JP2011105862A - Aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition having transparency, the composition having high flame retardancy which can not be conventionally achieved, or having a reduced use amount of a flame retardant. <P>SOLUTION: The aromatic polycarbonate resin composition contains: 100 parts by weight of (A) an aromatic polycarbonate resin (component A) having a branched structure with a branching rate of more than 1.1 mol% and not more than 1.5 mol%; and 0.005 to 12 parts by weight of (B) a flame retardant (component B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate resin composition having excellent flame retardancy while maintaining high transparency.

  Aromatic polycarbonate resins are used in a wide range of industrial fields as materials for various molded products by a simple and excellent processing method such as injection molding. Especially for applications that require high transparency, such as various lighting covers and protective covers for transmissive displays, make use of the high light transmittance of aromatic polycarbonate resin and the excellent transparency represented by extremely low haze. in use. In addition, in recent years, attention has been paid to flame retardancy at the time of fire in these applications, and there is a demand for a resin composition having high flame retardancy in addition to the above properties.

As a method for imparting flame retardancy to an aromatic polycarbonate resin, a flame retardant aromatic polycarbonate resin composition to which a bromine-based compound or a phosphorus-based compound has been conventionally proposed has been proposed, and OA equipment has a strong demand for flame retardancy. However, flame retardant aromatic polycarbonate resin compositions that replace these flame retardants have been developed and are being used in the products listed above. Examples of the purpose of changing the flame retardant include suppression of generation of a corrosive gas at the time of molding or improvement of product recyclability. Examples of flame retardants that can replace the flame retardants listed above include silicone compounds. In recent years, a flame retardant resin composition in which a silicone compound is blended with an aromatic polycarbonate resin has been intensively studied and various proposals have been made. For example, a method in which an alkali (earth) metal salt of perfluoroalkyl sulfonate and an organosiloxane having an alkoxy group, a vinyl group, and a phenyl group are blended with a polycarbonate resin (see Patent Document 1), and a perfluoroalkyl sulfonic acid with a polycarbonate resin. A method of blending an organopolysiloxane containing an alkali metal salt or an alkaline earth metal salt and an organoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group has been proposed (see Patent Document 2). Further, a method of blending a specific petroleum heavy oil or pitch and a silicone compound into the resin component (see Patent Document 3), and a unit represented by the formula R ₂ SiO _1.0 in a non-silicone resin having an aromatic ring And a method of blending a silicone resin having a unit represented by RSiO _1.5 (R is a hydrocarbon group) and having a weight average molecular weight of 10,000 or more and 270,000 or less (see Patent Document 4). Yes.

  However, the above-mentioned proposed polycarbonate resin composition has, for example, a drip in the case of a thin wall and cannot achieve the UL standard 94 V-0 rank, the silicone is not sufficiently dispersed and the molded product becomes clouded, or the wet heat treatment There were many cases where transparency and flame retardancy were not sufficient in that they aggregated and the transparency after wet heat treatment decreased.

  In order to suppress the drip, it is effective to use polytetrafluoroethylene having a fibril forming ability. However, when polytetrafluoroethylene is blended with an aromatic polycarbonate resin, there is a problem that the transparency of the molded product is lowered because polytetrafluoroethylene and the aromatic polycarbonate resin are incompatible.

  Specific examples are also described for a resin composition comprising an aromatic alkali resin and an organic alkali metal salt and poly (methyl hydrogen siloxane). However, such a resin composition is not sufficient because the resin composition itself becomes cloudy, and further, poor dispersion such as peeling occurs on the surface of the molded product. An example of a resin composition comprising an aromatic polycarbonate resin and an organic alkali metal salt and poly (phenylmethylhydrogensiloxane) is known (see Patent Document 6). Further, a resin composition comprising a polycarbonate having a branched structure and an organic metal salt (see Patent Document 7), and a resin composition comprising a polycarbonate having a branched structure, an organic metal salt and a specific siloxane compound are also specifically described. (See Patent Documents 8 and 9). Although the composition which maintains the outstanding flame retardance and transparency by these is provided, the further flame retardance improvement is calculated | required by diversification of a polycarbonate use and the thinning of a product. Various flame retardant polycarbonate resin compositions have been developed depending on the application, and the flame retardant level varies, but it is necessary to raise the flame retardant level of each material as much as possible, for example, in the electrical application With regard to the UL94 standard widely used as a flammability index, if the minimum thickness of a specimen that can achieve the flame retardance rank V-0 of the material can be reduced even by 0.1 mm, the use as a flame retardant material will be expanded and its effect Is very big. Also, if the amount of flame retardant used can be reduced even if the flame retardant level is the same, reducing the amount of gas generated during processing, improving workability, improving quality stability, and improving various physical properties. Connection is exactly what is strongly demanded.

