JP2013159703A - Composite fiber-reinforced polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in flame retardancy, rigidity, impact resistance and heat resistance.SOLUTION: A polycarbonate resin composition contains: 40-95 mass% of a polycarbonate resin (A); 5-60 mass% of a reinforcing filler (B) which comprises a glass fiber (B-1) and a carbon fiber (B-2) and has 5/95 to 95/5 of a mass ratio ((B-1)/(B-2)); a phosphazene compound (C) of 3-30 parts mass; and a fluoropolymer (D) of 0.001-1 parts mass on basis of 100 parts mass of the total of the (A) component and the (B) component.

Description

  The present invention relates to a polycarbonate resin composition having excellent rigidity. More specifically, the present invention relates to a composite reinforced polycarbonate resin composition excellent in flame retardancy, rigidity, impact resistance, and heat resistance.

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.
Among them, the flame-retardant polycarbonate resin composition is suitably used as a member of information / mobile devices such as computers, notebook computers, tablet terminals, smartphones, mobile phones, and OA devices such as printers and copiers. ing.

  In recent years, electronic appliances such as the above-mentioned information and mobile devices have been reduced in size and thickness, so that even if the materials used are thin, they have high flame retardancy and rigidity. There is also a need for materials that are superior to the above.

Several methods for increasing the rigidity of the polycarbonate resin have been studied, but the method of blending a fibrous reinforcing material such as glass fiber is the most effective for the demand for thin and high rigidity as described above. . As a means for imparting flame retardancy to such a glass fiber reinforced 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 an alternative method, many glass fiber reinforced polycarbonate resin compositions containing an organic phosphate are used. (For example, see Patent Documents 1 to 3)
However, resin compositions containing organic phosphate ester flame retardants are difficult to meet the thin-walled flame resistance required in recent years. In addition, the heat resistance is remarkably lowered.
Furthermore, since the glass-reinforced polycarbonate resin has a high specific gravity, it has not been possible to obtain a light, thin, small and high-strength molded product that has recently been required.

On the other hand, a carbon fiber reinforced polycarbonate resin in which carbon fiber and an organic phosphate ester are blended has been proposed. (For example, see Patent Documents 4 to 6)

However, the above-described carbon fiber reinforced polycarbonate resin still has a problem of reduction in flame retardancy and heat resistance. Furthermore, the polycarbonate resin blended with the carbon fiber has a drawback that impact resistance is remarkably lowered.

  Thus, a polycarbonate resin composition having an excellent balance between flame retardancy, rigidity, impact resistance, and heat resistance has been strongly desired, but a resin composition having such characteristics has not yet been obtained.

JP-A-8-201638 Japanese Laid-Open Patent Publication No. 10-30056 JP 2006-176612 A JP-A-9-48912 JP 2000-226508 A JP 2002-265767 A

  The present invention was devised in view of the above problems, and has a very high flame retardancy even when it is a thin-walled molded product, and further has excellent rigidity, impact resistance, and heat resistance. An object is to provide a composition.

  The inventor of the present invention has intensively studied to solve the above problems, and as a result, surprisingly high flame retardancy can be achieved by including glass fiber, carbon fiber, phosphazene compound, and fluoropolymer in polycarbonate resin. It was found that a composite fiber reinforced polycarbonate resin composition having excellent rigidity, impact resistance and heat resistance was obtained, and the present invention was completed.

  That is, the composite fiber reinforced polycarbonate resin composition of the present invention comprises 40 to 95% by mass of a polycarbonate resin (A), glass fiber (B-1) and carbon fiber (B-2), and (B-1) component ( B-2) Reinforcement filler (B) whose mass ratio (B-1 / B-2) is 5/95 to 95/5 (B) 3 to 30 parts by mass of the phosphazene compound (C) and 0.001 to 1 part by mass of the fluoropolymer (D) with respect to 100 parts by mass in total.

  At this time, it is also preferable to contain 0.5-10 mass parts of elastomer (E) with respect to a total of 100 mass parts of (A) component and (B) component, and elastomer (E) is a rubber-like polymer, A graft copolymer obtained by graft polymerization of at least one selected from an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester compound is preferable.

  Moreover, it is also preferable to contain 0.5-20 mass parts of styrene resin (F) with respect to a total of 100 mass parts of (A) component and (B) component, and styrene resin is an ABS resin. Is preferred.

  Furthermore, the phosphazene compound is preferably an aromatic phosphazene compound represented by the following formula (1) and / or (2).

