JP2012219177A - Polycarbonate resin composition and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin material excellent in flame retardancy, also in impact resistance, low temperature impact resistance, weatherability and wet heat stability and further in chemical resistance.SOLUTION: The polycarbonate resin composition comprises 100 pts.mass of a polycarbonate resin (A) having 22,000-30,000 viscosity-average molecular weight, 0.001-1 pt.mass of an organic sulfonic acid metal salt (B), 0.001-1 pt.mass of a fluoropolymer (C), 0.5-6 pts.mass of graft copolymer (D) prepared by graft polymerizing a (meth)acrylate ester compound with a diene-based rubber and having 160-240 nm average particle size, 0.01-0.5 pt.mass of a UV ray absorber (E), and 0.00001-5 pts.mass of at least one masking agent (F) selected from titanium oxide (F-1) or carbon black (F-2).

Description

  The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition that is excellent in flame retardancy, impact resistance, low temperature impact resistance, weather resistance, heat discoloration resistance, and also excellent in low mold contamination, and a molded body formed by molding the same. It is.

  Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. In particular, the flame-retardant polycarbonate resin composition is suitably used as a member of OA / information equipment such as computers, notebook computers, mobile phones, printers, and copying machines.

  As a means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant has been added to the polycarbonate resin. However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were.

As a technique for imparting flame retardancy to a thermoplastic resin without using a halogen compound, a technique using a phosphoric acid flame retardant has been actively studied (for example, see Patent Document 1). Polycarbonate resins containing flame retardants are widely used in various cases and battery packs.
However, if the amount of the phosphorus flame retardant is increased, the excellent heat resistance and excellent impact resistance inherent in the polycarbonate resin tend to be remarkably reduced. If an excessive amount of the phosphorus flame retardant is added, it is discarded. In some cases, phosphorus-based flame retardants may bleed out of the product and cause environmental pollution. In recent years, danger to humans has been pointed out.

  On the other hand, there is a growing need to use polycarbonate resin for products used outdoors, for example, battery packs used for power sources for driving electric bicycles, solar cell components, and various portable electronic device housings. However, the polycarbonate resin blended with the phosphorus-based flame retardant as described above has extremely poor wet heat stability, and is severely degraded when used outdoors or in humid environments. It had a fatal defect that the product life was shortened.

  Further, the polycarbonate resin has a defect in terms of weather resistance (light resistance) that causes discoloration and deterioration of physical properties due to long-term use. The conventional method of blending an ultraviolet absorber with a polycarbonate resin (see, for example, Patent Document 2 or 3) is still not sufficient in terms of the balance between weather resistance and flame retardancy, and is intended to increase impact resistance. (See, for example, Patent Document 4), however, impact resistance, low temperature impact resistance, weather resistance, wet heat stability, and chemical resistance are also insufficient. Is often a factor that reduces the weather discoloration described above. Thus, the present condition is that the polycarbonate resin material which can fully endure the use for outdoor use is not proposed until now.

  Under such circumstances, there has been a strong demand for the development of a polycarbonate resin material that has an excellent balance of flame retardancy, strength, weather resistance, heat discoloration, and the like, and that is particularly suitable for molded products for outdoor installation.

JP 59-202240 A JP-A-7-216206 Special Table 2003-534424 JP 2000-290487 A

  An object of the present invention is to provide a resin composition excellent in flame retardancy, impact resistance, low temperature impact resistance, weather resistance, heat discoloration resistance, and low mold contamination, and a resin molded product comprising the same. .

  The present inventors have developed a specific graft copolymer obtained by graft-polymerizing a specific polycarbonate resin with an organic sulfonic acid metal salt, a fluoropolymer, and a diene rubber with a (meth) acrylic acid ester compound, an ultraviolet absorber, and titanium oxide. Alternatively, the present inventors have found that a polycarbonate resin composition containing carbon black in a specific range is excellent in flame retardancy, impact resistance, low temperature impact resistance, weather resistance, and heat discoloration, and completed the present invention.

  That is, according to 1st invention of this invention, with respect to 100 mass parts of polycarbonate resin (A) whose viscosity average molecular weight [Mv] is 22,000-30,000, organosulfonic acid metal salt (B) 0.001. 1 to 1 part by mass, fluoropolymer (C) 0.001 to 1 part by mass, graft copolymer (D) having an average particle size of 160 to 240 nm obtained by graft polymerization of a (meth) acrylic ester compound to a diene rubber 0.5 to 6 parts by mass, 0.01 to 0.5 parts by mass of ultraviolet absorber (E), at least one concealing agent selected from titanium oxide (F-1) or carbon black (F-2) (F ) A polycarbonate resin composition characterized by containing 0.00001 to 5 parts by mass is provided.

  According to the second invention of the present invention, there is provided a polycarbonate resin composition characterized in that, in the first invention, the graft copolymer (D) has a sulfur content of 100 to 1,500 ppm. Is done.

  According to the third invention of the present invention, in the first or second invention, the organic sulfonic acid metal salt (B) is a fluorine-containing aliphatic sulfonic acid alkali metal salt. A composition is provided.

  According to a fourth aspect of the present invention, there is provided a polycarbonate resin composition according to any one of the first to third aspects, wherein the ultraviolet absorber (E) has a molecular weight of at least 500 g / mol. Provided.

  Moreover, according to the 5th invention of this invention, the molded object formed by shape | molding the polycarbonate resin composition of the invention in any one of 1-4 is provided.

  According to a sixth aspect of the present invention, there is provided the molded body according to the fifth aspect, wherein the molded body is a member for a secondary battery device.

  According to a seventh aspect of the present invention, there is provided the molded body according to the sixth aspect, which is a member for a battery device for an electric bicycle or an electric automobile.

  According to an eighth aspect of the present invention, there is provided the molded body according to the sixth or seventh aspect, which is a battery case for an electric bicycle or an electric automobile.

  According to a ninth aspect of the present invention, there is provided a molded body characterized in that in the fifth or sixth aspect, the member is a member for a secondary battery device for an outdoor installation storage battery.

  According to a tenth aspect of the present invention, in the fifth aspect, there is provided a molded body that is a member for a solar cell module.

  Further, according to an eleventh aspect of the present invention, in the fifth aspect, the portable device selected from the group consisting of a notebook computer, a PDA, a mobile phone, a portable audio player, a digital camera, an electronic book, an electronic dictionary, and a radio device. A molded body is provided which is a housing of an electronic device.

  The polycarbonate resin composition of the present invention is excellent in flame retardancy, impact resistance, low temperature impact resistance, weather resistance, heat discoloration resistance, and low mold contamination. For this reason, the molded product formed by molding the polycarbonate resin composition of the present invention is an OA equipment component that requires flame resistance, impact resistance, low temperature impact resistance, weather resistance, wet heat stability, chemical resistance, electronic It can be suitably used for electrical equipment parts, portable electronic equipment parts, automobile / bicycle equipment parts, industrial equipment parts, and the like.

