JP2015034191A - Transparent flame retardant thermoplastic resin composition and molded part thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent flame retardant thermoplastic resin composition satisfying fluidity, impact resistance and fire retardancy at high dimension while maintaining its high transparency, and a molded part thereof.SOLUTION: Provided is a transparent flame retardant thermoplastic resin composition comprising (C) phosphazene (C component) of 0.5 to 17 pts.wt. to 100 pts.wt. of a resin component made of (A) a polycarbonate resin (A component) of 0 to 50 pts.wt. and (B) a polycarbonate-polydiorganosiloxane copolymer resin (B component) of 100 to 50 pts.wt. and also comprising no drip prevention agent.

Description

  The present invention relates to a transparent flame retardant thermoplastic resin composition that satisfies a high level of fluidity, impact resistance, and flame retardancy while maintaining high transparency, and a molded article thereof. More specifically, by using phosphazene as a flame retardant for polycarbonate-based resins including polycarbonate-polydiorganosiloxane copolymer resins, high transparency is maintained without adding a drip inhibitor. The present invention relates to a transparent flame-retardant thermoplastic resin composition that can simultaneously achieve high impact properties, high fluidity, and high flame retardance, which have been difficult to achieve, and molded articles thereof.

  Aromatic polycarbonate resins are excellent in mechanical properties, dimensional accuracy, electrical properties, thermal properties, and the like, and are widely used as engineer plastics in various fields such as electrical, electronic equipment, automobile, and OA fields. Among these applications, there is a strong demand for flame retardant resin materials used, mainly for applications such as office automation equipment and home appliances. In order to meet these demands, consideration is given to making flame retardant aromatic polycarbonate resins. There have been many.

Conventionally, many flame retardant polycarbonate resin compositions to which halogen-based flame retardants, phosphorus-based flame retardants, metal salt-based flame retardants, silicone-based flame retardants and the like are added in order to impart flame retardancy to aromatic polycarbonate resins have been proposed. ing.
Halogen flame retardants containing halogen elements such as bromine and chlorine have an excellent flame retardant effect. However, it can be thermally decomposed during the molding process to generate hydrogen halide, which can cause mold corrosion and decrease the thermal stability of the resin composition. Another problem is that harmful substances are generated during combustion. Therefore, from the viewpoint of safety, impact on the environment during disposal and incineration, a flame retardant method using a flame retardant containing no halogen is required from the market.

  As non-halogen flame retardants, phosphoric flame retardants such as phosphate ester compounds, metal salt flame retardants, silicone flame retardants and the like are generally used. Phosphate ester compounds are widely used because they have a relatively good flame retardant effect and at the same time have an excellent plasticizing effect. However, in order to obtain a high flame retardant effect, it is necessary to add a large amount of a flame retardant, and there is a problem that the heat resistance of the composition is lowered or the impact strength is lowered. In addition, when flame retarded using red phosphorus, a high flame retardant effect can be obtained by adding a small amount, but there are problems such as coloring of the composition and generation of odor during molding.

  In addition, metal salt flame retardants and silicone flame retardants are used as flame retardants for polycarbonate resins. (Refer to Patent Document 3) However, the flame retardant formulation by adding a metal salt can obtain a high flame retardant effect by adding a small amount, but the reduction of the thermal stability of the resin by an alkali metal salt or the like, and There are problems such as white turbidity, and a plasticizing effect like a phosphorus flame retardant cannot be obtained. In addition, a resin composition to which a silicone compound is added has also been proposed. (Refer to patent documents 4 and 5) However, the flame retardant performance as obtained with the above-mentioned conventional flame retardant is not greatly improved, and even when a high concentration is added, the mechanical properties, moldability, The appearance may be adversely affected, which is not practical.

  In addition to this, as a technique for obtaining a high level of flame retardancy, there is a suppression of a resin dripping phenomenon in a combustion test. As a method therefor, there are a method using a resin having a branch unit as a base resin, and a method of adding polytetrafluoroethylene having a fibril-forming ability (hereinafter sometimes abbreviated as fibrillated PTFE) as a drip inhibitor. (See Patent Documents 6, 7, and 8). Among them, the method using an aromatic polycarbonate resin having a branch unit as the base resin is preferable in terms of excellent transparency, and although a drip improvement effect is recognized, it is sufficiently satisfactory in terms of both a drip prevention effect and fluidity. In addition, there is a problem that the impact resistance, which is a characteristic of the polycarbonate resin, is significantly reduced. The method of adding fibrillated PTFE is easy to obtain a drip-preventing effect, and since there is little decrease in fluidity due to the addition of fibrillated PTFE, a material that requires high flame resistance (V-0, V-1 according to UL standards). This is a method that has been widely applied to materials having (1). However, there is a problem that the transparency characteristic of the polycarbonate resin is impaired.

