JP2013107928A - Aromatic polycarbonate resin composition, and molded body thereof - Google Patents

Abstract

Disclosed is a flame retardant aromatic polycarbonate resin composition having excellent weather resistance and heat discoloration resistance, and excellent initial color tone and long-term color tone stability.
SOLUTION: To 100 parts by mass of an aromatic polycarbonate resin (A), 0.01 to 0.5 parts by mass of an organic sulfonic acid metal salt (B), 0.1 to 5 parts by mass of polysilane (C), ultraviolet rays The total amount of the benzotriazole-based ultraviolet absorber (D-1) as the absorber (D) and the non-benzotriazole-based ultraviolet absorber (D-2) having the maximum absorbance (λmax) at a wavelength of 260 to 340 nm An aromatic polycarbonate resin composition containing 0.1 to 2 parts by mass.
[Selection figure] None

Description

  The present invention relates to an aromatic polycarbonate resin composition and a molded article thereof. Specifically, the present invention relates to an aromatic polycarbonate resin composition excellent in flame retardancy, weather resistance, and heat discoloration resistance, and having good initial color tone and long-term color tone stability, and a molded product thereof.

  Aromatic polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical properties, and is widely used for, for example, automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. Yes. In particular, the flame-retardant aromatic polycarbonate resin composition is suitably used as a member of OA / information equipment such as a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

As a means for imparting flame retardancy to an aromatic polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the aromatic polycarbonate resin.
However, an aromatic polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may cause a decrease in thermal stability or corrosion of a molding machine screw or a molding die during molding processing. There was a thing.
In addition, the aromatic polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the aromatic polycarbonate resin, and causes a decrease in impact resistance and heat resistance. There was a limit.
In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.

Under such circumstances, in recent years, metal salt compounds typified by organic alkali metal salt compounds and organic alkaline earth metal salt compounds have been studied as useful flame retardants. Examples of the flame retardant technology of polycarbonate using such a metal salt compound include, for example, a method using an alkali metal salt of perfluoroalkylsulfonic acid having 4 to 8 carbon atoms (see Patent Document 1), non-halogen aromatic sulfonic acid. Examples include a method of imparting flame retardancy to an aromatic polycarbonate resin composition using an alkali metal salt compound of an aromatic sulfonic acid, such as a method of containing a sodium salt (see Patent Document 2).
However, the flame retardance imparted to the aromatic polycarbonate resin by the metal salt compound as described above is catalytic, and even if the blending amount is increased in order to obtain high flame retardancy, no effect is obtained. Or it had the subject that a flame retardance deteriorated on the contrary.

On the other hand, in recent years, studies have been made to improve the mechanical properties, lubricity, and flame retardancy by blending polysilane having a main chain composed of repeating silicon atoms with a resin (see, for example, Patent Documents 3 to 5).
However, the flame retardant effect by blending polysilane is very small, and a resin composition in which such a compound is blended with an aromatic polycarbonate resin is actually not satisfactory.

  In order to solve the problems in the case of using such a metal salt compound or polysilane, the present applicant has previously made a polycarbonate resin composition containing a metal salt compound and polysilane in a predetermined ratio in a polycarbonate resin. The thing was proposed (refer patent document 6).

  On the other hand, the present applicant has found an aromatic polycarbonate resin composition having excellent weather resistance and transparency without impairing the original properties of an aromatic polycarbonate resin, and having suppressed mold decolorization and discoloration during melt processing. Types of polycarbonate resin, benzotriazole ultraviolet absorber and non-benzotriazole ultraviolet absorber having a maximum absorbance (λmax) at a wavelength of 260 nm to 340 nm and an absorbance at a wavelength of 380 nm of 10% or less of λmax The aromatic polycarbonate resin composition which mix | blended the ultraviolet absorber of this is proposed (refer patent document 7).

Japanese Patent Publication No. 47-40445 JP 2000-169696 A JP 2003-268247 A JP 2003-277617 A JP 2003-277756 A JP 2010-180368 A JP 2009-286850 A

According to the study of the present inventor, the aromatic polycarbonate resin composition described in Patent Document 6 is remarkably excellent in flame retardancy, but is not sufficiently satisfactory in terms of weather resistance and heat discoloration. found.
In addition, although the aromatic polycarbonate resin composition of patent document 7 is excellent in a weather resistance, examination about the heat-resistant discoloration property when exposed to high temperature conditions for a long period is not made | formed.

  Therefore, the present invention improves the weather resistance and heat discoloration resistance of the flame retardant aromatic polycarbonate resin composition described in Patent Document 6, is excellent in weather resistance and heat discoloration resistance, and has an initial color tone and a long-term color tone. It is an object to provide a flame-retardant aromatic polycarbonate resin composition excellent in stability.

  In the process of intensive studies to solve the above problems, the present inventor has an initial color tone when a benzotriazole-based ultraviolet absorber is blended with the aromatic polycarbonate resin composition of Patent Document 6 in order to improve weather resistance. On the other hand, it was found that weather resistance and heat discoloration cannot be improved with non-benzotriazole ultraviolet absorbers such as malonic ester ultraviolet absorbers. Therefore, when a benzotriazole-based UV absorber and a non-benzotriazole-based UV absorber are used in combination, the excellent synergistic effect due to the coexistence of these two types of UV absorber and polysilane, the fragrance of Patent Document 7 can be obtained. Compared to a combination of a benzotriazole-based UV absorber and a non-benzotriazole-based UV absorber in a resin composition that does not contain polysilane, such as a group polycarbonate resin composition, not only weather resistance but also heat discoloration It has been found that the properties are significantly improved.

  The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

[1] 0.01 to 0.5 parts by mass of organic sulfonic acid metal salt (B), 0.1 to 5 parts by mass of polysilane (C), and 100% by mass of aromatic polycarbonate resin (A). The total amount of the benzotriazole-based ultraviolet absorber (D-1) as the agent (D) and the non-benzotriazole-based ultraviolet absorber (D-2) having the maximum absorbance (λmax) at a wavelength of 260 to 340 nm is 0. An aromatic polycarbonate resin composition containing from 1 to 2 parts by mass.

[2] The aromatic polycarbonate resin composition according to [1], wherein the non-benzotriazole ultraviolet absorber (D-2) is a malonic ester ultraviolet absorber.

[3] The aromatic polycarbonate resin composition according to [1] or [2], wherein the molecular weight of the malonic ester-based ultraviolet absorber is 220 to 500.

[4] The content ratio of the benzotriazole-based ultraviolet absorber (D-1) and the non-benzotriazole-based ultraviolet absorber (D-2) is benzotriazole-based ultraviolet absorber (D-1): non-benzotriazole by mass ratio. The aromatic polycarbonate resin composition according to any one of [1] to [3], wherein the ultraviolet absorber (D-2) is 40:60 to 90:10.

[5] The aromatic polycarbonate resin composition according to any one of [1] to [4], wherein the polysilane (C) is a cyclic polysilane.

[6] The aromatic polycarbonate resin composition according to any one of [1] to [5], wherein the organic sulfonic acid metal salt (B) is an alkali metal salt of perfluoroalkanesulfonic acid.

[7] The aromatic polycarbonate resin composition according to any one of [1] to [6], wherein the aromatic polycarbonate resin (A) contains 30% by mass or more of an aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more. object.

[8] An aromatic polycarbonate resin molded article obtained by molding the aromatic polycarbonate resin composition according to any one of [1] to [7].

  According to the present invention, high flame retardancy can be realized by blending an aromatic polycarbonate resin with an organic sulfonic acid metal salt and polysilane, and a benzotriazole-based ultraviolet absorber is further added to the system in which polysilane is present. And non-benzotriazole UV absorbers with specific light absorption characteristics can improve the weather resistance and heat discoloration without impairing the good color tone, and stabilize the initial color tone and color tone over a long period of time. The flame-retardant aromatic polycarbonate resin composition excellent in property can be provided.

