JP7044595B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition. More specifically, a thermoplastic resin that has a good surface appearance and flame retardancy while maintaining a high dielectric constant, and is suitable for electrical / electronic parts, home appliances, automobile-related parts, infrastructure-related parts, housing-related parts, etc. Regarding the composition.

Recently, the demand for flame retardancy of resin products has been increasing, and the resin composition constituting the resin product is required to have flame retardancy. In particular, resin electronic parts such as antenna parts and wiring boards may ignite due to short circuits, etc., so the resin composition that constitutes these parts is required to be flame-retardant, and in particular, parts with a very small wall thickness. Is relatively easy to ignite, so the demand for flame retardancy is even higher.

On the other hand, with the spread of satellite broadcasting, satellite communication, high-definition television broadcasting, mobile phones, etc., high-density information transmission / reception by radio waves has become widespread, and the frequency used has been increasing. Furthermore, in order to improve the spatial efficiency, including the improvement of transportation efficiency in mobile communication devices such as the Global Positioning System of navigation systems, the miniaturization of radio wave receiving and transmitting antennas and circuit boards has been promoted. ing. The basic structure of an antenna used for high frequency is a structure in which a metal foil such as copper foil is laminated on an antenna substrate, and in order to reduce the size of the antenna, it is necessary to use a material having a high dielectric constant as the antenna substrate. That is, the higher the dielectric constant of the antenna substrate, the shorter the wavelength of the radio wave that the antenna can send and receive, the higher the frequency, and the higher the frequency can be received even if the antenna substrate is made smaller.

As a method for producing a high-dielectric resin composition, for example, a method of adding barium titanate to a thermoplastic resin is known (Patent Document 1). Further, as a method for improving flame retardancy, a method in which a thermoplastic resin and a fluororesin are used in combination is known (Patent Document 2). However, when an attempt is made to improve the flame retardancy by a method of adding a fluororesin to a highly dielectric resin composition in which barium titanate is added to a thermoplastic resin, there is a problem that the dielectric constant is lowered.

Japanese Unexamined Patent Publication No. 63-246771 Japanese Unexamined Patent Publication No. 2016-84414

An object of the present invention is to provide a thermoplastic resin composition having a good surface appearance and flame retardancy while maintaining a high dielectric constant, and a molded product made of the same.

As a result of diligent studies to achieve the above object, the present inventors have added a fluororesin and barium titanate having a specific particle size to the thermoplastic resin to maintain a high dielectric constant and a good surface appearance. We have found that a thermoplastic resin composition having flame retardancy can be obtained, and further diligent studies have been carried out to complete the present invention.
Hereinafter, the present invention will be specifically described.

<Component A: Thermoplastic resin>
The thermoplastic synthetic resin is not particularly limited, and is not particularly limited, for example, urethane resin, chlorotrifluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and fluoride. Vinylidene resin, ethylene-tetrafluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, vinyl chloride resin, nilidene chloride resin, polyethylene, polypropylene, chlorinated polyolefin, hydrobridged polyolefin, modified polyolefin, ethylene-vinyl acetate copolymer weight Combined, ethylene-ethyl acrylate copolymer, polystyrene, ABS resin, polyamide, methacrylic resin, polyacetal, polycarbonate resin, cellulose resin, polyvinyl alcohol, polyurethane elastomer, polyimide, polyetherimide, polyamideimide, ionomer resin, polyphenylene oxide, Examples include methylpentene polymers, polyallylsulfones, polyallyl ethers, polyetherketones, polyphenylene sulfides, polysulfones, total aromatic polyesters, polyethylene terephthalates, polybutylene terephthalates, thermoplastic polyester elastomers, and blends of various polymer substances. can do. Among these, polycarbonate resin is preferable from the viewpoint of good mechanical properties.

The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method 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.

Typical examples of the dihydric phenol used here are 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) Pentan, 4,4'-(p-phenylenediisopropyridene) diphenol, 4,4'-(m-phenylenediisopropyriden) 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) esters, bis (4-hydroxy-3-methylphenyl) sulfides, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Will be. The preferred divalent phenol is bis (4-hydroxyphenyl) alkane, and among them, bisphenol A is particularly preferable from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to the bisphenol A-based polycarbonate resin, which is a general-purpose polycarbonate resin, a special polycarbonate resin produced by using other dihydric phenols can be used as the A component. For example, 4,4'-(m-phenylenediisopropyridene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis (4-hydroxy) as a part or all of the divalent phenol component. Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis (4-hydroxyphenyl) Polycarbonate resins (homogeneous polymers or copolymers) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "BCF") are subjected to water absorption. Suitable for applications where dimensional changes and morphological stability requirements are particularly strict. It is preferable to use these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol component constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is the following copolymerized polycarbonate resin (1) to (3). Is.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) in 100 mol% of the divalent phenol component constituting the polycarbonate resin, and A copolymerized 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 divalent phenol component constituting the polycarbonate resin, and A copolymerized 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%, further preferably 45 to 65 mol%) in 100 mol% of the divalent phenol component constituting the polycarbonate resin, and A copolymerized polycarbonate resin having a Bis-TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

These special polycarbonate Z seeds may be used alone or in admixture of two or more. Further, these can be mixed with a widely used bisphenol A type polycarbonate resin and used. For details on the production method and characteristics of these special polycarbonate Z seeds, see, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580 and the like. Are listed.

Among the various polycarbonate resins described above, those having a water absorption rate and Tg (glass transition temperature) within the following ranges by adjusting the copolymerization composition and the like have good hydrolysis resistance of the polymer itself. Moreover, since it is remarkably excellent in low warpage after molding, it is particularly suitable in fields where morphological stability is required.
(I) Polycarbonate resin 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., or (ii) Tg of 160 to 250 ° C. A polycarbonate resin having a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, and more preferably 0.14 to 0.27%, preferably 170 to 230 ° C.

