JP2023113988A - Thermoplastic resin composition and molding of the same - Google Patents

Abstract

To provide a resin composition having excellent electromagnetic wave shielding properties in the millimeter wave band, and also having low electromagnetic wave reflection properties at a specific frequency.SOLUTION: A thermoplastic resin composition comprises, relative to 100 pts.wt. of a component comprising (A) a thermoplastic resin (A component) 95-99.9 pts.wt. and (B) a carbon fiber (B component) 0.1-5 pts.wt., (C) a phosphorous compound (C component) 0.001-2 pts.wt. and (D) a phenolic compound (D component) 0.001-2 pts.wt.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a resin composition having excellent electromagnetic wave shielding properties in the millimeter wave band and low electromagnetic wave reflecting properties at a specific frequency, and a molded article made of the same.

In recent years, communication equipment has been used in all fields. As the use of 5G progresses, the frequencies used in communication equipment are becoming higher, and the electromagnetic wave shielding characteristics of the millimeter wave band have become an important technology for applications such as base stations and in-vehicle millimeter wave radars.

Known techniques for shielding electromagnetic waves from malfunctioning due to electromagnetic waves include methods of using a metal housing, methods of laminating a conductive film on a resin housing, and methods of painting and plating. (Patent Document 1). However, although metal housings are superior in performance, they are heavy and have a low degree of freedom in design. On the other hand, resin casings with a conductive film laminated, painted, or plated are not suitable for use in products with a long life cycle because the conductive film, paint, or plating may peel off. As a technique for imparting electromagnetic wave shielding properties by blending a conductive filler into a resin, a method of using carbon black and carbon fiber in combination or using metal-coated carbon fiber is known (Patent Documents 2 and 3). The resin composition whose electrical properties have been modified by this method has high electromagnetic wave shielding properties, but because it has high conductivity, it has high electromagnetic wave reflectance, and depending on the application of electronic devices, the reflected electromagnetic waves can become noise. , there is a problem that the measurement accuracy decreases.

JP 2012-229345 A JP-A-06-009819 JP 2015-108118 A

An object of the present invention is to provide a resin composition having excellent electromagnetic wave shielding properties in the millimeter wave band and low electromagnetic wave reflecting properties at specific frequencies, and a molded article made of the resin composition.

The inventors of the present invention have made intensive studies to solve these problems, and have found that by adding appropriate amounts of carbon fiber, phosphorus-based compound, and phenol-based compound to a thermoplastic resin, excellent electromagnetic wave shielding properties in the millimeter wave band can be obtained. and has low electromagnetic wave reflection characteristics at a specific frequency. That is, the above-mentioned problem is solved by: ( C) a phosphorus compound (component C) of 0.001 to 2 parts by weight and (D) a phenolic compound (component D) of 0.001 to 2 parts by weight. be.

The present invention will be specifically described below.

<A component: thermoplastic resin>
The thermoplastic synthetic resin is not particularly limited, and examples thereof include urethane resin, chlorotrifluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, Vinylidene resin, ethylene-tetrafluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, vinyl chloride resin, vinylidene chloride resin, polyethylene, polypropylene, chlorinated polyolefin, water-crosslinked polyolefin, modified polyolefin, ethylene-vinyl acetate copolymer coalescence, ethylene-ethyl acrylate copolymer, polystyrene, ABS resin, polyamide, methacrylic resin, polyacetal, polycarbonate resin, cellulosic resin, polyvinyl alcohol, polyurethane elastomer, polyimide, polyetherimide, polyamideimide, ionomer resin, polyphenylene oxide, Examples include methylpentene polymer, polyallyl sulfone, polyallyl ether, polyether ketone, polyphenylene sulfide, polysulfone, wholly aromatic polyester, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, and blends of various high molecular substances. can do. Among these, polycarbonate resins are preferred from the viewpoint of good mechanical properties.

The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of reaction methods include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of dihydric phenols used herein include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl ) propane (commonly known as bisphenol A or BPA), 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-hydroxy phenyl)pentane, 4,4′-(p-phenylenediisopropylidene)diphenol, 4,4′-(m-phenylenediisopropylidene)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-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, etc. is mentioned. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, of which bisphenol A is particularly preferred from the standpoint of impact resistance and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, special polycarbonate resins produced using other dihydric phenols can be used as component A. For example, as part or all of the dihydric 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 resin (homopolymer or copolymer) using fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as “BCF”) Suitable for applications with particularly strict requirements for dimensional change and shape stability. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is the following copolymerized polycarbonate resins (1) to (3). is.

(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 resin, and A copolymer polycarbonate resin having a BCF of 20 to 80 mol % (more preferably 25 to 60 mol %, still more preferably 35 to 55 mol %).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, and A copolymer polycarbonate resin having a BCF of 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).
(3) 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 resin, and A copolymer polycarbonate resin containing 20 to 80 mol % (more preferably 25 to 60 mol %, still more preferably 35 to 55 mol %) of Bis-TMC.

These special polycarbonate resins may be used alone or in combination of two or more. Moreover, these can also be used by mixing with a widely used bisphenol A type polycarbonate resin. The manufacturing method and characteristics of these special polycarbonate resins are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435 and JP-A-2002-117580. It is

Among the various polycarbonate resins described above, those having the water absorption rate and Tg (glass transition temperature) within the following range by adjusting the copolymer composition etc. have good hydrolysis resistance of the polymer itself, In addition, since it is remarkably excellent in low warpage properties after molding, it is particularly suitable in fields where shape stability is required.
(i) a polycarbonate resin having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and a Tg of 120 to 180°C, or (ii) a Tg of 160 to 250°C , preferably 170 to 230° C., and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption rate of the polycarbonate resin is obtained by measuring the water content after immersing a disk-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. is. Further, Tg (glass transition temperature) is a value determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

Carbonate precursors include carbonyl halides, diesters of carbonic acid and haloformates, and specific examples include phosgene, diphenyl carbonate and dihaloformates of dihydric phenols.

