JP2019006953A - Reinforced polycarbonate resin composition - Google Patents

Abstract

To provide a reinforced polycarbonate resin composition combining excellent strength, impact resistance, heat resistance, and flame retardancy.SOLUTION: The reinforced polycarbonate resin composition contains (C) 2-45 pts.wt. of a fluororesin (component C) based on 100 pts.wt. of a component comprising (A) 65-95 pts.wt. of a polycarbonate resin (component A) and (B) 5-35 pts.wt. of a fibrous filler (component B). The component C is a copolymer containing a polymerization unit comprising an olefin and a fluorine-containing olefin. The component C has a melting point of 200-280°C.SELECTED DRAWING: None

Description

  The present invention relates to a reinforced polycarbonate resin composition. More specifically, while maintaining excellent strength, it has good impact resistance, heat resistance, and flame resistance, and can be used suitably in various fields such as electric / electronic field, automobile field, infrastructure / communication field, etc. The present invention relates to a polycarbonate resin composition.

Polycarbonate resins are used in many applications such as mechanical parts, automobile parts, electrical / electronic parts, and office equipment parts because of their excellent properties such as mechanical strength, dimensional stability and flame retardancy. In recent years, with the miniaturization and high performance of parts, demands for the strength and heat resistance of the parts are increasing. At least one selected from the group consisting of polycarbonate resin as a material having improved strength and heat resistance, fibrous filler such as glass fiber and carbon fiber, plate-like filler such as talc, and granular filler such as calcium carbonate There is known a reinforced polycarbonate resin composition containing the above filler.
However, the polycarbonate resin has a drawback that the impact resistance is greatly reduced by adding glass fibers. Conventionally, various studies have been made on methods for improving impact resistance, which is reduced by adding glass fibers to a polycarbonate resin.
In general, in order to improve impact resistance, for example, a technique of blending an elastomer as described in Patent Documents 1 and 2 is known. However, while impact resistance is improved, there is a problem that heat resistance and flame retardancy are reduced.
Patent Documents 3 to 5 disclose a method of introducing a polycarbonate-polyorganosiloxane copolymer as a polycarbonate resin. However, even in this case, although the impact resistance is improved, there remains a problem that the heat resistance and the flame retardancy are lowered. In addition, in the improvement of impact resistance by alloying polycarbonate resin with other resins such as polyester resin and styrene resin, the heat resistance and flame retardancy are reduced, and the flame retardant property possessed by the glass reinforced resin composition In addition, a method for improving impact resistance while maintaining heat resistance is still insufficient.

On the other hand, a fluororesin represented by polytetrafluoroethylene (PTFE) is extremely superior in heat resistance, chemical resistance, weather resistance, electrical properties, and non-adhesiveness compared to other polymer materials. Because of its unique properties such as slipperiness, it is widely used in automobiles, aircraft, semiconductors, information and communication equipment, and familiar household items. As a technique for blending a fluororesin with a polycarbonate resin, an application as an anti-drip agent (Patent Documents 6 and 7) and an application as a slidability imparting material (Patent Documents 8 and 9) are known. However, since the fluororesin has a high melting point, its application as an alloy material is limited.
Patent Document 10 reports a resin composition in which a fluororesin having a melting point of 150 to 230 ° C. is blended with a polycarbonate resin. However, there is no description regarding the fibrous filler, and no mention is made of improving the impact resistance of the reinforced resin composition. Patent Document 11 reports a thermoplastic resin composition obtained by blending a base-treated fluorine-containing elastomer with a thermoplastic resin. However, there is no description regarding polycarbonate and there is no description regarding fibrous filler. In Patent Document 12, a slidable polycarbonate resin composition containing a fluoropolymer having no fibril-forming ability and carbon fiber in a polycarbonate resin is reported. However, there is no description regarding impact resistance and heat resistance.

Japanese Patent Laid-Open No. 3-27352 JP 2004-75747 A Japanese Patent Laid-Open No. 55-160052 Japanese Patent Laid-Open No. 2-173061 JP-A-7-26149 JP-A-50-44241 Japanese Patent Publication No. 60-38418 Japanese Unexamined Patent Publication No. 63-213555 JP2015-199892A Japanese Patent Laid-Open No. 5-171025 WO93 / 21272 Japanese Patent Laying-Open No. 2015-48409

  An object of the present invention is to provide a reinforced polycarbonate resin composition having good impact resistance, flame retardancy, and heat resistance while maintaining excellent strength, and a molded article comprising the same.

  As a result of intensive research aimed at achieving the above object, the present inventors have obtained excellent strength, heat resistance, flame resistance by blending a specific fluororesin with a component comprising a polycarbonate resin and a fibrous filler. The present inventors have found that a reinforced polycarbonate resin composition having excellent properties and impact resistance can be obtained. That is, according to the present invention, (1) (A) polycarbonate resin (component A) 50-95 parts by weight and (B) fibrous filler (component B) 5-50 parts by weight (C) A reinforced polycarbonate resin composition containing 2 to 45 parts by weight of a fluororesin (C component), wherein the C component contains a polymer unit represented by the following general formulas [1] and [2] A reinforced polycarbonate resin composition is provided wherein the C component has a melting point of 200 ° C. to 280 ° C.

