unit composed of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is used as a main resin, and an organic sulfonate, an organic sulfate, and an ester of phosphoric acid. In addition, a flame retardant polycarbonate composition comprising at least one compound selected from the group consisting of phosphonic acid esters and flame retardant is reported. However, no mention is made of an organometallic salt flame retardant containing a fluoroalkyl group, and the flame retardancy is not sufficient.

Japanese Patent Publication No. 60-38418 JP 2009-149780 A Japanese Patent No. 3129374 JP-A-11-323118 Japanese Patent Laid-Open No. 11-80529

  An object of the present invention is to provide a polycarbonate resin composition excellent in transparency and flame retardancy.

  As a result of intensive research aimed at achieving the above object, the present inventors have aimed at a polycarbonate resin composition containing a specific carbonate constituent unit and a polycarbonate resin composition containing a specific organometallic salt flame retardant. The present inventors have found that it is excellent in transparency and is also excellent in flame retardancy.

[上記式において、Ｗは炭素原子数１〜４のアルキレン基であり、Ｒ^１，Ｒ^２，Ｒ^３及びＲ^４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、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６〜１０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、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、ａは０または１であり、ｂ及びｃは夫々１〜４の整数である。]
で表されるカーボネート構成単位を含んでなるポリカーボネート樹脂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。 That is, according to the present invention, the weight of the alkali (earth) metal atom contained in (B) is 0.002 to 0.10 parts by weight per 100 parts by weight of (1) (A) polycarbonate resin (component A). And (C) a silicone compound having an aromatic group and a vinyl group bonded to a silicon atom and having a viscosity of 10 to 300 cSt at 25 ° C. C component) A flame retardant polycarbonate resin composition containing 0.1 to 7 parts by weight, wherein the polycarbonate resin of component A is represented by the following general formula [1]

[W is an alkylene group having 1 to 4 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 to 10 carbon atoms From the group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, 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 In the case where a plurality of groups are selected, they may be the same or different, a is 0 or 1, and b and c are each an integer of 1 to 4. ]
There is provided a flame retardant polycarbonate resin composition characterized by being a polycarbonate resin comprising a carbonate structural unit represented by the formula:

  One of the more preferable embodiments of the present invention is (2) a polycarbonate resin in which the component A is a carbonate constituent unit represented by the above formula [1] in a proportion of 5 to 95 mol% in all carbonate constituent units. It is a flame-retardant polycarbonate resin composition as described in said structure (1).

  One of the more preferable embodiments of the present invention is (3) a polycarbonate resin in which the component A is a proportion of 10 to 70 mol% of the carbonate structural unit represented by the above formula [1] in all carbonate structural units. It is a flame-retardant polycarbonate resin composition as described in said structure (1) or (2).

  One of the more preferable embodiments of the present invention is (4) a carbonate structure in which the carbonate structural unit represented by the above formula [1] is derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. It is a flame retardant polycarbonate resin composition according to any one of the constitutions (1) to (3), which is a unit.

  One of the more preferred embodiments of the present invention is that (5) B component is an alkali (earth) metal salt of a perfluoroalkyl sulfonate, an alkali (earth) metal salt of an aromatic sulfonate, and an alkali of an aromatic imide. (1) One or more organic alkali (earth) metal salt selected from the group consisting of (earth) metal salts, the flame retardancy according to any one of the above constitutions (1) to (4), It is a polycarbonate resin composition.

  One of the more preferable embodiments of the present invention is as described in any one of the above constitutions (1) to (5), wherein (6) the C component is a silicone compound containing a Si—H group in the molecule. It is a flame-retardant polycarbonate resin composition as described.

  One of the more preferred embodiments of the present invention is (7) a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less, and a light transmittance measured by ASTM D1003 is 50 to 99%. It is a flame retardant polycarbonate resin composition according to any one of the above constitutions (1) to (6) satisfying that

  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 structures (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-described configurations (1) to (7).

で表されるカーボネート構成単位を含んでなるポリカーボネート樹脂である。上記式〔１〕において、Ｗは炭素原子数１〜４のアルキレン基であり、炭素原子数１〜２のアルキレン基がより好ましい。Ｒ^１，Ｒ^２，Ｒ^３及びＲ^４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、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６〜１０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であり、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１０のアリール基、炭素原子数７〜２０のアラルキル基、カルボキシル基が好ましく、水素原子、炭素原子数１〜１０のアルキル基がより好ましい。これらは、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い。ａは０または１であり０が好ましい。ｂ及びｃは夫々１〜４の整数であり、１が好ましい。 Hereinafter, the details of the present invention will be described.
<Component A: Polycarbonate resin>
As described above, the polycarbonate resin component used as the component A of the present invention is represented by the following general formula [1].