  The aromatic polycarbonate resin composition of the present invention can be used in a wide range of industrial fields. For example, electrical and electronic equipment and parts thereof, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, It is suitable for use in fields such as building materials, various containers, leisure goods / miscellaneous goods, and lighting equipment. In particular, due to its excellent color tone, flame retardancy, weather resistance, and heat discoloration, it covers solar cell covers, optical elements of light guide plates (light guides) and light diffusers, lenses, goggles, motorcycle windshields, lamp covers, and glazing. It can be used in a wide range of applications such as vehicle materials such as window glass, carports and arcades, gymnasium roofing materials, and street light covers.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

[Overview]
The aromatic polycarbonate resin composition of the present invention comprises at least an aromatic polycarbonate resin (A), an organic sulfonic acid metal salt (B), a polysilane (C), and a benzotriazole-based ultraviolet absorber as an ultraviolet absorber (D). And an agent (D-1) and a non-benzotriazole ultraviolet absorber (D-2) having a maximum absorbance (λmax) at a wavelength of 260 to 340 nm. Moreover, the aromatic polycarbonate resin composition of this invention may contain the other component as needed.

[Aromatic polycarbonate resin (A)]
There is no restriction | limiting in the kind of aromatic polycarbonate resin used for the aromatic polycarbonate resin composition of this invention. Moreover, aromatic polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

  The aromatic polycarbonate resin (A) in the present invention is a polymer having a basic structure represented by the following general formula (1) and having a carbonic acid bond in which each carbon atom directly bonded to a carbonic acid bond is an aromatic carbon atom. It is.

(In formula (1), X ¹ is generally a divalent aromatic hydrocarbon group, but it may be one in which a hetero atom or a hetero bond is introduced for imparting various properties. Indicates the number of repetitions.)

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the aromatic polycarbonate polymer formed by making an aromatic dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the aromatic dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting with cyclic ether using carbon dioxide as a carbonate precursor may be used. The aromatic polycarbonate polymer may be linear or branched. Furthermore, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit, or may be a copolymer having two or more types of repeating units. Moreover, this copolymer can select various copolymerization forms, such as a random copolymer and a block copolymer. Normally, such an aromatic polycarbonate polymer is a thermoplastic resin.

<Aromatic dihydroxy compound>
Of the monomers used as the raw material for the aromatic polycarbonate resin, examples of the aromatic dihydroxy compound include the following.

  Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;

  Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

  2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

  2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

  2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A), 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-methoxy-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane, 1,1-bis (3-tert-butyl) -4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2- (4-hydroxy Phenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane, α, α′-bis (4-hydroxyphenyl) -1,4 Diisopropylbenzene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane, bis (4-hydroxyphenyl) Phenylmethane, bis (4-hydroxyphenyl) (4-propenylphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) naphthylmethane, 1-bis (4-hydroxyphenyl) ethane, 2- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-naphthylethane, 1-bis (4-hydroxy) Phenyl) butane, 2-bis (4-hydroxyphenyl) Tan, 2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexane, 1-bis (4-hydroxyphenyl) Octane, 2-bis (4-hydroxyphenyl) octane, 1-bis (4-hydroxyphenyl) hexane, 2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2, Bis (hydroxyaryl) alkanes such as 2-bis (4-hydroxyphenyl) nonane, 10-bis (4-hydroxyphenyl) decane, 1-bis (4-hydroxyphenyl) dodecane;

  1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 4-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3- Dimethylcyclohexane, 1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) 3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3 -Propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-ter -Butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane, 1,1-bis (4- Bis (hydroxyaryl) cycloalkanes such as hydroxyphenyl) -4-phenylcyclohexane;

  Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

  Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

  Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

  Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

  Of these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable in terms of impact resistance and heat resistance. (Ie bisphenol A) is preferred.

  In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

<Carbonate precursor>
Among the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

<Method for producing aromatic polycarbonate resin>
The manufacturing method of the aromatic polycarbonate resin used by this invention is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

(Interfacial polymerization method)
In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, the pH is usually kept at 9 or higher, and an aromatic dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted and then polymerized. An aromatic polycarbonate resin is obtained by interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for preventing the oxidation of the aromatic dihydroxy compound.

  The aromatic dihydroxy compound and carbonate precursor used in the reaction are as described above. Of the carbonate precursors, phosgene is preferably used, and the method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; . In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the aromatic dihydroxy compound and the alkali compound is usually 1: 1. In order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. It is preferably 9 or more, especially 1: 2.0 or more, and usually 1: 3.2 or less, particularly 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride; Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include aromatic hydroxy compounds having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among these, aromatic hydroxy compounds are preferable. Specific examples of such aromatic hydroxy compounds include alkyl such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Group-substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of aromatic dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of the obtained aromatic polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction solvent, catalyst, additive and the like is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is from the reaction (phosgenation) of the aromatic dihydroxy compound and phosgene to the start of the polymerization reaction. .
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

(Melted ester exchange method)
In the production of an aromatic polycarbonate resin by the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound is performed.

  The aromatic dihydroxy compound used is as described above.

  On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the aromatic dihydroxy compound and the carbonic acid diester used in the reaction is arbitrary as long as the desired aromatic polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the aromatic dihydroxy compound. Of these, 1.01 mol or more is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups of the obtained aromatic polycarbonate resin can be adjusted to a suitable range.

  In an aromatic polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, an aromatic polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, this operation can also adjust the molecular weight of the aromatic polycarbonate resin obtained normally.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing an aromatic polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. In the case of a batch method, the order of mixing the reaction substrate, reaction solvent, catalyst, additive, etc. is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, considering the stability of the resulting aromatic polycarbonate resin, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents, relative to the alkali metal and / or alkaline earth metal contained in the transesterification catalyst. Hereinafter, it is preferably 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

<Aromatic polycarbonate resin having a structural viscosity index N within a predetermined range>
As the aromatic polycarbonate resin (A) used in the present invention, an aromatic polycarbonate resin having a structural viscosity index N within a predetermined range (hereinafter, may be referred to as “aromatic polycarbonate resin (A-1)”) at a certain ratio. It is preferable to contain above.

The structural viscosity index N is an index for evaluating the flow characteristics of the melt. Usually, the melting characteristics of an aromatic polycarbonate resin can be expressed by the formula: γ = a · σ ^N. In the above formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.
In the above formula, when N = 1, Newtonian fluidity is shown, and the non-Newtonian fluidity increases as the value of N increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, an aromatic polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when an aromatic polycarbonate resin having a large structural viscosity index N is mixed with another aromatic polycarbonate resin, dripping at the time of combustion of the obtained aromatic polycarbonate resin composition can be suppressed and flame retardancy can be improved. it can.

  For this reason, in the aromatic polycarbonate resin composition of the present invention, the aromatic polycarbonate resin (A) has a structural viscosity index N of usually 1.2 or more, preferably 1.25 or more, more preferably 1.28. In addition, it is preferable that the aromatic polycarbonate resin (A-1) of 1.8 or less, preferably 1.7 or less is contained in a certain ratio or more. By containing the aromatic polycarbonate resin (A-1) having a high structural viscosity index N in this manner, dripping at the time of combustion of the aromatic polycarbonate resin composition of the present invention can be suppressed and flame retardancy can be improved. it can. Moreover, the moldability of the aromatic polycarbonate resin composition of this invention can be maintained in a favorable range by making the structural viscosity index N of aromatic polycarbonate resin (A-1) below the upper limit of the said range.