［式（１）中、ａ は３〜２５の整数であり、Ｒ^１、及びＲ^２は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。］

Wherein (1), a is an integer of 3 to 25, ^{R 1,} and ^{R 2} may be the same or different, an aryl group or an alkylaryl group. ]

［式（２）中、ｂは３〜１０，０００の整数であり、Ｒ^３及びＲ^４は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。Ｒ^５は、−Ｎ＝Ｐ（ＯＲ^３）_３基、−Ｎ＝Ｐ（ＯＲ^４）_３基、−Ｎ＝Ｐ（Ｏ）ＯＲ^３基、−Ｎ＝Ｐ（Ｏ）ＯＲ^４基から選ばれる少なくとも１種を示し、Ｒ^６は、−Ｐ（ＯＲ^３）_４基、−Ｐ（ＯＲ^４）_４基、−Ｐ（Ｏ）（ＯＲ^３）_２基、−Ｐ（Ｏ）（ＯＲ^４）_２基から選ばれる少なくとも１種を示す。］

[In Formula (2), b is an integer of ^{3 to} 10,000, R ³ and R ⁴ may be the same or different and each represents an aryl group or an alkylaryl group. R ⁵ is selected from -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. It represents at least one, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 ^{group, -P (O) (OR 4} ) 2 At least one selected from the group is shown. ]

  According to the composite fiber reinforced polycarbonate resin composition of the present invention, it is possible to simultaneously improve flame retardancy, rigidity, impact resistance, and heat resistance.

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

Overview]
The composite fiber reinforced polycarbonate resin composition of the present invention comprises 40 to 95% by mass of a polycarbonate resin (A), glass fiber (B-1) and carbon fiber (B-2), and (B-1) component ( B-2) Reinforcement filler (B) whose mass ratio (B-1 / B-2) is 5/95 to 95/5 (B) 3 to 30 parts by mass of the phosphazene compound (C) and 0.001 to 1 part by mass of the fluoropolymer (D) with respect to 100 parts by mass in total.

[2. Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin used for the polycarbonate resin composition of this invention. In addition, one type of polycarbonate resin may be used, or two or more types may be used in any combination and in any ratio.

  The polycarbonate resin in the present invention is a polymer having a basic structure having a carbonic acid bond represented by the following general formula (3).

In formula (3), X ¹ is generally a hydrocarbon, but for imparting various properties, X ¹ into which a hetero atom or hetero bond is introduced may be used.

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

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. 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 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 can be 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. 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 matters regarding the polycarbonate resin The molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, more preferably Is 17000 or more, and is usually 40000 or less, preferably 30000 or less, more preferably 24000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed. 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 intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of 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.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the polycarbonate resin. 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 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 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. Reinforcing filler (B)]
The reinforcing filler of the present invention consists of glass fiber (B-1) and carbon fiber (B-2), and the mass ratio of component (B-1) to component (B-2) (B-1 / B-2). ) Is 5/95 to 95/5.
By containing the reinforcing filler at such a ratio, the rigidity and impact resistance of the polycarbonate resin composition of the present invention can be effectively enhanced.
[4. Glass fiber (B-1)]
As glass fiber (B-1) used by this invention, if it is normally used for a thermoplastic resin, A glass, E glass, the alkali-resistant glass composition containing a zirconia component, a chopped strand, roving Any known glass fiber can be used regardless of the form of the glass fiber at the time of blending glass, a thermoplastic resin and glass fiber (long fiber) masterbatch, or the like. Especially, as a glass fiber used for this invention, an alkali free glass (E glass) is preferable from the objective of improving the thermal stability of the polycarbonate resin composition of this invention.

The number average fiber length of the glass fiber (B-1) is preferably 1 mm or more and 10 mm or less, more preferably 1.5 to 6 mm, and further preferably 2 to 5 mm.
When the number average fiber length exceeds 10 mm, the glass fibers are likely to fall off from the surface of the molded product, and the productivity tends to be lowered. If the number average fiber length is less than 1 mm, the glass fiber has a small aspect ratio, and therefore mechanical strength is likely to be insufficiently improved.
Note that the number average fiber length is an image analysis device based on an image obtained by observing 2000 glass fibers of a filler residue collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical with an optical microscope. Is a value calculated by. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

The diameter of the glass fiber is preferably 3 μm or more and 20 μm or less. These can be produced by pulverizing glass fiber strands using, for example, a hammer mill or a ball mill according to any conventionally known method. When the diameter of the glass fiber is less than 3 μm, the improvement of the mechanical strength is similarly insufficient, and when it exceeds 20 μm, the appearance tends to deteriorate. The diameter of the glass fiber is more preferably 5 μm or more and 15 μm or less, and further preferably 6 μm or more and 14 μm or less.