JP-A-6-306265 JP-A-6-336547 JP-A-9-169914 Japanese Patent Laid-Open No. 10-139964 Japanese Patent Publication No. 60-38419 JP 2003-147190 A Japanese Patent No. 3129374 Japanese Patent No. 3163596 JP 2007-31583 A

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

  As a result of intensive research aimed at achieving the above-mentioned object, the present inventors have never been able to maintain transparency by combining a polycarbonate resin having a branched structure with a limited branching rate and a flame retardant. The present inventors have found that an aromatic polycarbonate resin composition having high flame retardancy can be obtained, and have reached the present invention.

That is, according to the present invention, (1) (A) 100 parts by weight of aromatic polycarbonate resin (component A) having a branched structure with a branching ratio exceeding 1.1 mol% and not more than 1.5 mol% (B) ) An aromatic polycarbonate resin composition containing 0.005 to 12 parts by weight of a flame retardant (component B) is provided.
One of the more preferred embodiments of the present invention is that (2) a silicone compound in which the B component has (B-1) an alkali (earth) metal salt (B-1 component) and (B-2) an aromatic group ( It is an aromatic polycarbonate resin composition of the said structure (1) which is an at least 1 sort (s) flame retardant selected from the group which consists of B-2 component.
One of the more preferable embodiments of the present invention is (3) the above constitution (2), wherein 0.001 to 1.0 part by weight of the B-1 component is contained with respect to 100 parts by weight of the A component. The aromatic polycarbonate resin composition.
One of the more preferable embodiments of the present invention is the above-mentioned constitution (2), wherein 0.1 to 7.0 parts by weight of the B-2 component is contained per 100 parts by weight of the (4) A component. It is an aromatic polycarbonate resin composition in any one of-(3).
One of the more preferable embodiments of the present invention is that (5) the component B-1 is an alkali (earth) metal salt of a perfluoroalkyl sulfonate, an alkali (earth) metal salt of an aromatic sulfonate, and an aromatic imide The aromatic polycarbonate according to any one of the above constitutions (2) to (4), wherein the aromatic polycarbonate is one or more organic alkali (earth) metal salts selected from the group consisting of alkali (earth) metal salts of It is a resin composition.
One of the more preferable embodiments of the present invention is any one of the above constitutions (2) to (5), wherein (6) the B-2 component is a silicone compound containing a Si—H group in the molecule. This is an aromatic polycarbonate resin composition.
One of the more preferable embodiments of the present invention is (7) a molded article formed from the aromatic polycarbonate resin composition of any one of the above-mentioned configurations (1) to (6).

Hereinafter, the details of the present invention will be described.
<A component: aromatic polycarbonate resin>
The aromatic polycarbonate resin having a branching ratio exceeding 1.1 mol% and not more than 1.5 mol% used as the A component of the present invention is an aromatic polycarbonate resin having a branched structure (A-1 component) or A- If it is a mixture of one component and a linear aromatic polycarbonate resin (A-2 component), and the branching rate of the entire A component exceeds 1.1 mol% and satisfies 1.5 mol% or less, the branching rate is An aromatic polycarbonate resin having a branched structure exceeding 1.1 mol% and out of the range of 1.5 mol% or less may be included.

From the viewpoint of imparting more excellent flame retardancy, the A component preferably contains 20% to 100% by weight of the A-1 component, more preferably 70% to 100% by weight, more preferably 100% by weight. Is more preferable. The branching ratio as the whole component A is more than 1.1 mol% and 1.5 mol% or less, preferably more than 1.1 mol% and 1.4 mol% or less, more than 1.1 mol% and less than 1.35 mol% It is more preferable that The branching rate is the number of moles of the structural unit derived from the branching agent to the total number of moles of the structural unit derived from the dihydric phenol used for the production included in the entire resin (the number of moles of the structural unit derived from the branching agent / derived from the dihydric phenol. The total number of moles of structural units × 100 (expressed in mol%)), and the branching ratio can be measured by ¹ H-NMR measurement.