The “structural viscosity index N” is expressed by Log η _a = [(1−N) / N] × Log γ + C, which is derived from the above formula, for example, as described in Japanese Patent Application Laid-Open No. 2005-232442. It is also possible. In the above formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As can be seen from this equation, the N value can also be evaluated from γ and ηa in _a low shear region in which the viscosity behavior is greatly different. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

  In the aromatic polycarbonate resin composition of the present invention, the aromatic polycarbonate resin (A) is obtained by changing the above-described aromatic polycarbonate resin (A-1) having a structural viscosity index N in a predetermined range to a wholly aromatic polycarbonate resin (A). Among them, it is usually preferable to contain 30% by mass or more, particularly 50% by mass or more, particularly 60% by mass or more. By combining with the aromatic polycarbonate resin (A-1) having a structural viscosity index N within a predetermined range, the specific synergistic effect of the organic sulfonic acid metal salt (B) and the polysilane (C) according to the present invention can be remarkably exhibited. Because. In addition, there is no restriction | limiting in the upper limit of the said content, Although it is 100 mass% or less normally, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.

  In addition, 1 type may be used for the aromatic polycarbonate resin (A-1) in which the structural viscosity index N exists in a predetermined range, and 2 or more types may be used together by arbitrary combinations and a ratio.

<Other aromatic polycarbonate resins>
In addition, the aromatic polycarbonate resin (A) is an aromatic polycarbonate resin having a structural viscosity index N outside the predetermined range in addition to the aromatic polycarbonate resin (A-1) having the structural viscosity index N in the predetermined range. (Hereinafter, it may be referred to as “aromatic polycarbonate resin (A-2)”). Although there is no restriction | limiting in the kind, Especially a linear aromatic polycarbonate resin is preferable. Combining the aromatic polycarbonate resin (A-1) having a structural viscosity index N in a predetermined range with the linear aromatic polycarbonate resin, flame retardancy (anti-dripping property) of the obtained aromatic polycarbonate resin composition; The advantage that it is easy to balance moldability (fluidity) is obtained. From this point of view, the aromatic polycarbonate resin (A) is composed of an aromatic polycarbonate resin (A-1) having a structural viscosity index N in the above predetermined range and a linear aromatic polycarbonate resin. Is particularly preferred.

  When the aromatic polycarbonate resin (A) contains a linear aromatic polycarbonate resin, the proportion of the linear aromatic polycarbonate resin in the wholly aromatic polycarbonate resin (A) is usually 70% by mass or less, preferably 50% by mass. % Or less, more preferably 40% by mass or less, and usually more than 0% by mass, preferably 10% by mass or more, more preferably 15% by mass or more. By setting the linear aromatic polycarbonate resin in the above range, good dispersibility of the flame retardant and other additives can be easily obtained, and an aromatic polycarbonate resin composition excellent in flame retardancy and moldability can be easily obtained. The advantage is obtained.

  The aromatic polycarbonate resin (A) used in the present invention may contain only one kind of aromatic polycarbonate resin (A-2) having a structural viscosity index N deviating from the above predetermined range, and two or more kinds thereof. Any combination and ratio may be included. Therefore, the aromatic polycarbonate resin (A) used in the present invention may contain only one type of linear aromatic polycarbonate resin, or may contain two or more types in any combination and ratio.

<Method for producing aromatic polycarbonate resin (A-1)>
The aromatic polycarbonate resin (A-1) having the structural viscosity index N in the predetermined range may be produced according to the above-described method for producing an aromatic polycarbonate resin. At this time, when an aromatic polycarbonate resin having a branched structure (hereinafter, referred to as “branched polycarbonate resin” as appropriate) is produced, the aromatic polycarbonate resin (A-1) having a structural viscosity index N within the predetermined range is obtained. It is easy to obtain and preferable. This is because the branched polycarbonate resin tends to have a high structural viscosity index N.

  Examples of the method for producing the branched polycarbonate resin include the methods described in JP-A-8-259687, JP-A-8-245782, and the like. In the methods described in these documents, when the aromatic dihydroxy compound and the carbonic acid diester are reacted by the melt transesterification method, the structural viscosity index can be obtained without using a branching agent by selecting the catalyst conditions or the production conditions. And an aromatic polycarbonate resin excellent in hydrolysis stability can be obtained.

  As another method for producing a branched polycarbonate resin, a trifunctional or higher polyfunctional compound (branching agent) is used in addition to the aromatic dihydroxy compound and the carbonate precursor which are the raw materials of the polycarbonate resin described above. The method of copolymerizing these by a polymerization method or a melt transesterification method is mentioned.

  Examples of the trifunctional or higher functional compound include 1,3,5-trihydroxybenzene (phloroglucin), 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4 , 6-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri Polyhydroxy compounds such as (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane; 3,3-bis (4-hydroxyaryl) oxyindole (ie, isatin) Bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable.

The polyfunctional compound can be used by substituting a part of the aromatic dihydroxy compound. The amount of the polyfunctional aromatic compound used is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 10 mol% or less, preferably 3 mol, based on the aromatic dihydroxy compound. % Or less.
In addition, a polyfunctional compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

As for the branched structure contained in the branched polycarbonate resin obtained by the melt transesterification method, the structure of following formula (2A)-(2D) is mentioned, for example. In the following formulas (2A) to (2D), X ² , X ³ , X ⁴ and X ⁵ are a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, or 5 carbon atoms. 15 cycloalkylene groups, cycloalkylidene group having 5 to 15 carbon atoms, or, -O -, - S -, - CO -, - SO -, - SO 2 - from the group consisting of divalent groups represented by Indicates what will be chosen.

  As a method for producing a branched polycarbonate resin, among the methods described above, a production method for producing a branched polycarbonate resin by the above-described melt transesterification method is particularly preferable. This is because it can be manufactured from a relatively inexpensive and easily available industrial material. For this reason, the polycarbonate resin is also preferably produced by a melt transesterification method.

<Molecular weight>
The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, More preferably, it is 18000 or more, and is usually 40000 or less, preferably 30000 or less. By making the viscosity average molecular weight more than the lower limit of the above range, the mechanical strength of the aromatic polycarbonate resin composition of the present invention can be further improved, and more preferable when used for applications requiring high mechanical strength. Become. On the other hand, by making the viscosity average molecular weight not more than the upper limit of the above range, it is possible to suppress and improve the fluidity reduction of the aromatic polycarbonate resin composition of the present invention, so that the molding processability can be improved and the molding process can be easily performed. Become. Two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed. Good.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

<Terminal hydroxyl group concentration>
The terminal hydroxyl group concentration of the aromatic polycarbonate resin (A) used in the present invention is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. When the terminal hydroxyl group concentration of the aromatic polycarbonate resin (A) is not more than the above upper limit, the residence heat stability and color tone of the aromatic polycarbonate resin composition of the present invention can be further improved. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of an aromatic polycarbonate resin produced by the melt transesterification method. When the terminal hydroxyl group concentration of the aromatic polycarbonate resin (A) is not less than the above lower limit, it is possible to suppress a decrease in molecular weight and further improve the mechanical properties of the aromatic polycarbonate resin composition of the present invention.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

<Other aspects>
The aromatic polycarbonate resin (A) used in the present invention is not limited to an aromatic polycarbonate resin alone (the aromatic polycarbonate resin alone is not limited to an embodiment containing only one type of aromatic polycarbonate resin. For example, the monomer composition and molecular weight are It may be used in the meaning including an aspect including a plurality of different types of aromatic polycarbonate resins.), Or an alloy (mixture) of an aromatic polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, an aromatic polycarbonate resin is a copolymer with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with monomer, oligomer or polymer having phosphorus atom; copolymer with monomer, oligomer or polymer having dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene to improve optical properties A copolymer with an oligomer or polymer having an olefinic structure such as; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; May be.

  In addition, the aromatic polycarbonate resin (A) may contain an aromatic polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight [Mv] of the aromatic polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Furthermore, the aromatic polycarbonate ligomer contained is preferably 30% by mass or less of the aromatic polycarbonate resin (including the aromatic polycarbonate oligomer) (A).