The glass fiber (B-1) used in the present invention can be subjected to a surface treatment with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion to the polycarbonate resin.

Moreover, it is preferable that the glass fiber (B-1) used for this invention normally uses what bundled many these fibers as a chopped strand (chopped glass fiber) cut | disconnected to predetermined length, and this When the glass fiber (B-1) used in the present invention sometimes contains a sizing agent. In addition to the advantage of increasing the production stability of the polycarbonate resin of the present invention by blending the sizing agent, good mechanical properties can be obtained.
The sizing agent is not particularly limited, and examples thereof include urethane-based, epoxy-based, acrylic-based sizing agents. Among them, as the glass fiber sizing agent used in the present invention, urethane-based and epoxy-based sizing agents are more preferable, and epoxy-based sizing agents are more preferable.

Although there is no restriction | limiting in particular also about the cut length of a chopped strand (chopped glass fiber), Usually, 1-10 mm, Preferably it is 1.5-6 mm, More preferably, it is 2-5 mm.

The glass fiber (B-1) used in the present invention has a substantially round fiber cross section. Specifically, the cross section of the fiber cross section (major axis / minor axis) is 1 to 1.5. What is necessary is just a substantially circular glass fiber. The flatness is preferably 1 to 1.4, more preferably 1 to 1.2, and particularly preferably 1 to 1.1.
The flatness value is determined by an image analyzer from an image obtained by observing 2000 glass fibers of filler residue collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical with an optical microscope. It is a calculated average value.

[5. Carbon fiber (B-2)]
Examples of the carbon fiber used in the present invention include those produced by firing from raw materials such as acrylic fiber, petroleum or coal-based special pitch, cellulose fiber, lignin, etc., and various kinds such as flame resistance, carbonaceous or graphite There are several types. Acrylic fibers (PAN fibers), PAN-based carbon fibers using pitch as a raw material, and pitch-based carbon fibers are preferable.

The number average fiber length of the carbon fibers (B-2) is preferably from 1 mm to 10 mm, and the diameter of the carbon fibers is preferably from 5 μm to 20 μm.
When the number average fiber length exceeds 10 mm, the carbon fibers are likely to fall off from the surface of the molded product, and the productivity tends to be lowered. When the number average fiber length is less than 1 mm, the carbon fiber has a small aspect ratio, and thus mechanical strength is likely to be insufficiently improved.
Note that the number average fiber length is an image analysis device based on an image obtained by observing 2000 glass fibers of a filler residue collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical with an optical microscope. Is a value calculated by. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

  Similarly, when the diameter of the carbon fiber is less than 5 μm, the improvement of the mechanical strength is insufficient, and when it exceeds 20 μm, the appearance tends to deteriorate. The diameter of the carbon fiber is more preferably 6 μm or more and 15 μm or less.

  The surface of the carbon fiber can be subjected to a surface treatment with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving adhesion with the polycarbonate resin.

In addition, the carbon fiber (B-2) used in the present invention is usually preferably used as a chopped strand (chopped carbon fiber) obtained by cutting a number of these fibers into a predetermined length. When the carbon fiber (B-2) used in the present invention is sometimes blended with a sizing agent. In addition to the advantage of increasing the production stability of the polycarbonate resin of the present invention by blending the sizing agent, good mechanical properties can be obtained.
The sizing agent is not particularly limited, and examples thereof include urethane-based, epoxy-based, acrylic-based sizing agents. Among them, as the glass fiber sizing agent used in the present invention, urethane-based and epoxy-based sizing agents are more preferable, and epoxy-based sizing agents are more preferable.

Although there is no restriction | limiting in particular also about the cut length of a chopped strand (chopped carbon fiber), Usually, 1-20 mm, Preferably it is 2-10 mm, More preferably, it is 3-8 mm.

  The reinforcing filler (B) in the present invention is composed of glass fiber (B-1) and carbon fiber (B-2), and the mass ratio (B-) of the component (B-1) to the component (B-2). 1 / B-2) is 5/95 to 95/5, preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30.

