JP7267840B2 - Flame-retardant polycarbonate resin composition - Google Patents

Description

The present invention relates to flame-retardant polycarbonate resin compositions and molded articles thereof. More particularly, it relates to a polycarbonate resin composition with improved hydrolysis resistance, impact resistance, heat resistance and flame retardancy.

Aromatic polycarbonate resin has excellent mechanical properties and thermal properties, so by imparting flame retardancy, it is used in various applications, mainly in the fields of OA equipment, electronic and electrical equipment, etc. . In recent years, along with the reduction in thickness and weight in applications such as OA equipment and home electric appliances, there is an increasing demand for resin materials that have high impact, high flame resistance, and excellent molding appearance. In order to meet these demands, studies have been made on aromatic polycarbonate resins that meet the required safety standards of UL94 for thin flame-retardant resin materials that have high impact and excellent molding appearance.

As a method for imparting high flame retardancy to an aromatic polycarbonate resin, a combined use of a halogen-based flame retardant such as a bromine compound and a flame retardant aid such as antimony trioxide has been generally used. (See Patent Document 1) However, in recent years, due to the problem of the generation of hazardous substances during combustion, studies have been actively conducted to improve flame retardancy using organophosphorus flame retardants that do not contain bromine-containing halogen compounds. For example, many proposals have been made for compositions in which an organic phosphorus-based flame retardant and polytetrafluoroethylene having fibril-forming ability are added to an aromatic polycarbonate resin, and related findings are widely known. (See Patent Document 2) As a formulation for improving the toughness of an aromatic polycarbonate resin, a method of adding an impact modifier such as a graft polymer is known. (See Patent Document 3) In general, the addition of a flame retardant lowers the impact resistance and heat resistance, and the addition of an impact modifier lowers the flame resistance. have provided resin compositions having impact resistance and flame retardancy within a certain range. (See Patent Document 4) However, the heat resistance is still insufficient.

JP-A-2-199162 JP-A-2-115262 Japanese Patent Application Laid-Open No. 2009-203269 JP-A-2001-123056

In view of the above, an object of the present invention is to provide a polycarbonate resin composition which satisfies high levels of hydrolysis resistance, impact resistance, heat resistance and flame retardancy.

As a result of intensive studies to solve the above problems, the inventors of the present invention found that adding a phosphate ester flame retardant having a specific Bis-TMC structure to a polycarbonate resin improved hydrolysis resistance, impact resistance, The inventors have found that a polycarbonate resin composition having improved heat resistance and flame retardancy can be obtained, and have completed the present invention.

（式中、ｎは１～３０の整数である。）

（式中、ｎは１～３０の整数である。） According to the present invention, the above problem is solved by: (B) a phosphate ester-based flame retardant represented by the following formula (1) and the following formula (2) for 100 parts by weight of (A) a polycarbonate resin (component A); A flame-retardant polycarbonate resin composition characterized by containing 1 to 20 parts by weight of at least one phosphate ester flame retardant (component B) selected from the group consisting of phosphate ester flame retardants represented by achieved by

(Wherein, n is an integer from 1 to 30.)

(Wherein, n is an integer from 1 to 30.)

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 with a carbonate precursor. Examples of reaction methods 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 dihydric phenols used herein include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl ) propane (commonly known as 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-phenylenediisopropylidene)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)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. be done. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, of which bisphenol A is particularly preferred from the standpoint of impact resistance and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonates, which are general-purpose polycarbonates, special polycarbonates produced using other dihydric phenols can be used as component A.

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. Suitable for applications with particularly stringent demands on change and morphological stability. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more, of the total dihydric phenol components constituting the polycarbonate.

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

The manufacturing 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.

Among the various polycarbonates described above, those having a water absorption rate and Tg (glass transition temperature) within the following range by adjusting the copolymer composition etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage properties after molding, it is particularly suitable in fields where shape stability is required.
(i) a polycarbonate having a water absorption of 0.05-0.15%, preferably 0.06-0.13% and a Tg of 120-180°C, or (ii) a Tg of 160-250°C, A polycarbonate having a temperature of preferably 170 to 230° C. and 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 rate of polycarbonate is a value obtained by measuring the water content after immersing a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in water at 23 ° C. for 24 hours in accordance with ISO62-1980. be. Further, Tg (glass transition temperature) is a value determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

Carbonate precursors include carbonyl halides, diesters of carbonic acid and haloformates, and specific examples include phosgene, diphenyl carbonate and dihaloformates of dihydric phenols.

In producing an aromatic polycarbonate resin by interfacial polymerization of the dihydric phenol and a carbonate precursor, if necessary, a catalyst, a terminal terminator, and an antioxidant to prevent oxidation of the dihydric phenol. etc. may be used. In addition, the aromatic polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid It includes carbonate resins, copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic alcohols), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Moreover, the mixture which mixed 2 or more types of 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 trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, 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-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Structural units derived from a polyfunctional aromatic compound in the branched polycarbonate are preferably 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, still more preferably 0.05 to 0.8 mol %.

Further, particularly in the case of the melt transesterification method, a branched structural unit may occur as a side reaction. It is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, still more preferably 0.01 to 0.8 mol %. The ratio of such branched structures can be calculated by ¹ H-NMR measurement.

Aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as are preferably exemplified. Alicyclic diols are more suitable as bifunctional alcohols, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of a cyclic carbonate compound, which are methods for producing the polycarbonate resin of the present invention, can be found in various literatures and patent publications. It is a well-known method in

In producing the flame-retardant polycarbonate resin composition of the present invention, the viscosity-average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ and more. It is preferably 2.0×10 ⁴ to 3.5×10 ⁴ , more preferably 2.2×10 ⁴ to 3.0×10 ⁴ . Polycarbonate resins having a viscosity-average molecular weight of less than 1.8×10 ⁴ may not provide good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity-average molecular weight exceeding 4.0×10 ⁴ is inferior in versatility due to poor fluidity during injection molding.

The polycarbonate resin may be obtained by mixing substances having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity-average molecular weight exceeding the above range (5×10 ⁴ ) has improved entropy elasticity. As a result, good moldability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in moldability is even better than that of the branched polycarbonate. In a more preferred embodiment, component A is a polycarbonate resin having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ (component A-1-1) and an aromatic polycarbonate having a viscosity average molecular weight of 1×10 ⁴ to 3×10 ⁴ . A polycarbonate resin (component A-1) consisting of a resin (component A-1-2) and having a viscosity average molecular weight of 1.6×10 ⁴ to 3.5×10 ⁴ (hereinafter referred to as “polycarbonate resin containing a high molecular weight component ”) can also be used.

In such a polycarbonate resin containing a high molecular weight component (Component A-1), the molecular weight of Component A-1-1 is preferably 7×10 ⁴ to 2×10 ⁵ , more preferably 8×10 ⁴ to 2×10 ^{5 , and more preferably 8×10 4 to 2×10 5} . It is preferably 1×10 ⁵ to 2×10 ⁵ , particularly preferably 1×10 ⁵ to 1.6×10 ⁵ . The molecular weight of component A-1-2 is preferably 1×10 ⁴ to 2.5×10 ⁴ , more preferably 1.1×10 ⁴ to 2.4×10 ⁴ , 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 (component A-1) can be obtained by mixing the components A-1-1 and A-1-2 in various proportions and adjusting the mixture to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of A-1 component, A-1-1 component is 2 to 40% by weight, more preferably A-1-1-1 component is 3 to 30% by weight, and further The A-1-1 component is preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight.

