JP6276019B2 - Polycarbonate resin composition - Google Patents

Description

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

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, electric and electronic devices such as the above-mentioned information and mobile devices have been reduced in size and thickness. Therefore, even if the material used is thin, it has high flame retardancy and is also rigid. 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 ester have been adopted (see, for example, Patent Documents 1 to 3).

However, a material having high fluidity is required for molding a thin molded body required in recent years. However, the glass fiber reinforced polycarbonate resin composition as described above has insufficient fluidity, and the thin molded body is Couldn't get.
Moreover, although fluidity | liquidity can be improved by lowering | hanging the molecular weight of polycarbonate resin, or increasing the amount of organic phosphate ester, there also existed a subject that impact resistance will fall remarkably if such a method is used. .

  Furthermore, it is difficult to meet the thin flame retardant properties required in recent years with a resin composition containing only the organic phosphate ester flame retardant as described above. When the compounding amount of the acid ester is increased, the impact resistance and the heat resistance are remarkably lowered.

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

Japanese Patent Laid-Open No. 10-46017 Japanese Patent Laid-Open No. 10-30056 JP 2006-176612 A

  The present invention was devised in view of the above-mentioned problems, and has a highly flame-retardant property even in the case of a thin molded article, and further has a reinforced polycarbonate that is excellent in fluidity, rigidity, and impact resistance. It aims at providing a resin composition.

  As a result of intensive studies to solve the above problems, the present inventors surprisingly contain a glass-based reinforcing filler, a phosphate compound, a fluoropolymer, and a specific graft copolymer in a polycarbonate resin. As a result, the present inventors have found that it is possible to obtain extremely high flame retardancy and further excellent fluidity, rigidity, and impact resistance, thereby completing the present invention.

  That is, the polycarbonate resin composition of the present invention has a total of 100 masses of the component (A) and the component (B) composed of 40 to 95 mass% of the polycarbonate resin (A) and 5 to 60 mass% of the glass-based reinforcing filler (B). 3 to 30 parts by mass of the phosphoric ester compound (C), 0.001 to 1 part by mass of the fluoropolymer (D) and 0.5 to 10 parts by mass of the polyorganosiloxane-containing graft copolymer (E) It is characterized by doing.

  At this time, the glass-based reinforcing filler (B) is preferably at least one selected from a circular cross-section glass fiber, a flat cross-section glass fiber, and a glass flake.

Moreover, it is preferable that a phosphate ester compound (C) is a phosphate ester compound represented by following General formula (1).
[Wherein R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and p, q, r and s are each 0 or 1, k is an integer of 0 to 5, and X ¹ represents an arylene group. ]

  Moreover, although the ratio of a polycarbonate resin (A) and a glass-type reinforcement filler (B) is 40-65 mass% of a polycarbonate resin (A) and 35-60 mass% of a glass-type reinforcement filler (B), it is preferable.

  Moreover, (A) component which content of polyorganosiloxane containing graft copolymer (E) consists of polycarbonate resin (A) 40-95 mass% and glass-type reinforcement filler (B) 5-60 mass% ( It is more preferable that it is 1-6 mass parts with respect to the total 100 mass parts of B) component.

  According to the polycarbonate resin composition of the present invention, flame retardancy, fluidity, rigidity, and impact resistance can be enhanced at the same time.

  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

[1. Summary of the Invention]
The polycarbonate resin composition of the present invention has a total of 100 parts by mass of the component (A) and the component (B) composed of 40 to 95% by mass of the polycarbonate resin (A) and 5 to 60% by mass of the glass-based reinforcing filler (B). In contrast, the phosphoric acid ester compound (C) 3 to 30 parts by mass, the fluoropolymer (D) 0.001 to 1 part by mass and the polyorganosiloxane-containing graft copolymer (E) 0.5 to 10 parts by mass. It is characterized by.

[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 is a polymer having a basic structure having a carbonic acid bond represented by the following general formula (2).
In formula (2), X ² is usually a hydrocarbon group, but X ² 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. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

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

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

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

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

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

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

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

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

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

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

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

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 ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;

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

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

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

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

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a 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, carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin 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, 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.

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

  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 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. Glass-based reinforcing filler (B)]
The glass-based reinforcing filler (B) used in the present invention is a glass-based reinforcing filler, and preferred examples include glass fibers, flat cross-section glass fibers, and glass flakes.