  If the branching ratio is low, it is not preferable because high branching characteristics cannot be obtained, the melt tension is insufficient, and higher flame retardancy than ever before, particularly excellent anti-drip properties are hardly exhibited. On the other hand, if the branching ratio is high, the polymer is crosslinked, a gel is generated, and the impact resistance of the polymer is lowered. When the branching rate is high, the surface of the molded product tends to be more cloudy. As countermeasures, it is effective to increase the cylinder temperature or to make finer adjustments by lowering the injection speed. However, if the degree of branching is too high, the cloudiness of the molded product can be eliminated even if the molding temperature is increased. Even if it can be eliminated, the resin may deteriorate due to excessive increase in the molding temperature.

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

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

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

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

  The aromatic polycarbonate resin having a branched structure which is the A-1 component of the present invention preferably has a branching ratio of more than 1.1 mol% and 1.5 mol% or less, more preferably more than 1.1 mol% and 1.4 mol%. % Or less, more preferably more than 1.1 mol% and 1.35 mol% or less.

  The viscosity average molecular weight of the aromatic polycarbonate resin having a branched structure which is the A-1 component of the present invention is preferably in the range of 10,000 to 50,000, more preferably 16,000 to 30,000, and 18,000 to A range of 28,000 is even more preferred, with a range of 19,000-26,000 being most preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<B component: flame retardant>
Examples of the flame retardant used as the component B of the present invention include phosphorus flame retardants, organic metal salt flame retardants such as organic alkali (earth) metal salts, silicone flame retardants, and phosphazene flame retardants. Of these, at least one flame retardant selected from the group consisting of organic alkali (earth) metal salts and silicone compounds having an aromatic group is preferably used. Content of B component is 0.005-12 weight part with respect to 100 weight part of A component, Preferably it is 0.01-10 weight part, More preferably, it is 0.15-9 weight part. When the content is less than 0.005, sufficient flame retardancy cannot be obtained, and when it exceeds 12 parts by weight, sufficient mechanical properties cannot be obtained.

<B-1 component: Organic alkali (earth) metal salt>
As the organic alkali (earth) metal salt used as the B-1 component of the present invention, various metal salts conventionally used for flame-retarding polycarbonate resins can be used. List alkali (earth) metal salts of acids, alkali (earth) metal salts of aromatic imides, alkali (earth) metal salts of sulfate esters, and alkali (earth) metal salts of phosphoric acid partial esters Can do. (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. Among them, potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, diphenylsulfone sulfonate represented by the formula (4), 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 the B-1 component contained in the resin composition of the present invention is preferably 0.005 to 1.0 part by weight, more preferably 0.006, per 100 parts by weight of the aromatic polycarbonate resin (component A). To 0.3 parts by weight, more preferably 0.007 to 0.1 parts by weight, even more preferably 0.008 to 0.05 parts by weight, and most preferably 0.01 to 0.025 parts by weight. It is. When there is too much content of B-1 component, not only transparency which is the characteristics of this invention will be impaired, but depending on the case, resin will decompose | disassemble at the time of shaping | molding and it will become the direction where flame retardance conversely falls. 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.

<B-2 component: silicone compound>
The silicone compound used as the B-2 component of the present invention is not particularly limited as long as the flame retardancy and transparency as the object of the present invention can be obtained, but a silicone compound having an aromatic group is preferable, and further at 25 ° C. The viscosity is preferably 300 cSt or less. As the viscosity increases, the transparency of the molded product decreases. Further, in order for the B component silicone compound to effectively exhibit a flame retardant effect, the dispersed state in the combustion process is important. Viscosity is an important factor that determines the dispersion state. This is because if the silicone compound is too volatile during the combustion process, that is, if the viscosity of the silicone compound is too low, the silicone remaining in the system at the time of combustion is dilute. From this viewpoint considered to be difficult to form a structure, the viscosity at 25 ° C. is more preferably 10 to 300 cSt, still more preferably 15 to 200 cSt, and most preferably 20 to 170 cSt.

  The aromatic group of the B-2 component is bonded to the silicone atom, which improves compatibility with the polycarbonate resin and contributes to maintaining transparency, and is advantageous for forming a carbonized film during combustion. Therefore, 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.

（式（５）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（５）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）
（３）平均重合度が３〜１５０
であるシリコーン化合物の中から選択される少なくとも一種以上のシリコーン化合物である。 The silicone compound of the present invention is preferably a silicone compound containing a Si-H group. In particular, a silicone compound containing a Si—H group and an aromatic group in the molecule,
(1) The amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g.
(2) The ratio (aromatic group amount) in which the aromatic group represented by the following general formula (5) is contained is 10 to 70% by weight, and

(In formula (5), 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. (5) In the case where n is 2 or more, different types of X can be taken.
(3) Average polymerization degree is 3 to 150
And at least one silicone compound selected from silicone compounds.

