JP5774813B2 - Aromatic polycarbonate resin composition - Google Patents

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. It is used. 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, the resin composition itself is cloudy, and further, a dispersion failure such as peeling occurs on the surface of the molded product, and the characteristics are not sufficient. 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 (see Patent Documents 8 and 9). Are also specifically described. These provide a composition that maintains excellent flame retardancy and transparency, but the transparency exemplified therein is the transparency of a molded product having a relatively thin thickness, for example, a molded product having a thickness of 2 mm, No specific mention is made about the transparency of a molded product having a thickness of, for example, 4 mm or more, including examples.

  In recent years, with the diversification of uses of polycarbonate, not only the flame retardance level of materials but also transparency has become important. In addition, polycarbonate molded products are also becoming thinner and lighter, and the thickness of the product must be reduced. In many cases, it is necessary to provide a thick portion in a part of the product. Therefore, transparency in the thick part is also important as in the thin part. Polycarbonate resin is inherently transparent and is transparent even on a 5 mm thick plate, but due to the effects of blended additives, especially organic salt flame retardants, transparency is significantly impaired at 5 mm thickness even if transparent at 2 mm thickness. Or a 5 mm thick haze may be abnormally larger than expected from a 2 mm thick haze. Therefore, a problem has been pointed out that only thick portions of the molded product may become unnaturally strong and cloudy. That is, in the organic salt-based flame retardant composition, there is an unbalanced situation in which the transparency is improved as much as possible while maintaining the flame retardancy, and further, only the thick part unnaturally impairs the transparency. If it can be eliminated, and if the difference in transparency between the thick and thin parts can be reduced as much as possible, the degree of freedom in product design and coloring can be further increased. Thus, the characteristics of polycarbonate characterized by excellent transparency can be extracted more effectively. For example, regarding the UL94 standard widely used as a flame retardant index of materials in electrical applications, the transparency of the thick part is improved while maintaining the minimum thickness of the test piece that can achieve the flame retardant rank V-0 of the material. In this case, a great value is added to the material.

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 JP 2007-31583 A Japanese Patent No. 3163596

  The objective of this invention is providing the aromatic polycarbonate resin composition excellent in transparency (especially transparency of a thick molded article) and a flame retardance.

  As a result of intensive research aimed at achieving the above object, the present inventors have excellent flame retardancy and excellent transparency by combining specific amounts of specific silicone compounds and specific organic salt compounds. The inventors have found that an aromatic polycarbonate resin composition can be obtained, and have reached the present invention.

  That is, according to the present invention, the weight of the alkali (earth) metal atom contained in (B) is 0.0005 to 0.005 per 100 parts by weight of (1) (A) aromatic polycarbonate resin (component A). 010 parts by weight of an alkali (earth) metal salt (component B), (C) a silicone having a viscosity at 25 ° C. of 300 cSt or less and containing an aromatic group and containing no vinyl group bonded to a silicon atom An aromatic polycarbonate resin composition containing 0.1 to 7 parts by weight of the compound (component C) is provided.

  One of the more preferable embodiments of the present invention is that (2) the aromatic polycarbonate resin (A-2) having a branched structure in which the component A is (A-2) and the branching ratio is 0.1 to 2.0 mol%. The aromatic polycarbonate resin composition having the above-mentioned constitution (1), characterized in that it comprises 10% by weight to 100% by weight of the component).

  One of the more preferable embodiments of the present invention is (3) the aromatic polycarbonate of the above constitution (1) or (2), wherein the C component is a silicone compound containing a Si—H group in the molecule. It is a resin composition.

  One of the more preferred embodiments of the present invention is that (4) B component is an alkali (earth) metal salt of a perfluoroalkyl sulfonate, an alkali (earth) metal salt of an aromatic sulfonate, and an alkali of an aromatic imide. The aromatic polycarbonate resin composition according to any one of the above constitutions (1) to (3), wherein the composition is one or more organic alkali (earth) metal salts selected from the group consisting of (earth) metal salts It is a thing.

One of the more preferable embodiments of the present invention is (5) a molded article formed from the aromatic polycarbonate resin composition of any one of the above-mentioned configurations (1) to (4).
Hereinafter, the details of the present invention will be described.

