JP4515778B2 - Flame retardant aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame retardant aromatic polycarbonate resin composition and a molded article therefrom. More specifically, bromine compounds and chlorine compounds (halogen flame retardants) as flame retardants, and phosphorus compounds (phosphorus flame retardants) as flame retardants are substantially not included, and are based on resin drip prevention properties during combustion. The present invention relates to a flame retardant aromatic polycarbonate resin composition having good flame retardancy and excellent in appearance, heat stability, and heat and moisture resistance, and a molded article therefrom. Furthermore, this invention relates to the flame-retardant aromatic polycarbonate resin composition which gives the molded article excellent in transparency.

  Aromatic polycarbonate resins are formed into various molded products by a simple and excellent productivity method such as injection molding, and are used in a wide range of industrial fields. Specifically, aromatic polycarbonate resin is used for exterior members and internal parts in personal computers, notebook computers, laser beam printers, ink jet printers, OA equipment such as copy and fax, and home appliances.

  In recent years, in various applications, attention has been paid to flame retardancy at the time of fire, and a resin composition having high flame retardancy is demanded. As methods for imparting flame retardancy to aromatic polycarbonate resins, flame retardant aromatic polycarbonate resin compositions in which halogen compounds such as bromine compounds and chlorine compounds and phosphorus compounds are added as flame retardants have been proposed. While it is used for OA equipment, home appliances, and the like that have a strong demand for combustion, flame retardant aromatic polycarbonate resin compositions that replace these flame retardants have been developed and are being used in such products. Examples of the purpose of changing the flame retardant include suppression of generation of a corrosive gas at the time of molding or improvement of product recyclability.

  Examples of the flame retardant that can replace the flame retardant include a silicone compound. In recent years, a flame retardant resin composition in which a silicone compound is blended with an aromatic polycarbonate resin has been intensively studied and various proposals have been made.

  For example, a method in which an alkali (earth) metal salt of perfluoroalkanesulfonic acid and an organosiloxane having an alkoxy group, a vinyl group, and a phenyl group are blended with a polycarbonate resin (see Patent Document 1), and perfluoroalkanesulfonic acid is added to a polycarbonate resin. A method of blending an alkali metal salt or an alkaline earth metal salt with an organopolysiloxane containing an organoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group has been proposed (see Patent Document 2).

Further, a method of blending a specific petroleum heavy oil or pitch and a silicone compound into the resin component (see Patent Document 3), and a unit represented by the formula R ₂ SiO _1.0 in a non-silicone resin having an aromatic ring And a method of blending a silicone resin having a unit represented by RSiO _1.5 and having a weight average molecular weight of 10,000 to 270,000 (see Patent Document 4).

  However, none of the proposed polycarbonate resin compositions have sufficient transparency and flame retardancy. For example, in the case of a thin wall, a drip may occur and the UL standard 94 V-0 rank cannot be achieved, or the molded product may become clouded due to insufficient silicone dispersion.

  On the other hand, various flame retardant aromatic polycarbonate resin compositions containing a silicone compound containing a Si-H group or a silicone compound containing a reactive group have also been proposed. A resin composition comprising a specific ratio of an aromatic polycarbonate resin, an organic alkali metal salt, and poly (methyl hydrogen siloxane) is known (see Patent Document 5). However, such a resin composition is still not sufficient in terms of thermal stability.

  A resin composition comprising an aromatic polycarbonate resin, a silicone compound having a reactive group, and an aromatic vinyl resin containing an acid base (for example, an alkali metal sulfonate) is known (see Patent Document 6). Such a resin composition is proposed in the patent document as a resin composition having both good transparency and flame retardancy. However, such properties, particularly flame retardancy, are extremely poor in reproducibility, and good flame retardancy cannot be reproduced even if a resin composition that satisfies the requirements described in such literature is produced. Furthermore, the thermal stability is still insufficient, and the flame retardancy of the resin composition retained in the molding machine tends to be greatly reduced.

  In addition, a resin composition for laser marking comprising an aromatic polycarbonate resin, a silicone compound having a reactive group, and / or an organic metal salt is also known (see Patent Document 7).

  A resin composition comprising an aromatic polycarbonate resin, a silicone compound having a Si—H group, and a specific ratio of a radical generator and an organic alkali (earth) metal salt is known (see Patent Document 8). More specifically, the silicone compound is polymethylhydrogensiloxane having a specific viscosity. Such a resin composition has good flame retardancy based on excellent anti-drip properties, and excellent thermal stability and hydrolysis resistance. However, such a resin composition is still insufficient when high transparency is required, and further improvement is required in glossiness, hue, or sharpness of a molded article even when transparency is not required. was there. Also known is a resin composition comprising an aromatic polycarbonate resin, a silicone compound having a Si—H group, a radical generator, an organic alkali (earth) metal salt, and a fluorinated polymer having a fibril-forming ability (Patent Document 9). reference).

  A resin composition comprising an aromatic polycarbonate resin, an aromatic group-containing siloxane, an alkoxysilane and / or Si—H group-containing silicone compound, and a fluororesin having a fibril-forming ability is known (see Patent Document 10). However, such a resin composition is still not sufficient when good transparency is required.

  Aromatic polycarbonate resin, resin composition comprising aromatic group and Si-H group-containing organosiloxane, and the resin composition have good flame retardancy based on excellent anti-drip property, and excellent hue and transparency This is known (see Patent Documents 11 to 13). However, even in such a resin composition, there are cases where further improvement in flame retardancy and reduction in the amount of such organosiloxane while maintaining the flame retardancy are required.

  A polycarbonate resin composition having a flame retardancy and transparency, comprising a specific ratio of an aromatic polycarbonate resin, an organic alkali (earth) metal salt, and an epoxy resin, and a metal salt in such a resin composition It is also known that the decrease in transparency of the resin composition due to the above can be improved by blending an epoxy resin (see Patent Document 14).