In above general formula (1) ^represents R ^1, R 2, ^{R 3} and ^{R 4} are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

[In the above general formula [2], R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a fluorine atom, and R ⁸ represents a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. ]

One of the more preferable embodiments of the present invention is (2) In the above-mentioned constitution (1), in the general formula [1], R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. The reinforced polycarbonate resin composition.
One of the more preferable embodiments of the present invention is (3) in the above-mentioned constitution (1) or (2), wherein R ⁵ , R ⁶ and R ⁷ in the general formula [2] are fluorine atoms. The reinforced polycarbonate resin composition described.
One of the more preferable embodiments of the present invention is (4) the reinforced polycarbonate resin composition according to any one of the above constitutions (1) to (3), wherein the B component is glass fiber and / or carbon fiber. It is a thing.
One of the more preferable embodiments of the present invention is (5) a molded article made of the reinforced polycarbonate resin composition according to any one of the above-described configurations (1) to (4).

  The reinforced polycarbonate resin composition of the present invention is used in various applications such as various electronic / electric equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts, other agricultural materials, transport containers, playground equipment, and miscellaneous goods. It is useful and its industrial effect is exceptional.

Hereinafter, the present invention will be specifically described.
<Component A: Polycarbonate resin>
The polycarbonate resin used as the component A of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer by a solid phase transesterification method. Or obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.
The dihydroxy component used here may be any one that is usually used as a dihydroxy component of polycarbonate, and may be a bisphenol or an aliphatic diol. Examples of bisphenols include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t- Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxypheny) ) Octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4) -Hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-sulfoni Diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyl Diphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 2,2′-diphenyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl } Benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydro Cyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis Examples thereof include (4-hydroxyphenyl) -5,7-dimethyladamantane and bisphenol compounds having a siloxane structure represented by the following general formula [3].

(In the above general formula [3], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl having 2 to 9 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, wherein R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atom. 10 an alkoxy group, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, p and q are each an integer of 1 to 4, e is a natural number, f is 0 or a natural number, and e + f Is a natural number of 150 or less, and X is an alkylene group having 2 to 8 carbon atoms.)

  Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4′-bis (2- Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxy) Ethoxy) -3,3′-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-isopropylphenyl} propane, 2,2-bis {3-tert-butyl-4- (2-hydroxy) Ethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2-bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2 -Hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2,2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2- Bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-cyclohexyl-4- (2-hydroxyethyl) Xyl) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane, 9,9-bis {(2-hydroxy) Ethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,1-bis { (2-hydroxyethoxy) phenyl} cyclopentane, 4,4′-bis (2-hydroxyethoxy) diphenyl ether, 4,4′-bis (2-hydroxyethoxy) -3,3′-dimethyldiphenyl ether Ter, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D- Sorbitol (isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol Isoidide), and the like.

  Among these, aromatic bisphenols are preferable, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, represented by the general formula [3] Phenol compounds are preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-sulfonyldiphenol, and 9,9-bis (4 -Hydroxy-3-methylphenyl) fluorene, bisphenol compounds represented by the above general formula [4] are preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

The polycarbonate resin used as the component A of the present invention can be made into a branched polycarbonate resin by using a branching agent in combination with the dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.
These polycarbonate resins are produced by a reaction means known per se for producing ordinary polycarbonate resins, for example, a method in which an aromatic dihydroxy component is reacted with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight control, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas [4] to [6].

[In the formula [4], A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl moiety has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl moiety having 1 carbon atom). To 9), and r is an integer of 1 to 5, preferably 1 to 3. ]

[In the formulas [5] and [6], Y is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, Preferably it shows 1-5 divalent aliphatic hydrocarbon groups, and n shows the integer of 10-50. ]

Specific examples of the monofunctional phenols represented by the general formula [4] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas [5] to [6] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used.
The substituted phenols represented by the general formula [5] preferably have n of 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol.
Further, as the substituted phenols of the above general formula [6], compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

  Among these monofunctional phenols, monofunctional phenols represented by the above general formula [4] are preferable, more preferably alkyl-substituted or phenylalkyl-substituted phenols, particularly preferably p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. These monofunctional phenolic terminal terminators are desirably introduced at the terminal at least 5 mol%, preferably at least 10 mol%, based on all the terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

