JP7440306B2 - Polycarbonate resin composition and molded product thereof - Google Patents

Description

The present invention relates to polycarbonate resin compositions. In particular, the present invention relates to a polycarbonate resin composition that has good sustained antistatic properties, excellent thermal stability, high elastic modulus, and low anisotropy.

Polycarbonate resins are used in many applications such as mechanical parts, automobile parts, electrical/electronic parts, and office equipment parts due to their excellent properties such as mechanical properties, dimensional stability, and flame retardance. However, in some applications, antistatic properties (prevention of dust adsorption to resin materials) and further improvements in mechanical properties are required. As a method of imparting antistatic properties to resin materials, there is a method of using conductive carbon black, but the improvement in mechanical properties such as elastic modulus is small. There is also a method of using carbon fiber in order to improve mechanical properties at the same time, but this creates anisotropy and has disadvantages in terms of dimensional accuracy, such as warping in the molded product. When conductive carbon black or carbon fiber is used, the molded product is only black, so there is a drawback that it cannot be colored. A method to compensate for these shortcomings and achieve both improved mechanical properties, antistatic properties, coloring properties, and low anisotropy is to use an inorganic filler with low anisotropy and add an antistatic agent. A possible method is to do so. As the antistatic agent, a method using a sulfonic acid phosphonium salt (see Patent Document 1) and a method using a surfactant such as glycerin fatty acid ester (see Patent Document 2) have been proposed. However, the antistatic properties of the polycarbonate resin compositions described in Patent Documents 1 and 2 have a drawback that they are poor in durability, such as the effect being significantly reduced by one-time washing with water. On the other hand, a method using polyether ester amide (see Patent Document 3) has been proposed as a method for imparting sustained antistatic properties, but it has been reported that thermal stability during melt-kneading and injection molding deteriorates. There are disadvantages such as a decrease in heat resistance (deflection temperature under load).

Patent No. 4606762 Patent No. 6215717 Japanese Patent Application Publication No. 2002-129026

An object of the present invention is to provide a polycarbonate resin composition that has good sustained antistatic properties, excellent thermal stability, high elastic modulus, and low anisotropy, and a molded article thereof.

As a result of extensive research, the present inventors have discovered that the above problems can be solved by a polycarbonate resin composition containing a specific ion pair compound and an inorganic filler. That is, the present inventors have found that the above-mentioned problems can be achieved by the following polycarbonate resin composition and molded product thereof.

1. (A) 100 parts by weight of aromatic polycarbonate resin (component A), 0.3 to 10 parts by weight of (B) ion pair compound (component B) and 1 to 100 parts by weight of (C) inorganic filler (component C). A resin composition containing parts by weight of an ion pair compound, characterized in that the melting point is 80°C or lower and the 5% weight loss temperature measured by TG-TDA is 350°C or higher. thing.
2. The cation of the ion pair compound has a structure having at least one selected from the group consisting of an onium ion, an imidazole ring, and a pyridine ring, and the anion is an anion represented by the following formula (I) or (II). 1. The resin composition according to item 1 above.

[In the formula, R ₁ , R ₂ and R ₃ each represent a perfluoroalkyl group having 1 to 4 carbon atoms. ]

3. 3. The resin composition according to item 1 or 2 above, wherein the ion pair compound is a compound represented by the following formula (III).

[In the formula, R ₁ and R ₂ each represent a perfluoroalkyl group having 1 to 4 carbon atoms, R ₄ represents an alkyl group having 6 to 12 carbon atoms, and R ₅ represents an alkyl group having 10 to 20 carbon atoms. ]

4. 3. The resin composition according to item 3 above, wherein R ₄ is a straight chain alkyl group having 6 to 8 carbon atoms, and R ₅ is a straight chain alkyl group having 12 to 16 carbon atoms.
5. The resin according to item 3 or 4 above, wherein R ₁ and R ₂ are each a trifluoromethyl group, R ₄ is a straight chain alkyl group having 6 carbon atoms, and R ₅ is a straight chain alkyl group having 14 carbon atoms. Composition.
6. 6. The resin composition according to any one of items 1 to 5 above, wherein component C is at least one inorganic filler selected from the group consisting of glass, talc, mica, and wollastonite.
7. The molding shrinkage rate of the molded product obtained by molding the resin composition is such that the ratio (S1/S2) of the shrinkage rate in the direction perpendicular to the flow direction (S1) and the shrinkage rate in the parallel direction to the flow direction (S2) is less than 3.0. 7. The resin composition according to items 1 to 6 above.
8. 8. The resin composition according to any one of items 1 to 7 above, which contains 0.001 to 0.5 parts by weight of (D) a phosphorus stabilizer (Component D) per 100 parts by weight of Component A.
9. A molded article obtained by molding the resin composition according to any one of items 1 to 8 above.

The polycarbonate resin composition of the present invention has good lasting antistatic properties and is excellent in thermal stability, high elastic modulus and low anisotropy, so it meets the needs of antistatic properties (dustproof properties) and mechanical properties. It is useful for automotive interior parts, camera lens barrel materials that require dimensional accuracy, high elastic modulus, and antistatic properties. For example, some lens barrel materials require antistatic properties to prevent dust from adhering to the lens, but it is not appropriate to use fiber fillers such as carbon fiber due to concerns about filler slipping and anisotropy. Therefore, it is very useful to apply the present invention in combination with an inorganic filler such as talc having a small particle size and an ion pair compound. Therefore, the industrial effects of the present invention are extremely large.

(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as component A in the present invention is obtained by reacting dihydric phenol with a carbonate precursor. Examples of reaction methods include interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

Representative examples of dihydric phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) ) Propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)- 1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl) Pentane, 4,4'-(p-phenylene diisopropylidene) diphenol, 4,4'-(m-phenylene diisopropylidene) diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane , bis(4-hydroxyphenyl) oxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ketone, bis(4- Examples include hydroxyphenyl) ester, bis(4-hydroxy-3-methylphenyl) sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. It will be done. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance and is widely used.

In the present invention, in addition to bisphenol A type polycarbonate, which is a general-purpose polycarbonate, special polycarbonates produced using other dihydric phenols can be used as the A component.

For example, as part or all of the divalent phenol component, 4,4'-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxy phenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") has a size change due to water absorption. It is suitable for applications where requirements for change and morphological stability are particularly demanding. It is preferable to use these dihydric phenols other than BPA in an amount of 5 mol % or more, particularly 10 mol % or more of the total dihydric phenol components constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). be.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF is 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis - A copolymerized polycarbonate having a TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

These special polycarbonates may be used alone or in an appropriate mixture of two or more. Further, these can also be used in combination with a commonly used bisphenol A type polycarbonate.

The manufacturing method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Among the various polycarbonates mentioned above, those whose water absorption and Tg (glass transition temperature) are within the ranges of (i) or (ii) below by adjusting the copolymer composition etc. Since it has good decomposability and extremely low warpage after molding, it is particularly suitable in fields where morphological stability is required.
(i) A polycarbonate having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C.
(ii) Tg is 160 to 250°C, preferably 170 to 230°C, and water absorption is 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27% polycarbonate.

Here, the water absorption rate of polycarbonate is the value obtained by measuring the moisture content after immersing a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in water at 23°C for 24 hours in accordance with ISO62-1980. be. Moreover, Tg (glass transition temperature) is a value determined by differential scanning calorimeter (DSC) measurement based on JIS K7121.

Carbonyl halides, carbonic acid diesters, haloformates, etc. are used as carbonate precursors, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

When producing polycarbonate resin by interfacial polymerization of the dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant to prevent the dihydric phenol from oxidizing, etc. are added as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. , copolymerized polycarbonate resins in which difunctional alcohols (including alicyclics) are copolymerized, and polyester carbonate resins in which such difunctional carboxylic acids and difunctional alcohols are copolymerized together. Alternatively, it may be a mixture of two or more of the obtained polycarbonate resins.