<A component: aromatic polycarbonate resin>
The aromatic polycarbonate resin used as the A component of the present invention may be an aromatic polycarbonate resin (A-1 component) which is a linear polycarbonate, or an aromatic polycarbonate resin having a branched structure (A-2 component). ) Or a mixture of A-1 component and A-2 component. From the viewpoint of imparting more excellent flame retardancy, the A component preferably contains 10 to 100% by weight of the A-2 component, more preferably 70 to 100% by weight, and 90 to 100% by weight. More preferably, it is most preferably 100% by weight.

  Aromatic polycarbonate resin, which is a linear polycarbonate, is usually obtained by reacting a dihydric phenol and a carbonate precursor by interfacial polycondensation method or melt transesterification method, as well as carbonate prepolymer by solid phase transesterification method. A polymerized product or a product obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

  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 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 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. Selected by range.

  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 more preferably 0.01 to 500 ppm with respect to the polycarbonate resin after polymerization. Is used in a proportion of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

  The molecular weight of the aromatic polycarbonate resin, which is a linear polycarbonate, 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 decreases. Therefore, the viscosity average molecular weight is preferably 10,000 to 50,000, more preferably 14,000 to 30,000, still more preferably 18,000 to 26,000, and most preferably 19,000 to 23. , 000. Further, two or more kinds of 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 viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of a polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., as calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The aromatic polycarbonate which is the linear polycarbonate 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.

The aromatic polycarbonate resin having a branched structure in the present invention has a branching rate of 0.1 to 2.0 mol%. Preferably 0.2 to 1.0 mol%, more preferably 0.2 to 0.9 mol%, still more preferably 0.2 to less than 0.7 mol%, most preferably 0.2 to 0.4 mol%. Less than% mol. The branching rate is the number of moles of the structural unit derived from the branching agent relative to the total number of moles of the structural unit derived from the dihydric phenol used for the production included in the entire resin (number of moles of the structural unit derived from the branching agent / structure derived from the dihydric phenol This branching rate can be measured by ¹ H-NMR measurement. If the branching ratio is low, satisfactory branching characteristics cannot be obtained, the melt tension is too low, flame retardancy related to the composition, especially drip prevention, is difficult to be exhibited, and extrusion molding and blow molding are difficult. It is not preferable. On the other hand, if the branching ratio is high, the polymer is cross-linked, a gel is generated, and the impact resistance of the polymer is lowered.

  In the aromatic polycarbonate resin having a branched structure in the present invention, the total N (nitrogen) amount in the polycarbonate resin having a branched structure is preferably 0 to 20 ppm, more preferably 0 to 10 ppm. 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 20 ppm or the total Cl amount exceeds 200 ppm, the thermal stability is deteriorated, which is not preferable.

  The viscosity average molecular weight of the aromatic polycarbonate resin having a branched structure of the present invention is preferably in the range of 16,000 to 32,000, more preferably in the range of 17,000 to 30,000, and 19,000 to 26,000. The range of is particularly preferred. When the molecular weight exceeds 32,000, the melt tension may be high and the moldability may be poor, and when the molecular weight is less than 16,000, the drip prevention effect when the molded piece is burned becomes insufficient. Extrusion molding and blow molding may be difficult due to the difficulty of exhibiting flame retardancy and low melt tension.

The polycarbonate resin having a branched structure of the present invention is obtained by a reaction of a dihydric phenol, a branching agent, a monohydric phenol and phosgene.
Representative examples of the dihydric phenol used to obtain the polycarbonate resin having a branched structure of the present invention are 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), hydroquinone, resorcinol, 4, 4′-biphenol, 1,1-bis (4hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1 -Bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2, 2-bis (4-hydroxyphenyl) pentane, 4,4 ′-(p-phenylenediisopropylidene) dipheno 4,4 ′-(m-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) ) 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 (end terminator) used in the production of the polycarbonate resin having a branched structure 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 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 linear structure portion excluding the branched structure portion is The structure is derived from bisphenol A, and preferably has a structure derived from p-tert-butylphenol at the end.