  The compounding ratio of the polycarbonate resin (A) and the reinforcing filler (B) in the present invention is (A) component 40 to 95% by mass and (B) component 5 to 60% by mass. Preferably (A) is 50-90 mass% of component, (B) component is 10-50 mass%, More preferably, (A) component is 60-85 mass%, (B) is 15-40 mass%. is there.

[6. Phosphazene Compound (C)]
The phosphazene compound (C) used in the present invention is an organic compound having a -P = N- bond in the molecule, preferably a cyclic phosphazene compound represented by the following general formula (1), and the following general formula (2). A chain phosphazene compound represented by the following formula, and a group consisting of a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (1) and the following general formula (2) is crosslinked by a crosslinking group At least one compound selected.

In the formula (1), a is an integer of 3 to 25, and R ¹ and R ² may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group , A hydroxy group, an aryl group or an alkylaryl group.

In the formula (2), b is an integer of ^{3 to} 10,000, and R ³ and R ⁴ may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group A group, a hydroxy group, an aryl group or an alkylaryl group;
R ⁵ is selected from -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. It represents at least one, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 ^{group, -P (O) (OR 4} ) 2 At least one selected from the group is shown.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. Alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group and hexyl group are preferable, and carbon numbers such as methyl group, ethyl group and propyl group are preferable. 1-4 alkyl groups are particularly preferred.

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

Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group. Examples of the cycloalkenyl group include cycloalkenyl groups having 5 to 12 carbon atoms such as cyclopentyl group and cyclohexyl group. Is mentioned.

As an alkynyl group, aryls, such as C2-C8 alkynyl groups, such as an ethynyl group and a propynyl group, an ethynylbenzene group, etc. are mentioned, for example.

  Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (ie, tolyl) group, a dimethylphenyl (ie, xylyl) group, a trimethylphenyl group, and a naphthyl group. Among them, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

Examples of the alkylaryl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. Among them, aralkyl groups having 7 to 10 carbon atoms are preferable, and benzyl group is particularly preferable. .

Of these, R ¹ , R ² , R ³ and R ⁴ are preferably an aryl group or an arylalkyl group. By using such an aromatic phosphazene, the thermal stability of the polycarbonate resin composition of the present invention can be effectively enhanced. From such a viewpoint, R ¹ , R ² , R ³ and R ⁴ are more preferably aryl groups, and particularly preferably phenyl groups.

Examples of the cyclic and / or chain phosphazene compounds represented by the general formulas (1) and (2) include, for example, phenoxyphosphazene,
poly) tolyloxyphosphazenes such as o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene,
(poly) xylyloxyphosphazenes such as o, m-xylyloxyphosphazene, o, p-xylyloxyphosphazene, m, p-xylyloxyphosphazene,
o, m, p-trimethylphenyloxyphosphazene,
(Poly) phenoxytolyloxyphosphazenes such as phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazenes, phenoxy p-tolyloxyphosphazenes,
(Poly) phenoxytolyloxyxyloxyphosphazene, such as phenoxyo, m-xylyloxyphosphazene, phenoxyo, p-xylyloxyphosphazene, phenoxym, p-xylyloxyphosphazene,
Phenoxy o, m, p-trimethylphenyloxyphosphazene and the like can be exemplified, and cyclic and / or chain phenoxyphosphazene and the like are preferable.

As the cyclic phosphazene compound represented by the general formula (1), cyclic phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. . The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (1) is an integer of 3 to 8, and may be a mixture of compounds having different m.

The average m is preferably 3 to 5, and more preferably 3 to 4.
In particular, a mixture of compounds in which m = 3 is 50% by mass or more, m = 4 is 10 to 40% by mass, and m = 5 or more is 30% by mass or less in total.

As the chain phosphazene compound represented by the general formula (2), chain phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-mentioned method to reversion polymerization at a temperature of 220 to 250 ° C., and obtaining a linear dichlorophosphazene having a polymerization degree of 3 to 10,000. Examples include compounds obtained by substitution with a phenoxy group. N of general formula (2) of this linear phenoxyphosphazene compound becomes like this. Preferably it is 3-1000, More preferably, it is 3-100, More preferably, it is 3-25.