In producing a polycarbonate resin by interfacial polymerization of the dihydric phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, an antioxidant for preventing oxidation of the dihydric phenol, and the like are added. may be used. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. , copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Moreover, the mixture which mixed 2 or more types of obtained polycarbonate resin may be sufficient.

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 phloroglucine, 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-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Structural units derived from a polyfunctional aromatic compound in the branched polycarbonate resin preferably account for 100 mol% of the total of structural units derived from a dihydric phenol and structural units derived from such a polyfunctional aromatic compound. is 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, still more preferably 0.05 to 0.8 mol %. In addition, particularly in the case of the melt transesterification method, branched structural units may occur as a side reaction. It is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, still more preferably 0.01 to 0.8 mol %. The ratio of such branched structures can be calculated by ¹ H-NMR measurement.

Aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as are preferably exemplified. Alicyclic diols are more suitable as bifunctional alcohols, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of a cyclic carbonate compound, which are methods for producing the polycarbonate resin of the present invention, can be found in various literatures and patent publications. It is a well-known method in

In producing the thermoplastic resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ , more preferably 2.0×10 ⁴ to 3.5×10 ⁴ , more preferably 2.2×10 ⁴ to 3.0×10 ⁴ . Polycarbonate resins having a viscosity-average molecular weight of less than 1.8×10 ⁴ may not provide good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity-average molecular weight exceeding 4.0×10 ⁴ is inferior in versatility due to poor fluidity during injection molding.

The polycarbonate resin may be obtained by mixing substances having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity-average molecular weight exceeding the above range (5×10 ⁴ ) has improved entropy elasticity. As a result, good moldability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in moldability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, component A is a polycarbonate resin having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ (component A-1-1) and an aromatic polycarbonate having a viscosity average molecular weight of 1×10 ⁴ to 3×10 ⁴ . A polycarbonate resin (component A-1) consisting of a resin (component A-1-2) and having a viscosity average molecular weight of 1.6×10 ⁴ to 3.5×10 ⁴ (hereinafter referred to as “polycarbonate resin containing a high molecular weight component ”) can also be used.

In such a high-molecular-weight component-containing polycarbonate resin (component A-1), the molecular weight of component A-1-1 is preferably 7×10 ⁴ to 2×10 ⁵ , more preferably 8×10 ⁴ to 2×10 5 , and further preferably 8×10 4 to 2×10 ⁵ . It is preferably 1×10 ⁵ to 2×10 ⁵ , particularly preferably 1×10 ⁵ to 1.6×10 ⁵ . The molecular weight of component A-1-2 is preferably 1×10 ⁴ to 2.5×10 ⁴ , more preferably 1.1×10 ⁴ to 2.4×10 ⁴ , still more preferably 1.2×10 ⁴ . to 2.4×10 ⁴ , particularly preferably 1.2×10 ⁴ to 2.3×10 ⁴ .

The high-molecular-weight component-containing polycarbonate resin (component A-1) can be obtained by mixing the components A-1-1 and A-1-2 in various proportions and adjusting the mixture to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of A-1 component, A-1-1 component is 2 to 40% by weight, more preferably A-1-1 component is 3 to 30% by weight, still more preferably The content of component A-1-1 is 4 to 20% by weight, and the content of component A-1-1 is particularly preferably 5 to 20% by weight.

In addition, as a method for preparing the A-1 component, (1) a method in which the A-1-1 component and the A-1-2 component are polymerized independently and then mixed, and (2) JP-A-5-306336. Using a method for producing an aromatic polycarbonate resin showing multiple polymer peaks in a molecular weight distribution chart by GPC method in the same system, represented by the method shown in JP-A-2003-120002, such an aromatic polycarbonate resin is produced by the A- of the present invention. A method of manufacturing to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a manufacturing method (manufacturing method of (2)), separately manufactured A-1-1 component and / or A method of mixing with the A-1-2 component can be mentioned.

The viscosity-average molecular weight referred to in the present invention is obtained by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20° C. to determine the specific viscosity (η _SP ) calculated by the following formula.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
The viscosity-average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ M ^0.83
c=0.7
Calculation of the viscosity-average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is performed in the following manner. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble matter in the composition. Such soluble matter is collected by celite filtration. The solvent in the resulting solution is then removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of the component soluble in methylene chloride. From a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride, the specific viscosity at 20° C. is obtained in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is a copolymer resin containing dihydric phenol units represented by the following general formula (1) and hydroxyaryl-terminated polydiorganosiloxane units represented by the following general formula (3). is preferred.

[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, cycloalkyl group having 20 carbon atoms, 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 carboxy group; a and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group 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 are each independently 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; R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a halogen atom, or a an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms. an aryl group of up to 14, an aryloxy group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxy group represents a group selected from the group consisting of; when there is more than one, they may be the same or different; c is an integer of 1-10; d is an integer of 4-7; ]

[In the 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, an alkoxy group having 1 to 10 carbon atoms, e and f are integers of 1 to 4, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 4 or more and 150 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) from which the carbonate constitutional unit represented by the general formula (1) is derived 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-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl -4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)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- ter, 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 others, 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, 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 preferable. Moreover, these may be used alone or in combination of two or more.

In the carbonate structural unit represented by the general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, with a hydrogen atom or an alkyl group having 1 to 4 carbon atoms being particularly preferred. As the dihydroxyaryl-terminated polydiorganosiloxane (II) from which the carbonate structural unit represented by the general formula (3) is derived, for example, compounds represented by the following general formula (I) are preferably used.

p+q is preferably 4 to 120, more preferably 30 to 120, even more preferably 30 to 100, and most preferably 30 to 60.

Next, a method for producing the above preferred polycarbonate-polydiorganosiloxane copolymer resin will be described below. By reacting dihydric phenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of dihydric phenol (I) in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution, A mixed solution of chloroformate compounds is prepared comprising a chloroformate of dihydric phenol (I) and/or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group. Phosgene is preferred as the chloroformate-forming compound.

