JP2017088698A - Flame-retardant polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which is excellent in initial hue and color tone stability without impairing flame retardancy, optical characteristics, moist heat resistance, and the like.SOLUTION: The flame-retardant polycarbonate resin composition contains 0.01-5 pts.mass of a flame retardant (B), 0-1 pt.mass of a dripping inhibitor (C), and 0.01-1 pt.mass of a phosphite-based stabilizer (D) represented by formula (1) with respect to 100 pts.mass of a polycarbonate resin (A). (Rand Rare each independently a 2,4-di(substituted/unsubstituted phenylmethyl)-phenyl group.)SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a flame retardant polycarbonate resin composition and a molded article, and more particularly, a polycarbonate resin composition excellent in initial hue and color tone stability without impairing flame retardancy, optical characteristics, wet heat resistance, and the like, and a molded article thereof. About.

Polycarbonate resin is a highly functional resin with excellent physical properties such as impact resistance, heat resistance, weather resistance, and flame retardancy, and high light transmittance. Taking advantage of its properties, for example, automobiles, electrical and electronic equipment, houses It is widely used as a component manufacturing material in lighting equipment, optical applications and other industrial fields.
In particular, taking advantage of its excellent optical properties and flame retardancy, LED light sources have recently been used as members for lighting equipment and optical equipment, which are becoming mainstream.

  In particular, lighting covers, lighting signs, screens, various displays, display covers and lenses using LEDs as light sources have the effect of spreading the illumination light by imparting light diffusivity, and reduce the illumination efficiency. It is required to maintain high light transmittance so as not to occur. In addition, since the office and home lighting members require high flame retardancy, polycarbonate resins containing various flame retardants and diffusing agents are used.

In addition, for materials such as lighting equipment and optical equipment, materials with excellent color stability such as excellent initial hue and less discoloration under the usage environment are required. Polycarbonate resins containing flame retardants In many cases (for example, Patent Document 1-2), sufficient color tone stability cannot be obtained.
In addition, in order to improve the initial hue of the polycarbonate resin, a bluing dye is generally added, but there is a problem in that the light transmittance is lowered when the dye is added.

JP2015-113432A JP 2014-125499 A

  An object of the present invention is to provide a polycarbonate resin composition excellent in initial hue and color tone stability without impairing flame retardancy, optical characteristics, wet heat resistance, and the like.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have added flame retardant, optical characteristics, and heat and humidity resistance by adding a specific diphosphite stabilizer to a polycarbonate resin containing a flame retardant. It was found that a resin composition excellent in initial hue and color tone stability can be provided without impairing the above.
The present invention provides the following flame retardant polycarbonate resin composition and molded article.

[1] For 100 parts by mass of the polycarbonate resin (A), 0.01 to 5 parts by mass of the flame retardant (B), 0 to 1 part by mass of the anti-dripping agent (C), and a phosphine represented by the following general formula (1) A flame retardant polycarbonate resin composition comprising 0.01 to 1 part by mass of a phyto-based stabilizer (D).
(In general formula (1), R ¹ and R ² are each independently an aryl group represented by the following general formula (2).)
(In the general formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are And each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group or an aralkyl group.)

[2] The flame-retardant polycarbonate resin composition according to the above [1], wherein 20 to 100% by mass of the polycarbonate resin (A) is a polycarbonate resin having a branched structure.
[3] The flame-retardant polycarbonate resin composition according to the above [2], wherein the polycarbonate resin having a branched structure is a polycarbonate resin by blending a melting method polycarbonate resin and / or a branching agent.
[4] Further, any one of the above [1] to [3] containing 0.01 to 1 part by mass of another stabilizer different from the stabilizer (D) with respect to 100 parts by mass of the polycarbonate resin (A). The flame-retardant polycarbonate resin composition according to claim 1.
[5] The flame-retardant polycarbonate resin composition according to any one of [1] to [4], further comprising an ultraviolet absorber (E) and / or a fluorescent brightener (F).
[6] Any of [1] to [5] above, wherein the dye (G) having a maximum absorption wavelength in the range of 520 to 650 nm is not contained or the amount thereof is 1 ppm or less in the resin composition. The flame-retardant polycarbonate resin composition described in 1.
[7] The flame-retardant polycarbonate resin composition according to any one of the above [1] to [6], which is used for lighting parts or optical parts.
[8] A molded article of the aromatic polycarbonate resin composition according to any one of [1] to [7].
[9] The molded product according to [8], which is a lighting component or an optical component.
[10] The molded article according to the above [9], which is an illumination part or an optical part using an LED as a light source.