Here, the water absorption rate of the polycarbonate resin is a value obtained by measuring the water content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO62-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. Is. The Tg (glass transition temperature) is a value obtained by differential scanning calorimetry (DSC) measurement according to JIS K7121.

As the carbonate precursor, a carbonyl halide, a carbonic acid diester, a haloformate or the like is used, and specific examples thereof include phosgene, a diphenylcarbonate or a dihaloformate of a divalent phenol.

In producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc. are used as necessary. You may use it. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher functional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. , A copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including an alicyclic type), and a polyester carbonate resin obtained by copolymerizing the bifunctional carboxylic acid and the bifunctional alcohol together. Further, it may be a mixture of two or more of the obtained polycarbonate resins.

The branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl) hepten-2, 2. , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Etan, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris (4-hydroxy). Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is preferably 100 mol% in total of the structural unit derived from the dihydric phenol and the structural unit derived from the 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%. Further, particularly in the case of the molten ester exchange method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is also preferably 100 mol% in total with the structural unit derived from the divalent phenol. 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 the branched structure can be calculated by 1H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid. The alicyclic dicarboxylic acid such as is preferably mentioned. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction types such as the interfacial polymerization method, the molten transesterification method, the carbonate prepolymer solid phase ester exchange method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the methods for producing the polycarbonate resin of the present invention, are described in various documents and patent publications. This is a well-known method.

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. It is 2.0 × 10 ⁴ to 3.5 × 10 ⁴ , more preferably 2.2 × 10 ⁴ to 3.0 × 10 ⁴ . Polycarbonate resins with a viscosity ^average molecular weight of less than 1.8 × 104 may not provide good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight of more than ^4.0 × 104 is inferior in versatility in that it is inferior in fluidity during injection molding.

The polycarbonate resin may be obtained by mixing those 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 ) improves the entropy elasticity of the resin. As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which may be used when molding a reinforced resin material into a structural member. The improvement in molding processability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, the A component is a polycarbonate resin A-1-1-1 component having a viscosity average molecular weight of 7 × 10 ⁴ to 3 × 10 ⁵ ), and an aroma having a viscosity average molecular weight of 1 × 10 ⁴ to 3 × 10 ⁴ . A polycarbonate resin (A-1-1 component) composed of a group polycarbonate resin (A-1-1-2 component) and having a viscosity average molecular weight of 1.6 × 10 ⁴ to 3.5 × 10 ⁴ (hereinafter, “A-1-1 component)”. Polycarbonate resin containing a high molecular weight component (sometimes referred to as "polycarbonate resin") can also be used.

In the high molecular weight component-containing polycarbonate resin (A-1-1 component), the molecular weight of the A-1-1-1 component is preferably 7 × 10 ⁴ to 2 × 10 ⁵ , and more preferably 8 × 10 ⁴ to 2 ×. It is 10 ⁵ , more preferably 1 × 10 ⁵ to 2 × 10 ⁵ , and particularly preferably 1 × 10 ⁵ to 1.6 × 10 ⁵ . The molecular weight of the A-1-1-2 component is preferably 1 × 10 ⁴ to 2.5 × 10 ⁴ , more preferably 1.1 × 10 ⁴ to 2.4 × 10 ⁴ , and even more preferably 1.2 ×. It is 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 (A-1-1 component) is prepared by mixing the A-1-1-1 component and the A-1-1-2 component in various ratios to satisfy a predetermined molecular weight range. Can be obtained. It is preferable that the A-1-1-1 component is 2 to 40% by weight, and more preferably the A-1-1-1 component is 3 to 30% by weight in 100% by weight of the A-1-1 component. The A-1-1-1 component is more preferably 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

Further, as a method for preparing the A-1-1 component, (1) a method of independently polymerizing the A-1-1-1 component and the A-1-1-2 component and mixing them, (2). ) Such an aromatic polycarbonate resin using a method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by the GPC method represented by the method shown in JP-A-5-306336 in the same system. The aromatic polycarbonate resin obtained by the method for producing the A-1-1 component of the present invention so as to satisfy the conditions, and (3) the manufacturing method (the manufacturing method of (2)), and the separately manufactured A. Examples thereof include a method of mixing the 1-1-1 component and / or the A-1-1-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C. for 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 for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight M is calculated by the following formula.
η _SP / c = [η] +0.45 × [η] ² c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7

The viscosity average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve the soluble component in the composition. The soluble component is collected by cerite filtration. The solvent in the resulting solution is then removed. The solid after removing the solvent is sufficiently dried to obtain a solid having a component that dissolves in methylene chloride. From a solution in which 0.7 g of such a solid is dissolved in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is obtained in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

As the polycarbonate resin of the present invention, a polycarbonate-polydiorganosiloxane copolymer resin can also be used. The polycarbonate-polydiorganosiloxane copolymer resin is a copolymer prepared by copolymerizing a divalent phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). It is preferably a polymer resin.

［（上記一般式（１）において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１～１８のアルキル基、炭素原子数１～１８のアルコキシ基、炭素原子数６～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数２～１０のアルケニル基、炭素原子数６～１４のアリール基、炭素原子数６～１４のアリールオキシ基、炭素原子数７～２０のアラルキル基、炭素原子数７～２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ａ及びｂは夫々１～４の整数であり、Ｗは単結合もしくは下記一般式（２）で表される基からなる群より選ばれる少なくとも一つの基である。）

[(In the above general formula (1), R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms, respectively. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 2-10 carbon atoms alkenyl groups, 6-14 carbon atoms aryl groups, 6-14 carbon atoms aryloxy groups, carbon Represents a group selected from the group consisting of an alkoxy group having 7 to 20 atoms, an alkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and if there are a plurality of each, they may be the same. It may be different, where a and b are integers of 1 to 4, respectively, 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).)