In producing the chloroformate compound from the dihydric phenol (I), the total amount of the dihydric phenol (I) that induces the carbonate constitutional unit represented by the general formula (1) may be converted into the chloroformate compound at once. Alternatively, a part thereof may be added as a post-addition monomer to the subsequent interfacial polycondensation reaction as a reaction raw material. The post-addition monomer is added in order to facilitate the subsequent polycondensation reaction, and it is not necessary to add it unless necessary. Although the method of this chloroformate compound-producing reaction is not particularly limited, a method of conducting the reaction in a solvent in the presence of an acid binder is usually preferred. Furthermore, if desired, a small amount of antioxidant such as sodium sulfite and hydrosulfide may be added, preferably. The ratio of the chloroformate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalents) of the reaction. When phosgene, which is a suitable chloroformate-forming compound, is used, a method of blowing gasified phosgene into the reaction system can be suitably employed.

Examples of the acid binder include 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, and mixtures thereof. is used. The ratio of the acid binder to be used may also be appropriately determined in consideration of the stoichiometric ratio (equivalents) of the reaction in the same manner as described above. Specifically, per 1 mol of dihydric phenol (I) used to form a chloroformate compound of dihydric phenol (I) (usually 1 mol corresponds to 2 equivalents), 2 equivalents or a slightly excess amount thereof It is preferred to use an acid binding agent.

As the solvent, a solvent inert to various reactions, such as those used in the production of known polycarbonates, may be used singly or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

The pressure in the reaction for producing the chloroformate compound is not particularly limited and may be 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°C to 50°C. In many cases, the reaction generates heat, so cooling with water or ice is desirable. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. Known interfacial reaction conditions can be used for the pH range in the production reaction of the chloroformate compound, and the pH is usually adjusted to 10 or higher.

In the preparation of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, a chloroformate of dihydric phenol (I) and a chloroformate containing a carbonate oligomer of dihydric phenol (I) having terminal chloroformate groups are thus used. After preparing the mixed solution of the formate compound, while stirring the mixed solution, dihydroxyaryl-terminated polydiorganosiloxane (II) that induces the carbonate structural unit represented by the general formula (3) is charged for preparing the mixed solution. by adding at a rate of 0.01 mol/min or less per 1 mol of the dihydric phenol (I) added, and interfacial polycondensation of the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound , to obtain a polycarbonate-polydiorganosiloxane copolymer resin.

The polycarbonate-polydiorganosiloxane copolymer resin can be made into a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent together with a dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, 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-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Even if the method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin includes a branching agent in the mixed solution during the production reaction of the chloroformate compound, interfacial polycondensation after the production reaction is completed. A method in which a branching agent is added during the reaction may be used. The ratio of carbonate structural units derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, in the total amount of carbonate structural units constituting the copolymer resin, Especially preferred is 0.05 to 1.0 mol %. The amount of such branched structures can be calculated by ¹ H-NMR measurement.

The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure. The reaction temperature is selected from the range of −20 to 50° C. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally defined, but is usually 0.5 to 10 hours. In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin with a viscosity of [η _SP /c]. The resulting reaction product (crude product) is subjected to various post-treatments such as known separation and purification methods, and can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purity).

The content of the polydiorganosiloxane block represented by the following general formula (4) contained in the above general formula (3) is 1.0 to 10.0% by weight based on the total weight of the polycarbonate resin composition. 1.0 to 8.0% by weight is more preferred, 1.0 to 5.0% by weight is even more preferred, and 1.0 to 3.0% by weight is most preferred.

(In general formula (4) above, 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, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 4 to 150.)

<B component: carbon fiber>
The thermoplastic resin composition of the present invention contains carbon fibers as the B component. Any of cellulose-based, polyacrylonitrile-based, and pitch-based carbon fibers can be used as the carbon fiber. Alternatively, it can be obtained by spinning or molding a raw material composition consisting of a solvent and a polymer of aromatic sulfonic acids or their salts with a methylene type bond, followed by carbonization, and spinning without an infusibilization step. It is also possible to use the Furthermore, general-purpose type, medium modulus type, and high modulus type can all be used. Among these, the polyacrylonitrile system is particularly preferred.

Also, the average fiber diameter of the carbon fibers is not particularly limited, but is usually 3 to 15 μm, preferably 5 to 13 μm. Carbon fibers having an average fiber diameter within this range may exhibit good mechanical strength and fatigue properties without impairing the appearance of molded products. The number average fiber length of carbon fibers in the thermoplastic resin composition is preferably 60 to 500 μm, more preferably 80 to 400 μm, still more preferably 100 to 300 μm. The number-average fiber length is a value calculated by an image analysis device from optical microscopic observation, etc., from the residue of carbon fibers collected by processing such as high-temperature ashing of molded products, dissolution with solvents, and decomposition with chemicals. be. In addition, when calculating such a value, the value is obtained by a method that does not count fibers having a length equal to or less than the fiber length. The aspect ratio of the carbon fibers is preferably in the range of 10-200, more preferably in the range of 15-100, still more preferably in the range of 20-50. The aspect ratio of carbon fibers refers to the value obtained by dividing the average fiber length by the average fiber diameter.

Furthermore, the surface of the carbon fiber is preferably oxidized for the purpose of increasing adhesion to the matrix resin and improving mechanical strength. Although the oxidation treatment method is not particularly limited, for example, (1) a method of treating carbon fibers with an acid or alkali or a salt thereof, or an oxidizing gas; Preferable examples include a method of firing at a temperature of 700° C. or higher in the presence of an inert gas containing a compound, and (3) a method of subjecting carbon fibers to oxidation treatment followed by heat treatment in the presence of an inert gas.

Carbon fibers in the composition of the present invention are preferably metal-coated carbon fibers and carbon fibers and metal-coated carbon fibers. A metal-coated carbon fiber is obtained by coating a metal layer on the surface of a carbon fiber. Examples of metals include silver, copper, nickel, and aluminum, and nickel is preferred from the viewpoint of corrosion resistance of the metal layer. Examples of metal coating methods include ion plating, plating (electroplating, electroless plating), etc. Among them, plating is preferably used. Also in the case of such a metal-coated carbon fiber, the above-mentioned carbon fibers can be used as the original carbon fiber. The thickness of the metal coating layer is preferably 0.1-1 μm, more preferably 0.15-0.5 μm. More preferably, it is 0.2 to 0.35 μm.