  The flame retardant polycarbonate resin composition of the present invention is excellent in flame retardancy, optical properties, moisture and heat resistance, etc., and excellent in initial hue and color tone stability.

  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

The flame-retardant polycarbonate resin composition of the present invention is composed of 0.01 to 5 parts by mass of flame retardant (B), 0 to 1 part by mass of anti-dripping agent (C) and 100% by mass with respect to 100 parts by mass of polycarbonate resin (A). It contains 0.01 to 1 part by mass of a phosphite stabilizer (D) represented by the formula (1).
Hereinafter, each component, a molded body, a molding method thereof, and the like constituting the flame-retardant polycarbonate resin composition of the present invention will be described in detail.

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

  The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C (═O) —] —. In the formula, X is generally a hydrocarbon, but for imparting various properties, X into which a hetero atom or a hetero bond is introduced may be used.

  The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

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

  Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:

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 (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -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,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-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-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

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

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

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

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (especially from the viewpoint of impact resistance and heat resistance). That is, 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.

  Among the monomers used as the raw material for the 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

-Manufacturing method of polycarbonate resin The manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melting 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 described in detail.

-Interfacial polymerization method First, the case where a polycarbonate resin is manufactured by the interfacial polymerization method will be described.
In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a 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; It is done. 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 which sodium hydroxide and water Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and it 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 bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 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. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. 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 phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropenyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic 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 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 a resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. 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 between the reaction (phosgenation) of the dihydroxy compound and phosgene and 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).

-Melting method Next, the case where a polycarbonate resin is manufactured by a melting method will be described.
The melting method is also referred to as a melt transesterification method. For example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound 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. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired 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 dihydroxy compound, and above all, 1.01 mol or more is used. It 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 can be adjusted to a suitable range.

  In the 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, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the 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 a polycarbonate resin by the melting method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, 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 melting 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. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the polycarbonate resin and the like, the melt polycondensation reaction is preferably carried out continuously.

  In the melting 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, 1 type may be used for a catalyst deactivator and it 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 or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

In the present invention, the polycarbonate resin (A) is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, further 40 to 100% by mass, and particularly preferably 50 to 100% by mass of the polycarbonate resin (A). Is preferably a polycarbonate resin having a branched structure. As the polycarbonate resin having a branched structure, the above-described melt-processed polycarbonate resin and / or polycarbonate resin containing a branching agent is preferable.
A melt-processed polycarbonate resin tends to generate a branched structural unit as a side reaction.

  A polycarbonate resin containing a branching agent can be produced by a method of blending a branching agent when it is produced by the interface method or the melting method according to a conventional method. As the branching agent, a trifunctional or higher polyfunctional compound is preferably used.

Examples of the trifunctional or higher polyfunctional compound include 1,3,5-trihydroxybenzene, 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 (4- Polyhydroxy compounds such as hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane;
3,3-bis (4-hydroxyaryl) oxyindole (that is, isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred.

Such a polyfunctional compound may be used as a part of the dihydroxy compound, and the amount used is preferably 0.01 to 10 mol%, more preferably 0.1 to 3 mol, based on the hydroxy compound. %, More preferably 0.1 to 2 mol%.
In addition, 1 type may be used for a polyfunctional compound and it may use 2 or more types together by arbitrary combinations and a ratio.

The molecular weight of the polycarbonate resin (A) may be appropriately selected and determined, but is preferably a viscosity average molecular weight [Mv] converted from the solution viscosity, preferably 15,000 or more, more preferably 19,000 or more, and still more preferably. 21,000 or more, particularly 23,000 or more, preferably 36,000 or less, more preferably 34,000 or less, further preferably 32,000 or less, particularly preferably 30,000 or less, most preferably 29,000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is less than the upper limit of the above range, the fluidity of the polycarbonate resin composition of the present invention can be suppressed and improved, and the molding processability can be improved and the molding process can be easily performed.
The polycarbonate resin (A) may be used by mixing two or more kinds of polycarbonate resins having different viscosity average molecular weights. Moreover, when adjusting the viscosity average molecular weight of a polycarbonate resin (A) to the above-mentioned suitable range, it is also preferable to mix and adjust the polycarbonate resin whose Mv is outside the said suitable range.

In the present invention, the viscosity average molecular weight [Mv] of the polycarbonate resin is determined by using methylene chloride as a solvent and determining the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, It means a value calculated from Schnell's viscosity equation, that is, 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).