In addition, as a method for preparing the A-1 component, (1) a method in which the A-1-1 component and the A-1-2 component are polymerized independently and then mixed, and (2) JP-A-5-306336. Using a method for producing an aromatic polycarbonate resin showing multiple polymer peaks in a molecular weight distribution chart by GPC method in the same system, represented by the method shown in JP-A-2003-120002, such an aromatic polycarbonate resin is produced by the A- of the present invention. A method of manufacturing to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a manufacturing method (manufacturing method of (2)), separately manufactured A-1-1 component and / or A method of mixing with the A-1-2 component can be mentioned.

The viscosity-average molecular weight referred to in the present invention is obtained by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20° C. to determine the specific viscosity (η _SP ) calculated by the following formula.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
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 viscosity-average molecular weight of the polycarbonate resin in the flame-retardant polycarbonate resin composition of the present invention is calculated in the following manner. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble matter in the composition. Such soluble matter is collected by celite filtration. The solvent in the resulting solution is then removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of the component soluble in methylene chloride. From a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride, the specific viscosity at 20° C. is obtained 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.

A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin (component A) of the present invention. A polycarbonate-polydiorganosiloxane copolymer resin is a copolymer prepared by copolymerizing a dihydric phenol represented by the following general formula (3) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (5). It is preferably a polymeric resin.

［上記一般式（３）において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１～１８のアルキル基、炭素原子数１～１８のアルコキシ基、炭素原子数６～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数２～１０のアルケニル基、炭素原子数６～１４のアリール基、炭素原子数６～１４のアリールオキシ基、炭素原子数７～２０のアラルキル基、炭素原子数７～２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１～４の整数であり、Ｗは単結合もしくは下記一般式（４）で表される基からなる群より選ばれる少なくとも一つの基である。］

[In the above general formula (3), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, cycloalkyl group having 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, carbon atom represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group; e and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (4). ]

［上記一般式（４）においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１～１８のアルキル基、炭素原子数６～１４のアリール基及び炭素原子数７～２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１～１８のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数６～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数２～１０のアルケニル基、炭素原子数６～１４のアリール基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキル基、炭素原子数７～２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１～１０の整数、ｈは４～７の整数である。］

[In the above general formula (4), 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, a carbon represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms; R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a halogen atom, or a an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms. an aryl group of up to 14, an aryloxy group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group represents a group selected from the group consisting of; when there are more than one, they may be the same or different; g is an integer of 1-10; h is an integer of 4-7; ]

［上記一般式（５）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１～１２のアルキル基又は炭素数６～１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０～３００の自然数である。Ｘは炭素数２～８の二価脂肪族基である。］

[In the general formula (5), 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 substituted group 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, 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 from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) represented by the general formula (3) 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-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-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'-dimethyldiphenyl 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-hydroxyphenyl)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, 1,3-bis(4-hydroxyphenyl )-5,7-dimethyladamantane and the like.

Among others, 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, 1,4-bis{ 2-(4-Hydroxyphenyl)propyl}benzene is preferred, especially 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4′- Sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used alone or in combination of two or more.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (5), for example, the following compounds are preferably used.

Hydroxyaryl-terminated polydiorganosiloxane (II) is selected from phenols having olefinically unsaturated carbon-carbon bonds, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by subjecting the end of a polysiloxane chain having a degree of polymerization to a hydrosilylation reaction. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane, (2-methoxy-4 -allylphenol) terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. The molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to achieve even better low-outgassing properties and low-temperature impact resistance during high-temperature molding. If the upper limit of the preferred range is exceeded, a large amount of outgas is generated during high-temperature molding, and the low-temperature impact resistance may be poor.

Moreover, the diorganosiloxane polymerization degree (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300 in order to achieve high impact resistance. Such a diorganosiloxane polymerization degree (p+q) is preferably 10-200, more preferably 12-150, still more preferably 14-100. Below the lower limit of the preferred range, impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited, and above the upper limit of the preferred range, poor appearance appears.

The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as component A is preferably 0.1 to 50% by weight. The content of such polydiorganosiloxane component is more preferably 0.5 to 30% by weight, more preferably 1 to 20% 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 less susceptible to molding conditions is likely to be obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

In addition, other comonomers than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) are added in an amount of 10% by weight or less based on the total weight of the copolymer, as long as they do not interfere with the present invention. They can also be used in combination.

In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) and a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution. do.

In producing the oligomer of dihydric phenol (I), the whole amount of dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at one time, or part of it may be used as a post-addition monomer to form an interface in the latter stage. It may be added as a reaction raw material to the polycondensation reaction. The post-addition monomer is added in order to facilitate the subsequent polycondensation reaction, and it is not necessary to add it unless necessary.

The system of this oligomer-forming reaction is not particularly limited, but a system in which the reaction is carried out in a solvent in the presence of an acid binder is usually preferred.

The proportion of the carbonate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be preferably employed.

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. The ratio of the acid binder to be used may also be appropriately determined in consideration of the stoichiometric ratio (equivalents) of the reaction in the same manner as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mol corresponds to 2 equivalents). .

As the solvent, solvents inert to various reactions, such as those used in the production of known polycarbonates, may be used singly or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene, and the like. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

The reaction pressure for oligomer production is not particularly limited and may be normal pressure, increased pressure 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. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. The pH range of the oligomer-forming reaction is the same as the well-known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, the mixed solution is stirred until the molecular weight distribution (Mw/Mn) is 3 or less. A highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (5) is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are interfacially polycondensed. A polycarbonate-polydiorganosiloxane copolymer is thus obtained.

（上記一般式（５）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１～１２のアルキル基又は炭素数６～１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０～３００の自然数である。Ｘは炭素数２～８の二価脂肪族基である。）

(In the above general formula (5), 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 substituted group 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, 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 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

In carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalents) of the reaction. 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. Specifically, if a portion of the hydroxyaryl-terminated polydiorganosiloxane (II) used or, as noted above, the dihydric phenol (I) is added to this reaction step as a post-add monomer, two of the post-add monomers It is preferable to use 2 equivalents or more of the alkali with respect to the total number of moles of the phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mol corresponds to 2 equivalents).

Interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.
Terminal terminator or molecular weight modifier is usually used in such polymerization reaction. Examples of terminal terminating agents include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols and aliphatic carboxylic acids. Examples include chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of all dihydric phenol compounds used, and it is of course possible to use two or more kinds of compounds together. be.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to facilitate the polycondensation reaction.
The reaction time for such a polymerization reaction is preferably 30 minutes or longer, more preferably 50 minutes or longer. If desired, a small amount of antioxidant such as sodium sulfite, hydrosulfide, etc. may be added.

A branching agent can be used in combination with the above dihydric phenolic compound to form a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucine, phloroglucide, 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, trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1 -tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. . The ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 0.9 mol %, more preferably 0.01 to 0.8 mol %, particularly preferably 0.05 to 0.4 mol %. Incidentally, such a branched structure amount can be calculated by 1H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually normal pressure or the self-pressure of the reaction system is suitable. The reaction temperature is selected from the range of −20 to 50° C. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally defined, but is usually 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin with a viscosity of [η _SP /c].

The resulting reaction product (crude product) is subjected to various post-treatments such as known separation and purification methods, and can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purity).

The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molding is preferably in the range of 1 to 60 nm. Such average size is more preferably 3 to 55 nm, still more preferably 5 to 50 nm. Below the lower limit of the preferred range, sufficient impact resistance and flame retardancy may not be exhibited, and above the upper limit of the preferred range, impact resistance may not be exhibited stably. This provides a flame-retardant polycarbonate resin composition with excellent impact resistance and appearance.

（式中、ｎは１～３０の整数である。）

（式中、ｎは１～３０の整数である。） (B component: phosphate ester flame retardant)
The flame-retardant polycarbonate resin composition of the present invention is selected from the group consisting of a phosphate flame retardant represented by the following formula (1) and a phosphate ester flame retardant represented by the following formula (2) as component B. Contains at least one selected phosphate ester flame retardant.