It is a polycarbonate resin which comprises the carbonate structural unit represented by these. In the above formula [1], W is an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms. R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclohexane having 6 to 20 carbon atoms. An alkyl group, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms A group selected from the group consisting of 20 aralkyl groups, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups and carboxyl groups, hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, A cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a carboxyl group. Preferred, a hydrogen atom, more preferably an alkyl group having 1 to 10 carbon atoms. When there are a plurality of these, they may be the same or different. a is 0 or 1, and 0 is preferable. b and c are each an integer of 1 to 4, and 1 is preferable.

  As the carbonate structural unit represented by the above formula [1], for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9- Examples thereof include bis (3-methyl-4-hydroxyphenyl) fluorene and carbonate structural units derived from 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, and in particular 9,9-bis (4- A carbonate structural unit derived from hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene”) is preferably used. The dihydroxy compound for deriving the carbonate constituent unit other than the above formula [1] may be any compound that is usually used as a dihydroxy component of an aromatic polycarbonate. For example, 4,4′-biphenol, 1,1-bis ( 4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2 , 2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) decane (bisphenol DED), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol) Z), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '-(p-phenylenediisopropylidene) Diphenol, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, and the like are mentioned. Bisphenol Z, bisphenol C, bisphenol E, bisphenol M, bisphenol DED, and bisphenol AP are preferred, and bisphenol A, bisphenol M, and bisphenol DED are particularly preferred. Moreover, you may use these individually or in combination of 2 or more types.

  The polycarbonate resin (component A) comprising the carbonate structural unit represented by the above formula [1] can be made into a branched polycarbonate resin by using a branching agent in combination with the dihydroxy compound. Examples of the branching agent used in the branched polycarbonate resin include phloroglucin, phloroglucide, 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- [1,1-bis ( 4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane Bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof More than functional polyfunctional aromatic compounds are mentioned, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. 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%.

  In the polycarbonate resin used as the component A of the present invention, the carbonate constituent unit represented by the formula [1] is preferably in a proportion of 5 to 95 mol% in all carbonate constituent units, A ratio is more preferable, and a ratio of 30 to 60 mol% is still more preferable. When the carbonate structural unit represented by the above formula [1] is less than 5 mol%, the flame retardancy is unfavorable. Moreover, when the carbonate structural unit represented by the above formula [1] exceeds 95 mol%, the fluidity and the mechanical properties are remarkably lowered, which is not preferable.

  These polycarbonate resins are produced by a reaction means known per se for producing ordinary aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight control, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas [2] to [4].

［式中、Ａは水素原子、炭素数１〜９のアルキル基、アルキルフェニル基（アルキル部分の炭素数は１〜９）、フェニル基、またはフェニルアルキル基（アルキル部分の炭素数は１〜９）であり、ｒは１〜５、好ましくは１〜３の整数である］。

[In the formula, A represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion has 1 to 9 carbon atoms). And r is an integer from 1 to 5, preferably from 1 to 3].

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

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

  Specific examples of the monofunctional phenols represented by the general formula [2] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas [3] to [4] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used. The substituted phenols represented by the general formula [3] preferably have n of 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol. Further, as the substituted phenols of the above general formula [4], compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [2] are preferable, more preferably alkyl-substituted or phenylalkyl-substituted phenols, and particularly preferably p-tert-butylphenol or p- -Cumylphenol. These monofunctional phenolic terminal terminators are desirably introduced at the terminal at least 5 mol%, preferably at least 10 mol%, based on all the terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

  The polycarbonate resin used as the component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the spirit of the present invention is not impaired. Good.

