JP4571391B2 - Flame retardant aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame retardant polycarbonate resin composition and a molded article thereof. More specifically, it has good flame retardancy even if it does not substantially contain organic halogen flame retardants and phosphate ester flame retardants, and it is also important for rigidity, appearance of molded products when molded at high temperatures, and housing molded products The present invention relates to a flame retardant aromatic polycarbonate resin composition having excellent surface impact strength and a molded product thereof, particularly a housing for OA equipment.

  Aromatic polycarbonate resins have excellent mechanical properties, dimensional accuracy, electrical properties, and the like, and are widely used as engineering plastics in various fields such as the electrical / electronic equipment field, automobile field, and OA equipment field. Of these uses, in general, in the OA equipment field and the electronic / electric equipment field, the resin material is required to have flame retardancy.

  In order to meet these demands, flame retardant aromatic polycarbonate resins containing organic halogen flame retardants and phosphate ester flame retardants are widely used (see Non-Patent Document 1). However, in both organic halogen flame retardants and phosphate ester flame retardants, resin compositions containing such flame retardants should be burned or incinerated (thermal recycling), or disposed of in landfills. In some cases, environmental impacts may be considered a problem. These flame retardants are not easily replaceable because they have characteristics that are difficult to replace except for such environmental concerns. However, even if other characteristics are complemented by product design or the like, there is a growing trend to use flame retardant resin materials that do not substantially use these flame retardants.

  On the other hand, a flame retardant aromatic polycarbonate resin composition using a silicone compound or an organometallic salt compound has been proposed. For example, a flame retardant polycarbonate resin composition in which an organic alkali (earth) metal salt and a fluorinated polyolefin are blended with an aromatic polycarbonate resin is known (see Patent Document 1). A flame-retardant polycarbonate resin comprising a polycarbonate varnish and a silicone varnish having a specific viscosity and an organic sulfonic acid metal salt is known (see Patent Document 2). A flame retardant polycarbonate resin comprising a polycarbonate resin having a branched main chain and an aromatic group, a metal salt of an aromatic sulfur compound, and a fiber-forming fluorine-containing polymer is known (patent) Reference 3).

  However, in the OA equipment and electronic / electric equipment fields, high rigidity is often required due to the progress of thinning and weight reduction. Furthermore, particularly in the case of housing molded products, sufficient surface impact strength and good appearance are required. In addition, there is a strong demand for reduction in color, hue, warpage deformation, long-term characteristics (for example, heat and moisture resistance), and recyclability. The polycarbonate resin composition described above has not fully considered these requirements.

  Also, a flame retardant polycarbonate resin composition in which an alkoxy silane having an alkyl group having 6 to 20 carbon atoms and an alkali metal salt of an organic Bronsted acid such as an alkali metal salt of perfluoroalkyl sulfonic acid is blended with a polycarbonate resin is known. (See Patent Document 4). Furthermore, it is also known that the resin composition may contain glass fibers and other fillers. However, it is difficult to say that such a resin composition sufficiently satisfies the above requirements.

  It is publicly known that an aromatic polycarbonate resin composition using an alkoxysilane compound and an inorganic filler in combination has good thermal stability (see Patent Document 5), and further, an aromatic polycarbonate resin and an alkali metal perfluorosulfonate. A resin composition comprising polytetrafluoroethylene having a specific alkylalkoxysilane, talc, and fibril-forming ability is known (see Patent Document 6). However, even the resin composition of Patent Document 6 requires further improvement in order to sufficiently satisfy the above-described requirements particularly required for housing molded products.

"Polycarbonate resin handbook" (page 141, line 6 to page 143, line 5) (Seiichi Honma, published by Nikkan Kogyo Shimbun, 1992) JP 51-45159 JP-A-11-263903 Japanese Patent Laid-Open No. 11-217494 JP-A-8-208970 JP-A-6-322249 JP 2002-294063 A

  The object of the present invention is to have good flame retardancy without substantially containing an organic halogen flame retardant or phosphate ester flame retardant, and further, rigidity, appearance and hue at high temperature molding, and surface impact. An object of the present invention is to provide a flame retardant aromatic polycarbonate resin composition which is excellent in strength and long-term characteristics (for example, resistance to moist heat) and more preferably excellent in low warpage and recyclability.

  The present inventor has intensively studied to achieve such an object. As a result, an acidic group-containing organic compound not sufficiently studied in the invention of Patent Document 6 is blended, and an alkali (earth) metal salt of sulfonate and silicic acid are blended. By making the composition ratio with the salt mineral in a specific range, it is found that the appearance and hue of the molded article and long-term characteristics are compatible, and particularly when an acidic group-containing lubricant is used as the acidic group-containing organic compound, good The inventors have found that a sufficient surface impact strength can be obtained, and have further studied and completed the present invention.

The present invention includes (1) 100 parts by weight of an aromatic polycarbonate resin (component A), 1 to 50 parts by weight (component b) of a silicate mineral (component B), an alkali sulfonate (earth) metal salt (C Component) c parts by weight, 0.05 to 5 parts by weight of a silane compound (D component) represented by the following formula (1), and a lubricant having a carboxyl group and / or its acid anhydride group (E component) 0.01 to 5 parts by weight of the resin composition, wherein b (parts by weight) and c (parts by weight) are those relating to the flame-retardant aromatic polycarbonate resin composition satisfying the following formula (I).
0.008 ≦ c ≦ b / 100 (I)

（ここで式（１）中、Ｘは水素原子、ハロゲン原子、およびＲ^１Ｏ（Ｒ^１は炭素数１〜８のアルキル基を示し、該アルキル基はヘテロ原子を含有してよい）のいずれかを示し、Ｒ^２は炭素数４〜３０であり、フッ素原子で置換されてもよいアルキル基を示し、Ｒ^３は炭素数１〜３であり、ハロゲン原子で置換されてもよいアルキル基を示し、ｍは１、２、３または４であり、ｎは０、１、２または３であり、４−（ｍ＋ｎ）は０、１、２または３であり、Ｘ、Ｒ^２、およびＲ^３がそれぞれ複数存在するときは、それらは互いに同一であっても異なっていてもよい。）

(Wherein, in formula (1), X represents a hydrogen atom, a halogen atom, and R ¹ O (R ¹ represents an alkyl group having 1 to 8 carbon atoms, and the alkyl group may contain a hetero atom) R ² represents an alkyl group having 4 to 30 carbon atoms and may be substituted with a fluorine atom, and R ³ represents an alkyl group having 1 to ³ carbon atoms and optionally substituted with a halogen atom. M is 1, 2, 3 or 4, n is 0, 1, 2 or 3, 4- (m + n) is 0, 1, 2 or 3, X, R ² and R ³ When a plurality of are present, they may be the same or different from each other.)

  According to the configuration (1), the flame retardant aromatic has good flame retardancy, and further has excellent rigidity, appearance and hue at high temperature molding, surface impact strength, and long-term characteristics (for example, heat and humidity resistance). A polycarbonate resin composition is provided.

  One of the preferred embodiments of the present invention is that (2) the difficulty of the constitution (1) further comprising 0.01 to 1 part by weight of a fluorine-containing anti-dripping agent (F component) per 100 parts by weight of the A component. It is a flammable aromatic polycarbonate resin composition. In particular, in the case of a housing molded product, the V-0 rank in the vertical combustion test of UL standard 94 is often required. In order to achieve such V-0 rank, it is necessary to prevent melt dripping (drip). For such prevention, the molecular weight of the polycarbonate resin is improved, the blend of the branched polycarbonate resin or the ultrahigh molecular weight polycarbonate resin, and the fluorine-containing polymer. Formulations such as blending of an anti-drip agent (fluorine-containing anti-dripping agent) are typically exemplified. However, among these, the fluorine-containing anti-dripping agent is preferable in that flame retardancy due to the synergistic effect of the C component is exhibited and the influence on the molding processability of the resin composition is small. Therefore, according to this structure (2), said flame-retardant aromatic polycarbonate resin composition which has still more favorable flame retardance, maintaining moldability is provided.

One of the preferred embodiments of the present invention is that (3) when b (part by weight) satisfies 0.008 ≦ b / 1500, the following formula (II) is further satisfied in addition to the above formula (I). It is a flame-retardant aromatic polycarbonate resin composition of the said structure (1)-(2).
b / 1500 ≦ c (II)

  According to the configuration (3), the above flame retardant aromatic polycarbonate resin composition having an excellent balance of flame retardancy, hue of molded product, and heat and humidity resistance is provided.

  One of the preferred embodiments of the present invention is as follows: (4) The flame retardant according to any of the above constitutions (1) to (3), wherein the component B is at least one silicate mineral selected from mica, talc and wollastonite. The aromatic aromatic polycarbonate resin composition. According to the configuration (4), the flame-retardant aromatic polycarbonate resin composition having excellent low-warping property and excellent flame retardancy by sufficiently exhibiting the effect of the F component is provided. .