  The terminal hydroxyl group concentration of the polycarbonate resin 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. Thereby, the residence heat stability and color tone of polycarbonate resin can be improved more. Further, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly in a polycarbonate resin produced by a melting method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a resin composition can be improved more.

  In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a 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, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin).
However, the regenerated polycarbonate resin is preferably 80% by mass or less of the polycarbonate resin, and more preferably 50% by mass or less. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[Flame Retardant (B)]
The flame retardant polycarbonate resin composition of the present invention is 0.01 to 5 parts by mass, preferably 3.5 parts by mass or less, more preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). 0.5 parts by mass or less, more preferably 0.03 parts by mass or more.
Examples of the flame retardant (B) include metal salt flame retardants, siloxane flame retardants, phosphorus flame retardants, boron flame retardants, nitrogen flame retardants, halogen flame retardants, and the like in the present invention. Organometallic salt flame retardants and organosiloxane flame retardants are preferred.

[Organic metal salt flame retardant]
As the organic metal salt compound, an organic sulfonic acid metal salt is particularly preferable.
The metal of the metal salt compound is preferably an alkali metal or an alkaline earth metal, and alkali such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc. Metals: Alkaline earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and the like can be mentioned. Of these, sodium, potassium, and cesium are particularly preferable.

  Examples of organic sulfonic acid metal salts include organic sulfonic acid lithium salt, organic sulfonic acid sodium salt, organic sulfonic acid potassium salt, organic sulfonic acid rubidium salt, organic sulfonic acid cesium salt, organic sulfonic acid magnesium salt, organic sulfonic acid Examples include calcium salts, organic sulphonic acid strontium salts, and organic sulfonic acid barium salts. Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium salt, organic sulfonic acid potassium salt, and organic sulfonic acid cesium salt are particularly preferable.

  Of the organic sulfonic acid metal salt compounds, preferred examples include metal salts of fluorine-containing aliphatic sulfonic acids or aromatic sulfonic acids. Specific examples of preferable ones include potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, cesium perfluorobutane sulfonate, and the like. Fluorine-containing aliphatic sulfonic acid alkali metal salt: magnesium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, barium perfluorobutane sulfonate, magnesium trifluoromethane sulfonate, calcium trifluoromethane sulfonate, barium trifluoromethane sulfonate A fluorine-containing aliphatic sulfonic acid metal salt of a fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule;

  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, calcium (branched) calcium dodecylbenzene sulfonate Etc.

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. The alkali metal salt is more preferable, and specifically, potassium perfluorobutanesulfonate is preferable.
In addition, 1 type may be used for a metal salt compound, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the organometallic salt flame retardant is 0.01 to 5 parts by mass, preferably 0.01 to 1 part by mass, and more preferably 0.001 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is 05 parts by mass or more, more preferably 0.5 parts by mass or less, further preferably 0.2 parts by mass or less, and particularly preferably 0.15 parts by mass or less.

[Organosiloxane flame retardant]
As the flame retardant (B) used in the present invention, an organosiloxane flame retardant is also preferable.
As the organosiloxane flame retardant, polyorganosiloxane is preferable. Especially, as polyorganosiloxane, what has aromatic groups, such as a phenyl group, in a molecule | numerator is preferable. Examples of such polyorganosiloxane include polydiphenylsiloxane, polymethylphenylsiloxane, polydimethyldiphenylsiloxane, and phenyl group-containing cyclic siloxane.

  Furthermore, the polyorganosiloxane may contain a functional group such as a silanol group, an epoxy group, an alkoxy group, a hydrosilyl (SiH) group, or a vinyl group in addition to the organic group described above in the molecule. By containing these special functional groups, the compatibility between the polyorganosiloxane and the polycarbonate resin may be improved, or the reactivity during combustion may be improved, thereby increasing the flame retardancy.

  The content of silanol groups in the polyorganosiloxane is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, and usually 10% by mass or less, preferably It is 9 mass% or less, More preferably, it is 8 mass% or less, Most preferably, it is 7.5 mass% or less. When the silanol group content is within the above range, a high flame retardant effect tends to be obtained, and when the silanol group content is too large, the thermal stability and wet heat stability of the polycarbonate resin composition are significantly reduced. there is a possibility.

  The polyorganosiloxane may contain an alkoxy group in addition to the hydroxyl group, but the amount is preferably 10% by mass or less. This is because if the alkoxy group exceeds 10% by mass, gelation is likely to occur, and the mechanical properties of the polycarbonate resin composition may be deteriorated.