The viscosity average molecular weight of the component A of the present invention is preferably in the range of 10,000 to 50,000, more preferably 12,000 to 30,000, still more preferably in the range of 14,000 to 25,000, A range of 000 to 23,000 is most preferred. If the molecular weight exceeds 50,000, the melt viscosity is too high and the moldability may be inferior, and if the molecular weight is less than 10,000, the mechanical properties may be lowered. In addition, the viscosity average molecular weight as used in the field of this invention calculates | requires first using the Ostwald viscometer from the solution which melt | dissolved 0.7 g of polycarbonate resins in 20 ml of methylene chloride with the specific viscosity computed by following Formula,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The component A of the present invention is preferably substantially free of halogen atoms. “Substantially free of halogen atoms” means that the molecule does not contain halogen-substituted dihydric phenols, etc., and remains in trace amounts of solvents (halogenated hydrocarbons) and carbonate precursors remaining in the polycarbonate production method. Is not intended.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Among these, preferable components are selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides. 1 or more kinds of compounds, among which potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, diphenylsulfone sulfonate represented by the formula [5], di (p-toluenesulfone) imide One or more compounds selected from the group consisting of potassium salt and sodium salt of di (p-toluenesulfone) imide are more preferred. Most preferred is potassium perfluorobutane sulfonate.

[式中、ｎは０〜３を表し、ＭはＫあるいはＮａを表す。]

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

  The amount of component B contained in the resin composition of the present invention is 0.002 to 0.10 weight of alkali (earth) metal atom in component B with respect to 100 parts by weight of polycarbonate resin (component A). The amount is preferably 0.002 to 0.05 parts by weight, more preferably 0.002 to 0.03 parts by weight, and most preferably 0.002 to 0.012 parts by weight.

  For example, in the case of potassium perfluorobutanesulfonate, its content is 0.018 to 0.911 parts by weight, preferably 0.018 to 0.456 parts by weight, more preferably 0.018 to 0.273 parts by weight. Parts, most preferably 0.018 to 0.109 parts by weight. If the content of the B component is too large, not only the transparency of the thick molded product, which is a feature of the present invention, is impaired, but 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.

<C component: silicone compound>
The silicone compound used as the C component of the present invention contains an aromatic group represented by the following general formula [6] having a viscosity at 25 ° C. of 10 to 300 cSt, and does not contain a vinyl group bonded to a silicon atom. It is a silicone compound.

（式〔６〕中、Ｘはそれぞれ独立にＯＨ基、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基を示す。ｎは０〜５の整数を表わす。さらに式〔６〕中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula [6], each X independently represents an OH group or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group. N represents an integer of 0 to 5. In [6], when n is 2 or more, different types of X can be taken.

  The silicone compound used as the C component of the present invention is a silicone compound that does not contain a vinyl group bonded to a silicon atom. Silicone compounds containing vinyl groups bonded to silicon atoms tend to be less transparent when used in combination with organometallic salt flame retardants, and the cost, safety, and quality stability in the production of silicone compounds themselves There is a problem that it is disadvantageous in gender.

  Further, the flame retardancy of the silicone compound is influenced by its dispersion state in the combustion process, and is one of the factors that determine the dispersion state in which viscosity is applied. When the viscosity of the silicone compound used as component C increases, the dispersion state of the silicone compound deteriorates and the transparency of the molded product decreases. Therefore, the lower the viscosity, the more advantageous the transparency of the molded product. Conversely, if the silicone compound is too volatile during the combustion process, that is, if the viscosity is too low, the silicone remaining in the system at the time of combustion will be diluted, thus forming a uniform silicone structure at the time of combustion. It becomes difficult. Furthermore, if the viscosity is low and the volatility is high, stable production of the silicone compound itself becomes difficult. From this viewpoint, the viscosity at 25 ° C. is 10 to 300 cSt, preferably 15 to 200 cSt, and more preferably 20 to 170 cSt.

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

The silicone compound of the present invention is preferably a silicone compound containing a Si-H group. In particular, a silicone compound containing a Si—H group and an aromatic group in the molecule,
(1) The amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g.
(2) The ratio (aromatic group amount) of the aromatic group represented by the general formula [6] is 10 to 70% by weight, and (3) the average degree of polymerization is 3 to 150.
At least one silicone compound selected from the following silicone compounds is preferred.

  More preferably, the Si—H group-containing unit is selected from silicone compounds containing at least one or more structural units of the structural units represented by the following general formulas [7] and [8]. At least one silicone compound.

（式〔７〕および式〔８〕中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基、または下記一般式〔９〕で示される化合物を示す。α１〜α３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（８）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In Formula [7] and Formula [8], Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group, or the following general formula [ 9] wherein α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and the repeating unit in the case where m1 is 2 or more in formula (8) (Several different repeating units can be taken.)

