JP6956538B2 - Reinforced polycarbonate resin composition - Google Patents

Description

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

Polycarbonate resin is used in many applications such as mechanical parts, automobile parts, electrical / electronic parts, and office equipment parts because of its excellent properties such as mechanical strength, dimensional stability, and flame retardancy. In recent years, with the miniaturization and higher performance of parts, the demand for strength and heat resistance of parts has increased. At least one selected from the group consisting of a polycarbonate resin as a material with improved strength and heat resistance, a fibrous filler such as glass fiber and carbon fiber, a plate-like filler such as talc, and a granular filler such as calcium carbonate. Reinforced polycarbonate resin compositions containing the above fillers are known.
However, the polycarbonate resin has a drawback that the impact resistance is significantly lowered by adding the glass fiber. Conventionally, various methods for improving the impact resistance, which is lowered by adding glass fiber to the polycarbonate resin, have been studied.
Generally, in order to improve impact resistance, a technique of blending an elastomer such as Patent Documents 1 and 2 is known. However, while the impact resistance is improved, there is a problem that the heat resistance and the flame retardancy are lowered.
Patent Documents 3 to 5 disclose a method for introducing a polycarbonate-polyorganosiloxane copolymer as a polycarbonate resin. However, even in this case, while the impact resistance is improved, there remains a problem that the heat resistance and the flame retardancy are lowered. Further, even when the impact resistance is improved by alloying the polycarbonate resin with other resins such as polyester resin and styrene resin, the heat resistance and flame retardancy are lowered, and the flame retardancy of the glass reinforced resin composition is reduced. And the method of improving the impact resistance while maintaining the heat resistance is still insufficient.

On the other hand, fluororesins typified by polytetrafluoroethylene (PTFE) are extremely excellent in heat resistance, chemical resistance, weather resistance, and electrical properties as compared with other polymer materials, and are non-adhesive. Due to 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, application as a drip preventive agent (Patent Documents 6 and 7) and application as a slidability imparting material (Patent Documents 8 and 9) are known. However, since fluororesin has a high melting point, its application as an alloy material is limited.
Patent Document 10 reports a resin composition obtained by blending a fluororesin having a melting point of 150 to 230 ° C. with a polycarbonate resin. However, there is no description about the fibrous filler, and there is no description about improving the impact resistance of the reinforced resin composition. Patent Document 11 reports on a thermoplastic resin composition obtained by blending a base-treated fluorine-containing elastomer with a thermoplastic resin. However, there is no description about polycarbonate, and there is no description about fibrous filler. Patent Document 12 reports a slidable polycarbonate resin composition containing a fluoropolymer having no fibril-forming ability and carbon fibers in the polycarbonate resin. However, there is no description about impact resistance and heat resistance.

Japanese Unexamined Patent Publication No. 3-273052 Japanese Unexamined Patent Publication No. 2004-75747 Japanese Unexamined Patent Publication No. 55-160052 Japanese Unexamined Patent Publication No. 2-173061 Japanese Unexamined Patent Publication No. 7-26149 Japanese Unexamined Patent Publication No. 50-44241 Special Publication No. 60-38418 Japanese Unexamined Patent Publication No. 63-21355 Japanese Unexamined Patent Publication No. 2015-199892 Japanese Unexamined Patent Publication No. 5-171025 WO93 / 21272 JP-A-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 product made of the same.

As a result of diligent research to achieve the above object, the present inventors have excellent strength, heat resistance, and flame retardancy by blending a specific fluororesin with a component composed of a polycarbonate resin and a fibrous filler. We have found that a reinforced polycarbonate resin composition having properties and impact resistance can be obtained, and have reached the present invention. That is, according to the present invention, with respect to 100 parts by weight of the component consisting of (1) (A) 50 to 95 parts by weight of the polycarbonate resin (A component) and 5 to 50 parts by weight of (B) the fibrous filler (B component). (C) A reinforced polycarbonate resin composition containing 2 to 45 parts by weight of a fluororesin (C component), wherein the C component contains a polymerization 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 the above general formula [1], R ¹ , R ² , R ³ and R ⁴ each independently represent 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 represent 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 described in (2) the above configuration (1) ^{, wherein R 1} , R ² , R ³ and R ^{4 are hydrogen atoms in the above general formula [1].} Reinforced polycarbonate resin composition.
One of the more preferable embodiments of the present invention is (3) in the above general formula [2], wherein R ⁵ , R ⁶ and R ⁷ are fluorine atoms in the above configuration (1) or (2). The reinforced polycarbonate resin composition according to the above.
One of the more preferable embodiments of the present invention is (4) the reinforced polycarbonate resin composition according to any one of the above configurations (1) to (3), wherein the component B is glass fiber and / or carbon fiber. It is a thing.
One of the more preferable aspects of the present invention is (5) a molded product made of the reinforced polycarbonate resin composition according to any one of the above configurations (1) to (4).