  As glass fiber, if it is normally used for thermoplastic resin, A glass, E glass, alkali-resistant glass composition containing zirconia component, chopped strand, roving glass, thermoplastic resin and glass fiber (Long fiber) Any known glass fiber can be used regardless of the form of the glass fiber at the time of blending the masterbatch. 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 fibers 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.
In addition, the number average fiber length is an image analysis from an image obtained by observing 2,000 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 using an optical microscope. It is a value calculated by the device. 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 used in the present invention can be subjected to 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 to use a glass fiber that is usually a bundle of many of these fibers as a chopped strand (chopped glass fiber) cut into a predetermined length. At this time, the glass fiber should contain a sizing agent. Is preferred. In addition to the advantage of increasing the production stability of the polycarbonate resin composition 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 used in the present invention preferably has a substantially circular cross section. Specifically, the cross section of the fiber cross section (major axis / minor axis) is 1 to 1.5, and the cross section is substantially circular. It is preferable that the 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 calculated from an image obtained by observing, with an optical microscope, 2000 glass fibers of a filler residue collected by high temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical. Is an average value calculated by.

  The glass-based reinforcing filler (B) used in the present invention is preferably a flat cross-section glass fiber having a flat fiber cross section. As the flat cross-section glass fiber, the average value of the major axis of the fiber cross section is preferably 10 to 50 μm, and the average value of the ratio of the major axis to the minor axis (major axis / minor axis) is preferably 1.5 to 8. Is mentioned. By using such a flat cross-section glass fiber, the fluidity, rigidity, low warpage, impact resistance, and anisotropy of the polycarbonate resin composition of the present invention can be effectively increased.

The average value of the major axis of the fiber cross section of the flat cross-section glass fiber is preferably 10 to 50 μm, more preferably 12 to 40 μm, still more preferably 15 to 35 μm, and particularly preferably 18 to 30 μm.
Further, the average value of the ratio of the major axis to the minor axis (major axis / minor axis) of the flat cross-section glass fiber is preferably 1.5 to 8, more preferably 1.6 to 7, and further preferably 1.7 to. 6, particularly preferably 1.8-5. By using a flat cross-section glass fiber having an average value of the major axis and minor axis ratio (major axis / minor axis) in such a range, the fluidity, low warpage, and impact resistance of the polycarbonate resin composition of the present invention are used. , The anisotropy can be further increased.

  As the flat cross-section glass fiber, the cross-sectional shape includes an elliptical shape, a bowl shape, a trefoil shape, and a similar non-circular shape in addition to a flat cross-section, among others, mechanical strength, low warpage, From the viewpoint of anisotropy, a flat shape is preferable.

Moreover, the ratio (aspect ratio) of the average fiber length and the average fiber diameter of the flat cross-section glass fiber is preferably 2 to 120, more preferably 2.5 to 70, and further preferably 3 to 50. When the ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross-section glass fiber is less than 2, the mechanical strength tends to decrease. Conversely, when it exceeds 120, warp and anisotropy are present. In addition to the increase, the appearance of the molded product tends to deteriorate significantly.
The average fiber length of such flat cross-section glass fibers refers to the number average fiber diameter when the flat cross-sectional shape is converted to a true circle of the same area. The average fiber length refers to the number average fiber length in the polycarbonate resin composition of the present invention. The number average fiber length is a value calculated by an image analysis device from an image obtained by observing a filler residue collected by high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical with an optical microscope. It is. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

Various glass compositions represented by A glass, C glass, E glass, etc. are applied and the glass composition of the said flat cross-section glass fiber is not specifically limited. Such glass fibers may contain components such as TiO ₂ , SO ₃ , P ₂ O ₅ , CaO, MgO, B ₂ O ₃ as necessary. Among these, E glass (non-alkali glass) is preferable because the mechanical strength and thermal stability of the polycarbonate resin composition of the present invention are increased.

  The flat cross-section glass fiber used in the present invention is surface-treated with a silane coupling agent such as aminosilane or epoxysilane, a titanate coupling agent or an aluminate coupling agent for the purpose of improving the adhesion to the polycarbonate resin. be able to.