（上記一般式（２）においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１～１８のアルキル基、炭素原子数６～１４のアリール基及び炭素原子数７～２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１～１８のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数６～２０のシクロアルキル基、炭素原子数６～２０のシクロアルコキシ基、炭素原子数２～１０のアルケニル基、炭素原子数６～１４のアリール基、炭素原子数６～１０のアリールオキシ基、炭素原子数７～２０のアラルキル基、炭素原子数７～２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｃは１～１０の整数、ｄは４～７の整数である。）］

(In the above general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and 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 independently represent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of up to 14; an aryloxy group having 6 to 10 carbon atoms, 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. Represents a group selected from the group of, and if there are multiple, they may be the same or different, c is an integer of 1 to 10 and d is an integer of 4 to 7)].

［上記一般式（３）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１～１２のアルキル基又は炭素数６～１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基であり、ｅ及びｆは夫々１～４の整数であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。Ｘは炭素数２～８の二価脂肪族基である。］

[In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, they are unsubstituted aryl groups, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and 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 divalent phenol (I) for deriving the carbonate constituent unit represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, and 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'-dihydroxydiphenyle- Tel, 4,4'-dihydroxy-3,3'-dimethyldiphenylether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfonate, 4,4'-dihydroxydiphenylsulfide, 2,2 '-Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'- Diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2 -(4-Hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} ben Zen, 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-adamantandiyl) 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, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Of these, 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.

In the carbonate constituent unit represented by the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently preferably a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, respectively. , Or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is particularly preferable. R ⁹ and R ¹⁰ are each independently and preferably an alkyl group having a hydrogen atom and a carbon atom number of 1 to 10, and a hydrogen atom and an alkyl group having a carbon atom number of 1 to 4 are particularly preferable. As the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the general formula (3), for example, a compound represented by the following general formula (I) is preferably used.

ｐ＋ｑは４～１２０が好ましく、３０～１２０がより好ましく、３０～１００がさらに好ましく、３０～６０が最も好ましい。

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-mentioned preferable polycarbonate-polydiorganosiloxane copolymer resin will be described below. By the reaction of dihydric phenol (I) with a chloroformate-forming compound such as chloroformate of phosgene or dihydric phenol (I) in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution in advance, A mixed solution of a chloroformate compound containing a chloroformate of the dihydric phenol (I) and / or a carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group is prepared. Phosgene is suitable as the chloroformate-forming compound.

In producing the chloroformate compound from the divalent phenol (I), the entire amount of the divalent phenol (I) that induces the carbonate constituent unit represented by the above general formula (1) can be used as the chloroformate compound at a time. Well, or a part of it may be added as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage as a post-addition monomer. The post-added monomer is added in order to rapidly proceed with the polycondensation reaction in the subsequent stage, and it is not necessary to dare to add it when it is not necessary. The method for producing the chloroformate compound is not particularly limited, but a method in which the reaction is usually carried out in a solvent in the presence of an acid binder is preferable. Further, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add the antioxidant. The ratio of the chloroformate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) 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 preferably adopted.

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. Similarly to the above, the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, per mol of divalent phenol (I) used to form the chloroformate compound of divalent phenol (I) (usually 1 mol corresponds to 2 equivalents), 2 equivalents or slightly excess. It is preferable to use an acid binder.

As the solvent, a solvent inert to various reactions such as those used for producing a known polycarbonate may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The pressure in the reaction for producing the chloroformate compound is not particularly limited and may be normal pressure, pressurization, 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 in many cases, heat is generated during the reaction, so water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be unconditionally defined, but is usually 0.2 to 10 hours. As the pH range in the reaction for producing the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

In the production of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, chloro containing the chloroformate of the dihydric phenol (I) and the carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group in this way. After preparing the mixed solution of the formate compound, dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate structural unit represented by the general formula (3) while stirring the mixed solution was charged in preparing the mixed solution. By adding the dihydric phenol (I) at a rate of 0.01 mol / min or less per mol of the dihydric phenol (I), the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chlorohomate compound are subjected to interfacial polycondensation. , Polycarbonate-polydiorganosiloxane copolymer resin is obtained.

The polycarbonate-polydiorganosiloxane copolymer resin can be a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent in combination with a dihydric phenolic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl) hepten-2, 2. , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Etan, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris (4-hydroxy). Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

The method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin is a method in which a branching agent is contained in the mixed solution during the production reaction of the chloroformate compound, but the interfacial polycondensation after the completion of the production reaction is completed. A method in which a branching agent is added during the reaction may be used. The proportion of the carbonate constituent units derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, based on the total amount of the carbonate constituent units constituting the copolymer resin. Particularly preferably, it is 0.05 to 1.0 mol%. The amount of the branched structure can be calculated by 1H-NMR measurement.

The pressure in the system in the polycondensation reaction can be reduced pressure, normal pressure, or pressurization, but usually, normal pressure or the self-pressure of the reaction system can be preferably used. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be unconditionally specified, but it is usually carried out in 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 having a viscosity [η _SP / c]. The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purification degree) by subjecting various post-treatments such as known separation and purification methods.

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

（上記一般式（４）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１～１２のアルキル基又は炭素数６～１２の置換若しくは無置換のアリール基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。）

(In the above general formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is 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 or more and 150 or less.)

<B component: fluororesin>
The fluororesin used as the component B of the present invention is preferably a copolymer containing a polymerization unit represented by the following general formulas (5) and (6). When a fluororesin that does not contain this structure is used, the impact resistance may decrease.