The reinforced polycarbonate resin composition of the present invention is used for various applications such as various electronic / electrical equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts, other agricultural materials, transport containers, play 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 molten ester exchange method, or a carbonate prepolymer by a solid phase ester exchange method. It is obtained by polymerizing with the above, or by polymerizing with a ring-opening polymerization method of a cyclic carbonate compound.
The dihydroxy component used here may be any as long as it is usually used as the dihydroxy component of polycarbonate, and may be bisphenols or aliphatic diols. 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-hydroxyphenyl) 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) 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'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy- 3,3'-Dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3, 3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 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-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1,3-adamantane) Examples thereof include diyl) diphenol, 1,3-bis (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 independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, and alkenyl having 2 to 9 carbon atoms, respectively. A group or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ¹⁷ and R ¹⁸ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. An alkoxy group of 10 or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, p and q are integers of 1 to 4, respectively, e is a natural number, f is 0 or a natural number, and e + f. Is a natural number of 150 or less. X is an alkylene group having 2 to 8 carbon atoms.)

Examples of aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, and 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-hydroxyethoxy) -3,3'-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy)- 3-Isopropyl} propane, 2,2-bis {3-t-butyl-4- (2-hydroxyethoxy) 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} decan, 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-Cycloxyl-4- (2-hydroxyethoxy) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane , 9,9-bis {(2-hydroxyethoxy) 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, 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- Examples thereof include sorbitol (isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol (isoidide) and the like.

Of these, aromatic bisphenols are preferable, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, and 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, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, and bisphenol compounds represented by the above general formula [3] are preferable, and 2,2-bis (4-hydroxyphenyl) in particular. ) Propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyldiphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, according to the above general formula [4]. The bisphenol compound represented is preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used individually or in combination of 2 or more types.

The polycarbonate resin used as the component A of the present invention can be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) hepten-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) Etan, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4-[ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 1,1,1-tris (4-hydroxy) Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.
These polycarbonate resins are produced by a reaction means known per se for producing ordinary polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means for the manufacturing method will be briefly described.

In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out 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. A catalyst such as a tertiary amine or a quaternary ammonium salt can also be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method of distilling the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating in an inert gas atmosphere. .. 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 by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. It is also possible to use a catalyst usually used in a transesterification reaction to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.

In the present invention, a terminal terminator is used in the polymerization reaction. The terminal terminator is used for molecular weight regulation, and the obtained polycarbonate resin has excellent thermal stability as compared with the non-terminal-sealed polycarbonate resin. As such a terminal terminator, monofunctional phenols represented by the following general formulas [4] to [6] can be shown.

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

[In formulas [5] and [6], Y is -RO-, -R-CO-O- or -RO-CO-, where R is a single bond or 1 to 10 carbon atoms, Preferably, it represents a divalent aliphatic hydrocarbon group of 1 to 5, and n represents an integer of 10 to 50. ]

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

Among these monofunctional phenols, monofunctional phenols represented by the above general formula [4] are preferable, alkyl-substituted or phenylalkyl-substituted phenols are more preferable, and p-tert-butylphenol and p are particularly preferable. -Cumylphenol or 2-phenylphenol. It is desirable that the terminal terminator of these monofunctional phenols be introduced at the terminal at least 5 mol%, preferably at least 10 mol% with respect to the total terminal of the obtained polycarbonate resin, and the terminal terminator is used alone. Or a mixture of two or more types may be used.

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 preferably in the range of 18,000 to 28,000. Even more preferable, the range of 19,000 to 26,000 is most preferable. If the molecular weight exceeds 50,000, the melt viscosity may become too high and the moldability may be inferior, and if the molecular weight is less than 12,500, a problem may occur in mechanical strength. The viscosity average molecular weight referred to in the present invention was first determined by using an Ostwald viscometer to determine the specific viscosity calculated by the following formula from a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. The specific viscosity is inserted by the following formula to obtain the viscosity average molecular weight M.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
η _SP / c = [η] + 0.45 × ^{[η] 2} c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7

(B component: fibrous filler)
The fibrous filler used as the B component 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 whisker, calcium carbonate whisker, titanium oxide whisker, wallastnite, zonotrite, parigolskite (atapargite), and sepiolite, and heat-resistant organic fibers such as aramid fiber, polyimide fiber and polybenzthiazole fiber. Examples thereof include fibrous heat-resistant organic fillers and fibrous fillers in which different materials such as metals and metal oxides are surface-coated with respect to these fillers.
Examples of the filler surface-coated with different materials include metal-coated glass fibers and metal-coated carbon fibers. The surface coating method for different materials is not particularly limited, and for example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition method, ion plating method, CVD method (for example, For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method and the like 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 B component 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, further preferably 15 μm. On the other hand, the lower limit of the fiber diameter is more preferably 1 μm, further preferably 6 μm. The fiber diameter here refers to a number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after decomposing the molded product in a solvent or the resin with a basic compound, and the ashing residue collected after ashing in a crucible. It is a value calculated from an image observed with an electron microscope.

When the fibrous filler used as the B component of the present invention is glass fiber, various glass compositions typified by A glass, C glass, E glass and the like are applied to the glass composition of the glass fiber, and the glass composition is particularly limited. Not done. Such a glass filler may contain components such as _{TiO 2} , SO ₃ , and P ₂ O _{5, if necessary.} Among these, E glass (non-alkali glass) is more preferable.
Such glass fibers are preferably surface-treated with a well-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. Further, those which have been focused with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin or the like are preferable, and the epoxy resin and the urethane resin are mechanically strong. Especially preferable. The amount of the focusing agent adhered to the focused glass fiber is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, based on 100% by weight of the glass fiber.