Such carbon fibers and metal-coated carbon fibers are preferably bundled with olefin-based resin, styrene-based resin, acrylic-based resin, polyester-based resin, epoxy-based resin, urethane-based resin, or the like. In particular, carbon fibers treated with urethane-based resins and epoxy-based resins are suitable in the present invention because of their excellent mechanical strength.

The content of component B is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of components consisting of component A and component B. weight part. When the content of the B component is less than 0.1 parts by weight, the electromagnetic wave transmission loss becomes small, and when it exceeds 5 parts by weight, the electromagnetic wave reflectance becomes large.

<Component C: Phosphorus compound>
The type of phosphorus-based compound used as the C component of the present invention is not particularly limited, but it is preferably a phosphate ester-based compound. may have the effect of suppressing

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, diisopropyl phosphate and the like can be mentioned, among which triphenyl phosphate and trimethyl phosphate are preferred.

The content of component C is 0.001 to 2 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.01 parts by weight, based on 100 parts by weight of the component A and B. 0.1 parts by weight. If the content of the C component is outside the above range, the dispersibility of the carbon fibers will deteriorate and the electromagnetic wave reflectance will increase.

<D component: phenolic compound>
The type of phenolic compound used as the component D of the present invention is not particularly limited, but it is preferably a hindered phenolic antioxidant. The effect of suppressing the reflectance may be exhibited.

Phenolic antioxidants include, for example, α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfer) propionate , 2-tert-butyl-6-(3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N, N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis(2,6-di-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2 '-dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl -6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methyl phenyl)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-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 illustrated. All of these are readily available.

The content of component D is 0.001 to 2 parts by weight, preferably 0.01 to 0.5 parts by weight, more preferably 0.03 to 0.03 parts by weight, based on 100 parts by weight of component A and B. 0.08 part by weight. If the content of component D is outside the above range, the dispersibility of the carbon fibers will deteriorate and the electromagnetic wave reflectance will increase.

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

(I) Thermal Stabilizer Other Than Phosphorus Compound and Hindered Phenol Compound The thermoplastic resin composition of the present invention may also contain a heat stabilizer other than the phosphorus compound and the hindered phenol compound. . Such other heat stabilizers are preferably lactone-based stabilizers represented by reaction products 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 available commercially as Irganox HP-136 (trademark, CIBA SPECIALTY CHEMICALS). Further, stabilizers obtained by mixing said compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. 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, per 100 parts by weight of the component A and B. . Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. exemplified. The content of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of the component A and B. be. The thermoplastic resin composition of the present invention may optionally contain an epoxy compound. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically all those having epoxy functional groups can be applied. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexylcarboxylate, 2,2-bis(hydroxymethyl)-1-butanol of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, copolymers of styrene and glycidyl methacrylate, and the like. 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, per 100 parts by weight of the component A and B, More preferably, it is 0.005 to 0.1 parts by weight.

(II) Flame Retardant The thermoplastic resin composition of the present invention may contain a flame retardant. Incorporation of such compounds provides improved flame retardancy, but also provides, depending on the properties of each compound, improved antistatic properties, fluidity, stiffness, and thermal stability, for example. Examples of such flame retardants include (i) organic metal salt flame retardants (e.g., organic sulfonic acid alkali (earth) metal salts, organic borate metal salt flame retardants, and organic stannate metal salt flame retardants), ( ii) organic phosphorus-based flame retardants other than component C (e.g., organic group-containing monophosphate compounds, phosphate oligomeric compounds, phosphonate oligomeric compounds, phosphonitrile oligomeric compounds, phosphonic acid amide compounds, etc.), and (iii) silicone compounds Examples include silicone-based flame retardants and (iv) fibrillated PTFE, among which organometallic salt-based flame retardants and organic phosphorus-based flame retardants other than the C component are preferred. These may be used alone or in combination of two.

(i) Organometallic salt-based flame retardant The organometallic salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkali (earth) metal organic sulfonate. is preferably 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. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, with alkali metals or alkaline earth metals are included. Alkali metals that make up the metal salt include lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. Alkali metals are more preferred. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are suitable when the demand for transparency is higher. 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. Although the alkali metal in the alkali metal sulfonate can be properly used in consideration of these factors, the potassium sulfonate is most preferable because of its well-balanced properties in all respects. Such potassium salts and alkali metal sulfonate salts of other alkali metals can also be used in combination.

Specific examples of perfluoroalkylsulfonic acid alkali metal salts include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, rubidium perfluorohexanesulfonate, and the like can be mentioned, and these can be used alone or in combination of two or more. The perfluoroalkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.

Among these, potassium perfluorobutanesulfonate is particularly preferred. The alkali (earth) metal salt of perfluoroalkylsulfonate, which is an alkali metal, usually contains not a small amount of fluoride ions (F-). Since the presence of such fluoride ions can be a factor in deteriorating 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, and particularly preferably 10 ppm or less. In addition, it is preferable that the concentration is 0.2 ppm or more in terms of production efficiency. Such an alkali (earth) metal perfluoroalkylsulfonate having a reduced amount of fluoride ions is produced by a known production method and is contained in raw materials for producing a fluorine-containing organic metal salt. A method of reducing the amount of fluoride ions, a method of removing hydrogen fluoride and the like obtained by the reaction by gas generated during the reaction or by heating, and a purification method such as recrystallization and reprecipitation for the production of fluorine-containing organometallic salts. can be produced by a method of reducing the amount of fluoride ions using In particular, since organometallic salt-based flame retardants are relatively soluble in water, ion-exchanged water, especially water satisfying an electrical resistance value of 18 MΩ·cm or more, that is, an electrical conductivity of about 0.55 μS / cm or less, is used. It is also preferable to manufacture by a step of dissolving at a temperature higher than room temperature, washing, and then cooling to recrystallize.