JP-A-6-306265 JP-A-6-336547 JP-A-9-169914 Japanese Patent Laid-Open No. 10-139964 Japanese Patent Publication No. 60-38419 JP 2002-220526 A JP 2002-265774 A JP 2002-037997 A JP 2002-060612 A Japanese Patent Laid-Open No. 2002-294062 JP 2003-147188 A JP 2003-147189 A JP 2003-147190 A Japanese Patent No. 3169190

  The object of the present invention is to firstly have good flame retardancy without substantially containing a halogen-based flame retardant and a phosphorus-based flame retardant, and further excellent in appearance, thermal stability, and moist heat resistance. The object is to provide a flame retardant aromatic polycarbonate resin composition. Second, it is to provide a flame retardant aromatic polycarbonate resin composition having even better transparency.

  In order to achieve the above-mentioned object, the present inventors have focused on a silicone compound containing an aromatic group and a Si—H group at a specific ratio, which has both good transparency and drip prevention ability in the prior art. Furthermore, the following general formula (2)

（式（２）中、ＹはＨＯ−Ｙ−ＯＨであらわされる二価フェノールより誘導される二価の基をあらわす。）
の構造を基本骨格に有する化合物を併用することによってさらに良好な難燃性および熱安定性等が安定して得られることを見出した。かかる知見に基づき更なる検討を進め、本発明を完成するに至った。

(In formula (2), Y represents a divalent group derived from a dihydric phenol represented by HO—Y—OH.)
It has been found that by using together a compound having the above structure in the basic skeleton, better flame retardancy and thermal stability can be obtained stably. Further studies have been made based on this finding, and the present invention has been completed.

The present invention comprises (1) (A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) A silicone compound containing a Si—H group and an aromatic group in the molecule, wherein (i) the amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g. , (Ii) the following general formula (1)

（式（１）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（１）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。）
で示される芳香族基が含まれる割合（芳香族基量）が１０〜７０重量％、（ｉｉｉ）平均重合度が３〜１５０であるシリコーン化合物（Ｂ成分）０．１〜１０重量部、並びに
（Ｃ）下記一般式（２）で示される構造を基本骨格に有する化合物（Ｃ成分）０．０１〜５重量部からなる難燃性芳香族ポリカーボネート樹脂組成物にかかるものである。

(In formula (1), each X independently represents an OH group and a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (1), n is 2). In these cases, different types of X can be taken.)
(Iii) A silicone compound (component B) having an average degree of polymerization of 3 to 150 (component B) of 0.1 to 10 parts by weight, and (C) A flame retardant aromatic polycarbonate resin composition comprising 0.01 to 5 parts by weight of a compound (component C) having a structure represented by the following general formula (2) as a basic skeleton.

（式（２）中、ＹはＨＯ−Ｙ−ＯＨであらわされる二価フェノールより誘導される二価の基をあらわす。）

(In formula (2), Y represents a divalent group derived from a dihydric phenol represented by HO—Y—OH.)

  According to this structure (1), the flame-retardant aromatic polycarbonate resin composition which achieved the said objective is provided. In the present invention, it is considered that by using the specific B component, good flame retardancy is achieved by the structure-forming ability of the silicone during combustion of the Si-H group-containing silicone and the aromatic polycarbonate resin. Furthermore, the C component used in combination with the B component further improves the structure-forming ability of the aromatic polycarbonate resin and the Si-H group-containing silicone, or the formation of a silicone structure during combustion by the reactive group in the C component. It is thought to be involved. As a result, it is considered that the C component contributes to further improvement in flame retardancy. It has not been conventionally known to improve the performance of Si—H group-containing silicone as a flame retardant by such a C component.

  One of the preferred embodiments of the present invention is: (2) the flame retardant aromatic polycarbonate resin composition of the above constitution (1), wherein the component C is a polymer having a repeating unit represented by the general formula (2) It is a thing. According to this structure, formation of the said structure becomes easy and the flame-retardant aromatic polycarbonate resin composition excellent in the flame retardance is provided. Furthermore, the flame retardant aromatic polycarbonate resin composition which was more excellent in transparency is provided by the closeness of the refractive index difference of the A component and B component, and the improvement of compatibility.

  One of the preferred embodiments of the present invention is as follows: (3) The flame retardant aromatic polycarbonate resin composition of the constitution (2), wherein the component C is a polymer having a hydroxyl group and / or an epoxy group at the molecular chain terminal. It is a thing. According to this structure (3), the flame-retardant aromatic polycarbonate resin composition excellent in transparency is provided.

  One of the preferable aspects of the present invention is that (4) the constitution (1) to the constitution (1), wherein the component B is a silicone compound containing at least one of constitutional units represented by the following general formulas (3) and (4): It is a flame retardant aromatic polycarbonate resin composition of (3).

（式（３）および式（４）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（５）で示される化合物を示す。α^１〜α^３はそれぞれ独立に０または１を表わす。ｍ^１は０もしくは１以上の整数を表わす。さらに式（３）中においてｍ^１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 (3) and formula (4), 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 (5). Α ^{1 to} α ³ each independently represents 0 or 1. m ¹ represents 0 or an integer greater than or equal to ^1. Further, in Formula (3), when m ¹ is 2 or more, the repeating units are each different from each other. Can be taken as a repeating unit.)

（式（５）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。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ^２は０もしくは１以上の整数を表わす。さらに式（５）中においてｍ^２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 (5), 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 an integer of 0 or 1. Further, in the formula (5), when m ² is 2 or more, the repeating unit can take a plurality of different repeating units.

  Furthermore, one of the suitable aspects of the present invention is (5) the flame-retardant aromatic polycarbonate resin composition of (1) to (4), wherein the component B is a silicone compound comprising MD units or MDT units. (However, M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit). According to the constitution (4), particularly (5), the compatibility of the B component with the aromatic polycarbonate resin is further improved, and a flame retardant aromatic polycarbonate resin composition which achieves the above-mentioned object more satisfactorily is provided. .

  One of the preferred embodiments of the present invention is (6) at least one selected from a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). The flame retardant aromatic polycarbonate resin composition of the above (1) to (5), further comprising 0.001 to 0.3 part by weight of the above compound (component D). According to this configuration (6), a flame-retardant aromatic polycarbonate resin composition having even better flame retardancy is provided, and the aspect of such configuration (6) is extremely suitable in the present invention.

