JP2010202825A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition exhibiting transparency, and excellent in scratch resistance and flame retardancy. <P>SOLUTION: This flame-retardant polycarbonate resin composition, having transparency, and excellent in scratch resistance and flame retardancy, includes 0.05-5.0 pts.wt. of a phenyl group-containing silicone oil (component B) whose refractive index (nd) is 1.42-1.65; 0.01-30 pts.wt. of a flame retardant (component C), and 100 pts.wt. of an aromatic polycarbonate resin (component A). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a polycarbonate resin composition that is transparent and excellent in scratch resistance. Specifically, the present invention relates to a polycarbonate resin composition having excellent flame retardancy.

  Aromatic polycarbonate resins are used in a wide range of fields because they are transparent and have excellent flame retardancy, heat resistance and strength. A polymer alloy of an aromatic polycarbonate resin and a graft copolymer represented by an ABS resin has excellent moldability and is used in a wide range of applications such as office equipment, electrical and electronic equipment, and automobiles. ing.

  Among them, laser beam printers, copiers, office equipment such as notebook computers, liquid crystal televisions, and projectors, and housings for electrical and electronic equipment are further set to V-0 in the UL Standard (US Underwriters Laboratory Standard) -94. There are many demands for high flame retardancy that can be met, and a flame retardant polymer alloy in which a phosphate ester is blended with a graft copolymer represented by such an aromatic polycarbonate resin and ABS resin has been proposed. (Patent Document 1)

  On the other hand, in recent years, for OA related parts and the like, a design including a sensory part is also required. However, such a flame retardant polymer alloy has a problem that transparency is lowered although it is excellent in moldability and flame retardancy. The reduction in transparency is accompanied by the disadvantage that not only the light transmittance is lowered, but also the width of the design including coloring is reduced. In other words, it can be said that a material having transparency maintained, that is, a material having a low haze (a material having high transparency) in a molded product has a wide design range including a sensory part. Specifically, for materials with low haze, a transparent color (commonly known as a skeleton color) can be imparted using a dye-based colorant, and a pigment-based color material can be combined, or a pigment-based color material can be used alone Thus, it is possible to add a translucent color or an opaque color. Furthermore, light diffusibility can be expressed by addition of a light diffusing agent, and a desired level of light diffusibility can be imparted by controlling the amount of addition. Therefore, a decrease in transparency, that is, a decrease in light transmittance, makes it difficult to color the transparent color, and the width of the design related to the entire coloring including the sensory part and the addition of light diffusibility is reduced. It will end up. Therefore, it cannot be said that the transparency of the flame retardant polymer alloy is satisfactory. A flame retardant polymer in which an aromatic polycarbonate resin not containing a graft copolymer represented by an ABS resin and a phosphate ester are added has also been proposed. (Patent Document 2)

  However, OA related parts and the like are also required to have excellent scratch resistance from the viewpoint of enhancing durability as well as transparency. For this reason, this proposal cannot be said to be satisfactory in terms of durability, and the solution has not been clarified.

  On the other hand, as a method for imparting scratch resistance without impairing transparency, a polycarbonate resin composition containing an aromatic polycarbonate resin, a specific phenyl group-containing silicone oil, and polycaprolactone has been proposed. (Patent Document 3)

  However, it cannot be said that the flame retardancy of such a resin composition is satisfactory, and further, it cannot be said that the moldability is sufficient. Therefore, it cannot be said that the method for solving the technical problem is sufficiently disclosed.

JP-A-2-115262 Special table 2003-535173 gazette Japanese Patent No. 3474329

  In view of the above, an object of the present invention is to provide a polycarbonate resin composition having scratch resistance and flame retardancy improved to a higher level while maintaining its inherent transparency.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polycarbonate resin composition containing an aromatic polycarbonate resin, a specific silicone oil, and a flame retardant is a resin material that solves the above problems. The present invention was completed through the heading and further study.