(Wherein, n is an integer from 1 to 30.)

(Wherein, n is an integer from 1 to 30.)

In addition to having a Bis-TMC (trimethylcyclohexylidene bisphenol) structure, such a phosphate ester flame retardant has a methyl group introduced into the terminal phenoxy group, thereby improving the hydrolysis resistance of the flame retardant polycarbonate resin composition, Decrease in impact resistance and heat resistance can be suppressed. When a phosphate ester flame retardant or a condensed phosphate ester flame retardant that does not have a Bis-TMC structure is used, the impact resistance and heat resistance are reduced due to plasticization of the polycarbonate resin. Hydrolysis resistance is lowered. When using a phosphate ester flame retardant having a Bis-TMC structure that does not have a methyl group at the terminal phenoxy group, for example, a phosphate ester flame retardant represented by the following formula (6), heat resistance decreases. occurs.

In the above formulas (1) and (2), n is an integer of 1-30, preferably in the range of 1-10. When n is 31 or more, the surface appearance of the molded article is deteriorated.
The content of component B is 1 to 20 parts by weight, preferably 2 to 17.5 parts by weight, more preferably 3 to 15 parts by weight, per 100 parts by weight of component A. If the content of Component B is less than 1 part by weight, the flame retardant effect cannot be obtained, and if it exceeds 20 parts by weight, the impact resistance and heat resistance are lowered.

(Component C: impact modifier)
The flame-retardant polycarbonate resin composition of the present invention can contain an impact modifier as the C component. The impact modifier is a graft obtained by graft-polymerizing at least one compound containing a (meth)acrylic ester compound to one rubber selected from the group consisting of butadiene rubber, acrylic rubber and silicone-acrylic composite rubber. A polymer is preferable, and a graft polymer having a core-shell structure is more preferable. The core-shell type graft polymer has a rubber component with a glass transition temperature of 10° C. or less as a core, and a (meth)acrylic acid ester compound, an aromatic alkenyl compound, and a monomer selected from a vinyl compound copolymerizable therewith. It is a graft copolymer obtained by copolymerizing one or two or more of them as a shell.

The rubber component of component C includes butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, silicone-acrylic composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, Examples include nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to the unsaturated bond portion of these rubbers. , a rubber component containing no halogen atoms is preferred from the standpoint of environmental load. The glass transition temperature of the rubber component is preferably −10° C. or lower, more preferably −30° C. or lower, and from these points, butadiene rubber and acrylic silicone/acrylic composite rubber are particularly preferred as the rubber component. A composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber obtained by polymerizing so as to form an IPN structure in which two kinds of rubber components are intertwined with each other so as not to be separated. In the core-shell type graft polymer, the particle size of the core is preferably 240 to 300 nm, more preferably 250 to 290 nm, and even more preferably 260 to 280 nm in weight average particle size. Better impact resistance is achieved in the range of 240-300 nm. In addition, the particle size distribution is preferably a bidisperse type having two peaks, and is particularly preferably a bidisperse type having two peaks near 100 nm and 300 nm, which achieves better impact resistance than the monodisperse type with a single peak. be.

Styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like can be mentioned as the aromatic vinyl in the vinyl compound to be copolymerized with the rubber component as the shell of the core-shell type graft polymer. Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate and octyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate and butyl methacrylate. , cyclohexyl methacrylate, octyl methacrylate, etc., and methyl methacrylate is particularly preferred. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component, and from the viewpoint of mechanical properties and flame retardancy, it is more preferable not to contain an aromatic vinyl component. This is because the core-shell type graft polymer has excellent affinity with the aromatic polycarbonate resin, so that more rubber components are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is enhanced. This is because it is exhibited more effectively, and as a result, the impact resistance of the resin composition is improved. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (100% by weight of the shell in the case of a core-shell type polymer), preferably 10% by weight or more, more preferably 15% by weight or more. is preferred. The elastic polymer containing a rubber component having a glass transition temperature of 10°C or less may be produced by any polymerization method of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It may be a single-stage graft or a multi-stage graft. It may also be a mixture with a copolymer containing only the graft component, which is a by-product of the production. Further, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, a two-step swelling polymerization method, and the like. In addition, in the suspension polymerization method, the aqueous phase and the monomer phase are separately held and both are accurately supplied to a continuous disperser, and the particle size is controlled by the rotation speed of the disperser. In the method, a method of supplying the monomer phase through a fine orifice or porous filter having a diameter of several to several tens of μm into an aqueous liquid having dispersing ability to control the particle size may be performed. In the case of a core-shell type graft polymer, the reaction may be one-step or multi-step for both the core and the shell.

Such polymers are commercially available and readily available. For example, the rubber component containing butadiene rubber as the main component is the METABLEN E series manufactured by Mitsubishi Chemical Corporation (for example, E-875A whose shell component is mainly methyl methacrylate, and whose shell component is mainly methyl methacrylate/styrene). component E-870A, etc.). Those containing acrylic rubber as a main component include W series manufactured by Mitsubishi Chemical Corporation (for example, W-600A in which the shell component contains methyl methacrylate as a main component). Those having a silicone-acrylic composite rubber as a main component include METABLEN S series manufactured by Mitsubishi Chemical Corporation (for example, S-2001, S-2030, etc. whose shell component is a main component of methyl methacrylate).

The content of component C is preferably 1 to 10 parts by weight, more preferably 1.5 to 9 parts by weight, still more preferably 2 to 8 parts by weight, per 100 parts by weight of component A. If the content of the C component is less than 1 part by weight, sufficient impact resistance may not be obtained, and if it exceeds 10 parts by weight, the flame retardancy and appearance of the molded product may deteriorate.

(D component: anti-drip agent)
The flame-retardant polycarbonate resin composition of the present invention can contain an anti-dripping agent as the D component. By containing this anti-drip agent, good flame retardancy can be achieved without impairing the physical properties of the molded product.

As the anti-dripping agent of component D, a fluorine-containing polymer having fibril-forming ability can be mentioned. polymers, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, and polycarbonate resins made from fluorinated diphenols. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

PTFE having fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to bond PTFE to become fibrous by an external action such as a shearing force. Its molecular weight is 1,000,000 to 10,000,000, preferably 2,000,000 to 9,000,000 in terms of number average molecular weight determined from standard specific gravity. Such PTFE can be used not only in a solid form but also in an aqueous dispersion form. In addition, PTFE having such fibril-forming ability improves its dispersibility in resin, and it is also possible to use a PTFE mixture in which it is mixed with other resins in order to obtain good flame retardancy and mechanical properties. be.

Examples of commercially available PTFE having fibril-forming ability include Teflon (registered trademark) 6J manufactured by Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L manufactured by Daikin Industries, Ltd., and the like. Commercially available PTFE aqueous dispersions include Fluon AD-1 and AD-936 manufactured by Asahi I.C. Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and DuPont Fluon by Mitsui. Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. can be mentioned as a representative.

Examples of mixed PTFE include (1) a method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer to effect coprecipitation to obtain a coaggregated mixture (JP-A-60-258263; (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 of uniformly mixing an aqueous dispersion of PTFE and a solution of organic polymer particles and simultaneously removing the respective media from the mixture (see JP-A-06-220210, JP-A-08-188653, etc.). (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583); A method of uniformly mixing an aqueous dispersion and an organic polymer dispersion, further polymerizing a vinyl-based monomer in the mixed dispersion, and then obtaining a mixture (method described in JP-A-11-29679, etc.). can be used. Examples of commercially available PTFE in mixed form include "METABLEN A3800" (trade name) manufactured by Mitsubishi Chemical Corporation and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

The ratio of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, based on 100% by weight of the PTFE mixture. Good dispersibility of PTFE can be achieved when the proportion of PTFE is in this range. The ratio of component D indicates the net amount of anti-dripping agent, and in the case of mixed PTFE, indicates the net amount of PTFE.