（式〔９〕中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、ヘテロ原子含有官能基を有しても良い炭素数１〜２０の炭化水素基を示す。α４〜α８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式〔９〕中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In the formula [9], Z ^{4 to} Z ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group. Α 4 to α 8 are each independently 0. Alternatively, it represents 1. m2 represents 0 or an integer of 1 or more, and in formula [9], when m2 is 2 or more, the repeating unit may take a plurality of repeating units.

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

Z ^{1 to} Z ^{8 of} the structural units represented by the above general formulas [7], [8] and [9], and 1 to 1 carbon atoms which may have a hetero atom-containing functional group in X of the general formula [6] Examples of the hydrocarbon group 20 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as an allyl group, a phenyl group, and a tolyl group. Aryl groups and aralkyl groups such as these, and these groups may contain various functional groups such as an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, and a mercapto group. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group, and especially a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a propyl group, or a phenyl group is preferable.

  Among the structural units represented by the general formulas [7] and [8], when the silicone compound includes at least one structural unit represented by the formula, when it has a plurality of repeating units of siloxane bonds, they are randomly shared. Any form of polymerization, block copolymerization and tapered copolymerization can be employed.

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

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

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

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

Here, the amount of the aromatic group means a ratio of the aromatic group represented by the general formula [6] described above in the silicone compound, and can be determined by the following calculation formula.
Aromatic group amount = [A / M] x 100 (wt%)
Here, A and M in the above formula represent the following numerical values, respectively.
A = Total molecular weight of the aromatic group moiety represented by the general formula [6] contained in one molecule of the silicone compound M = Molecular weight of the silicone compound

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

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

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

In general, the structure of a silicone compound containing a Si—H group in the molecule is constituted by arbitrarily combining the following four types of siloxane units.
M units : (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2
D unit : (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit : (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. Trifunctional siloxane units
Q unit : tetrafunctional siloxane unit represented by SiO ₂

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

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

  Such a silicone compound having a Si—H bond can be produced by a method known per se. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-product hydrochloric acid and low-boiling components. Further, a silicone oil having a C1-C20 hydrocarbon group that may have an Si-H bond, an aromatic group represented by the general formula (6), and other heteroatom-containing functional groups in the molecule, cyclic When using siloxane or alkoxysilane as a starting material, use an acid catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc., and optionally add water for hydrolysis to advance the polymerization reaction, The target silicone compound can be obtained by removing the acid catalyst and low-boiling components used in the same manner.

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

  The content of the silicone compound as component C of the present invention is 0.1 to 7 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 0 to 100 parts by weight of the aromatic polycarbonate resin (component A). .1 to 2 parts by weight, most preferably 0.1 to 1 part by weight. If the content is too large, not only the transparency of the molded product is lowered, but also the heat resistance of the resin is lowered or gas is easily generated during processing, and if it is too little, the flame retardancy is not exhibited, In addition, there is a problem that the releasability during molding is lowered.

<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 amount of other thermoplastic resin blended varies depending on the type and purpose, but is usually preferably 10 to 500 parts by weight, more preferably 10 to 100 parts by weight per 100 parts by weight of the polycarbonate resin (component A). It is. Other thermoplastic resins include, for example, a polycarbonate resin that does not include the carbonate constituent unit represented by the above formula [1], a branched polycarbonate resin that does not include the carbonate constituent unit represented by the above formula [1], and a polyethylene resin. Typical plastics such as polypropylene resin and polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate) Engineering plastics, polyether ether ketone, polyether imide, polysulfone, polyether sulfone, polyphenylene sulfide and so-called super engineering plastics It can be given to. 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 [10], phosphite compounds represented by the following general formula [11], and phosphite compounds represented by the following general formula [12].

［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 [13] and a phosphonite compound represented by the following general formula [14].

［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 general formula [10] 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.

  Preferable specific examples of the phosphite compound represented by the general formula [11] 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, Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can be mentioned.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 [12] include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

  Preferable specific examples of the phosphonite compound represented by the general formula [13] 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′-bifu Nylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenedi Examples thereof include phosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, 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 [14] 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-butyl) Benzyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, 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.