The polycarbonate resin used as the component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. Good.
The viscosity average molecular weight of the polycarbonate resin used as the component A of the present invention is preferably in the range of 12,500 to 50,000, more preferably 16,000 to 30,000, and in the range of 18,000 to 28,000. Even more preferred is the range of 19,000 to 26,000. If the molecular weight exceeds 50,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 12,500, there may be a problem in mechanical strength. In addition, the viscosity average molecular weight as used in the field of this invention was calculated | required and calculated | required first using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin 0.7g in 20 ml of methylene chloride in the specific viscosity computed by following Formula. The viscosity average molecular weight M is determined by inserting the specific viscosity by the following formula.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(B component: fibrous filler)
The fibrous filler used as the component B of the present invention is, for example, glass fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker, boric acid. Represented by fibrous inorganic fillers such as aluminum whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, zonotolite, palygorskite (attapulgite), and sepiolite, and heat resistant organic fibers such as aramid fibers, polyimide fibers and polybenzthiazole fibers Examples thereof include fibrous heat-resistant organic fillers, and fibrous fillers in which different materials such as metals and metal oxides are coated on these fillers.
Examples of the filler whose surface is coated with a different material include metal-coated glass fibers and metal-coated carbon fibers. The surface coating method of different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition methods, ion plating methods, CVD methods ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned.
Among these fibrous fillers, glass fibers, carbon fibers, carbon milled fibers, and aramid fibers are preferable, and glass fibers and carbon fibers are more preferable. The fibrous filler used as the component B of the present invention preferably has a fiber diameter in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 18 μm and even more preferably 15 μm. On the other hand, the lower limit of the fiber diameter is more preferably 1 μm and even more preferably 6 μm. The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ash residue collected after ashing with a crucible. It is a value calculated from an image observed with an electron microscope.

When the fibrous filler used as the component B of the present invention is a glass fiber, various glass compositions represented by A glass, C glass, E glass and the like are applied as the glass composition of the glass fiber, and particularly limited. Not. Such a glass filler may contain components such as TiO ₂ , SO ₃ , and P ₂ O ₅ as necessary. Among these, E glass (non-alkali glass) is more preferable.
Such a glass fiber is preferably subjected to a surface treatment with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength. In addition, those that have been subjected to bundling treatment with olefin resin, styrene resin, acrylic resin, polyester resin, epoxy resin, urethane resin, etc. are preferable. From the viewpoint of mechanical strength, epoxy resin and urethane resin are preferred. Particularly preferred. The amount of the sizing agent attached to the glass fiber subjected to the sizing treatment is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, in 100% by weight of the glass fiber.

A flat cross-section glass fiber can also be used as the fibrous filler used as the component B of the present invention. As this flat cross-section glass fiber, the average value of the major axis of the fiber cross section is preferably 10 to 50 μm, more preferably 15 to 40 μm, still more preferably 20 to 35 μm, and the ratio of the major axis to the minor axis (major axis / minor axis). The glass fiber has an average value of preferably 1.5 to 8, more preferably 2 to 6, and further preferably 2.5 to 5. When the flat cross-section glass fiber having an average ratio of the major axis to the minor axis in this range is used, the anisotropy is greatly improved as compared with the case of using a non-circular cross-section fiber of less than 1.5.
In addition to the flat shape, the flat cross-sectional shape may include an elliptical shape, an eyebrow shape, a trefoil shape, or a similar non-circular cross-sectional shape. Of these, a flat shape is preferable from the viewpoint of improving mechanical strength and low anisotropy. Further, the ratio (aspect ratio) between 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, still more preferably 3 to 50, and the fiber length and the average fiber. When the ratio of diameters is less than 2, the effect of improving the mechanical strength may be reduced. When the ratio of the fiber length to the average fiber diameter exceeds 120, the anisotropy increases and the appearance of the molded product also deteriorates. There is. The average fiber diameter 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 reinforced polycarbonate resin composition of the present invention. The number-average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of the filler 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. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

Content of the fibrous filler used as B component of this invention is 5-50 weight part in the total 100 weight part of A component and B component, 5-35 weight part is preferable, 10-35 weight Part is more preferable, and 10 to 30 parts by weight is further preferable. When the content of the B component is less than 5 parts by weight, the strength and heat resistance are not sufficient, and when it exceeds 50 parts by weight, not only the impact resistance is lowered, but also the flame retardancy is deteriorated.
(C component: fluororesin)
The fluororesin used as the component C of the present invention has a melting point of 200 ° C. to 280 ° C., preferably 210 ° C. to 280 ° C., and more preferably 230 ° C. to 280 ° C. When the melting point of the fluororesin is lower than 200 ° C., the heat resistance is lowered. On the other hand, when the melting point is higher than 280 ° C., the compatibility with the polycarbonate resin is lowered, and the impact resistance is lowered.
The fluororesin used as the component C of the present invention is a copolymer containing polymer units represented by the following general formulas [1] and [2]. When a fluororesin that does not contain this structure is used, the impact resistance is reduced.