  More preferably, the Si—H group-containing unit is selected from silicone compounds containing at least one constituent unit represented by the formula among the constituent units represented by the following general formulas (6) and (7). At least one silicone compound.

（式（６）および式（７）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（８）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 (6) and Formula (7), 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 ( 8) and 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（８）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（８）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (8), 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. Or represents 1. m2 represents 0 or an integer greater than or equal to 1. Further, in the formula (8), when m2 is 2 or more, the repeating unit may take a plurality of different repeating units.

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

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

  Among the structural units represented by the general formulas (6) and (7), when the silicone compound containing at least one structural unit represented by the formula has a plurality of repeating units of siloxane bonds, they are randomly shared. Any form of polymerization, block copolymerization and tapered copolymerization can be employed.

  In the present invention, it is preferable that the amount of Si—H in the silicone compound be in the range of 0.1 to 1.2 mol / 100 g for the silicone compound containing the Si—H group preferred as the B-2 component. When the Si—H amount is in the range of 0.1 to 1.2 mol / 100 g, formation of a silicone structure is facilitated during combustion. More preferred is a silicone compound having a Si-H amount in the range of 0.1 to 1.0 mol / 100 g, most preferably in the range of 0.2 to 0.6 mol / 100 g. When the amount of Si—H is small, it is difficult to form a silicone structure, and when the amount of Si—H is large, the thermal stability of the composition is lowered. Here, the silicone structure refers to a network structure formed by a reaction between silicone compounds or a reaction between a resin and silicone.

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

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

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

Here, the amount of the aromatic group means a ratio of the aromatic group represented by the general formula (5) 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 aromatic group moieties represented by the general formula (5) contained in one molecule of the silicone compound M = Molecular weight of the silicone compound

  Further, the silicone compound used as the B-2 component of the present invention preferably has a refractive index at 25 ° C. in the range of 1.40 to 1.60. 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.

  Furthermore, the silicone compound used as the B-2 component of the present invention preferably has a volatilization amount of 18% or less by a heat loss method at 105 ° C./3 hours. More preferably, the silicone compound has a volatilization amount of 10% or less. When the volatilization amount is larger than 18%, there is a problem that the amount of the volatile matter from the resin increases when the resin composition of the present invention is extruded and pelletized, and more bubbles are generated in the molded product. There is a problem.

  The silicone compound used as the component B-2 may be linear or branched as long as the above conditions are satisfied, and the Si—H group may be a side in the molecular structure. It is possible to use various compounds having any of a chain, a terminal, a branch point, or a plurality of sites.

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

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

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

  Such a silicone compound having a Si—H bond can be produced by a method known per se. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-product hydrochloric acid and low-boiling components. In addition, a silicone oil having a C1-C20 hydrocarbon group that may have an Si-H bond, an aromatic group represented by the general formula (5), or other heteroatom-containing functional group in the molecule, cyclic When using siloxane or alkoxysilane as a starting material, use an acid catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc., and optionally add water for hydrolysis to advance the polymerization reaction, The target silicone compound can be obtained by removing the acid catalyst and low-boiling components used in the same manner.

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

  The content of the silicone compound used as the B-2 component of the present invention is preferably 0.1 to 7 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). 4 parts by weight, more preferably 0.1 to 2 parts by weight, most preferably 0.1 to 1 part by weight. If the content is too large, there is a problem that the heat resistance of the resin is lowered or gas is easily generated during processing, and if it is too small, there is a problem that flame retardancy is not exhibited.

<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, but many of the other resins and fillers impair transparency. Therefore, the selection of the type and quantity should take that point into consideration.

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

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

  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.

  Examples of such additives include anti-drip agents (such as fluorine-containing polymers having fibril-forming ability), heat stabilizers, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents (such as PTFE particles), and colorants. (Pigments and dyes such as carbon black and titanium oxide), fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial 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 (9), phosphite compounds represented by the following general formula (10), and phosphite compounds represented by the following general formula (11).

［式中Ｒ^８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^８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 ⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an 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 ⁸ 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^９、Ｒ^１０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 ⁹ and R ¹⁰ 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^１１、Ｒ^１２は炭素数１２〜１５のアルキル基である。なお、Ｒ^１１およびＲ^１２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 ¹¹ and R ¹² are alkyl groups having 12 to 15 carbon atoms. Note that R ¹¹ and R ¹² 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 (12) and a phosphonite compound represented by the following general formula (13).