  The average molecular weight (mass average molecular weight) of the polyorganosiloxane is not particularly limited and may be appropriately selected and used. Usually, 450 or more, preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 1, It is 700 or more, usually 300,000 or less, preferably 100,000 or less, more preferably 20,000 or less, and particularly preferably 15,000 or less. Those having a mass average molecular weight of less than the lower limit of the above range are difficult to produce, and the heat resistance of the polyorganosiloxane may be extremely reduced. Moreover, when the mass average molecular weight exceeds the upper limit of the above range, the dispersibility is poor or the flame retardancy tends to be reduced, and the mechanical properties of the polycarbonate resin composition tend to be lowered. The mass average molecular weight of the polyorganosiloxane is usually measured by GPC (gel permeation chromatograph).

  One type of organosiloxane flame retardant may be used alone, or two or more types may be used in combination.

  The properties of the organosiloxane flame retardant are not particularly limited and may be appropriately selected and used, such as solid and liquid. However, when it is liquid, the preferred viscosity is 25 ℃, usually 1 centistokes (cSt) or more, preferably 4 centistokes or more, and usually 500 centistokes or less, preferably 100 centistokes or less. It is.

The content of the organosiloxane flame retardant is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and the lower limit is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass. Part or more, particularly 0.4 part by weight or more is preferable. The upper limit is preferably 3 parts by mass or less, more preferably 1.5 parts by mass or less.
The organosiloxane flame retardant is preferably used in combination with an organic metal salt flame retardant. By using together, a flame retardance can be improved more.

[Anti-drip agent (C)]
The flame-retardant polycarbonate resin composition of the present invention contains 0 to 1 part by mass of the anti-dripping agent (C) with respect to 100 parts by mass of the polycarbonate resin (A).
The anti-dripping agent is preferably a fluoropolymer, and examples of the fluoropolymer include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having a fibril-forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J”, “Teflon (registered trademark) 6C” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Daikin Industries, Ltd. “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500H”, and the like are available. Furthermore, as commercially available products of aqueous dispersions of fluoroethylene resin, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon D” manufactured by Daikin Industries, Ltd. -1 "and the like.

Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like.
In addition, 1 type may contain fluoropolymer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the anti-dripping agent (C) is 0 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A), and when it is contained, it is preferably 0.001 part by mass or more, more preferably 0. 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, particularly preferably 0.0.03 parts by mass or more, preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass. Part or less, more preferably 0.1 part by weight or less, particularly preferably 0.05 part by weight or less. When the content of the anti-dripping agent (C) is less than 0.001 part by mass, the effect of improving the flame retardancy by the anti-dripping agent (C) is insufficient, and the content is the upper limit of the above range. In the case of exceeding, the appearance defect of the molded product obtained by molding the polycarbonate resin composition and the mechanical strength are liable to occur.

[Phosphite stabilizer (D)]
The flame-retardant polycarbonate resin composition of the present invention contains a phosphite stabilizer (D) represented by the following general formula (1).
(In general formula (1), R ¹ and R ² are each independently an aryl group represented by the following general formula (2).)

(In the general formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are And each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group or an aralkyl group.)

In the above formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and among them, a substituted or unsubstituted group. An alkyl group having 1 to 4 carbon atoms is preferred. R ⁷ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group or an aralkyl group, and among them, a hydrogen atom, substituted or unsubstituted The alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom is particularly preferable. As the compound represented by the general formula (1), for example, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, in which R ¹ and R ² are represented by the following formula (3), is particularly preferable. It is done.

In the present invention, it is most preferable to use a phosphite stabilizer in which R ¹ and R ² are the above formula (3) from the viewpoint of thermal stability, wet heat stability, and hue.

One type of phosphite stabilizer (D) may be contained, and two or more types may be mixed and contained.
The content of the phosphite stabilizer (D) is 0.01 to 1 part by weight, preferably 0.01 to 0.2 part by weight, more preferably 100 parts by weight of the polycarbonate resin (A). It is 0.01-0.1 mass part, More preferably, it is 0.01-0.05 mass part. If the amount is less than 0.01 parts by mass, the effect as a heat stabilizer is insufficient, the molecular weight at the time of molding and the hue are deteriorated, especially yellowing easily occurs at high temperature and high humidity, and 1 part by mass. If it exceeds the lower limit, the molecular weight and the hue are more likely to deteriorate.