According to the present invention, the problem is that the phenyl group-containing silicone oil (component B) 0 having a refractive index (nd) of 1.42 to 1.65 with respect to 100 parts by weight of the aromatic polycarbonate resin (component A). 0.05 to 3.0 parts by weight, preferably 0.08 to 2.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, and flame retardant (component C) 0.01 to 20 parts by weight, preferably Contains 0.03 to 15 parts by weight, more preferably 0.05 to 10 parts by weight, to provide a flame retardant polycarbonate resin composition.
The flame-retardant polycarbonate resin composition having such a configuration has characteristics not found in the prior art, which are excellent in transparency, flame retardancy, and scratch resistance.

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

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

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

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

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

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

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

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

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

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

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

  The branched polycarbonate resin can impart anti-drip performance and the like to the reinforced aromatic polycarbonate resin composition of the present invention. 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 structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is 0.1% in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 01 to 1 mol%, preferably 0.05 to 0.9 mol%, particularly preferably 0.05 to 0.8 mol%.

In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction. However, the amount of the branched structural unit is also 0.1% in a total of 100 mol% with a structural unit derived from a dihydric phenol. Those having a ratio of 001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids 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.

  Reaction methods such as interfacial polymerization, melt transesterification, carbonate prepolymer solid phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, include various documents and patent publications. This is a well-known method.

In producing the flame retardant 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 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably. a ^{1.4 × 10 4 ~3 × 10 4} , more preferably from ^{1.4 × 10 4 ~2.4 × 10 4} .

With an aromatic polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ , good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding.

The aromatic polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, an aromatic polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more suitable aspect, the A component is an aromatic polycarbonate resin (A-1-1 component) having a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ , and a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . An aromatic polycarbonate resin (A-1 component) consisting of an aromatic polycarbonate resin (A-1-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter referred to as “high” A molecular weight component-containing aromatic polycarbonate resin "may also be used).

In such a high molecular weight component-containing aromatic polycarbonate resin (A-1 component), the molecular weight of the A-1-1 component is preferably 7 × 10 ⁵ to 2 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ^5. More preferably, it is 1 × 10 ⁵ to 2 × 10 ⁵ , and particularly preferably 1 × 10 ^{5 to} 1.6 × 10 ⁵ . The molecular weight of the A-1-2 component is preferably 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 × 10 ^4. to 2.4 × 10 ^4, particularly preferably ^{1.2 × 10 4 ~2.3 × 10 4} .

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

  As the preparation method of the component A-1, (1) a method in which the components A-1-1 and A-1-2 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 the production method (production method of (2)), a separately produced A-1-1 component and / or Examples thereof include a method of mixing the A-1-2 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

  The calculation of the viscosity average molecular weight of the aromatic polycarbonate resin in the flame retardant polycarbonate resin composition of the present invention is performed as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

(B component: phenyl group-containing silicone oil)
The phenyl group-containing silicone oil of the present invention has a refractive index (nd) of 1.42 to 1.65, and the refractive index is preferably 1.43 to 1.59, more preferably 1.44 to 1.56. Preferably, 1.46 to 1.54 is most preferable. The phenyl group content is preferably 7 to 80% by weight, more preferably 30 to 70% by weight. When a phenyl group-containing silicone oil is added to a polycarbonate resin, if the refractive index (nd) is less than 1.42, the resulting composition becomes opaque and the refractive index (nd) exceeds 1.65 Again, the composition becomes opaque. Particularly preferred are phenyl group-containing silicone oils represented by the following formulas (1) to (4), and the repeating units in the structures represented by the following formulas (1), (2) and (4) may be random or block.

（式中、Ｐｈはフェニル基、ｘ、ｙはそれぞれ０≦ｘ≦１０、１≦ｙ≦１００の範囲の整数）

(Wherein Ph is a phenyl group, x and y are integers in the range of 0 ≦ x ≦ 10 and 1 ≦ y ≦ 100, respectively)

（式中、Ｐｈはフェニル基、ｍ、ｎはそれぞれ０≦ｍ≦１０、１≦ｎ≦１００の範囲の整数）

(Wherein Ph is a phenyl group, m and n are integers in the range of 0 ≦ m ≦ 10 and 1 ≦ n ≦ 100, respectively)

（式中、Ｐｈはフェニル基）

(Wherein Ph is a phenyl group)