The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2. , 4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl) Ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[ Trisphenol such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, Examples include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among which 1,1,1-tris(4-hydroxy Phenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

The structural unit derived from a polyfunctional aromatic compound in the branched polycarbonate is preferably 100% by mole in total of the structural unit derived from a dihydric phenol and the structural unit derived from such a polyfunctional aromatic compound. The amount is 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%.

In addition, particularly in the case of the melt transesterification method, branched structural units may be produced as a side reaction, and the amount of such branched structural units is also preferably within the total 100 mol% of the structural units derived from dihydric phenol. The content is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%. Note that the proportion of such a branched structure can be calculated by 1H-NMR measurement.

The aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, as well as cyclohexanedicarboxylic acid. Preferred examples include alicyclic dicarboxylic acids such as. As the difunctional alcohol, alicyclic diols are more suitable, and examples include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

The reaction formats of the interfacial polymerization method, melt transesterification method, carbonate prepolymer solid-phase transesterification method, and ring-opening polymerization method of cyclic carbonate compounds, which are the methods for producing the aromatic polycarbonate resin of the present invention, are described in various documents and patents. This is a well-known method from public publications.

The melt volume rate (300°C, 1.2 kg load) of the aromatic polycarbonate resin in the present invention is not particularly limited, but is preferably 1 to 60 cm ³ /10 min, more preferably 3 to 30 cm ³ /10 min, even more preferably is 5 to 20 cm ³ /10 min. A resin composition obtained from an aromatic polycarbonate resin having a melt volume rate of less than 1 cm ³ /10 min may have poor versatility due to poor fluidity during injection molding. On the other hand, polycarbonate resins with a melt volume rate exceeding 60 cm ³ /10 min may not provide good mechanical properties. Note that the melt volume rate is also called "MVR" and is measured in accordance with ISO1133.

A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the aromatic polycarbonate resin (component A) of the present invention. Polycarbonate-polydiorganosiloxane copolymer resin is a copolymer resin prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). Preferably, it is a polymeric resin.

[In the above general formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a 6 to 18 carbon atom; 20 cycloalkyl group, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, carbon atom Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there is a plurality of each, they may be the same or different. e and f are each integers of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). ]

[In the above general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a carbon Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a C 1 to 18 atom. Alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, 6 carbon atoms ~14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group, and carboxyl group When there are multiple groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

[In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. , q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) represented by general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 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-isopropyl) phenyl)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)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'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4, 4'-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4' -Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl) ) propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4 , 8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl) )-5,7-dimethyladamantane and the like.

Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 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 is preferred, especially 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'- Sulfonyldiphenol and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most suitable. Further, these may be used alone or in combination of two or more.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by subjecting the end of a polysiloxane chain having a degree of polymerization of Among these, preferred are (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane, particularly (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane. -allylphenol)-terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. In order to further exhibit excellent low outgassing properties during high temperature molding and low temperature impact properties, the molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, a large amount of outgas will be generated during high-temperature molding, and low-temperature impact properties may be poor.

Furthermore, in order to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance, which is a characteristic of the polycarbonate-polydiorganosiloxane copolymer, will not be effectively expressed, and if it exceeds the upper limit of this preferred range, poor appearance will appear.

The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.1 to 50% by weight. The content of the polydiorganosiloxane component is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. When it is above the lower limit of this preferred range, it has excellent impact resistance and flame retardancy, and when it is below the upper limit of this preferred range, it is easy to obtain a stable appearance that is not easily affected by molding conditions. The degree of polymerization of polydiorganosiloxane and the content of polydiorganosiloxane can be calculated by 1H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

In addition, other comonomers other than the above-mentioned dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be contained in an amount of 10% by weight or less based on the total weight of the copolymer, to the extent that it does not interfere with the present invention. They can also be used together.

In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution. do.

In producing an oligomer of dihydric phenol (I), the entire amount of dihydric phenol (I) used in the method of the present invention may be made into an oligomer at once, or a part thereof may be used as a post-added monomer to form an oligomer at the subsequent interface. It may be added as a reaction raw material to the polycondensation reaction. The post-addition monomer is added to speed up the subsequent polycondensation reaction, and there is no need to intentionally add it if it is not necessary.

The method of this oligomer production reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

The proportion of the carbonate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using a gaseous carbonate-forming compound such as phosgene, a method of blowing it into the reaction system can be suitably employed.

As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof are used. Similarly to the above, the proportion of the acid binder to be used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use the acid binder in an amount of 2 equivalents or slightly in excess of the number of moles of dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents). .

As the solvent, solvents inert to various reactions, such as those used in the production of known polycarbonates, may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride, and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

The reaction pressure for oligomer production is not particularly limited and may be at normal pressure, increased pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is generated during polymerization in many cases, it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be absolutely defined, it is usually carried out for 0.2 to 10 hours. The pH range of the oligomer production reaction is similar to known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In this way, the present invention obtains a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, and then, while stirring the mixed solution, the molecular weight distribution (Mw/Mn) is reduced to 3 or less. A highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3) is added to dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. A polycarbonate-polydiorganosiloxane copolymer is thereby obtained.

(In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. (where q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof are used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used or a part of the dihydric phenol (I) as described above is added to this reaction step as a post-addition monomer, the post-addition amount is It is preferable to use the alkali in an amount of 2 equivalents or in excess of the total number of moles of the hydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

Polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

In such polymerization reactions, terminal terminators or molecular weight regulators are usually used. Examples of the terminal capping agent include compounds having a monovalent phenolic hydroxyl group, including ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols and aliphatic carboxylic acids. Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of all the dihydric phenol compounds used, and it is naturally possible to use two or more types of compounds together. be.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to accelerate the polycondensation reaction.

The reaction time of this polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

A branching agent can be used in combination with the dihydric phenol compound described above to form a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl). ) Heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris (4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, Trisphenol such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among others, 1,1,1 -Tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane is preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred . The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9% based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. It is mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%. Note that the amount of branched structure can be calculated by ¹ H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually, the reaction can be suitably carried out at normal pressure or about the own pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since heat is generated during polymerization in many cases, it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as reaction temperature, it cannot be absolutely specified, but it is usually carried out for 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity of [η _SP /c].

The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (purification degree).

The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. Such average size is more preferably 1 to 30 nm, even more preferably 5 to 25 nm. If it is less than the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, and if it exceeds the upper limit of this preferred range, impact resistance may not be stably exhibited. This provides a resin composition with excellent impact resistance and appearance.

The average domain size of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded article of the present invention was evaluated by small angle X-ray scattering (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering and diffraction that occurs in a small-angle region where the scattering angle (2θ) is less than 10°. In this small-angle X-ray scattering method, when there are regions with different electron densities of about 1 to 100 nm in size in a substance, diffuse scattering of X-rays is measured based on the difference in electron density. The particle diameter of the object to be measured is determined based on this scattering angle and scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin that has an aggregated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in a range of less than 10° was measured to measure the small-angle X-ray scattering profile, and it was determined that the polydiorganosiloxane domain was a spherical domain and that the particle size distribution was uneven. Assuming that exists, a simulation is performed using commercially available analysis software from the tentative particle size and the tentative particle size distribution model, and the average size of the polydiorganosiloxane domain is determined. Small-angle X-ray scattering makes it possible to accurately, easily, and reproducibly measure the average size of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be measured accurately using transmission electron microscopy. can. Average domain size means the number average of individual domain sizes.