Specific examples of the alkali (earth) metal aromatic sulfonate include 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-dodecylphenyl ether disulfonate, poly(2,6-dimethylphenylene oxide) polysodium polysulfonate , poly(1,3-phenylene oxide) polysodium polysulfonate, poly(1,4-phenylene oxide) polysodium polysulfonate, poly(2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly(2-fluoro- 6-Butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, 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, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, Calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracene sulfonate. can. Of these alkali (earth) metal salts of aromatic sulfonates, 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 mixtures thereof (the former and the latter weight ratio of 15/85 to 30/70).

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfate esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfate esters, mention may be made in particular of alkali (earth) metal salts of sulfate esters of monohydric and/or polyhydric alcohols, such monohydric and/or polyhydric alcohols Sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, lauric acid monoglyceride sulfate esters, palmitate monoglyceride sulfates, stearate monoglyceride sulfates, and the like. The alkali (earth) metal salts of these sulfate esters are preferably 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)sulfanilimide, and N-( and alkali (earth) metal salts of phenylcarboxyl)sulfanilimide. The content of the organometallic salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and further It is preferably 0.01 to 0.3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(ii) Organic Phosphorus Flame Retardant Other than C Component As the organic phosphorus flame retardant other than C component, aryl phosphate compounds and phosphazene compounds are preferably used. Since these organic phosphorus flame retardants have a plasticizing effect, they are advantageous in terms of improving moldability. As the aryl phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (5) can be mentioned.

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

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

Suitable specific examples of dihydric phenols from which M is derived include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4 -hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.

Preferable specific examples of monohydric phenols from which Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are derived include phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol. is phenol, and 2,6-dimethylphenol.

Such monohydric phenol may be substituted with a halogen atom, and specific examples of phosphate compounds having a group 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, tris(4-bromophenyl)phosphate and the like.

On the other hand, specific examples of phosphate compounds not substituted with halogen atoms include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl)phosphate, and resorcinol bisdi(2,6-xylyl)phosphate). Preferred are phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphate ester oligomers based on bisphenol A bis(diphenyl phosphate). indicates that a small amount of other components with different polymerization degrees may be included, more preferably the component of m = 1 in the above formula [8] is 80% by weight or more, more preferably 85% by weight or more, and still more preferably 90% by weight or more).

Various phosphazene compounds known as conventional flame retardants can be used as the phosphazene compound, but phosphazene compounds represented by the following general formulas (6) and (7) are preferable.

(Wherein, X ¹ , X ² , X ³ and X ⁴ represent hydrogen, hydroxyl group, amino group, or an organic group containing no halogen atom, and r represents an integer of 3 to 10.)

Examples of the halogen-free organic groups represented by X ¹ , X ² , X ³ and X ⁴ in the formulas (6) and (7) include an alkoxy group, a phenyl group, an amino group and an allyl group. is mentioned. Among them, a cyclic phosphazene compound represented by the above formula (6) is preferable, and a cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula (6) are phenoxy groups is particularly preferable.

The content of the organic phosphorus flame retardant other than component C is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, with respect to 100 parts by weight of the component consisting of component A and component B, 5 to 20 parts by weight is more preferable. If the amount of the organic phosphorus flame retardant is less than 1 part by weight, it is difficult to obtain the flame retardant effect. may occur.

(iii) Silicone Flame Retardant A silicone compound used as a silicone flame retardant improves flame retardancy through a chemical reaction during combustion. As the compound, various compounds that have been proposed as flame retardants for aromatic polycarbonate resins can be used. When the silicone compound is burned, it combines with itself or with a component derived from the resin to form a structure, or through a reduction reaction during the formation of the structure. considered to be effective.

Therefore, it preferably contains a group that is highly active in such reactions, and more specifically, it preferably contains a predetermined amount of at least one group selected from alkoxy groups and hydrogen (that is, Si—H groups). 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 0.15 to 0.15 mol/100 g. A range of 6 mol/100 g is more preferred. Such a ratio can be obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline decomposition method. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group is particularly preferable.

Generally, the structure of a silicone compound is constructed by arbitrarily combining the 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} , and other monofunctional siloxane units, D units: 2 such as ( _CH3 ) _2SiO , _H ( _CH3 )SiO, _{H2SiO ,} H( _C6H5 )SiO, ( _CH3 )( _CH2 =CH) _SiO , ( _C6H5 )2SiO; Functional siloxane units, T units: ( _CH3 )SiO3 _/2 , ( _C3H7 )SiO3 _{/ 2} , HSiO3 _/2 , ( _CH2 =CH)SiO3 _{/2 ,} ( _C6H5 ) Trifunctional siloxane units such as SiO _3/2 , and Q units: tetrafunctional siloxane units represented by SiO ₂ .

Specifically, the structures of silicone compounds used in silicone-based flame retardants include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compounds are MmDn, MmTp, MmDnTp and MmDnQq, and more preferred structures are MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the 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. . The average degree of polymerization is preferably in the range of 3-150, more preferably in the range of 3-80, still more preferably in the range of 3-60, and most preferably in the range of 4-40. It comes to be excellent in flame retardance, so that it is such a suitable range. Furthermore, as described later, silicone compounds containing a predetermined amount of aromatic groups are excellent in transparency and hue. As a result, good reflected light can be obtained. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with that coefficient can be two or more siloxane units having different bonding hydrogen atoms and organic residues. .

The silicone compound may be linear or branched. Also, the organic residue that bonds to the silicon atom preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as tolyl groups. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group and propyl group is particularly preferred. Furthermore, the silicone compound used as the silicone-based 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-based flame retardants in their preferred aspects in that they exhibit favorable effects when they do not contain aryl groups. . Silicone compounds used as silicone flame retardants may contain reactive groups other than the Si—H groups and alkoxy groups. Examples of such reactive groups include amino groups, carboxyl groups, epoxy groups, vinyl groups, mercapto groups, and methacryloxy groups.