（式〔１５〕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。）

（式〔１６〕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。） Among the phosphorus-containing heat stabilizers, more preferred compounds include compounds represented by the following general formulas [15] and [16].

(In the formula [15], 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.)

(In the formula [16], 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 [15], R ¹⁰ and R ¹¹ are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound represented by the formula [15] include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, and 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 [16] 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.

  The phosphorus compound of the formula [16] can be produced by a known method. For example, there is a method of reacting a bisphenol compound represented by the following general formula [17] with phosphorus trichloride to obtain the corresponding phosphoric chloride, and then reacting it with a phenol represented by the following general formula [18]. .

（式〔１７〕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 [17], 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〔１８〕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 [18], 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 [17] 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 [18] 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, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 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-tri Methyl-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 (3,3-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxy Phenyl) propionate] methane etc. 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, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 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, N-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10- Tetraoxaspiro [5,5] undecane is more preferred.

  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 phosphorus-containing stabilizer, phenol-based antioxidant, or sulfur-containing antioxidant per 100 parts by weight of the polycarbonate resin (component A). It is preferable that 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 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the polycarbonate resin (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] Condensate with undecane) 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, 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 Hindered amines represented by-(2,2,6,6-tetramethyl) piperidinyl] siloxane.

  The content of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, per 100 parts by weight of the polycarbonate resin (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 the polycarbonate resin (component A).

  The resin composition of the present invention is excellent in flame retardancy, but an ordinary drip inhibitor can be used in combination in order to further reinforce such performance. However, in the resin composition of the present invention, the blending amount is suitably 0.2 parts by weight or less, preferably 0.1 parts by weight or less, and preferably 0.08 parts by weight or less with respect to 100 parts by weight of component A in order 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 0.05 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 2 mm thickness does not become less than 50%. 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 “Metablene A3000” (trade name), “Metablene A3700” (trade name), “Metablene A3750” (trade name), Shinpoly SN3307 (trade name), manufactured by Mitsubishi Rayon Co., Ltd. And “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, component C and optionally other components are mixed thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc., and then extruded as necessary. Examples of the method include granulating with a granulator, a briquetting machine, and the like, and then melt-kneading with a melt-kneader represented by a vent type biaxial ruder and pelletizing with a device such as a pelletizer. Alternatively, the A component, B component, C component and optionally other components are independently fed to a melt-kneader represented by a vented twin screw rudder, and a part of the A component and other components are reserved. After mixing, a method of supplying to the melt-kneader independently of the remaining components, after diluting and mixing the component B with water or an organic solvent, and then supplying to the melt-kneader, or after pre-mixing the diluted mixture with other components Also, a method of supplying to a melt kneader may be 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 transparent resin composition of the present invention gives a molded article excellent in transparency. The light transmittance measured by ASTM D1003 in a molded product having a thickness of 2 mm and a calculated average roughness (Ra) of 0.03 μm or less molded using the transparent resin composition of the present invention is 50 to 99. % Is preferable, more preferably 60 to 99%, still more preferably 70 to 99%, and most preferably 80 to 95%. 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 articles, a sheet | seat, a film, etc. by extrusion molding. 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 aromatic polycarbonate of the present invention has a wall thickness by using an unprecedented combination in a resin composition in which an organic metal salt flame retardant and a specific silicone compound are blended with a polycarbonate resin containing a specific carbonate structural unit. It has excellent flame retardancy while maintaining transparency in the molded product, and these techniques are not present in conventional flame retarding techniques. 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 further described below with reference to examples, but the present invention is not limited thereto.
The following items were evaluated.
(I) Transparency The pellets obtained from the respective compositions of the examples were dried at 120 ° C. for 5 hours with a hot air dryer, and by an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U / SMIV] A plate having a cylinder temperature of 300 ° C., a mold temperature of 90 ° C., a length of 150 mm × width of 150 mm, a thickness of 2.0 mm, and Ra of 0.03 μm was molded, and the light transmittance was measured by ASTM D1003. A sample having a light transmittance of 50% or more was evaluated as ○, and a sample having a light transmittance of less than 50% was evaluated as ×.
(Ii) Flame retardance The pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours in a hot air circulating dryer, and the cylinder temperature was 300 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 90 ° C. The vertical combustion test of UL standard 94 was conducted at thicknesses of 1.8 mm, 1.5 mm, 1.2 mm, and 1.0 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.
(Iii) Molding stability The pellets obtained from each composition of the examples were dried with a hot air dryer at 120 ° C. for 5 hours, and injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U · SM IV]. The molding stability when a plate having a cylinder temperature of 300 ° C., a mold temperature of 90 ° C., a length of 150 mm × width of 150 mm, a thickness of 3.0 mm, and a Ra of 0.03 μm was evaluated. The determination was made according to the following criteria.
○: Good releasability during molding and less gas generation.
X: Releasability at the time of molding is poor or gas generation is large.