The term "average domain size" used in connection with the present invention refers to the measured value obtained by measuring a 1.0 mm thick portion of a three-tiered plate manufactured by the method described in the Examples using the small-angle X-ray scattering method. show. In addition, analysis is performed using an isolated particle model that does not take into account interparticle interactions (interparticle interference).

(B component: ion pair compound)
The ion pair compound used in the present invention is used as an antistatic agent, has a melting point of 80°C or lower, and has a 5% weight loss temperature of 350°C or higher as measured by TG-TDA. Incidentally, one type of antistatic agent that is not an ion pair compound is a surfactant such as glycerin fatty acid ester, but resin compositions using this as component B have remarkable thermal stability and sustained antistatic properties. If the resin surface is wiped with water even once, the antistatic properties will be impaired. Additionally, there are polymeric materials such as polyether as antistatic agents that are not ion pair compounds, but resin compositions using these as component B have the disadvantage of poor thermal stability and deflection temperature under load.

The necessity for the melting point of the ion pair compound to be 80° C. or lower will be explained below. It is known that by adding an ion pair compound with a low melting point, particularly one that is liquid at room temperature, to a resin, the resin composition can have antistatic properties. The reason for this is that ion pair compounds with low melting points have organic compound moieties that are relatively large in size, which weakens the Coulomb force between positive and negative charges and increases affinity with the matrix resin. It is thought that it is appropriately dispersed in the resin composition and exhibits antistatic properties. In particular, when considering addition to polycarbonate resins, those with a melting point of 80° C. or lower are suitable for imparting good antistatic properties. On the other hand, ion pair compounds with a melting point exceeding 80°C have a strong Coulombic force or have a small organic compound site and low affinity with the resin, so they are difficult to disperse in the aromatic polycarbonate resin and have good antistatic properties. does not demonstrate. Note that the melting point of the ion pair compound is preferably 30°C or lower, more preferably 0°C or lower.

The necessity for the 5% weight loss temperature measured by TG-TDA to be 350° C. or higher will be explained below. If this temperature is low, thermal decomposition of the ion pair compound is likely to occur in environments where resin compounds are exposed to high temperatures, such as melt kneading and injection molding, and the compounds produced by the thermal decomposition are absorbed by the heat of the resin polymer. It also contributes to decomposition, causing problems such as a decrease in molecular weight. In particular, in the case of polycarbonate resin, the processing temperature during melt kneading, injection molding, etc. often reaches 300 to 350°C, so a temperature of 350°C or higher is appropriate. The 5% weight loss temperature of the ion pair compound measured by TG-TDA is preferably 355°C or higher, more preferably 360°C or higher.

Moreover, when the above-mentioned ion pair compound is used in combination with an inorganic filler, the sustained antistatic property is dramatically increased. Specifically, compared to the case where an inorganic filler is not used in combination, extremely high resistance to wiping with water or alcohol is imparted.

An ion pair compound having a melting point of 80°C or lower and a 5% weight loss temperature measured by TG-TDA of 350°C or higher has at least one cation selected from the group consisting of an onium ion, an imidazole ring, and a pyridine ring. It is preferable that the structure has a species, and the anion is an anion represented by the following formula (I) or (II).

[In the formula, R ₁ , R ₂ and R ₃ each represent a perfluoroalkyl group having 1 to 4 carbon atoms. ]
Further, the ion pair compound is preferably a compound represented by the following general formula (III).

[In the formula, R ₁ and R ₂ each represent a perfluoroalkyl group having 1 to 4 carbon atoms, R ₄ represents an alkyl group having 6 to 12 carbon atoms, and R ₅ represents an alkyl group having 10 to 20 carbon atoms. ]

More preferably, R ₄ is a straight chain alkyl group having 6 to 8 carbon atoms, and R ₅ is a straight chain alkyl group having 12 to 16 carbon atoms.
More preferably, R ₁ and R ₂ are each a trifluoromethyl group, R ₄ is a straight chain alkyl group having 6 carbon atoms, and R ₅ is a straight chain alkyl group having 14 carbon atoms.

The content of component B is 0.3 to 10 parts by weight, preferably 0.4 to 7 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of component A. If the content of component B is less than 0.3 parts by weight, good antistatic properties will not be exhibited, and if it is more than 10 parts by weight, thermal stability will deteriorate.

(Component C: inorganic filler)
Conventionally known inorganic fillers can be used, but the filler that is preferably used is at least one filler selected from the group consisting of acicular inorganic fillers, fibrous inorganic fillers, and plate-like inorganic fillers. It is. The acicular inorganic filler is an inorganic filler having a whisker-like, columnar, etc. shape, and is selected from wollastonite, boehmite, etc. The fibrous inorganic filler refers to a thin and long fibrous inorganic filler, and is selected from glass fiber, metal fiber, ceramic fiber, etc. The plate-shaped inorganic filler is an inorganic filler having a shape such as a flaky shape or a scale shape, and is selected from talc, mica, glass flakes, etc. Particularly suitable among the above inorganic fillers are glass, talc, mica and wollastonite.

(glass)
The glass fibers are not particularly limited to glass compositions such as A glass, C glass, and E glass, and may contain components such as TiO ₂ , SO ₃ , and P ₂ O ₅ as the case may be. However, E glass (alkali-free glass) is more preferred. Glass fiber is made by drawing molten glass using various methods and rapidly cooling it into a predetermined fibrous shape. There are no particular limitations on the quenching and stretching conditions in such a case. Further, the cross-sectional shape may be not only a perfect circle but also a shape other than a perfect circle such as an ellipse, a cocoon shape, or a trefoil shape. Furthermore, a mixture of perfectly circular glass fibers and glass fibers having shapes other than perfectly circular shapes may be used.

The fiber diameter of the glass fiber is preferably 1 to 25 μm, more preferably 3 to 17 μm. If the fiber diameter is too small, the fibers tend to break easily and the rigidity tends to decrease. Furthermore, since the surface area becomes large, a relatively large amount of coating material is required, which tends to have an adverse effect when flame retardancy is required. If the fiber diameter is too large, the appearance of the molded product is likely to deteriorate.

The fiber length of the glass fibers is preferably 50 to 500 μm, more preferably 100 to 400 μm, and even more preferably 120 to 300 μm as a number average fiber length in pellets or molded products made of the resin composition of the present invention. . The number average fiber length is a value calculated by an image analysis device from optical microscope observation of the glass fiber residue collected after dissolving the molded product in a solvent or decomposing the resin with a basic compound. . In addition, when calculating this value, the value is based on a method in which fibers with a diameter of 10 μm or less are not counted.

Examples of the sheet glass filler include glass flakes including metal coated glass flakes and metal oxide coated glass flakes. Glass flakes, which serve as the base of the plate-shaped glass filler, are plate-shaped glass fillers produced by a method such as a cylindrical blow method or a sol-gel method. The size of the raw material for such glass flakes can be selected from various sizes depending on the degree of crushing and classification. The average particle diameter of the glass flakes used as the raw material is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and even more preferably 30 to 300 μm. This is because those in the above range are excellent in both handleability and moldability. Usually, plate glass fillers crack when melted and kneaded with resin, and the average particle size thereof becomes smaller. The number average particle diameter of the plate glass filler in the resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and even more preferably 20 to 80 μm. The number average particle size is calculated using an image analysis device from images obtained by observing with an optical microscope the remains of the plate glass filler collected from treatments such as high-temperature ashing, dissolution with solvents, and decomposition with chemicals of molded products. is the value to be used. In addition, when calculating this value, the value is calculated using a method that uses the flake thickness as a guide and does not count flakes with a length shorter than that. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1.5 to 6 μm. A sheet glass filler having the above number average particle size and thickness achieves good mechanical strength, appearance, and moldability.