Furthermore, the aromatic polycarbonate resin (A) may be not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product (a so-called material recycled aromatic polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated aromatic polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, of the aromatic polycarbonate resin (A) contained in the aromatic polycarbonate resin composition of the present invention. More preferably. Since the regenerated aromatic polycarbonate resin is highly likely to have undergone deterioration such as thermal deterioration and aging deterioration, when such an aromatic polycarbonate resin is used in a larger amount than the above range, the aromatic polycarbonate resin of the present invention is used. This is because the hue and mechanical properties of the polycarbonate resin composition may be reduced.

[Organic sulfonic acid metal salt (B)]
The aromatic polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt (B). Thus, the flame retardance of the aromatic polycarbonate resin composition of the present invention can be improved by containing the organic sulfonic acid metal salt (B).

  The metal salt is effective in improving the flame retardancy of the aromatic polycarbonate resin composition, but among the metal salts, an organic metal salt is particularly preferable in terms of dispersibility in the aromatic polycarbonate resin, and the organic metal salt Among these, organic sulfonic acid metal salts are most preferable in that they are excellent in thermal stability when blended with an aromatic polycarbonate resin.

  As the metal of the organic sulfonic acid metal salt, alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs); magnesium (Mg), calcium (Ca), strontium (Sr), alkaline earth metals such as barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn ), Zirconium (Zr), molybdenum (Mo) and the like. Among them, in particular, the aromatic polycarbonate resin composition of the present invention can promote the formation of a carbonized layer at the time of combustion, can further improve the flame retardancy, and mechanical properties such as impact resistance of the aromatic polycarbonate resin, Alkali metals and alkaline earth metals are preferred, alkali metals are more preferred, and sodium, potassium, and cesium are most preferred because properties such as heat resistance and electrical characteristics can be maintained satisfactorily.

  Examples of organic sulfonic acid metal salts include organic sulfonic acid lithium (Li) salt, organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt, organic sulfonic acid rubidium (Rb) salt, organic sulfonic acid Examples thereof include a cesium (Cs) salt, an organic magnesium sulfonate (Mg) salt, an organic calcium sulfonate (Ca) salt, an organic sulfonic acid strontium (Sr) salt, and an organic sulfonic acid barium (Ba) salt. Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt compound, and organic sulfonic acid cesium (Cs) salt compound are particularly preferable.

  Among the organic sulfonic acid metal salts, preferred examples include metal salts of fluorine-containing aliphatic sulfonic acids or aromatic sulfonic acids. Specific examples of preferable ones are as follows.

  Alkaline of fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule, such as potassium perfluorobutanesulfonate, lithium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, cesium perfluorobutanesulfonate Metal salt; at least one in the molecule, such as magnesium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, barium perfluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, barium trifluoromethanesulfonate Fluorine-containing aliphatic sulfonic acid metal such as an alkaline earth metal salt of fluorine-containing aliphatic sulfonic acid having a C—F bond;

  Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate An alkali metal salt of an aromatic sulfonic acid having at least one aromatic group in the molecule; magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, (branched Aromatic sulfonic acid metal salts such as :) alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule, such as magnesium dodecylbenzene sulfonate and calcium (branched) calcium dodecylbenzene sulfonate;

  Among the above-described examples, alkali metal salts of fluorine-containing aliphatic sulfonic acids and alkali metal salts of aromatic sulfonic acids are more preferable, alkali metal salts of fluorine-containing aliphatic sulfonic acids are particularly preferable, and perfluoroalkanesulfonic acid. Alkali metal salts are more preferable, and specifically potassium perfluorobutanesulfonate, sodium perfluoroethanesulfonate, and the like are preferable.

  In addition, 1 type may be used for organic sulfonic acid metal salt (B), and it may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the organic sulfonic acid metal salt (B) in the aromatic polycarbonate resin composition of the present invention is 0.01 parts by mass or more, preferably 0.02 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Part or more, more preferably 0.03 part by weight or more, particularly preferably 0.05 part by weight or more, 0.5 part by weight or less, preferably 0.4 part by weight or less, more preferably 0.3 part by weight or less. The amount is particularly preferably 0.2 parts by mass or less. If the content of the organic sulfonic acid metal salt (B) is too small, the flame retardant property of the resulting aromatic polycarbonate resin composition may be insufficient. There is a possibility that a decrease in thermal stability and an appearance defect of the molded product and a decrease in mechanical strength may occur.

[Polysilane (C)]
The aromatic polycarbonate resin composition of the present invention contains polysilane (C). By containing polysilane (C) simultaneously with the above-mentioned organic sulfonic acid metal salt (B), the flame retardancy of the aromatic polycarbonate resin composition of the present invention can be remarkably improved. Although the details of the action mechanism of the synergistic effect of remarkable flame retardancy improvement by using this organic sulfonic acid metal salt (B) and polysilane (C) in combination are not clear, the catalytic action of the organic sulfonic acid metal salt (B) Thus, the Si—Si bond of polysilane (C) is partially cleaved under high temperature conditions during combustion, and a complex of aromatic polycarbonate resin (A) and polysilane (C) is efficiently formed to form a crosslinked structure. As a result, it is estimated that the anti-drip property during combustion is improved.

  The polysilane (C) used in the present invention is not particularly limited as long as it is a polymer having a Si-Si bond, and may take any form such as linear, branched, cyclic or network, Usually, it has at least one structural unit among the structural units represented by the following formulas (3A) to (3C).

  As such a polysilane, for example, a linear or cyclic polysilane composed of a structural unit represented by the formula (3A), a branched structure composed of a structural unit represented by the formula (3B) or (3C), Or a network polysilane, a combination of structural units represented by the above formulas (3A) to (3C), for example, formula (3A) and formula (3B), formula (3A) and formula (3C), formula (3B) and formula (3C), polysilanes composed of structural units represented by formulas (3A) to (3C), and the like. Of these, linear polysilanes and cyclic polysilanes are preferred because they tend to have excellent dispersibility in polycarbonate resins. The linear polysilane may be partially branched or networked.

  As linear polysilane which consists of a structural unit represented by the above formula (3A), specifically, for example, it can also be represented by the following formula (3D), and the structural unit represented by the formula (3A) As cyclic polysilane which consists of, specifically, it can also represent by following formula (3E), for example.

In the formulas (3A) to (3E), the substituent represented by R ^{1 to} R ⁹ represents at least one selected from a monovalent hydrocarbon group, a hydrogen atom, and a silyl group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, an aralkyl group, and the like. Among them, an alkyl group and an aryl group are preferable, and an alkyl group is particularly preferable. Preferably, a methyl group is more preferable.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, and hexyl group is preferable. The group is particularly preferred.

  Examples of the cycloalkyl group include cycloalkyl groups having 5 to 14 carbon atoms such as a cyclopentyl group and a cyclohexyl group. Among them, a cycloalkyl group having 5 to 8 carbon atoms is preferable.

  Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group. Examples of the cycloalkenyl group include cyclopentenyl groups and cyclohexenyl groups such as cyclopentenyl group and cyclohexenyl group. An alkenyl group is mentioned.

  Examples of the alkynyl group include alkynyl groups having 2 to 8 carbon atoms such as ethynyl group and propynyl group, and aryl-substituted alkynyl groups such as phenylethynyl group.

  Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (that is, tolyl) group, a dimethylphenyl (that is, xylyl) group, and a naphthyl group. -10 aryl groups are preferred, and phenyl groups are particularly preferred. Examples of the aralkyl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. Among them, aralkyl groups having 6 to 10 carbon atoms are preferable, and benzyl group is particularly preferable. preferable.