[Examples 1 to 14 and Comparative Examples 1 to 7]
The resin composition which consists of a mixture ratio of Table 1 and Table 2 was created in the following ways. The description will be made according to the symbols in the following table. Each component of the ratio of Table 1 and Table 2 was measured, it mixed uniformly using the tumbler, and this mixture was thrown into the extruder and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration is the first stage kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. Strands were extruded under conditions of a cylinder temperature and a die temperature of 300 ° C. and a vent suction of 3000 Pa, cooled in a water bath, then cut into strands with a pelletizer and pelletized. Using the above-described method, the obtained pellets were molded into test pieces for flame retardancy evaluation and transparency evaluation. The raw materials used in Tables 1 and 2 are as follows.

(A component)
PC-1: Polycarbonate resin in which the ratio of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene”) to bisphenol A is 50:50 in molar ratio .
(Method for producing PC-1)
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 23030 parts of ion exchange water and 3957 parts of 48.5% aqueous sodium hydroxide solution, and 3026 parts of biscresol fluorene, 1826 parts of bisphenol A and 10 parts of hydrosulfite were dissolved. Thereafter, 17183 parts of methylene chloride was added, and 1900 parts of phosgene was blown in for 60 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, a solution obtained by dissolving 96 parts of p-tert-butylphenol in 1300 parts of methylene chloride and 660 parts of a 48.5% aqueous sodium hydroxide solution were added and emulsified. The reaction was terminated by stirring at 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove polycarbonate. A solution with a concentration of 20% was obtained. The polycarbonate obtained by removing the solvent from this solution had a molar ratio of biscresol fluorene to bisphenol A of 50:50 (polymer yield 97%).

PC-2: Polycarbonate resin having a molar ratio of biscresol fluorene to bisphenol A of 10:90.
(Method for producing PC-2)
Except for using 605 parts of biscresol fluorene and 3286 parts of bisphenol A, the ratio of the constituent units of biscresol fluorene and bisphenol A is 10 in terms of molar ratio, in the same manner as in PC-1. : A polycarbonate of 90 was obtained (polymer yield 98%)

(A 'component)
PC-3: Polycarbonate resin made of bisphenol A.
(Method for producing PC-3)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 18024 parts of ion exchange water and 3441 parts of 48.5% aqueous sodium hydroxide solution, dissolved 3810 parts of bisphenol A and 8 parts of hydrosulfite, and then 17931 parts of methylene chloride. And 1900 parts of phosgene was blown in for 60 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, a solution obtained by dissolving 87.6 parts of p-tert-butylphenol in 1200 parts of methylene chloride and 688 parts of 48.5% aqueous sodium hydroxide solution were added and emulsified, and then 5.8 parts of triethylamine was added. The reaction was terminated by stirring at 28 to 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove polycarbonate. A solution with a concentration of 20% was obtained. The solvent was removed from this solution to obtain a polycarbonate composed of bisphenol A (polymer yield 97%).

PC-4: A branched polycarbonate resin made of bisphenol A.
(Manufacturing method of PC-4)
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 15020 parts of ion-exchanged water and 3441 parts of 48.5% aqueous sodium hydroxide solution were added to dissolve 3810 parts of bisphenol A and 8 parts of hydrosulfite, and then 17931 parts of methylene chloride. And 204 parts (1.00 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane was dissolved at a concentration of 25% in a 14% aqueous sodium hydroxide solution, At 25 ° C., 1900 parts of phosgene was blown for 80 minutes. After completion of the phosgene blowing, a solution obtained by dissolving 150 parts of p-tert-butylphenol in 1600 parts of methylene chloride and 688 parts of 48.5% aqueous sodium hydroxide solution were added, stirring was stopped, and the mixture was left standing for 10 minutes and then stirred. After 5 minutes of emulsification, a high emulsification dope was obtained by processing with a homomixer (Special Machine Industries Co., Ltd.) at a rotation speed of 1200 rpm and a bath frequency of 35 times. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove polycarbonate. A solution with a concentration of 20% was obtained. The solvent was removed from this solution to obtain a branched polycarbonate composed of bisphenol A (polymer yield 94%).