  A flame retardant resin composition in which a polycarbonate-polydiorganosiloxane copolymer-containing resin is used as a polycarbonate resin and fibrillated PTFE is blended is also known (Patent Document 9). Advanced flame retardant composition that achieves V-0 by UL standard because the oxygen index is improved by using polycarbonate-polydiorganosiloxane copolymer as a base resin, and the effect of preventing melt dripping by the addition of fibrillated PTFE. A thing is obtained. However, there is a problem that transparency is lowered.

In addition to this, as an example of applying a polycarbonate-polydiorganosiloxane copolymer-containing resin, there is an example in which a metal salt flame retardant is added, but a certain level of transparency and flame retardancy can be obtained. Since the processability is inferior, it is not suitable for a thin-walled molded product, and the molded product becomes cloudy depending on molding conditions.
As described above, at present, a transparent flame retardant material satisfying fluidity, impact resistance, and flame retardancy at a high level while maintaining high transparency has not been obtained.

  In contrast, phosphazene compounds provide the resin composition with excellent flame retardancy and high plasticizing effect, which are characteristic of phosphorus flame retardants, and mechanically compared to phosphate ester compounds and red phosphorus. It is suitable for obtaining a resin composition that satisfies high fluidity, impact resistance and flame retardancy at the same time because it is relatively difficult to lower the properties and thermal properties.

  Examples of the resin composition flame-retarded using a phosphazene compound include a method of blending a specific amount of a phosphazene compound with a polycarbonate resin (see Patent Documents 10 and 11), a phosphazene compound with an aromatic polycarbonate resin having a branch unit, and the like. (See Patent Document 12), flame retardant resin composition in which a phosphazene compound and a fluorine resin are blended in a polycarbonate resin composition (see Patent Documents 13 and 14), a phosphazene compound having a specific structure in a polycarbonate resin, A flame retardant polycarbonate resin composition containing a polytetrafluoroethylene resin, an impact resistance improver, and an ultraviolet absorber (see Patent Document 15) is disclosed. Resin compositions containing these phosphazene compounds exhibit excellent flame retardancy and heat resistance, but since they contain an anti-drip agent, high transparency cannot be maintained, and polycarbonate-polydiorganosiloxane co-polymers cannot be maintained. Since no polymer-containing resin is used, flame retardancy, impact resistance, and fluidity are not satisfied at a high level.

  Also disclosed is a resin composition that exhibits transparency and flame retardancy while maintaining high impact by blending a metal salt flame retardant with a polycarbonate-polyorganosiloxane copolymer-containing resin. However, since the phosphazene compound is not blended, the fluidity is greatly inferior, and the flame retardancy, impact resistance, and fluidity are not satisfied at a high level (see Patent Document 16).

Japanese Examined Patent Publication No. 47-44537 Japanese Examined Patent Publication No. 62-25706 Japanese Patent Publication No. 60-38418 Japanese Examined Patent Publication No. 62-60421 JP-A-5-86295 JP-A-11-323118 Japanese Patent No. 3129374 JP 2008-297424 A JP-A-8-81620 JP 51-37149 A JP2012-3144A JP 2012-1580 A JP 7-292233 A JP2013-1801A JP 2000-351893 A JP 2011-236287 A

  In view of the above, an object of the present invention is to provide a transparent flame-retardant thermoplastic resin composition that satisfies a high level of fluidity, impact resistance, and flame retardancy while maintaining a high degree of transparency, and a molded product thereof. There is to do.

  As a result of intensive studies to solve the above problems, the present inventor uses phosphazene as a flame retardant for a polycarbonate-based resin containing a polycarbonate-polydiorganosiloxane copolymer resin, so that no anti-drip agent is added. The inventors have found that high impact, high fluidity, and high flame retardance, which have been difficult to achieve so far, can be achieved at the same time while maintaining a high degree of transparency, and the present invention has been completed.

  According to the present invention, the above-mentioned problem is a resin component comprising (A) 0 to 50 parts by weight of a polycarbonate-based resin (component A) and (B) 100 to 50 parts by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component B). It is achieved by a transparent flame-retardant thermoplastic resin composition characterized by containing 0.5 to 17 parts by weight of (C) phosphazene (C component) and 100 parts by weight of an anti-drip agent. The Details of the present invention will be described below.