  One of the preferred embodiments of the present invention is (5) the flame retardant aromatic polycarbonate resin composition of the above constitutions (1) to (4), wherein the E component is an acidic group-containing lubricant, and is more preferred. One aspect is that the component (E) is an olefinic wax having a carboxyl group and / or an acid anhydride group thereof (hereinafter sometimes simply referred to as “carboxyl groups”) (5) It is a flame retardant aromatic polycarbonate resin composition. According to this configuration (5) (more preferably (6)), the flame-retardant aromatic polycarbonate resin composition having particularly excellent impact resistance is provided.

  One of the preferable aspects of the present invention is (7) Flame retardancy of the above constitutions (1) to (6), further comprising 1 to 30 parts by weight of liquid crystal polyester (G component) per 100 parts by weight of component A. It is an aromatic polycarbonate resin composition. While the resin composition comprising the A component to the E component has good heat resistance, it may be desirable to further improve the fluidity. For such improvement, various flow modifiers can be blended, but there is a limit to the formulation for reducing the molecular weight of the aromatic polycarbonate resin because of the need to maintain good impact resistance. When blended, heat resistance is sacrificed to some extent. Moreover, the compound normally mix | blended often worsens a flame retardance. In the present invention, it has also been found that when liquid crystal polyester is further blended, the characteristics of the resin composition comprising the components A to E can be maintained within an allowable range without significantly deteriorating and the fluidity can be improved. Therefore, according to the configuration (7), the above flame-retardant aromatic polycarbonate resin composition excellent in molding processability and rigidity is provided while maintaining its good flame retardancy, heat resistance, and low warpage. Is done.

  One of the preferred embodiments of the present invention is a housing molded article formed from (8) the flame-retardant aromatic polycarbonate resin composition having the constitutions (1) to (7). As already described, the present invention satisfies various characteristics particularly required for a housing molded product. Therefore, according to the configuration (8), an organic halogen flame retardant and a phosphate ester flame retardant are substantially used. Even if it is not contained, it has good flame retardancy, and also has excellent rigidity, appearance and hue at high temperature molding, surface impact strength, and long-term characteristics (for example, resistance to moist heat), and more preferably low warpage And a molded housing comprising a flame retardant aromatic polycarbonate resin composition excellent in recyclability.

Hereinafter, the details of the present invention will be described.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 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) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

  In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  These special polycarbonates may be used alone or in combination of two or more. These can also be used by mixing with a widely used bisphenol A type polycarbonate.

  The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resins, copolymerized polycarbonate resins copolymerized with bifunctional alcohols (including alicyclics), and polyester carbonate resins copolymerized with such bifunctional carboxylic acids and difunctional alcohols are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  Since the branched polycarbonate resin can synergistically improve the drip prevention ability of the flame retardant aromatic polycarbonate resin composition of the present invention, its use is preferable. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

The ratio of the polyfunctional compound in the branched polycarbonate resin is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, more preferably 0.01 to 0.8 mol in the total amount of the aromatic polycarbonate resin. The mol%, particularly preferably 0.05 to 0.4 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also preferably in the above-mentioned range in the total amount of the aromatic polycarbonate resin. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

  Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The reaction by the interfacial polymerization 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, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used.

  As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.

  In addition, catalysts such as tertiary amines and quaternary ammonium salts can be used for promoting the reaction, and monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, etc. as molecular weight regulators. Are preferably used. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. These monofunctional phenols having a relatively long chain alkyl group are effective when improvement in fluidity and hydrolysis resistance is required.

  The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually preferably maintained at 10 or higher.

  The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonic acid diester. The dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. . The degree of vacuum is changed stepwise, and finally the phenols produced at 133 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonic acid diester include diphenyl 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 accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, Alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkoxide of alkali metal or alkaline earth metal, organic acid salt of alkali metal or alkaline earth metal, zinc compound, boron compound, silicon compound, germanium compound, Examples thereof include catalysts usually used for esterification and transesterification of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. A catalyst may be used independently and may be used in combination of 2 or more types. 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, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl phenyl carbonate, etc. Compounds can be added.

  Further, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate resin after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

  The details of the reaction formats other than those described above are also well known in books and patent publications.

  In producing the flame retardant aromatic polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the aromatic polycarbonate resin is not particularly limited, but is preferably 10,000 to 50,000, more preferably. It is 14,000-30,000, More preferably, it is 14,000-24,000.

  Aromatic polycarbonate resins having a viscosity average molecular weight of less than 10,000 may not provide practically expected impact resistance, etc., and may not have sufficient drip-preventing ability, resulting in poor flame retardancy. Cheap. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 50,000 is inferior in versatility in that it is inferior in fluidity during injection molding. Moreover, the transparency that is a feature of the present invention may not be fully utilized due to an increase in the molding temperature.

  The aromatic polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, the aromatic polycarbonate resin having a viscosity average molecular weight exceeding the above range (50,000) further improves the drip prevention ability of the flame retardant aromatic polycarbonate resin composition of the present invention by improving the entropy elasticity of the resin. Synergistic improvement is possible. This improvement effect is even better than the branched polycarbonate. As more preferred embodiments, the A component is an aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-3-1), and the aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000. An aromatic polycarbonate resin (A3 component) having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter referred to as “high molecular weight component-containing aromatic polycarbonate resin”). Can also be used.

  In such a high molecular weight component-containing aromatic polycarbonate resin (A3 component), the molecular weight of the A-3-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably 100,000. 000 to 200,000, particularly preferably 100,000 to 160,000. The molecular weight of the A-3-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.

  The high molecular weight component-containing aromatic polycarbonate resin (A3 component) can be obtained by mixing the A-3-1 component and the A-3-2 component at various ratios and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in A100 component 100 weight%, A-3-1 component is 2 to 40 weight%, More preferably, A3-1 component is 3 to 30 weight%, More preferably, A- The 3-1 component is 4 to 20% by weight, and the A-3-1 component is particularly preferably 5 to 20% by weight.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method of producing so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a production method (production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) 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 viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
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

Moreover, the calculation method of the said viscosity average molecular weight is applied also to the viscosity average molecular weight measurement of the resin composition of this invention and the molded article shape | molded from this resin composition. That is, in the present invention, these viscosity average molecular weights are obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution obtained by dissolving 0.7 g of a molded product in 100 ml of methylene chloride into the above formula.

(B component: silicate mineral)
The silicate mineral of component B of the present invention will be further described. The B component is a silicate mineral composed of at least a metal oxide component and a SiO ₂ component. As the B component silicate mineral, orthosilicate, disilicate, cyclic silicate, chain silicate, and the like are suitable. The B component silicate mineral takes a crystalline state, and the crystals may be any transformation that each silicate mineral can take. Moreover, the shape of a crystal | crystallization can take various shapes, such as fiber shape and plate shape.

  The silicate mineral of component B may be a compound oxide, oxyacid salt (consisting of an ionic lattice), or a solid solution, and the compound oxide is a combination of two or more of a single oxide, and a single oxide And any combination of two or more of oxyacid salts, and also in solid solution, any of solid solutions of two or more metal oxides and solid solutions of two or more oxyacid salts may be used. .

The B component silicate mineral may be a hydrate. The form of crystal water in the hydrate is one that enters as hydrogen silicate ion as Si—OH, one that enters ionically as a hydroxide ion (OH ⁻ ) with respect to the metal cation, and H ₂ O molecules in the gaps in the structure. Any form of entry may be used.

  As the B component silicate mineral, an artificial synthetic product corresponding to a natural product can be used. As the artificial compound, silicate minerals obtained from various conventionally known methods, for example, various synthetic methods using solid reaction, hydrothermal reaction, ultrahigh pressure reaction and the like can be used.

  Specific examples of the silicate mineral in each metal oxide component (MO) include the following. Here, the description in parentheses is the name of a mineral or the like mainly composed of such a silicate mineral, and means that the compound in parentheses can be used as the exemplified metal salt.

As those containing K ₂ O in the _{component, K 2 O · SiO 2,} K 2 O · 4SiO 2 · H 2 O, K 2 O · Al 2 O 3 · 2SiO 2 ( _{Karushiraito), K} 2 O · Al ₂ O ₃ · 4SiO ₂ (leucite), and _{K 2 O · Al 2 O 3} · 6SiO 2 ( orthoclase), and the like.

As comprising Na ₂ O in the _component, Na ₂ O · SiO _2, and its _{hydrates, Na 2 O · 2SiO 2,} 2Na 2 O · SiO 2, Na 2 O · 4SiO 2, Na 2 O · 3SiO _{2 · 3H 2 O, Na 2} O · Al 2 O 3 · 2SiO 2, Na 2 O · Al 2 O 3 · 4SiO 2 ( _{jadeite), 2Na 2 O · 3CaO ·} 5SiO 2, 3Na 2 O · 2CaO · 5SiO _2, and _{Na 2 O · Al 2 O 3} · 6SiO 2 ( albite), and the like.