The content of component D is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, and still more preferably 0.2 to 1 part by weight with respect to 100 parts by weight of component A. Department. If the amount of the anti-drip agent exceeds the above range and is too small, the flame retardancy may be insufficient. On the other hand, if the amount of the anti-dripping agent exceeds the above range, the PTFE may precipitate on the surface of the molded article, resulting in a poor appearance and an increase in the cost of the resin composition.

The styrenic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and a halogen styrene optionally substituted with one or more groups selected from the group consisting of, for example, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene , methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene. The styrenic monomers may be used alone or in combination of two or more.

Acrylic monomers used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention include optionally substituted (meth)acrylate derivatives. Specifically, the acrylic monomer includes one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. optionally substituted (meth)acrylate derivatives such as (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate and glycidyl (meth)acrylate ) Maleimide optionally substituted by acrylate, an alkyl group having 1 to 6 carbon atoms, or an aryl group, such as maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid. but not limited to: The acrylic monomers may be used alone or in combination of two or more. Among these, (meth)acrylonitrile is preferred.

The amount of the acrylic monomer-derived units contained in the organic polymer used in the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, per 100 parts by weight of the styrene-based monomer-derived units. parts, more preferably 8 to 9 parts by weight. If the acrylic monomer-derived unit is less than 8 parts by weight, the coating strength may be lowered, and if it is more than 11 parts by weight, the surface appearance of the molded article may be deteriorated.

The polytetrafluoroethylene-based mixture of the present invention preferably has a residual water content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, still more preferably 0.1 to 0.4% by weight. 3% by weight. If the residual water content is more than 0.5% by weight, it may adversely affect flame retardancy.

In the process for producing the polytetrafluoroethylene-based mixture of the present invention, a coating layer containing one or more monomers selected from the group consisting of styrene-based monomers and acrylic monomers in the presence of an initiator outside the branched polytetrafluoroethylene. Further, after the step of forming the coating layer, drying is performed so that the remaining moisture content is 0.5 wt% or less, preferably 0.2 to 0.4 wt%, more preferably 0.1 to 0.3 wt%. It preferably includes steps. The drying step can be performed using methods known in the art such as, for example, hot air drying or vacuum drying methods.

The initiator used for the polytetrafluoroethylene-based mixture of the present invention can be used without limitation as long as it is used for the polymerization reaction of styrene-based and/or acrylic-based monomers. Examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. One or more of the above initiators may be used in the polytetrafluoroethylene-based mixture of the present invention, depending on the reaction conditions. The amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the type/amount of the monomer, and is 0.15 to 0.15 based on the amount of the total composition. It is preferred to use 25 parts by weight.

The polytetrafluoroethylene-based mixture of the present invention was produced by the suspension polymerization method according to the following procedure.
First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) were placed in a reactor, and then acrylic monomers and styrene were mixed with stirring. Cumene hydroperoxide was added as a monomer and a water-soluble initiator, and the reaction was carried out at 80 to 90° C. for 9 hours. After completion of the reaction, centrifugation was performed for 30 minutes in a centrifuge to remove moisture and obtain a paste-like product. After that, the product paste was dried in a hot air dryer at 80 to 100° C. for 8 hours. Thereafter, the dried product was pulverized to obtain the polytetrafluoroethylene-based mixture of the present invention.

Such a suspension polymerization method does not require a polymerization step by emulsification dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, and thus does not require an emulsifier and electrolytic salts for coagulating and precipitating latex after polymerization. In addition, in a polytetrafluoroethylene mixture produced by an emulsion polymerization method, the emulsifier and electrolyte salts in the mixture are easily mixed and difficult to remove, so sodium metal ions and potassium metal ions derived from such emulsifiers and electrolyte salts are reduced. It is difficult. Since the polytetrafluoroethylene-based mixture used in the present invention is produced by a suspension polymerization method, such emulsifiers and electrolyte salts are not used, so sodium metal ions and potassium metal ions in the mixture are reduced. can improve thermal stability and hydrolysis resistance.

Coated branched PTFE can also be used as an anti-drip agent in the present invention. The coated branched PTFE is a polytetrafluoroethylene-based mixture composed of branched polytetrafluoroethylene particles and an organic polymer. It has a coating layer made of a polymer containing units and/or acrylic monomer-derived units. The coating layer is formed on the surface of branched polytetrafluoroethylene. Also, the coating layer preferably contains a copolymer of a styrene-based monomer and an acrylic-based monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the anti-dripping effect will be insufficient when the amount of polytetrafluoroethylene added is small. The branched polytetrafluoroethylene is particulate and preferably has a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, still more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of molded articles is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. Moreover, when the particle size is larger than 0.6 μm, the surface appearance of the molded article may be deteriorated. The polytetrafluoroethylene used in the present invention preferably has a number average molecular weight of 1×10 ⁴ to 1×10 ⁷ , more preferably 2×10 ⁶ to 9×10 ⁶ . Fluoroethylene is more preferred in terms of stability. Either powder or dispersion form can be used. The content of the branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, and still more preferably 47 to 60 parts by weight with respect to 100 parts by weight of the total weight of the coated branched PTFE. 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of branched polytetrafluoroethylene is within this range, good dispersibility of branched polytetrafluoroethylene can be achieved.

(E component: silicate mineral)
The flame-retardant polycarbonate resin composition of the present invention can contain a silicate mineral as the E component. Such silicate minerals are minerals composed of at least a metal oxide component and a SiO ₂ component, and orthosilicates, disilicates, cyclic silicates, chain silicates, and the like are suitable. Silicate minerals take a crystalline state, and the crystals can take various shapes such as fibrous and plate-like.

The silicate mineral may be a composite oxide, an oxyate (consisting of an ion lattice), or a compound of a solid solution. Any combination of two or more kinds with an acid salt may be used, and the solid solution may be either a solid solution of two or more kinds of metal oxides or a solid solution of two or more kinds of oxyacid salts.

The silicate mineral may be a hydrate. The forms of water of crystallization in hydrates are those that enter as hydrogen silicate ions as Si—OH, those that ionically enter as hydroxide ions (OH ⁻ ) for metal cations, and those that enter as H ₂ O molecules in the interstices of the structure. It can be in any form of entry.

Silicate minerals can also be artificial synthetics corresponding to natural products. As artificial compounds, silicate minerals obtained by conventionally known various methods, for example, various synthesis methods using solid-state reaction, hydrothermal reaction, ultrahigh-pressure reaction, and the like, can be used.

Specific examples of silicate minerals in each metal oxide component (MO) include the following. Here, the notation in parentheses is the name of a mineral containing such a silicate mineral as a main component, and means that the compound in parentheses can be used as the exemplified metal salt.

Those containing K ₂ O as a component include K ₂ O.SiO ₂ , _{K 2} O.4SiO _{2.H 2} O, K ₂ O.Al ₂ O 3.2SiO ₂ (calcilite), K ₂ O. _Al2O3.4SiO2 (leucite ₎ , _{K2O.Al2O3.6SiO2} (orthoclase), _{and the like .}

Those containing Na ₂ O as a component include Na ₂ O.SiO ₂ and its hydrates, Na ₂ O.2SiO ₂ , 2Na ₂ O.SiO ₂ , Na ₂ O.4SiO ₂ , and Na ₂ O.3SiO. _{2.3H2O , Na2O.Al2O3.2SiO2 , Na2O.Al2O3.4SiO2 ( jadeite ) , 2Na2O.3CaO.5SiO2 , 3Na2O.2CaO.5SiO _ 2} , and _{Na2O.Al2O3.6SiO2 ( albite} ) _.