  Further, according to the present invention, (7) a molded article formed from the flame retardant aromatic polycarbonate resin composition of (1) to (6) is provided, and more preferably (8) the molded article is There is provided a molded article having the constitution (7) characterized in that the haze measured by a method according to ISO 13468-1 is in the range of 0.5 to 10.

Details of the present invention will be described below.
<About component A>
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, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5 -Dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) ) Fluorene and the like. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance.

  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 branched structure amount derived from 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 0.1 mol% in the total amount of the aromatic polycarbonate resin. 0.8 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 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the raw material dihydric phenol. 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 addition, the aromatic polycarbonate resin of each component in A3 component is represented by the ratio of the weight average molecular weight / number average molecular weight calculated as a value of standard polystyrene conversion by GPC measurement in a production method usually used industrially. The molecular weight distribution is in the range of 2 to 2.6.

  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 general formula. .

<About B component>
In the resin composition of the present invention, the silicone compound (component B) used as a flame retardant is a specific silicone compound having a Si—H group. That is, a silicone compound containing a Si—H group and an aromatic group in the molecule, wherein (i) the amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g,
(Ii) A silicone compound in which the ratio (aromatic group amount) of the aromatic group represented by the general formula (1) is 10 to 70% by weight, and (iii) the average degree of polymerization is 3 to 150.

  More preferably, when M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit, the silicone compound is composed of MD units or MDT units. That is, a silicone compound consisting only of M units and D units, or a silicone compound consisting only of M units, D units and T units is suitable as the B component.

As monovalent organic residues having 1 to 20 carbon atoms in Z ^{1 to} Z ^{8 of} the structural units represented by the general formulas (2), (3) and (4) and X in the general formula (1), Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group and allyl group, aryl group such as phenyl group and tolyl group, and An aralkyl group can be mentioned, and these groups may contain various functional groups such as an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, and a mercapto group. More preferably, it is a C1-C8 alkyl group, an alkenyl group, or an aryl group, and especially a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a propyl group, a vinyl group, or a phenyl group is preferable.

  Among the structural units represented by the general formulas (2) and (3), when the silicone compound includes at least one structural unit represented by the formula, when it has a plurality of repeating units of siloxane bonds, they are randomly shared. Any form of polymerization, block copolymerization and tapered copolymerization can be employed.

  In the present invention, in the silicone compound as the component (B), the amount of Si—H in the silicone compound is required to be in the range of 0.1 to 1.2 mol / 100 g. When the Si—H amount is in the range of 0.1 to 1.2 mol / 100 g, formation of a silicone structure is facilitated during combustion. More preferred is a silicone compound having a Si—H amount in the range of 0.12 to 1.0 mol / 100 g, and more preferably in the range of 0.15 to 0.6 mol / 100 g. When the amount of Si—H is less than 0.1 mol / 100 g, it becomes difficult to form a silicone structure. When the amount of Si—H is more than 1.2 mol / 100 g, the thermal stability of the composition is lowered and excessive Si—H groups are generated during wet heat treatment. Reacts with moisture in the air, generates hydrogen gas and foams, and the molded product becomes cloudy. In the present invention, the silicone structure refers to a network structure formed by a reaction between silicone compounds or a reaction between a resin and silicone.

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

  Further, the silicone compound (component B) of the present invention preferably has a volatilization amount of 18% or less by a heat loss method at 105 ° C./3 hours. More preferably, the silicone compound has a volatilization amount of 10% or less. When the volatilization amount is larger than 18%, the volatilization amount of the silicone compound at the time of producing the resin composition is increased, and there is a case where the molded product is molded from the resin composition of the present invention.

  The silicone compound containing the structural unit represented by the general formula may be linear or branched as long as the above conditions are satisfied, and the Si—H group is included in the molecular structure. It is possible to use various compounds having any of the side chain, terminal, branching point, or plural sites.

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

Specifically, the structure of the silicone compound used in the present invention has 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, q in the above formula are integers of 1 or more representing 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) In the present invention, the average degree of polymerization is in the range of 3 to 150, preferably in the range of 3 to 80, more preferably in the range of 3 to 60, still more preferably in the range of 4 to 40, and particularly preferably 4. The more preferable range is, the better the compatibility between good flame retardancy and transparency, and when any of m, n, p, q is 2 or more. The siloxane unit with the coefficient can be two or more siloxane units having different hydrogen atoms and organic residues to be bonded.)

  In the flame-retardant aromatic polycarbonate resin composition of the present invention, the dispersion state of the B component and the C component is important. This is because when the silicone compound is unevenly distributed, it becomes difficult to obtain a molded product with good transparency, such as the resin composition itself becoming cloudy and further peeling off on the surface of the molded product. Important factors that determine the dispersion state include the amount of aromatic groups in the silicone compound and the average degree of polymerization. In particular, the average degree of polymerization is important in a transparent resin composition.

  From this point of view, the silicone compound of the present invention is required to have an aromatic group amount in the range of 10 to 70% by weight in the silicone compound. More preferably, it is a silicone compound having an aromatic group content in the range of 15 to 60% by weight. If the amount of the aromatic group in the silicone compound is less than 10% by weight, the silicone compound is unevenly distributed, resulting in poor dispersion, and it becomes difficult to obtain a molded article having good transparency. When the amount of the aromatic group is more than 70% by weight, the rigidity of the molecule of the silicone compound itself is increased, so that it is unevenly distributed and poorly dispersed, and it becomes difficult to obtain a molded product with good transparency.

  In addition, the amount of the aromatic group herein refers to the ratio of the aromatic group represented by the following general formula (1) in the silicone compound, and can be determined by the following formula.

（式（１）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（１）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。）
（計算式） 芳香族基量＝〔Ａ／Ｍ〕×１００（重量％）
ここで、上記式におけるＡ、Ｍはそれぞれ以下の数値を表す。
Ａ＝シリコーン化合物１分子中に含まれる、全ての一般式（１）で示される芳香族基部分の合計分子量
Ｍ＝シリコーン化合物の分子量
前記のＢ成分のシリコーン化合物は、単独で用いてもよく２種以上を組合せて用いてもよい。

(In formula (1), each X independently represents an OH group and a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (1), n is 2). In these cases, different types of X can be taken.)
(Calculation formula) Aromatic group amount = [A / M] × 100 (% by weight)
Here, A and M in the above formula represent the following numerical values, respectively.
A = total molecular weight of all aromatic groups represented by the general formula (1) contained in one molecule of the silicone compound M = molecular weight of the silicone compound The above-mentioned silicone compound of component B may be used alone 2 A combination of more than one species may be used.