The polycarbonate resin having a branched structure of the present invention is preferably produced by the following first method or second method.
In the first production method, a polycarbonate oligomer is obtained by reacting a dihydric phenol with phosgene in the presence of a solvent. This is reacted with monohydric phenols. Next, after the branching agent is reacted with the obtained polycarbonate oligomer, the polycarbonate oligomer is emulsified and polymerized under non-stirring conditions. The reaction temperature from phosgenation to before emulsification is preferably 10 to 40 ° C, more preferably 15 to 30 ° C. The reaction temperature after emulsification is preferably 20 to 50 ° C, more preferably 30 to 40 ° C. The polymerization time is preferably 1 to 6 hours, more preferably 2 to 4 hours. The obtained reaction mixture is treated by usual means such as washing and separation to obtain the desired polycarbonate having the branched structure of the present invention.

  In the second production method, a dihydric phenol, a branching agent and phosgene are first reacted in the presence of a solvent to obtain a polycarbonate oligomer. This is reacted with monohydric phenol. After emulsifying the obtained polycarbonate oligomer, 1/30 to 1/200 of the amount of dihydric phenol reacted first, preferably 1/40 to 1/100 of dihydric phenol is added and stirred. It is a method of polymerizing under conditions.

  The reaction temperature from phosgenation to before emulsification is preferably 10 to 40 ° C, more preferably 15 to 30 ° C. The reaction temperature after emulsification is preferably 20 to 50 ° C, more preferably 30 to 40 ° C. When the polymerization reaction is continuously performed, the stirring speed in each polymerization tank is 100 rpm or less, preferably 50 rpm or less, and the high-viscosity emulsified fluid in the polymerization tank is not much in the residence time in the direction perpendicular to the fluid traveling direction by the piston flow. It is sufficient to mix so that there is no difference. The polymerization time is preferably 1 to 6 hours, more preferably 2 to 4 hours. The obtained reaction mixture is treated by usual means such as washing and separation to obtain the desired polycarbonate having the branched structure of the present invention.

  A tertiary amine such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, etc. can be used as a reaction catalyst, but this catalyst reacts with the chloroformate group and is thermally inactivated. Since the total N content in the polycarbonate resin having a branched structure increases due to the formation of a stable urethane bond or the remaining of the catalyst, the amount of tertiary amine used is 0. 0 with respect to the dihydric phenol used. 2 mol% or less is preferable, 0.1 mol% or less is more preferable, and 0.05 mol% or less is more preferable. In particular, the above reaction is preferably carried out without a catalyst.

  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.

  Moreover, the aromatic polycarbonate resin having a branched structure 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 above-mentioned 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.

  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.

<B component: organic alkali (earth) metal salt>
As the organic alkali (earth) metal salt used as the component B of the present invention, various metal salts conventionally used for flame-retarding polycarbonate resins can be used. Examples include alkali (earth) metal salts, alkali (earth) metal salts of aromatic imides, alkali (earth) metal salts of sulfate esters, and alkali (earth) metal salts of phosphoric acid partial esters. . (Here, the notation of alkali (earth) metal salt is used 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 component contained in the resin composition of the present invention is such that the weight of the alkali (earth) metal atom in the B component is 0.0005 to 0.005 per 100 parts by weight of the aromatic polycarbonate resin (A component). 010 parts by weight, preferably 0.0008 to 0.0080 parts by weight, more preferably 0.0010 to 0.0058 parts by weight, and most preferably 0.0011 to 0.0029 parts by weight. is there.

  For example, in the case of potassium perfluorobutanesulfonate, the content is 0.0043 to 0.0865 parts by weight, preferably 0.0069 to 0.0692 parts by weight, more preferably 0.0086 to 0.0502 parts by weight. Parts, most preferably 0.0095 to 0.0251 parts by weight.

  If the content of the B component is too large, not only the transparency of the thick molded product, which is a feature of the present invention, is impaired, but in some cases, the resin is decomposed during molding and the flame retardancy is decreased. . If the addition amount is too small, the flame retardancy becomes insufficient and the flame retardancy that is the object of the present invention is not exhibited.

<C component: silicone compound>
The silicone compound used as the component C of the present invention is a silicone containing an aromatic group represented by the following general formula (5) having a viscosity at 25 ° C. of 300 cSt or less and containing no vinyl group bonded to a silicon atom. A compound.