The glass filler is 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. In addition, glass fibers (including those coated with metal or metal oxide) and glass flakes (including those coated with metal or metal oxide) are olefin resins, styrene resins, acrylic resins, Preferably used are those treated with a polyester resin, an epoxy resin, a urethane resin, or the like. The amount of sizing agent deposited in the sizing-treated filler is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight based on 100% by weight of the filler.

Furthermore, the fibrous glass filler and sheet glass filler of the present invention include those whose surfaces are coated with different materials. Preferred examples of such different materials include metals and metal oxides. Examples of metals include silver, copper, nickel, and aluminum. Examples of metal oxides include cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide. Methods for surface coating of such dissimilar materials are not particularly limited, and include, for example, various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum evaporation method, ion plating method, CVD method. (for example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, and sputtering method.

(talc)
In the present invention, talc is hydrated magnesium silicate in terms of chemical composition, and is generally represented by _{the chemical formula 4SiO 2 .} Specifically, it is composed of 56 to 65% by weight of SiO ₂ , 28 to 35% by weight of MgO, and about 5% by weight of H ₂ O. Other minor components include 0.03 to 1.2% by weight of Fe ₂ O ₃ , 0.05 to 1.5% by weight of Al ₂ O ₃ , 0.05 to 1.2% by weight of CaO, and K ₂ O. It contains 0.2% by weight or less of Na ₂ O, and 0.2% by weight or less of Na 2 O. The particle size of talc has an average particle size of 0.1 to 15 μm (more preferably 0.2 to 12 μm, still more preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm) as measured by a sedimentation method. Preferably, the range is within the range. Further, it is particularly preferable to use talc having a bulk density of 0.5 (g/cm ³ ) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by X-ray transmission method, which is one of liquid phase sedimentation methods. A specific example of a device that performs such measurements is Sedigraph 5100 manufactured by Micromeritics.

There are no particular restrictions on the manufacturing method for pulverizing talc from raw stone, and axial flow milling, annular milling, roll milling, ball milling, jet milling, and container-rotating compression-shearing milling may be used. can do. Further, it is preferable that the pulverized talc be classified by various classifiers so that the particle size distribution is uniform. There are no particular restrictions on the classifiers, including impactor-type inertial force classifiers (variable impactors, etc.), inertial force classifiers using the Coanda effect (elbow jets, etc.), and centrifugal field classifiers (multi-stage cyclones, microplexes, dispersion separators, etc.). , AccuCut, Turbo Classifier, Turboplex, Micron Separator, Super Separator, etc.).

Further, talc is preferably in an agglomerated state from the viewpoint of ease of handling, and such manufacturing methods include a degassing compression method, a compression method using a sizing agent, and the like. Particularly preferred is a method using deaeration and compression because it is simple and does not mix unnecessary sizing agent resin components into the resin composition of the present invention.

(mica)
Mica having an average particle diameter of 10 to 100 μm as measured by microtrack laser diffraction method can be preferably used. More preferably, the average particle size is 20 to 50 μm. If the average particle diameter of mica is less than 10 μm, the improvement effect on rigidity is not sufficient, and even if it exceeds 100 μm, the improvement in rigidity is not sufficient, and mechanical strength such as impact properties may deteriorate significantly, which is not preferable. Mica having a thickness of 0.01 to 1 μm as measured by observation with an electron microscope can be preferably used. More preferably, the thickness is 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. The mica used is preferably muscovite mica, which has a Mohs hardness of about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogovite, and solves the problems of the present invention at a better level. Further, mica may be produced by either a dry pulverization method or a wet pulverization method. Dry pulverization is less costly and more common, while wet pulverization is effective in pulverizing mica more thinly and finely, and as a result, the effect of improving the rigidity of the resin composition is higher.

(Wollastonite)
The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm. Further, the aspect ratio (average fiber length/average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is determined by observing the reinforcing filler with an electron microscope, determining the diameter of each individual fiber, and calculating the number average fiber diameter from the measured value. The reason for using an electron microscope is that it is difficult to accurately measure the size of the target level using an optical microscope. The fiber diameter is determined by randomly extracting the filler whose fiber diameter is to be measured from the image obtained by electron microscopy, measuring the fiber diameter near the center, and calculating the number average fiber diameter from the measured value. Calculate the diameter. The observation magnification is approximately 1000 times, and the number of measurement lines is 500 or more (600 or less is suitable for the work). On the other hand, the average fiber length is measured by observing the filler with an optical microscope, determining the length of each filler, and calculating the number average fiber length from the measured value. Observation using an optical microscope begins with preparing a sample in which the fillers are dispersed so that they do not overlap each other. Observation is performed using a 20x objective lens, and the observed image is captured as image data into a CCD camera with approximately 250,000 pixels. Using the obtained image data using an image analysis device, the fiber length is calculated using a program that calculates the maximum distance between two points of the image data. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of lines to be measured is 500 or more (600 or less is suitable for the work).

In order to fully reflect the inherent whiteness of the wollastonite of the present invention in the resin composition, the iron content mixed in the raw material ore and the iron content mixed in due to the wear of the equipment when crushing the raw material ore are removed using a magnetic separator. It is preferable to remove it as much as possible. It is preferable that the iron content in wollastonite by such magnetic separator treatment is 0.5% by weight or less in terms of Fe2O3.

The content of component C is 1 to 100 parts by weight, preferably 5 to 90 parts by weight, and more preferably 10 to 80 parts by weight, based on 100 parts by weight of component A. If the content is less than 1 part by weight, the flexural modulus will be poor and sufficient sustainable antistatic properties will not be obtained. If the content exceeds 100 parts by weight, thermal stability will deteriorate and the molecular weight will decrease during extrusion or molding. becomes larger.

(Component D: phosphorus stabilizer)
The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer to the extent that it does not promote hydrolysis. Such phosphorus stabilizers improve thermal stability during manufacturing or molding processing, and improve mechanical properties, color, and molding stability. Examples of the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphorous acid, phosphonic acid, esters thereof, and tertiary phosphine. Specifically, the phosphite compounds include, for example, triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, triotadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, 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 include erythritol diphosphite and dicyclohexylpentaerythritol diphosphite. Furthermore, as other phosphite compounds, those having a cyclic structure that react with dihydric phenols 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'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and the like. Phosphate compounds 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, Examples include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferred.

Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite , Tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, -n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, etc., tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2, More preferred are 4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The above-mentioned phosphorus stabilizers can be used not only alone, but also as a mixture of two or more. Among the above-mentioned phosphorus stabilizers, an alkyl phosphate compound typified by trimethyl phosphate is preferably blended. Further, a combination of such an alkyl phosphate compound and a phosphite compound and/or a phosphonite compound is also a preferred embodiment. The content of component D is preferably 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight, and even more preferably 0.01 to 0.2 parts by weight based on 100 parts by weight of component A. Parts by weight.

(Other additives)
In order to improve the polycarbonate resin composition of the present invention, its thermal stability, and design, the additives used for these improvements are advantageously used. These additives will be specifically explained below.

(I) Heat stabilizer other than phosphorus stabilizer (i) Hindered phenol stabilizer A hindered phenol stabilizer can be blended into the polycarbonate resin composition of the present invention. Such a formulation exhibits the effect of suppressing, for example, deterioration of hue during molding and deterioration of hue during long-term use. Examples of hindered phenol stabilizers include α-tocopherol, butylated hydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butyl fer). Propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 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-butylphenol), 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-hydroxyphenyl)benzene -tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris 2[ 3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate ] Methane etc. are exemplified. All of these are easily available. The above hindered phenol stabilizers can be used alone or in combination of two or more. The content of the hindered phenol stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, per 100 parts by weight of component A.