[1. Summary of the Invention]
The polycarbonate resin composition of the present invention has a viscosity average molecular weight [Mv] of 22,000 to 30,000, relative to 100 parts by mass of the polycarbonate resin (A).
0.001 to 1 part by mass of organic sulfonic acid metal salt (B),
0.001-1 part by mass of fluoropolymer (C),
0.5 to 6 parts by mass of a graft copolymer (D) having an average particle size of 160 to 240 nm obtained by graft polymerization of a (meth) acrylic acid ester compound to a diene rubber,
UV absorber (E) 0.01 to 0.5 parts by mass,
It contains 0.00001 to 5 parts by mass of at least one concealing agent (F) selected from titanium oxide (F-1) or carbon black (F-2).

Hereinafter, the contents of the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is interpreted to be limited to such embodiments and specific examples. is not.
In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[2. Polycarbonate resin (A)]
-Molecular weight of polycarbonate resin (A) As for the molecular weight of polycarbonate resin (A), the viscosity average molecular weight [Mv] converted from solution viscosity needs to be in the range of 22,000-30,000. In the present invention, the molecular weight range is higher than the molecular weight that has been applied in such conventional injection molding applications. By setting the viscosity average molecular weight to 22,000 or more, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by setting the viscosity average molecular weight to 30,000 or less, the fluidity of the polycarbonate resin composition of the present invention is lowered. It is possible to improve the moldability and to improve the molding processability and to perform the molding process easily. The viscosity average molecular weight [Mv] is preferably 22,500 or more, preferably 28,000 or less, more preferably 27,000 or less.
Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

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 polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the following general formula (1). One type of polycarbonate resin may be used, or two or more types may be used in any combination and in any ratio.
In formula (1), X ¹ is generally a hydrocarbon group, but X ¹ into which a hetero atom or a hetero bond is introduced may be used for imparting various properties.

  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. Alternatively, 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 (4-hydroxy-3,5-dimethylphenyl) 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-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-hydroxyphenyl) butane,
2-bis (4-hydroxyphenyl) butane,
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,
2,2-bis (4-hydroxyphenyl) nonane,
10-bis (4-hydroxyphenyl) decane,
1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

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

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 and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

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

  Examples of the monomer that is a raw material for the aliphatic polycarbonate resin include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol Alkanediols such as

Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

Glycols such as 2,2'-oxydiethanol (ie, ethylene glycol), diethylene glycol, triethylene glycol, propylene glycol, spiroglycol, etc .;

1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  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

-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 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 First, the case where a polycarbonate resin is produced 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, 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 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 isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as 0-oxine benzoic 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 polycarbonate 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).

-Melt transesterification method Next, the case where a polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the 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, 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 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. 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 melt transesterification 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 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. 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 polycarbonate resin composition, 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 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 aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-Other matter regarding polycarbonate resin Although the terminal hydroxyl group density | concentration of polycarbonate resin is arbitrary and may be suitably selected and determined, it is 1,000 ppm or less normally, Preferably it is 800 ppm or less, More preferably, it is 600 ppm or less. Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the polycarbonate resin composition of this invention 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). 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 polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. 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.

[3. Organic sulfonic acid metal salt (B)]
An organic sulfonic acid metal salt (B) is used in the resin composition of the present invention.
The types of metals possessed by organic sulfonic acid metal salts include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); magnesium (Mg), calcium (Ca ), Alkaline earth metals such as strontium (Sr), barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Zinc (Zn), zirconium (Zr), molybdenum (Mo), etc. are mentioned. Among these, alkali metals or alkaline earth metals are preferable. Promotes the formation of a carbonized layer during the combustion of polycarbonate resin, further enhances flame retardancy, and maintains good properties such as impact resistance and other mechanical properties, heat resistance, and electrical properties of polycarbonate resin it can.
Of the alkali metals or alkaline earth metals, alkali metals are more preferred, sodium, potassium, cesium or lithium are more preferred, sodium, potassium and cesium are more preferred, and sodium and potassium are particularly preferred.

  Examples of preferred organic sulfonic acid metal salts (B) include organic sulfonic acid lithium (Li) salts, organic sulfonic acid sodium (Na) salts, organic sulfonic acid potassium (K) salts, and organic sulfonic acid rubidium (Rb) salts. , Organic sulfonic acid cesium (Cs) salt, organic sulfonic acid magnesium (Mg) salt, organic sulfonic acid calcium (Ca) salt, organic sulfonic acid strontium (Sr) salt, organic sulfonic acid barium (Ba) salt, and the like. . 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 (B), preferred are fluorine-containing aliphatic sulfonic acid metal salts, fluorine-containing aliphatic sulfonic acid imide metal salts, aromatic sulfonic acid metal salts, and aromatic sulfonamide. Metal salts are mentioned.

  Among them, specific examples of preferable ones include potassium nonafluorobutanesulfonate, lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, cesium nonafluorobutanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, Containing at least one C—F bond in the molecule, such as potassium trifluoromethanesulfonate, potassium pentafluoroethanesulfonate, potassium heptafluoropropanesulfonate, potassium decafluoro-4- (pentafluoroethyl) cyclohexanesulfonate; Alkali metal salts of fluoroaliphatic sulfonic acids;

  At least one C—F in the molecule, such as magnesium nonafluorobutanesulfonate, calcium nonafluorobutanesulfonate, barium nonafluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, barium trifluoromethanesulfonate, etc. An alkaline earth metal salt of a fluorine-containing aliphatic sulfonic acid having a bond;

  Disodium difluoromethane disulfonate, dipotassium difluoromethane disulfonate, sodium tetrafluoroethane disulfonate, dipotassium tetrafluoroethane disulfonate, dipotassium hexafluoropropane disulfonate, dipotassium hexafluoroisopropane disulfonate, disodium octafluorobutane disulfonate, A metal salt of a fluorinated aliphatic sulfonic acid, such as an alkali metal salt of a fluorinated aliphatic disulfonic acid having at least one C—F bond in the molecule, such as dipotassium octafluorobutanedisulfonate;

  Bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide sodium, In the molecule, such as potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane, etc. An alkali metal salt of a fluorine-containing aliphatic disulfonic imide having at least one C—F bond;

  Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorinated aliphatic sulfonimide having at least one C—F bond in the molecule; a metal salt of a fluorinated aliphatic sulfonic imide, such as

  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 Etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule;

  Magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) calcium dodecylbenzenesulfonate in the molecule An alkaline earth metal salt of an aromatic sulfonic acid having an aromatic group of: an aromatic sulfonic acid metal salt, etc.

  Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonamides such as alkali metal salts of aromatic sulfonamides having at least one aromatic group in the molecule, such as salts.

Among the above-mentioned examples, fluorine-containing aliphatic sulfonic acid metal salts are preferable. As the fluorine-containing aliphatic sulfonic acid metal salt, an alkali metal salt of a fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule is more preferable, and an alkali metal salt of perfluoroalkanesulfonic acid is particularly preferable. Specifically, potassium nonafluorobutanesulfonate is preferred.
As the aromatic sulfonic acid metal salt, an alkali metal salt of an aromatic sulfonic acid is more preferable, and an alkali of diphenyl sulfone-sulfonic acid such as dipotassium 3,3′-disulfonic acid dipotassium and diphenylsulfone-3-sulfonic acid potassium. Metal salts; sodium paratoluenesulfonate, and alkali metal salts of paratoluenesulfonic acid such as potassium paratoluenesulfonate and cesium paratoluenesulfonate are particularly preferable, and alkali metal salts of paratoluenesulfonic acid are more 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 average particle diameter of the organic sulfonic acid metal salt (B) is not particularly limited, and it is usually sufficient to use one in the range of 1 μm to 500 μm. In particular, transparency can be achieved by setting the average particle diameter to 20 to 200 μm. It is preferable because it tends to improve. By setting it within this range, it is considered that the dispersibility of the organic sulfonic acid metal salt in the polycarbonate resin is improved and the aggregation property is suppressed. From such a viewpoint, the average particle diameter is preferably 25 to 150 μm, more preferably 30 to 100 μm.
The average particle diameter was measured in the range of 0.1 to 10,000 μm using a Microtrac MT3300 laser diffraction scattering type particle size distribution measuring device manufactured by Nikkiso Co., Ltd. under a dispersion pressure of 200 kPa, and the cumulative frequency was 50%. Represents the volume average particle diameter (D50).

  Content of an organic sulfonic acid metal salt (B) is 0.001-1 mass part with respect to 100 mass parts of polycarbonate resin (A). The preferred lower limit is 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, particularly preferably 0.05 parts by mass or more, and the preferred upper limit is 0.75 parts by mass or less, more preferably 0.5 parts by mass. Part or less, particularly preferably 0.3 part by weight or less. If the content is too small, the flame retardancy of the obtained polycarbonate resin composition may be insufficient. On the other hand, if the content is too large, the thermal stability of the polycarbonate resin is deteriorated, and the appearance of the molded product is poor. There is a possibility that the mechanical strength is reduced.

[4. Fluoropolymer (C)]
The polycarbonate resin composition of the present invention contains 0.001 to 1 part by mass of the fluoropolymer (C) with respect to 100 parts by mass of the polycarbonate resin (A). One type of fluoropolymer (C) may be used, or two or more types may be used in any combination and in any ratio.

  Examples of the fluoropolymer (C) 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” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon F201L”, “Polyfluorocarbon” manufactured by Daikin Chemical Industries, Ltd. F103 "," Polyfluorocarbon FA500B "," Polyfluorocarbon FA500H "and the like. Further, commercially available products of aqueous dispersions of fluoroethylene resins include, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon D” manufactured by Daikin Chemical 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 (C) and 2 or more types may contain it by arbitrary combinations and a ratio.

The fluoropolymer (C) in the present invention preferably has a standard specific gravity value of 2.15 or more and 2.22 or less. When the standard specific gravity is less than 2.15, the combustion time is prolonged, the flame extinguishing property tends to be inferior, and the drip resistance, that is, the flame spread resistance tends to be lowered. Also, when the standard specific gravity exceeds 2.22, the drip resistance is lowered and the drawdown resistance is likely to be lowered. The standard specific gravity value is more preferably 2.16 to 2.21, and further preferably 2.17 to 2.20.
The standard specific gravity (also referred to as SSG) is a value measured by a water displacement method using a sample molded according to ASTM D4895.

  The fluoropolymer is produced by emulsion polymerization, and the standard specific gravity (SSG) can be adjusted by adjusting the polymerization conditions. For example, in the emulsion polymerization process of tetrafluoroethylene monomer, the polymerization initiator injection and It is possible by selecting the stop time and adjusting other polymerization conditions.

  The average particle size of the fluoropolymer (C) in the present invention is not particularly limited, but is preferably 300 to 1,000 μm. When the average particle size is less than 300 μm, the drip resistance of the polycarbonate resin composition of the present invention may be reduced. When the average particle size is more than 1,000 μm, the fluoropolymer is likely to aggregate, resulting in a molded product. In such a case, it is not preferable because it may cause appearance defects such as white spot foreign matter. From such a viewpoint, the average particle size of the fluoropolymer is more preferably 350 to 800 μm, further preferably 380 to 750 μm, and particularly preferably 400 to 700 μm.

  As described above, the content of the fluoropolymer (C) is 0.001 part by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), but preferably 0.01 part by mass or more. Preferably it is 0.05 parts by mass or more, particularly preferably 0.1 parts by mass or more, and the upper limit is 1 part by mass or less, preferably 0.75 parts by mass or less, more preferably 0.5 parts by mass or less. It is. When the content of the fluoropolymer (C) is less than or equal to the lower limit of the above range, the flame retardancy effect due to the anti-dripping agent becomes insufficient, and when the content exceeds the upper limit of the above range, the polycarbonate resin composition There is a possibility that the appearance defect or the mechanical strength of the molded product formed from the above will be deteriorated.

[5. Graft copolymer (D)]
The polycarbonate resin composition of the present invention contains a graft copolymer (D) having an average particle diameter of 160 to 240 nm obtained by graft polymerization of a (meth) acrylic acid ester compound to a diene rubber. By containing such a specific elastomer, the impact resistance of the polycarbonate resin composition can be improved. Conventionally, diene rubber has often been used as the elastomer, but the diene rubber is easily oxidatively deteriorated or discolored during molding. In the present invention, such a specific graft copolymer (D) Flame retardant polycarbonate resin excellent in impact resistance, low temperature impact resistance, weather resistance and wet heat stability when used in combination with the components (B) to (C) and components (E) to (F) described later Can be a material.

  The elastomer used in the present invention is a graft copolymer obtained by graft copolymerizing a diene rubber polymer with a (meth) acrylic acid ester compound copolymerizable therewith. As a manufacturing method of a graft copolymer, any manufacturing methods, such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, may be sufficient.

  The rubber component generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.