Li ₂ O and as including the components _{thereof, Li 2 O · SiO 2,} 2Li 2 O · SiO 2, Li 2 O · SiO 2 · H 2 O, 3Li 2 O · 2SiO 2, Li 2 O · Al 2 Examples include O ₃ · 4SiO ₂ (petalite), Li ₂ O · Al ₂ O ₃ · 2SiO ₂ (eucryptite), and Li ₂ O · Al ₂ O ₃ · 4SiO ₂ (spodumene).

As those containing BaO into its _components, and the like _{BaO · SiO 2, 2BaO · SiO} 2, BaO · Al 2 O 3 · 2SiO 2 ( celsian), and BaO _· TiO _{2 ·} 3SiO 2 (Bentoaito).

As including CaO its components, 3CaO · _SiO 2 (cement clinker minerals of alite), 2CaO · SiO ₂ (cement clinker minerals of _{belite), 2CaO · MgO · 2SiO 2} ( O Keruma night), 2CaO · Al ₂ O ₃ · SiO ₂ (Gerlenite), solid solution of akermanite and gehlenite (Merilite), CaO · SiO ₂ (Wollastonite (including both α-type and β-type)), CaO · MgO · 2SiO _{2 (Jiopusaido), CaO · MgO · SiO 2} ( ash magnesia _{olivine), 3CaO · MgO · 2SiO 2} ( _{Meruuinaito), CaO · Al 2 O 3} · 2SiO 2 ( anorthite), 5CaO · 6SiO ₂ · 5H ₂ O (tobermorite, other 5CaO · 6SiO ₂ · 9H ₂ O, etc. Tobermorite group hydrates such as 2CaO · SiO ₂ · H ₂ O (Hillebrandite), and wollastonite group hydrates such as 6CaO · 6SiO ₂ · H ₂ O (zonotolite) Gyrolite group hydrates such as 2CaO · SiO ₂ · 2H ₂ O (gyrolite), CaO · Al ₂ O ₃ · 2SiO ₂ · H ₂ O (lawsonite), CaO · FeO · 2SiO ₂ (headenite), 3CaO · 2SiO _{2 (Chirukoanaito), 3CaO · Al 2 O 3} · 3SiO 2 ( _{Guroshura), 3CaO · Fe 2 O 3} · 3SiO 2 ( Andhra _{Daito), 6CaO · 4Al 2 O 3} · FeO · SiO 2 ( pleo black Ait ), As well as clinozoite, olivine, olivine, vesuvite, oneolite, Examples include koutite and augite.

  Furthermore, Portland cement can be mentioned as a silicate mineral containing CaO as its component. The type of Portland cement is not particularly limited, and any of normal, early strength, ultra-early strength, moderate heat, sulfate resistance, white, and the like can be used. Furthermore, various mixed cements such as blast furnace cement, silica cement, fly ash cement and the like can be used as the B component.

  Moreover, blast furnace slag, a ferrite, etc. can be mentioned as a silicate mineral which contains other CaO in the component.

As what contains ZnO in its component, ZnO.SiO ₂ , 2ZnO.SiO ₂ (trothite), 4ZnO.2SiO ₂ .H ₂ O (heteropolar ore) and the like can be mentioned.

As including MnO into its _components, such as _{MnO · SiO 2, 2MnO · SiO} 2, CaO · 4MnO · 5SiO 2 ( rhodonite) and Coe write the like.

As the component containing FeO, FeO · SiO ₂ (ferrosilite), 2FeO · SiO ₂ (iron olivine), 3FeO · Al ₂ O ₃ · 3SiO ₂ (almandin), and 2CaO · 5FeO · 8SiO ₂ · H ₂ O (Tetsuakuchinosene) and the like can be mentioned.

Examples of those containing CoO as a component include CoO.SiO ₂ and 2CoO.SiO ₂ .

MgO · SiO ₂ (steatite, enstatite), 2MgO · SiO ₂ (forsterite), 3MgO · Al ₂ O ₃ · 3SiO ₂ (birop), 2MgO · 2Al ₂ O ₃・ 5SiO ₂ (cordierite), 2MgO.3SiO ₂ .5H ₂ O, 3MgO.4SiO ₂ .H ₂ O (talc), 5MgO.8SiO ₂ .9H ₂ O (attapulgite), 4MgO.6SiO ₂ .7H ₂ O (Sepiolite), 3MgO · 2SiO ₂ · 2H ₂ O (Chrysolite), 5MgO · 2CaO · 8SiO ₂ · H ₂ O (Translucentite), 5MgO · Al ₂ O ₃ · 3SiO ₂ · 4H ₂ O (Chlorite) _{, K 2 O · 6MgO · Al} 2 O 3 · 6SiO 2 · 2H 2 O ( phlogopite), _Na 2 O · _{MgO · 3Al 2 O 3 · 8SiO} 2 · H 2 O ( melee stone), as well as magnesium tourmaline, linearity stone, Kamintonsen stone, vermiculite, etc. smectite and the like.

As containing Fe ₂ O ₃ on the _component, and a Fe ₂ O 3 · SiO _2.

As those containing ZrO ₂ into its _components, ZrO 2 · SiO ₂ (zircon) and AZS refractory and the like.

As containing Al ₂ O ₃ on the _{component, Al 2 O 3 · SiO 2} ( sillimanite, under-leucite, _{kyanite), 2Al 2 O 3 · SiO} 2, Al 2 O 3 · 3SiO 2, 3Al 2 O 3 2SiO ₂ (mullite), Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O (kaolinite), Al ₂ O ₃ · 4SiO ₂ · H ₂ O (pyrophyllite), Al ₂ O ₃ · 4SiO ₂ · H ₂ O _{(bentonite), K 2 O · 3Na 2} O · 4Al 2 O 3 · 8SiO 2 ( _{nepheline), K 2 O · 3Al 2} O 3 · 6SiO 2 · 2H 2 O ( muscovite, sericite), _{K 2} O.6MgO.Al ₂ O ₃ .6SiO ₂ .2H ₂ O (phlogobite), various zeolites, fluorine phlogopite, biotite, and the like can be given.

  Among the silicate minerals, mica, talc, and wollastonite are particularly suitable because they have a high rigidity improving effect, good low warpage, and are easily available.

(talc)
In the present invention, talc is hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O, and is usually scaly particles having a layered structure. thereof include a SiO ₂ 56 to 65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less. As for the particle diameter of talc, the average particle diameter measured by the sedimentation method is 0.1 to 50 μm (more preferably 0.1 to 10 μm, still more preferably 0.2 to 5 μm, particularly preferably 0.2 to 3.5 μm). ) Is preferable. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

(Mica)
As the average particle diameter of mica, those having an average particle diameter of 10 to 100 μm measured by a microtrack laser diffraction method can be used. The average particle size is preferably 20 to 50 μm. If the average particle diameter of mica is less than 10 μm, the effect of improving the rigidity is not sufficient, and if it exceeds 100 μm, the rigidity of the rigidity is not sufficiently improved, and the mechanical strength such as impact characteristics is not significantly lowered. As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 0.3 μm. An aspect ratio of 5 to 200, preferably 10 to 100 can be used. The mica used (C-1 component) is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and solves the problems of the present invention at a better level. The mica may be pulverized by either dry pulverization or wet pulverization. The dry pulverization method is more inexpensive and more general, but the wet pulverization method is effective for pulverizing mica more thinly and finely (the rigidity improvement effect of the resin composition becomes higher).

(Wollastonite)
The fiber diameter of wollastonite is preferably from 0.1 to 10 μm, more preferably from 0.1 to 5 μm, still more preferably from 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. For the fiber diameter, for the image obtained by observation with an electron microscope, the filler for which the fiber diameter is to be measured is extracted at random, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter. The observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work). On the other hand, the measurement of average fiber length observes a filler with an optical microscope, calculates | requires individual length, and calculates a number average fiber length from the measured value. Observation with an optical microscope begins with the preparation of a dispersed sample so that the fillers do not overlap each other. Observation is performed under the condition of 20 times the objective lens, and the observed image is taken as image data into a CCD camera having about 250,000 pixels. The obtained image data is calculated by using a program for obtaining the maximum distance between two points of the image data using an image analysis device. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurement is 500 or more (600 or less is suitable for work).

The wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible. It is preferable that the iron content in wollastonite is 0.5% by weight or less in terms of Fe ₂ O ₃ by such magnetic separator processing.

  The silicate mineral (more preferably, mica, talc, wollastonite) in the present invention is preferably not surface-treated, but various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. It may be surface-treated. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes. Talc is particularly suitable for the silicate mineral in the present invention. Such talc is good together with wollastonite in terms of both rigidity and impact resistance, but has a great deterioration in hue and appearance (for example, generation of silver streak) when blended into an aromatic polycarbonate resin as it is. In the resin composition of the present invention, the resin composition containing talc as a silicate mineral is most remarkably improved in hue, and as a result, a resin composition containing talc can be applied to a wider range of technical fields. Is. For this reason, talc is particularly preferred as the silicate mineral.