(A component: polycarbonate resin)
The polycarbonate resin used 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 method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

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

Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate 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 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-hydroxyphenyl) 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 preferably 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 0.01-1 mol%, More preferably, it is 0.05-0.9 mol%, More preferably, it is 0.05-0.8 mol%.

In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably 100% by mole in total with the structural unit derived from dihydric phenol. The content is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and still more preferably 0.01 to 0.8 mol%. 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 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.

Reaction formats 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-based resin of the present invention, are various documents and patent publications. This is a well-known method.
In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate-based resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10. ^{4 to} 3 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 2.4 × 10 ⁴ .
With a 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.

In addition, the said polycarbonate-type resin may be obtained by mixing that whose viscosity average molecular weight is outside the said range. In particular, a 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 resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more preferable aspect, the A component has a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ polycarbonate resin A-1-1-1 component), and the viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . Polycarbonate resin (A-1-1 component) consisting of an aromatic polycarbonate resin (A-1-1-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ , Sometimes referred to as “high molecular weight component-containing polycarbonate resin”).

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

  The high molecular weight component-containing polycarbonate resin (A-1-1 component) is a mixture of the A-1-1-1 component and the A-1-1-2 component in various proportions so as to satisfy a predetermined molecular weight range. It can be obtained by adjusting. Preferably, in 100% by weight of the A-1-1 component, the A-1-1-1 component is 2 to 40% by weight, and more preferably, the A-1-1-1 component is 3 to 30% by weight. More preferably, the A-1-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

  Moreover, as a preparation method of A-1-1 component, (1) The method of superposing | polymerizing each A-1-1-1 component and A-1-1-2 component independently, and mixing these, (2 ) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method disclosed in Japanese Patent Application Laid-Open No. 5-306336 in the same system. And (3) an aromatic polycarbonate resin obtained by the production method (production method (2)) and A separately produced A. Examples thereof include a method of mixing the 1-1-1 component and / or the A-1-1-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved 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

  In addition, calculation of the viscosity average molecular weight of polycarbonate-type resin in the transparent flame-retardant resin composition of this invention is performed in the following way. 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: Polycarbonate-polydiorganosiloxane copolymer resin)
The polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). A copolymer resin prepared by copolymerization is preferred.

[In General Formula (1), R ¹ and R ² are each independently a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a cyclohexane having 6 to 20 carbon atoms. Alkyl group, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 3 to 14 carbon atoms, aryloxy group having 3 to 14 carbon atoms, 7 to 7 carbon atoms Represents a group selected from the group consisting of 20 aralkyl groups, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are plural groups, they may be the same or different. Well, e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). ]

[In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and It represents a group selected from the group consisting of carboxyl groups, and when there are a plurality thereof, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

[In General Formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number of 10-60. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

  Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2, -Bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2- Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4 ′ -Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldi Enyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro Xylphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1, 3-adamantanediyl) diphenol and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane.

Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis ( - hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.
As the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3), for example, the following compounds are preferably used.

  The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of. Of these, (2-allylphenol) -terminated polydiorganosiloxane, (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-) are particularly preferred. 4-Allylphenol) -terminated polydimethylsiloxane is preferred.

  The diorganosiloxane polymerization degree (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is a natural number of 10-60. If it exceeds 60, the incorporation of polydiorganosiloxane units in the polycarbonate becomes uneven and the proportion of polydiorganosiloxane units in the polymer molecule increases, resulting in a polycarbonate containing the unit and a polycarbonate not containing it. It becomes easy and mutual compatibility falls easily. As a result, the dispersion of the polydiorganosiloxane domain becomes non-uniform, the transparency is lost, the appearance defect is liable to occur, and sufficient flame retardancy cannot be obtained. The degree of diorganosiloxane polymerization (p + q) is preferably 12 to 58, more preferably 15 to 55, and still more preferably 20 to 50. Below the lower limit of this range, sufficient flame retardancy cannot be obtained, the polydiorganosiloxane domain diameter is small, and sufficient impact resistance is not exhibited. In the present invention, the polydiorganosiloxane domain means a domain mainly composed of polydiorganosiloxane dispersed in a polycarbonate matrix and may contain other components. As described above, the polydiorganosiloxane domain is not necessarily composed of a single component because the structure is formed by phase separation from the polycarbonate polycarbonate.