Examples of the crosslinked phosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a compound having a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. A compound having a 4,4′-oxydiphenylene group cross-linking structure, a compound having a 4,4′-thiodiphenylene group cross-linking structure, and the like. Can be mentioned.
In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (1) with the above-mentioned crosslinking group, or R ¹ in the above general formula (2). A crosslinked phenoxyphosphazene compound in which a chain phenoxyphosphazene compound that is a phenyl group is crosslinked by the above-mentioned crosslinking group is preferable from the viewpoint of flame retardancy, and a crosslinked phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound is crosslinked by the above-mentioned crosslinking group is more preferable. preferable.
The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (1) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (2) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound (C) is obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (1) and the cyclic phenoxyphosphazene compound represented by the general formula (1) with a crosslinking group. From the viewpoint of flame retardancy and mechanical properties, at least one member selected from the group consisting of the crosslinked phenoxyphosphazene compounds is preferable.

  Content of this phosphazene compound (C) is 3-30 mass parts with respect to a total of 100 mass parts of polycarbonate resin (A) and a reinforcement filler (B), 4-20 mass parts is preferable, 5-15 Part by mass is more preferable. By setting it as 3 mass parts or more, a flame retardance and fluidity | liquidity can fully be improved, and mechanical strength can be kept favorable by setting it as 30 mass parts or less.

[7. Fluoropolymer (D)]
The composite reinforced polycarbonate resin composition of the present invention contains 0.001 to 1 part by mass of the fluoropolymer (D) with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the reinforcing filler (B). There is no restriction | limiting in the kind of fluoropolymer, Moreover, 1 type of fluoropolymers may be used and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

An example of the fluoropolymer is 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 fibril-forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J”, “Teflon (registered trademark) 6C” manufactured by Mitsui DuPont Fluorochemicals, Daikin Chemical Industries, Ltd. “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500H” and the like manufactured by the company can be used. 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 the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the fluoropolymer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0, relative to 100 parts by mass in total of the polycarbonate resin (A) and the reinforcing filler (B). 0.05 parts by mass or more, particularly preferably 0.1 parts by mass or more, and usually 1 part by mass or less, preferably 0.75 parts by mass or less, more preferably 0.5 parts by mass or less. When the content of the fluoropolymer is less than or equal to the lower limit of the above range, the effect of improving the flame retardancy by the fluoropolymer may be insufficient, and when the content of the fluoropolymer exceeds the upper limit of the above range In addition, there is a possibility that a poor appearance of a molded product obtained by molding the polycarbonate resin composition or a decrease in mechanical strength may occur.

[8. Elastomer (E)]
The composite reinforced polycarbonate resin composition of the present invention may contain an elastomer (E). Thus, the impact resistance of a polycarbonate resin composition can be improved by containing an elastomer.

  The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. The method for producing the graft copolymer may be any method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft. From the viewpoint of easy control of productivity and particle size, an emulsion polymerization method is preferred, and a multistage emulsion polymerization method is more preferred. Examples of the multistage emulsion polymerization method include polymerization methods described in JP-A No. 2003-261629.

  The rubbery polymer generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, (partial) hydrogenated polybutadiene rubber, butadiene-styrene copolymer, (partial) hydrogenated polybutadiene-styrene copolymer, butadiene-styrene block copolymer, (partial) water. One or more vinyl monomers that can be copolymerized with butadiene and butadiene, such as a polybutadiene-styrene block copolymer, a butadiene-acrylonitrile copolymer, and an acrylic rubber copolymer based on butadiene-isobutyl acrylate Butadiene rubber such as a copolymer with polyisobutylene, polyisobutylene, polyisobutylene-styrene copolymer, isobutylene rubber such as polyisobutylene-styrene block copolymer, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl) Acrylate), butyla Polyalkyl acrylate rubber such as relate / 2-ethylhexyl acrylate copolymer, silicone rubber such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene -Ethylene-alpha olefin rubbers such as propylene rubber, ethylene-butene rubber, ethylene-octene rubber, ethylene-acrylic rubber, fluorine rubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, butadiene-styrene copolymer, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN (Interpenetrating Polymer composed of polyorganosiloxane rubber and polyalkyl acrylate rubber). Network) type composite rubber is preferred.

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, and (meth) acrylic acid ester compounds are preferable, and (meth) acrylic acid ester compounds are more preferable from the viewpoint of mechanical properties and surface appearance. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by weight or more of rubber component, more preferably 60% by weight or more. Moreover, what contains 10 weight% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same applies hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kane Ace (registered trademark, the same applies hereinafter) M-511 "," Kane Ace M-711 "," Kane Ace M-731 ", manufactured by Kaneka Corporation Kane Ace M-600 " "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01", and the like.

