JP7267839B2 - 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 flame-retardant polycarbonate resin composition that satisfies impact resistance, flame retardancy and chemical resistance at a high level.

Aromatic polycarbonate resins are widely used industrially due to their excellent mechanical properties and thermal properties. However, since the aromatic polycarbonate resin has a high melt viscosity, it has the drawback of poor flowability and poor moldability. In order to improve the fluidity of aromatic polycarbonate resins, many polymer alloys with other thermoplastic resins have also been developed. Among them, polymer alloys with styrene-based resins represented by ABS resins are widely used in the fields of OA equipment, electrical and electronic equipment, automobiles, and the like. In particular, there is a demand for flame retardancy in applications such as electrical and electronic equipment, and various flame-retardant resin compositions have been proposed.

However, in recent years, there have been demands for chemical resistance and long-term durability for products that are used outdoors or near outdoor locations. Resin materials containing

So far, methods using polycarbonate resin, acrylic rubber-reinforced styrene resin, and halogen-based flame retardant have been disclosed (Patent Documents 1 to 5), and directions for improving impact strength, flame retardancy, light resistance, etc. have been indicated. However, the current situation is that there are no reports of application examples for improving chemical resistance.

JP-A-8-165415 JP-A-3-259946 JP-A-63-81152 JP-A-60-13844 Japanese Patent Publication No. 61-34469

In view of the above, an object of the present invention is to provide a flame-retardant polycarbonate resin composition that satisfies high levels of impact resistance, flame retardancy and chemical resistance.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found a copolymer containing a polycarbonate resin, an aromatic alkenyl compound monomer unit and a vinyl cyanide compound monomer unit, and not containing polyorganosiloxane. , a graft copolymer obtained by graft-polymerizing an aromatic alkenyl compound monomer unit and a vinyl cyanide compound monomer unit to a composite rubber composed of polyorganosiloxane and an alkyl (meth)acrylate, and a halogen-based flame retardant. , an antimony compound, and an anti-drip agent satisfies a high level of impact resistance, flame retardancy, and chemical resistance, leading to the completion of the present invention.

According to the present invention, the above problem is solved by: (A) a polycarbonate-based resin (component A) and (B) an aromatic alkenyl compound monomer unit and a vinyl cyanide compound monomer unit, but no polyorganosiloxane. For a total of 100 parts by weight of the copolymer (component B), (C) a composite rubber composed of polyorganosiloxane and alkyl (meth)acrylate is added with an aromatic alkenyl compound monomer unit and a vinyl cyanide compound unit. 5 to 25 parts by weight of a graft copolymer obtained by graft polymerization of monomer units (Component C), (D) 5 to 30 parts by weight of a halogen flame retardant (Component D), (E) an antimony compound (Component E) 0. 5 to 3 parts by weight and (F) an anti-drip agent (component F) of 0.05 to 2 parts by weight.

The details of the present invention will be described below.

(A component: polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of 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 the methods for producing the polycarbonate-based resin of the present invention, can be found in various literatures and patent publications. This is a well-known method such as

In producing the flame-retardant polycarbonate resin composition of the present invention, the viscosity-average molecular weight (M) of the polycarbonate-based resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ , More preferably 2.0×10 ⁴ to 3.5×10 ⁴ , still 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-based 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-based resin may be obtained by mixing resins having a viscosity-average molecular weight outside the above range. In particular, a polycarbonate-based resin having a viscosity-average molecular weight exceeding the above range (5×10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas-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 (component A-1-1) having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ and an aromatic resin having a viscosity average molecular weight of 1×10 ⁴ to 3×10 ⁴ Polycarbonate resin (A-1 component) ⁽ hereinafter ^referred to as “high molecular weight component containing may be referred to as "polycarbonate-based resin") can also be used.

In such a high-molecular-weight component-containing polycarbonate resin (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 , More preferably 1×10 ⁵ to 2×10 ⁵ , particularly preferably 1×10 ⁵ to 1.6×10 ⁵ . The molecular weight of component A-1-1-2 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 . 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. can. Preferably, in 100% by weight of A-1 component, A-1-1 component is 2 to 40% by weight, more preferably A-1-1 component is 3 to 30% by weight, still more preferably The content of component A-1-1 is 4 to 20% by weight, and the content of component A-1-1 is 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-based 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-based 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 (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). It is preferably a polymeric resin.