（式中、Ｐｈはフェニル基、ｐ、ｑはそれぞれ０≦ｐ≦２５、０≦ｑ≦１００であり、７〜８０重量％のフェニル基含有量を与える値）

(Wherein Ph is a phenyl group, p and q are 0 ≦ p ≦ 25 and 0 ≦ q ≦ 100, respectively, giving a phenyl group content of 7 to 80% by weight)

  Two or more of these phenyl group-containing silicone oils may be used. Furthermore, as a typical commercial product of the phenyl group-containing silicone oil of the above formula (1), there is methylphenyl silicone oil SH-710 (refractive index 1.533) manufactured by Toray Dow Corning Silicone Co., Ltd. Available.

(C component: flame retardant)
As the flame retardant (component C) of the present invention, various compounds conventionally known as flame retardants for aromatic polycarbonate resins can be applied. More preferably, (i) an organophosphorous flame retardant (for example, a monophosphate compound, Phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (ii) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants) And (iii) a silicone flame retardant comprising a silicone compound. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

(C-1 component: organophosphorus flame retardant)
As the organophosphorus flame retardant of the present invention, a phosphate compound, particularly an aryl phosphate compound is suitable. Such a phosphate compound is effective in improving flame retardancy, and since the phosphate compound has a plasticizing effect, it is advantageous in that the molding processability of the resin composition of the present invention can be improved although the heat resistance is lowered. is there. As such phosphate compounds, various known phosphate compounds as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (I) can be mentioned.

（式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトンおよびビス（４−ヒドロキシフェニル）サルファイドからなる群より選ばれるジヒドロキシ化合物より誘導される二価フェノール残基であり、ｎは０〜５の整数、またはｎ数の異なるリン酸エステルの混合物の場合はそれらの平均値であり、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ独立したフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、およびｐ−クミルフェノールからなる群より選ばれるアリール基より誘導される一価フェノール残基である。）

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and bis (4 -Hydroxyphenyl) a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of sulfides, and n is an integer of 0 to 5, or an average value in the case of a mixture of n different phosphate esters. R ¹ , R ² , R ³ , and R ⁴ are each monovalent derived from an aryl group selected from the group consisting of independent phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. With phenolic residues is there.)

  The phosphate compound of the above formula (I) may be a mixture of compounds having different n numbers, in which case the average n number is preferably 0.5 to 1.5, more preferably 0.8. To 1.2, more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

  Preferable specific examples of the dihydric phenol for deriving X in the above formula (I) include resorcinol, bisphenol A, and dihydroxydiphenyl, and among them, resorcinol and bisphenol A are preferable.

Preferable specific examples of the monohydric phenol for deriving R ¹ , R ² , R ³ , and R ⁴ of the above formula (I) include phenol, cresol, xylenol, and 2,6-dimethylphenol. And 2,6-dimethylphenol.

  Specific examples of the phosphate compound of the above formula (I) are mainly composed of monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate ester oligomers mainly composed of bisphenol A bis (diphenyl phosphate) are preferred. Resorcinol bisdi (2,6- Xylyl) phosphate) -based phosphate oligomer, 4,4-dihydroxydiphenylbis (diphenylphosphate) -based phosphate oligomer, and bisphenol A bis (diphenyl) Phosphoric acid ester oligomer mainly containing Sufeto) are preferred.

  When using an organophosphorus flame retardant as the flame retardant, the blending amount is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the component A. Part. The effect which is anticipated by the blending of the organophosphorus flame retardant is exhibited as the preferable range is reached.

(C-2 component: organometallic salt flame retardant)
The organometallic salt flame retardant is advantageous in that the heat resistance is substantially maintained. The organometallic salt flame retardant most advantageously used in the present invention is an alkali (earth) metal sulfonate. Among them, an alkali (earth) metal salt of a fluorine-substituted organic sulfonic acid is preferable, and an alkali (earth) metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the fluorine-substituted organic sulfonate alkali (earth) metal salt is an alkali metal or alkaline earth metal, and examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of similar metals include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The organometallic salt flame retardant preferably has a fluoride ion content measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  When a fluorine-substituted organic sulfonic acid alkali (earth) metal salt is used as a flame retardant, the amount thereof is 0.01 to 1.0 part by weight, preferably 0.03 to 100 parts by weight of component A. 0.8 part by weight, more preferably 0.05 to 0.5 part by weight. The effect (for example, flame retardancy and antistatic property) expected by blending the fluorine-substituted organic sulfonate alkali (earth) metal salt is exhibited as the preferable range is reached.