In addition, the flat cross-section glass fiber used in the present invention is usually preferably used as a chopped strand (chopped glass fiber) obtained by converging a large number of these fibers into a predetermined length. It is preferable that the flat cross-section glass fiber used in 1 is mixed with a sizing agent. By blending the sizing agent, good mechanical properties can be obtained in addition to the advantage that the production stability of the polycarbonate resin composition of the present invention is enhanced.
The sizing agent is not particularly limited, and examples thereof include urethane-based, epoxy-based, acrylic-based, polyester-based, styrene-based, and olefin-based sizing agents. Of these, urethane-based and epoxy-based sizing agents are more preferable, and epoxy-based sizing agents are more preferable.
In addition, the adhesion amount of a sizing agent is 0.1-3 mass% normally in 100 mass% of flat cross-section glass fibers, Preferably it is 0.2-1 mass%.

In addition, the flat cross-section glass fiber used in the present invention may be in any form of flat cross-section glass fiber at the time of blending, such as chopped strand, roving glass, (long fiber) masterbatch of thermoplastic resin and flat cross-section glass fiber. Any known flat cross-section glass fibers can be used, but in the present invention, chopped strands (chopped glass fibers) are preferred from the viewpoint of productivity.
In addition, 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.

Moreover, it is also preferable that the glass-type reinforcement | strengthening filler (B) used for this invention is glass flakes.
The glass flakes used in the present invention are preferably glass flakes having an average thickness of 0.2 to 10 μm, more preferably 0.3 to 7 μm, and still more preferably 0.5 to 6 μm. When average thickness exceeds the upper limit of the said range, since the impact resistance and flame retardance of the polycarbonate resin composition of this invention are easy to fall, it is unpreferable. Further, if the average thickness is below the lower limit of the above range, the glass flakes are extremely fragile, and the rigidity and low warpage tend to decrease, which is also not preferable.

  Here, the average thickness of the glass flake is a value measured by the following method. That is, using a scanning electron microscope (SEM), the thickness is measured for 100 or more glass flakes, and the measured values are averaged. In this case, the glass flake alone may be observed with a scanning electron microscope, or may be measured by filling the glass flake with a resin, forming it, breaking it, and observing its broken surface. In any measurement method, it is necessary to adjust the sample stage of the scanning electron microscope with the sample stage fine movement device so that the glass flake cross section (thickness surface) is perpendicular to the irradiation electron beam axis of the scanning electron microscope.

  Moreover, 10-1000 micrometers is preferable, as for the average particle diameter of glass flakes, More preferably, it is 20-700 micrometers, More preferably, it is 50-200 micrometers. Here, the average particle diameter is calculated as the median diameter of the weight average distribution obtained by the standard sieving method.

  Such glass flakes have been subjected to surface treatment with a known surface treatment agent such as a silane coupling agent, methyl hydrogen siloxane, titanate coupling agent, or aluminate coupling agent from the viewpoint of improving mechanical strength. preferable. Further, glass flakes are preferably granulated or converged with a binder such as acrylic resin, urethane resin, epoxy resin, unsaturated polyester resin, etc. from the viewpoint of handling. However, the average particle diameter range and thickness range of the glass flakes described above are not applied to the granule or the aggregate obtained by such granulation or convergence. The glass composition of the glass flake is not particularly limited, and various glass compositions represented by A glass, C glass, E glass and the like can be appropriately selected and used.

In the present invention, the content ratio of the polycarbonate resin (A) and the glass-based reinforcing filler (B) is based on a total of 100 mass% of both, and the component (A) is 40 to 95 mass% and the component (B) is 5 to 60 mass%. It is. The content of the glass-based reinforcing filler (B) is preferably more than 10% by mass, more preferably more than 20% by mass, further preferably more than 30% by mass, and more than 35% by mass. Particularly preferred. Moreover, the upper limit is 60 mass% or less, Preferably it is 55 mass% or less.
Usually, when the content of the glass-based reinforcing filler exceeds 30% by mass, the elastic modulus tends to decrease, but the polycarbonate resin composition of the present invention contains more than 30% by mass of the glass-based reinforcing filler, or 35% by mass. Even if it is contained at a high filling rate of more than%, the elastic modulus does not decrease, and the fluidity, rigidity, impact resistance, and flame retardancy are excellent.