Li ₂ O.SiO ₂ , 2Li ₂ O.SiO 2 , Li ₂ O.SiO _{2 .H 2} O, _{3Li 2 O.2SiO 2} , and Li ₂ O.Al ₂ contain Li 2 O as a component. _{O3.4SiO2 (} petalite ₎ , _{Li2O.Al2O3.2SiO2 ( eucryptite} ), and _{Li2O.Al2O3.4SiO2 ( spodumene )} .

Examples of materials containing BaO include BaO.SiO ₂ , 2BaO.SiO ₂ , BaO.Al ₂ O _{3.2SiO 2} (celsian), and _BaO.TiO 2.3SiO ₂ (bentite).

Those containing CaO as a component include 3CaO·SiO ₂ (cement clinker mineral alite), 2CaO·SiO ₂ (cement clinker mineral belite), 2CaO·MgO·2SiO ₂ (okermanite), 2CaO· Al ₂ O ₃ .SiO ₂ (gehlenite), a solid solution of okermanite and gehlenite (melilite), CaO.SiO ₂ (wollastonite (including both α-type and β-type)), CaO.MgO. 2SiO ₂ (Diopside), CaO.MgO.SiO _{2 (} Olivine olivine), 3CaO.MgO.2SiO ₂ (Merwinite), CaO.Al ₂ O 3.2SiO ₂ (Anorthite), _5CaO.6SiO 2.5H Tobermorite group hydrates such as _2O ( _tobermorite , other _{5CaO.6SiO2.9H2O} , etc.), wollastonite group hydrates such as _{2CaO.SiO2.H2O} ( _{hillebrandite} ), 6CaO.6SiO xonotlite group hydrates such as ₂ ·H ₂ O (xonotlite), gyrolite group hydrates such as 2CaO·SiO ₂ ·2H ₂ O (gyrolite), CaO·Al ₂ O ₃ ·2SiO ₂ ·H ₂ O (lawsonite), CaO·FeO·2SiO ₂ (hedenkiite), 3CaO·2SiO ₂ (tilcoanite), 3CaO·Al ₂ O ₃ ·3SiO ₂ (grossura), 3CaO·Fe ₂ O ₃ ·3SiO ₂ (andradite), _{6CaO.4Al.sub.2O.sub.3.FeO.SiO.sub.2} (pleochroite), _as well _as clinozoisite, epilethite, brownite, vesuvianite, onoite, skoutite, and augite.

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

Examples of materials containing ZnO include ZnO.SiO ₂ , 2ZnO.SiO ₂ (troostite), and 4ZnO.2SiO ₂ .H ₂ O (hemimorphite).

Examples of materials containing MnO include MnO.SiO ₂ , 2MnO.SiO ₂ , CaO.4MnO.5SiO ₂ (rhodonite) and causerite.

Those containing FeO as a component include FeO.SiO ₂ (ferrosilite), 2FeO.SiO ₂ (ferroolivine), 3FeO.Al _{2 O} 3.3SiO ₂ (almandine), and 2CaO.5FeO.8SiO ₂ . H ₂ O (tetactinocenite) and the like.

Examples of materials containing CoO include CoO.SiO ₂ and 2CoO.SiO ₂ .

Those containing MgO as a _component include MgO.SiO ₂ (steatite, enstatite), 2MgO.SiO ₂ (forsterite), 3MgO.Al ₂ O 3.3SiO ₂ (byrope), and 2MgO.2Al ₂ O _{3 .} · 5SiO ₂ (cordierite), 2MgO · 3SiO ₂ · 5H ₂ O, 3MgO · 4SiO ₂ · H ₂ O (talc), 5MgO · 8SiO ₂ · 9H ₂ O (attapulgite), 4MgO · 6SiO ₂ · 7H ₂ O ( _sepiolite ), _{3MgO.2SiO2.2H2O} ( _chrysolite ) _, 5MgO.2CaO.8SiO2.H2O ( _peolite ), _{5MgO.Al2O3.3SiO2.4H2O (} chlorite _{) , K2O.6MgO.Al2O3.6SiO2.2H2O ( phlogovite )} , _{Na2O.3MgO.3Al2O3.8SiO2.H2O (} lansenite ₎ , and magnesium _tourmaline , _direct Cenite, cummintonne, vermiculite, smectite, and the like.

Examples of materials containing Fe ₂ O ₃ include Fe ₂ O ₃ ·SiO ₂ .

ZrO ₂ ·SiO ₂ (zircon) and AZS refractories are examples of materials containing ZrO ₂ .

Those containing Al ₂ O ₃ as a component include Al ₂ O ₃ .SiO ₂ (sillimanite, andalusite, kyanite), 2Al ₂ O ₃ .SiO ₂ , Al ₂ O ₃ .3SiO ₂ , 3Al ₂ O _{3 .} * _{2SiO2 (} mullite _{) , Al2O3.2SiO2.2H2O ( kaolinite ) , Al2O3.4SiO2.H2O ( pyrophyllite} ), _{Al2O3.4SiO2.H2} O (bentonite), K ₂ O.3Na ₂ O.4Al ₂ O 3.8SiO ₂ (nepheline), K ₂ O.3Al ₂ O 3.6SiO 2.2H _{2 O} (muscovite, _sericite ) _, K ₂ O.6MgO.Al ₂ O 3.6SiO _{2.2H 2} O (phlogovite), as _well as various zeolites, fluorophlogopites, and biotite.

Among the above silicate minerals, particularly preferred are mica, talc, and wollastonite.

(talc)
The talc in the present invention is a hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O, and is usually scaly particles having a layered structure, and also has a composition Specifically, it is composed of about 56 to 65% by weight of SiO ₂ , 28 to 35% by weight of MgO, and about 5% by weight of H ₂ O. Other minor components include 0.03-1.2% by weight of Fe ₂ O ₃ , 0.05-1.5% by weight of Al ₂ O ₃ , 0.05-1.2% by weight of CaO, and K ₂ O. is 0.2% by weight or less, and Na ₂ O is 0.2% by weight or less. Talc has an average particle size of 0.1 to 15 μm (more preferably 0.2 to 12 μm, still more preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm) as measured by a sedimentation method. A range is preferred. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g/cm ³ ) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method, which is one of liquid phase sedimentation methods. A specific example of an apparatus for performing such measurement is Sedigraph 5100 manufactured by Micromeritics.

In addition, there are no particular restrictions on the manufacturing method for grinding talc from raw ore, and axial flow milling, annular milling, roll milling, ball milling, jet milling, and container rotating compression shearing milling are used. can do. Furthermore, the talc after pulverization is preferably classified by various classifiers to have a uniform particle size distribution. There are no particular restrictions on classifiers, and impactor type inertial force classifiers (variable impactor, etc.), Coanda effect type inertial force classifiers (elbow jet, etc.), centrifugal field classifiers (multistage cyclone, microplex, dispersion separator) , AccuCut, Turbo Classifier, Turboplex, Micron Separator, Super Separator, etc.). Furthermore, talc is preferably in an agglomerated state from the viewpoint of ease of handling, etc. Examples of such production methods include a degassing compression method and a compression method using a sizing agent. In particular, the degassing compression method is preferable in that it is simple and does not mix unnecessary sizing agent resin components into the resin composition of the present invention.