（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。）

(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.

  When the viscosity of the silicone compound used as component C increases, the dispersion state of the silicone compound deteriorates and the transparency of the molded product decreases. Therefore, the lower the viscosity, the more advantageous the transparency of the molded product. The silicone compound used as the C component of the present invention is a silicone compound that does not contain a vinyl group bonded to a silicon atom. Silicone compounds containing vinyl groups bonded to silicon atoms tend to be less transparent when used in combination with organic salts, and are disadvantageous in terms of cost, safety, and quality stability in the production of silicone compounds themselves. There is a problem that there is. Further, the flame retardancy of the silicone compound is influenced by its dispersion state in the combustion process, and is one of the factors that determine the dispersion state in which viscosity is applied. This is because if the silicone compound is too volatile during the combustion process, that is, if the viscosity is too low, the silicone remaining in the system at the time of combustion will be diluted, thus forming a uniform silicone structure at the time of combustion. This is thought to be difficult. Furthermore, if the viscosity is low and the volatility is high, stable production of the silicone compound itself becomes difficult. From this viewpoint, the viscosity at 25 ° C. is preferably 10 to 300 cSt, more preferably 15 to 200 cSt, and still more preferably 20 to 170 cSt.

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

The silicone compound of the present invention is preferably a silicone compound containing a Si-H group. In particular, a silicone compound containing a Si—H group and an aromatic group in the molecule,
(1) The amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g.
(2) The ratio (aromatic group amount) in which the aromatic group represented by the general formula (5) is contained is 10 to 70% by weight, and (3) the average degree of polymerization 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, as for the silicone compound containing a Si—H group that is preferable as the C component, the Si—H amount in the silicone compound may be in the range of 0.1 to 1.2 mol / 100 g as described above. preferable. When the Si—H amount is in the range of 0.1 to 1.2 mol / 100 g, formation of a silicone structure is facilitated during combustion. More preferably, it is a silicone compound having a Si-H amount in the range of 0.2 to 1.0 mol / 100 g, and most preferably in the range of 0.2 to 0.6 mol / 100 g. When the amount of Si—H is small, it is difficult to form a silicone structure, and when the amount of Si—H is large, the thermal stability of the composition is lowered. Here, the silicone structure refers to a network structure formed by a reaction between silicone compounds or a reaction between a resin and silicone.

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

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

  From this viewpoint, the 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

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

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

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

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

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

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

  Such a silicone compound having a Si—H bond can be produced by a method known per se. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-product hydrochloric acid and low-boiling components. 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 as component C of the present invention is 0.1 to 7 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 0 to 100 parts by weight of the aromatic polycarbonate resin (component A). .1 to 2 parts by weight, most preferably 0.1 to 1 part by weight. If the content is too large, 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 B component, flame retardant other than C component (phosphate ester, red phosphorus, metal hydrate type, etc.), anti-drip agent (fluorine-containing polymer having fibril-forming ability, etc.), heat stabilizer, UV absorbers, light stabilizers, mold release agents, lubricants, sliding agents (PTFE particles, etc.), colorants (pigments such as carbon black and titanium oxide, dyes), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, charging Inhibitors, 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 A photochromic agent is mentioned.

  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 and C component, even when a release agent that tends to have an adverse effect on the flame retardancy is blended, good flame retardancy is achieved. Can be achieved. As such a release agent, those known per se can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-alkene polymer may be used. These may be modified with a functional group-containing compound such as acid modification), silicone compounds (Other than the component C of the present invention. Examples include linear or cyclic polydimethylsiloxane oil and polymethylphenyl silicone oil. These are also modified with functional group-containing compounds such as acid modification. ), Fluorine compounds (fluorine oil typified by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, and fluorine oil can be mentioned. Preferable mold release agents include saturated fatty acid esters. For example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, and lower fatty acid esters such as stearic acid stearate. , Higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The content of the release agent is preferably 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the 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 0.001 part by weight, more preferably 0.00001 to 0.0001 part 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, component C and optionally other components are mixed thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc., and then extruded as necessary. Examples of the method include granulating with a granulator, a briquetting machine, and the like, and then melt-kneading with a melt-kneader represented by a vent type biaxial ruder and pelletizing with a device such as a pelletizer. Alternatively, the A component, B component, C component and optionally other components are independently fed to a melt-kneader represented by a vented twin screw rudder, and a part of the A component and other components are reserved. After mixing, a method of supplying to the melt kneader independently of the remaining components, after diluting and mixing the C component with water or an organic solvent, and then supplying to the melt kneader or after premixing the diluted mixture with other components Also, a method of supplying to a melt kneader may be mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