  Such a silicone compound having a Si—H bond can be produced by a method known per se. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-product hydrochloric acid and low-boiling components. In the case where Si—H group, aromatic group represented by the general formula (1) in the molecule, silicone oil having other organic residues, cyclic siloxane or alkoxysilanes are used as starting materials, hydrochloric acid, sulfuric acid , By using an acid catalyst such as methanesulfonic acid, and optionally adding water for hydrolysis to advance the polymerization reaction, and then removing the used acid catalyst and low-boiling components in the same manner. A silicone compound can be obtained.

  The composition ratio of the B component silicone compound is 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). 5 parts by weight.

<About component C>
The component C of the present invention is a compound having a structure represented by the formula (2) in the basic skeleton, and more preferably a polymer having a repeating unit represented by the formula (2). Such a polymer is a polymer widely known as an epoxy resin or a phenoxy resin. Various dihydric phenols can be used as the dihydric phenol (HO-Y-OH) for deriving Y in the formula (2), and specific examples thereof include the production of the component A. What was illustrated as a dihydric phenol used is mentioned. Among them, bisphenol A is preferred as dihydric phenol (HO—Y—OH) because it has high versatility and good transparency can be obtained in combination with a suitable A component. This is because the A component and the C component are produced from a dihydric phenol having the same structure, so that the combination of the refractive index differences between the A component, the B component, and the C component is suitable, and between these three components. This is thought to be due to the improved compatibility.

  Two or more dihydric phenols (HO—Y—OH) in the formula (2) of the C component may be used. In such a case, even if the mixture is a mixture of two or more compounds, two or more are 1 The aspect contained in one compound may be sufficient. When two or more kinds are contained in one polymer (that is, a copolymer), they may be any embodiment of a random copolymer, a block copolymer, and a graft copolymer. In the case where the aromatic polycarbonate resin of component A is a copolymer produced from two or more dihydric phenols, the composition ratio of dihydric phenol (HO—Y—OH) in component C is determined according to the component A. It is preferable to make it almost the same as the composition ratio of the dihydric phenol.

  As described above, the component C of the present invention is preferably a polymer having a hydroxyl group and / or an epoxy group at the molecular chain end. Such polymers are believed to effectively promote silicone structure formation upon combustion. On the other hand, the addition of a large amount of component C causes a decrease in transparency, and excessive reactivity conversely promotes the decomposition of the aromatic polycarbonate resin and inhibits the formation of the structure. It is preferable to select. Moreover, the number average molecular weight of C component becomes like this. Preferably it is 800-20,000, More preferably, it is 1,500-15,000. In such a suitable molecular weight range, the compatibility with the aromatic polycarbonate resin becomes better, which has a favorable effect on the transparency and flame retardancy of the resin composition. The number average molecular weight is calculated as a value in terms of standard polystyrene in GPC measurement.

  The composition ratio of the component C is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). It is.

  The total amount of component B and component C is 0.11 to 15 parts by weight, preferably 0.25 to 6 parts by weight, more preferably 0, based on 100 parts by weight of aromatic polycarbonate resin (component A). .5-4 parts by weight is advantageous.

<About D component>
The flame retardant aromatic polycarbonate resin composition of the present invention may further contain at least one compound selected from a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt as component D. By blending this D component, flame retardancy can be further improved, and in particular, drip prevention is improved. On the other hand, the aromatic polycarbonate resin composition containing the component D generally has low thermal stability and hydrolysis resistance. However, the flame-retardant aromatic polycarbonate resin composition of the present invention can suppress such deterioration of thermal stability and hydrolysis resistance due to the combined effect of the B component and the C component. As a result, the flame-retardant aromatic polycarbonate resin composition of the present invention exhibits more preferable practical characteristics by the combined use of component D. In the present invention, the D component is referred to as a flame retardant improving agent. The amount of component D as the flame retardant improver is 0.001 to 0.3 parts by weight, preferably 0.005 to 0.3 parts by weight, per 100 parts by weight of the aromatic polycarbonate resin (component A). More preferably, the range of 0.005 to 0.2 parts by weight is appropriate.

  Examples of the radical generator used as the D component in the present invention include organic peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and dicumyl peroxide, Examples thereof include 3-dimethyl-2,3-diphenylbutane (dicumyl) and the like, which are commercially available under trade names such as Perhexine 25B, Parkmill D, and NOFMER BC manufactured by NOF Corporation. In particular, those that generate as little radicals as possible at the time of melt kneading and that generate stable radicals to some extent at the time of combustion are preferred, so 2,3-dimethyl-2,3-diphenylbutane (dicumyl) is more preferred as a radical generator. be able to.

  As the alkali metal salt and alkaline earth metal salt used as the component D of the present invention, various metal salts conventionally used for flame-retarding polycarbonate resins can be used. Or a metal salt of a sulfate ester. These may be used alone or in combination of two or more. The alkali metal of component D includes lithium, sodium, potassium, rubidium and cesium, and the alkaline earth metal includes beryllium, magnesium, calcium, strontium and barium, particularly preferably lithium, sodium, Potassium.

  Examples of the metal salt of organic sulfonic acid include alkali metal salt of aliphatic sulfonic acid, alkaline earth metal salt of aliphatic sulfonic acid, alkali metal salt of aromatic sulfonic acid, alkaline earth metal salt of aromatic sulfonic acid, etc. Is mentioned. Preferred examples of such aliphatic sulfonic acid metal salts include alkali (earth) alkane sulfonates and alkali sulfonates in which part of the alkyl group of the alkali (earth) alkane sulfonate is substituted with a fluorine atom. (Earth) metal salts and alkali (earth) metal salts of perfluoroalkanesulfonic acid can be mentioned, and these can be used alone or in combination of two or more (where alkali (earth) Class) The term “metal salt” is used to include both alkali metal salts and alkaline earth metal salts).