A flat cross-section glass fiber can also be used as the fibrous filler used as the B component of the present invention. 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, 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). It is a glass fiber having an average value of preferably 1.5 to 8, more preferably 2 to 6, and even more preferably 2.5 to 5. When a flat cross-section glass fiber having an average value of the ratio of the major axis to the minor axis in this range is used, the anisotropy is greatly improved as compared with the case where a non-circular cross-section fiber of less than 1.5 is used.
Further, as the flat cross-sectional shape, in addition to the flat shape, a non-circular cross-sectional shape having an elliptical shape, an eyebrows shape, a trefoil shape, or a similar shape can be mentioned. Of these, a flat shape is preferable from the viewpoint of improving mechanical strength and low anisotropy. The ratio (aspect ratio) of the average fiber length to 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. If the ratio of the diameter is less than 2, the effect of improving the mechanical strength may be small, and if the ratio of the fiber length to the average fiber diameter exceeds 120, the anisotropy becomes large and the appearance of the molded product deteriorates. There is. The average fiber diameter of such a flat cross-sectional glass fiber means a number average fiber diameter when the flat cross-sectional shape is converted into a perfect circle having 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 high-temperature ashing of the molded product, dissolution with a solvent, decomposition with a chemical, or the like with an optical microscope. Is. Further, when calculating such a value, the value is obtained by a method in which the fiber diameter is used as a guide and the length shorter than that is not counted.

The content of the fibrous filler used as the B component of the present invention is 5 to 50 parts by weight, preferably 5 to 35 parts by weight, out of a total of 100 parts by weight of the A component and the B component, and 10 to 35 parts by weight. Parts are more preferable, and 10 to 30 parts by weight are even more preferable. If the content of the B component is less than 5 parts by weight, the strength and heat resistance are not sufficient, and if 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 C component 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. If 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 C component of the present invention is a copolymer containing a polymerization unit represented by the following general formulas [1] and [2]. When a fluororesin that does not contain this structure is used, the impact resistance is lowered.

[In the above general formula [1], R ¹ , R ² , R ³ and R ⁴ each independently represent 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 represent 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 polymerization 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-. Examples thereof include polymerization units derived from heptene, 3-methyl-1-hexene and the like. Among them, polymerization units derived from ethylene, propylene, 1-butene and isobutylene are preferable, and polymerization units derived from ethylene and propylene are more preferable. Preferably, a polymerization unit derived from ethylene is most preferred. These polymerization units may be used alone or in combination of two or more.
Examples of the polymerization unit represented by the above formula [2] include tetrafluoroethylene, 1,1,2-trifluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, 1-fluoroethylene, and hexafluoropropylene. , Octafluoro-1-butene, decafluoro-1-pentene, octafluoroisobutylene, perfluorobutylethylene, preferably tetrafluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, Polymerization units derived from hexafluoropropylene and perfluorobutylethylene are more preferable, and polymerization units derived from tetrafluoroethylene are even more preferable. These polymerization units may be used alone or in combination of two or more.

The molar ratios [1] / [2] of the above general formulas [1] and [2] constituting the fluororesin used as the C component of the present invention are preferably 95/5 to 5/95, and 90/10 to 10 / 90 is more preferable, 80/20 to 20/80 is even more preferable, and 70/30 to 30/70 is most preferable.
The content of the fluororesin used as the C component of the present invention is 2 to 45 parts by weight, preferably 2 to 30 parts by weight, and 2 to 15 parts by weight with respect to 100 parts by weight of the component composed of the A component and the B component. The portion is more preferable. 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) Heat Stabilizer The reinforced polycarbonate resin composition of the present invention can contain various known stabilizers. Examples of the stabilizer include a phosphorus-based stabilizer and a hindered phenol-based antioxidant.
(I) Phosphorus Stabilizer The reinforced polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer to the extent that hydrolyzability is not promoted. Such phosphorus-based stabilizers improve thermal stability during manufacturing or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof, and tertiary phosphine.

Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phenylphosphite, diisopropylmonophenylphosphenyl, monobutyldiphenylphosphenyl, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) 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, bis (nonylphenyl) penta Examples thereof include erythritol diphosphite and dicyclohexylpentaerythritol diphosphite. Further, as another phosphite compound, a compound which reacts with divalent phenols and has a cyclic structure can also 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'-Etilidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and so on. Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Phosphonite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and 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 , Tetrakiss (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-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) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are 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 the alkyl group is substituted by 2 or more. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, triphenylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus-based stabilizer can be used not only by one type but also by mixing two or more types. Among the phosphorus-based stabilizers, it is preferable that an alkyl phosphate compound typified by trimethyl phosphate is blended. It is also a preferred embodiment to use such an alkyl phosphate compound in combination with a phosphite compound and / or a phosphonite compound.

(Ii) Hindered Phenol Stabilizer A hindered phenolic stabilizer can be added to the reinforced polycarbonate resin composition of the present invention. Such a formulation has an effect of suppressing deterioration of hue during molding processing and deterioration of hue during long-term use, for example.
Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, cinapyl 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'- Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (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-butylpheno) , 2,2-thiodiethylenebis- [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) isocyanurate, 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-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3', 3',) 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like are exemplified. All of these are readily available. The above hindered phenolic stabilizers can be used alone or in combination of two or more.
The blending amount of the phosphorus-based stabilizer and the hindered phenol-based stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0, based on 100 parts by weight of the component composed of the A component and the B component, respectively. It is 5.5 parts by weight, more preferably 0.005 to 0.3 parts by weight.