  Examples of the diene rubber in the graft copolymer used in the present invention include polybutadiene, (partially) hydrogenated polybutadiene, butadiene-styrene copolymer, (partially) hydrogenated polybutadiene-styrene copolymer, and butadiene-styrene block copolymer. One type that can be copolymerized with butadiene and butadiene, such as a polymer, (partially) hydrogenated polybutadiene-styrene block copolymer, butadiene-acrylonitrile copolymer, acrylic rubber copolymer based on butadiene-isobutyl acrylate Examples include butadiene rubbers such as copolymers with the above vinyl monomers, and isobutylene rubbers such as polyisobutylene, polyisobutylene-styrene copolymers, and polyisobutylene-styrene block copolymers. Butadiene rubber is preferred.

  As such a butadiene-based rubber, among them, 1,3-butadiene 75-100% by mass and one or more vinyl monomers copolymerizable with 1,3-butadiene 0-30% by mass are copolymerized. Polybutadiene, butadiene-styrene copolymer, and butadiene-styrene block copolymer obtained by copolymerization with those obtained in this manner are preferred, but if the styrene content is high at this time, the polycarbonate resin composition of the present invention is difficult. Since flammability and impact resistance may be reduced, a smaller styrene content is more preferable.

  Particularly, the butadiene rubber is obtained by copolymerizing 95 to 100% by mass of 1,3-butadiene and 0 to 5% by mass of one or more vinyl monomers that can be copolymerized with 1,3-butadiene. More preferred are polybutadiene, butadiene-styrene copolymer, and butadiene-styrene block copolymer obtained by copolymerizing with each other, and particularly preferred is polybutadiene consisting essentially of 100 mass% of 1,3-butadiene. Polybutadiene substantially 100% by mass means a rubber composed only of butadiene, but it contains a small amount of other components in order to increase the thermal stability of the rubbery polymer and to facilitate particle size control. May be. However, in this case, the other component is usually 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less in the butadiene rubber.

Moreover, as the (meth) acrylic acid ester compound to be graft-polymerized to the diene rubber in the graft copolymer used in the present invention, methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl acrylate;
Aryl methacrylates such as phenyl methacrylate and naphthyl methacrylate;
Examples include glycidyl group-containing methacrylates such as glycidyl acrylate and glycidyl methacrylate. Among them, methacrylic acid alkyl esters are preferable, and methyl methacrylate is more preferable in terms of the balance between heat resistance and polycarbonate resin.
In addition, the said (meth) acrylic acid ester compound can use 1 type (s) or 2 or more types.

In addition to the (meth) acrylic acid ester compound, other vinyl monomers may be contained as desired. Other vinyl monomers include, for example,
Aromatic vinyls such as styrene and α-methylstyrene;
Unsaturated nitriles such as acrylonitrile and methacrylonitrile;
Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
Maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide;
Α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (eg maleic anhydride);
Etc.

Furthermore, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene;
Polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate;
Carboxylic acid allyl esters such as trimethacrylic acid ester, triacrylic acid ester, allyl acrylate, allyl methacrylate;
Crosslinkable monomers such as di- and triallyl compounds such as diallyl phthalate, diallyl sebacate, and triallyl triazine can also be used in combination.

The content of the diene rubber in the graft copolymer used in the present invention is 50 to 50% in a total of 100% by mass of the diene rubber, the (meth) acrylic acid ester compound, other monomers and the crosslinkable monomer. It is preferable that it is 95 mass%, More preferably, it is 70-90 mass%, More preferably, it is 75-85 mass%.
When the content of the diene rubber is not more than the above lower limit value, the polycarbonate resin of the present invention is not preferable because it may cause a decrease in impact resistance and a decrease in flame retardancy. Moreover, when the content of the diene rubber exceeds the above upper limit, it is also not preferable because it may cause a decrease in impact resistance and a decrease in flame retardancy.

Moreover, the (meth) acrylic acid ester compound to be graft-copolymerized to the diene rubber is preferably 100 to 100% in the total of 100% by mass of the (meth) acrylic acid ester compound, the other monomer and the crosslinkable monomer. % By mass, more preferably 75 to 100% by mass, still more preferably 90 to 100% by mass, particularly preferably substantially 100% by mass.
When the content of the (meth) acrylic acid ester compound is less than the above lower limit value, the polycarbonate resin of the present invention may cause a decrease in impact resistance and a decrease in flame retardancy, which is not preferable. Further, when the content of the (meth) acrylic acid ester compound exceeds the above upper limit, it is also not preferable because it may cause a decrease in impact resistance and a decrease in flame retardancy.

The production method of the graft copolymer (D) is not particularly limited, and any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization may be used. However, a multi-stage graft may be used, but an emulsion polymerization method is preferable and a multi-stage emulsion polymerization method is more preferable in terms of easy control of productivity and particle size. Examples of the multistage emulsion polymerization method include polymerization methods described in JP-A No. 2003-261629.
The graft copolymer used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of improving impact resistance, flame retardancy, and surface appearance.

The graft copolymer (D) used in the present invention preferably has a sulfur content in the range of 100 to 1,500 ppm. When the sulfur content is less than the above lower limit value, the graft copolymer tends to be inferior in heat resistance, and when the sulfur content exceeds the upper limit value, discoloration tends to be remarkable when heat aging occurs, making the polycarbonate resin composition difficult. Since flame retardance, hue, discoloration resistance, continuous productivity, and wet heat stability are significantly reduced, it is not preferable.
From such a viewpoint, the sulfur content is more preferably 200 to 1,000 ppm, further preferably 300 to 800 ppm, and most preferably 400 to 700 ppm.

  The sulfur content of the graft copolymer is mainly composed of sulfur contained in an emulsifier, a dispersant, a polymerization initiator, a heat stabilizer, etc. used in the pulverization process during the production of the graft copolymer. Inorganic sulfates, organic sulfonates, mercaptan compounds, and thioether compounds are applicable. After the graft copolymer is produced, the sulfur-containing graft copolymer in the above-mentioned range can be obtained by removing and adjusting the amount of the sulfur-containing component in a post-treatment process such as washing and powdering.

The sulfur content can be determined by combustion ion chromatography. Specifically, using AQF-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd., temperature: 900 to 1000 ° C., purge gas: oxygen 600 ml / min, combustion time: 8 minutes, absorption liquid 0.09% hydrogen peroxide water 25 ml It was burned under the conditions, and column: IonPacAS12A, eluent: 2.7 mM Na ₂ CO ₃ +0.3 mM NaHCO ₃ , regenerating solution: 15 mM H ₂ SO ₄ , flow rate: 1 with an ICS-90 type ion chromatograph manufactured by Dionex. The amount of sulfate ion (SO ₄ ²⁻ ) is measured under the conditions of 3 ml / min, analysis time: 20 minutes, and converted to the amount of sulfur (S).