  Preferable examples of alkane sulfonic acid used for alkane sulfonic acid alkali (earth) metal salt include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methylbutane sulfonic acid, hexane sulfonic acid, heptane sulfone. An acid, octanesulfonic acid, etc. are mentioned, These can be used combining 1 type (s) or 2 or more types. In addition, a metal salt in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

  On the other hand, preferred examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, Examples thereof include perfluoroheptanesulfonic acid and perfluorooctanesulfonic acid, and those having 1 to 8 carbon atoms are particularly preferable. These can be used alone or in combination of two or more.

  Preferred examples of the alkali (earth) metal salt of alkanesulfonic acid include sodium ethanesulfonate, and preferred examples of the alkali (earth) metal salt of perfluoroalkanesulfonic acid include potassium perfluorobutanesulfonic acid.

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.

  Among the alkali (earth) metal salts listed above, more preferable components include alkali (earth) metal salts of aromatic sulfonic acid and alkali (earth) metal salts of perfluoroalkanesulfonic acid.

<About the characteristic which the composition of this invention has>
As described above, according to the present invention, an aromatic polycarbonate resin (component A), a Si—H group-containing silicone compound (component B), a compound having the structure of the above general formula (2) as a basic skeleton (component C), and If necessary, the combination of flame retardant modifier (component D) provides excellent anti-drip properties during combustion and does not contain halogenated flame retardants such as bromine compounds as flame retardants (hereinafter sometimes referred to simply as “halogen-free”). A flame retardant aromatic polycarbonate resin composition is provided. In the resin composition of the present invention, other resins, fillers, or various additives can be blended as is usually blended in the polycarbonate resin composition. Details of these other resins, fillers or additives will be described later.

<Other additive components>
Although the A component, the B component, the C component, and the D component in the flame-retardant aromatic polycarbonate resin composition of the present invention have been described above, fillers, other resins, and various types that can be further blended in the composition The additive will be described.

  The flame retardant aromatic polycarbonate resin composition of the present invention may further contain a filler as an E component. This filler (E component) can be used to improve the mechanical strength, rigidity, heat-and-moisture resistance, and flame resistance of molded products, and to improve specific functions such as other improvements in electrical and electronic functions. And As this filler, those known as fillers to be blended with the aromatic polycarbonate resin are used. The compounding quantity of E component is 0.001-100 weight part with respect to 100 weight part of resin components (A component). In particular, when improvement in mechanical strength or the like is more important than transparency, the amount is preferably 1 to 80 parts by weight, more preferably 3 to 60 parts by weight. On the other hand, in the case of maintaining transparency and improving moisture resistance and flame resistance, it is preferably 0.001 to 1 part by weight, more preferably 0.003 to 0.8 part by weight, and still more preferably Is 0.005 to 0.6 parts by weight.

  Examples of the component E include talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, metal flake, Examples thereof include metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, and various whiskers.

  In the resin composition of the present invention, a thermoplastic resin other than the component A can be blended in order to improve the mechanical properties, chemical properties or electrical properties of the molded product. The amount of the other thermoplastic resin blended varies depending on the type and purpose, but is usually 0.001 to 30 parts by weight per 100 parts by weight of the aromatic polycarbonate resin (component A). Especially when transparency is required, the amount of other thermoplastic resin is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight per 100 parts by weight of component A. Is appropriate. On the other hand, when other characteristics are more important than transparency, the amount of the other thermoplastic resin is preferably 2 to 20 parts by weight per 100 parts by weight of component A.

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

  In the resin composition of the present invention, additives known per se can be blended in a small proportion for imparting various functions and improving properties to the molded product. These additives are used in usual amounts as long as the object of the present invention is not impaired.

  Examples of such additives include flame retardants other than the B component and the C component (such as phosphate ester, red phosphorus, and metal hydrate), anti-drip agents (such as fluorine-containing polymers having fibril-forming ability), heat stabilizers, UV absorbers, light stabilizers, release agents, lubricants, sliding agents (PTFE particles, etc.), colorants (pigments such as carbon black and titanium oxide, dyes), metallic pigments (metal flakes, metals or metal oxide coatings) Plate filler, etc.), light diffusing agent (acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brightener, phosphorescent pigment, fluorescent dye, antistatic agent, flow modifier, crystal Nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers typified by graft rubber, heat ray shielding agents (phthalocyanines) System compounds, metal boride particles, and metal oxide fine particles) or photochromic agents.

  The flame retardant aromatic polycarbonate resin composition of the present invention is improved in the aromatic polycarbonate resin for the purpose of improving its thermal stability, antioxidant property, light stability (ultraviolet light stability) and mold release property. The additives used in are preferably used. Hereinafter, these additives will be specifically described.

  The flame-retardant aromatic polycarbonate resin composition of the present invention can contain a phosphorus-containing stabilizer as a heat stabilizer. As the phosphorus-containing stabilizer, any of phosphite compounds, phosphonite compounds, and phosphate compounds can be used.

  Examples of the phosphite compound include 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) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ite, 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, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  Still other phosphite compounds that 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, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl- Phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.

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

  For example, α-tocopherol, butylhydroxytoluene, sinapyl 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′-methylenebis (4-ethyl-6-tert) -Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylpheno) 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-) Droxybenzyl) 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-thiodiethylenebis- [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) isocyanurate Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di-tert -Butyl-4-hydroxyphenyl) propionate] methane and the like.

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

  All of these are readily available. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

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

  The phosphorus-containing heat stabilizer, phenolic antioxidant, and sulfur-containing antioxidant listed above can be used alone or in combination of two or more. More preferably, the phosphorus-containing stabilizer is blended as an essential component in the flame-retardant aromatic polycarbonate resin of the present invention.

  The proportion of these stabilizers in the composition is 0.0001 to 1 for each of the phosphorus-containing stabilizer, phenol-based antioxidant, or sulfur-containing antioxidant per 100 parts by weight of the aromatic polycarbonate resin (component A). A part by weight is preferred. More preferably, it is 0.0005 to 0.5 parts by weight per 100 parts by weight of component A. More preferably, it is 0.001-0.2 weight part.

