JP2006206703A - Conductive thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive thermoplastic resin composition comprising a polymer alloy of an aromatic polycarbonate resin and a thermoplastic polyester resin, wherein the composition shows little change of conductivity at the time of residence, has a stable conductivity and is excellent in appearance, flowability and impact resistance. <P>SOLUTION: The conductive thermoplastic resin composition comprises 100 pts.wt. of the sum of (A) 10-95 pts.wt. of an aromatic polycarbonate resin (component A) and (B) 5-90 pts.wt. of a thermoplastic polyester resin (component B), (C) 0.1-10 pts.wt. of a conducting agent (component C) composed of a conductive carbon black and/or a hollow carbon fibril, and (D) 0.01-5 pts.wt. of at least one phosphorous compound (component D) selected from the group consisting of a phosphate represented by a specific structure and a phosphite represented by another specific structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a conductive thermoplastic resin composition. More specifically, the present invention relates to a conductive thermoplastic resin composition that is excellent in appearance, fluidity, impact resistance, and conductivity, has little variation in conductivity derived from the manufacturing process, and can exhibit stable conductivity. This characteristic relates to a conductive thermoplastic resin composition suitable for automobile exterior parts, electrical / electronic / OA equipment parts, machine parts, and the like.

  Conventionally, many resin materials have been used in place of metal materials for electrical / electronic / OA equipment parts, machine parts, automotive exterior / skin parts, and the like. In recent years, with regard to automobile outer plate parts, vertical metal plates such as fenders, door panels, rear panels, etc., have been actively studied for converting from conventional metal materials to plastics. Advantages of plasticization include weight reduction, design freedom, possible module assembly, and pedestrian protection.

  Such automobile exterior / skin parts are usually painted for coloring, and electrostatic coating is generally performed for the purpose of improving the adhesion efficiency of the paint. Electrostatic coating is a coating method in which a high voltage is applied to a grounded object to be coated and a paint spraying device, and charged paint particles are sprayed onto the object to be coated having the opposite polarity, thereby efficiently attaching the paint. Since the thermoplastic resin is electrically insulating, it is necessary to impart conductivity in order to perform electrostatic coating.

  On the other hand, for example, OA equipment and electronic equipment are becoming smaller and lighter, higher integration, and higher precision, and as a result, the adhesion of dust and dust to electrical and electronic parts is reduced as much as possible, and errors due to static electricity disturbances. The demand from the market for conductive resins that are effective in preventing operation is increasing year by year. For example, IC chips used in semiconductors, IC trays, wafers, internal parts of hard disks used in computers, etc. are more demanding and should be given antistatic properties to completely prevent dust and dust from adhering. is required. In addition, electrical conductivity is required for components that need to be provided with electromagnetic wave shielding properties, such as a notebook computer housing, a PDA housing, a pachinko component substrate, a camera shutter, and a mobile phone housing.

  For such applications, a device has been devised to impart conductivity by blending conductive carbon black with a thermoplastic resin that is inherently electrically insulating.

  By the way, polycarbonate resin is excellent in impact resistance, heat resistance, dimensional stability, etc. as a general-purpose engineering plastic. Due to its characteristics, it can be used in a wide range of fields such as electrical / electronic / OA equipment parts, machine parts, automotive exterior / skin parts, etc. Used in. For this reason, studies have been made to add conductive carbon black to a polycarbonate resin, but there has been a problem that characteristics such as melt fluidity and impact resistance are significantly lowered.

  In order to solve this problem, Patent Document 1 proposes a resin composition comprising an aromatic polycarbonate resin, an aromatic polyester resin, an elastomer, and carbon black. However, since the amount of carbon black added is large, fluidity, The impact and appearance were not satisfactory. Although the same composition is described also in patent document 2, there is no description regarding electroconductivity, and also about the disclosed composition, there existed a problem of the mechanical physical property at the time of residence, or the electroconductive fall.