(mica)
Mica having an average particle size of 10 to 100 μm as measured by a microtrack laser diffraction method can preferably be used. More preferably, the average particle size is 20-50 μm. If the average particle size of mica is less than 10 μm, the effect of improving rigidity is not sufficient, and if it exceeds 100 μm, the rigidity is not sufficiently improved, and mechanical strength such as impact resistance is significantly lowered. Mica having a thickness of 0.01 to 1 μm as actually measured by observation with an electron microscope can preferably be used. More preferably, the thickness is 0.03 to 0.3 μm. The aspect ratio is preferably 5-200, more preferably 10-100. The mica used is preferably muscovite mica, which has a Mohs hardness of about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogovite, and solves the problems of the present invention at a better level. Moreover, the mica may be produced by either a dry pulverization method or a wet pulverization method as the pulverization method. The dry pulverization method is cheaper and more common, while the wet pulverization method is effective in pulverizing the mica more thinly and finely, resulting in a higher effect of improving the rigidity of the resin composition.

(Wollastonite)
The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, even more preferably 0.1 to 3 μm. The aspect ratio (average fiber length/average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining the individual fiber diameter, and calculating the number average fiber diameter from the measured value. An electron microscope is used because it is difficult with an optical microscope to accurately measure the size of the level of interest. The fiber diameter is obtained by randomly extracting the filler to be measured for the fiber diameter from the image obtained by observing the electron microscope, measuring the fiber diameter near the center, and calculating the number average fiber Calculate the diameter. The magnification of observation is about 1000 times, and the number of lines to be measured is 500 or more (600 or less is suitable for work). On the other hand, to measure the average fiber length, the filler is observed with an optical microscope, the individual lengths are obtained, and the number average fiber length is calculated from the measured values. Observation with an optical microscope begins with preparing a sample in which the fillers are dispersed so that they do not overlap each other. Observation is performed under the condition of a 20-fold objective lens, and the observed image is captured as image data by a CCD camera having approximately 250,000 pixels. The obtained image data is used with an image analyzer, and a program for determining the maximum distance between two points of the image data is used to calculate the fiber length. Under these conditions, the size of one pixel corresponds to a length of 1.25 μm, and the number of lines to be measured is 500 or more (600 or less is suitable for work).

In order to fully reflect the original whiteness of the wollastonite of the present invention in the resin composition, the iron content mixed in the raw material ore and the iron content mixed in by abrasion of the equipment when pulverizing the raw material ore are removed by a magnetic separator. It is preferable to remove as much as possible by It is preferable that the content of iron in wollastonite is 0.5% by weight or less in terms of Fe ₂ O ₃ by such magnetic separation treatment.

Silicate minerals (more preferably, mica, talc, and wollastonite) are preferably not surface-treated, but may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. may be Further, it may be granulated by granulating with a sizing agent such as various resins, higher fatty acid esters, and wax.

The content of component E is preferably 0.1 to 50 parts by weight, more preferably 0.15 to 40 parts by weight, and still more preferably 0.2 to 30 parts by weight with respect to 100 parts by weight of component A. is. As component E is added, flame retardancy and rigidity are improved. However, if the amount exceeds 50 parts by weight, the impact resistance may be significantly lost and appearance defects such as silver may occur.

(Other additives)
(i) Phosphorus Stabilizer Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphines.

Specific examples of phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenyl Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 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, distearylpentaerythritol 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 pentaerythritol diphosphite, bis( nonylphenyl)pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite.

Furthermore, as other phosphite compounds, those having a cyclic structure which react with dihydric phenols can also 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 and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

Phosphate compounds 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, Diisopropyl phosphate and the like can be mentioned, and triphenyl phosphate and trimethyl phosphate are preferred.

Phosphonite compounds 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′-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3′-biphenylenediphosphonite, 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, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2, 4-di-tert-butylphenyl)-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable.

Phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like.

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

（式（７）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。） The phosphorus-based stabilizers can be used singly or in combination of two or more. Among the above phosphorus-based stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (7) are preferable.

(In formula (7), 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 or different.)

As described above, the phosphonite compound is preferably tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite, 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), both of which can be used.

Among the above formula (7), more preferred phosphite compounds are distearylpentaerythritol 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.

Distearylpentaerythritol diphosphite is commercially available as Adekastab PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and both of them can be used. Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is Adekastab 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 Chemicals), and Irgaofos 126 and 126FF (trademarks, manufactured by CIBA SPECIALTY CHEMICALS), etc. are commercially available, and any of them can be used. Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is commercially available as Adekastab PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and is readily available. Bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite is Adekastab PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , manufactured by Dover Chemical), and any of them can be used.

The above phosphorus-based stabilizers can be used alone or in combination of two or more. The content of the phosphorus stabilizer is preferably 0.01 to 1.0 parts by weight, more preferably 0.03 to 0.8 parts by weight, still more preferably 0.03 to 0.8 parts by weight, based on 100 parts by weight of component A. 05 to 0.5 parts by weight. If the content is less than 0.01 parts by weight, the effect of suppressing thermal decomposition during processing may not be exhibited, and mechanical properties may deteriorate. .

(ii) Phenolic Stabilizer The resin composition of the present invention may contain a phenolic stabilizer. Phenol-based stabilizers generally include hindered phenol, semi-hindered phenol, and less hindered phenol compounds, but hindered phenol compounds are particularly preferred from the viewpoint of providing thermal stability to polypropylene resins. used for 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 -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-thiodiethylenebis-[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5- triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4 -hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2[3(3,5- Di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, 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-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-4-hydroxyphenyl ) Propionate is preferably used, and is excellent in suppressing deterioration of mechanical properties due to thermal decomposition during processing, represented by the following formula (8) (3, 3', 3'', 5, 5', 5 ''-Hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, and 1,3,5 represented by the following formula (9) -Tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is more preferably used.

The above phenolic stabilizers may be used alone or in combination of two or more. The content of the phenolic stabilizer is preferably 0.05 to 1.0 parts by weight, more preferably 0.07 to 0.8 parts by weight, still more preferably 0.07 to 0.8 parts by weight, per 100 parts by weight of component A. 1 to 0.5 parts by weight. If the content is less than 0.05 parts by weight, the effect of suppressing thermal decomposition during processing may not be exhibited, and mechanical properties may deteriorate. .

Either one of the phosphorus-based stabilizer and the phenol-based stabilizer is preferably blended, and a combination thereof is more preferred. When used in combination, it is preferable that 0.01 to 0.5 parts by weight of a phosphorus stabilizer and 0.01 to 0.5 parts by weight of a phenolic stabilizer are blended with 100 parts by weight of component A.

(iii) Ultraviolet Absorber The flame-retardant polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Benzophenone-based UV absorbers include, 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-sulfoxytrihydrate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′,4,4′ -tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4- hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Benzotriazoles include, 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-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 vinyl monomers copolymerizable with said monomers 2-hydroxyphenyl-2H such as copolymers with and copolymers of 2-(2′-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer -A polymer having a benzotriazole skeleton is exemplified.

In the hydroxyphenyltriazine 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, etc. exemplified. Furthermore, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc., in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl A compound having a phenyl group is exemplified.

Cyclic imino esters include, for example, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-m-phenylenebis(3,1-benzoxazin-4-one) , and 2,2′-p,p′-diphenylenebis(3,1-benzoxazin-4-one).

Cyanoacrylates include, for example, 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy ]methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

Furthermore, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet-absorbing monomer and/or photostable monomer and a monomer such as alkyl (meth)acrylate It may be a polymer-type UV absorber obtained by copolymerizing with a body. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester. be.

Among the above compounds, compounds represented by any of the following formulas (10), (11) and (12) are more preferably used in the present invention.

The above UV absorbers can be used alone or in combination of two or more.
The content of the ultraviolet absorber is preferably 0.1 to 3 parts by weight, more preferably 0.12 to 2 parts by weight, and still more preferably 0.15 to 1 part by weight with respect to 100 parts by weight of component A. is. If the content of the ultraviolet absorber is less than 0.1 parts by weight, sufficient light resistance may not be exhibited, and if it is more than 3 parts by weight, it is not preferable from the viewpoint of poor appearance and deterioration of physical properties due to gas generation.