(C component: alkali sulfonate (earth) metal salt)
The sulfonic acid alkali (earth) metal salt in the present invention is a metal salt of perfluoroalkyl sulfonic acid and alkali metal or alkaline earth metal, or a metal of aromatic sulfonic acid and alkali metal or alkaline earth metal salt. Say salt.

  Examples of the alkali metal constituting the metal salt of the present invention include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, rubidium and cesium having larger ionic radii are suitable when the requirement for transparency is higher, but these are not general-purpose and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium, which are advantageous in terms of cost and flame retardancy, may be disadvantageous in terms of transparency. Considering these, the alkali metal in the sulfonic acid alkali metal salt can be properly used. In any respect, the sulfonic acid potassium salt having an excellent balance of properties is most preferable. Such potassium salts and sulfonic acid alkali metal salts comprising 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. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8. Of these, potassium perfluorobutanesulfonate is particularly preferred.

The alkali (earth) metal salt of perfluoroalkylsulfonic acid composed of an alkali metal is usually mixed with not less than fluoride ions (F ⁻ ). The presence of such fluoride ions can be a factor that lowers the flame retardancy, so it is preferably reduced as much as possible. The ratio of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Moreover, it is suitable that it is 0.2 ppm or more in terms of production efficiency. The alkali (earth) metal salt of perfluoroalkylsulfonic acid having a reduced amount of fluoride ions is contained in a raw material when producing a fluorine-containing organometallic salt using a known production method. A method for reducing the amount of fluoride ions, a method for removing hydrogen fluoride and the like obtained by the reaction by a gas generated during the reaction or heating, and a purification method such as recrystallization and reprecipitation for producing a fluorine-containing organometallic salt Can be produced by a method of reducing the amount of fluoride ions using, for example. In particular, since the B component is relatively soluble in water, ion-exchanged water, particularly water having an electric resistance value of 18 MΩ · cm or more, that is, an electric conductivity of about 0.55 μS / cm or less, and from room temperature is used. It is preferable to produce by a process of dissolving at high temperature and washing, then cooling and recrystallization.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone Α, α, α-trifluoroacetophenone sodium 4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, Nene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, naphthalene Examples thereof include a formalin condensate of sodium sulfonate and a formalin condensate of sodium anthracene sulfonate. Among these aromatic sulfonate alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonate alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3′-disulfonate are preferable, and particularly a mixture thereof (the former and the latter). Is preferably 15/85 to 30/70).

(D component: Silane compound)
The D component of the present invention is a silane compound represented by the following formula (1).

（ここで式（１）中、Ｘは水素原子、ハロゲン原子、およびＲ^１Ｏ（Ｒ^１は炭素数１〜８のアルキル基を示し、該アルキル基はヘテロ原子を含有してよい）のいずれかを示し、Ｒ^２は炭素数４〜３０であり、フッ素原子で置換されてもよいアルキル基を示し、Ｒ^３は炭素数１〜３であり、ハロゲン原子で置換されてもよいアルキル基を示し、ｍは１、２、３または４であり、ｎは０、１、２または３であり、４−（ｍ＋ｎ）は０、１、２または３であり、Ｘ、Ｒ^２、およびＲ^３がそれぞれ複数存在するときは、それらは互いに同一であっても異なっていてもよい。）

(Wherein, in formula (1), X represents a hydrogen atom, a halogen atom, and R ¹ O (R ¹ represents an alkyl group having 1 to 8 carbon atoms, and the alkyl group may contain a hetero atom) R ² represents an alkyl group having 4 to 30 carbon atoms and may be substituted with a fluorine atom, and R ³ represents an alkyl group having 1 to ³ carbon atoms and optionally substituted with a halogen atom. M is 1, 2, 3 or 4, n is 0, 1, 2 or 3, 4- (m + n) is 0, 1, 2 or 3, X, R ² and R ³ When a plurality of are present, they may be the same or different from each other.)

Specific examples of the alkoxysilane compound of component C include, for example, X being a methoxy group, butyltrimethoxysilane, isobutyltrimethoxysilane, butylmethyldimethoxysilane, butyldimethylmethoxysilane, tert-butyltrimethoxysilane, tert-butyl. Dimethylmethoxysilane, dibutyldimethoxysilane, and tributylmethoxysilane (when R ² is an alkyl group having 4 carbon atoms, hereinafter simply referred to as “R ² = C ₄ ”); pentyltrimethoxysilane, and methylpentyldimethoxysilane ^(R 2 _{= C} 5); hexyl trimethoxysilane, trihexyl silane, hexyl trimethoxy silane to nonafluoro and nonafluorohexyl methyldimethoxysilane _{^{(R 2 = C 6),}} ; cycloheptylmethyl di methemoglobin Kishishiran ^(R 2 _{= C} 7); octyltrimethoxysilane, methyl octyl dimethoxysilane, dimethyl octyl silane and tridecafluorooctyltrimethoxysilane _{^{(R 2 = C 8),}} ; nonyl trimethoxysilane ^(R 2 = _{C 9} ); Decyltrimethoxysilane, decylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and heptadecafluorodecyltrimethoxysilane (R ² = C ₁₀ ); dodecyltrimethoxysilane, and dodecylmethyldimethoxysilane (R ² = C _12); tetradecyl trimethoxysilane _{^{((R 2 = C 14)}} ; octadecyl trimethoxysilane, methyl octadecyl dimethoxysilane and dimethyl octadecyl silane, ^(R 2 _{= C 18)} Eicosyltrimethoxysilane (R ² = C ₂₀ ), docosyltrimethoxysilane, docosylmethyldimethoxysilane (R ² = C ₂₂ ), etc. Examples of X other than methoxy group include the above silane compounds Silane compounds in which the methoxy group is substituted with an ethoxy group, a hydrogen atom, a chlorine atom, or the like.

  Specific examples of m = 4 include silane compounds such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetraisobutoxy silane, and tetraaceto silane. Illustrated.

  It is considered that the silane compound of the present invention is easily bonded to the silicate mineral surface by the reactive group (X). Such a bond reduces the reactive site on the surface of the silicate mineral, thereby suppressing the reaction between the active site on the surface and the aromatic polycarbonate resin composition. On the other hand, the acidic group-containing organic compound of the E component also reacts or has close affinity with the surface of the silicate mineral and coats the surface of the silicate mineral. Due to these synergistic effects, the resin composition of the present invention has a high thermal stability, exhibits an excellent appearance of a molded product, and these combinations provide a resin composition maintaining good wet heat resistance. Furthermore, although the mechanism is unclear, it is considered that the effect of the present invention can be obtained by synergistically combining the action of the alkali (earth) metal sulfonate of the C component with the action of the silane compound.

  In the present invention, the silicate mineral is particularly preferably contained in the aromatic polycarbonate resin by the synergistic effect because it has an alkyl group having an appropriate length in the D component and a highly slippery component in the E component. When the material is melt-kneaded, it can escape from the action of high shearing force. As a result, the heat generation on the surface is reduced, and the reaction at the reaction active point is further suppressed. Therefore, in said formula (1), it does not have functional groups, such as an epoxy group which has reactivity with aromatic polycarbonate resin like a normal silane coupling agent. In this respect, the mechanism is unclear, but it is considered that the action of the alkali (earth) sulfonate of the C component is synergistically combined with the action of the silane compound. Further, the low affinity suppresses an increase in viscosity when the silicate mineral is melt-kneaded in the aromatic polycarbonate resin. Therefore, the silicate mineral is in a state excellent in dispersion and mixing properties, and as a result, uniform dispersion is achieved, contributing to good impact resistance as well as non-affinity action with aromatic polycarbonate resin. it is conceivable that.

As described above, the silane compound preferably further has R ² while having a certain amount of X in the above formula (1). Therefore, in the above formula (1), 4- (m + n) = 0 and m = 2 (that is, n = 2) or m = 3 (that is, n = 1) is preferable. In particular, m = 3 and n = 1 are preferable. Further, in the above formula (1), X is preferably a methoxy group or an ethoxy group, and particularly preferably a methoxy group, from the viewpoint of handleability and reactivity.

On the other hand, the greater the number of carbon atoms in R ² (the longer the chain length), the higher the non-affinity for the aromatic polycarbonate resin. However, the greater the number of carbon atoms in R ^2, the lower the thermal stability of itself and the tendency for the hue to deteriorate. Thus the number of carbon atoms in ^{R 2} is preferably a 4 to 18, more preferably 4 to 10.

(E component: an organic compound containing an acidic group)
The acidic group-containing organic compound which is the E component of the present invention is an organic compound having an acidic group represented by a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group. Preferred is an organic compound having at least one of a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group and a phosphinic acid group. In particular, an organic compound having at least one acidic group selected from a carboxyl group, a carboxylic acid anhydride group, and a phosphonic acid group is preferable, and an organic compound having a carboxyl group and / or a carboxylic acid anhydride group is particularly preferable.