  Moreover, the flame-retardant polycarbonate resin composition of this invention contains 0.01-1 mass part of other stabilizers different from the said stabilizer (D) with respect to 100 mass parts of polycarbonate resin (A). It is also preferable. As other stabilizers, phosphorus stabilizers other than the stabilizer (D) and hindered phenol stabilizers are preferable, and hindered phenol stabilizers are more preferable. By using the stabilizer (D) and a hindered phenol stabilizer in combination, the hue stability under various temperature and humidity conditions is improved, and a resin composition suitable for a member used in various environments. You can get things. 1-40 are preferable and, as for mass ratio of content of the hindered phenol-type stabilizer with respect to content of the said stabilizer (D), 2-20 are more preferable.

  Examples of the hindered phenol stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphoate, 3,3 ', 3 ", 5,5', 5" -hexa-te t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di- tert-Butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentyl) Eniru) ethyl] -4,6-di -tert- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such a phenol-based stabilizer include, for example, trade names (hereinafter the same) “Irganox 1010” and “Irganox 1076” manufactured by BASF, “ADEKA STAB AO-50” manufactured by ADEKA, “ Adekastab AO-60 "etc. are mentioned.
In addition, 1 type may contain hindered phenolic antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  As the phosphorus stabilizer other than the phosphite stabilizer (D), any known one can be used. Specific examples include phosphorous such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid. Oxoacids; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; of group 1 or 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate Examples of the phosphate include organic phosphate compounds, organic phosphite compounds (excluding the phosphite compound (D) of the general formula (1)), and organic phosphonite compounds.

  Examples of organic phosphite compounds other than the phosphite compound (D) of the general formula (1) include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris. (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, Examples include tristearyl phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

[Ultraviolet absorber (E)]
The flame retardant polycarbonate resin composition of the present invention preferably further contains an ultraviolet absorber (E).
Examples of the ultraviolet absorber (E) include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds And organic ultraviolet absorbers. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorbent, the transparency and mechanical properties of the flame retardant polycarbonate resin composition of the present invention are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy -5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable. Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Yakuhin Kagaku Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “TINUVIN P”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 327” manufactured by BASF ”,“ Tinuvin 328 ”and the like.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4,4′-dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorb 103 ", joint medicine “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 "," ADEKA STAB 1413 "manufactured by ADEKA," ADEKA STAB LA-51 "and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such a salicylate compound include, for example, “Seesorb 201” and “Seesorb” manufactured by Sipro Kasei Co., Ltd. 202 ”,“ Kemisorb 21 ”,“ Kemisorb 22 ”manufactured by Chemipro Kasei Co., Ltd., and the like.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Pharmaceutical Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35”, “Ubinur N-N-” manufactured by BASF 539 "and the like.

  Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Specific examples of such an oxalinide compound include “Sanduboa” manufactured by Clariant Corporation. VSU "etc. are mentioned.

  As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by BASF, and the like.

When the flame retardant polycarbonate resin composition of the present invention contains an ultraviolet absorber (E), its content is usually 0.05 parts by mass or more, preferably 0 with respect to 100 parts by mass of the polycarbonate resin (A). .1 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass or less. When the content of the ultraviolet absorber (E) is less than the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and the content of the ultraviolet absorber (E) is the upper limit of the above range. If it exceeds, mold deposits and the like may occur, which may cause mold contamination.
In addition, 1 type may contain ultraviolet absorber (E) and 2 or more types may contain it by arbitrary combinations and a ratio.

[Fluorescent brightener (F)]
The flame retardant polycarbonate resin composition of the present invention preferably further contains a fluorescent brightening agent (F).
As the fluorescent brightening agent (F), for example, benzoxazole series, stilbene series, benzimidazole series, naphthalimide series, rhodamine series, coumarin series, oxazine series, thiophene series, styrene biphenyl series, pyrazolone series and the like are conventionally known. Various fluorescent brighteners can be used. In particular, a white fluorescent whitening agent selected from benzoxazole-based compounds and coumarin-based compounds having a molecular weight of 300 to 1,000 is preferable from the viewpoint of thermal stability. Also, for example, distyrylbiphenyl blue fluorescent light-emitting agent, arylethynylbenzene blue fluorescent light-emitting agent, quinkipyridine-based fluorescent light-emitting agent, sexiphenyl-based blue fluorescent light-emitting agent, dimesitylborylanthracene-based fluorescent light-emitting agent, quinacridone-based fluorescent light emission White organic light emitters and blue organic light emitters selected from agents and the like can also be used as compounds exhibiting a fluorescent whitening effect.