(B component)
B-1: Perfluorobutanesulfonic acid potassium salt (Megafac F-114P manufactured by Dainippon Ink, Inc.)
B-2: Potassium diphenyl sulfone sulfonate (KSS manufactured by UC Japan)
B-3: Sodium paratoluenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)

(C component)
C-1: linear silicone containing Si—H group and aromatic group and not containing vinyl group bonded to silicon atom [viscosity at 25 ° C .: 51 cSt]
(Production of C-1)
A 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 301.9 g of water and 150 g of toluene, and cooled to an internal temperature of 5 ° C. A mixture of trimethylchlorosilane (21.7 g), methyldichlorosilane (23.0 g), dimethyldichlorosilane (12.9) and diphenyldichlorosilane (76.0) was charged into the dropping funnel and dropped into the flask over 2 hours while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged for 4 hours with stirring at an internal temperature of 20 ° C., then left to stand to remove the separated hydrochloric acid aqueous layer, added with 10% aqueous sodium carbonate solution, stirred for 5 minutes and then left to stand. The separated aqueous layer was removed. Then, it wash | cleaned 3 times with ion-exchange water, and it confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling substances, and then insoluble materials were removed by filtration to obtain a silicone compound C-1. This silicone compound C-1 had an Si—H group content of 0.21 mol / 100 g, an aromatic group content of 49% by weight, and an average degree of polymerization of 8.0.

C-2: Silicone having a branched structure containing a Si—H group and an aromatic group and not containing a vinyl group bonded to a silicon atom [viscosity at 25 ° C .: 11 cSt]
(Production of C-2)
In a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, 100.7 g of 1,1,3,3-tetramethyldisiloxane, 60.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclo 129.8 g of tetrasiloxane, 143.8 g of octaphenylcyclotetrasiloxane and 99.1 g of phenyltrimethoxysilane were charged, and 25.0 g of concentrated sulfuric acid was further added. After cooling to an internal temperature of 10 ° C., 13.8 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. This toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound C-2. This silicone compound C-2 had an Si—H group content of 0.50 mol / 100 g, an aromatic group content of 30% by weight, and an average degree of polymerization of 10.95.

C-3: a linear silicone containing a Si—H group and an aromatic group and not containing a vinyl group bonded to a silicon atom [viscosity at 25 ° C .: 160 cSt]
(Production of C-3)
In a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, 16.2 g of hexamethyldisiloxane, 61.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 103.8 g of octamethylcyclotetrasiloxane and diphenyldimethoxy 391.0 g of silane was charged, and 25.0 g of concentrated sulfuric acid was added with further stirring. After cooling to an internal temperature of 10 ° C., 29.4 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound C-3. This silicone compound C-3 had an Si—H group content of 0.20 mol / 100 g, an aromatic group content of 50% by weight, and an average degree of polymerization of 42.0.

C-4: linear silicone containing Si—H group and aromatic group and not containing vinyl group bonded to silicon atom [viscosity at 25 ° C .: 270 cSt]
(Production of C-4)
Hexamethyldisiloxane 1 in a 1 L flask equipped with a stirrer, cooling device, and thermometer
5.9 g, 1,3,5,7-tetramethylcyclotetrasiloxane 147.3 g, octamethylcyclotetrasiloxane 14.5 g and diphenyldimethoxysilane 395.1 g were added, and 25.0 g of concentrated sulfuric acid was added while stirring. did. After cooling to an internal temperature of 10 ° C., 29.7 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound C-4. This silicone compound C-4 had an Si—H group content of 0.49 mol / 100 g, an aromatic group content of 50 wt%, and an average degree of polymerization of 45.5.