In above general formula (1) ^represents R ^1, R 2, ^{R 3} and ^{R 4} are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

[In the above general formula [2], R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a fluorine atom, and R ⁸ represents a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. ]

Examples of the polymer unit represented by the above formula [1] include ethylene, propylene, 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1- Polymerized units derived from heptene, 3-methyl-1-hexene and the like can be mentioned, among which polymerized units derived from ethylene, propylene, 1-butene and isobutylene are preferred, and polymerized units derived from ethylene and propylene are more preferred. Preferably, polymerized units derived from ethylene are most preferred. These polymerized units may be used alone or in combination of two or more.
Examples of the polymer unit represented by the above formula [2] include tetrafluoroethylene, 1,1,2-trifluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, 1-fluoroethylene, hexafluoropropylene. , Preferred are polymer units derived from octafluoro-1-butene, decafluoro-1-pentene, octafluoroisobutylene, perfluorobutylethylene, tetrafluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, Polymerized units derived from hexafluoropropylene and perfluorobutylethylene are more preferred, and polymerized units derived from tetrafluoroethylene are more preferred. These polymerized units may be used alone or in combination of two or more.

The molar ratio [1] / [2] of the general formulas [1] and [2] constituting the fluororesin used as the component C of the present invention is preferably 95/5 to 5/95, and 90/10 to 10 / 90 is more preferred, 80/20 to 20/80 is even more preferred, and 70/30 to 30/70 is most preferred.
Content of the fluororesin used as C component of this invention is 2-45 weight part with respect to 100 weight part of components which consist of A component and B component, 2-30 weight part is preferable, 2-15 weight Part is more preferred. When the content of the C component is less than 2 parts by weight, the impact resistance is lowered, and when it is more than 45 important parts, not only the impact resistance is lowered, but also the strength is lowered.

(Other additives)
In order to improve the reinforced polycarbonate resin composition of the present invention and its thermal stability and design, the additives used for these improvements are advantageously used. Hereinafter, these additives will be specifically described.
(I) Thermal Stabilizer The reinforced polycarbonate resin composition of the present invention can contain various known stabilizers. Examples of the stabilizer include phosphorus stabilizers and hindered phenol antioxidants.
(I) Phosphorous stabilizer The reinforced polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer to the extent that it does not promote hydrolyzability. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like. Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used.

  For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-ter -Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4 -Phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis ( Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -phenyl -Phenylphosphonite is more preferred.
Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. The tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, an alkyl phosphate compound typified by trimethyl phosphate is preferably blended. A combination of such an alkyl phosphate compound and a phosphite compound and / or phosphonite compound is also a preferred embodiment.

(Ii) Hindered phenol stabilizer A hindered phenol stabilizer can be blended in the reinforced polycarbonate resin composition of the present invention. Such blending exhibits an effect of suppressing, for example, hue deterioration during molding and hue deterioration during long-term use.
Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4′-methylene bis (2,6- Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′- Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Nbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di- tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Anurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di-tert -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types.
The amount of the phosphorus stabilizer and the hindered phenol stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0 parts per 100 parts by weight of the component consisting of the component A and the component B, respectively. 0.5 part by weight, more preferably 0.005 to 0.3 part by weight.

(Iii) Heat stabilizer other than the above The reinforced polycarbonate resin composition of the present invention may contain a heat stabilizer other than the phosphorus stabilizer and the hindered phenol stabilizer. Preferable examples of such other heat stabilizers include lactone stabilizers represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Is done. Details of such a stabilizer are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the component consisting of the A component and the B component. .
Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, with respect to 100 parts by weight of the component consisting of the component A and the component B. is there.

  An epoxy compound can be mix | blended with the reinforced polycarbonate resin composition of this invention as needed. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 1,2-epoxy-4-butane of 2,2-bis (hydroxymethyl) -1-butanol. Examples include (2-oxiranyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate. The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight with respect to 100 parts by weight of the component consisting of the component A and the component B. More preferably, it is 0.005 to 0.1 parts by weight.

(II) Flame retardant A flame retardant can be mix | blended with the reinforced polycarbonate resin composition of this invention. The compounding of such a compound brings about an improvement in flame retardancy, but besides that, based on the properties of each compound, for example, an improvement in antistatic property, fluidity, rigidity and thermal stability is brought about. Examples of such flame retardants include (i) organic metal salt flame retardants (for example, organic sulfonate alkali (earth) metal salts, organic borate metal salt flame retardants, organic stannate metal salt flame retardants, etc.), ii) organophosphorous flame retardants (for example, organic group-containing monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, etc.), (iii) silicone flame retardants comprising silicone compounds (Iv) fibrillated PTFE, among which organometallic salt flame retardants and organic phosphorus flame retardants are preferred. These may be used alone or in combination.