  0.0001-0.1 mass part is preferable with respect to 100 mass parts of polycarbonate resin (A), and, as for content of a fluorescent whitening agent (F), 0.001-0.05 mass part is more preferable.

  Specific examples of the benzoxazole-based compound as the optical brightener include 4- (benzoxazol-2-yl) -4 ′-(5-methylbenzoxazol-2-yl) stilbene, 4,4′-bis ( And benzoxazol-2-yl) stilbene, 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole), 4,4′-bis (benzoxazol-2-yl) furan and the like. Of these, stilbene benzoxazole compounds such as 4,4'-bis (benzoxazol-2-yl) stilbene are preferable.

Specific examples of the coumarin compound include 3-phenyl-7-aminocoumarin and 3-phenyl-7- (imino-1 ′, 3 ′, 5′-triazine-2′-diethylamino-4′-chloro). -Coumarin, 3-phenyl-7- (imino-1 ', 3', 5'-triazine-2'-diethylamino-4'-methoxy) -coumarin, 3-phenyl-7-naphthotriazole coumarin, 4-methyl- Examples include 7-hydroxycoumarin. Of these, phenylallyltriazolyl coumarin compounds such as 3-phenyl-7-naphthotriazole coumarin are preferred.

[Dye (G)] The flame-retardant polycarbonate resin composition of the present invention is excellent in initial hue and color tone stability. Therefore, a blueing agent is often blended in order to improve the hue of the polycarbonate resin, but the resin composition of the present invention does not need or is blended with such a blueing agent. The content can be suppressed to a very small amount. Therefore, the flame-retardant polycarbonate resin composition of the present invention preferably does not contain the dye (G) having the maximum absorption wavelength in the range of 520 to 650 nm, or the amount is 1 ppm in the resin composition. The following is preferable.

The dye (G) can be used without any problem as long as it is used as a bluing agent in the polycarbonate resin composition. From the viewpoint of the absorption wavelength, the maximum absorption wavelength is in the range of 520 to 650 nm. Are preferred.

Examples of the dye (G) having a maximum absorption wavelength of 520 nm or more and 650 nm or less include, for example, a monoazo dye represented by the general name Solvent Violet 21, and a general name Solvent.
Examples include triarylmethane dyes represented by Blue 2, phthalocyanine dyes represented by the general name Solvent Blue 25, and anthraquinone dyes represented by the general name Solvent Violet 13. Among these, anthraquinone dyes are preferable.

As the anthraquinone dye, those having an anthraquinone structure in the molecular structure can be used.
Specific examples of preferable anthraquinone-based bluing agents include, for example, the general names Solvent Violet 13, Solvent Violet 14, Solvent Violet 31, Solvent Violet 33, Solvent Violet 36, Solvent Blue 45, SolVel Blue45, Solvent Blue94, SolVel Blue94, Solvent Blue94, .

[Other additives]
The flame-retardant polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include mold release agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, and antibacterial agents.

[Release agent]
The flame retardant polycarbonate resin composition of the present invention preferably contains a release agent.
Preferred examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, and aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Is mentioned.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  When using a mold release agent, it is 0.05-2 mass parts normally with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 0.1-1 mass part. If the content of the release agent is not less than the above lower limit value, the effect of improving the releasability can be sufficiently obtained, and if it is not more than the above upper limit value, degradation of hydrolysis resistance due to excessive mixing of the release agent, injection Problems such as mold contamination during molding can be prevented.

[Antistatic agent]
The flame-retardant polycarbonate resin composition of the present invention may contain an antistatic agent as long as the quality such as flame retardancy of the resin composition is not impaired. The antistatic agent is not particularly limited, but is preferably a sulfonic acid phosphonium salt represented by the following general formula (4).

(In General Formula (4), R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group, and may have a substituent, and R ^{2 to} R ⁵ are each independently a hydrogen atom or carbon. (It is an alkyl group or an aryl group of formulas 1 to 10, and these may be the same or different.)

R ¹ in the general formula (4) is an alkyl group having 1 to 40 carbon atoms or an aryl group, and an aryl group is preferable from the viewpoint of transparency, heat resistance, and compatibility with a polycarbonate resin. A group derived from an alkylbenzene or alkylnaphthalene ring substituted with an alkyl group of 1 to 34, preferably 5 to 20, particularly 10 to 15 is preferable. R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, preferably an alkyl having 2 to 8 carbon atoms, more preferably 3 to 6 carbon atoms. It is an alkyl group, and a butyl group is particularly preferable.