［上記一般式（６）において、Ｒ^５、Ｒ^６およびＲ^７は夫々独立して水素原子またはフッ素原子を表し、Ｒ^８は水素原子または炭素原子数１～５のフルオロアルキル基を表す。］

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

Examples of the polymerization unit represented by the above formula (6) include ethylene, propylene, 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene and 1-. Polymerization units derived from heptene, 3-methyl-1-hexene, hexafluoropropylene, octafluoro-1-butene, decafluoro-1-pentene, octafluoroisobutylene, perfluorobutylethylene and the like can be mentioned, among which ethylene and Polymerization units derived from propylene, 1-butene, isobutylene, hexafluoropropylene and perfluorobutylethylene are preferable, polymerization units derived from ethylene and propylene are more preferable, and polymerization units derived from hexafluoropropylene and ethylene are more preferable. Is more preferable. It should be noted that these polymerization units may be used alone or in combination of two or more.

The molar ratio (5) / (6) of the general formulas (5) and (6) constituting the fluororesin used as the B component of the present invention is preferably 95/5 to 5/95, and 90/10 to 10 / 90 is more preferable, 80/20 to 20/80 is even more preferable, and 70/30 to 30/70 is most preferable.

The content of the fluororesin used as the B component of the present invention is 5 to 80 parts by weight, preferably 20 to 60 parts by weight, and more preferably 30 to 30 parts by weight in 100 parts by weight of the resin component composed of the A component and the B component. 50 parts by weight. When the content of the B component is less than 5 parts by weight, excellent flame retardancy cannot be obtained, and when it is more than 80 parts by weight, appropriate aggregation of barium titanate cannot be obtained in the fluororesin, and further, the fluororesin Since the dielectric constant is low, a high dielectric resin composition cannot be obtained.

The fluororesin used as the component B of the present invention preferably has a melting point of 170 ° C. to 280 ° C., more preferably 170 ° C. to 250 ° C., and even more preferably 180 ° C. to 230 ° C. If the melting point of the fluororesin is lower than 170 ° C., the heat resistance may decrease. On the other hand, when the melting point is higher than 280 ° C., the compatibility with the polycarbonate resin may decrease, and the impact resistance may decrease.

<C component: barium titanate>
The average particle size of barium titanate used as the C component of the present invention is 4 to 10 μm, preferably 6 to 10 μm, and more preferably 7 to 9 μm. When the average particle size is less than 4 μm, large aggregation of barium titanate in the fluororesin occurs and the contact area with the thermoplastic resin decreases, so that the dielectric constant decreases, and further, water addition such as carbonate bond and ester bond decreases. When a thermoplastic resin having a bonding group that is easily decomposed is used, the flame retardancy deteriorates. If the average particle size exceeds 10 μm, the surface appearance of the molded product deteriorates. The particle size is D50, which is an integrated 50% obtained from the volume frequency particle size distribution measurement of the laser diffraction / scattering method.

The content of the C component is 1 to 60 parts by weight, preferably 10 to 50 parts by weight, and more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. If the content is less than 1 part by weight, the high dielectric resin composition cannot be obtained, and if it exceeds 60 parts by weight, the surface appearance of the molded product is deteriorated.

The barium titanate in the present invention is not particularly limited whether it is commercially available as barium titanate powder (BaTIO ₃ ) having a high dielectric constant or manufactured . Further, for the purpose of enhancing the dielectric properties of these barium titanate, commercially available barium titanate powder is fired at a high temperature and used by pulverizing it, or a magnesium compound or other additives are added when producing the barium titanate powder. You may use the barium titanate. Further, the shape of barium titanate is spherical, columnar, flaky, needle-shaped and the like, and is not particularly limited.

In the present invention, the ratio (weight ratio) of the B component to the C component (B component / C component) is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, and 0.9. ~ 1.1 is more preferable. If the weight ratio is less than 0.5 or more than 1.5, a highly dielectric resin composition may not be obtained.

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

(I) Thermal Stabilizer The thermoplastic resin composition of the present invention can contain various known stabilizers. Examples of the stabilizer include a phosphorus-based stabilizer and a hindered phenol-based antioxidant.
(I) Phosphorus-based stabilizer The thermoplastic resin composition of the present invention preferably contains a phosphorus-based stabilizer to the extent that it does not promote hydrolyzability. Such phosphorus-based stabilizers improve thermal stability during manufacturing or molding, and improve mechanical properties, hue, and molding stability. Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof, and tertiary phosphine. Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phenylphosphite, 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 thereof include erythritol diphosphite and dicyclohexylpentaerythritol diphosphite. Further, as another phosphite compound, a compound that reacts with divalent phenols and has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-). Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite , 2,2'-Etilidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and dioctyl phosphate. Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

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

(Ii) Hindered Phenolic Stabilizer A hindered phenol stabilizer can be added to the thermoplastic resin composition of the present invention. Such a formulation has an effect of suppressing deterioration of hue during molding and deterioration of hue during long-term use, for example. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-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), triethyleneglycol-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-methyl6- (3) -Tert-Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1,-Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-Methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 , 4'-di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylpheno) , 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-) Hydroxy-3', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide) , N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert- Butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl- 4-Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethylisocyanurate, and tetrakis [methylene-3- (3', 3',) 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like are exemplified. All of these are easily available. The above hindered phenolic stabilizers can be used alone or in combination of two or more. The blending amount of the phosphorus-based stabilizer and the hindered phenol-based stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 100 parts by weight, based on 100 parts by weight of the resin component composed of the A component and the B component, respectively. It is 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight.

(Iii) Thermal stabilizers other than the above The thermoplastic resin composition of the present invention may contain other thermal stabilizers other than the phosphorus-based stabilizers and hindered phenol-based stabilizers. As such other heat stabilizers, for example, lactone-based stabilizers typified by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene are preferably exemplified. Will be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above-mentioned company is preferably exemplified. The blending amount of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the component composed of the A component and the B component. .. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The blending amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of the resin component composed of the A component and the B component. Is. An epoxy compound can be added to the thermoplastic resin composition of the present invention, if necessary. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically all compounds having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3', 4-'-epoxycyclohexylcarboxylate, and 1,2-epoxy-4-butanol of 2,2-bis (hydroxymethyl) -1-butanol. Examples thereof include a (2-oxylanyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate. The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, based on 100 parts by weight of the resin component composed of the A component and the B component. Yes, more preferably 0.005 to 0.1 parts by weight.