  As the organic metal salt flame retardant other than the fluorine-substituted organic sulfonic acid alkali (earth) metal salt, a metal salt of an organic sulfonic acid containing no fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal salt of an alkyl sulfonate, and these can be used alone or in combination of two or more (here, alkali The (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  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.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sodium sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiof 2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4- potassium sulfonate, naphthalene sulfone Examples thereof include a formalin condensate of sodium acid and a formalin condensate of sodium anthracene sulfonate.

  Among the metal salts of organic sulfonic acids that do not contain fluorine atoms, alkali (earth) metal salts of aromatic sulfonates are preferred, and potassium salts are particularly preferred. When blending such an aromatic sulfonate alkali (earth) metal salt as a flame retardant, its content is 0.01 to 1 part by weight, preferably 0.03 to 0 parts per 100 parts by weight of component A. 0.8 parts by weight, more preferably 0.05 to 0.5 parts by weight.

(C-3 component: silicone flame retardant)
The silicone compound used as the silicone-based flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone-based flame retardant is represented by the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .

  Here, the coefficients m, n, p, and q in the above formulas 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. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue.

  When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (II) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（ＩＩ）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（ＩＩ）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (II), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (II), n is 2) In these cases, different types of X can be taken.)

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

  As the silicone compound having a Si—H group, a silicone compound containing at least one of structural units represented by the following general formulas (III) and (IV) is preferably exemplified.

（式（ＩＩＩ）および式（ＩＶ）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（Ｖ）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。ｍ１は０もしくは１以上の整数を表わす。さらに式（ＩＶ）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (III) and formula (IV), 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 (V). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and the repeating unit in the case where m1 is 2 or more in formula (IV) is a plurality of repeating units different from each other. Can take units.)

（式（Ｖ）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。ｍ２は０もしくは１以上の整数を表わす。さらに式（Ｖ）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (V), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m 2 Represents 0 or an integer greater than or equal to 1. Further, in the formula (V), when m2 is 2 or more, the repeating unit can take a plurality of different repeating units.

  Examples of the silicone compound having an alkoxy group in the silicone compound used for the silicone-based flame retardant include at least one compound selected from compounds represented by the general formula (VI) and the general formula (VII).

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

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

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

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

  When using a silicone-based flame retardant as the flame retardant, the blending amount is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 0 to 100 parts by weight of component A. .3 to 3 parts by weight.

  The flame retardant (C-1 component), (C-2 component) and (C-3 component) may be used alone or in combination of two or more. Preferably, it is a phosphorus flame retardant (C-1 component) from the viewpoints of moldability and flame retardancy.

(D component: fluorine-containing anti-drip agent)
The fluorine-containing anti-drip agent (D component) used in the present invention is a fluorine-containing compound that prevents melting and dropping during combustion and further improves flame retardancy, and is typically polytetrafluoro having fibril forming ability. Ethylene is mentioned. Hereinafter, polytetrafluoroethylene may be simply referred to as PTFE. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 from Daikin Chemical Industries, and F-201L. . Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of these mixed forms of PTFE include “METABRENE A3800” (trade name), “METABBRENE A3700” (trade name), “METABBRENE A3750” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., GE Specialty Chemicals “BLENDEX B449” (trade name) manufactured by PIC, “POLY TS AD001” (trade name) manufactured by PIC, “SN3307” manufactured by SHINE POLYMER, and the like can be mentioned.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.

(About the content of each component)
In the polycarbonate resin composition of the present invention, the content of the B component is 0.05 to 3.0 parts by weight, preferably 0.08 to 2.0 parts by weight, and more preferably 0. 1 to 1.0 part by weight. If the component B is less than 0.05 parts by weight, the resulting molded article has insufficient slidability, and if it exceeds 3.0 parts by weight, the transparency is insufficient and is inappropriate.