  Examples of the silyl group include silyl groups having 1 to 10 silicon atoms such as a silyl group, a disilanyl group, and a trisilanyl group. Among them, a silyl group having 1 to 6 silicon atoms is preferable. In the silyl group, at least one of its hydrogen atoms may be substituted with a functional group such as an alkyl group, an aryl group, or an alkoxy group.

  The degree of polymerization of polysilane, that is, x, y and z in formulas (3A) to (3C), or the sum of these formulas (3A) to (3C) is usually 2 or more, preferably 5 Above, more preferably 10 or more, and usually 500 or less, preferably 400 or less, more preferably 300 or less. When it is composed of any one of the structural units represented by formulas (3A) to (3C) and x, y, and z are 1, since it is a silane monomer, that is, a silane monomer, the heat resistance is extremely reduced, and aromatic When a group polycarbonate resin composition is used, it is not preferable because it tends to gasify (volatilize) and tends to cause mold contamination, mechanical properties and flame retardancy. In addition, a polysilane having a polymerization degree exceeding 500 is not preferable because it is very difficult to produce and the dispersibility in the polyaromatic carbonate resin is extremely lowered.

  In the formula (3D), the polymerization degree of the linear polysilane, that is, m is usually 1 or more, preferably 3 or more, more preferably 5 or more, and usually 300 or less, preferably 100 or less, more preferably 50. Hereinafter, it is more preferably 30 or less. Such a range is preferable for the same reason as described above.

  The degree of polymerization of the cyclic polysilane in formula (3E), that is, n is usually 4 or more, preferably 5 or more, usually 12 or less, preferably 10 or less, more preferably 8 or less, and particularly preferably n = 5. Degree. Those having n of 3 or less are difficult to produce due to chemical structure, and those having n of 12 or more are also difficult to produce.

  In the formulas (3A) to (3E), a, b, c, d, e, f, g, h, and i represent 0 or 1. When a, b, c, d, e, f, g, h and i are 0, polysilane is an organic functional group such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, and an aralkyl group. It means having a hydrocarbon group such as a group, a hydrogen atom, and a silyl group. When a, b, c, d, e, f, g, h, and i are 1, Group, a cycloalkyloxy group, an alkenyloxy group, a cycloalkenyloxy group, an alkynyloxy group, an aryloxy group, an aralkyloxy group and other oxyhydrocarbon groups, a hydroxyl group, and a silyloxy group. From the viewpoint of the heat resistance of the polysilane, a, b, c, d, e, f, g, h and i are preferably 0, but intentionally for improving the affinity with the resin, or It may be 1 unintentionally due to oxidation action or the like.

  When the polysilane has an acyclic structure (linear, branched, or network), the terminal substituent is usually a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or a silyl group.

  Examples of such a polysilane include polydialkylsilanes such as polydimethylpolysilane, polymethylpropylsilane, polymethylbutylsilane, polymethylpentylsilane, polydibutylsilane, polydihexylsilane, and dimethylsilane-methylhexylsilane copolymer; Polyalkylarylsilanes such as methylphenylsilane, methylphenylsilane-phenylhexylsilane copolymer; polydiarylsilanes such as polydiphenylsilane; dimethylsilane-methylphenylsilane copolymer, dimethylsilane-phenylhexylsilane copolymer, And cyclic polysilanes such as dialkylsilane-alkylarylsilane copolymers such as dimethylsilane-methylnaphthylsilane copolymer. Details of such polysilanes are described in, for example, R.A. D. Miller, J.M. Michl; Chemical Review, 89, 1359 (1989); Matsumoto; Japan Journal of Physics, Vol. 37, p. 5425 (1998).

  Of these, cyclic polydiphenylsilane is particularly preferred.

  In addition, polysilane (C) may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The molecular weight of the polysilane (C) is a number average molecular weight, usually 300 or more, preferably 400 or more, more preferably 500 or more, and usually 200,000 or less, preferably 100,000 or less, more preferably 50,000 or less, more preferably 10,000 or less. It is. When the polysilane number average molecular weight is less than 300, the heat resistance of the polysilane is lowered, and the flame retardancy of the aromatic polycarbonate resin composition of the present invention may be lowered. It is also not preferable because the dispersibility and compatibility in the resin are extremely lowered, and there is a risk of lowering mechanical properties and flame retardancy.

  The production method of polysilane (C) used in the present invention is not particularly limited as long as it is a known method, and may be appropriately selected and used. For example, a silicon-containing monomer having a specific structural unit is used as a raw material, magnesium Dehalogenation condensation polymerization of halosilanes using magnesium as a reducing agent (magnesium reduction method), dehalogenation condensation polymerization of halosilanes in the presence of antkari metal (capping method), and dehalogenation condensation polymerization of halosilanes by electrode reduction Method, method of dehalogenating polycondensation of halosilanes by electrode reduction, method of dehydrogenating polycondensation of hydrazine in the presence of a metal catalyst, method of anionic polymerization of disilene crosslinked with biphenyl, etc., ring opening of cyclic silanes Examples of polymerization methods include polysilanes that can be obtained. Purity, molecular weight distribution, a point easily controlled impurity content such as of sodium, chlorine and the like, magnesium reduction method from the viewpoint industrial merit is great in terms of production cost and safety are particularly preferred. Note that silanol groups may be generated by adding water to the obtained polysilane.

  The content of polysilane (C) in the aromatic polycarbonate resin composition of the present invention is 0.1 parts by mass or more, preferably 0.2 parts by mass or more, with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Preferably it is 0.3 mass part or more, 5 mass parts or less, Preferably it is 4 mass parts or less, More preferably, it is 3 mass parts or less. If the content of polysilane (C) is too small, the resulting flame retardant property of the aromatic polycarbonate resin composition may be insufficient. A decrease in mechanical strength may occur.

[Ultraviolet absorber (D)]
The aromatic polycarbonate resin composition of the present invention comprises a benzotriazole ultraviolet absorber (D-1) as a UV absorber (D) and a non-benzotriazole UV having a maximum absorbance (λmax) at a wavelength of 260 to 340 nm. Contains two types of UV absorbers together with the absorber (D-2).

  In the aromatic polycarbonate resin composition of the present invention, the absorption wavelength dispersion effect obtained by using a benzotriazole-based UV absorber (D-1) and a non-benzotriazole-based UV absorber (D-2) having specific light absorption characteristics in combination. In addition to expressing the effect of improving weather resistance and initial color tone in a well-balanced manner, by adding these to a system in which polysilane (C) coexists, heat discoloration can be further improved, and the color tone can be stabilized over the initial and long term. The flame-retardant aromatic polycarbonate resin composition excellent in property can be provided.

  Examples of the benzotriazole-based ultraviolet absorber (D-1) used in the present invention include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole and 2- (2-hydroxy-3,5-di-). -Tert-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (3,5-di-tert-octyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) -2H -Benzotriazole, 2- (3-lauryl-5-methyl-2-hydroxyphenyl) -2H-benzotriazole 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro -2H-benzotriazole, 2- (3,5-bis (1-methyl-1-phenylethyl) -2-hydroxyphenyl) -2H-benzotriazole, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-methylphenyl) methane, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) methane, Bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-cumylphenyl) methane, bis (3- (2H-benzotriazole-2) Yl) -2-hydroxy-5-octylphenyl) methane, 1,1-bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-methylphenyl) octane, 1,1-bis ( 3- (2H-5-chlorobenzotriazol-2-yl) -2-hydroxy-5-methylphenyl) octane, 1,2-ethanediylbis (3- (2H-benzotriazol-2-yl) -2-hydroxybenzoate ), 1,12-dodecanediylbis (3- (2H-benzotriazol-2-yl) -4-hydroxybenzoate), 1,3-cyclohexanediylbis (3- (5-chloro-2H-benzotriazole-2) -Yl) -2-hydroxybenzoate), 1,4-butanediylbis (3- (2H-benzotriazol-2-yl)- 4-hydroxy-5-methylphenylethanoate), 3,6-dioxa-1,8-octanediylbis (3- (5-methoxy-2H-benzotriazol-2-yl) -4-hydroxyphenylethanoate) 1,6-hexanediylbis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-tert-butylphenyl) propionate), p-xylenediylbis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl) propionate), bis (3- (2H-benzotriazol-2-yl) -4-hydroxytoluyl) malonate, bis (2- (3- (2H -Benzotriazol-2-yl) -4-hydroxy-5-octylphenyl) ethyl) terephthalate, bis (3- ( H-benzotriazol-2-yl) -4-hydroxy-5-propyltoluyl) octadioate, 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-methylphenol, 2- (2H -Benzotriazol-2-yl) -6-phthalimidoethyl-4-methylphenol, 2- (2H-benzotriazol-2-yl) -6-phthalimidooctyl-4-methylphenol, 2- (2H-benzotriazole- 2-yl) -6-phthalimidomethyl-4-tert-butylphenol, 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-cumylphenol, 2- (2H-benzotriazole-2- Yl) -4,6-bis (phthalimidomethyl) phenol and the like. In, 2- (2-hydroxy -5-tert-octylphenyl) -2H- benzotriazole is preferred.