  Further, the graft copolymer (D) used in the present invention has an average particle size of 160 to 240 nm. When the average particle size is smaller than the lower limit value, the impact resistance of the polycarbonate resin composition of the present invention is insufficient, which is not preferable. Further, when the average particle size exceeds the upper limit, flame retardancy and fire resistance of the polycarbonate resin composition of the present invention are reduced, impact resistance at high temperature molding is also reduced, and initial hue is also deteriorated. Therefore, it is not preferable. From such a viewpoint, the average particle diameter is more preferably 170 to 220 nm, and further preferably 180 to 210 nm.

  In addition, an average particle diameter is calculated | required by the volume average particle diameter D50 when the graft copolymer solution after superposition | polymerization is measured with a dynamic light scattering method. For the measurement, for example, “Microtrac particle size analyzer 9230UPA” manufactured by Nikkiso Co., Ltd. can be used.

  The content of the graft copolymer (D) is 0.5 parts by mass or more, preferably 0.75 parts by mass or more, more preferably 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is above, More preferably, it is 1.5 mass parts or more. Moreover, it is 6 mass parts or less, Preferably it is 5 mass parts or less, More preferably, it is 4 mass parts or less. When the content of the graft copolymer (D) is smaller than the lower limit of the range, the impact resistance of the polycarbonate resin composition of the present invention becomes insufficient, and when the content exceeds the upper limit of the range. , Flame resistance, impact resistance, hue, and discoloration resistance are significantly reduced.

[6. UV absorber (E)]
Examples of the ultraviolet absorber (E) used in the present invention include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid Examples thereof include organic ultraviolet absorbers such as ester compounds and hindered amine compounds. In these, an organic ultraviolet absorber is preferable, a benzotriazole compound, a triazine compound, and a cyanoacrylate compound are more preferable, and a benzotriazole compound is further more preferable. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

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- (2N-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], particularly 2- (2 ′ -Hydroxy-5'-tert-octylphenyl) benzotriazole is preferred.
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, Inc. “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinubin P”, “Tinubin 234”, “Tinubin 326” manufactured by Ciba Specialty Chemicals , “Tinuvin 327”, “tinuvin 328”, etc.

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′-dimethoxybenzophenone and the like.
Specific examples of such benzophenone compounds include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102” and “Seesorb 103” manufactured by Sipro Kasei Co., Ltd., “Biosorb 100” manufactured by Kyodo Pharmaceutical Co., Ltd. ”,“ Biosorb 110 ”,“ Biosorb 130 ”,“ Chemisorb 10 ”,“ Chemsorb 11 ”,“ Chemsorb 11S ”,“ Chemsorb 12 ”,“ Chemsorb 13 ”,“ Chemsorb 111 ”, manufactured by BASF "Ubinur 400", BASF "Ubinur M-40", BASF "Ubinur MS-40", Cytec Industries "Thiasorb UV9", "Thiasorb UV284", "Thiasorb UV531,""ThiasorbUV24", Adeka Made by Adekas Bed 1413 "," 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 Yakuhin Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35”, “Ubinur N-N-” manufactured by BASF. 539 "and the like.

  Examples of the triazine compound include a compound having a 1,3,5-triazine skeleton. Specific examples of such a triazine compound include “LA-46” manufactured by Adeka Co., Ltd., Ciba Specialty Chemicals. “Tinuvin 1577ED”, “Tinuvin 400”, “Tinuvin 405”, “Tinuvin 460”, “Tinuvin 477-DW”, “Tinuvin 479”, and the like are available.

  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 Ciba Specialty Chemicals, and the like.

Although the molecular weight of the ultraviolet absorber (E) in the present invention is not particularly limited, a molecular weight of 500 g / mol or more is particularly preferable. Thus, by selecting the ultraviolet absorber having a molecular weight of 500 g / mol or more, the thermal stability of the polycarbonate resin composition of the present invention is improved, and the low mold contamination is improved.
For this reason, the burden of the mold maintenance at the time of a shaping | molding process reduces, and there exists an effect which improves the productivity of the polycarbonate resin composition molded object of this invention, and the external appearance of the polycarbonate resin molded product of this invention becomes favorable. From such a viewpoint, the molecular weight of the ultraviolet absorber (E) is more preferably 550 g / mol or more, further preferably 600 g / mol or more, and particularly preferably 700 g / mol or more.
In general, higher molecular weight organic compounds have a significantly reduced compatibility with the polycarbonate resin and tend to be inferior in dispersibility. Therefore, the molecular weight of the ultraviolet absorber (E) is usually 3000 g / mol or less, more preferably, It is 2500 g / mol or less, more preferably 2000 g / mol or less, and particularly preferably 1500 g / mol or less.

The content of the ultraviolet absorber is 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and 0.5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). The amount is preferably 0.4 parts by mass or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance is insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, a mold deposit or the like occurs, Prone to mold contamination.
In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[7. Concealing agent (F): titanium oxide (F-1) or carbon black (F-2)]
In the present invention, titanium oxide (F-1) or carbon black (F-2)] is contained as a concealing agent in an amount of 0.00001 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). When both titanium oxide (F-1) and carbon black (F-2)] are contained, the total amount is included.

[Titanium oxide (F-1)]
Titanium oxide (F-1) in the present invention functions to improve the light shielding properties, whiteness, light reflection characteristics and the like of the molded product obtained from the polycarbonate resin composition. As for the titanium oxide used for titanium oxide (F-1), a manufacturing method, a crystal form, an average particle diameter, etc. are not specifically limited. There are sulfuric acid method and chlorine method in the production method of titanium oxide, but titanium oxide produced by sulfuric acid method tends to be inferior in whiteness of the composition to which this is added, so the object of the present invention can be effectively achieved. To achieve this, those produced by the chlorine method are preferred.

  The crystal form of titanium oxide includes a rutile type and an anatase type, but a rutile type crystal form is preferred from the viewpoint of light resistance. It is preferable that the average particle diameter of a titanium oxide (F-1) is 0.1-0.7 micrometer, More preferably, it is 0.1-0.4 micrometer. When the average particle size is less than 0.1 μm, the light shielding property of the molded product is inferior, and when it exceeds 0.7 μm, the surface of the molded product is easily roughened, and the mechanical strength of the molded product tends to be lowered. Two or more types of titanium oxide having different average particle diameters may be mixed and used.

  Titanium oxide (F-1) is preferably pretreated with an alumina surface treatment agent before being surface treated with an organosiloxane surface treatment agent described later. Alumina hydrate is preferably used as the alumina-based surface treatment agent. Furthermore, it may be pretreated with silicic acid hydrate together with alumina hydrate. The pretreatment method is not particularly limited, and any method can be used. Pretreatment with alumina hydrate and, if necessary, silicic acid hydrate is preferably carried out in the range of 1 to 15% by weight with respect to titanium oxide.