［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 (9) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenylmono (Tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite are mentioned.

  Preferred specific examples of the phosphite compound represented by the general formula (10) 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 (11) include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

  Preferable specific examples of the phosphonite compound represented by the general formula (12) 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 (E2-1 component), tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4- One kind or two or more kinds of di-tert-butylphenyl) -3,3′-biphenylenediphosphonite (component E2-3) can be used in combination, but these three kinds of mixtures are preferable. In the case of three kinds of mixtures, the mixing ratio is preferably in the range of 100: 37 to 64: 4 to 14 by weight ratio of E2-1 component, E2-2 component and E2-3 component, and 100: 40 to 60 : The range of 5-11 is more preferable.

  Preferable specific examples of the phosphonite compound represented by the general formula (13) 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) Phenyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, and bis (2,4-di-tert-butylphenyl) -phenyl-phenyl Phosphonite is more preferred. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- One or two of phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite can be used in combination. It is a mixture. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, and more preferably in the range of 5: 2 to 3.

  On the other hand, as phosphate compounds, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate, and trimethyl phosphate is preferable.

  Among the above phosphorus-containing heat stabilizers, more preferred compounds include compounds represented by the following general formulas (14) and (15).

（式（１４）中、Ｒ^１３およびＲ^１４は、それぞれ独立して炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を示す。）

(In formula (14), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

（式（１５）中、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^２１、Ｒ^２２、およびＲ^２３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^１９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^２０は水素原子またはメチル基を示す。）

(In the formula (15), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, An aryl group or an aralkyl group, R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁰ represents a hydrogen atom or a methyl group.)

In the formula (14), R ¹³ and R ¹⁴ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound represented by the formula (14) 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.

  Specific examples of the compound represented by the formula (15) include phosphites derived from 2,2′-methylenebis (4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, 2 Phosphites derived from 2,2′-methylenebis (4,6-di-tert-butylphenol) and phenol, in particular derived from 2,2′-methylenebis (4,6-di-tert-butylphenol) and phenol. The phosphites are preferred.

  In addition, the phosphorus compound of Formula (15) can be manufactured by a well-known method. For example, there is a method in which a bisphenol compound represented by the following general formula (16) is reacted with phosphorus trichloride to obtain a corresponding phosphoric acid chloride, and then it is reacted with a phenol represented by the following general formula (17). .

（式（１６）中、Ｒ^２４、Ｒ^２５、Ｒ^２６、およびＲ^２７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^２８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^２９は水素原子またはメチル基を示す。）

(In the formula (16), R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ 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 ²⁸ represents hydrogen. And represents an atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁹ represents a hydrogen atom or a methyl group.)

（式（１７）中、Ｒ^３０、Ｒ^３１、およびＲ^３２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 (17), R ³⁰ , R ³¹ and R ³² 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 (16) 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 (17) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tert- Butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6 Examples include tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, and 2,6-di-tert-butyl-4-s-butylphenol. And compounds having two or more alkyl substituents are preferred.

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

  Specific examples of such phenolic antioxidants include, for example, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3 , 5-Di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert- Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-me Renbis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-tert- Butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [ 2-tert-butyl-4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) fe Ru] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8, 10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2, 2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6-di-) tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N , N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-) Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3 -(3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane can be mentioned and can be preferably used.

  More preferably, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl) -2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Further, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate is preferable.

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

  The phosphorus-containing heat stabilizer, phenolic antioxidant, and sulfur-containing antioxidant listed above can be used alone or in combination of two or more. A phosphorus-containing stabilizer is more preferable, and it is particularly preferable that the phosphorus-containing heat stabilizer contains the compound of the general formula (14).

  The proportion of these stabilizers in the composition is 0.0001 to 1 for each of the phosphorus-containing stabilizer, phenol-based antioxidant, or sulfur-containing antioxidant per 100 parts by weight of the aromatic polycarbonate resin (component A). It is preferable that it is a weight part. 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 B of the present invention. For example, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, etc. are used. Those modified with a functional group-containing compound such as acid modification are also used. ), 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 aromatic 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 aromatic 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 aromatic polycarbonate resin (component A).