  These benzotriazole ultraviolet absorbers (D-1) may be used alone or in combination of two or more in any combination and ratio.

  On the other hand, the non-benzotriazole ultraviolet absorber (D-2) having a maximum absorbance (λmax) at a wavelength of 260 to 340 nm has an absorbance in the wavelength range of 350 to 400 nm, which is 10% of the maximum absorbance at a wavelength of 260 to 340 nm. In the following, since it has almost no absorption in the visible light region, it has a characteristic that initial coloring is small even when blended with an aromatic polycarbonate resin.

  As the non-benzotriazole ultraviolet absorber (D-2) used in the present invention, a malonic ester ultraviolet absorber is preferable. As the malonic acid ester UV absorber, any conventionally known malonic acid esters can be used. Among them, 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters are preferable.

  As the above-mentioned 2- (1-arylalkylidene) malonic acid esters, those represented by the following general formula (4) are particularly preferable.

(In Formula (4), Q represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkenyl group having 2 to 10 carbon atoms, which may have a substituent, and R ¹¹ and R < ¹² > represents a C1-C6 alkyl group each independently.)

In general formula (4), Q is preferably a hydrogen atom, an alkyl group, an alkoxy group or an alkenyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The alkyl group in Q or the alkyl group in the alkoxy group may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group. Group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and the like. Moreover, as an alkenyl group, what has an ester group as a substituent is preferable, The carbon number is 3-10 normally including the carbon number in a substituent, Preferably it is 4-8.
As the malonic acid ester-based ultraviolet absorber, those which are 2- (alkylidene) malonic acid esters in which Q itself is the malonic acid ester moiety of the above general formula (4) are preferable, and in particular, the general formula (4) Of these, those having the same malonic acid ester residue (especially those having a para-position thereof) are preferred.

In general formula (4), R ¹¹ and R ¹² are each preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group represented by R ¹¹ and R ¹² may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples include n-butyl group, i-butyl group, s-butyl group, t-butyl group. More preferably, R ¹¹ and R ¹² are each a methyl group.

  The molecular weight of the above-mentioned malonic ester UV absorber is usually 220 to 500, preferably 240 to 450. When the molecular weight is less than 220, the number of mold deposits increases, which may lead to poor appearance of the resulting molded product. On the contrary, when the molecular weight exceeds 500, the bleedability to the surface of the molded product is lowered, and the effect of improving weather resistance may be reduced.

  As a commercial item of the malonic acid ester ultraviolet absorber as described above, for example, products “PR-25” (maximum absorption wavelength: 308 nm), “B-CAP” (maximum absorption wavelength: 320 nm) manufactured by Clariant Japan Ltd. Etc.

  These non-benzotriazole ultraviolet absorbers (D-2) may be used alone or in combination of two or more in any combination and ratio.

  The content of the ultraviolet absorber (D) in the aromatic polycarbonate resin composition of the present invention is such that the benzotriazole-based ultraviolet absorber (D-1) and the non-benzotriazole-based ultraviolet are based on 100 parts by mass of the aromatic polycarbonate resin (A). The total amount of the absorbent (D-2) is 0.1 to 2 parts by mass, preferably 0.15 to 1 part by mass, and more preferably 0.15 to 0.8 part by mass. When the content of the ultraviolet absorber (D) is less than 0.1 parts by mass, the weather resistance of the aromatic polycarbonate resin composition of the present invention is insufficient, and when it exceeds 2 parts by mass, the initial coloration is easy. More mold deposits.

  In the aromatic polycarbonate resin composition of the present invention, in order to effectively obtain an excellent effect by using a benzotriazole-based UV absorber (D-1) and a non-benzotriazole-based UV absorber (D-2) in combination. The content ratio of the benzotriazole-based ultraviolet absorber (D-1) and the non-benzotriazole-based ultraviolet absorber (D-2) is (D-1) :( D-2) = 40: 60 to 90 in mass ratio. : 10 is preferable. When the content ratio of the benzotriazole ultraviolet absorber (D-1) is less than the above range, the weather resistance of the resulting aromatic polycarbonate resin composition is insufficient, and when it is more than the above range, initial coloration is likely to occur. Sometimes.

  In the present invention, as described above, in the aromatic polycarbonate resin composition containing polysilane (C), the benzotriazole-based UV absorber (D-1) and the non-benzotriazole-based UV absorber (D-2) The effect of improving the weather resistance and heat discoloration by blending can be effectively exhibited. In order to enhance the excellent effect of the combination of this polysilane (C) with the benzotriazole-based UV absorber (D-1) and the non-benzotriazole-based UV absorber (D-2), the aromatic polycarbonate resin composition of the present invention is used. The polysilane (C) is 0.2 to 20 times by mass with respect to the total amount of the benzotriazole-based UV absorber (D-1) and the non-benzotriazole-based UV absorber (D-2) contained in the product, particularly It is preferable to use it so that it may become 0.5-10 mass times.

[Other ingredients]
The aromatic polycarbonate resin composition of the present invention may contain other components in addition to those described above as needed, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than the aromatic polycarbonate resin (A), various resin additives, and the like. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

<Other resins>
Examples of other resins other than the aromatic polycarbonate resin (A) include the following.
Thermoplastic polyester resins such as polycarbonate resin (PC) other than aromatic polycarbonate resin, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin (PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin);
Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin;
Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethacrylate resin (PMMA resin);
1 type of other resin may be contained and 2 or more types may be contained by arbitrary combinations and ratios.

<Resin additive>
Examples of the resin additive include heat stabilizers, antioxidants, mold release agents, inorganic fillers, other than the benzotriazole-based ultraviolet absorber (D-1) and non-benzotriazole-based ultraviolet absorber (D-2). UV absorbers, dyes and pigments (pigments such as carbon black and titanium oxide, dyes such as bluing agents), flame retardants, flame retardant aids, anti-dripping agents, antistatic agents, impact resistance improvers, anti-fogging agents , Lubricants, antiblocking agents, fluidity improvers, plasticizers, compatibilizers, dispersants, antibacterial agents and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

  Hereinafter, the example of an additive suitable for the aromatic polycarbonate resin composition of this invention is demonstrated concretely.

(Heat stabilizer)
Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Among these, the organic phosphate compound represented by the following general formula (5A) and / or the organic phosphite compound represented by the following general formula (5B) are preferable.

In the general formula (5A), R ²⁰ represents an alkyl group or an aryl group. Among them, R ²⁰ is usually an alkyl group having 1 or more, preferably 2 or more, and usually 30 or less, preferably 25 or less, or an aryl group having usually 6 or more and usually 30 or less carbon atoms. More preferably, R ²⁰ is preferably an alkyl group rather than an aryl group. In the case where R ²⁰ is present 2 or more, may be different even R ²⁰ together are each identical.
In general formula (5A), k is usually 0 or more, preferably 1 or more, and usually represents an integer of 2 or less.