(Iii) Heat Stabilizers Other Than The Phosphorus Stabilizers and Hindered Phenol Stabilizers Other than the Phosphorus Stabilizers and Hindered Phenol Stabilizers can be added to the reinforced polycarbonate resin composition of the present invention. As such other heat stabilizers, for example, lactone-based stabilizers typified by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene are preferably exemplified. Will be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above-mentioned company is preferably exemplified. The blending amount of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the component composed 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 blending 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, based on 100 parts by weight of the component composed of the A component and the B component. be.

An epoxy compound can be added to the reinforced polycarbonate resin composition of the present invention, if necessary. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically all compounds having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3', 4-'-epoxycyclohexylcarboxylate, and 1,2-epoxy-4-butanol of 2,2-bis (hydroxymethyl) -1-butanol. Examples thereof include a (2-oxylanyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, a copolymer of styrene and glycidyl methacrylate, and the like. 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, based on 100 parts by weight of the component composed of the A component and the B component. , More preferably 0.005 to 0.1 parts by weight.

(II) Flame Retardant A flame retardant can be added to the reinforced polycarbonate resin composition of the present invention. The formulation of such a compound brings about an improvement in flame retardancy, but other than 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) organometal salt-based flame retardants (for example, organosulfonic acid alkali (earth) metal salts, organoborate metal salt-based flame retardants, and organophosphorus metal salt-based flame retardants), ( ii) Organophosphorus flame retardant (for example, organic group-containing monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, etc.), (iii) Silicone flame retardant composed of silicone compound. , (Iv) fibrillated PTFE, among which organometal salt-based flame retardants and organophosphorus flame retardants are preferred. These may be used alone or in combination of two.

(I) Organic metal salt-based flame retardant The organic metal salt compound is an alkaline (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkaline (earth) metal salt of an organic sulfonic acid. Is preferable. This organic sulfonic acid alkali (earth) metal salt includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. It includes metal salts of acids, as well as metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40, and alkali metals or alkaline earth metals. 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 preferably, it is an alkali metal. Among such alkali metals, rubidium and cesium having a larger ionic radius are preferable when the demand for transparency is higher, but they are not versatile 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. In consideration of these, the alkali metal in the alkali metal sulfonic acid salt can be used properly, but in all respects, the potassium sulfonic acid salt having an excellent balance of characteristics is the most suitable. Such a potassium salt and a sulfonic acid alkali metal salt composed of another alkali metal can also be used in combination.
Specific examples of the alkali metal salt of perfluoroalkyl sulfonic acid include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluoro. Sodium butane sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutane sulfonate, perfluorooctane sulfonic acid Examples thereof include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. Here, the number of carbon atoms of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8.

Of these, potassium perfluorobutane sulfonate is particularly preferable. Alkali perfluoroalkyl sulfonic acid (earth) metal salts composed of alkali metals are usually contaminated with ^{not a small amount of fluoride ions (F −).} Since the presence of such fluoride ions can be a factor for lowering the flame retardancy, it is preferable to reduce the fluoride ions as much as possible. The ratio of such fluoride ions can be measured by an ion chromatography method. The fluoride ion content is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Further, it is preferable that the production efficiency is 0.2 ppm or more.
The perfluoroalkylsulfonic acid alkali (earth) metal salt having a reduced amount of fluoride ion is contained in a raw material for producing a fluorine-containing organic metal salt using a known production method. A method of reducing the amount of fluoride ions, a method of removing hydrogen fluoride obtained by the reaction by gas generated during the reaction or by heating, and a purification method of recrystallizing and reprecipitating a fluorine-containing organic metal salt for production. It can be produced by a method of reducing the amount of fluoride ions or the like using. In particular, organic metal salt-based flame retardants are relatively soluble in water, so ion-exchanged water, especially water satisfying an electrical resistance value of 18 MΩ · cm or more, that is, an electrical conductivity of about 0.55 μS / cm or less is used. It is preferable that the product is produced by a step of melting at a temperature higher than room temperature, washing, and then cooling and recrystallizing.

Specific examples of the aromatic sulfonic acid alkali (earth) metal salt include, for example, diphenylsulfide-4,4'-disodium disulfonate, diphenylsulfide-4,4'-dipotassium disulfonate, potassium 5-sulfoisophthalate, and the like. Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysodium polysulfonate , Poly (1,3-phenylene oxide) poly sulfonate polysodium, poly (1,4-phenylene oxide) poly sulfonate polysodium, poly (2,6-diphenylphenylene oxide) poly sulfonate polypotassium, poly (2-fluoro-) 6-Butylphenylene oxide) Lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl -3,3'-Calcium disulfonate, sodium diphenylsulfon-3-sulfonate, potassium diphenylsulfon-3-sulfonate, diphenylsulfon-3,3'-dipotassium disulfonate, diphenylsulfon-3,4'-disulfonic acid Dipotassium, α, α, α-sodium trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, Calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalene sulfonate, formalin condensate of sodium anthracene sulfonate, etc. may be mentioned. can. Among these aromatic sulfonic acid alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonic acid alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferable, and mixtures thereof (the former and the latter) are particularly preferable. The weight ratio of 15/85 to 30/70) is preferable.