(ii) Heat stabilizers other than those mentioned above The polycarbonate resin composition of the present invention may also contain heat stabilizers other than the above-mentioned phosphorus stabilizers and hindered phenol stabilizers. Suitable examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. 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 this compound can be used. Furthermore, stabilizers prepared by mixing this compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The content of the lactone 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 component A. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The content of the sulfur-containing stabilizer is preferably 0.001 to 0.1 part by weight, more preferably 0.01 to 0.08 part by weight, based on 100 parts by weight of component A. An epoxy compound can be added to the polycarbonate resin composition of the present invention, if necessary. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4- of 2,2-bis(hydroxymethyl)-1-butanol; Examples include (2-oxiranyl)cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, and copolymers of styrene and glycidyl methacrylate. The content of such an epoxy compound is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and even more preferably 0.005 parts by weight, based on 100 parts by weight of component A. ~0.1 part by weight.

(II) Flame retardant A flame retardant can be blended into the polycarbonate resin composition of the present invention. Incorporation of such compounds provides improved flame retardancy, but also provides other benefits, such as improved antistatic properties, fluidity, stiffness, and thermal stability, depending on the properties of each compound. Such flame retardants include (i) organometallic salt flame retardants (for example, organic sulfonic acid alkali (earth) metal salts, organic borate metal salt flame retardants, and organic stannate metal salt flame retardants); ii) an organophosphorus flame retardant (for example, an organic group-containing monophosphate compound, a phosphate oligomer compound, a phosphonate oligomer compound, a phosphonitrile oligomer compound, a phosphonic acid amide compound, etc.), (iii) a silicone flame retardant consisting of a silicone compound , (iv) fibrillated PTFE, among which organic metal salt flame retardants and organic phosphorus flame retardants are preferred. These may be used alone or in combination.

(i) Organic metal salt flame retardant The organic metal salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkali (earth) metal salt of an organic sulfonic acid. It is preferable that The organic sulfonic acid alkali (earth) metal salts include fluorine-substituted alkyl sulfones such as metal salts of perfluoroalkyl sulfonic acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and alkali metals or alkaline earth metals. Included are metal salts of acids and metal salts of aromatic sulfonic acids having from 7 to 50 carbon atoms, preferably from 7 to 40 carbon atoms, with alkali metals or alkaline earth metals. Alkali metals constituting the metal salt include lithium, sodium, potassium, rubidium, and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. More preferred are alkali metals. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are preferred when transparency is required, but they are not widely used and are difficult to purify, resulting in lower costs. 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. The alkali metal in the alkali metal sulfonate can be selected depending on these considerations, but potassium sulfonate is the most suitable because it has excellent balance of properties in all respects. Such a potassium salt and an alkali metal sulfonic acid salt consisting of another alkali metal can also be used in combination.

Specific examples of alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluorobutanesulfonate. Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Examples include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. The number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, even more preferably in the range of 1 to 8.

Among these, potassium perfluorobutanesulfonate is particularly preferred. A considerable amount of fluoride ion (F-) is usually mixed into the alkali (earth) metal salt of perfluoroalkylsulfonic acid made of an alkali metal. Since the presence of such fluoride ions can be a factor in reducing flame retardancy, it is preferable to reduce them as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, particularly preferably 10 ppm or less. Further, in terms of manufacturing efficiency, it is preferable that the content is 0.2 ppm or more. Such an alkali (earth) metal salt of perfluoroalkylsulfonic acid with a reduced amount of fluoride ions can be produced by using a known production method and contained in the raw materials for producing the fluorine-containing organic metal salt. Methods for reducing the amount of fluoride ions, methods for removing hydrogen fluoride etc. obtained by the reaction by using gas generated during the reaction or heating, and purification methods such as recrystallization and reprecipitation for producing fluorine-containing organometallic salts. It can be manufactured by a method of reducing the amount of fluoride ions using fluoride ions. In particular, organic metal salt flame retardants are relatively easily soluble in water, so use ion-exchanged water, especially water that satisfies an electrical resistance value of 18 MΩ·cm or more, that is, an electrical conductivity of about 0.55 μS/cm or less. , and is preferably manufactured by a process of dissolving and washing at a temperature higher than room temperature, and then cooling and recrystallizing.

Specific examples of aromatic sulfonic acid alkali (earth) metal salts include, for example, disodium diphenylsulfide-4,4'-disulfonate, dipotassium diphenylsulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecyl phenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate , polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, 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 diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, diphenylsulfone-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, Examples include calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracene sulfonate. can. Among these alkali (earth) metal salts of aromatic sulfonic acids, potassium salts are particularly preferred. Among these alkali (earth) metal salts of aromatic sulfonates, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferred, and in particular mixtures thereof (the former and the latter) are preferred. The weight ratio of 15/85 to 30/70) is suitable.

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfuric esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfuric esters, mention may be made in particular of alkali (earth) metal salts of sulfuric esters of monohydric and/or polyhydric alcohols; Examples of sulfuric esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, pentaerythritol mono-, di-, tri-, and tetra-sulfate ester, and lauric acid monoglyceride sulfate. Examples include esters, sulfuric esters of palmitic acid monoglyceride, and sulfuric esters of stearic acid monoglyceride. Preferred examples of the alkali (earth) metal salts of these sulfuric esters include alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N-(p-tolylsulfonyl)-p-toluenesulfimide, N-(N'-benzylaminocarbonyl)sulfanylimide, and N-( Examples include alkali (earth) metal salts of phenylcarboxyl) sulfanylimide. The content of the organic metal salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and even more preferably 0.01 to 1 part by weight, per 100 parts by weight of component A. The amount is 0.3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(ii) Organic phosphorus flame retardant As the organic phosphorus flame retardant, aryl phosphate compounds and phosphazene compounds are preferably used. Since these organic phosphorus flame retardants have a plasticizing effect, they are advantageous in that they can improve moldability. As the aryl phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, but more preferably one or more phosphate compounds represented by the following general formula (4) can be mentioned.

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

The phosphate compound of the above formula may be a mixture of compounds having different m numbers; in the case of such mixtures, the average m number is preferably from 0.5 to 1.5, more preferably from 0.8 to 1. 2, more preferably 0.95 to 1.15, particularly preferably 1 to 1.14.

Preferred specific examples of the dihydric phenol inducing the above M include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxydiphenyl)methane, -hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.

Preferred specific examples of the monohydric phenol for inducing the above Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol, and among them, preferred are are phenol and 2,6-dimethylphenol.

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

On the other hand, specific examples of phosphate compounds that are not substituted with halogen atoms include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl) phosphate, and resorcinol bis di(2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphate ester oligomers mainly composed of bisphenol A bis(diphenyl phosphate). indicates that it may contain a small amount of other components having different degrees of polymerization, and more preferably the component m=1 in the formula (4) is 80% by weight or more, more preferably 85% by weight or more, even more preferably (Indicates that the content is 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 (5) and (6) are preferable.

(In the formula, X ¹ , X ² , X ³ , and X ⁴ represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom. Also, r represents an integer from 3 to 10.)

In the above formulas (5) and (6), the organic groups not containing a halogen atom represented by X ¹ , X ² , X ³ , and X ⁴ include, for example, an alkoxy group, a phenyl group, an amino group, an allyl group, etc. can be mentioned. Among these, a cyclic phosphazene compound represented by the above formula (5) is preferred, and a cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula (5) are phenoxy groups is particularly preferred.

The content of the organic phosphorus flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and even more preferably 5 to 20 parts by weight, based on 100 parts by weight of component A. If the content of the organic phosphorus flame retardant is less than 1 part by weight, it is difficult to obtain a flame retardant effect, and if it exceeds 50 parts by weight, problems such as strand breakage and surging may occur during kneading and extrusion, resulting in reduced productivity. may occur.