(I) Organometallic salt flame retardant The organometallic salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40, preferably an alkali (earth) metal salt of an organic sulfonate. It is preferable that The alkali (earth) metal salt of the organic sulfonate includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, and alkali metals or alkaline earth metals are included. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, rubidium and cesium having larger ionic radii are suitable when the requirement for transparency is higher, but these are not general-purpose and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. Considering these, the alkali metal in the sulfonic acid alkali metal salt can be properly used. In any respect, the sulfonic acid potassium salt having an excellent balance of properties is most preferable. Such potassium salts and sulfonic acid alkali metal salts comprising other alkali metals can be used in combination.
Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

Of these, potassium perfluorobutanesulfonate is particularly preferred. The alkali (earth) metal salt of perfluoroalkylsulfonic acid composed of an alkali metal is usually mixed with not less than fluoride ions (F ⁻ ). The presence of such fluoride ions can be a factor that lowers the flame retardancy, so it is preferably reduced as much as possible. The ratio of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Moreover, it is suitable that it is 0.2 ppm or more in terms of production efficiency.
Such alkali (earth) metal salt of perfluoroalkylsulfonic acid having a reduced amount of fluoride ion is contained in a raw material when producing a fluorine-containing organometallic salt using a known production method. A method for reducing the amount of fluoride ions, a method for removing hydrogen fluoride and the like obtained by the reaction by a gas generated during the reaction or heating, and a purification method such as recrystallization and reprecipitation for producing a fluorine-containing organometallic salt Can be produced by a method of reducing the amount of fluoride ions using, for example. In particular, organic metal salt flame retardants are relatively soluble in water, and therefore ion-exchanged water, especially water that has an electric resistance of 18 MΩ · cm or more, that is, an electric conductivity of about 0.55 μS / cm or less is used. In addition, it is preferable to produce by a process of dissolving at a temperature higher than room temperature and washing, then cooling and recrystallization.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sodium sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiof 2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4- potassium sulfonate, naphthalene sulfone Examples thereof include a formalin condensate of sodium acid and a formalin condensate of sodium anthracene sulfonate. Among these aromatic sulfonate alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonate alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3′-disulfonate are preferable, and particularly a mixture thereof (the former and the latter). Is preferably 15/85 to 30/70).

  Preferable examples of the organic metal salt other than the alkali (earth) metal sulfonate include an alkali (earth) metal salt of a sulfate ester and an alkali (earth) metal salt of an aromatic sulfonamide. Examples of alkali (earth) metal salts of sulfates include alkali (earth) metal salts of sulfates of monovalent and / or polyhydric alcohols, and such monovalent and / or polyhydric alcohols. Examples of sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, and lauric acid monoglyceride sulfate. Examples include esters, sulfates of palmitic acid monoglyceride, and sulfates of stearic acid monoglyceride. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N- (N′-benzylaminocarbonyl) sulfanilimide, and N- ( And an alkali (earth) metal salt of phenylcarboxyl) sulfanilimide. The content of the organometallic salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, with respect to 100 parts by weight of the component consisting of the A component and the B component. Preferably it is 0.01-0.3 weight part, Most preferably, it is 0.03-0.15 weight part.

(Ii) Organophosphorus Flame Retardant As the organophosphorus flame retardant, an aryl phosphate compound or a phosphazene compound is preferably used. Since these organophosphorous flame retardants have a plasticizing effect, they are advantageous in that molding processability can be improved. Various known phosphate compounds as conventional flame retardants can be used as the aryl phosphate compound, and more preferably, one or more phosphate compounds represented by the following general formula [7] can be mentioned.

(However, M in the above formula represents a divalent organic group derived from a dihydric phenol, and Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each a monovalent organic group derived from a monohydric phenol. A, b, c and d are each independently 0 or 1, m is an integer of 0 to 5, and m is an average value in the case of a mixture of phosphate esters having different degrees of polymerization m. Represents a value between 0 and 5.)

The phosphate compound of the above formula may be a mixture of compounds having different m numbers, in which case the average m number is preferably 0.5 to 1.5, more preferably 0.8 to 1. 2, More preferably, it is 0.95-1.15, Most preferably, it is the range of 1-1.14.
Preferable specific examples of the dihydric phenol for deriving M include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide are exemplified, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferable.
Preferable specific examples of the monohydric phenol for deriving Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Are phenol and 2,6-dimethylphenol.

  The monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

  On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Phosphate oligomers mainly composed of phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate) and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate) are preferred Indicates that it may contain a small amount of other components having different degrees of polymerization, more preferably the component of m = 1 in the formula [7] is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Contains over 90% by weight Are shown.).

  As the phosphazene compound, various known phosphazene compounds can be used as conventional flame retardants, and phosphazene compounds represented by the following general formulas [8] and [9] are preferable.

(In the formula, X ¹ , X ² , X ³ , and X ⁴ represent hydrogen, a hydroxyl group, an amino group, or an organic group that does not contain a halogen atom. R represents an integer of 3 to 10.)