The content of the elastomer (E) in the present invention is usually 0.5 parts by mass or more, preferably 1 part by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the reinforcing filler (B). The amount is preferably 1.5 parts by mass or more, and usually 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 6 parts by mass or less, and particularly preferably 5 parts by mass or less. If the elastomer content is less than or equal to the lower limit of the above range, the effect of improving the flame retardancy and impact resistance of the elastomer may be insufficient. If the elastomer content exceeds the upper limit of the above range, In addition, the flame retardancy and heat resistance may be reduced, and the appearance of the molded product obtained by molding the polycarbonate resin composition may be deteriorated.

[9. Styrene resin (F)]
The composite reinforced polycarbonate resin composition of the present invention may contain a styrene resin (F).
Here, the styrene resin (F) is obtained by polymerizing at least one selected from styrene monomers and, if necessary, other vinyl monomers copolymerizable with these and rubbery polymers. Resin.

  Examples of the styrene monomer used in the styrene resin (F) include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl. Examples include styrene derivatives such as naphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable. These may be used alone or in combination of two or more.

  Other vinyl monomers copolymerizable with these styrenic monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; aryl esters of acrylic acid such as phenyl acrylate benzyl acrylate; methyl acrylate and ethyl acrylate Alkyl esters of acrylic acid such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate and dodecyl acrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; methyl methacrylate, ethyl Methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate Methacrylic acid alkyl esters such as acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, and dodecyl methacrylate; Epoxy group-containing methacrylic acid esters such as glycidyl methacrylate; Maleimides such as maleimide, N-methylmaleimide, and N-phenylmaleimide Body; α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid, and anhydrides thereof. Preferred are alkyl acrylates and alkyl methacrylates.

  These vinyl monomers may be used alone or in a combination of two or more.

  As the rubbery polymer copolymerizable with the styrene monomer, a rubber having a glass transition temperature of 10 ° C. or lower is suitable. Specific examples of such rubbery polymers include diene rubber, acrylic rubber, ethylene / propylene rubber, silicone rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component so that they cannot be separated from each other. Composite rubber (IPN type rubber) having a structure entangled with each other is preferable, and diene rubber, acrylic rubber and the like are preferable. (In this specification, “(meth) acrylate” refers to one or both of “acrylate” and “methacrylate”. The same applies to “(meth) acryl” and “(meth) acrylo”). )

Examples of the diene rubber include polybutadiene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, and ethylene-propylene-hexadiene copolymer. Examples thereof include ethylene, propylene and non-conjugated diene terpolymers, lower alkyl ester copolymers of butadiene- (meth) acrylic acid, and lower alkyl ester copolymers of butadiene-styrene- (meth) acrylic acid.
Examples of the lower alkyl ester of (meth) acrylic acid include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
The proportion of the lower alkyl ester of (meth) acrylic acid in the lower alkyl ester copolymer of butadiene- (meth) acrylic acid or the lower alkyl ester copolymer of butadiene-styrene- (meth) acrylic acid is 30% by weight of the rubber. % Or less is preferable.

  Examples of the acrylic rubber include acrylic acid alkyl ester rubber, and the carbon number of the alkyl group is preferably 1-8. Specific examples of the alkyl acrylate include ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, and the like. An ethylenically unsaturated monomer may optionally be used in the acrylic acid alkyl ester rubber. Specific examples of such compounds include di (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene, isoprene and the like. Examples of the acrylic rubber include a core-shell type polymer having a crosslinked diene rubber as a core.

  These rubbery polymers may also be used alone or in combination of two or more.

  Examples of the styrene resin (F) used in the present invention include a styrene homopolymer, a copolymer of styrene and (meth) acrylonitrile, a copolymer of styrene and (meth) acrylic acid alkyl ester, and styrene. Of (meth) acrylonitrile and other copolymerizable monomers, graft copolymer obtained by polymerizing styrene in the presence of rubber, graft polymerization of styrene and (meth) acrylonitrile in the presence of rubber And the like, and the like. More specifically, polystyrene, styrene-butadiene-styrene copolymer (SBS resin), hydrogenated styrene-butadiene-styrene copolymer (hydrogenated SBS), hydrogenated styrene-isoprene-styrene copolymer (SEPS). ), High impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), styrene-maleic anhydride copolymer (SMA resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene -Acrylic rubber copolymer (ASA resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS Fat), acrylonitrile - ethylene-propylene rubber - styrene copolymer (AES resin) and styrene -IPN type rubber copolymer resin, or mixtures thereof. Further, it may have stereoregularity such as syndiotactic polystyrene. In addition, aromatic vinyl monomers can be widely used in place of the above styrene.