  Titanium oxide pretreated with alumina hydrate and, if necessary, silicic acid hydrate can be further improved in thermal stability by surface treatment with an organosiloxane surface treatment agent. In addition, the uniform dispersibility in the polycarbonate resin composition and the stability of the dispersion state are improved.

  As the organosiloxane surface treating agent, a reactive functional group-containing organosilicon compound having a reactive functional group that reacts with the surface of the inorganic compound particles is preferable. Examples of reactive functional groups include Si-H groups, Si-OH groups, Si-NH groups, and Si-OR groups, but those having Si-H groups, Si-OH groups, and Si-OR groups. More preferred are Si-H group-containing organosilicon compounds having Si-H groups.

  The Si—H group-containing organosilicon compound is not particularly limited as long as it is a compound having a Si—H group in the molecule, and may be appropriately selected and used. Among them, poly (methyl hydrogensiloxane), polycyclo (Methylhydrogensiloxane), poly (ethylhydrogensiloxane), poly (phenylhydrogensiloxane), poly [(methylhydrogensiloxane) (dimethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (ethylmethylsiloxane) )] Copolymer, poly [(methylhydrogensiloxane) (diethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (hexylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (octylmethy) Siloxane)] copolymer, poly [(methylhydrogensiloxane) (phenylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethoxysiloxane)] copolymer, poly [(methylhydrogensiloxane) (dimethoxysiloxane)] Copolymer, poly [(methylhydrogensiloxane) (3,3,3-trifluoropropylmethylsiloxane)] copolymer, poly [(dihydrogensiloxane) ((2-methoxyethoxy) methylsiloxane)] copolymer, poly [( Polyorganohydrogensiloxanes such as dihydrogensiloxane) (phenoxymethylsiloxane)] copolymers are preferred.

  Surface treatment methods using an organosiloxane surface treatment agent for titanium oxide include (1) a wet method and (2) a dry method. In the wet method, a mixture of an organosiloxane-based surface treatment agent and a solvent is added with alumina hydrate, and if necessary, titanium oxide pretreated with silicic acid hydrate. Furthermore, it is a method of heat-processing at 100-300 degreeC after that. In the dry method, pretreated titanium oxide and polyorganohydrogensiloxane are mixed with a Henschel mixer in the same manner as described above, and an organic solution of polyorganohydrogensiloxane is sprayed on the pretreated titanium oxide. And a method of heat-treating at 100 to 300 ° C.

The treatment amount of the siloxane compound is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of titanium oxide (F-1). When the amount of treatment is less than the above lower limit, the surface treatment effect is low, and the hue and discoloration resistance of the polycarbonate resin composition of the present invention are likely to be lowered. Moreover, when the amount of treatment exceeds the above upper limit, the amount of gas generated in the polycarbonate resin composition of the present invention is increased, which may cause mold contamination and poor appearance of the molding surface, which is not preferable.
From such a viewpoint, the amount of treatment is more preferably 0.1 to 6 parts by mass, further preferably 0.5 to 5 parts by mass, and 1 to 4 parts by mass with respect to 100 parts by mass of titanium oxide (F-1). Particularly preferred.

  The content of titanium oxide (F-1) is 0.00001 parts by mass or more, preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A). In particular, it is 0.1 parts by mass or more and 5 parts by mass or less, preferably 4.5 parts by mass or less, more preferably 4 parts by mass or less. If the titanium oxide is less than 0.00001 parts by mass, the light-shielding property is inferior, and if it exceeds 5 parts by mass, the impact resistance of the molded product may be reduced, and the fluidity and appearance may be reduced. Titanium oxide may easily fall off from the product surface.

[Carbon black (F-2)]
Carbon black (F-2) used in the present invention is not limited in its production method, raw material type, etc., and any conventionally known one, such as oil furnace black, channel black, acetylene black, ketjen black, etc. Can be used. Among these, oil furnace black is preferable from the viewpoint of colorability and cost.

  The average particle size of the carbon black (F-2) may be selected and determined as appropriate, but is preferably 5 to 60 nm, more preferably 7 to 55 nm, and particularly preferably 10 to 50 nm. By setting the average particle size to 5 nm or more, fluidity and antistatic properties tend to be improved, and by setting the average particle size to 60 nm or less, the appearance of the molded product is improved and carbon black is prevented from falling off from the molded product surface. be able to. The average particle diameter of carbon black can be obtained using a transmission electron microscope.

Nitrogen adsorption specific surface area of the carbon black (F-2) is preferably less than 1,000 m ² / g, is preferably Among them, 50 to 400 m ² / g. By making the nitrogen adsorption specific surface area less than 1,000 m ² / g, the fluidity of the glass fiber reinforced resin composition of the present invention and the appearance of the molded product tend to be improved, which is preferable. The nitrogen adsorption specific surface area can be measured according to JIS K6217.

Further, DBP absorption amount of carbon black ^is preferably less than 300 cm 3/100 g, is preferably Among them 30~200cm ³ / 100g. The DBP absorption amount by less than 300 cm ^3/100 g, tends to increase the appearance of fluidity and a molded article of the resin composition.
The DBP absorption can be measured according to JIS K6217. Carbon black (F-2) is not particularly limited with respect to its pH, but it is usually 2 to 10, preferably 3 to 9, and more preferably 4 to 8.

  Carbon black (F-2) can be used alone or in combination of two or more. Furthermore, carbon black (F-2) can be granulated using a binder, and can also be used in a master batch that is melt-kneaded at a high concentration in another resin.

Content of carbon black (F-2) is 0.00001-5 mass parts with respect to 100 mass parts of polycarbonate resin (A). If the carbon black (F-2) is less than 0.00001 part by mass, the light shielding property is poor, and if it exceeds 5 parts by mass, the fluidity and the appearance are deteriorated, and the carbon black easily falls off from the surface of the molded product.
The carbon black content is usually selected and used as appropriate in accordance with the balance between continuous productivity, concealability, and desired hue.

  In addition, as above-mentioned, content 0.00001-5 mass parts of shielding agent (F) prescribed | regulated by this invention is defined as a total amount of titanium oxide (F-1) and carbon black (F-2). Is done.

[8. Other ingredients]
[Phosphorus stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer. By containing a phosphorus-based stabilizer, the hue of the polycarbonate resin is improved, and further, discoloration resistance and continuous productivity are improved.
Any known phosphorous stabilizer 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 Phosphates of Group 1 or Group 2B metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; phosphate compounds, phosphite compounds, phosphonite compounds and the like are mentioned, and phosphite compounds are particularly preferred. By selecting a phosphite compound, a polycarbonate resin composition having higher discoloration resistance and continuous productivity can be obtained.