The polydiorganosiloxane content in the total weight of the copolymer resin is preferably 0.5 to 30% by weight. The polydiorganosiloxane component content is more preferably 0.7 to 20% by weight, still more preferably 1 to 10% by weight. Above the lower limit of the preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of the preferred range, a stable appearance that is hardly affected by the molding conditions is easily obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

  In this invention, hydroxyaryl terminal polydiorganosiloxane (II) may use only 1 type, and may use 2 or more types. Further, within the range not hindering the production method of the present invention, other comonomer other than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) is 10% by weight or less based on the total weight of the copolymer. It can also be used in combination in the range.

  In the present invention, a chloroformate-forming compound such as divalent phenol (I) and phosgene or chloroformate of divalent phenol (I) in a mixed solution of an organic solvent insoluble in water and an aqueous alkaline solution in advance. To prepare a mixed solution of a chloroformate compound containing a chloroformate of dihydric phenol (I) and / or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group. As the chloroformate-forming compound, phosgene is preferred.

In producing the chloroformate compound from the dihydric phenol (I), the whole amount of the dihydric phenol (I) used in the production method of the present invention may be converted to the chloroformate compound at one time, or a part thereof may be used. A post-added monomer may be added as a reaction raw material to a subsequent interfacial polycondensation reaction. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.
The method for this chloroformate compound formation reaction is not particularly limited, but usually a method of carrying out in a solvent in the presence of an acid binder is preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them.

The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using the phosgene which is a suitable chloroformate formation compound, the method of blowing gasified phosgene into a reaction system can be employ | adopted suitably.
Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Is used.
The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, 2 equivalents or slightly more than 2 equivalents per mole of dihydric phenol (I) used for forming the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents). It is preferable to use an acid binder.

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

  The molar ratio of the organic solvent insoluble in water is preferably 8 moles or more, more preferably 10 moles or more, still more preferably 12 moles or more, particularly preferably 14 moles or more, per mole of dihydric phenol (I). The upper limit is not particularly limited, but 50 mol or less is sufficient from the viewpoint of the size and cost of the apparatus. By setting the molar ratio of the organic solvent to the dihydric phenol (I) within such a range, it becomes easier to control the average size and normalized dispersion of the polydiorganosiloxane domain to appropriate values.

The pressure in the formation reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, heat is generated with the reaction, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.
As the pH range in the formation reaction of the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

  In the present invention, after preparing a mixed solution of the chloroformate of the dihydric phenol (I) and the chloroformate compound containing the carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group in this way, While stirring the mixed solution, the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the formula (4) is added in an amount of 0.01 mol per 1 mol of the dihydric phenol (I) charged in preparing the mixed solution. The polycarbonate-polydiorganosiloxane copolymer resin is obtained by adding the hydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound by interfacial polycondensation.

[In General Formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number of 10-60. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

  The polycarbonate-polydiorganosiloxane copolymer resin of the present invention can be made into a branched polycarbonate copolymer by using a branching agent in combination with the above dihydric phenol compound. 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-hydroxyphenyl) 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 polycarbonate copolymer is produced by a branching agent used in the interfacial polycondensation reaction after completion of the production reaction, even if the branched solution is contained in the mixed solution during the production reaction of the chloroformate compound. May be added. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol% in the total amount of carbonate constituent units constituting the copolymer. Especially preferably, it is 0.05-1.0 mol%. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

  The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but can usually be suitably performed at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.

In some cases, the obtained polycarbonate copolymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η _SP / C] can also be obtained as a polycarbonate copolymer.
The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) after various post-treatments such as a known separation and purification method.

The viscosity-average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably in the range of 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . The viscosity average molecular weight is more preferably 1.0 × 10 ^{4 to} 4.0 × 10 ⁴ , further preferably 1.5 × 10 ^{4 to} 3.5 × 10 ⁴ , and particularly preferably 1.7 × 10 ⁴ to 2. .5 × 10 ⁴ . When the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is less than 5.0 × 10 ³ , practical mechanical strength is difficult to obtain in many fields, and when it exceeds 5.0 × 10 ⁴ , the melt viscosity is It is high and generally requires a high molding temperature, so it tends to cause problems such as thermal degradation of the resin.
The content of the polycarbonate-polydiorganosiloxane copolymer resin is 100 to 50 parts by weight, preferably 95 to 55 parts by weight, more preferably 90 to 60 parts by weight, in 100 parts by weight of the resin component. When the content is less than 50 parts by weight, flame retardancy and impact resistance are not sufficiently exhibited.