(iii) Silicone flame retardant Silicone compounds used as silicone flame retardants improve flame retardancy through chemical reactions during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. Silicone compounds have high flame retardancy, especially when polycarbonate resin is used, by bonding themselves or with resin-derived components to form a structure during combustion, or by a reduction reaction during the formation of the structure. It is thought that it gives an effect.

Therefore, it is preferable to contain a group having high activity in such a reaction, and more specifically, it is preferable to contain a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (i.e., 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 more preferably in the range of 0.15 to 0. A range of 6 mol/100 g is more preferable. This ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound using an alkaline decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and a methoxy group is particularly preferred.

Generally, the structure of a silicone compound is constructed by arbitrarily combining four types of siloxane units shown below. That is, M units: ( _CH3 )3SiO1 _{/ 2} , H( _CH3 ) _{2SiO1/ 2} , _H2 ( _CH3 )SiO1 _/2 , ( _CH3 ) ₂ ( _CH2 =CH) _{SiO1 /2 ,} ( _{CH3 ) 2} ( _C6H5 )SiO1 _/ 2, ( _CH3 )( _C6H5 )( _CH2 =CH)SiO1 _/2 , monofunctional siloxane unit, D unit: 2 such as ( _CH3 ) _2SiO , H( _{CH3 )} SiO, _H2SiO , H( _C6H5 )SiO, ( _CH3 )( _CH2 = _{CH)SiO, (C6H5 ) 2SiO} , etc. Functional siloxane unit, T unit: ( _CH3 )SiO3 _/2 , ( _C3H7 )SiO3 _{/ 2} , HSiO3 _/2 , ( _CH2 =CH)SiO3 _{/2 ,} ( _C6H5 ) A trifunctional siloxane unit such as SiO _3/2 , and a tetrafunctional siloxane unit represented by Q unit: SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone flame retardant includes the following specific formulas: Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferred structure is MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, even more preferably in the range of 3 to 60, particularly preferably in the range of 4 to 40. The more suitable the range, the better the flame retardancy. Furthermore, as will be described later, silicone compounds containing a predetermined amount of aromatic groups have excellent transparency and hue. As a result, good reflected light can be obtained. In addition, when any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with that coefficient can be two or more types of siloxane units with different bonding hydrogen atoms or organic residues. .

The silicone compound may be linear or may 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. Specifically, such organic residues include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and decyl groups, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, Also included are aralkyl groups such as tolyl. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, particularly preferred are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, and propyl group. Furthermore, the silicone compound used as the silicone flame retardant preferably contains an aryl group. On the other hand, silane compounds and siloxane compounds used as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone flame retardants in their preferred embodiments, in that preferable effects can be obtained when they do not contain aryl groups. . The silicone compound used as a silicone flame retardant may contain a reactive group in addition to the Si--H group and alkoxy group, and such reactive groups include, for example, an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples include a group, a mercapto group, and a methacryloxy group.

The content of the silicone flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 5 parts by weight, based on 100 parts by weight of component A.

(iv) Polytetrafluoroethylene (fibrillated PTFE) with fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or may be a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene mixture consisting of fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has an extremely high molecular weight and exhibits a tendency for PTFE to bond together and become fibrous due to external effects such as 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 number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380° C., as disclosed in, for example, JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380°C of 107 to 1013 poise, preferably 108 to 1012 poise, as measured by the method described in this publication. Such PTFE can be used not only in solid form but also in aqueous dispersion form. Such fibrillated PTFE also improves its dispersibility in resins, and it is also possible to use PTFE mixtures in mixed form with other resins in order to obtain even better flame retardancy and mechanical properties.

Furthermore, as disclosed in JP-A-6-145520, a material having a structure in which the fibrillated PTFE is used as a core and a low molecular weight polytetrafluoroethylene is used as a shell is also preferably used.

Commercially available products of such fibrillated PTFE include, for example, Teflon (registered trademark) 6J from DuPont Mitsui Fluorochemical Co., Ltd. and Polyflon MPA FA500 and F-201L from Daikin Chemical Industries, Ltd.

As for the mixed form of fibrillated PTFE, (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 co-agglomerated mixture (JP-A-60-258263; (2) method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (method described in Japanese Patent Application Laid-Open No. 4-272957). (3) A method in which an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles are uniformly mixed, and each medium is simultaneously removed from the mixture (JP-A-06-220210, JP-A No. 08-188653), (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (method described in JP-A-9-95583), method), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, then polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (JP-A-11-1999) Those obtained by the method described in Japanese Patent No. 29679 and the like can be used.

Commercial products of fibrillated PTFE in the form of these mixtures include Metablane, typified by Mitsubishi Rayon Co., Ltd.'s "Metablane A3000" (trade name), "Metablane A3700" (trade name), and "Metablane A3800" (trade name). A series, SN3300B7 (trade name) manufactured by Shine Polymer, and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals are exemplified.

The proportion of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and more preferably 10% to 90% by weight, based on 100% by weight of the mixture. % to 80% by weight is most preferred.

When the proportion of fibrillated PTFE in the mixed form is within this range, good dispersibility of fibrillated PTFE can be achieved. The content of fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, and more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of component A. More preferably 5 parts by weight.

(III) Dyes and Pigments The polycarbonate resin composition of the present invention further contains various dyes and pigments and can provide molded articles exhibiting various designs. The dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, quinacridone dyes, Examples include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, 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 other fluorescent dyes that emit light, it is possible to provide an even better design effect that takes advantage of the emitted color.

(IV) Fluorescent brightener In the polycarbonate resin composition of the present invention, the optical brightener is not particularly limited as long as it is used to improve the color tone of the resin to white or bluish-white, such as stilbene-based, Examples include benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specifically, for example, CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Co., Ltd., and "Hakkor PSR" manufactured by Showa Kagaku Co., Ltd. can be mentioned. The fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy to the visible region. The content of the optical brightener is preferably 0.001 to 0.1 part by weight, more preferably 0.001 to 0.05 part by weight, based on 100 parts by weight of the components A and B. Even if it exceeds 0.1 part by weight, the effect of improving the color tone of the composition is small.

(V) Compound having heat ray absorption ability The polycarbonate resin composition of the present invention can contain a compound having heat ray absorption ability. Such compounds include phthalocyanine near-infrared absorbers, ATO, ITO, metal oxide near-infrared absorbers such as iridium oxide and ruthenium oxide, immonium oxide, and titanium oxide, lanthanum boride, cerium boride, and tungsten boride. Suitable examples include various metal compounds with excellent near-infrared absorbing ability, such as metal boride-based and tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near-infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (both natural and artificial), and fullerene, with carbon black and graphite being preferred. 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, and 0.001 to 0 parts by weight based on 100 parts by weight of component A. .07 parts by weight is more preferred. The content of the metal oxide near-infrared absorber, metal boride near-infrared absorber, and carbon filler in the polycarbonate resin composition of the present invention is preferably in the range of 0.1 to 200 ppm (weight ratio), and 0.1 to 200 ppm (weight ratio). The range of 5 to 100 ppm is more preferable.

(VI) Light Diffusing Agent The polycarbonate resin composition of the present invention can be blended with a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymer fine particles, low refractive index inorganic fine particles such as calcium carbonate, and composites thereof. Such polymer fine particles are already known as light diffusing agents for polycarbonate resins. More preferred examples include crosslinked acrylic particles with a particle size of several μm and crosslinked silicone particles typified by polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a columnar shape, and an amorphous shape. Such a spherical shape does not necessarily have to be a perfect sphere, but includes a deformed one, and such a cylindrical shape includes a cube. A preferable light diffusing agent is spherical, and the more uniform the particle size is, the more preferable it is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 3 parts by weight based on 100 parts by weight of component A. . In addition, two or more types of light diffusing agents can be used in combination.