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

(iv) polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or mixed fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture comprising fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has a very high molecular weight and tends to bind PTFE together by an external action such as a shearing force to form a fibrous form. Its number average molecular weight ranges from 1.5 million to tens of millions. Such a 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 JP-A-6-145520, for example. That is, the fibrillated PTFE has a melt viscosity of 10 ⁷ to 10 ¹³ poise, preferably 10 ⁸ to 10 ¹² poise at 380° C. measured by the method described in the publication. Such PTFE can be used not only in a solid form but also in an aqueous dispersion form. In addition, such fibrillated PTFE improves its dispersibility in resins, and it is also possible to use PTFE mixtures in the form of mixtures with other resins in order to obtain better flame retardancy and mechanical properties.

Further, as disclosed in JP-A-6-145520, those having such a fibrillated PTFE as a core and a low-molecular-weight polytetrafluoroethylene as a shell are also preferably used.

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

Mixed forms of fibrillated PTFE include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer to co-precipitate to obtain a co-aggregated mixture (JP-A-60-258263; (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (described in JP-A-4-272957). (3) A method in which an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles are uniformly mixed, and the respective media are simultaneously removed from the mixture (JP-A-06-220210, JP-A-06-220210; 08-188653, etc.), (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (described in JP-A-9-95583, method), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (JP-A-11- 29679) can be used.

Commercial products of fibrillated PTFE in a mixed form include METABLEN represented by "METABLEN A3000" (trade name), "METABLEN A3700" (trade name), and "METABLEN A3800" (trade name) of Mitsubishi Rayon Co., Ltd. A series, Shine Polymer's SN3300B7 (trade name), and GE Specialty Chemicals' "BLENDEX B449" (trade name) are exemplified.

The ratio of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and 20% by weight, based on 100% by weight of the mixture. Weight percent to 80 weight percent is most preferred.

Good dispersibility of the fibrillated PTFE can be achieved when the proportion of the fibrillated PTFE in the mixed form is in this range. The content of fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, with respect to 100 parts by weight of components A and B. 0.1 to 0.5 parts by weight is more preferable.

(III) Dyes and Pigments The thermoplastic resin composition of the present invention further contains various dyes and pigments to provide molded articles exhibiting various design properties. The dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, Examples include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the thermoplastic resin composition of the present invention can 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 brightening agent or other fluorescent dye that emits light, it is possible to impart a better design effect by making use of the luminescent color.

(IV) Fluorescent brightener In the thermoplastic resin composition of the present invention, the fluorescent brightener is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white. , benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Co., Ltd., and "Hakkor PSR" manufactured by Showa Chemical Co., Ltd., and the like. Here, the fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy in the visible region. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, per 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 Ability to Absorb Heat Rays The thermoplastic resin composition of the present invention can contain a compound having ability to absorb heat rays. Examples of such compounds include phthalocyanine near-infrared absorbers, metal oxide near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide and titanium oxide, lanthanum boride, cerium boride and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity, such as metal 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 readily available. Examples of carbon fillers include carbon black, graphite (both natural and artificial) and fullerenes, preferably carbon black and graphite. These can be used singly or in combination of two or more. The content of the phthalocyanine-based near-infrared absorbent is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, per 100 parts by weight of the component A and B. , 0.001 to 0.07 parts by weight are more preferable. The content of the metal oxide near-infrared absorber, the metal boride near-infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the thermoplastic resin composition of the present invention. A range of 0.5 to 100 ppm is more preferred.

(VI) Light diffusing agent The thermoplastic resin composition of the present invention may be blended with a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymeric fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer microparticles are already known microparticles as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane are exemplified. The shape of the light diffusing agent is exemplified by a spherical shape, a discoidal shape, a columnar shape, and an amorphous shape. Such spheres do not have to be perfect spheres and include deformed ones, and such cylinders include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 part by weight with respect to 100 parts by weight of the component A and B. ~3 parts by weight. Two or more light diffusing agents can be used in combination.

(VII) High Light Reflection White Pigment The thermoplastic resin composition of the present invention may be blended with a high light reflection white pigment to impart a light reflection effect. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment. The content of the high light reflection white pigment is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, per 100 parts by weight of the component A and B. Two or more kinds of the high light reflection white pigment can be used in combination.

(VIII) Ultraviolet absorber The thermoplastic resin composition of the present invention may be blended with an ultraviolet absorber to impart weather resistance. Specific examples of such UV absorbers include benzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzene oxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy -4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like. Specific examples of benzotriazole-based UV absorbers include 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-benzotriazolephenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2 -hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, and a copolymer of said monomer and a vinyl-based monomer copolymerizable with said monomer, or a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and said monomer and a vinyl-based monomer copolymerizable with said monomer; Examples thereof include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as polymers. Specifically, the ultraviolet absorber is hydroxyphenyltriazine-based, 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, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc., in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl A compound having a phenyl group is exemplified. Specifically, cyclic iminoester-based UV absorbers include, 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). Further, as the ultraviolet absorber, specifically in the 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. Further, the above ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and/or photostable monomer and a monomer such as alkyl (meth)acrylate It may be a polymer-type ultraviolet absorber obtained by copolymerizing with a body. Preferred examples of the UV-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 the (meth)acrylic acid ester. be. Among them, benzotriazole and hydroxyphenyltriazine are preferred in terms of ultraviolet absorption ability, and cyclic iminoester and cyanoacrylate are preferred in terms of heat resistance and hue. Specific examples thereof include "Chemisorb 79" manufactured by Chemipro Kasei Co., Ltd., "TINUVIN 234" manufactured by BASF Japan Ltd., and the like. The ultraviolet absorbers may be used singly or as a mixture of two or more.

The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 parts by weight with respect to 100 parts by weight of the component A and B. to 1 part by weight, particularly preferably 0.05 to 0.5 part by weight.