  The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. The average size is more preferably 2 to 30 nm, still more preferably 5 to 25 nm. If it is less than the lower limit of such a suitable range, the impact resistance and flame retardancy are not sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, the impact resistance may not be stably exhibited. As a result, a polycarbonate resin composition excellent in both impact resistance and flame retardancy is provided.

  Furthermore, even if the average size of the polydiorganosiloxane domain is in a suitable range, if its normalized dispersion exceeds 40%, good and stable transparency may not be exhibited. The normalized dispersion of the polydiorganosiloxane domain size is preferably 40% or less, more preferably 30% or less, still more preferably 25% or less, and most preferably 20% or less. The lower limit of such normalized dispersion is practically preferably 7% or more, more preferably 10% or more. Providing a polycarbonate-polydiorganosiloxane copolymer-containing resin excellent in both transparency, impact resistance, and flame retardancy, and its molded article, by having such an appropriate average domain size and its normalized dispersion Is done.

  The average domain size and the normalized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded product in the present invention were evaluated by a small angle X-ray scattering method (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region within a scattering angle (2θ) <10 °. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in the substance, the X-ray diffuse scattering is measured by the difference in electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which a polydiorganosiloxane domain is dispersed in a polycarbonate polymer matrix, X-ray diffuse scattering occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there is a particle size, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, can be accurately, simply, and reproducibly reproduced. Can be measured. The average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of the particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size with the average domain size, and is represented by the following formula (1).

In the above formula (1), σ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.
The terms “average domain size” and “normalized dispersion” used in connection with the present invention are the measurement of the 1.0 mm thickness of the three-stage plate produced by the method described in the Examples by the small angle X-ray scattering method. The measured values obtained by In addition, the analysis was performed using an isolated particle model that does not take into account the interparticle interaction (interparticle interference).

The content of the polydiorganosiloxane derived from the polycarbonate-polydiorganosiloxane copolymer resin in the resin composition of the present invention is preferably 0.5 to 8.4% by weight. More preferably, it is 0.8-7.0 weight%, More preferably, it is 1.0-6.0 weight%, Most preferably, it is 1.2-5.5 weight%. When the amount is less than 0.5% by weight, sufficient impact resistance and flame retardancy are not exhibited. When the amount exceeds 8.4% by weight, flame retardancy may not be exhibited. The polydiorganosiloxane content in the composition was calculated from the PDMS amount contained in the polycarbonate-polydiorganosiloxane copolymer resin (PC-PDMS copolymer resin) by the following formula.
PDMS amount in composition (% by weight) = {(PDMS amount in PC-PDMS copolymer resin) / (weight of entire composition)} × 100

(C component: Phosphazene)
The phosphazene used in the present invention can impart flame retardancy to the resin composition by containing a phosphorus atom and a nitrogen atom in the molecule. The phosphazene is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure in the molecule. Here, the phosphazene structure represents a structure represented by the formula: -P (R2) = N- [wherein R2 is an organic group]. The phosphazene compound is represented by general formulas (5) and (6).

(Wherein X ₁ , X ₂ , X ₃ and X ₄ represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom. N represents an integer of 3 to 10).
In the above formulas (5) and (6), examples of the organic group not containing a halogen atom represented by X ₁ , X ₂ , X ₃ , or X ₄ include an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned.
Among these, cyclic phenoxyphosphazene represented by the general formula (7) is preferable.

〔式中ｍは３〜２５の整数を示す。Ｐｈはフェニル基を示す。〕

[Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. ]

Commercially available phosphazene compounds include SPS-100, SPR-100, SA-100, SPB-100, SPB-100L (above, manufactured by Otsuka Chemical Co., Ltd.), FP-100, FP-110 (above, Fushimi Pharmaceutical). Manufactured).
The content of phosphazene is 0.5 to 17 parts by weight, preferably 0.8 to 15 parts by weight, more preferably 1 to 13 parts by weight, based on 100 parts by weight of the total of component A and component B. is there. When the content is less than 0.5 parts by weight, flame retardancy is not manifested, and when it exceeds 17 parts by weight, dripping is generated at the time of combustion due to a decrease in the viscosity of the resin composition, and flame retardancy is reduced. , Since the impact resistance is greatly reduced by the plasticizing effect, it is not preferable.