  In the case of a blend of a polycarbonate resin and a polyester resin, it is generally known that physical properties are deteriorated by an ester exchange reaction at the time of melting. On the other hand, for example, Patent Document 3 suppresses transesterification by adding a phosphate compound having a specific structure, and Patent Document 4 adds a phosphite compound having a specific structure. It has been proposed. However, in Patent Documents 3 and 4, there is no specific description regarding the addition of the conductive agent, and the conductive agent and the phosphorus compound are only effective in suppressing deterioration of the resin itself such as impact resistance and yellowing prevention. There is no description of the synergistic effect when used in combination. Normally, it is considered that there is almost no deterioration of carbon black at a temperature at which a thermoplastic resin is molded, so that a decrease in conductivity is hardly taken into consideration. However, in the case of a blend of a polycarbonate resin and a polyester resin, it is assumed that the dispersion state of the two types of resins and the balance between the dispersion and aggregation of the carbon black have a great influence on the conductivity, so that the conductivity changes due to residence. It is considered a thing.

  Patent Document 5 discloses a conductive sheet made of polycarbonate, aromatic polyester, and carbon black, and Patent Document 6 discloses a thermoplastic polyester and an aromatic polycarbonate. A conductive resin composition comprising conductive carbon, in which the conductive carbon is selectively dispersed in the thermoplastic polyester layer, has been proposed in any literature from the viewpoint of transesterification prevention and thermal stabilization. A composition containing sodium hydrogen phosphate is disclosed. However, there is no description regarding the change in conductivity during residence and measures for improving the same, and none of the disclosed compositions has improved the decrease in conductivity during residence.

Japanese Patent Application Laid-Open No. 58-136362 Japanese Unexamined Patent Publication No. 62-185743 JP-A 63-265949 Japanese Unexamined Patent Publication No. 3-977752 Japanese Unexamined Patent Publication No. 7-330925 JP 2001-40196 A

  As a result of intensive studies aimed at providing a conductive thermoplastic resin composition that has solved the above-mentioned conventional drawbacks, a specific conductive agent is added to a polymer alloy of an aromatic polycarbonate resin and a thermoplastic polyester resin. In the added system, it has been found that a specific phosphorus compound has a role of stabilizing the conductivity at the time of residence, and has reached the composition of the present invention. That is, an object of the present invention is to provide a conductive thermoplastic resin composition that has little change in conductivity during residence, has stable conductivity, and is excellent in appearance, fluidity, and impact resistance. is there.

That is, the gist of the present invention is as follows.
(C) Conductive carbon black with respect to a total of 100 parts by weight of (A) aromatic polycarbonate resin (component A) 10 to 95 parts by weight and (B) thermoplastic polyester resin (component B) 5 to 90 parts by weight And / or 0.1 to 10 parts by weight of a conductive agent (component C) made of hollow carbon fibrils, and (D) a phosphate ester represented by the following general formula (I) and represented by the following general formula (II) A conductive thermoplastic resin composition containing 0.01 to 5 parts by weight of a phosphorus compound (D component) that is at least one selected from the group consisting of phosphites.

O = P (OH) _n (OR) _3-n (n is an integer of 0 to 2) (I)
(In the formula, R is an alkyl group or an aryl group, and each may be the same or different.)

（式中、Ｒ'はアルキル基またはアリール基であり、それぞれ同一であっても異なっていても良い。）

(In the formula, R ′ represents an alkyl group or an aryl group, which may be the same or different.)

  The conductive thermoplastic resin composition of the present invention is characterized by excellent conductivity, fluidity, appearance, impact resistance, little change in conductivity during residence, stable conductivity, and dimensional stability. It is a resin composition having excellent properties and heat resistance. Therefore, as a major application of the conductive thermoplastic resin composition having such features, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side moldings, garnishes, wheel caps, doors Car exterior parts such as handles, hood bulges, fuel lids, and various spoilers.