In the above formulas [8] and [9], examples of the organic group not containing a halogen atom represented by X ¹ , X ² , X ³ , X ⁴ include an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned. Among them, the cyclic phosphazene compound represented by the above formula [8] is preferable, and the cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula [8] are phenoxy groups is particularly preferable.
The content of the organophosphorous flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the component consisting of the A component and the B component. Part is more preferable. If the blending amount of the organic phosphorus flame retardant is less than 1 part by weight, it is difficult to obtain a flame retardant effect, and if it exceeds 50 parts by weight, strand breakage or surging occurs during kneading extrusion, resulting in reduced productivity. May occur.

(Iii) Silicone Flame Retardant A silicone compound used as a silicone flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as a flame retardant for aromatic polycarbonate resin can be used. Silicone compounds are highly flame retardant, especially when polycarbonate resins are used, either by themselves when bonded or by bonding with components derived from the resin to form a structure, or by a reduction reaction during the formation of the structure. It is thought to provide an effect.
Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.
Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is, M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _{1 / 2} , monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 , D unit: _{2 such as} (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Functional siloxane unit, T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) trifunctional siloxane units SiO _3/2, etc., Q unit: 4 represented by SiO ₂ It is a functional siloxane units.

  Specific examples of the structure of the silicone compound used in the silicone-based flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferred structure is MmDn or MmDnTp.

  Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more that indicate the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue. As a result, good reflected light can be obtained. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. On the other hand, silane compounds and siloxane compounds as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone-based flame retardants in their preferred embodiments in that it is preferable to contain no aryl group. . The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.
The content of the silicone flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the component consisting of the A component and the B component. 5 parts by weight.

(Iv) Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer. Fibrilized PTFE has an extremely high molecular weight and tends to be bonded to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in, for example, JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. Such PTFE can be used in solid form or in the form of an aqueous dispersion. Such fibrillated PTFE can also be used in a mixed form with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties.
Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.
Examples of such commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like.

As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A-11-29679, etc.) can be used.
Commercial products of these mixed forms of fibrillated PTFE include methabrene represented by Mitsubishi Rayon Co., Ltd.'s "methabrene A3000" (trade name), "methabrene A3700" (trade name), and "methabrene A3800" (trade name). Examples include A series, SN3300B7 (trade name) manufactured by Shine Polymer, and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.
The proportion of fibrillated PTFE in the mixed form is preferably 1% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, and more preferably 20% by weight in 100% by weight of the mixture. Most preferred is from 80% to 80% by weight.
When the ratio of fibrillated PTFE in the mixed form is within such a range, good dispersibility of the fibrillated PTFE can be achieved. The content of fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, with respect to 100 parts by weight of the component consisting of component A and component B. 0.1-0.5 weight part is further more preferable.

(III) Dye and Pigment The reinforced polycarbonate resin composition of the present invention can further provide a molded product containing various dyes and pigments and exhibiting various design properties. Examples of dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. In addition, by blending a fluorescent brightening agent or other fluorescent dyes that emit light, a better design effect utilizing the luminescent color can be imparted.

(IV) Fluorescent whitening agent In the reinforced polycarbonate resin composition of the present invention, the fluorescent whitening agent is not particularly limited as long as it is used for improving the color tone of the resin to white or bluish white. , Benzimidazole, benzoxazole, naphthalimide, rhodamine, coumarin, and oxazine compounds. Specifically, for example, CI Fluorescent Brightener 219: 1, Eastman Chemical OB-1 manufactured by Eastman Chemical Co., Ltd., “Hackol PSR” manufactured by Showa Chemical Co., Ltd., and the like can be mentioned. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part. The content of the optical brightener is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, with respect to 100 parts by weight of the component composed of the A component and the B component. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

(V) Compound having heat ray absorbing ability The reinforced polycarbonate resin composition of the present invention may contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near infrared absorbers, metal oxide-based near infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide, and titanium oxide, lanthanum boride, cerium boride, and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity such as metal borides and tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight with respect to 100 parts by weight of the component consisting of the A component and the B component. 0.001-0.07 part by weight is more preferable. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the polycarbonate resin composition of the present invention. A range of 5 to 100 ppm is more preferable.

(VI) Light diffusing agent The reinforced polycarbonate resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles that are already known as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 100 parts by weight of the component consisting of the component A and the component B. ~ 3 parts by weight. Two or more light diffusing agents can be used in combination.

(VII) White pigment for high light reflection The reinforced polycarbonate resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight with respect to 100 parts by weight of the component composed of the A component and the B component. Two or more kinds of white pigments for high light reflection can be used in combination.

(VIII) Ultraviolet Absorber The reinforced polycarbonate resin composition of the present invention can be provided with weather resistance by blending an ultraviolet absorber.
Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzi. Loxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxybenzophenone, and And 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.
Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like.
Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The Among them, benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable in terms of heat resistance and hue. Specifically, for example, Chemipro Kasei Co., Ltd. “Chemisorb 79”, BASF Japan Co., Ltd. “Tinubin 234” and the like can be mentioned. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 to 100 parts by weight of the component composed of the component A and the component B. -1 part by weight, particularly preferably 0.05-0.5 part by weight.