  Furthermore, a suitable aspect as E component of this invention is the said acidic group containing lubricant, More preferably, it is a lubricant which has at least 1 sort (s) of the acidic group illustrated above. More preferred E component is a lubricant having at least one acidic group selected from a carboxyl group, a carboxylic acid anhydride group and a phosphonic acid group, and particularly preferably a carboxyl group and / or a carboxylic acid anhydride group. It has a lubricant. In the acidic group-containing lubricant, the concentration of the acidic group is in the range of 0.05 to 10 meq / g, more preferably in the range of 0.1 to 6 meq / g, and still more preferably in the range of 0.5 to 4 meq / g.

  Here, the lubricant is a compound widely known for reducing friction with an apparatus or a mold in plastic molding and obtaining a good mold release, and specifically includes olefin wax, higher fatty acid (for example, Examples thereof include aliphatic carboxylic acids having 16 to 60 carbon atoms, polyalkylene glycols having a polymerization degree of about 10 to 200, silicone oils, and fluorocarbon oils. Examples of olefin waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and α-olefin polymer as paraffin wax. Examples of polyethylene wax include polyethylene having a molecular weight of about 1,000 to 15,000. Examples include polypropylene. This molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (gel permeation chromatography).

  Examples of a method for bonding carboxyl groups to such a lubricant (excluding higher fatty acids) include, for example, (a) a method of copolymerizing a monomer having a carboxyl group and an α-olefin monomer, and (b) the above The method etc. which couple | bond or copolymerize the compound or monomer which has carboxyl groups with respect to a lubricant can be mentioned.

  In the method (a), a living polymerization method can be employed in addition to radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible. The form of the copolymer can be used as a copolymer of various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer in addition to the random copolymer. In the method (b), a radical generator such as peroxide or 2,3-dimethyl-2,3-diphenylbutane (commonly called “dicumyl”) is added to a lubricant, particularly an olefinic wax, if necessary, and a high temperature. A method of reacting or copolymerizing under the above can be adopted. In this method, a reactive site is thermally generated in the lubricant, and a compound or monomer that reacts with the active site is reacted. Other methods for generating active sites required for the reaction include methods such as irradiation with radiation and electron beams and application of external force by mechanochemical techniques. Furthermore, a method in which a monomer that generates an active site required for the reaction is copolymerized in advance in the lubricant. Examples of active sites for the reaction include unsaturated bonds, peroxide bonds, steric hindrance and thermally stable nitroxide radicals.

  Examples of the compound or monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.

  More preferable as the E component of the present invention is that the carboxyl group is preferably in the range of 0.05 to 10 meq / g, more preferably 0.1 to 6 meq per 1 g of the carboxyl group-containing lubricant in the olefin wax. It is a carboxyl group-containing olefin wax which is contained in the range of / g, more preferably in the range of 0.5 to 4 meq / g. Furthermore, the molecular weight of the olefin wax is preferably 1,000 to 10,000.

  As a preferred embodiment of the E component, a copolymer of an α-olefin and maleic anhydride can be exemplified, and such a copolymer that satisfies the above carboxyl group content ratio and molecular weight is particularly preferable. Is preferred. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

(F component: Fluorine-containing anti-dripping agent)
Examples of the fluorine-containing anti-drip agent as the F component include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexa Fluoropropylene copolymer, etc.), partially fluorinated polymers as disclosed in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

  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 mechanical properties. is there.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., and Polyflon MPAFA500 and F-201L from Daikin Industries, Ltd. Commercially available aqueous dispersions of PTFE include Asahi IC Fluoropolymers 'full-on AD-1, AD-936, Daikin Industries' full-on D-1 and D-2, Mitsui Dupont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixture dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form include “Metablene A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved. In addition, the ratio of the said F component shows the quantity of a net fluorine-containing dripping inhibitor, and in the case of mixed form PTFE, it shows a net PTFE quantity.

(G component: Liquid crystalline polyester)
The flame-retardant aromatic polycarbonate resin composition of the present invention can contain a conventionally known flow-modifying component in order to improve the fluidity during molding. Examples of such flow-modifying components include plasticizers (such as phosphate esters, phosphate ester oligomers, phosphazene oligomers, fatty acid esters, aliphatic polyesters, and aliphatic polycarbonates), high rigidity and high fluidity. Other thermoplastic resins and thermoplastic resin oligomers (for example, polymers obtained by polymerizing at least one component selected from styrene, acrylonitrile, and polymethyl methacrylate, oligomers, oligomers of high-rigidity polycarbonate, etc.) ), Liquid crystal polymers (such as liquid crystal polyesters), rigid molecules (such as poly p-phenylene compounds), and lubricants (such as mineral oils, synthetic oils, higher fatty acid esters, higher fatty acid amides). , Polyorganosiloxane, Olefin waxes, polyalkylene glycols, and typified fluorine oil), and the like. In order to more effectively utilize the point of having good flame retardancy without substantially containing a phosphate ester flame retardant in the present invention, it is preferable not to contain a phosphate ester, and (poly) If the amount of the olefin compound or (poly) vinyl compound is too large, flame retardancy may be impaired. Therefore, in the above, as the flow modifying component, a liquid crystal polymer is particularly suitable, and liquid crystal polyester is particularly suitable. The blending of the liquid crystal polyester contributes to further improvement of the rigidity of the resin composition.

  The “liquid crystal polyester” of the G component of the present invention is a thermotropic liquid crystal polyester, and has a property that polymer molecular chains are aligned in a certain direction in a molten state. The arrangement state of the molecular chains may be any of nematic, smectic, cholesteric, and discotic, and may exhibit two or more forms. Furthermore, the structure of the liquid crystal polyester may be any of a main chain type, a side chain type, a rigid main chain bent side chain type, etc., but a main chain type liquid crystal polyester is preferred.

  Further, the heat resistance of the liquid crystal polyester may be in any range, but it is suitable that the liquid crystal polyester melts at a portion close to the processing temperature of the aromatic polycarbonate resin to form a liquid crystal phase. In this respect, it is more preferable that the deflection temperature under load of the liquid crystalline polyester is 150 to 280 ° C, preferably 180 to 250 ° C. Such liquid crystal polyesters belong to the so-called heat-resistant category II. In the case of such heat resistance, excellent processability is achieved as compared with type I having higher heat resistance, and good flame retardancy is achieved as compared with type III having lower heat resistance.

  The liquid crystal polyester used in the present invention includes polyester and polyester amide, preferably aromatic polyester and aromatic polyester amide, and partially containing aromatic polyester and aromatic polyester amide in the same molecular chain. Is also a preferred example.

  Particularly preferred are wholly aromatic polyesters and wholly aromatic polyester amides containing one or more compounds selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines as constituent components. .

More specifically,
1) A polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof,
2) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more aromatic dicarboxylic acids and alicyclic dicarboxylic acids and derivatives thereof, and c) aromatic diols Polyester comprising at least one or more of alicyclic diol, aliphatic diol and derivatives thereof,
3) Mainly a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more of aromatic hydroxyamines, aromatic diamines and derivatives thereof, and c) aromatic dicarboxylic acids. Polyester amide comprising one or more of acid, alicyclic dicarboxylic acid and derivatives thereof, and
4) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof; b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof; and c) aromatic dicarboxylic acids. A polyester amide comprising one or more of acid, alicyclic dicarboxylic acid and derivatives thereof, and d) at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof,
Among them, polyesters composed mainly of one kind or two or more kinds of the above-mentioned 1) aromatic hydroxycarboxylic acid and derivatives thereof are particularly preferred. Furthermore, you may use a molecular weight modifier together with said structural component as needed.

  Preferred examples of the specific compound constituting the liquid crystalline polyester of the present invention include naphthalene compounds such as 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid. Biphenyl compounds such as 4,4′-diphenyldicarboxylic acid and 4,4′-dihydroxybiphenyl, para-substituted benzene compounds such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p-phenylenediamine And their nuclear-substituted benzene compounds (substituents are selected from chlorine, bromine, methyl, phenyl, 1-phenylethyl), meta-substituted benzene compounds such as isophthalic acid and resorcin, and the following general formula (2), It is a compound represented by (3) or (4). Among these, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are particularly preferable, and a liquid crystal polyester obtained by mixing both is preferable. As for the ratio of both, the range of 80-50 mol% is preferable for the former, the range of 75-60 mol% is more preferable, the range of the latter is 20-50 mol%, and the range of 25-40 mol% is more preferable.

[但し、上記一般式（２）、（３）、（４）において、ＸはＣ_１〜Ｃ_４のアルキレン基及びアルキリデン基、−Ｏ−、−ＳＯ−、−ＳＯ_２−、−Ｓ−、並びに−ＣＯ−より選ばれる基であり、Ｙは−（ＣＨ_２）_ｎ−（ｎ＝１〜４）、及びＯ（ＣＨ_２）_ｎＯ−（ｎ＝１〜４）より選ばれる基である。]

[However, the general formula (2), in (3), (4), X is an alkylene group and an alkylidene group _{C 1 ~C 4, -O -,} - SO -, - SO 2 -, - S-, And Y is a group selected from — (CH ₂ ) _n — (n = 1 to 4) and O (CH ₂ ) _n O— (n = 1 to 4). . ]

  The liquid crystalline polyester used as the G component in the resin composition of the present invention contains polyalkylene terephthalate that does not partially exhibit an anisotropic molten phase in the same molecular chain in addition to the above-described constituent components. May be. In this case, the alkylene group has 2 to 4 carbon atoms.