Here, the phosphite compound is a trivalent phosphorus compound represented by the general formula P (OR) ₃ , and R represents a monovalent or divalent organic group. Examples of such phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphine. Phyto, monooctyl diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, Bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butylphenyl) octyl phosphite, 2,2-methylene (4,6-di-tert-butylphenyl) octyl phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphite, 6- [3- (3 -Tert-butyl-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] -dioxaphosphine and the like. It is done.

  Among such phosphite compounds, the aromatic phosphite compound represented by the following formula (2) and / or (3) effectively increases the discoloration resistance of the polycarbonate resin composition of the present invention. More preferred.

In the formula ^{(2), R 1, R} 2 and ^{R 3} are 6 or more carbon atoms, a 30 following aryl group. R ¹ , R ² and R ³ may be the same or different.
As the phosphite compound represented by the above formula (2), triphenyl phosphite, tris (monononylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, etc. are preferable, Of these, tris (2,4-di-tert-butylphenyl) phosphite is more preferable. Specific examples of such organic phosphite compounds include, for example, “Adeka Stub 1178” manufactured by Adeka Corporation, “Sumilyzer TNP” manufactured by Sumitomo Chemical Co., Ltd., “JP-351” manufactured by Johoku Chemical Industry Co., Ltd. 2112 "," Irgaphos 168 "manufactured by Ciba Specialty Chemicals," JP-650 "manufactured by Johoku Chemical Industry Co., Ltd. and the like.

Further, the formula (3) in, ^{R 4} and ^{R 5} are at least 6 carbon atoms, represents the 30 following aryl group. R ⁴ and R ⁵ may be the same or different.
Examples of the phosphite compound represented by the above formula (3) include bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite and bis (2,6-di-tert-butyl). More preferred is phenyl) octyl phosphite. Specific examples of such an organic phosphite compound include “ADEKA STAB PEP-24G” and “ADEKA STAB PEP-36” manufactured by Adeka Corporation.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phosphorus stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, based on 100 parts by mass of the polycarbonate resin. 0.5 parts by mass or less, preferably 0.3 parts by mass or less, more preferably 0.1 parts by mass or less. When the content of the phosphorus stabilizer is less than the lower limit of the above range, the hue, discoloration resistance, and continuous productivity may be insufficient, and the content of the phosphorus stabilizer is the upper limit of the above range. In the case of exceeding, discoloration resistance is not only deteriorated, but also moist heat stability tends to be lowered, which is not preferable.

[Phenolic stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phenol-based stabilizer. As a phenol type stabilizer, a hindered phenol type antioxidant is mentioned, for example. Specific examples thereof 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-hydroxyphenylpropionamide), 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-tert-butyl-a, a ′, a ″-(mesi Tylene-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-pentylphenyl) ethyl] -4,6-di-te t- 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 phenolic antioxidants include “Irganox 1010” and “Irganox 1076” manufactured by Ciba Specialty Chemicals, “Adekastab AO-50” and “Adekastab AO” manufactured by Adeka. -60 "and the like.
In addition, 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phenol-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 100 parts by mass of the polycarbonate resin (A). 0.5 parts by mass or less. When the content of the phenol-based stabilizer is less than the lower limit of the range, the effect as the phenol-based stabilizer may be insufficient, and the content of the phenol-based stabilizer exceeds the upper limit of the range. If this is the case, the effect may reach its peak and not economical.

[Lubricant]
Moreover, it is also preferable to contain a lubricant if necessary. Examples of the lubricant include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.

  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 aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term “aliphatic” is used as a term including 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.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  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 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons 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 of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.
In addition, 1 type may contain the lubricant mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the lubricant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is as follows. When the content of the lubricant is less than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the lubricant exceeds the upper limit of the above range, degradation of hydrolysis resistance, injection There is a possibility of mold contamination during molding.

[Dye and pigment]
Moreover, it is also preferable to contain a dye / pigment if necessary. Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium cobalt Oxide pigments such as green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; ferrocyan pigments such as bitumen It is done.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

Of these, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[9. Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. 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 the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin;
Polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) And the like; polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins;
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

-Resin additive Examples of the resin additive other than those described above include, for example, an antistatic agent, an antifogging agent, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[10. Method for producing resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin (A), organic sulfonic acid metal salt (B), fluoropolymer (C), graft copolymer (D), ultraviolet absorber (E) and hiding agent (F), as required. Other ingredients to be blended in accordance with, for example, various mixers such as a tumbler and Henschel mixer, after pre-mixing, such as Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader The method of melt-kneading with a mixer is mentioned.

In addition, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and fed 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.
Further, the resin melt-kneaded by an extruder can be directly made into an injection molded product, a blow molded product, an extruded molded product or the like without going through pellets.

[11. Molded body]
The polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a 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.
Since the polycarbonate resin composition of the present invention is a polycarbonate resin material having excellent flame retardancy, impact resistance, low temperature impact resistance, weather resistance, wet heat stability, and chemical resistance, it can be used as a molded product in various applications.

  Examples of molded products include battery devices, electrical and electronic equipment, information terminal equipment, home appliances, OA equipment, machine parts, vehicle parts, building parts, various containers, leisure goods / miscellaneous goods, lighting equipment parts or members, etc. Is mentioned. Among these, it is particularly suitable for use in parts or members of battery devices, electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, lighting equipment, etc., and is particularly suitable for products used in an external environment or installed outdoors. It can be preferably used as a part or member of a product.

Taking such an example, the battery device includes a secondary battery device, a battery pack used for an electric bicycle such as an electric assist bicycle or an electric bicycle, or a battery device for driving power of an electric vehicle, It can be preferably used as a cover, a connector, a protective member or the like.
Moreover, it can use preferably also for the member for solar cell modules, for example, the frame material for modules.

  Examples of electrical and electronic equipment, information terminal equipment, home appliances, and office automation equipment include display devices such as personal computers, game machines, televisions, and electronic paper, printers, copiers, scanners, fax machines, electronic notebooks, and personal digital assistants (PDAs). Terminal), electronic desk calculator, electronic dictionary, camera, video camera, mobile phone, battery pack, recording medium drive and reader, mouse, numeric keypad, CD player, MD player, portable radio / audio player, and the like. Among them, notebook PCs, PDAs, mobile phones, portable audio players, portable tablet terminals, electronic books, electronic dictionaries, wireless devices, cameras, video cameras, portable game consoles, etc. It can be suitably used for a battery case for a battery pack for power supply.

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) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. A molding method using a hot runner method can also be used.
The obtained molded article of the present invention can be used as a practical molded article having high flame retardancy and mechanical properties without impairing the excellent properties of the polycarbonate resin as described above.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

In the following Examples and Comparative Examples, the components used are as shown in Table 1 and Table 2 below.