［上記一般式（１）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（２）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 (1), 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 (2). ]

［上記一般式（２）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 (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, 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（３）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 (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a 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 (1) include 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1 -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropyl phenyl)propane, 2,2-bis(3-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 (3), 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 (3) 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（３）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 (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a 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. ]

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 %. The amount of such branched structures can be calculated by ¹ H-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 40 nm. Such average size is more preferably 1 to 30 nm, more preferably 5 to 25 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.

The average domain size of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded article in the present invention was evaluated by small angle X-ray scattering (SAXS). The small-angle X-ray scattering method is a method of measuring diffuse scattering/diffraction occurring in a small-angle region within a scattering angle (2θ)<10°. In this small-angle X-ray scattering method, if there are regions with different electron densities on the order of 1 to 100 nm in a substance, diffuse scattering of X-rays is measured from the difference in electron densities. Based on this scattering angle and scattering intensity, the particle diameter of the object to be measured is determined. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the electron density difference between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in the range of less than 10° scattering angle (2θ) is measured to measure the small-angle X-ray scattering profile, and the polydiorganosiloxane domain is a spherical domain and the particle size distribution varies. Assuming the existence of , the average size of the polydiorganosiloxane domains is obtained by performing a simulation using commercially available analysis software from the hypothetical particle size and hypothetical particle size distribution model. According to the small-angle X-ray scattering method, the average size of the polydiorganosiloxane domains dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, easily, and with good reproducibility. can. Average domain size means the number average of individual domain sizes.

The term "average domain size" used in connection with the present invention is a measured value obtained by measuring a 1.0 mm thick portion of a three-tiered plate produced by the method described in Examples by such a small-angle X-ray scattering method. show. In addition, the analysis was performed using an isolated particle model that does not consider the interaction between particles (interference between particles).

(Component B: Copolymer containing aromatic alkenyl compound monomer units and vinyl cyanide compound monomer units and not containing polyorganosiloxane)
The resin composition of the present invention contains, as the component B, a copolymer containing aromatic alkenyl compound monomer units and vinyl cyanide compound monomer units and not containing polyorganosiloxane. Such copolymers are copolymers composed of aromatic alkenyl compound monomer units and vinyl cyanide compound monomer units, and other monomer units copolymerizable with these monomer units. It is a polymer composed of one or more selected from vinyl monomers and rubbery polymers. Examples of compounds from which aromatic alkenyl compound monomer units are derived include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Moreover, acrylonitrile, methacrylonitrile, etc. can be mentioned as a compound which derives a vinyl cyanide compound monomer unit. Among these, styrene is preferably used as the compound from which the aromatic alkenyl compound monomer unit is derived, and acrylonitrile is preferably used as the compound from which the vinyl cyanide compound monomer unit is derived. In addition, as compounds that induce other vinyl compound monomer units, epoxy group-containing methacrylic acid esters such as (meth)acrylic acid esters and glycidyl methacrylate, maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide α,β-unsaturated carboxylic acids such as , acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid and their anhydrides, and methyl methacrylate is preferably used. Examples of the rubber-like polymer copolymerizable with the aromatic alkenyl compound monomer units include polybutadiene, polyisoprene, diene-based copolymers (e.g., random copolymers and block copolymers of styrene/butadiene, acrylonitrile/ Butadiene copolymers, (meth)acrylic acid alkyl esters and butadiene copolymers, etc.), copolymers of ethylene and α-olefins (e.g., ethylene/propylene random copolymers and block copolymers, ethylene/ Butene random copolymers and block copolymers, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (e.g., ethylene methacrylate copolymers, ethylene butyl acrylate copolymers, etc.), ethylene and aliphatic Copolymers with vinyl (e.g., ethylene/vinyl acetate copolymers), ethylene/propylene and non-conjugated diene terpolymers (e.g., ethylene/propylene/hexadiene copolymers), acrylic rubbers (e.g., polybutyl acrylates, poly(2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate). Specific examples of the copolymer include AS resin, ABS resin, MABS resin, AES resin, ASA resin, MAS resin and the like. Here, AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber and styrene, ASA resin is a copolymer resin mainly composed of acrylonitrile, styrene and acrylic rubber, MABS resin is methyl methacrylate, acrylonitrile, butadiene, and copolymer resin mainly composed of styrene, and MAS resin are copolymer resins mainly composed of methyl methacrylate, acrylic rubber, and styrene. Among these, AS resins, AES resins, ASA resins, etc. that do not contain a butadiene component are preferred, and it is also possible to use a mixture of two or more of these polymers. The ratio of the aromatic alkenyl compound monomer unit to the vinyl cyanide compound monomer unit in component B is 50 to 90% by weight of the aromatic alkenyl compound monomer unit to the vinyl cyanide compound monomer unit. It is preferably 10 to 50% by weight (provided that the sum of the aromatic alkenyl compound monomer unit and the vinyl cyanide compound monomer unit is 100% by weight).