  In the present invention, the basic production method of the liquid crystal polyester as the G component is not particularly limited and can be produced according to a known polycondensation method of polyester. The liquid crystalline polyester also has a logarithmic viscosity value of at least about 2.0 dl / g, such as about 2.0-10.0 dl / g when dissolved in pentafluorophenol at 60% at a concentration of 0.1% by weight ( IV values) are generally indicated.

  Among these, particularly preferred is a wholly aromatic polyester having an IV of 2.0 to 10.0 dl / g mainly composed of an aromatic hydroxycarboxylic acid represented by p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. It is.

(About the composition ratio of each component)
In the present invention, aromatic polycarbonate resin (component A) 100 parts by weight, silicate mineral (component B) 1 to 50 parts by weight (b parts by weight), sulfonate alkali (earth) metal salt (component C) c A resin composition comprising 0.05 to 5 parts by weight of a silane compound (component D) represented by the following formula (1), wherein b (parts by weight) and c (parts by weight) are represented by the following formula ( It is a requirement to satisfy I).
0.008 ≦ c ≦ b / 100 (I)

  The resin composition of the present invention is excellent in the above-described characteristics of the present invention by containing an appropriate proportion of an alkali (earth) sulfonate metal salt (component C) with respect to the B component silicate mineral. In particular, it is excellent in all of its hue, heat and humidity resistance, and flame retardancy. In the above formula (I), if c is less than 0.008, good hue and flame retardancy will not be achieved in the present invention, and if it exceeds b / 100, the heat and humidity resistance will be poor. The upper limit of c is preferably b / 200, more preferably b / 250.

On the other hand, the lower limit satisfies the following formula (II) when b (part by weight) satisfies 0.008 ≦ b / 1500,
b / 1500 ≦ c (II)
Furthermore, when 0.008 ≦ b / 1000 is satisfied, the following formula (III) is satisfied.
b / 1000 ≦ c (III)

  The component ratio of each component is 5-30 parts by weight, more preferably 8-25 parts by weight, more preferably 100 parts by weight of the B component. When the component B is less than 1 part by weight per 100 parts by weight of the component A, effects such as improvement in rigidity are not sufficiently exhibited, and when it exceeds 50 parts by weight, the surface impact strength tends to decrease. In the preferred range of the B component, both good rigidity and surface impact strength can be achieved at a high level.

  The composition ratio of the D component depends on the particle size of the B component, but the range of b / 25 to b / 5 is more than the weight ratio of the B component per 100 parts by weight of the A component (b parts by weight). The range of b / 20 to b / 8 is more preferable. The composition ratio of the D component per 100 parts by weight of the A component is preferably 0.1 to 3 parts by weight, and more preferably 0.2 to 1.5 parts by weight. If the D component is less than 0.05 parts by weight per 100 parts by weight of the A component, good hue, appearance, surface impact strength, etc. cannot be obtained, and even if it exceeds 5 parts by weight, the surface impact strength is reduced or flame retardant Sexuality begins to decline.

  The component E is preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight, and further preferably 0.2 to 0.8 parts by weight per 100 parts by weight of the component A. It is. In such a range, it is possible to achieve both good impact resistance and flame retardancy. Furthermore, the wet heat deterioration of the composition is also suppressed.

  The component F is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 part by weight, and further preferably 0.1 to 0.6 part by weight per 100 parts by weight of the component A. It is. In such a range, it is possible to achieve both a sufficient melt dripping preventing effect and good appearance and flow characteristics.

  Furthermore, the G component is preferably 1 to 30 parts by weight per 100 parts by weight of the A component, more preferably 3 to 20 parts by weight, and particularly preferably 4 to 15 parts by weight. Within such a range, good fluidity can be obtained without significantly affecting the flame retardancy and the appearance of the molded product.

(Other additives)
(Phosphorus stabilizer)
In the present invention, it is preferable to contain a phosphorus stabilizer in order to obtain a flame retardant aromatic polycarbonate resin composition having a better hue and stable fluidity. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

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

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

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

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

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, a phosphate compound typified by trimethyl phosphate is preferably blended. Further, when the liquid crystal polyester of the F component is contained, trialkyl phosphites such as tridecyl phosphite, trioctyl phosphite and trioctadecyl phosphite, and dialkyl pentaerythritol represented by distearyl pentaerythritol diphosphite It is preferable that diphosphite is blended. By blending such phosphite, unnecessary transesterification reaction between the liquid crystal polyester and the aromatic polycarbonate resin is suppressed, the viscoelastic properties of the liquid crystal polyester are effectively exhibited, and the fluidity and rigidity of the resin composition are improved. The

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

  The compounding amount of the phosphorus stabilizer and the hindered phenol stabilizer is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin (component A). More preferably, it is 0.005-0.3 weight part. When the amount of the stabilizer is too much less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be lowered.

(UV absorber)
Since the flame retardant aromatic polycarbonate resin composition of the present invention is excellent in hue and appearance, it may be used without being coated. In such a case, good light resistance may be required, and in such a case, it is effective to add an ultraviolet absorber.

  Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5- Benzoyl-4-hydroxy-2 Methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

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

  The compounding quantity of a ultraviolet absorber is 0.01-2 weight part with respect to 100 weight part of aromatic polycarbonate resin (A component), Preferably it is 0.03-2 weight part, More preferably, it is 0.02-1 weight part. More preferably, it is 0.05 to 0.5 parts by weight.

(Light stabilizer)
In the resin composition of this invention, the said ultraviolet absorber and a light stabilizer can be used together. 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, tetrakis (2 , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-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]}, and polymethylpropyl 3-oxy- [4- (2,2,6,6- Tetrame Le) piperidinyl] hindered amine light stabilizer typified by a siloxane is exemplified. The above light stabilizers may be used alone or in a mixture of two or more. The blending amount of the light stabilizer is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and 0.02 to 1 part by weight based on 100 parts by weight of the aromatic polycarbonate resin (component A). Further preferred.

(Fluorescent brightener)
The resin composition of the present invention can exhibit a very good hue, particularly in the region where the proportion of the silicate mineral is 10 parts by weight or less, so that the resin composition itself should be used for an application requiring light diffusibility. Is also possible. Furthermore, even when such a function is not required, it may be necessary to adjust the hue. In such a case, the blending of the optical brightener is effective. Examples of the fluorescent whitening agent include coumarin-based, naphthalimide-based, and benzoxazolyl-based fluorescent whitening agents. Among them, a coumarin-based fluorescent whitening agent is preferable. ) Hakkol PSR is preferably exemplified. The compounding amount of the optical brightener is 0.0001 to 3 parts by weight, preferably 0.0005 to 1 part by weight, more preferably 0.0005 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate resin (component A). More preferably, the amount is 0.001 to 0.5 parts by weight, and particularly preferably 0.001 to 0.1 parts by weight.

(Other flame retardants)
The resin composition of the present invention achieves good flame retardancy without substantially containing an organic halogen flame retardant or a phosphate ester flame retardant. It does not hinder the flame retardant effect. However, in order to make better use of the characteristics of the present invention, it is preferable that the flame retardant aromatic polycarbonate resin composition of the present invention does not substantially contain an organic halogen flame retardant or a phosphate ester flame retardant. On the other hand, in order to improve the flame retardancy by taking advantage of the features of the present invention, for example, a silicone flame retardant and various organic alkali (earth) metal salts can be further blended.

  Such a silicone flame retardant is a compound having a siloxane bond and improves the flame retardancy by a chemical reaction at the time of combustion. Various compounds conventionally proposed as a flame retardant for aromatic polycarbonate resin should be used. Can do. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. A range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group. Therefore, it is considered that the C component of the present invention contributes in improving the flame retardancy by some action during the combustion.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
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 Monofunctional siloxane units such as (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. A trifunctional siloxane unit of
Q unit : a tetrafunctional siloxane unit represented by SiO ₂ .

The structure of the silicone-based flame retardant according to the present invention is specifically represented by the following formulas: 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 .

  Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more that indicate the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  Furthermore, the silicone flame retardant of the present invention may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group and tolyl group. Groups and aralkyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. Especially as an alkyl group, C1-C4 alkyl groups, such as a methyl group, an ethyl group, a propyl group, are preferable.

  Furthermore, it is preferable that the silicone-based flame retardant of the present invention contains an aryl group because an aromatic polycarbonate resin composition having excellent flame retardancy and transparency can be provided. More preferably, the proportion (aromatic group amount) of the aromatic group represented by the following general formula (5) is preferably 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（５）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。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 monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (5), n is 2) In these cases, different types of X can be taken.)