  A release agent can be blended in the flame-retardant aromatic polycarbonate resin composition of the present invention as necessary. As such a release agent, those known per se can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-alkene polymer may be used. These may be modified with a functional group-containing compound such as acid modification), silicone compounds (Other than the component B of the present invention. Examples include linear or cyclic polydimethylsiloxane oil and polymethylphenyl silicone oil), fluorine compounds (fluorine oil typified by polyfluoroalkyl ether, etc.), paraffin There may be mentioned wax, beeswax and the like. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, and fluorine oil can be mentioned. The release agent is preferably 0.01 to 0.3 parts by weight with respect to 100 parts by weight of component A.

  Preferable mold release agents include saturated fatty acid esters. For example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, and lower fatty acid esters such as stearic acid stearate. , Higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used.

  The flame retardant aromatic polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber. This is because the resin composition is often used for a part that is directly exposed to light by utilizing its transparency and a part that guides light in a more preferable embodiment. Even an opaque molded product may require improved weather resistance.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane. Benzophenone compounds represented by

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], condensate with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol The benzotriazole type compound represented by can be mentioned.

  Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6-bis (2,4-dimethyl). And hydroxyphenyltriazine compounds such as phenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Further, examples of the ultraviolet absorber include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) and 2,2′-m-phenylenebis (3,1-benzoxazin-4-one). And cyclic imino ester compounds such as 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one).

  Also, 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-butanetetra Carboxylate, 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]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane. It can also include hindered amine light stabilizers represented by, such light stabilizers in combination with the ultraviolet absorber and various antioxidants, exhibit better performance in terms of weather resistance.

  The ultraviolet absorber and the light stabilizer have a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and / or the light stable monomer, an alkyl (meth) acrylate, etc. It may be a polymer-type ultraviolet absorber and / or light stabilizer copolymerized with the above monomer. The UV-absorbing monomer and light-stable monomer contain a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a hindered amine skeleton in the ester substituent of (meth) acrylic acid ester. The compound is preferably exemplified.

  The composition ratio of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, still more preferably 0.05 to 100 parts by weight of the component A, respectively. -0.6 parts by weight.

  In addition, the flame retardant aromatic polycarbonate resin composition of the present invention can be blended with a bluing agent in order to counteract the yellowishness based on an ultraviolet absorber or the like. Any bluing agent can be used without any problem as long as it is usually used for polycarbonate resin. In general, anthraquinone dyes are preferred because they are readily available. Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No. (Color Index No) 60725; Trade name “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Violet 31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No. 60725; trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA. No. 61500; trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation, generic name Solvent Violet 36 [CA. No. 68210; Trade name: “Macrolex Violet 3R” manufactured by Bayer, Inc., generic name: Solvent Blue 97 [trade name: “Macrolex Blue RR” manufactured by Bayer, Inc.], and generic name: Solvent Blue 45 [CA. No. 61110; trade name “Polycinslen Blue RLS” manufactured by Clariant Co., Ltd.] and the like. Macrolex Blue RR, Macrolex Violet B and Polysynthrene Blue RLS are particularly preferable.

  Although the flame-retardant aromatic polycarbonate resin composition of the present invention is excellent in anti-drip property, a normal anti-drip agent can be used in combination to further reinforce such performance. However, in the transparent resin composition which is a preferred embodiment of the present invention, the blending amount is suitably 0.1 parts by weight or less with respect to 100 parts by weight of component A and 0.08 parts by weight or less in order not to impair such transparency. Is more preferable, and 0.05 part by weight or less is more preferable. Examples of such an anti-drip agent include a fluorine-containing polymer having a fibril forming ability. Polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is particularly preferable.

  PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and transparency. . As a commercial product of PTFE in a mixed form, “Metablene A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and the like can be mentioned.

<Regarding Production Method and Molding Method of Resin Composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, component A, component B, component C and optionally other components are mixed thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc., and then extruded as necessary. Examples thereof include a method of granulating with a granulator, a briquetting machine, etc., then melt-kneading with a melt-kneader represented by a vent type biaxial ruder, and pelletizing with a device such as a pelletizer.

  Alternatively, the A component, B component, C component and optionally other components are independently fed to a melt-kneader represented by a vented twin screw rudder, and a part of the A component and other components are reserved. After mixing, the method of supplying the melt kneader independently of the remaining components, the components B and C are diluted and mixed with water or an organic solvent, and then supplied to the melt kneader, or the diluted mixture is mixed with other components. Examples thereof include a method of supplying the mixture to a melt-kneader after preliminary mixing. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

  The flame-retardant aromatic polycarbonate resin composition of the present invention can usually be produced in various products by injection molding such pellets to obtain molded products. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerlessness can be used. Also in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra-molding) Including those using critical fluids), rapid heating / cooling mold forming, heat insulating mold forming and in-mold remelt molding, and combinations of these, etc. can be used.

  The flame-retardant aromatic polycarbonate resin composition of the present invention can also be used in the form of various shaped extrusions, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be formed into a molded product by rotational molding without melt-kneading.

  Furthermore, various surface treatments can be performed on the molded product formed from the resin composition. Surface treatment includes decorative coating, hard coat, water / oil repellent coat, hydrophilic coat, UV absorbing coat, infrared absorbing coat, electromagnetic wave absorbing coat, heat generating coat, antistatic coat, antistatic coating, conductive coating, and meta coating. Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed. In particular, a transparent sheet coated with a transparent conductive layer is preferred.

  According to the present invention, a molded article formed from the flame-retardant aromatic polycarbonate resin composition of the present invention is provided by the above-described production method and molding method, and more preferably, transparent molding formed from the resin composition. Goods are provided. A representative example of such a transparent molded product is a transparent sheet.