  Content of C component is 0.01-20 weight part with respect to 100 weight part of A component, Preferably it is 0.03-15 weight part, More preferably, it is 0.05-10 weight part. If the component C is less than 0.01 parts by weight, the flame retardancy and moldability are insufficient, and if it exceeds 20 parts by weight, the heat resistance and mechanical strength are remarkably lowered, which is inappropriate.

  The content of component D is preferably 0.03 to 1 part by weight, more preferably 0.04 to 0.5 part by weight, and still more preferably 0.05 to 0.3 part by weight with respect to 100 parts by weight of component A. It is. If the D component is less than 0.03 parts by weight, the flame retardancy is insufficient, and if it exceeds 1 part by weight, the transparency becomes insufficient, which is not preferable.

(Other additives)
In addition to the above-mentioned components A to D, various additives that are usually blended in a polycarbonate resin can be blended in the flame retardant polycarbonate resin composition of the present invention.

(I) Phosphorus stabilizer It is preferable that the flame retardant polycarbonate resin composition of the present invention is blended with a phosphorus stabilizer to the extent that does not promote hydrolyzability. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

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

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

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

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

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

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, an alkyl phosphate compound typified by trimethyl phosphate is preferably blended. A combination of such an alkyl phosphate compound and a phosphite compound and / or phosphonite compound is also a preferred embodiment.

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

  The blending amount of the phosphorus stabilizer and the hindered phenol stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, and still more preferably 100 parts by weight of component A. 0.005 to 0.3 parts by weight.

(III) Reinforcing filler Various known fillers can be blended in the polycarbonate resin composition of the present invention as a reinforcing filler. However, since the resin composition of the present invention requires transparency, a silicate mineral filler or a glass filler that does not impair the transparency is preferable as the reinforcing filler. Examples of such silicate mineral fillers include talc, mascobite mica, synthetic fluorine mica, smectite, and wollastonite. Examples of the glass filler include glass fiber, glass flake, and glass milled fiber. As the silicate mineral filler and the glass filler, fillers whose surfaces are coated with metal oxides such as titanium oxide, zinc oxide, cerium oxide, and silicon oxide can also be used.

The reinforcing filler may be previously surface treated with various surface treatment agents. Such surface treatment agents include silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydrides). Etc.) and various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.
The reinforcing filler can be blended up to 100 parts by weight based on 100 parts by weight of component A. The upper limit is preferably 25 parts by weight, more preferably 20 parts by weight.

(IV) Heat stabilizers other than those described above The flame retardant polycarbonate resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and hindered phenol stabilizers. Preferable examples of such other heat stabilizers include lactone stabilizers represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Is done. Details of such a stabilizer are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the component A.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A.

(V) Ultraviolet Absorber In the flame-retardant polycarbonate resin composition of the present invention, an ultraviolet absorber can be blended for the purpose of imparting light resistance.
Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5- Benzoyl-4-hydroxy-2-methoxy Phenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like.

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

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

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

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

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

  Among them, benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable in terms of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The blending amount of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 part by weight, most preferably 100 parts by weight of the component A. Is 0.05 to 0.5 parts by weight.

(VI) Mold Release Agent It is preferable to add a mold release agent to the polycarbonate resin composition of the present invention for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among these, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the component A. is there. In such a range, the polycarbonate resin composition has good release properties and release properties. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good release properties and roll release properties without impairing good hue.

(VII) Other components other than the above In addition to the above, the flame-retardant polycarbonate resin composition of the present invention contains few additives known per se for imparting various functions to molded products and improving properties. A proportion can be blended. These additives are used in usual amounts as long as the object of the present invention is not impaired.
Examples of such additives include sliding agents (for example, PTFE particles), colorants (for example, pigments and dyes such as carbon black and titanium oxide), light diffusing agents (for example, acrylic crosslinked particles, silicone crosslinked particles, calcium carbonate particles), fluorescence Dyes, fluorescent brighteners, light stabilizers (typified by hindered amine compounds), inorganic phosphors (for example, phosphors having aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterials Agents, photocatalytic antifouling agents (eg fine particle titanium oxide, fine particle zinc oxide), flow modifiers, radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

(Production of polycarbonate resin composition)
In producing the polycarbonate resin composition of the present invention, the production method is not particularly limited. However, in order to achieve good dispersibility of the silicone oil, a preferred method for producing the resin composition of the present invention is a method of melt-kneading each component using a multi-screw extruder such as a twin-screw extruder.