(VII) White pigment for high light reflection The 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, titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of component A. Note that two or more types of white pigments for high light reflection can be used in combination.

(VIII) Ultraviolet absorber A UV absorber can be added to the polycarbonate resin composition of the present invention to impart weather resistance. Specific examples of such ultraviolet absorbers include benzophenone, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzophenone. Roxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy Examples include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Specific examples of the ultraviolet absorber include benzotriazole-based agents such as 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole. , 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'- Methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl) ) benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolphenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2 -Hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole A copolymer of a vinyl monomer copolymerizable with the monomer, or a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer. Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as polymers. Specifically, the ultraviolet absorber is hydroxyphenyltriazine type, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4, 6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol , 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl) )-5-butyloxyphenol and the like. Furthermore, the phenyl group of the above-mentioned exemplified compounds is 2,4-dimethyl, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Examples include compounds that have a phenyl group. Specifically, the ultraviolet absorber is a cyclic imino ester type, for example, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1 -benzoxazin-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazin-4-one). In addition, as the ultraviolet absorber, specifically cyanoacrylate type, for example, 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2- Examples include cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene. Furthermore, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that it can combine such ultraviolet absorbing monomer and/or photostable monomer with a monomer such as alkyl (meth)acrylate. It may also be a polymer-type ultraviolet absorber copolymerized with the UV absorber. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester. Ru. Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferred in terms of ultraviolet absorbing ability, and cyclic iminoester-based and cyanoacrylate-based are preferred in terms of heat resistance and hue. Specific examples include Chemipro Kasei Co., Ltd.'s "Chemisorb 79" and BASF Japan Co., Ltd.'s "Tinuvin 234". The above-mentioned ultraviolet absorbers 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, even more preferably 0.05 to 1 part by weight, and especially Preferably it is 0.05 to 0.5 parts by weight.

(IX) Other resins and elastomers In the polycarbonate resin composition of the present invention, other resins and elastomers may be used in place of some of the resin components to achieve the effects of the present invention, to the extent that the effects of the present invention are not impaired. It is also possible to use small proportions within the range. The amount of other resins and elastomers to be blended is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of components A and B. 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. Examples include resins such as , phenol resin, and epoxy resin. Examples of elastomers include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate/styrene/butadiene), which is a core-shell type elastomer. rubber, MB (methyl methacrylate/butadiene) rubber, MAS (methyl methacrylate/acrylonitrile/styrene) rubber, and the like.

(X) Other additives The 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.

<About production of resin composition>
The 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 various reinforcing fillers and additives described above can also be blended. The reinforced polycarbonate resin composition of the present invention can be produced into various products by injection molding the pellets produced as described above. Furthermore, it is also possible to directly make a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product from the resin melt-kneaded in an extruder without going 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 injection molding of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. Further, for molding, either a cold runner method or a hot runner method can be selected. The resin composition of the present invention can also be used in the form of various extrusion molded products, sheets, films, etc. by extrusion molding. In addition, an inflation method, a calendar method, a casting method, etc. can also be used for forming sheets and films. Furthermore, by applying a specific stretching operation, it is also possible to form a heat-shrinkable tube. Further, the resin composition of the present invention can be made into a molded article by rotational molding, blow molding, or the like.

<Manufacture of molded products>
A resin molded article made of the polycarbonate resin composition of the present invention can usually be obtained by injection molding such pellets. In such injection molding, it is possible to manufacture not only by the usual cold runner molding method but also by a hot runner which enables runnerless molding. In addition, injection molding includes not only normal 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, and foam molding (super (including methods using critical fluids), rapid heating/cooling mold molding, adiabatic mold molding, in-mold remelting molding, and molding methods consisting of combinations thereof.

The molding shrinkage rate of a molded article formed by molding the resin composition of the present invention is such that the ratio (S1/S2) of the shrinkage rate in the direction perpendicular to the flow (S1) and the shrinkage rate in the parallel direction to the flow (S2) is 3. It is preferably less than 0, more preferably less than 2.5, and even more preferably less than 2.0.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Note that "parts" are based on weight unless otherwise specified.

Based on the ingredients and contents shown in Tables 2 to 5, various ingredients were mixed using a tumbler and melt-kneaded using a twin screw extruder (Japan Steel Works, Ltd. TEX30α-38.5BW-3V), Various pellets were obtained. Components other than component C and component H were mixed in advance in a V-type blender and supplied from the first supply port of the extruder. Component C was supplied from the second supply port using a side feeder. The H component was supplied to the extruder from the middle of the cylinder (between the first supply port and the second supply port) using a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Kogyo Co., Ltd.). The obtained pellets were molded into test pieces for evaluation using an injection molding machine (molding conditions are described in each evaluation item).
The components used are as follows.

(A component)
A-1: Teijin Ltd. Panlite L-1225WX (viscosity average molecular weight: 19700)
A-2: Teijin Ltd. Panlite L-1225WP (viscosity average molecular weight: 22400)
(B component)
B-1: Trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide (manufactured by Kanto Chemical Co., Ltd.)
B-2: Perfluorobutanesulfonic acid 1-butyl-3-methylimidazolium salt (manufactured by Mitsubishi Materials Corporation)
B-3 (comparison): Methylethylbis(trifluoromethylsulfonyl)imide (manufactured by Mitsubishi Materials Corporation)
B-4 (comparison): Potassium perfluorobutane sulfonate (manufactured by Dainippon Ink and Chemicals Co., Ltd.: Megafac F-114P)
B-5 (comparison): Dodecylbenzenesulfonic acid tetrabutylphosphonium salt (manufactured by Takemoto Yushi Co., Ltd.)
(C component)
C-1: Circular cross-section chopped glass fiber (manufactured by Nittobo Co., Ltd.: CSG 3PE-455)
C-2: Glass milled fiber (manufactured by Nittobo Co., Ltd.: PFE-301)
C-3: Flat cross-section chopped glass fiber (manufactured by Nittobo Co., Ltd.: CSG 3PA-830)
C-4: Glass flakes (manufactured by Nippon Sheet Glass Co., Ltd.: MEG160FY-M02)
C-5: Talc (manufactured by Katsumitsuyama Mining Co., Ltd.: Victorilight TK-RC)
C-6: Wollastonite (manufactured by Kinseimatec Co., Ltd.: SH-1800)
(D component)
D-1: Phosphorous stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd.: trimethyl phosphate (TMP))
(Other ingredients)
E: Acid-modified olefin wax which is a copolymer of maleic anhydride and α-olefin (manufactured by Mitsubishi Chemical Corporation: Diakarna DC30M)
F: Decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-3103)
G: Stearic acid triglyceride (manufactured by Riken Vitamin Co., Ltd.: Rikemar SL-900)
H: Diglycerin monolaurate (manufactured by Riken Vitamin Co., Ltd.: Poem DL-100)

[Evaluation of resin composition]
1. Antistatic property (before wiping with water or alcohol): Surface resistivity After drying the various pellets in a hot air circulation dryer at 120°C for 6 hours, 150U), a flat plate test piece with a long side of 90 mm x a short side of 50 mm x a thickness of 2 mm was prepared. The cylinder temperature was 280°C in Examples 1 to 11, 34, and 35 and Comparative Examples 1 to 8, and 300°C in Examples 12 to 33 and Examples 36 to 38. Further, the mold temperature was 100°C. After conditioning the prepared flat test piece at 23°C and 50% relative humidity for 48 hours or more, it was measured using a resistivity meter (high resistance resistivity meter MCP-HT450 manufactured by Mitsubishi Chemical Analytic Co., Ltd.). The surface resistivity was measured at a voltage of 1000V. A surface resistivity of 10 ¹² Ω/□ or less was ◎, 10 ¹³ to 10 ¹⁴ Ω/□ was rated ○, and a surface resistivity of 10 ¹⁵ Ω/□ or more was rated ×.