(iv) Hindered Amine Light Stabilizer The flame-retardant polycarbonate resin composition of the present invention may contain a hindered amine light stabilizer. Hindered amine light stabilizers are generally called HALS (Hindered Amine Light Stabilizer) and are compounds having a 2,2,6,6-tetramethylpiperidine skeleton in their structure, such as 4-acetoxy-2,2,6 ,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2, 2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis(2,2,6,6-tetra methyl-4-piperidyl)oxalate, bis(2,2,6,6-tetramethyl-4-piperidyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2, 2,6,6-tetramethyl-4-piperidyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate, bis(1,2,2,6,6-pentamethyl-4- piperidyl) carbonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)oxalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)malonate, bis(1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4- piperidyl) terephthalate, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis(2,2,6,6-tetra methyl-4-piperidyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis(2,2,6,6-tetramethyl- 4-piperidyl tolylene-2,4-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6 -tetramethyl-4-piperidyl)-benzene-1,3,5-tricarboxylate, N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N- Methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine - N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl) Polycondensate of butylamine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6- tetramethyl-4-piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}], tetrakis(2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tris(2,2 ,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, 1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl oxy}butyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine, and 1,2,3,4- Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro (5,5) undecane] condensates with diethanol, and the like.

Hindered amine light stabilizers are broadly classified into NH type (hydrogen is bonded to the nitrogen atom), NR type (an alkyl group (R) is bonded to the nitrogen atom), There are three types of N-OR type (an alkoxy group (OR) is bonded to the nitrogen atom), but when applied to a polycarbonate resin, from the viewpoint of the basicity of the hindered amine light stabilizer, the low basicity NR It is more preferable to use the N-OR type.

Among the above compounds, compounds represented by the following formulas (13) and (14) are more preferably used in the present invention.

A hindered amine light stabilizer can be used individually or in combination of 2 or more types. The content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, and still more preferably 0.08 to 0.7 part by weight, relative to 100 parts by weight of component A. parts by weight, particularly preferably 0.1 to 0.5 parts by weight. If the content of the hindered amine light stabilizer is more than 1 part by weight, it is not preferable because the appearance may be deteriorated due to gas generation and the physical properties may be deteriorated due to decomposition of the polycarbonate resin. Moreover, if it is less than 0.05 parts by weight, sufficient light resistance may not be exhibited.

(v) Release Agent It is preferable to further add a release agent to the flame-retardant polycarbonate resin composition of the present invention for the purpose of improving productivity during molding and reducing distortion of molded articles. Known release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc., those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds ( fluorine oil represented by polyfluoroalkyl ether), paraffin wax, and beeswax. Fatty acid esters are particularly preferred release agents. Such fatty acid esters are esters of fatty alcohols and fatty carboxylic acids. Such fatty alcohols may be monohydric alcohols or polyhydric alcohols having a valence of 2 or more. The number of carbon atoms in the alcohol is in the range of 3-32, more preferably in the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol-hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid ester of the present invention.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, more preferably 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, 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 cetoleic acid can be mentioned. . Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

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

The fatty acid ester of the present invention may be either a partial ester or a full ester. However, since partial esters usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures, full esters are more preferable. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4-20, still more preferably in the range of 4-12, from the viewpoint of thermal stability. Incidentally, the acid value can be substantially zero. Further, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Furthermore, the iodine value is preferably 10 or less. Incidentally, the iodine value can be substantially zero. These properties can be obtained by the method specified 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 component A. is. Within this range, the flame-retardant polycarbonate resin composition has good release properties and roll release properties. In particular, such an amount of fatty acid ester provides a flame-retardant polycarbonate resin composition having good releasability and roll release property without impairing good hue.

(vi) Dyes and Pigments The flame-retardant polycarbonate resin composition of the present invention further contains various dyes and pigments to provide molded articles exhibiting various designs. By blending a fluorescent brightening agent or other fluorescent dye that emits light, it is possible to impart a better design effect by making use of the luminescent color. It is also possible to provide a flame-retardant polycarbonate resin composition that is colored with a very small amount of dye and pigment and has vivid color development.

Examples of fluorescent dyes (including fluorescent brighteners) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, and xanthene-based fluorescent dyes. , xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and are less likely to deteriorate during molding of polycarbonate resin, are preferred.

Dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, and quinacridones. dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, various plate-like fillers having a metal film or a metal oxide film are suitable.
The content of the dye or pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, per 100 parts by weight of component A.

(vii) Other Heat Stabilizers The flame-retardant polycarbonate resin composition of the present invention may also contain heat stabilizers other than the phosphorus-based stabilizer and phenol-based stabilizer described above. Such other heat stabilizers are preferably used in combination with either of these stabilizers and antioxidants, and particularly preferably in combination with both. Such other heat stabilizers include, for example, lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers is described in JP-A-7-233160). Such a compound is available commercially as Irganox HP-136 (trademark, CIBA SPECIALTY CHEMICALS). Further, stabilizers obtained by mixing said compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. Such premixed stabilizers may also be utilized in the present invention. The 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, per 100 parts by weight of component A.

Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. exemplified. Such stabilizers are particularly effective when the resin composition is applied to rotomolding. The amount of the sulfur-containing stabilizer to be blended 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.

(viii) Filler In the flame-retardant polycarbonate resin composition of the present invention, various fillers other than silicate minerals as component E can be blended as reinforcing fillers to the extent that the effects of the present invention are exhibited. . For example, calcium carbonate, glass fiber, glass beads, glass balloon, glass milled fiber, glass flakes, carbon fiber, carbon flakes, carbon beads, carbon milled fiber, graphite, vapor growth ultrafine carbon fiber (fiber diameter is 0.1 μm) less than), carbon nanotubes (fiber diameter is less than 0.1 μm, hollow), fullerenes, metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, metal oxide particles, Examples include metal oxide fibers, metal oxide balloons, and various whiskers (potassium titanate whiskers, aluminum borate whiskers, basic magnesium sulfate, etc.). These reinforcing fillers may be contained singly or in combination of two or more.
The content of these fillers is preferably 0.1 to 60 parts by weight, more preferably 0.5 to 50 parts by weight, per 100 parts by weight of component A.

(ix) Other Resins and Elastomers In the resin composition of the present invention, other resins and elastomers may be used in small proportions within the range where the effects of the present invention are exhibited.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. , phenolic resins, and epoxy resins.
Examples of elastomers include isobutylene/isoprene rubber, ethylene/propylene rubber, acrylic elastomers, polyester elastomers, and polyamide elastomers.

(x) Other additives In addition, the flame-retardant polycarbonate resin composition of the present invention may be blended with a small proportion of additives known per se in order to impart various functions to molded articles and improve their properties. can be done. These additives are added in normal amounts as long as they do not impair the object of the present invention.
Such additives include sliding agents (e.g. PTFE particles), coloring agents (e.g. carbon black, pigments such as titanium oxide, dyes), light diffusing agents (e.g. acrylic crosslinked particles, silicone crosslinked particles, ultra-thin glass flakes, carbonic acid calcium particles), fluorescent dyes, inorganic phosphors (e.g. phosphors with aluminate as the mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g. fine particles of titanium oxide , fine particles of zinc oxide), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

Since the flame-retardant polycarbonate resin composition of the present invention is excellent in hydrolysis resistance, impact resistance, heat resistance and flame retardancy, it is widely useful in the field of OA equipment, electronic and electrical equipment, and other various fields. is. Therefore, the industrial effects of the present invention are extremely large.