(Examples 1-9, Comparative Examples 1-7)
[Production of resin pellets]
Each component described in Table 1 and Table 2 above was blended in the proportions (mass ratios) described in Table 4 and Table 5 below, mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. Supplied to a twin screw extruder (TEX30HSST), kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded in a strand shape is rapidly cooled in a water tank, and a pelletizer is used To obtain pellets of a polycarbonate resin composition.

[Preparation of test piece]
After the pellets obtained by the above production method were dried at 80 ° C. for 5 hours, using a SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds. The test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm was injection molded under the following conditions.
Moreover, after drying the pellet obtained by said manufacturing method at 80 degreeC for 5 hours, using a Sumitomo Heavy Industries, Ltd. injection molding machine (Cycap M-2, clamping force 75T), cylinder temperature 280 An ISO multipurpose test piece (3 mm thick) and a flat test piece having a length of 100 mm, a width of 50 mm, and a thickness of 3 mm were injection molded under the conditions of ℃ and a mold temperature of 80 ℃.

[Flame retardance evaluation]
The flame retardant evaluation of each polycarbonate resin composition was performed by conditioning the test piece for UL test (0.8 mm thickness) obtained by the above method for 48 hours in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50%. The test was conducted in accordance with the UL94 test (combustion test of plastic materials for equipment parts) defined by the US Underwriters Laboratories (UL). 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 3 below.

ここで残炎時間とは、着火源を遠ざけた後の、試験片の有炎燃焼を続ける時間の長さである。また、ドリップによる綿着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火されるかどうかによって決定される。さらに、５試料のうち、１つでも上記基準を満たさないものがある場合、Ｖ−２を満足しないとしてＮＲ（ｎｏｔ ｒａｔｅｄ）と評価した。

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.

[SWOM treatment (weather resistance test)]
The ISO multipurpose test piece (3 mm thickness) and flat plate test piece (3 mm thickness) obtained by the above-described method were sprayed using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ° C. and sprayed (12 minutes) / 60 minutes) for 300 hours.

[Impact resistance evaluation]
Using the ISO multi-purpose test piece (3 mm thickness) molded at 280 ° C. obtained by the above-described method, in accordance with ISO 179, V notches of R = 0.25 and R = 0.1 were added, and 23 ° C. (R = Notched Charpy impact strength (unit: kJ / m ² ) was measured under the conditions of 0.25 and R = 0.1) and −30 ° C. (R = 0.25). Further, the test piece after the SWOM treatment was also provided with a V-notch of R = 0.25, and the Charpy impact strength with notch was measured under the condition of 23 ° C. by the same method as described above.

[Yellow Index (YI) (discoloration test)]
According to JIS K-7105, the above flat test piece (3 mm thickness) was used as a test piece, and was measured by a reflection method using an SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. (initial YI).
Moreover, it measured also about the test piece after carrying out the SWOM process for 300 hours to the said flat test piece (YI after a SWOM process). Furthermore, the measurement was performed also on the test piece after the plate-like test piece was aged for 12 hours at a temperature of 120 ° C. (YI after 12 h aging).

[Mold contamination]
Using a PS-40 mold machine manufactured by Nissei Resin Co., Ltd., using a drop mold, 50 shots and 100 shots were continuously molded at a molding temperature of 320 ° C and a mold temperature of 80 ° C. The presence or absence of deposits was evaluated according to the following criteria.
○: There are few deposits on the mold. X: There are very many deposits on the mold.
The above evaluation results are shown in Tables 4 and 5.

From Examples 1 to 9 shown in Table 4, polycarbonate resin (A), organic sulfonic acid metal salt (B), fluoropolymer (C), graft copolymer (D), UV absorption satisfying the requirements specified in the present invention. It can be seen that the polycarbonate resin composition containing a predetermined amount of the agent (E) and the masking agent (F) has UL flame retardancy of V-0 and is excellent in impact resistance. In addition, when the notch R is extremely small or at a low temperature, it has excellent impact resistance, and also has excellent weather resistance and heat discoloration. On the other hand, as shown in the comparative example of Table 5, it does not meet the requirements specified in the present invention It can be seen that the polycarbonate resin composition of the comparative example cannot satisfy the physical property balance of flame retardancy, impact resistance, low temperature impact resistance, weather resistance, and heat discoloration, and is inferior in any property.
In addition, when the ultraviolet absorber (E) is specified (Examples 4, 6 and 7), it can be seen that the low mold contamination is excellent.
Therefore, from the above examples and comparative examples, the effect of simultaneously satisfying high flame retardancy and impact resistance, low temperature impact resistance, weather resistance, and heat discoloration can be obtained for the first time by the configuration of the present invention. It was confirmed.

  The polycarbonate resin composition of the present invention is a polycarbonate resin material that is also excellent in flame retardancy, impact resistance, low temperature impact resistance, weather resistance, heat discoloration resistance, and low mold contamination, so it can be used as a molded product in various applications. Suitable for parts or members of battery devices, electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, lighting equipment, etc., especially for products used in external environments or products installed outdoors. Since it can be preferably used as a component / member, the industrial utility is very high.

Claims (11)

For 100 parts by mass of the polycarbonate resin (A) having a viscosity average molecular weight [Mv] of 22,000 to 30,000,
0.001 to 1 part by mass of organic sulfonic acid metal salt (B), 0.001 to 1 part by mass of fluoropolymer (C), and an average particle diameter obtained by graft polymerization of a (meth) acrylic acid ester compound to a diene rubber 160-240 nm graft copolymer (D) 0.5-6 parts by mass, UV absorber (E) 0.01-0.5 parts by mass, titanium oxide (F-1) or carbon black (F-2) A polycarbonate resin composition comprising 0.00001 to 5 parts by mass of at least one concealing agent (F) selected from:   The polycarbonate resin composition according to claim 1, wherein the graft copolymer (D) has a sulfur content of 100 to 1,500 ppm.   The polycarbonate resin composition according to claim 1 or 2, wherein the organic sulfonic acid metal salt (B) is a fluorine-containing aliphatic sulfonic acid alkali metal salt.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the ultraviolet absorber (E) has a molecular weight of at least 500 g / mol.   A molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 4.   The molded body according to claim 5, wherein the molded body is a member for a secondary battery device.   The molded body according to claim 6, which is a member for a battery device for an electric bicycle or an electric automobile.   The molded article according to claim 6 or 7, which is a battery case for an electric bicycle or an electric automobile.   The molded body according to claim 5 or 6, which is a member for a secondary battery device for an outdoor storage battery.   The molded article according to claim 5, which is a member for a solar cell module.   6. The molded body is a housing of a portable electronic device selected from the group consisting of a notebook personal computer, a PDA, a mobile phone, a portable audio player, a digital camera, an electronic book, an electronic dictionary, and a wireless device. The molded body described.