(IX) Antistatic Agent The reinforced polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight with respect to 100 parts by weight of the component consisting of the A component and the B component. Parts, more preferably in the range of 1.5 to 3 parts by weight.

Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, per 100 parts by weight of the component consisting of the A component and the B component. Parts, more preferably 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.
Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The amount of the ammonium salt is suitably 0.05 parts by weight or less with respect to 100 parts by weight of the component consisting of the A component and the B component. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The amount of the polymer is suitably 5 parts by weight or less with respect to 100 parts by weight of the component comprising the A component and the B component.

(X) Filler In the reinforced polycarbonate resin composition of the present invention, various known fillers can be blended as reinforcing fillers other than the fibrous filler. Examples of such fillers include various plate-like fillers and granular fillers. Here, the plate-like filler is a filler whose shape is plate-like (including those having irregularities on the surface and those having a curved plate). The granular filler is a filler having a shape other than these including an indefinite shape.
As plate-like fillers, glass-flake, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and these fillers are coated with different materials such as metals and metal oxides. A material etc. are illustrated preferably. The particle size is preferably in the range of 0.1 to 300 μm. The particle size is about 10 μm in terms of the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. In the region of 10-50 μm, laser diffraction is performed. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method is referred to, and in the region of 50 to 300 μm, the value is by the vibration sieving method. Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane, titanate, aluminate, and zirconate, and olefin resin, styrene resin, acrylic resin, polyester resin. It may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins and urethane resins, higher fatty acid esters, and the like.

(XI) Other resins and elastomers In the reinforced polycarbonate resin composition of the present invention, other resins and elastomers exhibit the effects of the present invention instead of a part of the resin component within a range not impairing the effects of the present invention. In a range to be used, a small percentage can be used. The blending amount of other resins and elastomers is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, most preferably with respect to 100 parts by weight of the component consisting of the A component and the B component. 3 parts by weight or less.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. And resins such as phenol resins and epoxy resins. As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber, MB (methyl methacrylate / butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber, and the like.

(XII) Other Additives The reinforced polycarbonate resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and photochromic agents. .

<About production of resin composition>
The reinforced polycarbonate resin composition of the present invention can be pelletized by melt kneading using an extruder such as a single screw extruder or a twin screw extruder. In producing such pellets, the above-mentioned various reinforcing fillers and additives can be blended. The reinforced polycarbonate resin composition of the present invention can produce various products by injection molding the pellets produced as described above. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known.
In addition, either a cold runner method or a hot runner method can be selected for molding. Moreover, the resin composition of this invention can also be utilized in the form of various profile extrusion-molded articles, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

<Manufacture of molded products>
The resin molded body made of the reinforced polycarbonate resin composition of the present invention can usually be obtained by injection molding such pellets to obtain a molded product. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerlessness can be used. Also in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra-molding) Including those using critical fluids), rapid heating / cooling mold forming, heat insulating mold forming and in-mold remelt molding, and combinations of these, etc. can be used.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

1. Evaluation of fluororesin 1-1. Melting | fusing point It calculated | required as temperature corresponding to the maximum value in the heat of fusion curve when it heated up at the speed | rate of 10 degree-C / min using the differential scanning calorimetry (DSC) apparatus.

2. 2. Evaluation of glass-reinforced polycarbonate resin composition 2-1. Impact resistance (Charpy impact strength)
After the pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours, the cylinder temperature was 300 ° C. and the mold temperature was 80 ° C. using an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.). A test piece (size: length 80 mm × width 10 mm × thickness 4 mm) was molded. Notched Charpy impact strength was measured in accordance with ISO 179 (measurement condition 23 ° C.). The notched Charpy impact strength is preferably greater than 10 kJ / m ² .
2-2. Heat resistance (deflection temperature under load)
A test piece (dimensions: length 80 mm × width 10 mm × thickness 4 mm) molded under the same conditions as in 2-1 was measured for load deflection temperature (load 1.80 MPa) in accordance with ISO75-1. The deflection temperature under load is preferably higher than 140 ° C.
2-3. Strength (flexural modulus)
A test specimen (dimensions: length 80 mm × width 10 mm × thickness 4 mm) molded under the same conditions as in 2-1 was measured for flexural modulus in accordance with ISO178. The flexural modulus is preferably greater than 3,500 MPa.
2-4. Flame retardance UL94 rank was evaluated at a thickness of 3.0 mm in accordance with a method (UL94) defined by US Underwriter Laboratory. The test piece was molded by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated. It is important not to drip during the combustion test, and it is preferably V-1 or V-0 in the UL94 rank.