The mode for carrying out the present invention summarizes the preferable range of each of the above requirements, and for example, the representative examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described with reference to the following examples. In addition, unless otherwise specified, parts in the examples are parts by weight, and %s are % by weight. In addition, evaluation was implemented by the following method.
(Evaluation of polycarbonate resin composition)
(i) Molded product appearance A molded plate (length 90 mm × width 50 mm) with a thickness of 2 mm and an arithmetic average roughness (Ra) of 0.03 µm was molded at a cylinder temperature of 250 ° C., a mold temperature of 60 ° C., and an injection speed of 30 mm / s. and the presence or absence of silver streaks was observed. For the evaluation, the 11th shot from immediately after the purge was discarded, and the molded product up to the 20th shot was used for silver streak evaluation. In addition, the case where the silver streak was not confirmed was indicated by "◯", and the case where the silver streak was confirmed was indicated by "x".
(ii) Hydrolysis resistance An ISO bending test piece obtained by the following method was subjected to a pressure cooker test under conditions of 120°C x 100% RH x 48 hours using a highly accelerated life tester. The viscosity-average molecular weight was measured before and after the treatment. When the molecular weight after the treatment was 60% or more of the molecular weight before the treatment, it was indicated as "O", and when it was less than 60%, it was indicated as "X".
(iii) Charpy impact strength Notched Charpy impact strength was measured according to ISO 179 using an ISO bending test piece obtained by the following method.
(iv) Deflection temperature under load An ISO bending test piece obtained by the following method was used to measure the deflection temperature under load at 1.80 MPa according to ISO 75-1 and ISO 75-2.
(v) Flame Retardancy A V test was carried out according to UL94 using a UL test piece obtained by the following method. "not V" indicates the case where the judgment could not satisfy any of the criteria of V-0, V-1 and V-2.

[Examples 1 to 24, Comparative Examples 1 to 6]
A mixture was fed through the first feed port of the extruder with the composition shown in Tables 1 and 2. Such a mixture was obtained by mixing the following pre-mixture of (i) with the other ingredients in a V-blender. That is, (i) a mixture of an anti-dripping agent as component D and a polycarbonate resin as component A, which is uniformly mixed by shaking the entire bag in a polyethylene bag so that component D is 2.5% by weight of the mixture. It is a mixed mixture. The supply amount of the mixture was precisely measured by a meter [CWF manufactured by Kubota Corporation]. Extrusion is carried out using a vented twin-screw extruder (Japan Steel Works, Ltd. TEX30α-38.5BW-3V) with a diameter of 30 mmφ, a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa. A pellet was obtained. The extrusion temperature was 260° C. from the first supply port to the die. Some of the obtained pellets were dried at 90 to 100°C for 6 hours in a hot air circulating dryer, and then subjected to an ISO bending test piece at a cylinder temperature of 250°C and a mold temperature of 70°C using an injection molding machine. (ISO 179, ISO 75-1 and ISO 75-2) and UL specimens were molded.

In addition, each component of symbol notation in Table 1 and Table 2 is as follows.
(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Limited)
A-2: Aromatic polycarbonate resin (Polycarbonate resin powder with a viscosity average molecular weight of 23,900 made from bisphenol A and phosgene by a conventional method, Panlite L-1250WP (product name) manufactured by Teijin Limited)

（式中、ｎは１～３０の整数である。）
Ｂ－２：下記式（２）で表されるリン酸エステル系難燃剤

（式中、ｎは１～３０の整数である。）
Ｂ－３：下記式（６）で表されるリン酸エステル系難燃剤

（式中、ｎは１～３０の整数である。）
Ｂ－４：レゾルシノールビス（ジ－２，６－キシリルホスフェート）を主成分とするリン酸エステル（大八化学工業（株）製：ＰＸ２００（商品名）） (B component)
B-1: Phosphate ester flame retardant represented by the following formula (1)

(Wherein, n is an integer from 1 to 30.)
B-2: Phosphate ester flame retardant represented by the following formula (2)

(Wherein, n is an integer from 1 to 30.)
B-3: Phosphate ester flame retardant represented by the following formula (6)

(Wherein, n is an integer from 1 to 30.)
B-4: Phosphate ester containing resorcinol bis(di-2,6-xylyl phosphate) as a main component (manufactured by Daihachi Chemical Industry Co., Ltd.: PX200 (trade name))

(C component)
C-1: Silicone-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is 70 wt% of silicone-acrylic composite rubber as the main component and the shell is 30 wt% of methyl methacrylate as the main component, Mitsubishi Chemical ( Co., Ltd. METABLEN S-2001 (product name))
C-2: Butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is 70 wt% with butadiene rubber as the main component and the shell is 30 wt% with methyl methacrylate and styrene as the main components, Kaneka Corporation Made by Kaneace M-701 (product name))
C-3: Butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is 60 wt% with butadiene rubber as the main component and the shell is 40 wt% with methyl methacrylate as the main component, Kaneace manufactured by Kaneka Co., Ltd. M-711 (product name))
C-4: Acrylic core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is composed mainly of butadiene-acrylic composite rubber and butyl acrylate at 60 wt% and the shell is composed mainly of methyl methacrylate at 40 wt%, METABLEN W-600A (product name) manufactured by Mitsubishi Chemical Corporation)

(D component)
D-1: PTFE (Polyflon MPA FA500H (trade name) manufactured by Daikin Industries, Ltd.)
D-2: Coated PTFE (polytetrafluoroethylene (polytetrafluoroethylene content: 50% by weight) coated with a styrene-acrylonitrile copolymer, SN3307 (trade name) manufactured by Shine Polymer)
D-3: Coated PTFE (polytetrafluoroethylene coated with a copolymer of methyl methacrylate and butyl acrylate (polytetrafluoroethylene content: 50% by weight), manufactured by Mitsubishi Chemical Corporation, Metabrene A3750 (trade name))
D-4: Covered branched PTFE (branched polytetrafluoroethylene (polytetrafluoroethylene content: 50% by weight) coated with a styrene-acrylonitrile copolymer, SN3300B7 (trade name) manufactured by Shine Polymer)

(E component)
E: Talc (manufactured by Hayashi Kasei Co., Ltd.; HST 0.8 (trade name), average particle size 3.5 μm)

(other ingredients)
STB-1: Phenolic heat stabilizer (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531, BASF Japan Co., Ltd. Irganox 1076 (product name))
STB-2: Phosphorus-based heat stabilizer (tris (2,4-di-tert-butylphenyl) phosphite, Irgafos 168 (product name) manufactured by BASF Japan Ltd.)
WAX-1: Fatty acid ester release agent (Rikemal SL900 (product name) manufactured by Riken Vitamin Co., Ltd.)
WAX-2: Olefin-based wax obtained by copolymerization of α-olefin and maleic anhydride (manufactured by Mitsubishi Chemical Corporation; Diacarna 30M (trade name))

Claims (4)

(A) Per 100 parts by weight of polycarbonate resin (component A), (B) a phosphate ester flame retardant represented by the following formula (1) and a phosphate ester flame retardant represented by the following formula (2) 1 to 20 parts by weight of at least one phosphate flame retardant (component B) and (E) silicate mineral (component E) 0.1 to 50 parts by weight selected from the group consisting of A flame-retardant polycarbonate resin composition.

(Wherein, n is an integer from 1 to 30.)

(Wherein, n is an integer from 1 to 30.) It is characterized by containing 1 to 10 parts by weight of (C) an impact modifier (component C) and 0.05 to 2 parts by weight of (D) an anti-drip agent (component D) with respect to 100 parts by weight of component A. The flame-retardant polycarbonate resin composition according to claim 1. Graft copolymerization in which at least one compound containing a (meth)acrylic acid ester compound is graft-polymerized to one rubber selected from the group consisting of butadiene-based rubbers, acrylic rubbers, and silicone-acrylic composite rubbers. 3. The flame-retardant polycarbonate resin composition according to claim 2, which is a coalescence. A molded article comprising the flame-retardant polycarbonate resin composition according to any one of claims 1 to 3 .