The content of component B is preferably 20 to 60 parts by weight, more preferably 35 to 55 parts by weight, and 40 to 50 parts by weight in a total of 100 parts by weight of components A and B. is more preferred. If the content of component B is less than 20 parts by weight, chemical resistance may not be exhibited, and if it exceeds 60 parts by weight, impact resistance and flame retardancy may be greatly reduced.

(Component C: Graft copolymer obtained by graft-polymerizing aromatic alkenyl compound monomer units and vinyl cyanide compound monomer units to composite rubber composed of polyorganosiloxane and alkyl (meth)acrylate)
The resin composition of the present invention comprises a composite rubber composed of polyorganosiloxane and alkyl (meth)acrylate as component C, and aromatic alkenyl compound monomer units and vinyl cyanide compound monomer units graft-polymerized. containing a graft copolymer. Among graft copolymers, a graft copolymer having a core-shell structure is more preferable as an impact modifier. The core-shell type graft copolymer is copolymerized with a composite rubber composed of polyorganosiloxane and alkyl (meth)acrylate as a core, and an aromatic alkenyl compound monomer unit and a vinyl cyanide compound monomer unit as a shell. It is a graft copolymer. 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 copolymer, the particle size of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and still more preferably 0.15 to 0.5 μm in weight average particle size. . Better impact resistance is achieved in the range of 0.05-0.8 μm.

Examples of the aromatic alkenyl compound monomer unit to be copolymerized with the rubber component as the shell of the core-shell type graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of vinyl cyanide compound monomer units include acrylonitrile and methacrylonitrile.

Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of alkyl (meth)acrylates include methyl methacrylate and methacrylic acid. Ethyl, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate and the like can be mentioned, and methyl methacrylate is particularly preferred. Among these, it is particularly preferable to contain an alkyl (meth)acrylate such as methyl methacrylate as an essential component, and from the viewpoint of mechanical properties and thermal stability, 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 polycarbonate resin, so that more rubber components are present in the resin, and the good impact resistance of the polycarbonate resin is exhibited more effectively. This is because the impact resistance of the resin composition is improved as a result. More specifically, the alkyl (meth)acrylate accounts for 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. It is preferably contained. The core-shell type graft polymer may be produced by any polymerization method of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage grafting or multi-stage grafting. I don't mind. 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, one commercially available under the trade name of METABLEN SRK200A, which contains acrylonitrile and styrene as shell components and acrylonitrile and styrene as core components, is available from Mitsubishi Chemical Corporation.

The content of component C is 5 to 25 parts by weight, preferably 8 to 23 parts by weight, and more preferably 10 to 21 parts by weight, per 100 parts by weight of components A and B combined. Addition of component C improves impact resistance and chemical resistance, but if the amount exceeds 25 parts by weight, flame retardancy is reduced.

(Component D: halogen-based flame retardant)
The resin composition of the present invention contains a halogen-based flame retardant as the D component. Brominated polycarbonates (including oligomers) are particularly preferred. Brominated polycarbonate is excellent in heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, structural units represented by the following formula (4) are preferably at least 60 mol%, more preferably at least 80 mol% of all structural units, and particularly preferably substantially the following It is a brominated polycarbonate compound consisting of structural units represented by the formula (4).

式（４）中、Ｘは臭素原子、Ｒは炭素数１～４のアルキレン基、炭素数１～４のアルキリデン基または－ＳＯ_２－である。
また、かかる式（４）において、好適にはＲはメチレン基、エチレン基、イソプロピリデン基、－ＳＯ_２－、特に好ましくはイソプロピリデン基を示す。

In formula (4), X is a bromine atom, and R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms or —SO ₂ —.
In the formula (4), preferably R represents a methylene group, ethylene group, isopropylidene group, -SO ₂ -, particularly preferably isopropylidene group.