  The silicone flame retardant of the present invention may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, a vinyl group, and a mercapto group. Examples thereof include a group and a methacryloxy group.

  As the silicone compound having a Si—H group in the silicone-based flame retardant of the present invention, a silicone compound containing at least one of structural units represented by the following general formulas (6) and (7) is preferably exemplified.

（式（６）および式（７）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、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（６）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 each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (8). Α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in formula (6), when m1 is 2 or more, each of the repeating units represents a plurality of 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、炭素数１〜２０の一価の有機残基を示す。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 represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α 4 to α 8 each independently represents 0 or 1. m 2 represents 0. Alternatively, it represents an integer of 1 or more, and the repeating unit in the case where m2 is 2 or more in formula (8) can take a plurality of different repeating units.

  In the silicone flame retardant of the present invention, examples of the silicone compound having an alkoxy group include at least one compound selected from compounds represented by the general formula (9) and the general formula (10).

（式（９）中、β^１はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^１、γ^２、γ^３、γ^４、γ^５、およびγ^６は炭素数１〜６のアルキル基およびシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキル基である。δ^１、δ^２、およびδ^３は炭素数１〜４のアルコキシ基を示す。）

(In formula (9), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

（式（１０）中、β^２およびβ^３はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^７、γ^８、γ^９、γ^１０、γ^１１、γ^１２、γ^１３およびγ^１４は炭素数１〜６のアルキル基、、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキルである。δ^４、δ^５、δ^６、およびδ^７は炭素数１〜４のアルコキシ基を示す。）

(In formula (10), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 12 carbon atoms. And at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.)

  The silicone flame retardant is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and still more preferably 0.005 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). 08-2 parts by weight. With such a suitable composition ratio, an aromatic polycarbonate resin composition having an excellent synergistic effect with the B component to the D component and having good flame retardancy is provided.

  Similarly, various organic alkali (earth) metal salts can be further blended in the aromatic polycarbonate resin composition of the present invention. For example, an alkali (earth) metal salt of a sulfate ester can be mentioned, and in particular, an alkali (earth) metal salt of a sulfate ester of a monovalent and / or polyhydric alcohol can be mentioned. Specific examples thereof include, for example, methyl Sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, lauric acid monoglyceride sulfate, palmitic acid monoglyceride sulfuric acid Examples thereof include esters and sulfates of stearic acid monoglyceride. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other organic alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, Examples thereof include N- (N′-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide. The blending ratio of these organic alkali (earth) metal salts is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight per 100 parts by weight of component A.

(Filler)
In the aromatic polycarbonate resin composition of the present invention, various fillers other than the component B can be blended as reinforcing fillers as long as the effects of the present invention are exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, vapor grown ultrafine carbon fiber (fiber diameter is 0.1 μm Carbon nanotubes (fiber diameter is less than 0.1 μm, hollow), fullerene, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, metal oxide particles, Examples include metal oxide fibers, metal oxide balloons, and various whiskers (such as potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more.

(Other resins and elastomers)
In the resin composition of the present invention, other resins and elastomers can be used in a small proportion within a range in which the effects of the present invention are exhibited.

  Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

  As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

  In addition, the flame retardant aromatic polycarbonate resin composition of the present invention may contain a small amount of additives known per se for imparting various functions to the molded article and improving the properties. These additives are used in usual amounts as long as the object of the present invention is not impaired.

  Examples of such additives include sliding agents (for example, PTFE particles), colorants (for example, pigments and dyes such as carbon black and titanium oxide), light diffusing agents (for example, acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, carbonic acid Calcium particles), fluorescent dyes, inorganic phosphors (for example, phosphors containing aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (for example, fine particle titanium oxide) , Fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the flame-retardant aromatic polycarbonate resin composition of this invention. For example, components A to E and optionally other components are mixed thoroughly using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc. Examples thereof include granulation with a briquetting machine and the like, followed by melt kneading with a melt kneader typified by a vent type biaxial ruder, and pelletization with a device such as a pelletizer.

  As a method for supplying each component to the melt-kneader, (i) A component to E component and other components are each independently supplied to the melt-kneader, and (ii) A component to E component and other components. A method in which a part is premixed and then supplied to the melt kneader independently of the remaining components, (iii) a method in which the component C is diluted and mixed with water or an organic solvent and supplied to the melt kneader, and further (iv) Examples include a method in which the diluted mixture is premixed with other components and then supplied to the melt kneader. In addition, when there exists a liquid thing in the component to mix | blend (for example in said (iii) and (iv)), what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like. Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

(Molding)
A molded article comprising the flame-retardant aromatic polycarbonate resin composition of the present invention can be usually obtained by injection molding the pellet. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, according to this invention, a flame-retardant aromatic polycarbonate resin composition can be extrusion-molded and it can also be made into shapes, such as various profile extrusion-molded articles, a sheet | seat, a film. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the flame-retardant aromatic polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

(surface treatment)
Further, the molded article of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. In particular, since the resin composition of the present invention is suitable for a housing molded product, it is preferable to perform plating for electromagnetic wave shielding, and the resin composition of the present invention is also excellent in such plating characteristics.

  The flame retardant aromatic polycarbonate resin composition of the present invention comprises a silicate mineral, an alkali (earth) sulfonate metal salt, a specific silane compound, and an acidic group-containing organic compound (particularly an acidic group-containing lubricant) at a specific ratio. By combining, it has good flame retardancy even if it does not substantially contain organic halogen flame retardants or phosphate ester flame retardants, and furthermore, rigidity, appearance and hue at high temperature molding, surface impact strength In addition, it has been found that a resin composition excellent in long-term characteristics (for example, resistance to moist heat) can be obtained, and further combined with a fluorine-containing anti-dripping agent, and by using a suitable silicate mineral, low warpage and recycling Provided are a flame retardant aromatic polycarbonate resin composition having excellent properties, and a molded product thereof (particularly preferably a molded housing product). This invention provides the resin composition which has the said characteristic which is not in a conventionally well-known composition by this structure. The flame-retardant aromatic polycarbonate resin composition of the present invention is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and particularly has good characteristics corresponding to housing molded products of OA equipment and electrical and electronic equipment. Is satisfied. In particular, personal computers, notebook computers, game machines (home game machines, arcade game machines, pachinko machines, slot machines, etc.), display devices (CRT, liquid crystal, plasma, projector, organic EL, etc.), printers, copiers, It is suitable for housing molded products such as scanners and fax machines (including these multifunction devices).

  The flame-retardant aromatic polycarbonate resin composition of the present invention is useful for a wide variety of other applications, such as portable information terminals (so-called PDAs), cellular phones, portable books (dictionaries, etc.), portable televisions, recording media (CDs). , MD, DVD, next-generation high-density disk, hard disk, etc.) drive, recording medium (IC card, smart media, memory stick, etc.) reader, optical camera, digital camera, parabolic antenna, electric tool, VTR, iron, hair Examples include dryers, rice cookers, microwave ovens, audio equipment, lighting equipment, refrigerators, air conditioners, air purifiers, negative ion generators, and typewriters. Uses resin products formed from flame retardant aromatic polycarbonate resin composition Rukoto can. Other resin products include lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio visual parts, auto mobile computer parts, and other vehicle parts. it can. As is clear from the above, the industrial effect exhibited by the present invention is extremely great.

  The form of the present invention considered to be the best by the present inventor 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) Rigidity (flexural modulus)
The flexural modulus (MPa) was measured according to ISO178. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick.

(Ii) Flame retardance A UL 94 standard vertical flame test was conducted at a thickness of 1.5 mm, and the grade was evaluated.

(Iii) Hue and Appearance The molded housing of the notebook computer shown in FIG. 1 was molded, and the hue and presence or absence of silver streaks were observed. In the evaluation, the 10th shot immediately after the purge was discarded, the 11th shot was used for hue evaluation, and the molded product up to 20th shot was then used for silver streak evaluation. The hue was measured using a color computer (TC-1800MK-II: manufactured by Tokyo Denshoku Co., Ltd.) for the L value and b value in the mirror surface portion of the housing molded product. In addition, the case where all silver streaks occurred was evaluated as x, the case where the silver streak occurred once was evaluated as Δ, and the case where it did not occur was evaluated as ○. In addition, since the brightness increases as the L value increases, the molded product has a stronger whiteness in visual observation, and the blueness increases as the b value is smaller (a negative value with a larger absolute value). Therefore, the molded product has a stronger white feeling in visual observation. Therefore, in such evaluation, the larger the L value and the smaller the b value, the better.

(Iv) Surface impact strength Of the housing molded product of the notebook computer shown in FIG. 1 created for the above-described appearance evaluation, a portion indicated by a broken line in FIG. 2 is cut out from the molded product of the 20th shot (the boss and rib are on the back surface). A sample for evaluation was cut out so as not to exist, and the sample was subjected to a surface impact test. Evaluation was performed with a high-speed impact tester (manufactured by Shimadzu Corporation). A high speed surface impact test was conducted at a hitting core diameter of 6.4 mm, a pedestal base of 12.8 mm, and a hitting core collision speed of 7 m / s, and the energy value until breakage was measured. The measurement was performed on four cut samples, and the average value was taken. Moreover, the ratio which showed the ductile fracture | rupture form was shown in the sample of 4 points | pieces.