As the organic metal salt other than the alkali (earth) metal salt of sulfonic acid, an alkali (earth) metal salt of a sulfate ester and an alkali (earth) metal salt of an aromatic sulfonamide are preferably exemplified. Examples of the alkali (earth) metal salt of the sulfate ester include an alkali (earth) metal salt of the sulfate ester of monovalent and / or polyhydric alcohols, such monovalent and / or polyhydric alcohols. Sulfate esters include methyl sulfate ester, ethyl sulfate ester, lauryl sulfate ester, hexadecyl sulfate ester, polyoxyethylene alkylphenyl ether sulfate ester, pentaerythritol mono, di, tri, tetrasulfate ester, and lauric acid monoglyceride sulfate. Examples thereof include an ester, a sulfate ester of palmitate monoglyceride, and a sulfate ester of stearate monoglyceride. As the alkali (earth) metal salt of these sulfate esters, an alkali (earth) metal salt of lauryl sulfate ester is preferable. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfoimide, N- (N'-benzylaminocarbonyl) sulfanylimide, and N- ( Examples thereof include alkali (earth) metal salts of phenylcarboxyl) sulfanylimide. The content of the organic metal salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, based on 100 parts by weight of the component composed of the A component and the B component. It is preferably 0.01 to 0.3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(Ii) Organophosphorus flame retardant As the organophosphorus flame retardant, an aryl phosphate compound and a phosphazene compound are preferably used. Since these organophosphorus flame retardants have a plasticizing effect, they are advantageous in that molding processability can be improved. As the aryl phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one kind or two or more kinds of 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 divalent phenol, and Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are monovalent organic groups derived from monovalent phenol, respectively. A, b, c and d are independently 0 or 1, m is an integer of 0 to 5, and in the case of a mixture of phosphate esters having different degrees of polymerization m, m is the average value thereof. It represents a value from 0 to 5.)

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

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

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-kisilyl) phosphate, and resorcinol bisdi (2,6-kisilyl) phosphate). A phosphate oligomer mainly composed of a phosphate oligomer, a phosphate oligomer mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and a phosphate ester oligomer mainly composed of bisphenol A bis (diphenyl phosphate) are suitable (here, if the main component is used). Indicates that other components having different degrees of polymerization may be contained in a small amount, and more preferably, the component of m = 1 in the above formula [7] is 80% by weight or more, more preferably 85% by weight or more, still more preferably. It indicates that it is contained in an amount of 90% by weight or more).

As the phosphazene compound, various phosphazene compounds conventionally known as flame retardants can be used, but 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 organic groups that do not contain hydrogen, hydroxyl groups, amino groups, or halogen atoms, and r represents an integer of 3 to 10.)

In the above formulas [8] and [9] ^{, examples of the halogen atom-free organic group represented by X 1} , X ² , X ³ , and X ⁴ include an alkoxy group, a phenyl group, an amino group, and an allyl group. Can be mentioned. Of these, the cyclic phosphazene compound represented by the above formula [8] is preferable, and further, ^{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 organophosphorus flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and 5 to 20 parts by weight with respect to 100 parts by weight of the component composed of the A component and the B component. The portion is more preferable. If the blending amount of the organophosphorus flame retardant is less than 1 part by weight, the flame retardant effect is difficult to obtain, and if it exceeds 50 parts by weight, there is a problem that strand breakage or surging occurs during kneading extrusion and productivity decreases. May occur.

(Iii) Silicone-based flame retardant A silicone compound used as a silicone-based flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. Silicone compounds are highly flame-retardant, especially when a polycarbonate resin is used, by binding themselves during combustion or by binding to components derived from the resin to form a structure, or by a reduction reaction during structure formation. It is believed to give an effect.
Therefore, it preferably contains a group having high activity in such a reaction, and more specifically, it contains a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (that is, Si—H group). preferable. The content ratio of such groups (alkoxy group, Si—H group) is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and 0.15 to 0. The range of 6 mol / 100 g is more preferable. Such a ratio is obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline 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 formed by arbitrarily combining four types of siloxane units shown below. That is, M unit: (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} , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ = CH) SiO _1/2, etc. monofunctional siloxane unit, D unit: (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, etc. 2 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 unit such as SiO 3/2, Q unit: A tetrafunctional siloxane unit represented by SiO ₂ .

Specific examples of the structure of the silicone compound used in the silicone flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq and DnTpQq. Among them, the preferable structure of the silicone compound is MmDn, MmTp, MmDnTp, MmDnQq, and the more preferable structure is MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the total of the coefficients in each formula is the average degree of polymerization of the silicone compound. .. The 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 more suitable the range, the better the flame retardancy. Further, as will be described later, the silicone compound containing a predetermined amount of 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 organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and decyl group, cycloalkyl group such as cyclohexyl group, and aryl group such as phenyl group. Also, an aralkyl group such as a trill group can be mentioned. More preferably, it is an alkyl group having 1 to 8 carbon atoms, 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, the silane compound and the siloxane compound as the organic surface treatment agent for the titanium dioxide pigment are clearly distinguished from the silicone-based flame retardant in their preferred embodiments in that a preferable effect can be obtained when they do not contain an aryl group. .. The silicone compound used as a silicone-based flame retardant may contain a reactive group in addition to the Si—H group and the alkoxy group, and the reactive group includes, for example, an amino group, a carboxyl group, an epoxy group, and vinyl. Examples include groups, mercapto groups, and methacryloxy groups.
The content of the silicone-based flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 1 to 1 part by weight with respect to 100 parts by weight of the component composed of the A component and the B component. 5 parts by weight.