  Among these, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) are particularly preferable. An acrylonitrile-butadiene-styrene copolymer (ABS resin) is preferred.

  Examples of the method for producing these styrene resins (F) include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.

  These styrenic resins (F) may be used alone or in combination of two or more.

  The composite reinforced polycarbonate resin composition of the present invention is 0.5 to 20 parts by mass of styrene resin (F), preferably 100 parts by mass in total of polycarbonate resin (A) and reinforced filler (B). It contains 2 to 15 parts by mass, more preferably 3 to 10 parts by mass. When the content of the styrenic resin (F) in the aromatic polycarbonate resin composition is less than the lower limit, the effect of improving the appearance and impact resistance of the molded product due to the blending of the styrenic resin (F) can be sufficiently obtained. If the amount is higher than the above upper limit, the heat resistance and surface hardness tend to decrease.

[10. Phosphorus stabilizer]
The composite reinforced polycarbonate resin composition of the present invention preferably contains a phosphorus-based stabilizer as necessary. 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 Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “Adeka Stub 1178”, “Adeka Stub 2112”, “Adeka Stub HP-10” manufactured by Adeka Corporation, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 "," JP-3CP "," Irgaphos 168 "manufactured by Ciba Specialty Chemicals, and the like.
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 part by mass or more, preferably 0.01 part by mass or more, more preferably 100 parts by mass in total of the polycarbonate resin (A) and the reinforcing filler (B). It is 0.02 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the phosphorus stabilizer is less than or equal to the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.

[11. Phenolic stabilizer]
The composite reinforced 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, for example, “Irganox 1010” and “Irganox 1076” manufactured by Ciba Specialty Chemicals, “Adekastab AO-50” and “Adekastab” manufactured by Adeka. AO-60 "etc. are mentioned.
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 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the reinforcing filler (B). The amount is usually 1 part by mass or less, preferably 0.5 part by mass or less. When the content of the phenolic stabilizer is not more than the lower limit of the above range, the effect as the phenolic stabilizer may be insufficient, and the content of the phenolic stabilizer exceeds the upper limit of the above range. If this is the case, the effect may reach its peak and not economical.

[12. 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 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts per 100 parts by mass in total of the polycarbonate resin (A) and the reinforcing filler (B). It is 1 part by mass or less, preferably 1 part by mass or less. When the content of the lubricant is less than or equal to 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, the hydrolysis resistance is reduced, injection There is a possibility of mold contamination during molding.

[13. Other ingredients]
The composite reinforced 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, polybutylene terephthalate resin; polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resins; polyimide resins; Examples include imide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone 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 include ultraviolet absorbers, dyes and pigments, antistatic agents, antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, examples of additives suitable for the composite reinforced polycarbonate resin composition of the present invention will be specifically described.

... Ultraviolet absorbers Examples of ultraviolet absorbers 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 ester compounds And organic ultraviolet absorbers such as hindered amine compounds. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is 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”, “Kemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, Inc. “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinuvin P”, “Tinubin 234”, “Tinubin 326” manufactured by Ciba Specialty Chemicals, “Tinuvin 327”, “Tinuvin 328” and the like can be mentioned.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4,4′-dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorb 103 ", joint medicine “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 "," ADEKA STAB 1413 "," ADEKA STAB LA-51 "manufactured by Adeka Corporation 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 Corporation. 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, for example, “LA-46” manufactured by ADEKA Corporation, Ciba Specialty Chemicals Co., Ltd. “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.

  Content of a ultraviolet absorber is 0.01 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (A) and a reinforcement filler (B), Preferably it is 0.1 mass part or more, Usually 3 parts by mass or less, preferably 1 part by mass or less. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause 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.

... Dye / pigment 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; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown , Titanium Cobalt Green, Cobalt Green, Cobalt Blue, Oxide Pigment such as Copper-Chromium Black, Copper-Iron Black, Chromic Acid Pigment such as Yellow Lead, Molybdate Orange, etc. Etc.

  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, titanium oxide, 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 in total of the polycarbonate resin (A) and the reinforcing filler (B). . If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[14. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the composite reinforced 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), reinforcing filler (B), phosphazene compound (C), fluoropolymer (D), and other components blended as required, such as tumblers and Henschel mixers. Examples of the method include premixing using various mixers such as Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, and the like.

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.