(IX) Antistatic Agent The thermoplastic resin composition of the present invention may be required to have antistatic performance, and in such cases, it preferably contains an antistatic agent. Examples of such antistatic agents include (1) arylsulfonic acid phosphonium salts typified by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and tetrafluoroborate phosphonium salts. Phosphonium borate salts are mentioned. The content of the phosphonium salt is appropriately 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, per 100 parts by weight of the component A and B. parts, more preferably 1.5 to 3 parts by weight. Examples of antistatic agents include (2) organic lithium sulfonate, organic sodium sulfonate, organic potassium sulfonate, organic cesium sulfonate, organic rubidium sulfonate, organic calcium sulfonate, organic magnesium sulfonate, and organic barium sulfonate. organic sulfonic acid alkali (earth) metal salts such as Such metal salts are also used as flame retardants, as described above. More specific examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the organic alkali (earth) metal sulfonate is appropriately 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, per 100 parts by weight of the component A and B. parts, more preferably 0.005 to 0.2 parts by weight. Especially preferred are alkali metal salts such as potassium, cesium and rubidium.

Examples of antistatic agents include (3) organic sulfonate ammonium salts such as alkylsulfonate ammonium salts and arylsulfonate ammonium salts. The amount of the ammonium salt is appropriately 0.05 parts by weight or less per 100 parts by weight of the component A and B. The antistatic agent includes, for example, (4) a polymer containing a poly(oxyalkylene) glycol component such as polyetheresteramide as its constituent component. The amount of the polymer is suitably 5 parts by weight or less per 100 parts by weight of the component A and B.

(X) Filler The thermoplastic resin composition of the present invention may contain various fillers known as reinforcing fillers other than carbon fiber. As such fillers, fibrous fillers other than various carbon fibers, plate-like fillers and granular fillers can be used. Here, the plate-like filler is a filler having a plate-like shape (including those having irregularities on the surface and those having curved plates). Particulate fillers are fillers of shapes other than these, including irregularly shaped fillers.

Examples of fibrous fillers other than carbon fiber include glass fiber, metal-coated glass fiber and glass milled fiber. The glass fiber that serves as the substrate of such a fibrous glass filler is obtained by stretching molten glass by various methods and quenching it to form a predetermined fibrous shape. Quenching and stretching in such a case are not particularly limited either. In addition, the shape of the cross section may be a shape other than a perfect circle, such as an elliptical shape, a cocoon shape, a flattened shape, a three-leaf shape, or the like. Further, a mixture of a perfect circular shape and a shape other than a perfect circular shape may be used. The flat shape means that the average value of the major axis of the fiber cross section is 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and the average value of the ratio of the major axis to the minor axis (major axis/minor axis) is 1.5. ˜8, preferably 2-6, more preferably 2.5-5.

The average fiber diameter of the fibrous glass filler having a high aspect ratio such as glass fiber is preferably 1-25 μm, more preferably 3-17 μm. When a filler having an average fiber diameter within this range is used, it may be possible to exhibit good mechanical strength without impairing the appearance of the molded article. The fiber length of the high aspect ratio fibrous glass filler is preferably 60 to 500 μm, more preferably 100 to 400 μm, particularly preferably 120 to 350 μm, as the number average fiber length in the thermoplastic resin composition. The number-average fiber length is a value calculated by an image analysis device from an optical microscope image of the residue of the filler collected by processing such as high-temperature incineration of the molded product, dissolution with a solvent, and decomposition with chemicals. is. In addition, when calculating such a value, the value is based on a method in which the fiber diameter is used as a guideline, and fibers with a length smaller than that are not counted. The aspect ratio of the high aspect ratio fibrous glass filler is preferably 10-200, more preferably 15-100, even more preferably 20-50. The aspect ratio of the filler refers to the value obtained by dividing the average fiber length by the average fiber diameter.

Glass-milled fibers are usually produced by making glass fibers into short fibers using a pulverizer such as a ball mill. The aspect ratio of fibrous glass fillers having a low aspect ratio, such as glass milled fibers, is preferably 2-10, more preferably 3-8. The fiber length of the fibrous glass filler having a low aspect ratio is preferably 5 to 150 μm, more preferably 9 to 80 μm as the number average fiber length in the thermoplastic resin composition. The average fiber diameter is preferably 1-15 μm, more preferably 3-13 μm.

Plate-shaped fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and plate-shaped fillers obtained by coating these fillers with different materials such as metals and metal oxides. Materials and the like are preferably exemplified. Its particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods, in the region up to about 10 μm, and laser diffraction in the region of 10 to 50 μm.・A value based on the median diameter (D50) of the particle size distribution measured by the scattering method, and in the range of 50 to 300 μm, the value obtained by the vibratory sieving method. Such particle size is the particle size in the resin composition. The plate-like fillers may be surface-treated with various silane-based, titanate-based, aluminate-based, and zirconate-based coupling agents. , epoxy resins, urethane resins, and other resins, higher fatty acid esters, and the like, or may be granules subjected to compression.

(XI) Other Resins and Elastomers In the thermoplastic resin composition of the present invention, other resins and elastomers can be used in place of a part of the resin component to exhibit the effects of the present invention within a range that does not impair the effects of the present invention. It can also be used in a small proportion within the range. The amount of other resins and elastomers to be blended is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and most preferably 100 parts by weight of the resin component consisting of components A and B. is 3 parts by weight or less. Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. , phenolic resins, and epoxy resins. Examples of elastomers include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and MBS (methyl methacrylate/sterene/butadiene), which is a core-shell type elastomer. rubber, MB (methyl methacrylate/butadiene) rubber, MAS (methyl methacrylate/acrylonitrile/styrene) rubber, and the like.

(XII) Other Additives The thermoplastic 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. .
<Regarding the production of the resin composition>
The thermoplastic 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 preparing such pellets, the above various reinforcing fillers and additives can be blended.

<About manufacturing molded products>
The thermoplastic resin composition of the present invention can be used to produce various products by injection molding the pellets produced as described above. Further, it is also possible to directly form sheets, films, profile extrusion moldings, direct blow moldings, and injection moldings from resins melted and 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 of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic molding, rapid heat and cool molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. For molding, either cold runner method or hot runner method can be selected. The resin composition of the present invention can also be used in the form of various profile extrudates, sheets, films, and the like by extrusion molding. In addition, the inflation method, calender method, casting method, and the like can be used for forming sheets and films. Furthermore, it is also possible to mold it as a heat-shrinkable tube by subjecting it to a specific stretching operation. The resin composition of the present invention can also be molded by rotational molding, blow molding, or the like.