Specific examples of such phosphonium sulfonates include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate. , Tributylmethylphosphonium dibutylbenzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, trioctylmethylphosphonium diisopropylnaphthylsulfonate, and the like. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is preferred because it is compatible with polycarbonate and easily available.
These may be used alone or in combination of two or more.

  When the flame retardant polycarbonate resin composition of the present invention contains an antistatic agent, the content is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, it is 0.2-3.0 mass parts, More preferably, it is 0.3-2.0 mass parts, Most preferably, it is 0.5-1.8 mass parts. If the content of the antistatic agent is less than 0.1 parts by mass, the antistatic effect cannot be obtained. If the content exceeds 5.0 parts by mass, the flame retardancy and mechanical strength are reduced, and the surface of the molded product is silver or peeled. Is likely to cause poor appearance.

[Method for Producing Flame Retardant Polycarbonate Resin Composition]
There is no restriction | limiting in the manufacturing method of the flame-retardant polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples thereof include polycarbonate resin (A), flame retardant (B), anti-dripping agent (C) and phosphite stabilizer (D) according to the present invention, and other compounds blended as necessary. The ingredients are mixed in advance using various mixers such as a tumbler, Henschel mixer, and super mixer, and then mixed with a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. The method of melt-kneading is mentioned.

  Also, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and supplied to an extruder using a feeder and melt kneaded to produce the polycarbonate resin composition of the present invention. You can also.

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 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.

Examples of a method for melt-kneading after mixing each component in advance by the above method include a method using a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader and the like.
The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Polycarbonate resin molded product]
The flame-retardant polycarbonate resin composition of the present invention can be produced by molding pelletized pellets by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets.

Examples of molding methods include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating molds. Molding method used, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. A molding method using a hot runner method can also be used.
There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  Examples of the molded product of the flame-retardant polycarbonate resin composition of the present invention include various lighting parts or optical parts, such as various lighting covers, lighting signs, transmissive screens, various displays, light diffusion sheets for liquid crystal display devices, It can be suitably used for a light diffusion plate, various lenses, and the like.

Examples of lighting covers include fluorescent lamps and incandescent bulb covers and lamp shades, bathroom lights, chandeliers, stands, brackets, lanterns, ceiling lights, pendant lights, garage lights, eaves lights, gatepost lights, porch lights, and gardens. Covers for lights, entrance lights, step lights, stair lights, guide lights, security lights, downlights, base lights, electric signs, sign lights, etc., and covers for automotive lamps including automobiles, motorcycles, etc. Can be suitably used.
In particular, the flame-retardant polycarbonate resin composition of the present invention can be suitably used particularly for lighting parts and optical parts using LEDs as light sources.

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, unless otherwise specified, “part” means “part by mass” based on the mass standard, and “ppm” represents “mass ppm”.

The raw material components used in the examples and comparative examples are as shown in Table 1 below.

(Examples 1-27, Comparative Examples 1-8)
Each component shown in Table 1 was mixed for 20 minutes with a tumbler in the amounts (parts by mass or ppm) shown in the table below Table 3, and then a twin screw extruder manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. Supplied to TEX30XCT, kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 290 ° C., the molten resin composition extruded in a strand form is rapidly cooled in a water tank, and pelletized using a pelletizer A pellet of polycarbonate resin composition was obtained.

Measurement and evaluation methods used in Examples and Comparative Examples are as follows.
[Initial hue (YI)]
About each resin composition pellet obtained above, the injection molding machine “J50” manufactured by Nippon Steel Co., Ltd. was used, and injection molding was performed under conditions of a resin temperature of 280 ° C. and a mold temperature of 80 ° C., and a length of 90 mm and a width of A three-stage plate having a thickness of 50 mm and thicknesses of 1, 2, and 3 mm was obtained as a test piece.
A 1 mm thick portion of the test piece was measured with a spectral color difference meter “SE-6000” manufactured by Nippon Denshoku Industries Co., Ltd., with a C2 light source / 2-degree field of view, a reflection method, and an initial yellowness (“initial hue (YI)” )) Was measured.

[Total light transmittance (%)]
About 1 mm thickness part of the three-stage plate test piece obtained above, using Nippon Denshoku Industries Co., Ltd. haze meter “NDH-4000”, in accordance with ASTM-D1003, with D65 light source, 1 mm thickness of the test piece The total light transmittance (unit:%) was measured.