In General Formula (5B), R ²¹ represents an alkyl group or an aryl group. In particular, R ²¹ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Two R ²¹ may be the same or different.

Preferred specific examples of the organic phosphite compound represented by the general formula (5B) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and the like.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  When the aromatic polycarbonate resin composition of the present invention contains a heat stabilizer, the content of the heat stabilizer is usually 0.001 to 1 part by mass, preferably 100 parts by mass of the aromatic polycarbonate resin (A). Is 0.01 to 0.7 parts by mass, more preferably 0.03 to 0.5 parts by mass. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

(Antioxidant)
Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4,6- Lis (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5- Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphosphinic acid tetrakis (2, 4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2 4,8,10-tetraoxaspiro (5,5) undecane and the like.

  When the aromatic polycarbonate resin composition of the present invention contains an antioxidant, the content of the antioxidant is usually 0.01 to 1 part by mass, preferably 100 parts by mass of the aromatic polycarbonate resin (A). Is 0.02 to 0.8 parts by mass, more preferably 0.02 to 0.5 parts by mass. If there are too few antioxidants, the antioxidant effect may become inadequate, and if there are too many antioxidants, an effect may reach | attain and it may become economical.

(Release agent)
Examples of the release agent include olefin wax, olefin wax containing carboxyl group and / or carboxylic anhydride group, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax, etc. Is mentioned.

  As the olefin wax, polyethylene wax and / or 1-alkene polymer is particularly preferable. As the polyethylene wax, those generally known at present can be used, and those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, those obtained by separating and purifying low molecular weight components from polyethylene polymer, and the like can be mentioned. As the 1-alkene polymer, a polymer obtained by polymerizing 1-alkene having 5 to 40 carbon atoms can be used. The molecular weight and the degree of branching of the olefin wax are not particularly limited, but the molecular weight is usually 1,000 or more as the number average molecular weight.

  The olefin wax containing a carboxyl group and / or a carboxylic acid anhydride group is a compound containing a carboxyl group and / or a carboxylic acid anhydride group, preferably maleic acid and / or olefin wax, by post-treatment. Those modified by post-treatment with maleic anhydride. In addition, a compound containing a carboxyl group and / or a carboxylic anhydride group that can be copolymerized with raw material monomers when polymerizing or copolymerizing ethylene and / or 1-alkene, preferably maleic acid and / or maleic anhydride Can be copolymerized. Such a copolymer is preferable because it contains a carboxyl group and / or a carboxylic anhydride group in a high concentration and stably. The carboxyl group or carboxylic anhydride group may be bonded to any part of the olefin wax. The concentration is not particularly limited, but is usually 0.1 to 6 meq / g per gram of olefin wax. Examples of commercially available olefin-based olefin waxes containing a carboxyl group and / or a carboxylic acid anhydride group include the product “Diacarna-PA30” manufactured by Mitsubishi Chemical Corporation. Examples of types of products include Mitsui Petrochemical's products “2203A” and “1105A”. These may be used as a mixture of two or more.

  If an olefinic wax containing a carboxyl group and / or a carboxylic anhydride group is added when an inorganic filler is blended in the aromatic polycarbonate resin composition of the present invention, release from the mold during melt molding The effect of suppressing the impact strength reduction due to the blending of the inorganic filler is expressed not only for further improving the property, but a more preferable result is obtained.

  The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Specific examples of these include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol mono Examples thereof include stearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Among these, stearyl stearate, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferable.

  When the aromatic polycarbonate resin composition of the present invention contains a release agent, the content of the release agent is usually 0.01 to 5 parts by mass, preferably 100 parts by mass of the aromatic polycarbonate resin (A). Is 0.02 to 3 parts by mass, more preferably 0.03 to 2 parts by mass. If the amount of the release agent is too small, the effect of improving the mold releasability may be insufficient, and if the amount of the release agent is too large, problems such as mold contamination will occur.

(Inorganic filler)
Inorganic fillers include talc, mica, glass flakes, glass beads, calcium carbonate, titanium oxide and other plate-like or granular inorganic fillers, glass fibers, glass milled fibers, wollastonite, carbon fibers, metal-based conductive materials. Fibrous fillers such as conductive fibers can be used.

  When the aromatic polycarbonate resin composition of the present invention contains an inorganic filler, the content of the inorganic filler is usually 1 to 100 parts by mass, preferably 3 with respect to 100 parts by mass of the aromatic polycarbonate resin (A). -70 mass parts. When there are too few inorganic fillers, the improvement effect of rigidity etc. by having mix | blended the inorganic filler can fully be acquired, and when too large, fluidity | liquidity and a moldability will be impaired.

  The inorganic filler may be surface-treated with a silane coupling agent or the like. By this surface treatment, the decomposition of the aromatic polycarbonate resin is suppressed, and the moisture heat resistance is improved.

(Antistatic agent)
Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium salt of dodecylbenzenesulfonate, sodium alkyl sulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like. It is done. The blending amount of the antistatic agent is appropriately selected within a range not impairing the object of the present invention.

[Method for producing aromatic polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the aromatic polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include the aromatic polycarbonate resin (A), organic sulfonic acid metal salt (B), polysilane (C), ultraviolet absorber (D) (benzotriazole-based ultraviolet absorber (D-1) according to the present invention. And a non-benzotriazole ultraviolet absorber (D-2)), and other components to be blended as necessary, for example, using various mixers such as a tumbler and a Henschel mixer, Examples thereof include a melt kneading method using a mixer such as a roll, a brabender, a single screw kneading extruder, a twin screw kneading extruder, or a kneader.

Also, for example, without mixing each component in advance, or only a part of the components are mixed in advance, and fed to an extruder using a feeder, and melt-kneaded, the aromatic polycarbonate resin composition of the present invention It can also be manufactured.
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The aromatic polycarbonate resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

[Aromatic polycarbonate resin molding]
The aromatic polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a molded body (aromatic polycarbonate resin molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of the molded body include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, and home appliances, and is particularly suitable for use in parts of electrical and electronic equipment.

  Examples of the electric and electronic devices include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, and mobile phones. Battery pack, recording medium drive and reader, mouse, numeric keypad, CD player, MD player, portable radio / audio player, and the like.

  The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the polycarbonate resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Can be mentioned. A molding method using a hot runner method can also be used.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

  The components used in Examples and Comparative Examples are as follows.

Aromatic polycarbonate resin (a-1): Bisphenol A type aromatic polycarbonate resin obtained by the melt ester method, viscosity average molecular weight 27000, structural viscosity index 1.4
Aromatic polycarbonate resin (a-2): Bisphenol A type aromatic polycarbonate resin obtained by interfacial polymerization, “Iupilon (registered trademark) E-2000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 27000, Structural viscosity index 1.1

Organic sulfonic acid metal salt (b-1): Potassium perfluorobutanesulfonate, “F-114P” manufactured by Dainippon Ink Co., Ltd., molecular weight 338
Organic sulfonic acid metal salt (b-2): sodium perfluoroethanesulfonate, “EF-23” manufactured by Mitsubishi Materials Corporation, molecular weight 222

Polysilane (c-1): Cyclic polydiphenylsilane (decaphenylcyclopentasilane), “Ogsol SI-30-10” manufactured by Osaka Gas Chemical Company, polystyrene equivalent molecular weight (catalog value) 600
Cyclic siloxane (x-1): C ₄₈ H ₄₀ O ₄ Si ₄ , “LS-8980” manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 793

Benzotriazole-based ultraviolet absorber (d-1a): “Seesorb 709” manufactured by Sipro Kasei Co., Ltd., molecular weight 323, maximum absorption wavelength 341 nm
Benzotriazole ultraviolet absorber (d-1b): “LA-31” manufactured by ADEKA, molecular weight 659, maximum absorption wavelength 350 nm

  Non-benzotriazole UV absorber (malonic ester UV absorber) (d-2a): “PR-25” manufactured by Clariant Japan Co., Ltd., molecular weight 250, maximum absorption wavelength 308 nm, maximum absorbance in the wavelength range of 350 to 400 nm 10% or less of absorbance at an absorption wavelength of 308 nm

  Non-benzotriazole ultraviolet absorber (malonic acid ester ultraviolet absorber) (d-2b): “B-CAP” manufactured by Clariant Japan Co., Ltd., molecular weight 418, maximum absorption wavelength 320 nm, maximum absorbance in the wavelength range of 350 to 400 nm 10% or less of absorbance at an absorption wavelength of 320 nm

  Release agent (e-1): stearyl stearate, “Yunistar M9676” manufactured by NOF Corporation, molecular weight 536

  In addition, the structural formula of the used ultraviolet absorber is as follows.