(V) Moisture and heat resistance Of the housing molded product of the notebook computer shown in FIG. 1 created for the above-mentioned appearance evaluation, a portion indicated by a broken line in FIG. It was cut out so as not to exist) to make a sample for evaluation, and this sample was subjected to a pressure cooker tester (Hirayama Seisakusho Co., Ltd. super accelerated life test apparatus (PC-305III / V)) at 120 ° C., relative humidity 100%, 2 The treatment was performed for 24 hours under atmospheric pressure. From the viscosity average molecular weight before and after the treatment, the retention rate was calculated and evaluated.

(Vi) Recyclability Molding the notebook PC housing molding shown in Fig. 1 and collecting the molding from the 21st shot to the 150th shot including the sprue, which has many small holes with a diameter of 8mm. Was pulverized at a processing capacity of 70 kg / h by a pulverizer (SB-210 manufactured by Horai Iron Works Co., Ltd.) equipped with a screen made of a screen, and uniformly blended with a V-type blender to obtain a pulverized product of each molded product. . The pulverized product is dried and molded in the same manner as the evaluation of the virgin pellets, and a bending test piece, a UL test piece and a laptop housing made of 100% of the pulverized product are formed, and the bending elastic modulus, hue and appearance are evaluated. Went.

The following were used as raw materials.
(A component)
PC-1: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation from bisphenol A, p-tert-butylphenol as a terminal terminator, and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WX, viscosity) Average molecular weight 19,700)
PC-2: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation from bisphenol A and p-tert-butylphenol as a terminal terminator and phosgene (manufactured by Teijin Chemicals Ltd .: CM-1000, viscosity average molecular weight) 16,000)
PC-3: a linear aromatic polycarbonate resin synthesized from bisphenol A and p-tert-butylphenol as a terminal terminator and phosgene by an interfacial polycondensation method, having a viscosity average molecular weight of 15,200, 10 parts by weight, viscosity Aromatic polycarbonate resin pellets (component B) having an average molecular weight of 23,700 are melt-mixed with 80 parts by weight, and those with 120,000 having a molecular weight of 29,500.
TALC: Talc (Hayashi Kasei Kogyo Co., Ltd .: Upn HS-T0.8)
MICA: Mica (Coop Chemical Co., Ltd .: Micro Mica MK-100)
WSN: Wollastonite (manufactured by NYCO: NYGLOS4)
(C component)
Bayowet: perfluorobutanesulfonic acid potassium salt having a fluoride ion content of 40 ppm (Bayeret C4 manufactured by Bayer)
KSS: 2: 8 mixture of diphenylsulfone-3,3′-disulfonic acid dipotassium salt and diphenylsulfone-3-monosulfonic acid dipotassium salt (KSS manufactured by UCB Japan)
(D component)
D048: Isobutyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-048)
D3103: Decyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd .: KBM3103)
(Other than D component)
D403: γ-glycidoxypropyl-trimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone Co., Ltd.)
D13: Methyltrimethoxysilane (“KBM-13” manufactured by Shin-Etsu Silicone Co., Ltd.)
(E component)
DC30: acid-modified olefin wax made of a copolymer of maleic anhydride and α-olefin (manufactured by Mitsubishi Chemical Corporation: Diacarna PA30M)
MAH: Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade)
(F component)
PTFE: Polytetrafluoroethylene having a fibril forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA500)
B449: A mixture of polytetrafluoroethylene particles having fibril-forming ability and styrene-acrylonitrile copolymer particles (polytetrafluoroethylene content 50% by weight) (BLENDEX B449 manufactured by GE Specialty Chemicals)
(G component)
LCP: Liquid crystalline polyester resin (Polyplastics Co., Ltd .: Vectra A950)
(Other)
TMP: Phosphorous stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP)

[Examples 1-9, Comparative Examples 1-6]
An aromatic polycarbonate resin, a silicate mineral, an alkali metal sulfonate, and a silane compound, and other components having the compositions shown in Tables 1 and 2 are uniformly mixed using a tumbler to prepare a premix, and the mixture Was supplied from a first supply port located at the screw root of the extruder. In addition, when supplying to a tumbler, the master mixed uniformly with the powder of PC-2 so that each component might become the following density | concentrations was created, and this master was supplied to the tumbler. That is, C-1, C-2, D-1 to D-4, and TMP were 10% by weight master, and PTFE was 2.5% by weight master (comparative example: except for an example having too much silane). . The obtained preliminary mixture is supplied to the first supply port (screw base portion) of a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, and the cylinder temperature is 280 ° C., the screw rotational speed is 150 rpm, and the discharge is performed. It was melt-extruded and pelletized at an amount of 20 kg / h and a vent vacuum of 3 kPa.

  The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours. After drying, test pieces for evaluation of flexural modulus and flammability were molded by an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 300 ° C., a mold temperature of 80 ° C., and a molding cycle of 40 seconds. Further, the pellets after drying were used in an injection molding machine having a cylinder inner diameter of 50 mmφ (ULTRA220-NIVA manufactured by Sumitomo Heavy Industries, Ltd.), and the notebook PC housing molding shown in FIG. Molding was performed at 75 ° C. and an injection speed of 75 mm / sec. Each characteristic was measured using these molded articles. The results are shown in Tables 1 and 2. Note that the notebook PC housing molded products prepared in the examples and the evaluation of the recyclability thereof were all good without any warping.

  As is clear from the above table, it can be seen that the flame-retardant aromatic polycarbonate resin composition of the present invention has good characteristics that cannot be achieved by other silane compounds or other composition ratios.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic front perspective view of a molded product simulating a notebook personal computer housing used in Examples (length 178 mm × width 245 mm × edge height 10 mm, thickness 1.2 mm). It is the surface side front schematic diagram of the molded article used in the Example, and shows the gate position, the state of the weld line, and the cutout portion of the sample for evaluation. It is the back side front schematic diagram of the molded article used in the Example, and shows a mode that there is a boss with a rib (the part of a matte surface becomes a boss with a rib on both upper and lower sides).

Explanation of symbols

1 Molded product body imitating the housing of a notebook PC 2 Matte surface part 3 Mirror surface part 4 Gate (pin gate 0.8mmφ, 5 locations)
5 Approximate weld line 6 Cutout part 7 for evaluation sample Rib boss (corresponding to the back side of the mirror part)
8 Ribbed boss (corresponding to the back side of the mirror)

Claims (8)

Aromatic polycarbonate resin (component A) 100 parts by weight, silicate mineral (component B) 1 to 50 parts by weight (b parts by weight), alkali sulfonate (earth) metal salt (component C) c parts by weight, A resin composition comprising 0.05 to 5 parts by weight of a silane compound (D component) represented by formula (1) and 0.01 to 5 parts by weight of an acidic group-containing organic compound (E component), wherein b ( Parts by weight) and c (parts by weight) are flame retardant aromatic polycarbonate resin compositions satisfying the following formula (I).
0.008 ≦ c ≦ b / 100 (I)

(Wherein, in formula (1), X represents a hydrogen atom, a halogen atom, and R ¹ O (R ¹ represents an alkyl group having 1 to 8 carbon atoms, and the alkyl group may contain a hetero atom) R ² represents an alkyl group having 4 to 30 carbon atoms and may be substituted with a fluorine atom, and R ³ represents an alkyl group having 1 to ³ carbon atoms and optionally substituted with a halogen atom. M is 1, 2, 3 or 4, n is 0, 1, 2 or 3, 4- (m + n) is 0, 1, 2 or 3, X, R ² and R ³ When a plurality of are present, they may be the same or different from each other.)   Furthermore, the flame-retardant aromatic polycarbonate resin composition of Claim 1 formed by containing 0.01-1 weight part of fluorine-containing anti-dripping agents (F component) per 100 weight part of A component. 3. The method according to claim 1, wherein when b (part by weight) satisfies 0.008 ≦ b / 1500, the following formula (II) is further satisfied in addition to the formula (I). Flame retardant aromatic polycarbonate resin composition.
b / 1500 ≦ c (II)   The flame retardant aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the component B is at least one silicate mineral selected from mica, talc and wollastonite.   The flame retardant aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the E component is an acidic group-containing lubricant.   The flame retardant aromatic polycarbonate resin composition according to claim 5, wherein the component E is an olefin wax having a carboxyl group and / or an acid anhydride group thereof.   Furthermore, the flame-retardant aromatic polycarbonate resin composition of any one of Claims 1-6 formed by containing 1-30 weight part of liquid crystalline polyester (G component) per 100 weight part of A component.   A housing molded article formed from the flame retardant aromatic polycarbonate resin composition according to any one of claims 1 to 7.

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