  The resin composition of the present invention is excellent in anti-drip properties, but a normal anti-drip agent can be used in combination to further reinforce such performance. However, in the resin composition of the present invention, the blending amount is suitably 0.2 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” does not impair transparency, for example, to use PTFE in an amount that does not exceed 5% of the haze of a 2 mm thick plate. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 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) manufactured by Mitsubishi Rayon Co., Ltd., and GE Specialty Chemicals “BLENDEX B449” (trade name) and the like.

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

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

  The transparent resin composition of the present invention gives a molded article excellent in transparency. The haze of the molded product having a thickness of 2 mm, which is calculated using the transparent resin composition of the present invention and has a calculated average roughness (Ra) of 0.03 μm or less, is preferably 0.05 to 10.0%, more Preferably it is 0.05 to 7.0%, more preferably 0.05 to 5.0%, and most preferably 0.1 to 1.0%. 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.

The resin composition of the present invention can also 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 resin composition of the present invention is a resin composition obtained by mixing an organic alkali (earth) metal salt and a silicone compound containing an aromatic group with an aromatic polycarbonate resin having a limited branching rate. By limiting the blending amount of organic alkali (earth) metal salt to a narrow range before, it has high flame retardance that has never been achieved while maintaining transparency in thick molded products. These technologies are not found in conventional flame retardant technologies. The aromatic polycarbonate resin composition of the present invention can impart a high degree of flame retardancy without using a brominated flame retardant or a phosphorus flame retardant, which is considered to have a high environmental load, and further reduces the thickness of the molded product. Since transparency is maintained in both the thick part and the thick part, it is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and the industrial effect produced is extremely great.

  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 each composition of the examples were dried with a hot air dryer at 120 ° C. for 6 hours, and then injected with an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U · SM IV]. A plate having a cylinder temperature of 335 ° C., a mold temperature of 90 ° C., a length of 150 mm × width of 150 mm, a thickness of 2.0 mm and a Ra of 0.03 μm was molded, and the haze was measured according to JIS K7105. A haze of 5% or less was evaluated as ◯, a haze greater than 5% and less than 20% was evaluated as Δ, and a test having 20% or more as x.

(Ii) Flame retardance The pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours in a hot air circulation dryer, and the cylinder temperature was 325 using an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at 0 ° C. and a mold temperature of 80 ° C. The vertical combustion test of UL standard 94 was conducted at thicknesses of 1.5 mm and 1.1 mm, and the grade was evaluated. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated.

[Examples 1-31 and Comparative Examples 1-5]
The resin composition which consists of a mixture ratio of Table 1-Table 3 was created in the following ways. The description will be made according to the symbols in the following table. Each component of the ratio of Table 1-Table 3 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. The strand was extruded under the conditions of cylinder temperature and die temperature of 290 ° C. and vent suction of 3000 Pa, cooled in a water bath, then strand-cut with a pelletizer and pelletized. Using the above-described method, the obtained pellets were molded into test pieces for flame retardancy evaluation and transparency evaluation. The raw materials used in Tables 1 to 3 are as follows.

(A component)
(A-1 component)
PC-B14H: Aromatic polycarbonate resin having a branched structure (branch rate 1.46 mol%, molecular weight 24,900)
(Manufacturing method of PC-B14H)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2340 parts of ion-exchanged water, 947 parts of a 25% aqueous sodium hydroxide solution, and 0.7 parts of hydrosulfite, and 710 parts of bisphenol A was dissolved with stirring (bisphenol A solution). ) After that, 2299 parts of methylene chloride, 112 parts of 48.5% sodium hydroxide aqueous solution, aqueous solution of 1,1,1-tris (4-hydroxyphenyl) ethane dissolved in 25% concentration in 14% sodium hydroxide aqueous solution 59.5 parts (1.56 mol%) was added, and phosgenation reaction was performed by blowing 357 parts of phosgene over 15 minutes at 15 to 25 ° C. After the completion of phosgenation, 243 parts of an 11% strength p-tert-butylphenol methylene chloride solution and 88 parts of a 48.5% aqueous sodium hydroxide solution were added, stirring was stopped, and the mixture was allowed to stand for 10 minutes and then stirred. After 5 minutes of emulsification, the mixture was processed with a homomixer (Special Machine Industries Co., Ltd.) at a rotation speed of 1200 rpm and a bath frequency of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization. After completion of the reaction, 5728 parts of methylene chloride was added for dilution, the methylene chloride phase was separated from the reaction mixture, 5000 parts of ion-exchanged water was added to the separated methylene chloride phase and mixed with stirring, and the stirring was stopped. The phase and the organic phase were separated. Next, water washing was repeated until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water to obtain a purified polycarbonate resin solution. Next, methylene chloride was evaporated at a liquid temperature of 75 ° C. with a 1000 L kneader in which 100 L of ion-exchanged water was added to the purified polycarbonate resin solution to obtain a granular material. 25 parts of the granular material and 75 parts of water were put into a hot water treatment tank equipped with a stirrer and stirred and mixed at a water temperature of 95 ° C. for 30 minutes. Subsequently, the mixture of the granular material and water was separated by a centrifugal separator to obtain a granular material containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, this granular material was continuously supplied at 50 kg / hr (in terms of polycarbonate resin) to a SUS316L conductive heat receiving groove type biaxial stirring continuous dryer controlled at 140 ° C., and the condition of an average drying time of 3 hours And dried to obtain a polycarbonate resin particle having a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 24,900 and a branching ratio of 1.46 mol%.