(II) Flame Retardant A flame retardant can be added to the thermoplastic resin composition of the present invention. The formulation of such compounds results in improved flame retardancy, but is also based on the properties of each compound, for example, improved antistatic properties, fluidity, rigidity, and thermal stability. Examples of such flame retardants include (i) organometal salt flame retardants (eg, organosulfonic acid alkali (earth) metal salts, organoborate metal salt flame retardants, organophosphorus metal salt flame retardants, etc.), ( ii) Organophosphorus flame retardant (for example, organic group-containing monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, etc.), (iii) Silicone flame retardant composed of silicone compound. , (Iv) fibrillated PTFE, among which organometal salt-based flame retardants and organophosphorus flame retardants are preferred. These may be used alone or in combination of two.

(I) Organic metal salt-based flame retardant The organic metal salt compound is an alkaline (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkaline (earth) metal salt of an organic sulfonic acid. Is preferable. This organic sulfonic acid alkali (earth) metal salt includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. It contains a metal salt of an acid and a metal salt of an aromatic sulfonic acid having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms and an alkali metal or an alkaline earth metal. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. Among such alkali metals, rubidium and cesium having a larger ionic radius are preferable when the demand for transparency is higher, but they are not versatile and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. In consideration of these, the alkali metal in the sulfonic acid alkali metal salt can be used properly, but in all respects, the sulfonic acid potassium salt having an excellent balance of characteristics is most suitable. It is also possible to use such a potassium salt in combination with a sulfonic acid alkali metal salt composed of another alkali metal.

Specific examples of the perfluoroalkyl sulfonic acid alkali metal salt include potassium trifluoromethanesulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluoro. Sodium butane sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutane sulfonate, perfluorooctane sulfonic acid Examples thereof include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutane sulfonate, rubidium perfluorohexanesulfonate, and the like, and these can be used alone or in combination of two or more. Here, the number of carbon atoms of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8.

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

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

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

(Ii) Organophosphorus flame retardant As the organophosphorus flame retardant, an aryl phosphate compound and a phosphazene compound are preferably used. Since these organophosphorus flame retardants have a plasticizing effect, they are advantageous in that molding processability can be improved. As the aryl phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one kind or two or more kinds of phosphate compounds represented by the following general formula (7) can be mentioned.

（但し上記式中のＭは、二価フェノールから誘導される二価の有機基を表し、Ａｒ^１、Ａｒ^２、Ａｒ^３、およびＡｒ^４はそれぞれ一価フェノールから誘導される一価の有機基を表す。ａ、ｂ、ｃ及びｄはそれぞれ独立して０または１であり、ｍは０～５の整数であり、重合度ｍの異なるリン酸エステルの混合物の場合はｍはその平均値を表し、０～５の値である。）

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

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

Suitable specific examples of the dihydric phenol that induces M are hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, and bis (4). -Hydroxyphenyl) ketones and bis (4-hydroxyphenyl) sulphide are exemplified, with resorcinol, bisphenol A, and dihydroxydiphenyl being preferred.

Preferable specific examples of the monovalent phenol for inducing Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol, which are preferable. Is phenol, and 2,6-dimethylphenol.

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

On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-kisilyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Phosphate oligomers mainly composed of phosphate oligomers, phosphite oligomers mainly composed of 4,4-dihydroxydiphenylbis (diphenylphosphate), and phosphate ester oligomers mainly composed of bisphenol A bis (diphenylphosphate) are suitable (here, the main constituent is Indicates that other components having different degrees of polymerization may be contained in a small amount, and more preferably, the component of m = 1 in the above formula (7) is 80% by weight or more, more preferably 85% by weight or more, still more preferably. It is shown that it is contained in an amount of 90% by weight or more).
As the phosphazene compound, various phosphazene compounds conventionally known as flame retardants can be used, but phosphazene compounds represented by the following general formulas (8) and (9) are preferable.

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は、水素、水酸基、アミノ基、またはハロゲン原子を含まない有機基を表す。また、ｒは３～１０の整数を表す。）

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

In the above formulas (8) and (9), examples of the organic group containing no halogen atom represented by X ¹ , X ² , X ³ and X ⁴ include an alkoxy group, a phenyl group, an amino group and an allyl group. Can be mentioned. Of these, the cyclic phosphazene compound represented by the above formula (8) is preferable, and further, the cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula (8) are phenoxy groups is particularly preferable.

The content of the organic phosphorus flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and 5 to 20 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. The weight part is more preferable. If the blending amount of the organophosphorus flame retardant is less than 1 part by weight, the flame retardant effect is difficult to obtain, and if it exceeds 50 parts by weight, the strands are broken or surging occurs during kneading extrusion, and the productivity is lowered. May occur.

(Iii) Silicone-based flame retardant A silicone compound used as a silicone-based flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. Silicone compounds are highly flame-retardant, especially when a polycarbonate resin is used, by binding themselves during combustion or by binding to a component derived from the resin to form a structure, or by a reduction reaction during structure formation. It is believed to give an effect.

Therefore, it is preferable to contain a group having high activity in such a reaction, and more specifically, it is preferable to contain at least one group selected from an alkoxy group and a hydrogen (that is, Si—H group) in a predetermined amount. preferable. The content ratio of such groups (alkoxy group, Si—H group) is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and 0.15 to 0. The range of 6 mol / 100 g is more preferable. This ratio is determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is composed of any combination of the following four types of siloxane units. That is, M unit: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _{1 / 2} , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ = CH) 1 functional siloxane unit such as SiO _1/2 , D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ = CH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. 2 Functional siloxane unit, T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ = CH) SiO _3/2 , (C ₆ H ₅ ) Trifunctional siloxane unit such as SiO _3/2 , Q unit: A tetrafunctional siloxane unit represented by SiO ₂ .