The brominated polycarbonate has few remaining chloroformate group terminals, and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. Such terminal chlorine content was determined by dissolving a sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine to react with terminal chlorine (terminal chloroformate), and measuring this with an ultraviolet-visible spectrophotometer (Hitachi U -3200). When the terminal chlorine content is 0.3 ppm or less, the thermal stability of the flame-retardant polycarbonate resin composition becomes better, and molding at high temperatures becomes possible. As a result, a resin composition having excellent moldability is provided. be.

In addition, the brominated polycarbonate preferably has few remaining terminal hydroxyl groups. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less, per 1 mol of the structural unit of the brominated polycarbonate. The amount of terminal hydroxyl groups can be obtained by dissolving a sample in deuterated chloroform and measuring by ¹ H-NMR method. Such a terminal hydroxyl group content is preferable because the thermal stability of the flame-retardant polycarbonate resin composition is further improved.

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015-0.1, more preferably in the range of 0.015-0.08. The specific viscosity of the brominated polycarbonate is calculated according to the formula for calculating the specific viscosity used in calculating the viscosity average molecular weight of the polycarbonate resin as component A of the present invention.

The content of component D is 5 to 30 parts by weight, preferably 7 to 20 parts by weight, and more preferably 10 to 15 parts by weight, per 100 parts by weight of components A and B combined. If the content is less than 5 parts by weight, the flame retardant effect is small, and if it exceeds 30 parts by weight, the impact resistance and chemical resistance of the composition are lowered.

(E component: antimony compound)
The resin composition of the present invention contains an antimony compound as the E component. A halogen-based flame retardant is preferably used in combination with a halogen-based flame retardant because the flame retardancy of the resin composition can be further enhanced by using the antimony oxide compound in combination with the halogen-based flame retardant. Antimony compounds include antimony trioxide, antimony tetroxide, antimony pentoxide represented by (NaO)p.( _{Sb.sub.2O.sub.5} ) _.qH.sub.2O (p=0 to ₁ , q=0 to 4) and antimony. Sodium oxide can be used, and antimony pentoxide is particularly excellent in thermal stability. The antimony compound is preferably used as particles with a particle size of 0.02 to 5 μm. The content of component E is 0.5 to 3 parts by weight, preferably 0.7 to 2.5 parts by weight, more preferably 1 to 2 parts by weight, with respect to the total 100 parts by weight of components A and B. be. If the content is less than 0.5 parts by weight, the flame-retardant effect of the composition due to the synergistic action with the halogen-based flame retardant is small, and if it exceeds 3 parts by weight, the impact resistance of the composition decreases.

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

As the anti-dripping agent of the F component, 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, more 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. Commercially available products of these mixed forms of PTFE include "METABLEN A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., 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 proportion of the F component indicates the net amount of the anti-dripping agent, and in the case of mixed PTFE, indicates the net amount of PTFE.

The content of component F is 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.2 to 1 part by weight, with respect to the total 100 parts by weight of components A and B. weight part. If the amount of the anti-drip agent exceeds the above range and is too small, the flame retardancy will be insufficient. On the other hand, if the amount of the anti-drip agent exceeds the above range and is too large, not only will the impact resistance decrease, but the cost of the resin composition will increase.

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.

(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.

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 (5) are preferred.

（式（５）中、ＲおよびＲ’は炭素数６～３０のアルキル基または炭素数６～３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In formula (5), 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 (5), 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-based stabilizer is preferably 0.01 to 1.0 parts by weight, more preferably 0.03 to 0.8 parts by weight, with respect to 100 parts by weight of the total of component A and component B. , more preferably 0.05 to 0.5 parts by weight. If the content is less than 0.01 part by weight, the effect of suppressing thermal decomposition during processing may not be exhibited, and the mechanical properties may not 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 (6) (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 (7) -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 phenol-based stabilizer is preferably 0.05 to 1.0 parts by weight, more preferably 0.07 to 0.8 parts by weight, per 100 parts by weight of the total of the A component and the B component. , more preferably 0.1 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. In the case of combined use, 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 respect to a total of 100 parts by weight of components A and B. preferably.

(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 one of the following formulas (8), (9) and (10) 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 parts by weight with respect to the total 100 parts by weight of the components A and B. .15 to 1 part by weight. 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, appearance defects and deterioration of physical properties may occur 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 (11) and (12) 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, still more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the components A and B combined. 08 to 0.7 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 parts by weight with respect to 100 parts by weight of the total of components A and B. ~0.5 parts by weight. 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 above dye and 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 the total of the A component and the B component.