Moreover, the conductive thermoplastic resin composition of the present invention can be suitably used for applications requiring electrical conductivity such as, for example, electrical / electronic / OA equipment, in addition to automotive exterior parts. For example, IC chips used in semiconductors, IC trays, wafers, internal parts of hard disks used in computers, etc. need to be optimally conductive in order to provide antistatic properties and completely prevent dust and dust from adhering. It is not satisfied if it is too high or too low. For such applications, a volume resistivity in the range of 2 × 10 ² to 1 × 10 ⁸ Ωcm is selected. On the other hand, in applications where conductivity is required for imparting electromagnetic wave shielding properties, such as notebook computer housings, PDA housings, pachinko parts substrates, camera shutters, mobile phone housings, etc., the volume resistivity is within this range. It is not limited.

  Whatever range of volume resistivity is required, the composition of the present invention, which has improved conductivity change due to stagnation during component molding, can be suitably used.

(A) Aromatic polycarbonate resin (component A)
The aromatic polycarbonate resin which is the A component of the present invention (hereinafter sometimes abbreviated as A component) is obtained by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with a carbonate precursor. A thermoplastic aromatic polycarbonate polymer or copolymer which may be branched. Although the manufacturing method of aromatic polycarbonate resin is not specifically limited, Usually, it can manufacture by the phosgene method (interfacial polymerization method) or the melting method (transesterification method) etc. conventionally known.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A) Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2 , 2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl) Phenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro) -4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4- Hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4-hydroxyphenyl) Bis (exemplified by -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Hydroxyaryl) alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) silane Bis (hydroxyaryl) cycloalkanes exemplified by rhohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, Cardo structure-containing bisphenols exemplified by 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, etc. Dihydroxy diaryl ethers, such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, etc .; 4,4′-dihydroxydiphenyl Sulfoxide, 4,4'-dihydroxy Dihydroxydiaryl sulfoxides exemplified by -3,3'-dimethyldiphenyl sulfoxide and the like; dihydroxydiaryls exemplified by 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone and the like Sulfones; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like. These aromatic dihydroxy compounds may be used alone or in combination of two or more. Among these, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) is particularly preferably used from the viewpoint of impact resistance.

  As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate or the like is used. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate, diethyl carbonate and the like Dialkyl carbonates; dihaloformates of dihydric phenols and the like.

  The aromatic polycarbonate resin may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1, Polyhydroxy compounds represented by 1-tri (4-hydroxyphenyl) ethane or the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichloroisatin The aromatic dihydroxy compound may be used by substituting a part of the aromatic dihydroxy compound with 5-bromoisatin or the like. Range are preferred, particularly preferred is 0.1 to 2 mol%.

  In producing the aromatic polycarbonate resin by reacting the dihydric phenol and the carbonate precursor by the interfacial polymerization method or the melt transesterification method, a terminal stopper may be used as necessary.

  In the case of the interfacial polymerization aromatic polycarbonate resin, a terminal stopper or a molecular weight modifier is usually used. Examples of the terminal terminator or the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group or a monovalent carboxylic acid derivative structure. Examples of the compound having a monovalent phenolic hydroxyl group include substituted phenols such as phenol, alkylphenol, halogenated phenol, alkoxyphenol, and alkoxycarbonylphenol. Specifically, phenol, methylphenol, pn -Butylphenol, p-tert-butylphenol, p-tert-octylphenol, allylphenol, cumylphenol, naphthylphenol, naphthol, bromophenol, tribromophenol, trifluorophenol, methoxyphenol, butoxyphenol, methoxycarbonylphenol, butoxycarbonyl Phenol, dodecyloxycarbonylphenol, octadecyloxycarbonylphenol and the like can be mentioned. Examples of the compound having a monovalent carboxylic acid derivative structure include carboxylic acid, carboxylic acid chloride and the like, and specifically, acetic acid, acrylic acid, formic acid, propionic acid, propiolic acid, butyric acid, isobutyric acid, methacrylic acid. Acid, palmitic acid, stearic acid, pyruvic acid, acetoacetic acid, glycolic acid, lactic acid, glyceric acid, hexafluoroacetic acid, benzoic acid, naphthoic acid, methylbenzoic acid, butylbenzoic acid, vinylbenzoic acid, pentafluorobenzoic acid, pentabromo Examples thereof include carboxylic acids such as benzoic acid, methyl naphthoic acid, and ethyl naphthoic acid, and carboxylic acid chlorides derived from these carboxylic acids.