2. Antistatic property (wet wiping resistance): Surface resistivity 1. A 500 g cylindrical weight wrapped in a Kimtowel (manufactured by Nippon Paper Crecia Co., Ltd.) moistened with water was placed on top of the flat test piece prepared above, and the weight was slid 20 times to wipe the surface with water. The surface was then gently wiped three times with a dry Kimwipe to remove water. After that, 1. The surface resistivity was evaluated using the same method. 1. ◎ if ^the surface resistivity is the same order as the initial ^value evaluated by /□ or more) was △, and cases where the deterioration was 3 orders of magnitude or more, or 10 ¹⁵ Ω/□ or more were marked ×.

3. Antistatic property (alcohol wiping resistance): Surface resistivity 1. A 500 g cylindrical weight wrapped in Kimtowel (manufactured by Nippon Paper Crecia Co., Ltd.) moistened with ethanol was placed on top of the flat test piece prepared in , and the surface was wiped with ethanol by sliding it five times. Next, the surface was gently wiped three times with a dry Kimwipe to wipe off the ethanol. After that, 1. The surface resistivity was evaluated using the same method. 1. ◎ if ^the surface resistivity is the same order as the initial ^value evaluated by /□ or more) was △, and cases where the deterioration was 3 orders of magnitude or more, or 10 ¹⁵ Ω/□ or more were marked ×.

4. Thermal stability: Viscosity average molecular weight After drying the various pellets in a hot air circulation dryer at 120°C for 6 hours, they were molded into ISO dumbbell test pieces using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). was created. The cylinder temperature was 280°C in Examples 1 to 11, 34, and 35 and Comparative Examples 1 to 8, and 300°C in Examples 12 to 33 and Examples 36 to 38. Further, the mold temperature was 100°C. The viscosity average molecular weight (M ₁ ) of the molded dumbbell test piece and the viscosity average molecular weight (M ₀ ) of the pellet were measured by the method described in the specification. ◎ if M ₀ - _{M 1} ≦1.5 (×10 ³ ) is satisfied, ○ if 1.5 (×10 ³ ) < M ₀ - M ₁ ≦2.0 (×10 ³ ) is satisfied, 2 The case where .0(×10 ³ )<M ₀ −M ₁ ≦2.5(×10 ³ ) was satisfied was Δ, and the case where 2.5(×10 ³ )<M ₀ −M ₁ was satisfied was evaluated as ×.

5. Mechanical properties: Flexural modulus 4. By cutting both ends of the ISO dumbbell test piece obtained by the method described above, a test piece with a thickness of 4 mm, a width of 10 mm, and a length of 80 mm was prepared, and then the flexural modulus was measured in accordance with ISO178. When the bending elastic modulus was 4,000 MPa or more, it was rated ◎, when it was 3,000 to 4,000 MPa, it was ○, and when it was 3,000 MPa or less, it was rated ×.

6. Anisotropy: Molding shrinkage rate After drying the various pellets in a hot air circulation dryer at 120°C for 6 hours, the long side (flowing) was A flat plate with a width of 100 mm (parallel to the flow), a short side (perpendicular to the flow) of 50 mm, and a thickness of 4 mm was molded. The cylinder temperature was 280°C in Examples 1 to 11, 34, and 35 and Comparative Examples 1 to 8, and 300°C in Examples 12 to 33 and Examples 36 to 38. Moreover, the mold temperature was 100°C. Furthermore, after adjusting the condition for at least 48 hours at 23°C and 50% relative humidity, the dimensions of the flat plate were measured using a three-dimensional measuring machine (XYZAX AXCEL manufactured by Tokyo Seimitsu Co., Ltd.) in the direction perpendicular to the flow. The molding shrinkage rate in the parallel direction was calculated. When the shrinkage rate in the direction perpendicular to the flow is S1, and the shrinkage rate in the parallel direction to the flow is S2, the ratio (S1/S2) is less than 2.0: ◎, 2.0 to 3. A score of 0 was marked as ◯, and a score of 3.0 or more was marked as △.

[Evaluation of ion pair compounds]
1.5% Weight Loss Temperature Measured using a TG-DTA analyzer (Thermo plus EVO2 manufactured by Rigaku) in an air atmosphere at a temperature increase rate of 20° C./min.
Table 1 shows the melting points and 5% weight loss temperatures of B-1 to B-5.

[Examples 1 to 38, Comparative Examples 1 to 8]
Tables 2 to 5 show the evaluation results. Examples 1 to 38 all showed good results. Comparative Example 1 does not contain component C and is inferior in sustained antistatic property (alcohol wiping resistance) and flexural modulus. In Comparative Example 2, the content of component B exceeds 10 parts by weight, and the thermal stability is poor. In Comparative Example 3, the content of the C component exceeds 100 parts by weight, and the thermal stability is poor. In Comparative Examples 4 and 5, the melting point of component B exceeds 80° C., so antistatic properties are not exhibited. In Comparative Example 6, the 5% weight loss temperature of component B is less than 350° C., so the sustained antistatic property is poor. Comparative Example 7 contains a surfactant-type antistatic agent (component H) and is inferior in sustained antistatic properties and thermal stability. In Comparative Example 8, since the content of component B is less than 0.3 parts by weight, antistatic properties are not exhibited.

Claims (8)

Consisting of (A) 100 parts by weight of aromatic polycarbonate resin (component A), (B) 0.3 to 10 parts by weight of an ion pair compound (component B), and (C) glass, talc, mica, and wollastonite. A resin composition containing 1 to 100 parts by weight of at least one inorganic filler (component C) selected from the group, wherein the ion pair compound has a melting point of 80°C or less, and is prepared in an air atmosphere using TG- DTA . 2. A resin composition characterized by having a 5% weight loss temperature of 350° C. or higher measured at a heating rate of 20° C./min . The cation of the ion pair compound has a structure having at least one selected from the group consisting of an onium ion, an imidazole ring, and a pyridine ring, and the anion is an anion represented by the following formula (I) or (II). The resin composition according to claim 1, characterized in that:
[In the formula, R ₁ , R ₂ and R ₃ each represent a perfluoroalkyl group having 1 to 4 carbon atoms. ] The resin composition according to claim 1 or 2, wherein the ion pair compound is a compound represented by the following formula (III).
[In the formula, R ₁ and R ₂ each represent a perfluoroalkyl group having 1 to 4 carbon atoms, R ₄ represents an alkyl group having 6 to 12 carbon atoms, and R ₅ represents an alkyl group having 10 to 20 carbon atoms. ] 4. The resin composition according to claim 3, wherein R ₄ is a straight chain alkyl group having 6 to 8 carbon atoms, and R ₅ is a straight chain alkyl group having 12 to 16 carbon atoms. 5. The method according to claim 3 or 4, wherein R ₁ and R ₂ are each a trifluoromethyl group, R ₄ is a straight chain alkyl group having 6 carbon atoms, and R ₅ is a straight chain alkyl group having 14 carbon atoms. Resin composition. The molding shrinkage rate of the molded article formed by molding the resin composition is such that the ratio (S1/S2) of the shrinkage rate in the direction perpendicular to the flow (S1) and the shrinkage rate in the parallel direction to the flow (S2) is less than 3.0. The resin composition according to any one of claims 1 to 5, characterized in that: The resin composition according to any one of claims 1 to 6, containing 0.001 to 5 parts by weight of (D) a phosphorus stabilizer (component D) per 100 parts by weight of component A. A molded article obtained by molding the resin composition according to any one of claims 1 to 7.