  The resin composition of the present invention does not contain an anti-drip agent. When the anti-drip agent is contained, the transparency is lowered and the effect of the present invention cannot be obtained. Further, when a flame retardant other than phosphazene is used as the C component, the desired flame retardancy cannot be obtained because the anti-drip agent is not contained. The anti-drip agent is a compound that prevents drip during combustion, and examples thereof include a fluorine-containing polymer having a fibril forming ability.

(Other additives)
(I) Phosphorus stabilizer Examples of the phosphorous stabilizer 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, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl 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, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  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- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl 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, phosphonite compounds or phosphite compounds represented by the following general formula (8) are preferable.

（式（８）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (8), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same as or different from each other.)

As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.
Among the above formulas (8), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-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) Ru-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 Bis- [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) isocyanate 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-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2- 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [ Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy- Examples include 5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  Either of the phosphorus stabilizer and the hindered phenol antioxidant is preferably blended, and the combination of these is more preferred. The blending amount of the phosphorus stabilizer and the hindered phenol antioxidant is preferably 0.001 to 3 parts by weight, more preferably 0.005 to 2 parts per 100 parts by weight of the total of component A and component B, respectively. Part by weight, more preferably 0.01 to 1 part by weight. In the case of combined use, 0.01 to 0.3 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.3 parts by weight of a hindered phenol-based antioxidant with respect to a total of 100 parts by weight of the component A and the component B Is more preferably blended.

(Iii) Release agent It is preferable to mix | blend a release agent with the transparent flame-retardant polycarbonate resin composition of this invention further for the purpose of the productivity improvement at the time of the shaping | molding, and the reduction of the distortion of a molded article. 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 the above, 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 100 parts by weight of the total of the component A and the component B. -0.5 parts by weight. In such a range, the resin composition has good release properties and roll release properties. In particular, such an amount of fatty acid ester provides a resin composition having good release properties and roll release properties without impairing good hue.

(Iv) Ultraviolet Absorber The resin composition of the present invention can contain an ultraviolet absorber. Since the resin composition of the present invention is excellent in transparency, it is very suitable for use in transmitting light.
In the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2-hydroxy Examples include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

  In the benzotriazole series, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 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-chlorobenzotriazole, 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-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomer copolymerizable with the monomer And 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, 2-hydroxyphenyl-2H-benzotriazole skeleton A polymer having

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-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 Illustrated. 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.

In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) -4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), and the like.
In the case of cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-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) acrylate. The

Of these, benzotriazoles and hydroxyphenyltriazines are preferred in terms of ultraviolet absorption, and cyclic iminoesters and cyanoacrylates are preferred in terms of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and still more preferably 0.03 based on a total of 100 parts by weight of the component A and the component B. To 1 part by weight, more preferably 0.05 to 0.5 part by weight.

(V) Dye / pigment The resin composition of the present invention can further contain various dyes / pigments and can provide molded products that exhibit various design properties. Since the resin composition of the present invention is excellent in transparency, it is very suitable for use in transmitting light. Therefore, for example, by adding a fluorescent brightening agent, the resin composition of the present invention is given higher light transmittance and natural transparency, and a fluorescent brightening agent or other fluorescent dye that emits light is added. By doing so, the further better design effect which utilized the luminescent color can be provided. In addition, a resin composition which is finely colored with a very small amount of dye and pigment and has high transparency can also be provided.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight and more preferably 0.00005 to 0.5 part by weight with respect to 100 parts by weight of the total of the A component and the B component.

(Vi) Other Heat Stabilizers The resin composition of the present invention may contain other heat stabilizers other than the above phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail 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. In the present invention, such a premixed stabilizer can also be used. 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. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. 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, based on 100 parts by weight of the total of the component A and the component B. is there.

(Vii) Other additives In addition, the resin composition of the present invention may contain a small amount of additives known per se for imparting various functions to the molded article and improving the properties. These additives are used in usual amounts as long as the object of the present invention is not impaired.
Such additives include fluorescent dyes, inorganic phosphors (for example, phosphors having aluminate as a base crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, and photocatalytic antifouling agents (for example, fine particles). (Titanium oxide, fine particle zinc oxide), radical generator, infrared absorber (heat ray absorber), photochromic agent, and the like. In addition to the C component phosphazene, other flame retardants may be used in combination as long as the purpose of this patent is not impaired.

(Manufacture of resin composition)
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, the A component to the C component and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, and then extruded granulated as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of a method of premixing a part of each component include a method of premixing components other than the components A and B in advance, and then mixing them with the thermoplastic resins of components A and B or supplying them directly to an extruder.