  Also, in the case of an ester exchange aromatic polycarbonate resin, the amount ratio of the terminal hydroxy terminal structure is usually adjusted by adjusting the molar ratio of the raw dihydroxy compound and the carbonic acid diester or by adjusting the degree of vacuum. Can be adjusted. Further, as a more aggressive method, an adjustment method in which a terminal terminator is added separately during the reaction is also well known. Examples of the terminal terminator used here include monohydric phenols, monocarboxylic acids, and carbonic acid diesters. For example, monohydric phenols and monohydric carboxylic acids having 9 or more carbon atoms are preferably used. P-propylphenol, o-sec-butylphenol, p-tert-butylphenol, cumylphenol, tert-octylphenol, phenylphenol, naphthylphenol, 4-hydroxy-p-quarterphenyl, butylbenzoic acid, octylbenzoic acid , Phenylbenzoic acid, naphthalenecarboxylic acid, and the like. As the carbonic acid diesters, for example, carbonic acid diesters derived from monohydric phenols having 9 or more carbon atoms are preferably used. Phenyl carbonate, di (butylphenyl) carbonate DOO, phenyl cumyl phenyl carbonate, di (nonylphenyl) carbonate, and the like methylphenyl naphthyl phenyl carbonate.

  Furthermore, the aromatic polycarbonate resin of the present invention may be a polyester carbonate copolymerized with an aromatic or aliphatic bifunctional carboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include aliphatic bifunctional carboxylic acids having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. Such aliphatic difunctional carboxylic acid may be linear, branched or cyclic. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Preferred examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid.

  Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used.

  Aromatic polycarbonate resins are the above-mentioned different polycarbonate resins of various dihydric phenols, branched polycarbonate resins containing branching components, aromatic polycarbonate resins having different production methods, aromatic polycarbonate resins having different terminal terminators, various polyester carbonates, It may be a mixture of two or more of various aromatic polycarbonate resins such as a polycarbonate-polyorganosiloxane copolymer.

The molecular weight of the aromatic polycarbonate resin is preferably in the range of 10,000 to 35,000 in terms of viscosity average molecular weight converted from the solution viscosity. When the viscosity average molecular weight of the aromatic polycarbonate is less than 10,000, the impact resistance of the molded product obtained from the conductive thermoplastic resin composition according to the present invention may be insufficient. There exists a possibility that the moldability of resin composition itself may fall. Here, the viscosity average molecular weight [M] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ostwald viscometer. That is, it means a value calculated from η = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity [η] is a value obtained by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl) and calculating by the following formula (Equation 1).

  A more preferred range for the viscosity average molecular weight is 13,000 to 28,000, with 15,000 to 25,000 being particularly preferred.

  Moreover, the aromatic polycarbonate resin which is A component of this invention may contain the aromatic polycarbonate oligomer for the purpose of the improvement of a molded article external appearance, and the improvement of fluidity | liquidity. The viscosity average molecular weight of the aromatic polycarbonate oligomer is preferably 1,500 to 9,500, more preferably 2,000 to 9,000. The content of the polycarbonate oligomer is preferably used in the range of 30% by weight or less in the aromatic polycarbonate resin.