(Iv) Polytetrafluoroethylene having the ability to form fibrils (fibrillated PTFE)
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. The fibrillated PTFE has an extremely high molecular weight and tends to bond the PTFE to each other to form a fibrous form due to an external action such as a shearing force. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. Such a number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C., for example, as disclosed in Japanese Patent Application Laid-Open No. 6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in such publication in ^{the range of 10 7} to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. It is also possible to use such fibrillated PTFE in a mixed form with another resin in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties.
Further, as disclosed in Japanese Patent Application Laid-Open No. 6-145520, a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell is also preferably used.
Examples of commercially available products of such fibrillated PTFE include Teflon (registered trademark) 6J of Mitsui-Dupont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Chemical Industry Co., Ltd.

Examples of the fibrillated PTFE in the mixed form include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coaggregating mixture (Japanese Patent Laid-Open No. 60-258263). (A method described in Japanese Patent Application Laid-Open No. 63-154744, etc.), (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). The method described), (3) A method of uniformly mixing an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution and simultaneously removing each medium from such a mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 06-220210). 08-188653, etc.), (4) A method for polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (Japanese Patent Laid-Open No. 9-95583). Method) and (5) A method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl-based monomer is further polymerized in the mixed dispersion to obtain a mixture (Japanese Patent Laid-Open No. 11-). The one obtained by the method described in Japanese Patent Application Laid-Open No. 29679 etc.) can be used.
Commercially available products of these mixed forms of fibrillated PTFE include Mitsubishi Rayon Co., Ltd.'s "Metabrene A3000" (trade name), "Metabren A3700" (trade name), and "Metabren A3800" (trade name). Examples thereof include the A series, SN3300B7 (trade name) manufactured by Shine Composer, and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.
The proportion of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, 20% by weight, based on 100% by weight of the mixture. Most preferably from% to 80% by weight.
Good dispersibility of fibrillated PTFE can be achieved when the proportion of fibrillated PTFE in the mixed form is in such a range. The content of the fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the component composed of the A component and the B component. 0.1 to 0.5 parts by weight is more preferable.

(III) Dyeing Pigment The reinforced polycarbonate resin composition of the present invention can further provide a molded product containing various dyeing pigments and exhibiting various designs. The dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthracinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, and quinacridone dyes. Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the polycarbonate resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is suitable as the metallic pigment. Further, by blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, a better design effect that makes the best use of the emitted 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 to improve the color tone of the resin or the like to white or bluish white. , Benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, oxazine-based compounds and the like. Specific examples thereof include CI Fluorescent Fluorescent 219: 1, Eastman Chemical Company's EASTOBRITE OB-1, and Showa Chemical Co., Ltd.'s "Hackor PSR". Here, the fluorescent whitening agent has an action of absorbing the ultraviolet energy of light rays and radiating this energy to the visible part. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, based on 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 can 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, titanium oxide, lanthanum boride, cerium boride and tungsten boride. Various metal compounds having excellent near-infrared absorbing ability such as metal boride-based and tungsten oxide-based near-infrared absorbing agents, and carbon fillers are preferably exemplified. 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 fullerenes, 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, based on 100 parts by weight of the component composed of the A component and the B component. , 0.001 to 0.07 parts by weight is more preferable. The content of the metal oxide-based near-infrared ray absorber, the metal boride-based near-infrared ray 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. The range of 5 to 100 ppm is more preferable.

(VI) Light Diffusing Agent The reinforced polycarbonate resin composition of the present invention may be blended with a light diffusing agent to impart a light diffusing effect. Examples of such a light diffusing agent include high molecular weight fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as a light diffusing agent for polycarbonate resin. More preferably, acrylic crosslinked particles having a particle size of several μm and silicone crosslinked particles typified by polyorganosylsesquioxane are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a pillar shape, and an amorphous shape. Such a sphere includes a deformed one that does not have to be a perfect sphere, and such a pillar shape includes a cube. The preferred light diffusing agent is spherical, and the more uniform the particle size, the more preferable. 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, still more preferably 0.01, based on 100 parts by weight of the component composed of the A component and the B component. ~ 3 parts by weight. Two or more types of 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 blended with a white pigment for high light reflection to impart a light reflection effect. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferable. 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, based on 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 blended with an ultraviolet absorber to impart weather resistance.
Specific examples of such an ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzine in the benzophenone system. 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-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy Examples thereof include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole system. , 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-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazo- , 2- (2-Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) ) Benzotriazol, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2 -Hydroxy-3- (3,4,5,6-tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole Copolymerization of a vinyl-based monomer copolymerizable with the monomer or 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer Examples thereof include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as polymers.