[Examples 1 to 17 and Comparative Examples 1 to 7]
The components A to C and various additives were mixed in the blending amounts shown in Tables 1 and 2 with a blender, and then melt-kneaded using a vent type twin screw extruder to obtain pellets. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin-screw extruder used was TEX30α (completely meshing, rotating in the same direction, double thread screw) manufactured by Nippon Steel Works. The extrusion conditions are a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 270 ° C. from the first supply port to the second supply port and 280 ° C. from the second supply port to the die part. did. The evaluation results of the obtained pellets are shown in Table 1 and Table 2.

In addition, the detail of each used component is as follows.
(A component)
A-1: Polycarbonate resin powder having a viscosity average molecular weight of 22,400 obtained by the following production method [Production method]
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2340 parts of ion-exchanged water, 947 parts of a 25% aqueous sodium hydroxide solution and 0.7 parts of hydrosulfite, and 2,2-bis (4-hydroxyphenyl) under stirring. ) After dissolving 710 parts of propane (hereinafter sometimes referred to as “bisphenol A”) (bisphenol A solution), 2299 parts of methylene chloride and 112 parts of 48.5% aqueous sodium hydroxide solution were added, and the temperature was 15-25 ° C. The phosgenation reaction was performed by blowing 354 parts of phosgene over about 90 minutes. After completion of the phosgenation, 125 parts of 11% strength p-tert-butylphenol in methylene chloride and 88 parts of 48.5% aqueous sodium hydroxide solution were added to stop stirring. After 5 minutes of emulsification, the mixture was processed with a homomixer (Special Machine Industries Co., Ltd.) at a rotational speed of 1200 rpm and a pass count of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated with stirring to obtain polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate resin powder.
A-2: Polycarbonate resin powder having a viscosity average molecular weight of 19,800 obtained by the following production method [Production method]
A polycarbonate resin powder was obtained in the same manner as in the production method of A-1, except that the methylene chloride solution of 11% p-tert-butylphenol was changed to 128 parts.

(B component)
B-1: Circular cross-section chopped glass fiber (manufactured by Nittobo Co., Ltd .; CSG 3PE-455 (trade name), fiber diameter 13 μm, cut length 3 mm, urethane sizing agent)
B-2: Carbon fiber (manufactured by Toho Tenax Co., Ltd .; HT C422, fiber diameter 7 μm)
B-3: Glass milled fiber (PFE-301 manufactured by Nitto Boseki Co., Ltd., average fiber diameter 9 μm, average fiber length 30 μm, silane coupling agent treatment)
B-4: Flat section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CSG 3PA-830, major axis 27 μm, minor axis 4 μm, cut length 3 mm, epoxy sizing agent)
(C component)
C-1: ethylene / tetrafluoroethylene copolymer (melting point: 275 ° C.)
C-2: ethylene / tetrafluoroethylene copolymer (melting point: 231 ° C.)
C-3: ethylene / tetrafluoroethylene copolymer (melting point: 191 ° C.)
C-4: ethylene / tetrafluoroethylene copolymer (melting point: 285 ° C.)
C-5: Polytetrafluoroethylene (manufactured by Daikin Industries, Ltd .: Lubron L7 (trade name)) (melting point: 327 ° C.)
(Other ingredients)
TMP: Phosphate stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP (trade name))
TN: Tetrabromobisphenol A carbonate oligomer (manufactured by Teijin Limited: Fireguard FG8500 (trade name))
F114: perfluorobutanesulfonic acid potassium salt (Megafac F-114P (trade name) manufactured by Dainippon Ink, Inc.)
UV: Benzotriazole ultraviolet absorber (Kemipro Kasei Kogyo Co., Ltd .: Chemisorb 79 (trade name))
DC: Copolymer of maleic anhydride and α-olefin (Diacarna DC30M (trade name) manufactured by Mitsubishi Chemical Corporation)

Claims (5)

(C) Fluororesin (C component) with respect to 100 parts by weight of component consisting of 50 to 95 parts by weight of polycarbonate resin (component A) and (B) 5 to 50 parts by weight of fibrous filler (component B) A reinforced polycarbonate resin composition containing 2 to 45 parts by weight, wherein the C component is a copolymer containing polymer units represented by the following general formulas [1] and [2], and the melting point of the C component is A reinforced polycarbonate resin composition having a temperature of 200 ° C to 280 ° C.

In above general formula (1) ^represents R ^1, R 2, ^{R 3} and ^{R 4} are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

[In the above general formula [2], R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a fluorine atom, and R ⁸ represents a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. ] The reinforced polycarbonate resin composition according to claim ¹ , wherein, in the general formula [1], R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. In the above general formula (2), R ^5, R ⁶ and R ⁷ are reinforced polycarbonate resin composition according to claim 1 or 2, characterized in that a fluorine atom.   B component is glass fiber and / or carbon fiber, The reinforced polycarbonate resin composition in any one of Claims 1-3 characterized by the above-mentioned.   The molded object which consists of a reinforced polycarbonate resin composition in any one of Claims 1-4.