  A typical example of the twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. In addition, melt kneaders such as FCM (manufactured by Farrel, trade name), Ko-Kneader (manufactured by Buss, trade name), and DSM (manufactured by Krauss-Maffei, trade name) can be given as specific examples. Among the above, the type represented by ZSK is more preferable. In such a ZSK type twin screw extruder, the screw is a fully meshed type, and the screw includes various screw segments having different lengths and pitches, and various kneading disks having different widths (and corresponding kneading segments). It consists of

  A more preferable embodiment in the twin screw extruder is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw having a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of the screw length (L) to the diameter (D) in the twin-screw extruder is preferably 20 to 45, more preferably 28 to 42. When L / D is large, uniform dispersion is likely to be achieved, whereas when it is too large, decomposition of the resin is likely to occur due to thermal degradation. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

  Furthermore, as an extruder, what has a vent which can deaerate the water | moisture content in a raw material and the volatile gas generate | occur | produced from melt-kneading resin can be used preferably. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Furthermore, although the supply method to the extruder of B component-D component and another additive (it is only called "additive" in the following illustration) to an extruder is not specifically limited, The following method is illustrated typically. (I) A method of supplying the additive into the extruder independently of the polycarbonate resin. (Ii) A method in which the additive and the polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to the extruder. (Iii) A method of melt-kneading an additive and a polycarbonate resin in advance to form a master pellet.

  One of the methods (ii) is a method in which all necessary raw materials are premixed and supplied to the extruder. In another method, a master agent containing a high concentration of additives is prepared, and the master agent is independently or further premixed with the remaining polycarbonate resin and then supplied to the extruder. The master agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Other premixing means include, for example, a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. A high-speed stirring type mixer such as a super mixer is preferable. Yet another premixing method is, for example, a method in which a polycarbonate resin and an additive are uniformly dispersed in a solvent and then the solvent is removed.

  The resin extruded from the extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized. Furthermore, when it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

(About a molded article made of the resin composition of the present invention)
The flame-retardant polycarbonate resin composition of the present invention obtained as described above can be usually produced by injection molding the pellets produced as described above to produce various products. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.

  In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, the resin composition of this invention can also be utilized in the form of various profile extrusion-molded articles, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

  Thereby, a molded article of a polycarbonate resin composition having excellent transparency, scratch resistance and flame retardancy is provided. That is, according to the present invention, (B) a phenyl group-containing silicone oil having a refractive index (nd) of 1.42 to 1.65 (B) with respect to 100 parts by weight of (A) aromatic polycarbonate resin (component A) ( Provided is a molded article obtained by melt-molding a flame retardant polycarbonate resin composition containing B component) 0.05 to 3.0 parts by weight and (C) flame retardant (component C) 0.01 to 20 parts by weight. Is done.

  Furthermore, various surface treatments can be performed on the molded article made of the flame-retardant polycarbonate resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  The flame-retardant polycarbonate resin composition of the present invention is excellent in transparency, and further has excellent scratch resistance, and excellent flame retardancy, so that various electronic and electrical devices (particularly bezels for televisions), It is useful for various applications such as office automation equipment, vehicle parts, machine parts, other agricultural materials, transport containers, playground equipment, and miscellaneous goods, and the industrial effects that it plays are exceptional.