[4. Phosphate ester compound (C)]
The polycarbonate resin composition of the present invention contains 3 to 30 parts by mass of the phosphate ester compound (C) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). Thus, the flame retardance and fluidity | liquidity of the polycarbonate resin composition of this invention can be improved by containing a phosphate ester compound.

The phosphate ester compound in the present invention may be a low molecule, an oligomer, or a polymer. From the viewpoint of thermal stability, for example, phosphoric acid represented by the general formula (1) An ester compound is particularly preferred.
The phosphate ester compound represented by the general formula (1) may be a mixture of compounds having different k numbers, and in the case of a mixture of condensed phosphate esters having different k, k is a value of the mixture. Average value. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

  Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.

R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

Specific examples of the phosphate ester compound represented by the general formula (1) include
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

  The acid value of the phosphoric acid ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less, particularly preferably Is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by mass or less, and still more preferably 0.9 parts by mass or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the polycarbonate resin composition of the present invention tends to be deteriorated in thermal stability and hydrolysis resistance.

  As the phosphoric ester compound (C) used in the present invention, in addition to the above, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- ( 2,3-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Naturally, a polyester resin, a polycarbonate resin, and an epoxy resin containing a phosphate ester moiety are also included.

  The content of the phosphate ester (C) is 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). It is 6 parts by mass or more and 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 15 parts by mass or less. When the blending amount of the phosphoric ester (C) is less than 3 parts by mass, the flame retardancy is insufficient, and when it exceeds 30 parts by mass, a remarkable decrease in heat resistance and a decrease in mechanical properties are caused.

[5. Fluoropolymer (D)]
The 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 glass-based 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 a fibril-forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J”, “Teflon (registered trademark) 6C” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Daikin Industries, Ltd. “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500H”, and the like are available. Furthermore, as commercially available products of aqueous dispersions of fluoroethylene resin, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon D” manufactured by Daikin Industries, Ltd. -1 "and the like.
Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like.
In addition, 1 type may contain fluoropolymer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the fluoropolymer (D) is 0.001 parts by mass or more, preferably 0.01 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). Or more, more preferably 0.05 parts by mass or more, particularly preferably 0.1 parts by mass or more, and 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 (D) is less than or equal to the lower limit of the above range, the effect of improving the flame retardancy by the fluoropolymer is insufficient, and when the content of the fluoropolymer exceeds the upper limit of the above range, the polycarbonate The appearance defect of the molded product which shape | molded the resin composition and the fall of mechanical strength arise.

[6. Polyorganosiloxane-containing graft copolymer (E)]
The polycarbonate resin composition of the present invention is 0.5 to 10 parts by mass of the polyorganosiloxane-containing graft copolymer (E) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). contains. Thus, the flame retardance of a polycarbonate resin composition, fluidity | liquidity, and impact resistance can be improved by containing a polyorganosiloxane containing graft copolymer.

  The polyorganosiloxane-containing graft copolymer used in the present invention is a graft copolymer obtained by graft copolymerizing a rubbery polymer containing polyorganosiloxane 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 polyorganosiloxane-containing rubbery polymer usually 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 are not particularly limited as long as it contains a polyorganosiloxane rubber. For example, a polyorganosiloxane rubber, a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl acrylate rubber (IPN type), etc. These may be used alone or in combination of two or more.

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 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 polyorganosiloxane-containing graft copolymer used in the present invention is preferably of the core / shell type graft copolymer type in terms of impact resistance and surface appearance. In particular, at least one rubber component selected from polyorganosiloxane rubber, (IPN type) composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber is used as a core layer, and an aromatic vinyl compound and vinyl cyanide are provided around the core layer. A core / shell type graft copolymer comprising a shell layer formed from at least one monomer component selected from a compound and a (meth) acrylic acid ester compound is particularly preferred. The core / shell type graft copolymer preferably contains 20% by mass or more of a rubber component, and more preferably contains 40% by mass or more.

  As such a core / shell type polyorganosiloxane-containing graft copolymer, for example, “Metabrene (registered trademark, hereinafter the same) S-2001”, “Metabrene SRK-200”, “Metabrene S-2100” manufactured by Mitsubishi Rayon Co., Ltd. ”,“ Metabrene S-2030 ”,“ Metabrene SX-005 ”,“ Kaneace (registered trademark, the same applies hereinafter) MR-01 ”,“ Kaneace MR-02 ”manufactured by Kaneka Corporation.