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

[Production of resin pellets]
Nippon Steel Works equipped with 1 vent after blending the components described in Table 2 other than carbon fiber in the proportions (mass ratios) described in Tables 3 to 4 and mixing for 20 minutes with a tumbler. Supplied from company (TEX30HSST) from an upstream feeder, and further kneaded under the conditions of a rotation speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 280 ° C. The molten resin extruded in the above was quenched in a water bath and pelletized using a pelletizer to obtain a composite reinforced polycarbonate resin composition pellet.

[Preparation of test piece]
After drying the pellets obtained by the above-mentioned production method at 80 ° C. for 5 hours, using a SE100DU injection molding machine manufactured by Sumitomo Machine Co., Ltd., injection molding was performed under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., A test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was molded.
Similarly, after the pellets obtained by the above-described production method were dried at 80 ° C. for 5 hours, a cylinder temperature of 280 ° C. and a mold using a Saicap M-2 manufactured by Sumitomo Heavy Industries, Ltd. and a clamping force of 75T were used. Injection molding was performed at a temperature of 80 ° C. to form an ISO multipurpose test piece (4 mm) and an ISO multipurpose test piece (3 mm).

[Flame retardance evaluation]
The flame resistance of each polycarbonate resin composition was evaluated by conditioning the test specimen for UL test obtained by the above method for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was conducted in accordance with UL94 test (combustion test of plastic materials for equipment parts) defined by 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 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. In addition, in Tables 3-4, it describes with "flame retardance."

[rigidity]
Using the ISO multipurpose test piece (4 mmt) obtained by the above method, the flexural modulus was measured and evaluated according to ISO178. In Tables 3 to 4, it is expressed as “elastic modulus (unit: GPa)”.

[Shock resistance]
Using the ISO multipurpose test piece (3 mmt) obtained by the above-mentioned method, Charpy with a notch was measured and evaluated according to ISO179. In Tables 3 to 4, “impact resistance (unit: kJ / m ² )” is used.

[Heat-resistant]
Using the ISO multi-purpose test piece (4 mmt) obtained by the above method, the deflection temperature under 1.80 MPa load was measured and evaluated in accordance with ISO75. In Tables 3 to 4, it is expressed as “heat resistance (unit: ° C.)”.

As shown in the examples of Table 3, it can be seen that the resin composition of the present invention is excellent in flame retardancy, rigidity, impact resistance, and heat resistance.
On the other hand, looking at the comparative examples in Table 4, it can be seen that the glass fiber alone (Comparative Example 1) as the reinforcing filler is inferior in elastic modulus, and the carbon fiber alone (Comparative Example 2) is inferior in impact resistance. Moreover, it turns out that it is inferior to a flame retardance, impact resistance, and heat resistance when phosphoric acid ester is used instead of phosphazene as a flame retardant (Comparative Examples 3-6).

Claims (6)

Polycarbonate resin (A) 40-95 mass%, which consists of glass fiber (B-1) and carbon fiber (B-2), (B-1) component (B-2) mass ratio (B-1 / B-2) Reinforcing filler (B) having 5/95 to 95/5 (B) From 5 to 60% by mass of component (A) and component (B) for a total of 100 parts by mass,
3-30 parts by mass of a phosphazene compound (C),
A polycarbonate resin composition comprising 0.001 to 1 part by mass of a fluoropolymer (D).   The polycarbonate resin composition according to claim 1, wherein 0.5 to 10 parts by mass of the elastomer (E) is contained with respect to 100 parts by mass in total of the component (A) and the component (B). The elastomer (E) is a graft copolymer obtained by graft polymerizing at least one selected from an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester compound to a rubbery polymer. The polycarbonate resin composition according to claim 1 or 2.   The polycarbonate resin composition according to claim 1 or 2, comprising 0.5 to 20 parts by mass of a styrene resin (F) with respect to 100 parts by mass of the total of the component (A) and the component (B). .   The polycarbonate resin composition according to claim 4, wherein the styrenic resin is an ABS resin. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the phosphazene compound is an aromatic phosphazene compound represented by the following formula (1) and / or (2).

Wherein (1), a is an integer of 3 to 25, ^{R 1,} and ^{R 2} may be the same or different, an aryl group or an alkylaryl group. ]

[In Formula (2), b is an integer of ^{3 to} 10,000, R ³ and R ⁴ may be the same or different and each represents an aryl group or an alkylaryl group. R ⁵ is selected from -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. It represents at least one, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 ^{group, -P (O) (OR 4} ) 2 At least one selected from the group is shown. ]