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

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

The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of the organic residue include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl group such as a phenyl group. Also, an aralkyl group such as a trill group can be mentioned. More preferably, it is an alkyl group having 1 to 8 carbon atoms, an alkenyl group or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. On the other hand, the silane compound and the siloxane compound as the organic surface treatment agent for the titanium dioxide pigment are clearly distinguished from the silicone flame retardant in the preferred embodiment in that a preferable effect can be obtained when the aryl group is not contained. .. The silicone compound used as a silicone-based flame retardant may contain a reactive group in addition to the Si—H group and the alkoxy group, and the reactive group includes, for example, an amino group, a carboxyl group, an epoxy group, and vinyl. Examples include groups, mercapto groups, and methacryloxy groups.

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

(Iv) Polytetrafluoroethylene having the ability to form fibrils (fibrillated PTFE)
The fibrillated PTFE may be a fibrillated PTFE alone or a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer. The fibrillated PTFE has an extremely high molecular weight and tends to bond the PTFE to each other to form a fibrous form due to an external action such as a shearing force. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. Such a number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C., for example, as disclosed in Japanese Patent Application Laid-Open No. 6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. It is also possible to use such fibrillated PTFE in a mixed form with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties.

Further, as disclosed in Japanese Patent Application Laid-Open No. 6-145520, a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell is also preferably used.

Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J of Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Chemical Industry Co., Ltd.

As the fibrillated PTFE in a mixed form, (1) a method of mixing an aqueous dispersion of a fibrillated PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coaggregating mixture (Japanese Patent Laid-Open No. 60-258263). (A method described in Japanese Patent Application Laid-Open No. 63-154744, etc.), (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). The method described), (3) A method of uniformly mixing an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution, and simultaneously removing each medium from such a mixture (Japanese Patent Laid-Open No. 06-220210, JP-A). 08-188653 and the like), (4) A method for polymerizing a monomer forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Japanese Patent Laid-Open No. 9-95583). Method) and (5) A method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl-based monomer is further polymerized in the mixed dispersion to obtain a mixture (Japanese Patent Laid-Open No. 11-). The one obtained by the method described in Japanese Patent Publication No. 29679 etc.) can be used.

Commercially available products of these mixed forms of fibrillated PTFE include Mitsubishi Rayon Co., Ltd.'s "Metabren A3000" (trade name), "Metabren A3700" (trade name), and "Metabren A3800" (trade name). Examples thereof include the A series, SN3300B7 (trade name) manufactured by Shine Composer, and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

The proportion of fibrillated PTFE in the mixed form is preferably 1% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, 20% by weight, based on 100% by weight of the mixture. Most preferably from% to 80% by weight.

Good dispersibility of fibrillated PTFE can be achieved when the proportion of fibrillated PTFE in the mixed form is within such range. The content of the fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the resin component composed of the A component and the B component. , 0.1-0.5 parts by weight is more preferable.

(III) Dyeing Pigment The thermoplastic resin composition of the present invention can further provide a molded product containing various dyeing pigments and exhibiting various designs. The dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthracinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, and quinacridone dyes. Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the thermoplastic resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is suitable as the metallic pigment. Further, by blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, a better design effect that makes the best use of the emitted color can be imparted.

(IV) Fluorescent whitening agent In the thermoplastic resin composition of the present invention, the fluorescent whitening agent is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white, and is, for example, a stillben type. , Benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, oxazine-based compounds and the like. Specific examples thereof include CI Fluorescent Fluorescent 219: 1, Eastman Chemical Company's EASTOBRITE OB-1, and Showa Kagaku Co., Ltd.'s "Hackor PSR". Here, the fluorescent whitening agent has an action of absorbing the ultraviolet energy of light rays and radiating this energy to the visible portion. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, based on 100 parts by weight of the resin component composed of the A component and the B component. .. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

(V) Compound having heat ray absorbing ability The thermoplastic resin composition of the present invention can contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide, titanium oxide, lanthanum borate, cerium boride and tungsten boride. Various metal compounds having excellent near-infrared absorbing ability such as metal boride-based and tungsten oxide-based near-infrared absorbing agents, and carbon fillers are preferably exemplified. As such a phthalocyanine-based near-infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerenes, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on 100 parts by weight of the resin component composed of the A component and the B component. It is preferably 0.001 to 0.07 parts by weight, and more preferably 0.001 to 0.07 parts by weight. The content of the metal oxide-based near-infrared ray absorber, the metal boride-based near-infrared ray absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the thermoplastic resin composition of the present invention, and is 0. The range of .5 to 100 ppm is more preferable.

(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 a light diffusing agent include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are already known as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles typified by polyorganosylsesquioxane, and the like are exemplified. The shape of the light diffusing agent is exemplified by a spherical shape, a disk shape, a pillar shape, an amorphous shape, and the like. Such a sphere includes a deformed one that does not have to be a perfect sphere, and such a pillar includes a cube. The preferred light diffusing agent is spherical, and it is preferable that the particle size is uniform. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0. It is 01 to 3 parts by weight. Two or more kinds of light diffusing agents can be used in combination.