  The flame-retardant aromatic polycarbonate resin composition of the present invention is substantially free of halogen-based flame retardants and phosphorus-based flame retardants, has good flame retardancy, and further has appearance, thermal stability, and moisture resistance. A resin composition having excellent thermal properties, more preferably having even better transparency, comprising a conventionally known aromatic polycarbonate resin and a silicone compound having a specific amount of aromatic groups and Si-H groups. In the resin composition, the performance of the silicone compound as a flame retardant is further improved without impairing transparency and thermal stability.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.
The various physical properties in the examples were measured by the following methods.
(I) Flame retardance A 2.8 mm thick UL combustion test piece prepared according to the UL standard was tested based on the UL standard 94 using a test piece treated at a temperature of 70 ° C. for 168 hours. The evaluation was performed by the number of test pieces that produced drip out of the five test pieces and the total burning time (seconds) of the five test pieces.
(II) Heat resistance A UL combustion test piece having a thickness of 2.8 mm was molded after being retained for 10 minutes at a cylinder temperature of 300 ° C. A test was performed based on UL standard 94 using a test piece treated at a temperature of 70 ° C. for 168 hours. Evaluation was performed by the number of test pieces that produced drip out of the five test pieces.
(III) Molded Product Appearance A square plate-shaped molded product having a size of 150 mm × 150 mm and a thickness of 2.0 mm was visually observed and evaluated according to the following criteria.
○: Good (no peeling, glossy, uniform appearance)
×: Defect (with peeling, no gloss, non-uniform appearance)
(IV) Transparency A haze value obtained by measuring the transparency of a square plate-shaped molded product having a size of 150 mm × 150 mm and a thickness of 2.0 mm according to JIS K7105, and visually evaluating the hue of the molded product based on the following criteria. did. When the appearance of the molded product was “x” and the transparency by visual observation was “x”, the haze measurement was not performed and “−” was described.
○: colorless and transparent ×: cloudy or colored

[Examples 1 to 6 and Comparative Examples 1 to 4]
The resin composition described in Table 1 was prepared as follows. The description will be made according to the symbols in the following table.
Each component in the ratio of Table 1 was weighed, and further phosphite antioxidant (IRGAFOS168 manufactured by Ciba Geigy Japan): 0.01 parts by weight, phenol antioxidant (IRGANOX 1076 manufactured by Ciba Geigy Japan): 0.01 parts by weight , UV absorber (Kemipro Kasei Kogyo Co., Ltd. Chemisorb 79): 0.1 part by weight, mold release agent (Riken Vitamin Co., Ltd. Riquemar SL900): 0.1 part by weight weighed, using a tumbler The mixture was uniformly mixed, and the mixture was put into an extruder to prepare a resin composition.

  As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration consists of the first kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. The strand was extruded under conditions of a cylinder temperature and a die temperature of 280 ° C. and a vent suction of 3,000 Pa, cooled in a water bath, then cut into a strand with a pelletizer and pelletized.

  The obtained pellets were dried at 120 ° C. for 5 hours in a hot air circulating dryer and tested at an injection molding machine with a clamping force of 1470 N [IS150EN manufactured by Toshiba Corp.] at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C. A piece was molded. Moreover, the used raw materials etc. corresponding to the symbols described in Table 1 are as follows (note that the symbols of the raw materials represent the same contents other than the table).

(A component)
PC-1: Linear polycarbonate resin powder (aromatic polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. Such aromatic polycarbonate resin is produced without using an amine-based catalyst. In the terminal of the aromatic polycarbonate resin, the ratio of the terminal hydroxyl group was 10 mol%, and the aromatic polycarbonate resin contained 25 ppm of phosphonite antioxidant [Clariant Sandstab P-EPQ]. (The viscosity average molecular weight was 22,500)
PC-2: Branched aromatic polycarbonate resin (Taflon IB2500 manufactured by Idemitsu Petrochemical Co., Ltd.)

(B component)
Synthesis Example-1
300 g of water and 150 g of toluene were charged into a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, and cooled to an internal temperature of 5 ° C. Into the dropping funnel, a mixture of 21.7 g of trimethylchlorosilane, 22.0 g of methyldichlorosilane, 13.2 g of dimethyldichlorosilane and 76.2 g of diphenyldichlorosilane was added and dropped into the flask over 2 hours while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged for 4 hours at an internal temperature of 20 ° C., then left to stand to remove the separated hydrochloric acid aqueous layer, added with a 10% aqueous sodium carbonate solution, stirred for 5 minutes and then left to stand. The separated aqueous layer was removed. Then, it further wash | cleaned 5 times with ion-exchange water, and it confirmed that the toluene layer became neutral. This toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound B-1.

Synthesis Example-2
In a 1 L flask equipped with a stirrer, a cooling device and a thermometer, 15.9 g of hexamethyldisiloxane, 60.2 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 103.4 g of octamethylcyclotetrasiloxane and diphenyldimethoxy 390.0 g of silane was charged, and 25.0 g of concentrated sulfuric acid was added while stirring. After cooling to an internal temperature of 10 ° C., 30.0 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 10 to 20 ° C. for 5 hours. Then, 8.5 g of water and 300 g of toluene were added, stirred for 30 minutes, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% aqueous sodium sulfate solution, and it was confirmed that the toluene layer became neutral. This toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insoluble materials were removed by filtration to obtain a silicone compound B-2.

Synthesis example-3
Charge 168.0 g of 1,1,3,3-tetramethyldisiloxane, 92.5 g of octamethylcyclotetrasiloxane, 49.7 g of octaphenylcyclotetrasiloxane and 295.0 g of phenyltrimethoxysilane, and add 25 g of concentrated sulfuric acid. Then, a silicone compound B-3 was obtained in the same manner as in Synthesis Example-2 except that 42.0 g of water was dropped.
B-1: Silicone compound prepared according to Synthesis Example-1 0.21 mol / 100 g, aromatic group amount 49% by weight, average polymerization degree 11.0 Silicone compound B-2: According to Synthesis Example-2 Silicone compound B-3 having an Si-H amount of 0.20 mol / 100 g, an aromatic group amount of 50% by weight, and an average degree of polymerization of 43.0: The Si-H amount prepared according to Synthesis Example-3 was 0.00. Silicone compound having 49 mol / 100 g, aromatic group content of 31% by weight and average degree of polymerization of 12.0