It is a front side perspective schematic diagram of the molded product which imitated the bezel used in the example (length 250 mm × width 300 mm × width 40 mm × edge height 10 mm, thickness 2.0 mm). It is the surface side front schematic diagram of the molded article shape | molded with the pin gate used in the Example, and shows the cut-out part of the sample for abrasion resistance and transparency measurement. It is a back surface front schematic diagram of the molded article which imitated the bezel used in the example, and shows a mode that there is a boss with a rib. (Boss shape: 6.5 mm outer diameter, 2.5 mm inner diameter, 10 mm height)

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

The following examples further illustrate the present invention. The evaluation was based on the following method.
(1) Scratch resistance: A reciprocating friction and wear tester AFT-15M manufactured by Orientec Co., Ltd. was used as an evaluation device. A test piece (material: 50% polyester, 50% nylon) having Tachijin Co., Ltd. attached to the tip of a cylinder having a diameter of 10 mmφ and a length of 30 mm was mounted on a fixed-side test piece holder.
On the other hand, after drying the obtained pellet with a hot air dryer at 100 ° C. for 6 hours, the bezel molded product (substantially uniform wall thickness) shown in FIG. 1 was obtained by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). And the average wall thickness is 2.0 mm) was molded at a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and an injection speed of 30 mm / sec. The gate of the bezel molded product was a four-point pin gate (gate diameter φ1.5 mm, cross-sectional area 1.77 mm ² ). Next, a molded plate (length 40 mm × width 50 mm) was cut out from the molded product, and the molded plate was fixed on a base that reciprocates. The tip part of the test piece was brought into contact with the flat part of the molded plate in a state where a load of 200 g was applied in a state where the cylindrical axis direction of the test piece and the plane normal direction of the molded plate were parallel. In such a contact state, the surface condition of the molded plate after the test was reciprocated 50 times a distance of 10 mm one way at a rate of 1 reciprocation 2 seconds on one straight line in an atmosphere of 23 ° C. and relative humidity 50% RH. Was visually determined from a distance of 30 cm under an artificial light source of 2,000 to 4,000 lx (based on ISO / FDIS 3668).
The evaluation was performed according to the following criteria.
○: No scratch occurred △: Scratch occurred ×: Scratch occurred (2) Transparency: The same molding plate as “(1) Scratch resistance” was used, and Murakami Color Research Laboratory's reflection / transmission was used. A haze was measured in accordance with ASTM D-1003 using a rate meter (HR-100 type).
(3) Flame retardancy: UL standard 94 vertical combustion test was performed at thicknesses of 0.8 mm and 2.4 mm, and the grade was evaluated.

[Examples 1 to 15 and Comparative Examples 1 to 8]
Various additives shown in Tables 1 and 2 were blended in various blending amounts into polycarbonate resin powder produced from bisphenol A and phosgene by an interfacial condensation polymerization method, mixed in a blender, and then vented twin screw extruder ( Nippon Steel Works Co., Ltd .: TEX30α (completely meshed, rotating in the same direction, two-thread screw) was melt kneaded to obtain pellets. The additives were preliminarily prepared with a polycarbonate resin powder in a concentration of 10 times the blending amount in advance using a Henschel mixer, and then the whole was mixed by a blender. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 260 ° C. from the first supply port to the die part.

  After drying the obtained pellets at 100 ° C. for 6 hours in a hot air circulating dryer, using an injection molding machine, the cylinder temperature was 260 ° C. and the mold temperature was 60 ° C., and the firing speed was 50 mm / sec. Molded plates for flame retardancy evaluation having a length of 125 mm, a width of 13 mm, a thickness of 0.8 mm, and 2.4 mm were formed. As an injection molding machine, SG-150U manufactured by Sumitomo Heavy Industries, Ltd. was used. Further, a molded plate was prepared by the method described in “(1) Scratch resistance” and “(2) Transparency”. Each evaluation result of the obtained molded plate is shown in Tables 1 and 2.