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

(VIII) Ultraviolet absorber The thermoplastic resin composition of the present invention can be blended with an ultraviolet absorber to impart weather resistance. Specific examples of such an ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzine in the benzophenone system. Loxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4'-Dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy Examples thereof include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole system. , 2- (2-Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazo- , 2- (2-Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) ) Benzotriazol, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2 -Hydroxy-3- (3,4,5,6-tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole Copolymerization of the monomer with a copolymerizable vinyl-based monomer or 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl-based monomer copolymerizable with the monomer Examples thereof include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as polymers. Specifically, in the hydroxyphenyltriazine system, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4, 6-Diphenyl-1,3,5-triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol , 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) )-5-Butyloxyphenol and the like are exemplified. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified. Specific examples of the ultraviolet absorber include 2,2'-p-phenylenebis (3,1-benzoxazine-4-one) and 2,2'-m-phenylenebis (3,1) in the cyclic iminoester system. -Benzoxazine-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazine-4-one) and the like are exemplified. As the ultraviolet absorber, specifically, in the case of cyanoacrylate, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-2-bis]. Examples thereof include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene. Further, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that such an ultraviolet-absorbing monomer and / or a photostable monomer and a single amount such as an alkyl (meth) acrylate are used. It may be a polymer-type ultraviolet absorber copolymerized with a body. As the ultraviolet-absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. The skeleton. Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability, and cyclic iminoester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue. Specific examples thereof include ChemiPro Kasei Co., Ltd. "Chemisorb 79" and BASF Japan Ltd. "Chinubin 234". The ultraviolet absorber may be used alone or in a mixture of two or more kinds.

The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0, with respect to 100 parts by weight of the resin component composed of the A component and the B component. It is 05 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 is preferable to include an antistatic agent. Examples of such antistatic agents include (1) an aryl sulfonic acid phosphonium salt typified by dodecylbenzene sulfonic acid phosphonium salt, an organic sulfonic acid phosphonium salt such as an alkyl sulfonic acid phosphonium salt, and a tetrafluoroborate phosphonium salt. Examples include phosphonium borate salt. The content of the phosphonium salt is preferably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, and more preferably 1 to 3.5 parts by weight with respect to 100 parts by weight of the component composed of A component and B component. It is in the range of 1.5 to 3 parts by weight, more preferably 1.5 to 3 parts by weight. Examples of the antistatic agent include (2) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium sulfonate, and barium organic sulfonate. Examples thereof include organic sulfonic acid alkali (earth) metal salts such as. As described above, such a metal salt is also used as a flame retardant. More specifically, examples of such a metal salt include a metal salt of dodecylbenzene sulfonic acid and a metal salt of perfluoroalkane sulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is appropriately 0.5 part by weight or less, preferably 0.001 to 0.3 part by weight, based on 100 parts by weight of the component composed of A component and B component. Parts, more preferably 0.005 to 0.2 parts by weight. Alkali metal salts such as potassium, cesium, and rubidium are particularly preferred.

Examples of the antistatic agent include (3) an ammonium alkyl sulfonic acid salt and an ammonium organic sulfonic acid salt such as an ammonium aryl sulfonic acid salt. It is appropriate that the ammonium salt is 0.05 parts by weight or less with respect to 100 parts by weight of the component composed of the A component and the B component. Examples of the antistatic agent include polymers containing a poly (oxyalkylene) glycol component such as (4) polyether ester amide as a component thereof. 5 parts by weight or less is appropriate for the polymer with respect to 100 parts by weight of the resin component composed of the A component and the B component.

(X) Filler The thermoplastic resin composition of the present invention can be blended with various known fillers as reinforcing fillers other than the fibrous filler. As such a filler, various plate-shaped fillers and granular fillers can be used. Here, the plate-shaped filler is a filler whose shape is plate-shaped (including those having irregularities on the surface and those having a curved plate). The granular filler is a filler having a shape other than these, including an indefinite shape.

Plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-like fillers in which different materials such as metals and metal oxides are surface-coated on these fillers. Materials and the like are preferably exemplified. The particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to a value based on the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods, in the region up to about 10 μm, and laser diffraction in the region of 10 to 50 μm. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method, and is the value by the vibration type sieving method in the region of 50 to 300 μm. Such a particle size is the particle size in the resin composition. The plate-like filler may be surface-treated with various silane-based, titanate-based, aluminate-based, and zirconate-based coupling agents, and may be surface-treated, and may be olefin-based resin, styrene-based resin, acrylic-based resin, or polyester-based resin. , An epoxy-based resin, various resins such as a urethane-based resin, a higher fatty acid ester, or the like, or the granulated product which has been focused or compressed.

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

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

The thermoplastic resin composition of the present invention is useful for various applications such as electric / electronic parts, home electric appliances, automobile-related parts, infrastructure-related parts, housing-related parts, etc., and its industrial effect is exceptional. ..

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

The following will be further described with reference to examples. The following items were evaluated.
(I) Surface appearance The three-stage plate with holes obtained by the following method was visually confirmed, and those with a smooth surface and no lumps or white streaks were confirmed as ○, and some lumps or white streaks were confirmed. The thing was set as x.
(Ii) Dielectric change rate The dielectric constant of a 2 mm thick portion of a three-stage plate with holes obtained by the following method was measured at a frequency of 100 MHz using an impedance analyzer (trade name: E4991A, manufactured by Keysight Technology Co., Ltd.). The value of the dielectric constant of the compositions of Examples 1 to 9 and Comparative Examples 1 to 6 is set to [dielectric constant 1], and the content of the B component in the compositions of Examples 1 to 9 and Comparative Examples 1 to 6 is 0 parts by weight. The value of the permittivity at the time of was set to [dielectric constant 2], and the permittivity change rate was calculated from the following formula.
Permittivity change rate (%) = 100 × ([dielectric constant 1]-[dielectric constant 2]) / [dielectric constant 2]
(Iii) Flame retardancy A V test was carried out according to UL94 using UL test pieces obtained by the following method. The case where the determination could not meet any of the criteria of V-0, V-1, and V-2 was indicated as "notV".