  The content of the polyorganosiloxane-containing graft copolymer (E) in the present invention is 0.5 parts by mass or more with respect to 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). Yes, preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 6 parts by mass or less. When the content of the polyorganosiloxane-containing graft copolymer (E) is not more than the lower limit of the above range, the fluidity, flame retardancy, and impact resistance improvement effect of the polyorganosiloxane-containing graft copolymer becomes insufficient. When the content of the polyorganosiloxane-containing graft copolymer exceeds the upper limit of the above range, the flame retardancy and heat resistance are deteriorated, and the appearance of the molded product obtained by molding the polycarbonate resin composition is deteriorated.

[7. Phosphorus stabilizer]
The 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 STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, 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 parts by mass or more, preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). Preferably it is 0.02 mass part or more, and is 1 mass part or less normally, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part 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.

[8. 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 ″-(me Citylene-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-t rt- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such a phenolic antioxidant include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Is mentioned.
In addition, 1 type may be contained for the phenol type stabilizer, and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the phenol-based stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). Moreover, it is 1 mass part or less normally, Preferably it is 0.5 mass part 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.

[9. 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 15000, 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 and comprise one ester may each be used 1 type, and may use 2 or more types together by arbitrary combinations and a 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 15000 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 5000 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 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the glass-based reinforcing filler (B). Usually 2 parts 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.

[10. 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 other resins include styrene resins such as polystyrene resin, AS resin, ABS resin, and ASA resin; thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polyethylene Polyolefin resins such as 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 a ratio.

-Resin additive Examples of the resin additive include an ultraviolet absorber, a dye / pigment, 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.

[11. Production method of polycarbonate 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), glass-based reinforcing filler (B), phosphate ester compound (C), fluoropolymer (D), polyorganosiloxane-containing graft copolymer (E), and necessary Other ingredients to be blended depending on the type are mixed in advance using various mixers such as tumblers and Henschel mixers, and then Banbury mixers, rolls, brabenders, single-screw kneading extruders, twin-screw kneading extruders, kneaders, etc. The method of melt-kneading with these mixers 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.

  Furthermore, as a particularly preferable method for producing the polycarbonate resin composition of the present invention, the polycarbonate resin (A), the phosphate ester compound (C), the fluoropolymer (D), and the polyorganosiloxane-containing graft copolymer (E) are used. , And appropriate other additives, etc., mixed well with a V-type blender, etc., prepared in advance, and supplied from the first chute of the twin-screw extruder with a vent, glass-based reinforcing filler (B) Can be supplied from a second chute in the middle of the extruder and melt kneaded and pelletized.

[12. 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 has an excellent balance of fluidity, rigidity, impact resistance and flame retardancy, it can be used as a molded product in various applications.

Examples of molded products include electrical and electronic equipment, information terminal equipment, home appliances, OA equipment, machine parts, vehicle parts, building members, various containers, leisure goods and miscellaneous goods, medical equipment, lighting equipment parts and members. Is mentioned.
Electric and electronic devices, information terminal devices, home appliances, and OA devices include, for example, display devices such as personal computers, game machines, TVs, electronic paper, printers, copiers, scanners, fax machines, electronic notebooks; PDAs, mobile phones, tablets Various portable terminals such as terminals; electronic desk calculators, electronic dictionaries; cameras, video cameras and their lenses; battery packs, recording media drives and reading devices, mice, numeric keys, CD players, MD players, portable radio / audio players, etc. Parts.
Among them, the polycarbonate resin composition of the present invention is particularly suitable 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. Can be used.

  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.

  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.

(Examples 13 to 14, Reference Examples 1 to 12, 15 to 19, Comparative Examples 1 to 7)
[Production of resin pellets]
Japan except for glass-based reinforcing fillers in the components described in Table 2 below, in proportions (mass ratios) described in Tables 3 to 5 and mixed in a tumbler for 20 minutes, followed by Japan with 1 vent. Supplied to the steelworks company (TEX30HSST) from the upstream feeder, while further supplying the glass-based reinforcing filler from the middle of the barrel by the side feeder, under the conditions of a rotation speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280 ° C. The molten resin that was kneaded and extruded into a strand shape was quenched in a water bath and pelletized using a pelletizer to obtain a pellet of a polycarbonate resin composition.