In addition, the content of each component indicated by symbols in Tables 1 and 2 is as follows.
(Component A)
PC-1: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation method from bisphenol A, p-tert-butylphenol as a terminal terminator, and phosgene (manufactured by Teijin Chemicals Ltd .: L-1225WS (trade name)) , Viscosity average molecular weight 20,900)
PC-2: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation from bisphenol A, p-tert-butylphenol as a terminal stopper, and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WX (product) Name), viscosity average molecular weight 19,700)
(B component)
B-1: Methylphenyl silicone oil having a refractive index (nd) of 1.533 (manufactured by Toray Dow Corning Silicone Co., Ltd., SH710)
(For comparison of B component)
B-2: Dimethyl silicone oil having a refractive index (nd) of 1.404 (manufactured by Toray Dow Corning Silicone Co., Ltd., SH200)
(C component)
C-1: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd., CR-741 (trade name))
C-2: MegaFuck F-114P (trade name) (Dainippon Ink Chemical Co., Ltd., perfluorobutanesulfonic acid potassium salt)
(D component)
D-1: Polyflon MPA FA500 (trade name) (manufactured by Daikin Industries, Ltd., polytetrafluoroethylene)
D-2: Polytetrafluoroethylene-containing mixed powder METABLEN A3750 (trade name) (manufactured by Mitsubishi Rayon Co., Ltd., the polytetrafluoroethylene-based mixture is a mixture of polytetrafluoroethylene and an acrylic copolymer ( Polytetrafluoroethylene content 50% by weight))
(Other)
SL: Riquemar SL900 (trade name) (saturated fatty acid ester release agent manufactured by Riken Vitamin Co., Ltd.)
TMP: TMP (trade name) (Phosphorus stabilizer manufactured by Daihachi Chemical Industry Co., Ltd.)

  As apparent from Tables 1 and 2, it can be seen that the flame-retardant polycarbonate resin composition of the present invention is transparent and excellent in scratch resistance, and further has excellent flame resistance.

1 Molded product body imitating bezel 2 Mirror surface 3 Gate (4 pin gates 1.5mmφ)
4 Sample cutout position for scratch resistance test 5 Ribbed boss (outer diameter 6.5 mm, inner diameter 2.5 mm, height 10 mm)

Claims (7)

  0.05 to 3.0 parts by weight of phenyl group-containing silicone oil (component B) having a refractive index (nd) of 1.42 to 1.65 with respect to 100 parts by weight of aromatic polycarbonate resin (component A), and A flame retardant polycarbonate resin composition containing 0.01 to 20 parts by weight of a flame retardant (component C). The flame retardant according to claim 1, wherein the phenyl group-containing silicone oil (component B) is one or more phenyl group-containing silicone oils selected from the group consisting of compounds represented by the following formulas [1] to [4]. Polycarbonate resin composition.

(Wherein Ph is a phenyl group, x and y are integers in the range of 0 ≦ x ≦ 10 and 1 ≦ y ≦ 100, respectively)

(Wherein Ph is a phenyl group, m and n are integers in the range of 0 ≦ m ≦ 10 and 1 ≦ n ≦ 100, respectively)

(Wherein Ph is a phenyl group)

(Wherein Ph is a phenyl group, p and q are 0 ≦ p ≦ 25 and 0 ≦ q ≦ 100, respectively, giving an integer of 7 to 80% by weight of phenyl group content)   The flame retardant (C component) was selected from the group consisting of a phosphate compound (C-1 component), an alkali (earth) sulfonate metal salt (C-2 component), and a silicone compound (C-3 component). The flame retardant polycarbonate resin composition according to claim 1, wherein the flame retardant polycarbonate resin composition is one or more flame retardants. The flame retardant polycarbonate resin composition according to claim 3, wherein the flame retardant (component C) is a phosphate compound represented by the following formula (I).

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and bis (4 -Hydroxyphenyl) a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of sulfides, n is an integer from 0 to 5, or in the case of a mixture of n different phosphate esters, R ¹ , R ² , R ³ , and R ⁴ are average values each derived from an aryl group selected from the group consisting of independent phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Residual phenol Group.)   The flame-retardant polycarbonate resin composition according to any one of claims 1 to 4, comprising 0.03 to 1 part by weight of a fluorine-containing anti-dripping agent (D component) with respect to 100 parts by weight of the A component.   The molded object shape | molded with the flame-retardant polycarbonate resin composition of any one of Claims 1-5.   The bezel for televisions formed with the flame-retardant polycarbonate resin composition of any one of Claims 1-5.

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