[Heat-resistant discoloration (ΔYI)]
The three-stage plate test piece was exposed in a hot air circulating dryer for 200 hours in an atmosphere at 120 ° C., and the yellowness was measured for a 1 mm thick part after the exposure, and the difference from the initial hue was measured as ΔYI. .

[Weather resistance (ΔYI)]
Three-stage plate specimens were measured using a sunshine weatherometer “SUN-HC-B” (carbon arc type) manufactured by Suga Test Instruments Co., Ltd., with a black panel temperature of 63 ° C., a humidity of 50% in the tank, and a rainfall cycle of 12 minutes / 60 minutes. After exposure, the yellowness of 1 mm thickness after exposure was measured, and the difference from the yellowness of the initial hue was measured as ΔYI.

[Moisture and heat resistance (ΔMv)]
Expose the three-stage plate specimen in a high temperature and humidity chamber at 80 ° C and 95% atmosphere for 100 hours, measure the viscosity average molecular weight (Mv) after exposure, and determine the difference from the viscosity average molecular weight before exposure. Measured as ΔMv.

[Evaluation of hue by visual inspection of plate]
The hue of the three-stage plate specimen was evaluated visually under the D65 light source according to the following criteria.
○: Hue good △: Slightly yellow ×: Clearly yellow

[Flame retardance (UL94 / 1.5mm)]
About each resin composition pellet obtained above, using an injection molding machine “SE100DU” manufactured by Sumitomo Heavy Industries, Ltd., injection molding was performed under the conditions of a resin temperature of 300 ° C. and a mold temperature of 80 ° C., a length of 127 mm, A molded piece having a width of 12.7 mm and a thickness of 1.5 mm was obtained as a test piece for UL test.
The obtained test specimen for UL test was conditioned for 48 hours in a high-temperature chamber at 23 ° C and 50% relative humidity, and the UL94 test (plastic for equipment parts) established by the US Underwriters Laboratories (UL). The test was carried out according to the material combustion test). UL94V is a method for evaluating flame retardancy from the afterflame time and drip properties after a burner flame is indirectly fired for 10 seconds on a test piece held vertically. V-0, V-1 and V-2 In order to have the flame retardancy, it is necessary to satisfy the criteria shown in Table 2 below.

  Here, the afterflame 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.

The obtained results are shown in Tables 3 to 6 below.

  The flame-retardant polycarbonate resin composition of the present invention is excellent in flame retardancy, optical characteristics, moisture and heat resistance, etc., and excellent in initial hue and color tone stability, and thus can be suitably used for various lighting parts or optical parts. , Its industrial applicability is very high.

Claims (10)

Phosphite-based stability represented by 0.01 to 5 parts by weight of flame retardant (B), 0 to 1 part by weight of anti-dripping agent (C) and the following general formula (1) with respect to 100 parts by weight of polycarbonate resin (A) A flame retardant polycarbonate resin composition comprising 0.01 to 1 part by mass of an agent (D).
(In general formula (1), R ¹ and R ² are each independently an aryl group represented by the following general formula (2).)
(In the general formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are And each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group or an aralkyl group.)   2. The flame-retardant polycarbonate resin composition according to claim 1, wherein 20 to 100 mass% of the polycarbonate resin (A) is a polycarbonate resin having a branched structure.   The flame-retardant polycarbonate resin composition according to claim 2, wherein the polycarbonate resin having a branched structure is a polycarbonate resin obtained by blending a melt polycarbonate resin and / or a branching agent.   Furthermore, 0.01-1 mass part of other stabilizers different from the said stabilizer (D) are contained with respect to 100 mass parts of polycarbonate resin (A). Flame retardant polycarbonate resin composition.   Furthermore, the flame-retardant polycarbonate resin composition of any one of Claims 1-4 containing a ultraviolet absorber (E) and / or a fluorescent whitening agent (F).   The difficulty according to any one of claims 1 to 5, wherein the dye (G) having a maximum absorption wavelength in the range of 520 to 650 nm is not contained, or even if contained, the amount thereof is 1 ppm or less in the resin composition. Flammable polycarbonate resin composition.   The flame-retardant polycarbonate resin composition according to claim 1, wherein the flame-retardant polycarbonate resin composition is used for lighting parts or optical parts.   A molded article of the aromatic polycarbonate resin composition according to any one of claims 1 to 7.   The molded article according to claim 8, which is an illumination part or an optical part.   The molded article according to claim 9, wherein the molded article is an illumination part or an optical part using an LED as a light source.