[Preparation of test piece]
The pellets obtained by the above method are dried at 80 ° C. for 5 hours, and then injected using a SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. under conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. A UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was molded.
Similarly, after the pellet obtained by the above-mentioned method was dried at 80 ° C. for 5 hours, the cylinder temperature was measured using an injection molding machine (Sycap M-2, clamping force 75T) manufactured by Sumitomo Heavy Industries, Ltd. Injection molding was performed under the conditions of 280 ° C. and a mold temperature of 80 ° C. to form an ISO multipurpose test piece (4 mm thickness) and an ISO multipurpose test piece (3 mm thickness).

[Fluidity evaluation]
Similarly, after the pellet obtained by the above-mentioned method was dried at 80 ° C. for 5 hours, the cylinder temperature was measured using an injection molding machine (Sycap M-2, clamping force 75T) manufactured by Sumitomo Heavy Industries, Ltd. A bar flow molded product having a width of 20 mm and a thickness of 1 mm was injection molded under the conditions of 300 ° C., mold temperature of 80 ° C. and injection pressure of 150 MPa, and the flow length (unit: mm) was evaluated.
A larger value of this bar flow flow length means that the flowability is high and the moldability is good, which is preferable. In Tables 3-5, it describes with "fluidity."

[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 Table 3, “flame retardant” is indicated.
Furthermore, the total burning time (unit: SEC) of all five was counted and evaluated. A smaller total combustion time means that it has good flame retardancy, and is preferable.
In Tables 3-5, it describes with "total combustion time."

[rigidity]
Using the ISO multipurpose test piece (4 mmt) obtained by the above method, the flexural modulus (unit: GPa) was measured and evaluated according to ISO178.
In Tables 3 to 5, it is expressed as “elastic modulus”.

[Shock resistance]
Using the ISO multi-purpose test piece (3 mmt) obtained by the above method, the Charpy impact strength with notch (unit: kJ / m ² ) was measured and evaluated according to ISO 179.
In Tables 3 to 5, “impact resistance” is used.

As shown in the examples of the above table, it can be seen that the resin composition of the present invention has an excellent balance of fluidity, rigidity, impact resistance, and flame retardancy.
On the other hand, when the comparative example of Table 4 and Table 5 is seen, when the polyorganosiloxane containing graft copolymer is not contained, fluidity | liquidity and a flame retardance are inferior (Comparative Examples 1, 4, and 6). Moreover, it turns out that it is inferior to fluidity | liquidity and a flame retardance also when a butadiene containing graft copolymer is used instead of a polyorganosiloxane containing graft copolymer (Comparative Examples 2, 3, 5, 7).

  Since the polycarbonate resin composition of the present invention has an excellent balance of fluidity, rigidity, impact resistance, and flame retardancy, it can be widely used for automobile materials, electrical and electronic equipment materials, housing materials, and other industrial parts manufacturing materials. In particular, it can be used favorably 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, and industrial use. Sex is very high.

Claims (3)

Phosphoric ester compound (C) with respect to 100 parts by mass of (A) component and (B) component consisting of 40 to 65 % by mass of polycarbonate resin (A) and 35 to 60% by mass of glass-based reinforcing filler (B) 3 to 30 parts by mass, fluoropolymer (D) 0.001 to 1 part by mass and polyorganosiloxane-containing graft copolymer (E) 0.5 to 10 parts by mass, and the glass-based reinforcing filler (B) A polycarbonate resin composition, which is a flat cross-section glass fiber having an average value of a major axis / minor axis ratio (major axis / minor axis) of 1.8 to 8 . The polycarbonate resin composition according to claim 1, wherein the phosphoric ester compound (C) is represented by the following general formula (1).
[Wherein R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and p, q, r and s are each 0 or 1, k is an integer of 0 to 5, and X ¹ represents an arylene group. ] The polyorganosiloxane-containing graft copolymer the content of (E) is, relative to total 100 parts by weight of component (A) and component (B) according to claim 1 or 2, characterized in that 1 to 6 parts by weight The polycarbonate resin composition described in 1.