Specifically, in the hydroxyphenyltriazine system, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4, 6-Diphenyl-1,3,5-triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol , 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) ) -5-Butyloxyphenol and the like are exemplified. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified.
Specific examples of the ultraviolet absorber are cyclic iminoesters, for example, 2,2'-p-phenylenebis (3,1-benzoxazine-4-one) and 2,2'-m-phenylenebis (3,1). -Benzooxazine-4-one), and 2,2'-p, p'-diphenylenebis (3,1-benzoxazine-4-one) and the like are exemplified.
As the ultraviolet absorber, specifically, in the case of a cyanoacrylate type, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-2-bis]. Examples thereof include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

Further, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that such an ultraviolet-absorbing monomer and / or a photostable monomer and a single amount of an alkyl (meth) acrylate or the like are used. It may be a polymer-type ultraviolet absorber copolymerized with the body. As the ultraviolet absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. NS. Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability, and cyclic iminoester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue. Specific examples thereof include Chemipro Kasei Co., Ltd. "Chemisorb 79" and BASF Japan Ltd. "Chinubin 234". The UV absorber may be used alone or in a mixture of two or more.
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 further preferably 0.05 with respect to 100 parts by weight of the component composed of the A component and the B component. It is ~ 1 part by weight, particularly preferably 0.05 to 0.5 part by weight.

(IX) Antistatic Agent The reinforced polycarbonate resin composition of the present invention may be required to have antistatic performance, and in such a case, it is preferable to contain an antistatic agent. Examples of such an antioxidant include (1) an aryl sulfonic acid phosphonium salt typified by dodecylbenzene sulfonic acid phosphonium salt, an organic sulfonic acid phosphonium salt such as an alkyl sulfonic acid phosphonium salt, and a tetrafluoroborate phosphonium salt. Phosphonium borate salt can be mentioned. The content of the phosphonium salt is preferably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, and more preferably 1 to 3.5 parts by weight with respect to 100 parts by weight of the component composed of the A component and the B component. It is in the range of 1.5 to 3 parts by weight, more preferably 1.5 to 3 parts by weight.

Examples of the antistatic agent include (2) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Organic sulfonic acid alkali (earth) metal salts such as. As described above, such a metal salt is also used as a flame retardant. More specifically, examples of such a metal salt include a metal salt of dodecylbenzene sulfonic acid and a metal salt of perfluoroalkane sulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is preferably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, based on 100 parts by weight of the component composed of the A component and the B component. Parts, more preferably 0.005 to 0.2 parts by weight. Alkali metal salts such as potassium, cesium, and rubidium are particularly suitable.
Examples of the antistatic agent include (3) an ammonium salt of alkyl sulfonic acid and an ammonium salt of organic sulfonic acid such as an ammonium salt of aryl sulfonic acid. It is appropriate that the ammonium salt is 0.05 parts by weight or less with respect to 100 parts by weight of the component composed of the A component and the B component. Examples of the antistatic agent include polymers containing a poly (oxyalkylene) glycol component such as (4) polyether ester amide as a component thereof. 5 parts by weight or less is appropriate for the polymer with respect to 100 parts by weight of the component composed of the A component and the B component.

(X) Filler The reinforced polycarbonate resin composition of the present invention can be blended with various fillers known as reinforced fillers other than the fibrous filler. Examples of such a filler include various plate-shaped fillers and granular fillers. Here, the plate-shaped filler is a filler having a plate-like shape (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.
Plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-like fillers in which different materials such as metals and metal oxides are surface-coated on these fillers. Materials and the like are preferably exemplified. The particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to a value based on 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 up to about 10 μm, and laser diffraction in the region of 10 to 50 μm. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method, and is the value by the vibration sieving method in the region of 50 to 300 μm. Such particle size is the particle size in the resin composition. The plate-shaped filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based, and may be surface-treated, and may be olefin-based resin, styrene-based resin, acrylic-based resin, or polyester-based resin. , An epoxy-based resin, various resins such as a urethane-based resin, a higher fatty acid ester, or the like, or a granulated product which has been subjected to a focusing treatment or a compression treatment.

(XI) Other Resins and Elastomers In the reinforced polycarbonate resin composition of the present invention, other resins and elastomers are used instead of some of the resin components to exert the effects of the present invention as long as the effects of the present invention are not impaired. It can also be used in a small proportion within the range of the above. The blending amount of the other resin or elastomer 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, and most preferably 5 parts by weight or less, based on 100 parts by weight of the component composed of the A component and the B component. It is 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. , Phenolic resin, epoxy resin and other resins. Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / sterene / butadiene), which is a core-shell type elastomer. Examples thereof include rubber, MB (methyl methacrylate / butadiene) rubber, and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

(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, photochromic agents and the like. ..

<Manufacturing 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 strengthening fillers and additives can also be blended. The reinforced polycarbonate resin composition of the present invention can usually produce various products by injection molding pellets produced as described above. Further, it is also possible to directly convert the resin melt-kneaded by the extruder into a sheet, a film, a modified extrusion molded product, a direct blow molded product, and an injection molded product without passing through pellets. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by injection of supercritical fluid), insert molding, and insert molding, depending on the intended purpose. Molded products can be obtained using injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known.
Further, either a cold runner method or a hot runner method can be selected for molding. Further, the resin composition of the present invention can also be used in the form of various deformed extruded products, sheets, films and the like by extrusion molding. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be made into a molded product by rotary molding, blow molding or the like.

<Manufacturing of molded products>
The resin molded product made of the reinforced polycarbonate resin composition of the present invention can usually be injection-molded with such pellets to obtain a molded product. In such injection molding, it is possible to manufacture by a hot runner that enables runner-less as well as a usual cold runner type molding method. 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). (Including those using a critical fluid), rapid heating and cooling mold molding, heat insulating mold molding and in-mold remelt molding, and a molding method consisting of a combination thereof can be used.