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

The transparent resin composition of the present invention gives a molded article excellent in transparency. The 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 0.05-5.0%, More preferably, it is 0.05-2.0%, Most preferably, it is 0.1-1.0%. 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 blending an aromatic polycarbonate resin with an organic alkali (earth) metal salt and a silicone compound containing an aromatic group. (Earth) By limiting the compounding amount of metal salt to a narrow range, it has excellent flame retardancy while maintaining transparency in thick molded products. There is nothing in technology. 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 between thick molded product and thin molded product 150 mm long × 150 mm wide, 2.0 mm thick, Haze of a square plate shaped product with Ra of 0.03 μm, 150 mm long × 150 mm wide, thickness 5. The haze of a square plate-like molded product having 0 mm and Ra of 0.03 μm was measured according to JIS K7105.
(Ii) Flame retardancy A UL 94 standard vertical flame test was conducted at thicknesses of 2.4 mm and 3.2 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 shown here.

[Examples 1-46 and Comparative Examples 1-17]
The resin composition which consists of a mixture ratio of Table 1-Table 8 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 8 was measured, it mixed uniformly using the tumbler, and this mixture was thrown into the extruder and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration is the first stage kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. Strands were extruded under conditions of cylinder temperature and die temperature of 280 ° C. and vent suction of 3000 Pa, cooled in a water bath, then cut into strands with a pelletizer, and pelletized. The obtained pellets were dried at 120 ° C. for 6 hours in a hot air circulating dryer, and evaluated for flame retardancy at a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C. using an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. 2mm-thick square plate shaped product for haze evaluation at a cylinder temperature of 320 ° C and a mold temperature of 80 ° C by injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U / SMIV] And a 5 mm thick square plate-shaped molded product and a test piece for vertical combustion test evaluation were molded.

The raw materials used in Tables 1 to 8 are as follows.
(Component A)
PC-L1: Linear polycarbonate resin (polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal stopper. 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 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. 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 15,500.)

PC-B1: Aromatic polycarbonate resin having branched structure (PC-B1 production method)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2867 parts of ion-exchanged water, 1105 parts of a 25% aqueous sodium hydroxide solution and 1 part of hydrosulfite, and 750 parts of bisphenol A was dissolved with stirring, and then 2252 parts of methylene chloride. Then, 370 parts of phosgene was blown into the reaction at 15 to 25 ° C. over about 40 minutes to obtain a polycarbonate oligomer. To this reaction mixture was added 159.6 parts of 11% strength p-tert-butylphenol in methylene chloride, and then 1,1,1-tris (4-hydroxyphenyl) ethane was added to 5% strength aqueous sodium hydroxide solution. 55.9 parts (0.28 mol%) of an aqueous solution in which 5% was dissolved and 118.3 parts of a 48.5% aqueous sodium hydroxide solution were added, and the mixture was vigorously stirred and highly emulsified, and then allowed to stand for 3 hours. To complete the reaction. After completion of the reaction, 9000 parts of methylene chloride was added for dilution, and then the methylene chloride phase was separated from the reaction mixture. After 8000 parts of ion-exchanged water was added to the methylene chloride phase and stirred, the stirring was stopped, The organic phase was separated. This operation was repeated (four times) until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water. Next, 100 L of ion-exchanged water was put into a 1000 L kneader, and the organic phase (organic solvent solution) obtained at a water temperature of 42 ° C. was gradually added to the kneader to evaporate methylene chloride to obtain a granular material. Subsequently, the mixture of the powder and water was put into a hot water treatment tank with a stirrer controlled at a water temperature of 95 ° C., and stirred and mixed for 30 minutes at a mixing ratio of 25 parts of powder and 75 parts of water. This mixture of powder and water was separated with a centrifuge to obtain a powder 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 granular material. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25600 and a branching rate of 0.28 mol%.