  As a premixing method, for example, when A and B components having powder form are included, a part of the powder and an additive to be blended are mixed to prepare a master batch of the additive diluted with powder. And a method using such a master batch. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

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

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. 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.

(Manufacture of decorative molded bodies)
The resin composition of the present invention can produce a molded product with more excellent design by decorative molding. In such injection molding, film insert decorative molding can be mainly used, but not only ordinary film insert decorative molding, but also injection compression molding, injection press molding, gas assist injection molding, foam molding (injecting supercritical fluid) Can be combined with other molding techniques such as ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Although it does not specifically limit as a decorating film, The thing by which a decorating layer, an adhesive layer, etc. are laminated | stacked sequentially on a base film is used preferably. In addition, as a decorative film, there is a so-called “insert film” that does not peel off the base film after the molding resin adheres to the decorative film, and a transfer layer in which only the base film is peeled off after the molded product adheres to the decorative film. There is a so-called “transfer film” that leaves only the resin in the molded product. Examples of the base film include polyethylene terephthalate, polyethylene naphthalate, polypropylene and acrylic, and polyethylene terephthalate is preferable. The decorative layer is a layer that imparts functionality such as decorativeness and electromagnetic shielding to the surface of the molded product. The decorative layer can be formed of a resin binder and a pigment or dye. The decorative layer may use a resin binder and a concealing metal pigment or inorganic pigment. The decorative layer may be a metal vapor-deposited layer in order to give a metallic luster. The adhesive layer is a layer for bonding the decorative layer and the molded product. The decorative layer and the adhesive layer are formed by various printing methods such as silk printing and gravure printing.

The decorative film is placed in the mold cavity after the long decorative film is wound into a roll and fed into the mold, and the decorative film is processed and trimmed in the mold. Alternatively, it may be sent out of the mold and wound into a roll again. Alternatively, a sheet decoration film may be placed. Alternatively, the cut end portion coming out from the feed roll obtained by winding the long decorative film into a roll shape is gripped by the pinch means and dragged into the mold, and is held by the fixing member on the downstream side of the mold. The decorative film may be cut at the upstream side of the mold.
The decorative film is decorated at the same time as the injection molding by injecting the resin composition of the present invention into the cavity that is clamped by adhering the decorative film to the movable or fixed cavity inner surface by vacuum suction. I can.

(About molded products)
Various types of surface treatment can be performed on the molded article of the present invention. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.
Moreover, in order to give the external appearance of the molded product of the present invention, various insert moldings are possible, and examples include film insert molding and in-mold molding.

  Specific examples of the molded product in which the resin composition of the present invention is used are suitable for application to internal parts and housings of OA equipment and home appliances. These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs (registered trademark) / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, etc. The resin product formed from the transparent flame-retardant thermoplastic resin composition of the present invention can be used for various parts such as the casing. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

  The transparent flame-retardant thermoplastic resin composition of the present invention and its molded article simultaneously achieve high impact, high fluidity and high flame retardance that have been difficult to achieve while maintaining high transparency. Therefore, it is widely useful in OA applications, electrical and electronic applications, and other various fields. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the invention that the present inventor considers to be the best is an aggregation 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. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. Evaluation was carried out by the following method.

(Evaluation of thermoplastic resin composition)
(I) Amount of polydiorganosiloxane (PDMS) in composition The amount of PDMS in the composition was calculated from the amount of PDMS contained in the added polycarbonate-polydiorganosiloxane copolymer resin (PC-PDMS copolymer resin).
(PDMS amount in the composition) = {(PDMS amount in the PC-PDMS copolymer resin) × 100} / (weight of the entire composition)
(Ii) Flame retardance Using a test piece prepared by the following method, a V combustion test was performed in thicknesses of 2.0 mm and 3.0 mm in accordance with UL94 standards. In addition, it is preferable that a flame retardance rank passes ((circle)) to V-0 or V-1 class. When it became V-2 or notV, it was set as the rejection (x).
(Iii) Charpy impact strength According to ISO 179, the Charpy impact strength with a notch was measured (test condition 23 ° C.) using a test piece prepared by the following method.
(Iv) Transparency Haze was measured according to JIS K7105 using a test piece (2 mm thick flat plate) prepared by the following method. Those having a haze of 2% or less were rated as ◯, and those having a haze greater than 2% were evaluated as x.
(V) Fluidity An Archimedean spiral flow length having a channel thickness of 2 mm and a channel width of 8 mm was measured with an injection molding machine [SG150U manufactured by Sumitomo Heavy Industries, Ltd.]. The measurement was performed at a cylinder temperature of 260 ° C., a mold temperature of 70 ° C., and an injection pressure of 98 MPa.