PC-B14L: Aromatic polycarbonate resin having a branched structure (branch ratio 1.46 mol%, molecular weight 20,100)
(Manufacturing method of PC-B14L)
359 parts of phosgene, 59.8 parts (1.57 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane in a 14% strength aqueous sodium hydroxide solution at a 25% concentration, 11% strength A polycarbonate resin granule having a branched structure was obtained in the same manner as in the method for producing PC-B14H except that 280 parts of p-tert-butylphenol in methylene chloride was used. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 20,100 and a branching ratio of 1.46 mol%.

PC-B13: Aromatic polycarbonate resin having a branched structure (branching rate: 1.30 mol%, molecular weight: 24,900
(Manufacturing method of PC-B13)
356 parts of phosgene, 53.4 parts (1.40 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane in a 14% strength aqueous sodium hydroxide solution at a 25% concentration, 11% strength A polycarbonate resin powder having a branched structure was obtained in the same manner as in the method for producing PC-B14H, except that it was changed to 237 parts of a methylene chloride solution of p-tert-butylphenol. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 24,900 and a branching rate of 1.30 mol%.

PC-B11: Aromatic polycarbonate resin having a branched structure (branch rate 1.12 mol%, molecular weight 24,800
(Manufacturing method of PC-B11)
355 parts of phosgene, 45.7 parts (1.20 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane in a 14% strength aqueous sodium hydroxide solution at a 25% concentration, 11% strength A polycarbonate resin powder having a branched structure was obtained in the same manner as in the method for producing PC-B14H, except that it was changed to 228 parts of a methylene chloride solution of p-tert-butylphenol. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 24,800 and a branching rate of 1.12 mol%.

PC-B15: Aromatic polycarbonate resin having a branched structure (branching rate 1.52 mol%, molecular weight 24,800
(Manufacturing method of PC-B15)
357 parts of phosgene, 61.0 parts (1.60 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane at a 25% concentration in a 14% aqueous sodium hydroxide solution, an 11% concentration Except for changing to 245 parts of p-tert-butylphenol in methylene chloride, a polycarbonate resin powder having a branched structure was obtained in the same manner as in the production method of PC-B14H. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 24,800 and a branching ratio of 1.52 mol%.

PC-B10: Aromatic polycarbonate resin having a branched structure (branching rate: 1.05 mol%, molecular weight: 25,000
(Manufacturing method of PC-B10)
354 parts of phosgene, 41.9 parts (1.10 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane in a 14% strength aqueous sodium hydroxide solution at a 25% concentration, 11% concentration A polycarbonate resin powder having a branched structure was obtained in the same manner as in the method for producing PC-B14H, except that the solution was changed to 223 parts of a methylene chloride solution of p-tert-butylphenol. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25,000 and a branching rate of 1.05 mol%.

(A-2 component)
PC-L1: Linear polycarbonate resin (polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. Such a polycarbonate resin is produced without using an amine catalyst and is an aromatic polycarbonate resin. The ratio of the terminal hydroxyl group in the terminal was 10 mol%, and the viscosity average molecular weight was 25,500.)
PC-L2: Linear polycarbonate resin (a polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. Such a polycarbonate resin is produced without using an amine catalyst and is an aromatic polycarbonate resin. The ratio of the terminal hydroxyl group in the terminal was 10 mol%, and the viscosity average molecular weight was 19,700.)
PC-L3: a linear polycarbonate resin (a polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. This polycarbonate resin is produced without using an amine catalyst and is an aromatic polycarbonate resin. The ratio of the terminal hydroxyl group in the terminal was 10 mol%, and the viscosity average molecular weight was 15,500.)