The embodiment of the present invention, which the present inventor considers to be the best at present, is a collection of preferable ranges of the above-mentioned requirements. For example, a representative example thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

1. 1. Evaluation of fluororesin 1-1. It was determined as the temperature corresponding to the maximum value in the heat of fusion curve when the temperature was raised at a rate of 10 ° C./min using a melting point differential scanning calorimetry (DSC) device.

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 under the condition of 120 ° C. for 5 hours, the cylinder temperature was 300 ° C. and the mold temperature was 80 ° C. by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). A test piece (dimensions: length 80 mm × width 10 mm × thickness 4 mm) was formed in the above. The notched Charpy impact strength was measured in accordance with ISO179 (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 2-1 was measured for deflection temperature under load (load 1.80 MPa) in accordance with ISO75-1,2. The deflection temperature under load is preferably higher than 140 ° C.
2-3. Strength (flexural modulus)
A test piece (dimensions: length 80 mm × width 10 mm × thickness 4 mm) molded under the same conditions as 2-1 was measured for flexural modulus in accordance with ISO178. The flexural modulus is preferably greater than 3,500 MPa.
2-4. Flame Retardant The UL94 rank was evaluated with a thickness of 3.0 mm in accordance with the method (UL94) specified by Underwriter Laboratory, Inc. of the United States. 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. In addition, when the judgment could not meet any of the criteria of V-0, V-1, and V-2, it was decided to indicate "notV". It is important not to drip during the combustion test, and it is preferably V-1 or V-0 in 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 bent twin-screw extruder to obtain pellets. For each of the various additives to be used, a premix with the polycarbonate resin was prepared in advance with a concentration of 10 to 100 times the blending amount as a guide, and then the whole mixture was mixed with a blender. The vent type twin-screw extruder was manufactured by The Japan Steel Works, Ltd .: TEX30α (complete meshing, rotating in the same direction, double-threaded screw). The extrusion conditions are a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum degree 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 portion. bottom. The evaluation results of the obtained pellets are shown in Tables 1 and 2.

The details of each component used are as follows.
(Component A)
A-1: Polycarbonate resin powder having a viscosity average molecular weight of 22,400 obtained by the following production method [Manufacturing method]
2340 parts of ion-exchanged water, 947 parts of 25% sodium hydroxide aqueous solution, and 0.7 part of hydrosphenol were charged into a thermometer, agitator, and a reactor with a reflux cooler, and 2,2-bis (4-hydroxyphenyl) was added under stirring. ) 710 parts of propane (hereinafter sometimes referred to as "bisphenol A") is dissolved (bisphenol A solution), then 2299 parts of methylene chloride and 112 parts of 48.5% sodium hydroxide aqueous solution are added, and the temperature is 15 to 25 ° C. A phosgenation reaction was carried out by blowing 354 parts of phosgen over about 90 minutes. After completion of phosgenation, 125 parts of methylene chloride solution of 11% concentration p-tert-butylphenol and 88 parts of 48.5% sodium hydroxide aqueous solution were added, stirring was stopped, and the mixture was left to stand for 10 minutes and then stirred. After 5 minutes of emulsification, it was treated with a homomixer (Special Machinery Chemical Industry Co., Ltd.) at a rotation speed of 1200 rpm and a number of passes 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 no 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 and washed with water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, it is poured into a kneader filled with warm water. Methylene chloride was evaporated with stirring to obtain a polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation type 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 manufacturing method [Manufacturing 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 p-tert-butylphenol having an 11% concentration was changed to 128 parts.

(B component)
B-1: Circular cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .; CSG 3PE-455 (trade name), fiber diameter 13 μm, cut length 3 mm, urethane-based focusing 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 cross-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-based focusing 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: Potassium perfluorobutane sulfonate (Mega Fvck F-114P (trade name) manufactured by Dainippon Ink Co., Ltd.)
UV: Benzotriazole-based UV absorber (manufactured by Chemipro 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 (4)

(A) Fluororesin (C component) with respect to 100 parts by weight of the component consisting of 50 to 95 parts by weight of the polycarbonate resin (A component) and 5 to 50 parts by weight of the (B) fibrous filler (B component). A reinforced polycarbonate resin composition containing 2 to 45 parts by weight.
The C component is a copolymer containing a polymerization unit represented by the following general formulas [1] and [2] .
Ri melting point 231 ° C. to 280 ° C. der of the component C, and
The polycarbonate resin is a polycarbonate resin prepared using aromatic bisphenols.
A reinforced polycarbonate resin composition characterized by the above.

In above general formula ^{(1), R 1, R 2, R} 3 and ^{R 4} represents a hydrogen atom. ]

In above general formula ^(2), R 5, ^{R 6} and ^{R 7} represents a full Tsu atom, ^{R 8} represents a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. ] The polycarbonate resin is a polycarbonate resin prepared using bisphenol A, and
The C component is an ethylene / tetrafluoroethylene copolymer.
The reinforced polycarbonate resin composition according to claim 1. The reinforced polycarbonate resin composition according to claim 1 or 2 , wherein the component B is glass fiber and / or carbon fiber. A molded product made of the reinforced polycarbonate resin composition according to any one of claims 1 to 3.