<Indication formula of each silicone compound>
C-1: M ₂ ^DH ₂ D ₁ D ^φ2 _{3
^{C-2: M H 3 D}} H 2 D 3.5 D φ2 1.45 T φ 1
C-3: M ₂ ^DH ₁₀ D ₁₄ D ^φ2 ₁₆
C-4: M ₂ ^DH ₂₅ D ₂ D ^φ2 _16.5
Each symbol in the above formula represents the following siloxane units, and the coefficient (subscript) of each symbol represents the number of siloxane units (degree of polymerization) in one molecule.
M: (CH ₃ ) ₃ SiO _1/2
M ^H : H (CH ₃ ) ₂ SiO _1/2
D: (CH ₃ ) ₂ SiO
_{^{D H: H (CH 3)}} SiO
D ^φ2 : (C ₆ H ₅ ) ₂ SiO
^Tφ : (C ₆ H ₅ ) SiO _3/2

C-5: Silicone containing an aromatic group and not containing a vinyl group bonded to a silicon atom [viscosity at 25 ° C .: 15 cSt] (KF56 manufactured by Shin-Etsu Chemical Co., Ltd.)

(C 'component)
C-6: Silicone having a branched structure containing a Si—H group and an aromatic group and not containing a vinyl group bonded to a silicon atom [viscosity at 25 ° C .: 330 cSt]
(Production of C-6)
In a 1 L flask equipped with a stirrer, a cooling device and a thermometer, 15.9 g of hexamethyldisiloxane, 147.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 43.6 g of octamethylcyclotetrasiloxane and diphenyldimethoxy 395.1 g of silane was charged, and 25.0 g of concentrated sulfuric acid was added with further stirring. After cooling to an internal temperature of 10 ° C., 29.7 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound C-6. This silicone compound C-6 had an Si—H group content of 0.46 mol / 100 g, an aromatic group content of 50% by weight, and an average degree of polymerization of 49.5. The characteristic formula is expressed as M ₂ ^DH ₂₅ D ₆ D ^φ2 _16.5 .

C-7: Silicone containing an aromatic group and containing a vinyl group bonded to a silicon atom and having a branched structure [viscosity at 25 ° C .: 16 cSt] (KR219 manufactured by Shin-Etsu Chemical Co., Ltd.)

(Other ingredients)
IRX: hindered phenol antioxidant (Irganox 1076 manufactured by Ciba Specialty Chemicals)
VP: Fatty acid ester mainly composed of pentaerythritol tetrastearate (Roxyol VPG861 manufactured by Cognis Japan Co., Ltd.)

Claims (8)

(A) Alkali perfluoroalkyl sulfonate in an amount such that the weight of the alkali (earth) metal atom contained in (B) is 0.002 to 0.10 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A). (1 ) one or more flame retardants (component B) selected from the group consisting of (earth) metal salts and aromatic sulfonate alkali (earth) metal salts , and (C) a viscosity at 25 ° C. of 10 to 300 cSt. A flame retardant polycarbonate resin composition containing 0.1 to 7 parts by weight of a silicone compound (component C) containing an aromatic group and not containing a vinyl group bonded to a silicon atom, wherein the polycarbonate resin of component A is The following general formula [1]

[W is an alkylene group having 1 to 4 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 to 10 carbon atoms From the group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, 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 In the case where a plurality of groups are selected, they may be the same or different, a is 0 or 1, and b and c are each an integer of 1 to 4. ]
A flame retardant polycarbonate resin composition, which is a polycarbonate resin comprising a carbonate structural unit represented by the formula:   The flame-retardant polycarbonate resin composition according to claim 1, wherein the component A is a polycarbonate resin in which the carbonate structural unit represented by the formula [1] is a proportion of 5 to 95 mol% in all carbonate structural units.   The flame-retardant polycarbonate resin composition according to claim 1 or 2, wherein the component A is a polycarbonate resin in which the carbonate structural unit represented by the formula [1] is a ratio of 10 to 70 mol% in all carbonate structural units. .   The carbonate constituent unit represented by the formula [1] is a carbonate constituent unit derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Flame retardant polycarbonate resin composition. The flame retardant polycarbonate resin composition according to any one of claims 1 to 4 , wherein the component C is a silicone compound containing a Si-H group in the molecule. In smooth flat plate thickness 2mm with 0.03μm following arithmetic average roughness (Ra), any one of claims 1 to 5 in which the light transmittance measured in ASTM D1003 satisfy that the 50 to 99% The flame-retardant polycarbonate resin composition according to Item. An injection-molded article comprising the flame-retardant polycarbonate resin composition according to any one of claims 1 to 6 . The extrusion molded product which consists of a flame-retardant polycarbonate resin composition as described in any one of Claims 1-6 .