The electromagnetic wave transmission loss in the frequency range of 67 to 110 GHz of the thermoplastic resin composition of the present invention is preferably 15 dB or more. Furthermore, the electromagnetic wave reflectance is preferably 15% or less at at least one frequency in the frequency range of 67 to 110 GHz. The electromagnetic wave transmission loss is more preferably 20 dB or more, more preferably 25 dB or more. Although the upper limit is not particularly limited, it is preferably 90 dB or less. Further, the electromagnetic wave reflectance is more preferably 10% or less, more preferably 5% or less. Although the lower limit is not particularly limited, it is preferably 0.01% or more. The electromagnetic wave transmission loss and the electromagnetic wave reflectance are numerical values measured by the method described in Examples.

The thermoplastic resin composition of the present invention has excellent electromagnetic wave shielding properties in the millimeter wave band and low electromagnetic wave reflection properties at specific frequencies. It is useful for construction materials, infrastructure-related parts, housing-related parts, etc., and its industrial effect is exceptional.

The mode for carrying out the present invention summarizes the preferable range of each of the above requirements, and for example, the representative examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described with reference to the following examples. In addition, unless otherwise specified, parts in the examples are parts by weight, and %s are % by weight. In addition, evaluation was implemented by the following method.
<Evaluation of electromagnetic wave transmission loss (dB) and electromagnetic wave reflectance (%)>
Using a test piece (150 mm×150 mm×2 mmt) obtained by the following method, measurement was performed at 23° C. and 50% RH atmosphere. The equipment, measurement method, and measurement frequency are as follows.
[measuring device]
Horn antenna: FSS-05 (manufactured by HVS)
Dielectric lens: FSS-06 (manufactured by HVS)
Network analyzer: N5227A (manufactured by Keysight Technologies)
Millimeter wave controller: N5261A (manufactured by Keysight Technologies)
[Measuring method]
Free space method [measurement conditions]
Frequency: 67-110GHz

<Method for calculating electromagnetic wave characteristics>
Electromagnetic wave transmission loss and electromagnetic wave reflectance were calculated by the following formulas.
Electromagnetic wave reflectance (%) = S ₁₁ ² × 100
S ₁₁ (reflection loss) = intensity of reflected wave electromagnetic wave/intensity of incident wave electromagnetic wave (amplitude ratio of incident wave and reflected wave)
Electromagnetic transmission loss (dB) = -20logS ₂₁
S ₂₁ = transmitted wave electromagnetic wave intensity/incident wave electromagnetic wave intensity (amplitude ratio of incident wave and transmitted wave)
The electromagnetic wave transmission loss is preferably 15 dB or more in the frequency range of 67 to 110 GHz, and the electromagnetic wave reflectance is preferably 15% or less at at least one frequency in the frequency range of 67 to 110 GHz.

[Examples 1 to 10, Comparative Examples 1 to 6]
A mixture having the composition shown in Table 1 was fed through the first feed port of the extruder. Such a mixture was obtained by mixing in a V-blender. The twin-screw extruder has a diameter of 30 mmφ, and has a total of 10 barrel configurations (referred to as C1 to C10 cylinders from the upstream) having a supply port at C1 at the most upstream part and C5 at the downstream thereof. A square co-rotating twin-screw extruder (“TEX30αIII” manufactured by Japan Steel Works, Ltd.) was used. Extrusion conditions were temperature C1: 280° C., C2-10: 290° C., screw rotation speed 200 rpm, discharge rate 25 kg/h, vent vacuum degree 3 kPa, and pellets were obtained by melt-kneading. A portion of the obtained pellets was dried at 120°C for 6 hours in a hot air circulating dryer, and then tested using an injection molding machine at a cylinder temperature of 290°C and a mold temperature of 90°C at a size of 150 mm x 150 mm x 2 mmt. Strips were molded and evaluated. Table 1 shows the evaluation results.
In addition, each component of symbol notation in Table 1 is as follows.

<Material>
(A component)
A-1: Aromatic polycarbonate resin, manufactured by Teijin Limited Panlite L-1225WX (product name)
(B component)
B-1: Nickel-coated carbon fiber, manufactured by Teijin Limited HTC923 (product name)
B-2: Carbon fiber, manufactured by Teijin Limited HTC422 (product name)
(C component)
C-1: Ethyldiethylphosphonoacetate Johoku Chemical Industry Co., Ltd. JC-224 (product name)
C-2: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa 3,9-diphosphaspiro[5,5]undecane, Ltd. ADEKA ADEKA STAB PEP36 (product name)
(D component)
D-1: Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Adeka Co., Ltd. AO-50 (product name)
D-2: 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8, 10-tetraoxaspiro[5,5]undecane, Adeka Co., Ltd. AO-80 (product name)

Claims (8)

(A) thermoplastic resin (A component) 95 to 99.9 parts by weight and (B) carbon fiber (B component) 0.1 to 5 parts by weight of 100 parts by weight of component (C) phosphorus compound ( A thermoplastic resin composition comprising 0.001 to 2 parts by weight of component C) and 0.001 to 2 parts by weight of (D) a phenolic compound (component D). 2. The thermoplastic resin composition according to claim 1, wherein component A is a polycarbonate resin. 3. The thermoplastic resin composition according to claim 1, wherein component B is nickel-coated carbon fiber. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the C component is a phosphate compound. The thermoplastic resin composition according to any one of claims 1 to 4, wherein component D is a hindered phenolic antioxidant. The thermoplastic resin composition according to any one of claims 1 to 5, which has an electromagnetic wave transmission loss of 15 dB or more in a frequency range of 67 to 110 GHz. The thermoplastic resin composition according to any one of claims 1 to 6, which has an electromagnetic wave reflectance of 15% or less at at least one frequency in the frequency range of 67 to 110 GHz. A molded article made of the thermoplastic resin composition according to any one of claims 1 to 7.