(B-1 component)
B-1-1: Perfluorobutane sulfonic acid potassium salt (Megafac F-114P manufactured by Dainippon Ink Co., Ltd.)
B-1-2: Sodium perfluorobutanesulfonic acid salt (Megafac F-114S manufactured by Dainippon Ink Co., Ltd.)
B-1-3: Potassium diphenylsulfonesulfonate (KSS manufactured by UCB Japan)

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

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

B-2-3: Silicone compound containing Si—H group and aromatic group (production of B-2-3)
In a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, 16.2 g of hexamethyldisiloxane, 61.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 103.8 g of octamethylcyclotetrasiloxane, and diphenyl 391.0 g of dimethoxysilane was charged, and 25.0 g of concentrated sulfuric acid was added with further stirring. After cooling to an internal temperature of 10 ° C., 29.4 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. This toluene solution was heated to 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain silicone compound B-2-3. This silicone compound B-2-3 was a silicone compound having an Si—H group amount of 0.20 mol / 100 g, an aromatic group amount of 50 wt%, and an average degree of polymerization of 42.0.

B-2-4: Silicone compound having Si-H group and aromatic group (production of B-2-4)
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. This toluene solution was heated to 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain silicone compound B-2-4. This silicone compound B-2-4 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>
B-2-1: M ₂ ^DH ₂ D ₁ D ^φ2 ₃
B-2-2: ^MH ₃ ^DH ₂ D _3.5 D ^φ2 _1.45 T ^φ ₁
B-2-3: M ₂ ^DH ₁₀ D ₁₄ D ^φ2 _{16
^{B-2-4: M 2 D H}} 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
B-2-5: Silicone containing an aromatic group (KF56 manufactured by Shin-Etsu Chemical Co., Ltd.)
B-2-6: Silicone containing an aromatic group (KR219 manufactured by Shin-Etsu Chemical Co., Ltd.)

(Other ingredients)
IRS: Phosphite compound (Irgafos 168 manufactured by Ciba Specialty Chemicals)
IRX: hindered phenol antioxidant (Irganox 1076 manufactured by Ciba Specialty Chemicals)
PEP: Pentaerythritol diphosphite compound (Adeka Stub PEP-36 manufactured by Asahi Denka Kogyo Co., Ltd.)
TM: Trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.)
VP: Fatty acid ester mainly composed of pentaerythritol tetrastearate (Roxyol VPG861 manufactured by Cognis Japan Co., Ltd.)
UV: UV absorber (Kemipro Kasei Kogyo Co., Ltd. Chemisorb 79)
VB: Brewing agent (manufactured by Bayer: Macrolex Violet B)

  As is clear from the above, the transparent flame-retardant aromatic polycarbonate resin composition of the present invention mainly comprises a polycarbonate resin having a branched structure limited to a narrow range of branching and a flame retardant, and has transparency. It maintains a high level of flame retardancy that has never been achieved. Such properties are not present in conventional flame retardant aromatic polycarbonate resins. Therefore, it is extremely useful not only for lighting covers and protective covers for transmissive displays, but also for various industrial applications such as the OA equipment field and the electrical and electronic equipment field, and the industrial effects that it exhibits are extremely large.

Claims (7)

  (B) Flame retardant (component B) 0.005 to 100 parts by weight of aromatic polycarbonate resin (component A) having a branching ratio of more than 1.1 mol% and not more than 1.5 mol% (A) An aromatic polycarbonate resin composition containing 12 parts by weight.   B component is at least one selected from the group consisting of (B-1) alkali (earth) metal salt (B-1 component) and (B-2) silicone compound having aromatic group (B-2 component) The aromatic polycarbonate resin composition according to claim 1, which is a flame retardant.   The aromatic polycarbonate resin composition according to claim 2, comprising 0.005 to 1.0 part by weight of the B-1 component with respect to 100 parts by weight of the A component.   The aromatic polycarbonate resin composition according to claim 2 or 3, wherein 0.1 to 7.0 parts by weight of the B-2 component is contained with respect to 100 parts by weight of the A component.   Component B-1 is selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides. The aromatic polycarbonate resin composition according to any one of claims 2 to 4, wherein the aromatic polycarbonate resin composition is one or more organic alkali (earth) metal salts.   The aromatic polycarbonate resin composition according to any one of claims 2 to 5, wherein the B-2 component is a silicone compound containing a Si-H group in the molecule.   The molded article formed from the aromatic polycarbonate resin composition of any one of Claims 1-6.