[Production of resin pellets]
The components shown in Tables 2 and 3 were blended at the ratios shown in Tables 2 and 3, mixed for 20 minutes with a tumbler, and then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent, screw rotation speed 200 rpm The molten resin kneaded under conditions of a discharge rate of 15 kg / hour and a barrel temperature of 270 ° C., the molten resin extruded in a strand form is rapidly cooled in a water tank, and pelletized using a pelletizer to obtain pellets of an aromatic polycarbonate resin composition It was.

[Evaluation of initial YI (yellow index: yellowness)]
After the pellets of the aromatic polycarbonate resin composition were dried at 120 ° C. for 5 hours, the cylinder temperature was 300 ° C., the mold temperature was 80 ° C., and the molding cycle was 30 seconds using a J50-EP injection molding machine manufactured by Nippon Steel. The two-stage plate of 110 mm × 35 mm, thickness 2 mm and 3 mm was manufactured by injection molding under the conditions of With respect to this plate, YI (yellowness) at a thickness of 3 mm was measured with a color meter “SE-2000” manufactured by Nippon Denshoku Industries Co., Ltd.
This YI is preferably less than 3, and if it is 3 or more, the initial color tone is inferior.

[Evaluation of weather resistance]
Using the above-mentioned two-stage plate as a test piece, the test was conducted for 24 hours under the conditions of a black panel temperature of 63 ° C. and no rain using a weathering tester “Metalring Weather Meter M6T” manufactured by Suga Test Instruments Co., Ltd. The pieces were treated and the change in YI (ΔYI) before and after treatment was measured.
This ΔYI is preferably small, and if it is 10 or more, the weather resistance is poor.

[Evaluation of heat discoloration]
Using the above-mentioned two-stage plate as a test piece, using a thermostat “Perfect Oven PH-200” manufactured by ESPEC CORP. For 500 hours (heat resistance discoloration evaluation I) or 1000 hours (heat resistance discoloration) The test piece was heat-treated over evaluation II), and the change (ΔYI) in YI before and after the treatment was measured.
The ΔYI in the heat discoloration evaluation I is preferably small, and if it is 1 or more, the heat discoloration is poor.
Moreover, it is preferable that ΔYI in the heat discoloration evaluation II is small, and if it is 2.5 or more, the heat discoloration is poor.

[Evaluation of flame retardancy]
After the pellets of the aromatic polycarbonate resin composition were dried at 120 ° C. for 5 hours, the cylinder temperature was 260 ° C., the mold temperature was 80 ° C., and the molding cycle was 30 seconds using a J50-EP type injection molding machine manufactured by Nippon Steel. The test piece of length 125mm, width 13mm, and thickness 1.5mm was shape | molded on these conditions.
The obtained specimens were conditioned for 48 hours in a temperature-controlled room at 23 ° C and 50% humidity, and UL94 test (combustion test for plastic materials for equipment parts) established by US Underwriters Laboratories (UL). ) And evaluated. UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.

[Evaluation results]
The above evaluation results are shown in Tables 2 and 3 below.

[Discussion]
From the above results, the following can be understood.
In Comparative Example 3 containing an organic sulfonic acid metal salt but no polysilane and no ultraviolet absorber, the weather resistance, heat discoloration resistance and flame retardancy are poor.
In Comparative Example 1 in which only the benzotriazole ultraviolet absorber is added to the formulation of Comparative Example 3, the weather resistance and heat discoloration are improved, but the flame retardancy is not improved.
In Comparative Example 2 in which cyclic siloxane is further added to the formulation of Comparative Example 1, flame retardancy is improved, but heat discoloration is rather impaired.
In Comparative Example 4 in which polysilane is added to the formulation of Comparative Example 3, flame retardancy and heat discoloration are improved, but weather resistance is not improved.
In Comparative Examples 5 and 6 in which only the benzotriazole ultraviolet absorber is blended with respect to the blend of Comparative Example 4, the weather resistance is improved compared to Comparative Example 4, but the initial YI increases.
On the other hand, in Comparative Examples 7 and 8 in which only the non-benzotriazole ultraviolet absorber is blended with respect to the blend of Comparative Example 4, although the weather resistance is slightly improved, the heat discoloration resistance is impaired in Comparative Example 7. .
Even if polysilane, a benzotriazole-based ultraviolet absorber, and a non-benzotriazole-based ultraviolet absorber are blended, the flame retardancy is inferior in Comparative Example 9 in which no organic sulfonic acid metal salt is blended.

  On the other hand, in Examples 1-6 using all of organic sulfonic acid metal salt, polysilane, benzotriazole-based UV absorber and non-benzotriazole-based UV absorber, initial YI, weather resistance, heat discoloration and flame retardancy Good results are obtained in all of the sexes.

  Reference Example 1 contains an organic sulfonic acid metal salt, polysilane, a benzotriazole-based UV absorber and a non-benzotriazole-based UV absorber, and the structural viscosity index N of the aromatic polycarbonate resin is 1.2. Since the ratio of the above aromatic polycarbonate resin is small, the other properties are good, but the flame retardancy is poor.

Claims (8)

  For 100 parts by mass of the aromatic polycarbonate resin (A), 0.01 to 0.5 parts by mass of the organic sulfonic acid metal salt (B), 0.1 to 5 parts by mass of the polysilane (C), and an ultraviolet absorber (D ) As a total amount of benzotriazole ultraviolet absorber (D-1) and non-benzotriazole ultraviolet absorber (D-2) having a maximum absorbance (λmax) at a wavelength of 260 to 340 nm. An aromatic polycarbonate resin composition comprising 2 parts by mass.   The aromatic polycarbonate resin composition according to claim 1, wherein the non-benzotriazole ultraviolet absorber (D-2) is a malonic ester ultraviolet absorber.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the malonic acid ester UV absorber has a molecular weight of 220 to 500.   The content ratio of the benzotriazole-based ultraviolet absorber (D-1) and the non-benzotriazole-based ultraviolet absorber (D-2) is benzotriazole-based ultraviolet absorber (D-1) by mass ratio: non-benzotriazole-based ultraviolet absorber Agent (D-2) = 40: 60-90: 10 The aromatic polycarbonate resin composition according to any one of claims 1 to 3.   The aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the polysilane (C) is a cyclic polysilane.   The aromatic polycarbonate resin composition according to any one of claims 1 to 5, wherein the organic sulfonic acid metal salt (B) is an alkali metal salt of perfluoroalkanesulfonic acid.   The aromatic polycarbonate resin composition according to any one of claims 1 to 6, comprising 30% by mass or more of an aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more in the aromatic polycarbonate resin (A).   The aromatic polycarbonate resin molded object formed by shape | molding the aromatic polycarbonate resin composition of any one of Claims 1 thru | or 7.