(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 components A and B combined.

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, based on 100 parts by weight of components A and B in total. be.

(viii) Filler The flame-retardant polycarbonate resin composition of the present invention may contain various fillers as reinforcing fillers within the range where 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 in total of the A component and the B component.

(ix) White Pigment for High Light Reflection The flame-retardant polycarbonate resin composition of the present invention may be blended with a white pigment for high light reflection to impart a light reflection effect. Examples of such white pigments include titanium oxide, zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, calcined kaolin and the like, with titanium oxide being the most widely used. As the titanium oxide to be used, titanium oxide having an average particle size of 0.1 to 5.0 μm and having been surface-treated with an organic substance is preferable. (In the present invention, the titanium oxide component of the titanium oxide pigment is referred to as "TiO2", and the entire pigment including the surface treatment agent is referred to as "titanium oxide".) The crystal form of TiO2 is either anatase type or rutile type. may be used, and they can be mixed and used as needed. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. It should be noted that rutile type crystals may contain anatase type crystals. Furthermore, TiO2 can be produced by the sulfuric acid method, the chlorine method, and other various methods, but the chlorine method is more preferable. Further, the titanium oxide of the present invention is more preferably in the form of particles, although the shape thereof is not particularly limited. Titanium oxide is generally used for various coloring applications, and the average particle size of titanium oxide used as the white pigment of the present invention is preferably 0.10 to 5.0 μm, and preferably 0.15 to 2.0 μm. 0 μm is more preferable, and 0.18 to 1.5 μm is even more preferable. If the average particle size is less than 0.10 μm, poor appearance such as silver tends to occur when the particles are highly filled. Incidentally, the average particle size is calculated by measuring individual single particle sizes from electron microscopic observation and calculating the number average thereof.

The titanium oxide used in the present invention is preferably surface-treated with an organic compound. When titanium oxide that has not been organically treated is used, the appearance deteriorates due to yellowing, and the reflectance of the molded product is significantly reduced, and sufficient solar reflectance may not be obtained. may not be suitable for As such a surface treating agent, various treating agents such as polyol-based, amine-based, and silicone-based agents can be used. Examples of polyol-based surface treatment agents include pentaerythritol, trimethylolethane, and trimethylolpropane, and examples of amine-based surface treatment agents include triethanolamine acetate and trimethylolamine acetate. Examples of silicone-based surface treatment agents include alkylchlorosilanes (such as trimethylchlorosilane), alkylalkoxysilanes (such as methyltrimethoxysilane), and hydrogenpolysiloxane. Examples of hydrogenpolysiloxane include alkylhydrogenpolysiloxane and alkylphenylhydrogenpolysiloxane. Methyl and ethyl groups are preferred as such alkyl groups. Titanium oxide surface-treated with such an alkylalkoxysilane and/or hydrogenpolysiloxane provides the resin composition of the present invention with better light reflectivity. The amount of the organic compound used for surface treatment is preferably 0.05 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 1.5 to 2.5 parts by weight, per 100 parts by weight of titanium oxide. It is in the range of parts by weight. If the amount of surface treatment is less than 0.05 parts by weight, sufficient thermal stability may not be obtained, and if it exceeds 5 parts by weight, it is not preferable from the viewpoint of molding defects such as silver. The organic compound surface treatment agent is preferably applied in advance to titanium oxide (more preferably, titanium oxide coated with another metal oxide). However, a method in which the surface treatment agent is separately added when the raw materials of the resin composition are melt-kneaded and the titanium oxide is surface-treated in the melt-kneading step may be used.

The content of the white pigment for high light reflection is preferably 0.1 to 10 parts by weight, more preferably 0.15 to 7.5 parts by weight, based on 100 parts by weight of the components A and B combined. , more preferably 0.15 to 5 parts by weight. If the content of the white pigment for high light reflection is less than 0.1 parts by weight, sufficient white appearance and light-shielding properties may not be obtained. It is not preferable because it may decrease. Two or more kinds of the high light reflection white pigment can be used in combination.

(x) 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.