[Examples 1-12, Comparative Examples 1-8]
The mixture which has a composition shown to Table 1 and Table 2 and has AC component as a main component was supplied from the 1st supply port of the extruder. Extrusion is performed using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ and melt kneading at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vacuum degree of the vent of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 260 degreeC from the 1st supply port to the die part.
A part of the obtained pellets was dried in a hot air circulation dryer at 100 ° C. for 6 hours, and then a test piece for evaluation (UL94, conforming to ISO179, 2 mm thick lithographic plate) was molded using an injection molding machine. .

The respective components indicated by symbols in Table 1 and Table 2 are as follows.
(A component)
PC: aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 19,800 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX manufactured by Teijin Ltd.)
(B component)
PC-PDMS-1: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 37)
PC-PDMS-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 2.1%, PDMS polymerization degree 37)
PC-PDMS-3: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 8.4%, PDMS polymerization degree 37)
PC-PDMS-4: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 12.6%, PDMS polymerization degree 37)
PC-PDMS-5: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 0.8%, PDMS polymerization degree 37)
(C component)
C-1: Cyclic phenoxyphosphazene (Fushimi Pharmaceutical Co., Ltd .: FP-110 (trade name))
C-2: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
C-3: Perfluorobutanesulfonic acid potassium salt (Dainippon Ink Chemical Co., Ltd. MegaFuck F-114P (trade name))
C-4: An organosiloxane flame retardant containing Si-H group, methyl group and phenyl group (X-40-2600J (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.)
(Other ingredients)
IRGX-1: Phenol-based thermal stabilizer (Ciba Specialty Chemicals KK; IRGANOX 1076 (trade name))
IRGX-2: Phosphite-based thermal stabilizer (Ciba Specialty Chemicals KK; IRGAFOS168 (trade name))
VPG861: Pentaerythritol release agent (manufactured by Cognis Japan KK; Roxyol VPG861 (trade name))
PTFE-1: Polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., Polyflon MP FA500B (trade name))
PTFE-2: SN3307 (manufactured by Shin polymer, the polytetrafluoroethylene-based mixture is a mixture of polytetrafluoroethylene particles and styrene-acrylonitrile copolymer particles produced by suspension polymerization (containing polytetrafluoroethylene) 50 weight%) SN3307 (trade name))

  From the above table, by using phosphazene as a flame retardant for the polycarbonate resin containing the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, it is possible to maintain this high transparency without adding a drip inhibitor. It can be seen that high impact, high fluidity, and high flame retardance, which were difficult to achieve by the same time, can be achieved simultaneously.

Claims (10)

  (C) with respect to 100 parts by weight of a resin component comprising (A) 0 to 50 parts by weight of a polycarbonate-based resin (component A) and (B) 100 to 50 parts by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component B). A transparent flame-retardant thermoplastic resin composition containing 0.5 to 17 parts by weight of phosphazene (component C) and containing no anti-drip agent. The transparent flame-retardant thermoplastic resin composition according to claim 1, wherein the component C is a cyclic phenoxyphosphazene represented by the following formula (7).

[Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. ]   The transparent flame-retardant thermoplastic resin composition according to claim 1 or 2, wherein the content of diorganosiloxane derived from component B in the composition is 0.5 to 8.4% by weight.   Haze is 2.0 or less, The transparent flame-retardant thermoplastic resin composition in any one of Claims 1-3 characterized by the above-mentioned. The UL94 test achieves V-0 at a thickness of 3.0 mm, and the Charpy impact strength (with notch) in ISO 179 standard is 15 kJ / m ² or more. Transparent flame retardant thermoplastic resin composition. The UL94 test achieves V-0 at a thickness of 2.0 mm, and has Charpy impact strength (notched) in ISO 179 standard of 15 kJ / m ² or more. Transparent flame retardant thermoplastic resin composition.   The molded object which consists of a resin composition in any one of Claims 1-6.   A transparent flame retardant sheet comprising the resin composition according to claim 1.   The decorative molded body which consists of a resin composition in any one of Claims 1-6.   A tablet decorative casing, a mobile phone decorative casing, or a notebook decorative casing made of the resin composition according to claim 1.