[Manufacturing of barium titanate 1]
A suspension obtained by adding 720 g of pure water to 130 g of barium chloride dihydrate and 130 g of oxalic acid dihydrate and stirring at a temperature of 55 ° C. for 0.5 hours was used as solution A. Further, a solution obtained by adding 560 g of pure water to 256 g of a 15.3 wt% titanium tetrachloride aqueous solution in terms of TiO ₂ and diluting the solution was used as solution B. Then, the solution B was added to the solution A over 30 minutes at a reaction temperature of 55 ° C. with stirring, and after the addition, aging was carried out for 0.5 hours while continuing the stirring. After the aging was completed, the barium titanyl oxalate was collected by filtration. Then, the recovered barium titanyl oxalate was repulped with pure water and allowed to stand and dry at 80 ° C. for 24 hours to obtain a powder of barium titanyl oxalate. 20 g of the obtained barium titanate oxalate powder was charged into an alumina crucible, the temperature was raised over 5 hours, and firing was performed at 1050 ° C. for 15 hours to obtain barium titanate. The obtained barium titanate was crushed in a dairy pot to obtain barium titanate particles [barium titanate 1]. The average particle size D50 of [barium titanate 1] (integrated 50% obtained from the volume frequency particle size distribution measurement by the laser diffraction / scattering method) was 4 μm.

[Manufacturing of barium titanate 2]
Barium titanate particles [barium titanate 2] were obtained by the same production method as barium titanate 1 except that the firing temperature was 1350 ° C. and the firing time was 20 hours. The average particle size D50 of [barium titanate 2] was 12 μm.

[Examples 1 to 9, Comparative Examples 1 to 6]
A mixture having the composition shown in Table 1 and composed of the components excluding the fluororesin of the component B was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. The fluororesin of component B was supplied from the second supply port using a side feeder. The twin-screw extruder has a diameter of 30 mmφ and is equipped with one vent of a total of 10 barrel configurations (referred to as C1 to C10 cylinders from the upstream) having a supply port at C1 at the uppermost stream and C5 at the downstream thereof. A "TEX30αIII" meshing type co-rotating twin-screw extruder manufactured by Japan Steel Works, Ltd. was used. The extrusion conditions were a temperature of C1: 260 ° C., a temperature of C2 to 10: 280 ° C., a screw rotation speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum degree of 3 kPa, and melt-kneading to obtain pellets.

A part of the obtained pellets is dried at 120 ° C. for 6 hours in a hot air circulation type dryer, and then using an injection molding machine, the cylinder temperature is 280 ° C. and the mold temperature is 80 ° C. with holes for evaluation 3. A step plate (width 50 mm x length 100 mm x thickness 3.0 mm, 2.0 mm, 1.0 mm) and a UL test piece (width 13 mm x length 125 mm x thickness 2.0 mm) were prepared and evaluated above. did. The evaluation results are shown in Table 1.

Each component of the symbol notation in Table 1 is as follows.
(Component A)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Limited)
A-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 25,000, PDMS amount 8.4%, PDMS degree of polymerization 37, Teijin Limited Panlite W-0111)
(B component)
B-1: ETFE (manufactured by Asahi Glass Co., Ltd., LH-8000, melting point 180 ° C)
B-2: FEP (manufactured by Daikin, Neo-Flon FEP NP-20, melting point 270 ° C)
(C component)
C-1: Barium titanate (manufactured by Nippon Chemical Industrial Co., Ltd., Pulceram BTD-UP2, average particle size D50: 2 μm)
C-2: Barium titanate (barium titanate 1, average particle size D50: 4 μm)
C-3: Barium titanate (manufactured by Nippon Chemical Industrial Co., Ltd., Pulceram BTD-UP, average particle size D50: 8 μm)
C-4: Barium titanate (barium titanate 2, average particle size D50: 12 μm)
(Other ingredients)
STB-3: Phosphorus-based heat stabilizer (trimethyl phosphate, TMP manufactured by Daihachi Chemical Industry Co., Ltd.)
UV: Benzotriazole-based UV absorber (Cemisorb 79 manufactured by Chemipro Kasei Kogyo Co., Ltd.)

Claims (5)

(C) The average particle size is 4 to 100 parts by weight of the resin component (A) consisting of 20 to 95 parts by weight of the thermoplastic resin (A component) and 5 to 80 parts by weight of the fluororesin (B component). A thermoplastic resin composition containing 40 to 60 parts by weight of barium titanate (C component) having a thickness of 10 μm. The characteristic is that the component A is a polycarbonate resin or a polycarbonate-polyorganosiloxane copolymer resin composed of a polycarbonate block represented by the following general formula (1) and a polydiorganosiloxane block represented by the following general formula (3). The thermoplastic resin composition according to claim 1.

[(In the above general formula (1), R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms, respectively. ~ 20 cycloalkyl groups, 6-20 carbon atoms cycloalkoxy groups, 2-10 carbon atoms alkenyl groups, 6-14 carbon atoms aryl groups, 6-14 carbon atoms aryloxy groups, carbon Represents a group selected from the group consisting of an alkoxy group having 7 to 20 atoms, an alkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and if there are a plurality of each, they may be the same. It may be different, where a and b are integers of 1 to 4, respectively, 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 independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and 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 independently represent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of up to 14; an aryloxy group having 6 to 10 carbon atoms, 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. Represents a group selected from the group of, and if there are multiple, they may be the same or different, c is an integer of 1 to 10 and d 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 independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, they are unsubstituted aryl groups, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and e and f. Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, 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. .) The invention according to claim 1 or 2, wherein the component B is a copolymer containing a polymerization unit represented by the following general formulas (5) and (6), and has a melting point of 170 ° C. to 280 ° C. Thermoplastic resin composition.

[In the above general formula (6), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a fluorine atom, and R ⁸ represents a hydrogen atom or a fluoroalkyl group having 1 to 5 carbon atoms. ] The thermoplastic resin composition according to any one of claims 1 to 3 , wherein the ratio (weight ratio) of the B component to the C component (B component / C component) is 0.5 to 1.5. A molded product obtained by molding the thermoplastic resin composition according to any one of claims 1 to 4 .