(xi) 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 the molded article and improve its 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. pigments such as carbon black, dyes), light diffusing agents (e.g. acrylic crosslinked particles, silicon crosslinked particles, ultra-thin glass flakes, calcium carbonate particles). , fluorescent dyes, inorganic phosphors (for example, phosphors with aluminate as the mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (for example, fine particle titanium oxide, fine particle oxidation zinc), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

(Production of thermoplastic resin composition)
Any method may be employed to produce the thermoplastic resin composition of the present invention. For example, components A to F and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and optionally extrusion granulated. A method of granulating such a preliminary mixture with an apparatus, a briquetting machine, etc., followed by melt-kneading with a melt-kneader typified by a vented twin-screw extruder, and then pelletizing with a pelletizer can be mentioned.

In addition, there is a method of supplying each component independently to a melt kneader represented by a vented twin-screw extruder, or a method of premixing a part of each component and then supplying the rest of the components independently to a melt kneader. There are also methods of Examples of the method of pre-mixing a part of each component include a method of pre-mixing the components other than the A component and then mixing it with the thermoplastic resin of the A component or directly supplying it to an extruder.

As a method of pre-mixing, for example, when a component in the form of powder is included as the A component, a part of the powder and the additive to be blended are blended to produce a master batch of the additive diluted with the powder. A method using a masterbatch is mentioned. Furthermore, a method of supplying one component independently from the middle of the melt extruder may also be used. When the components to be blended include liquid ones, a so-called liquid injection device or liquid addition device can be used for supplying the components to the melt extruder.

As the extruder, it is preferable to use an extruder having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin. A vacuum pump is preferably installed from the vent for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to install a screen in front of the die portion of the extruder to remove foreign matters and the like mixed in the extruded raw material to remove the foreign matters from the resin composition. Such screens include wire meshes, screen changers, sintered metal plates (such as disk filters), and the like.

Examples of the melt-kneader include a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more screws, in addition to the twin-screw extruder.

The resin extruded as described above is either directly cut and pelletized, or is pelletized by forming strands and then cutting the strands with a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust during pelletization. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation. , and air bubbles (vacuum air bubbles) generated inside the strands and pellets can be appropriately reduced. These formulations enable high-cycle molding and a reduction in the proportion of defects such as silver. The shape of the pellets can be any general shape such as columnar, prismatic, and spherical, but is more preferably columnar. The diameter of such a cylinder is preferably 1-5 mm, more preferably 1.5-4 mm, still more preferably 2-3.3 mm. On the other hand, the length of the cylinder is preferably 1-30 mm, more preferably 2-5 mm, and even more preferably 2.5-3.5 mm.

(Regarding a molded article made of the resin composition of the present invention)
The resin composition of the present invention can be produced into various products by injection molding the pellets obtained by the above-described method. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic molding, rapid heat and cool molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. For molding, either cold runner method or hot runner method can be selected.

Further, the resin composition in the present invention can be used in the form of various profile extrudates, sheets, films, etc. by extrusion molding. In addition, the inflation method, calender method, casting method, and the like can be used for forming sheets and films. Furthermore, it is also possible to mold it as a heat-shrinkable tube by subjecting it to a specific stretching operation. The resin composition of the present invention can also be molded by rotational molding, blow molding, or the like.

Specific examples of molded articles in which the resin composition of the present invention is used include those suitable for application to living materials, housing equipment materials, building materials, interior goods, OA equipment, internal parts of home appliances, housings, and the like. . Examples of these products include personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio equipment, laser discs (registered trademark) and compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, suitcases and household materials such as cleaning tools, and housing equipment materials such as bathrooms, toiletries, and bathroom vanities, and resin products formed from the thermoplastic resin composition of the present invention for various parts such as these housings. can be used. Other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

Since the flame-retardant polycarbonate resin composition of the present invention is compatible with impact resistance, flame retardancy and chemical resistance at a high level, it can be used not only for outdoor/indoor use, but also for housing equipment, building materials, and living materials. It is widely useful in various fields such as applications, infrastructure equipment applications, automobile applications, OA/EE applications, outdoor equipment applications, and others. 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 thermoplastic resin composition)
(i) Impact resistance (fracture mode after high-speed surface impact test)
Using a flat plate of 45 mm long × 50 mm wide × 2 mm thick obtained by the following method, according to JIS K7211-2, using a high-speed puncture impact tester "Hydroshot HTM-P10" (manufactured by Shimadzu Corporation), 23 A punching test was performed at a punching test speed of 7 m/sec in an environment of °C, and the fracture mode (ductility/brittleness) after punching was determined.
(ii) Chemical resistance Using an ISO tensile test piece obtained by the following method, 0.8% strain is applied by a 3-point bending test method, and then salad oil (manufactured by Nisshin Co., Ltd.) is impregnated. It was covered with a damp cloth and left at 23° C. for 96 hours, and the presence or absence of a change in appearance was checked. In addition, evaluation was implemented by the following reference|standard.
○: No change in appearance △: Fine cracks observed ×: Large cracks leading to breakage (iii) Flame retardance UL test piece obtained by the following method V test was performed according to UL94.