(Other than B component)
Synthesis example 4
The procedure was the same as in Synthesis Example-1, except that 550 g of water and 130 g of toluene were charged and a mixture of 21.0 g of trimethylchlorosilane, 51.5 g of methyldichlorosilane, 84.2 g of dimethyldichlorosilane and 14.0 g of phenyltrichlorosilane was added dropwise. As a result, a silicone compound B-4 was obtained.
B-4 (Comparative): Silicone compound prepared according to Synthesis Example 4 having a Si—H amount of 0.45 mol / 100 g, an aromatic group amount of 5.1% by weight, and an average degree of polymerization of 17.0

<Indication formula of each silicone compound>
B-1: M ₂ ^DH ₂ D ₁ D ^φ2 ₃
B-2: M ₂ ^DH ₁₀ D ₁₄ D ^φ2 _{16
^{B-3: M H 5 D}} 2.5 D φ2 0.5 T φ 3
B-4: M ₃ ^DH ₇ D ₁₀ T ^φ ₁ (Comparison)
Each symbol in the above formula represents the following siloxane unit, and the coefficient of each symbol represents the degree of polymerization of each siloxane unit in one molecule.
M: (CH ₃ ) ₃ SiO _1/2
M ^H : H (CH ₃ ) ₂ SiO _1/2
D: (CH ₃ ) ₂ SiO
_{^{D H: H (CH 3)}} SiO
D ^φ2 : (C ₆ H ₅ ) ₂ SiO
^Tφ : (C ₆ H ₅ ) SiO _3/2

(C component)
C-1: Phenoxy resin (number average molecular weight 16,000, PKFE manufactured by InChem Corp.)
C-2: Phenoxy resin (number average molecular weight 13,000, PKHH manufactured by InChem Corp.)
C-3: Epoxy resin (epoxy equivalent 1800 g / eq, manufactured by Toto Kasei Co., Ltd. Epototo YD-017)
C-4: Epoxy resin (epoxy equivalent 500 g / eq, Etototo YD-011 manufactured by Toto Kasei Co., Ltd.)

(D component)
D-1: Perfluorobutanesulfonic acid potassium salt (Dai Nippon Ink Chemical Co., Ltd. MegaFuck F-114P)
D-2: Potassium salt of diphenylsulfone sulfonic acid (KSS manufactured by UC Japan)

  As is apparent from the above table, the flame-retardant aromatic polycarbonate resin composition of the present invention has a combustible time reduced in addition to its drip prevention performance by the combined use of the B component and the C component, and the resin composition has excellent transparency. It can be seen that the flame retardancy can be improved while maintaining the properties.

  The flame-retardant aromatic polycarbonate resin composition of the present invention comprises a silicone compound (component B) having a specific Si—H group as a flame retardant and a compound having a structure represented by the above general formula (2) as a basic skeleton ( C component), substantially containing no halogen-based flame retardant, phosphorus-based flame retardant, having good flame retardancy, and excellent in appearance, such characteristics are in the OA equipment field, It is extremely useful for various industrial applications such as electrical and electronic equipment.

  In particular, according to a preferred embodiment of the present invention, a flame retardant aromatic polycarbonate resin composition having excellent transparency can be obtained. This flame retardant resin composition has anti-drip property and transparency due to containing a specific silicone compound (component B) as a flame retardant and a polymer having a repeating unit of the above general formula (2). It is what you have. This resin composition with good transparency can be molded and used as a transparent sheet. Not only lighting covers and protective covers for transmissive displays, but also light guide parts, solar cell covers and substrates, lenses, lens arrays, It is useful for applications such as couplers, touch panels, resin windows, game machine parts (such as pachinko front covers and circuit covers), prisms, and mirrors. That is, it is extremely useful and valuable for various industrial applications such as the OA equipment field, electrical and electronic equipment field, vehicle field, agricultural field, fishery field, and civil engineering and building field.

Claims (8)

(A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) A silicone compound containing a Si—H group and an aromatic group in the molecule, wherein (i) the amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g. , (Ii) the following general formula (1)

(In formula (1), each X independently represents an OH group and a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (1), n is 2). In these cases, different types of X can be taken.)
(Iii) A silicone compound (component B) having an average degree of polymerization of 3 to 150 (component B) of 0.1 to 10 parts by weight, and (C) A flame retardant aromatic polycarbonate comprising 0.01 to 5 parts by weight of a compound (component C) having a basic skeleton having a structure represented by the following general formula (2) having a number average molecular weight of 800 to 16,000 Resin composition.

(In formula (2), Y represents a divalent group derived from a dihydric phenol represented by HO—Y—OH.)   The flame retardant aromatic polycarbonate resin composition according to claim 1, wherein the component C is a polymer having a repeating unit represented by the general formula (2).   The flame retardant aromatic polycarbonate resin composition according to claim 2, wherein the component C is a polymer having a hydroxyl group and / or an epoxy group at the molecular chain terminal. The flame retardant aromatic according to any one of claims 1 to 3, wherein the component B is a silicone compound containing at least one of structural units represented by the following general formulas (3) and (4). Polycarbonate resin composition.

(In formula (3) and formula (4), 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 (5). Α ^{1 to} α ³ each independently represents 0 or 1. m ¹ represents 0 or an integer greater than or equal to ^1. Further, in Formula (3), when m ¹ is 2 or more, the repeating units are each different from each other. Can be taken as a repeating unit.)

(In formula (5), 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 an integer of 0 or 1. Further, in the formula (5), when m ² is 2 or more, the repeating unit can take a plurality of different repeating units.   The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the B component is a silicone compound comprising MD units or MDT units. (However, M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit)   The flame-retardant aromatic polycarbonate resin composition further comprises at least one compound (component D) selected from a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt with respect to 100 parts by weight of the component A. The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 5, comprising 0.001 to 0.3 parts by weight.   The molded article formed from the flame-retardant aromatic polycarbonate resin composition of any one of the said Claims 1-6.   The molded article according to claim 7, wherein the molded article has a haze measured by a method according to ISO 13468-1 in the range of 0.5 to 10.