PC-B2: aromatic polycarbonate resin having a branched structure (PC-B2 production method)
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 2867 parts of ion-exchanged water, 1105 parts of 25% aqueous sodium hydroxide and 1 part of hydrosulfite, and 750 parts of bisphenol A was dissolved under stirring (bisphenol A solution). Then, 55.9 parts (0.28 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane was dissolved at a 5% concentration in 2252 parts of methylene chloride and a 5% aqueous sodium hydroxide solution were added. A polycarbonate oligomer was obtained by blowing and reacting 370 parts of phosgene for about 40 minutes at 15 to 25 ° C.
To this reaction mixture, 159.6 parts of 11% strength p-tert-butylphenol in methylene chloride and 118.3 parts of 48.5% aqueous sodium hydroxide solution were added, and the mixture was vigorously stirred and highly emulsified. After adding 74 parts of the solution, the reaction was completed by slowly stirring for 3 hours so that the emulsification did not break. After completion of the reaction, the same treatment as in the method for producing PC-B1 was performed to obtain a polycarbonate resin powder having a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 25500 and a branching rate of 0.28 mol%.
PC-B3: Aromatic polycarbonate resin having a branched structure (Taflon IB2500 manufactured by Idemitsu Petrochemical Co., Ltd.) (branching rate 0.3 mol%)

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

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

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

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

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

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

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

(C 'component)
C-6: Silicone having a branched structure containing a Si—H group and an aromatic group and not containing a vinyl group bonded to a silicon atom [viscosity at 25 ° C .: 330 cSt]
(Production of C-6)
In a 1 L flask equipped with a stirrer, a cooling device and a thermometer, 15.9 g of hexamethyldisiloxane, 147.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 43.6 g of octamethylcyclotetrasiloxane and diphenyldimethoxy 395.1 g of silane was charged, and 25.0 g of concentrated sulfuric acid was added with further stirring. After cooling to an internal temperature of 10 ° C., 29.7 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound C-6. This silicone compound C-4 had an Si—H group content of 0.46 mol / 100 g, an aromatic group content of 50 wt%, and an average degree of polymerization of 49.5. Indication formula is M ₂ ^DH ₂₅ D ₆ D ^φ2 _16.5
It is expressed.
C-7: Silicone having a branched structure containing an aromatic group and a vinyl group bonded to a silicon atom [viscosity at 25 ° C .: 16 cSt] (KR219 manufactured by Shin-Etsu Chemical Co., Ltd.)

(Other ingredients)
IRS: Phosphite compound (Irgafos 168 manufactured by Ciba Specialty Chemicals)
IRX: hindered phenol compound (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)

  From the comparison between Examples and Comparative Examples in Tables 1 to 8, it can be seen that the aromatic polycarbonate resin composition of the present invention is excellent in transparency while maintaining a certain flame retardancy.

  As is clear from the above, the transparent flame-retardant aromatic polycarbonate resin composition of the present invention mainly contains a silicone compound as an anti-drip agent and is excellent in transparency. Such characteristics are not present in conventional flame-retardant aromatic polycarbonate resins, and such resin compositions have high thermal stability even when melted at high temperatures such as injection molding. 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 (4)

(A) An organic alkali (soil) in an amount such that the weight of the alkali (earth) metal atom contained in (B) is 0.0005 to 0.010 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). Class) Metal salt (component B), (C) Silicone compound (C component) containing an aromatic group and a Si—H group and having no vinyl group bonded to a silicon atom, having a viscosity at 25 ° C. of 300 cSt or less An aromatic polycarbonate resin composition containing 0.1 to 7 parts by weight and containing no polytetrafluoroethylene having fibril-forming ability .   The A component contains (A-2) 10 wt% to 100 wt% of an aromatic polycarbonate resin (A-2 component) having a branched structure with a branching ratio of 0.1 to 2.0 mol%. The aromatic polycarbonate resin composition according to claim 1. B component is selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides The aromatic polycarbonate resin composition according to claim 1 or 2 , wherein the organic alkali (earth) metal salt is the above. The molded article formed from the aromatic polycarbonate resin composition of any one of Claims 1-3 .