[Examples 1 to 12, Comparative Examples 1 to 12]
A mixture having the composition shown in Tables 1 and 2, except the B component, was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing in a V-blender. The B component was supplied from the second supply port using a side feeder. 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 250° 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 evaluation test using an injection molding machine at a cylinder temperature of 260°C and a mold temperature of 60°C. Specimens (ISO tensile test pieces (ISO527-1 and ISO527-2 compliant), UL test pieces (1.5 mm thick) and flat plates of 45 mm long x 50 mm wide x 2 mm thick were molded.

In addition, each component indicated by symbols in Tables 1 and 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)
(B component)
B-1: Acrylonitrile-styrene copolymer (Rytac-A BS-207 (trade name) manufactured by Nippon A&L Co., Ltd., weight average molecular weight in terms of standard polystyrene by GPC measurement: 78,000, acrylonitrile component content: 26 weight %, styrene component content: 74% by weight)
B-2: Acrylonitrile-styrene copolymer (Rytac-A BS-218 (trade name) manufactured by Nippon A&L Co., Ltd., weight average molecular weight in terms of standard polystyrene by GPC measurement: 78,000, acrylonitrile component content: 26 weight %, styrene component content: 74% by weight)
(C component)
C-1: Acrylic-silicone core-shell type copolymer (80 wt% composed mainly of a composite rubber having a structure in which the core is a dimethylsiloxane polymer and an (n-butyl acrylate) polymer intertwined with each other, and the shell is acrylonitrile and a graft copolymer having a core-shell structure containing 20 wt% of styrene as a main component, Metabrene SRK200A (product name) manufactured by Mitsubishi Chemical Corporation)
C-2: Acrylic-silicone core-shell type graft copolymer (80 wt% composed mainly of a composite rubber in which the core has a structure in which a didimethylsiloxane polymer and an (n-butyl acrylate) polymer are intertwined with each other; is 20 wt% of methyl methacrylate as a main component, a graft copolymer having a core-shell structure, manufactured by Mitsubishi Chemical Corporation Metabrene S-2030 (product name))
(D component)
D: Halogen-based flame retardant (brominated carbonate oligomer having a bisphenol A skeleton, manufactured by Teijin Limited FG-8500 (product name)
(E component)
E-1: Antimony compound (antimony trioxide, PATOX-K (product name) manufactured by Nippon Seiko Co., Ltd.)
E-2: Antimony compound (antimony pentoxide, manufactured by NYACOAL: BURNEX6220 (trade name))
(F component)
F: Coated PTFE (polytetrafluoroethylene (polytetrafluoroethylene content: 50% by weight) coated with a styrene-acrylonitrile copolymer, SN3307 (trade name) manufactured by Shine Polymer)
(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.)

Claims (4)

(A) Polycarbonate resin (component A) and (B) a copolymer (component B) containing aromatic alkenyl compound monomer units and vinyl cyanide compound monomer units and not containing polyorganosiloxane, total 100 (C) A graft copolymer obtained by graft-polymerizing an aromatic alkenyl compound monomer unit and a vinyl cyanide compound monomer unit to a composite rubber composed of (C) polyorganosiloxane and an alkyl (meth)acrylate. 5 to 25 parts by weight of polymer (component C), (D) 5 to 30 parts by weight of halogen flame retardant (component D), (E) 0.5 to 3 parts by weight of antimony compound (component E) and (F) drip An inhibitor (F component) containing 0.05 to 2 parts by weight, and the content of B component is 20 to 60 parts by weight in a total of 100 parts by weight of A component and B component. A flame-retardant polycarbonate resin composition. 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the E component is antimony trioxide. 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the E component is antimony pentoxide. The flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, wherein the content of component B is 35 to 55 parts by weight in a total of 100 parts by weight of component A and component B. .