  Furthermore, as the aromatic polycarbonate resin as component A of the present invention, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins can be used. . Used products include optical recording media such as optical discs, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, eyeglass lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. In addition, as the recycled aromatic polycarbonate resin, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

(B) Thermoplastic polyester resin (component B)
The thermoplastic polyester resin which is the B component of the present invention (hereinafter sometimes abbreviated as B component) includes a dicarboxylic acid component comprising a dicarboxylic acid or a reactive derivative thereof, and a diol component comprising a diol or an ester derivative thereof. Is a polymer or copolymer obtained by a condensation reaction. The production of the thermoplastic polyester resin is carried out by reacting the dicarboxylic acid component and the diol component with heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., according to a conventional method, and by-produced water or lower alcohol. Is discharged outside the system. Either batch type or continuous type polymerization method can be used, and the degree of polymerization can be increased by solid phase polymerization.

  The dicarboxylic acids may be either aromatic dicarboxylic acids or aliphatic dicarboxylic acids, but aromatic dicarboxylic acids are preferred from the viewpoints of heat resistance and dimensional stability. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylether dicarboxylic acid 4,4′-biphenylmethanedicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid, and the like, terephthalic acid, 2,6-naphthalenedicarboxylic acid Is particularly preferred. These aromatic dicarboxylic acids may be used alone or in combination of two or more, and together with the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, etc. One or more alicyclic dicarboxylic acids or the like can be used in combination.

  Examples of diols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, triethylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aliphatic diols such as 6-hexanediol, decamethylene glycol, 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, trans- or Alicyclic diols such as cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxy Ethyl ether Aromatic diols like, and the like. These may be used alone or in combination of two or more. Further, as a diol component, a long chain diol having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like is used in combination with the above diols and copolymerized. You may let them.

  Preferred examples of these thermoplastic polyester resins include polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene naphthalate resin (PEN), polybutylene. Examples thereof include naphthalate resin (PBN) and poly (1,4-cyclohexanesimethylene terephthalate) resin (PCT). Polyethylene terephthalate resin (PET) is particularly preferable because of its excellent conductivity.

  Specific examples of other thermoplastic polyester resins include, for example, polypivalolactone resins obtained by ring-opening polymerization of lactones, poly (ε-caprolactone) resins, and the like, and liquid crystal polymers that form liquid crystals in a molten state (Thermotropic Liquid Crystal Polymer, TLCP). Examples of liquid crystal polyester resins currently in the category and currently on the market include X7G from Eastman Kotak, Xyday from Dartco, Econol from Sumitomo Chemical, Vectra from Celanese.

  Moreover, the thermoplastic polyester resin of the present invention can be branched by introducing a small amount of a branching agent. Although there is no restriction | limiting in the kind of branching agent, A trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, etc. are mentioned.

  The polyethylene terephthalate resin particularly preferably used as the component B of the present invention is a saturated polyester polymer obtained by a condensation reaction of terephthalic acid as a main component as a dicarboxylic acid component and ethylene glycol as a diol component as a main component. Or it is a copolymer, It is a thermoplastic polyester resin which contains an ethylene terephthalate unit as a repeating unit, Preferably it is 70 mol% or more, More preferably, it is 80 mol% or more. The polyethylene terephthalate resin contains diethylene glycol, which is a side reaction product during polymerization, as a copolymerization component. The amount of diethylene glycol is about 0.5 mol% or more, preferably 6 mol% or less, more preferably 5 mol% or less, in 100 mol% of the total amount of diol components.

  The intrinsic viscosity of the thermoplastic polyester resin is preferably 0.4 to 1.5 dl / g, more preferably 0.5 to 1.2 dl / g. Here, the intrinsic viscosity is measured at 30 ° C. in a solvent of phenol / tetrachloroethane = 50/50 (weight ratio). If the intrinsic viscosity is less than 0.4, the impact resistance tends to decrease, and if it exceeds 1.5, the fluidity tends to decrease. Moreover, the amount of terminal carboxyl groups of the thermoplastic polyester resin is preferably 5 to 50 eq / t, more preferably 10 to 30 eq / t. When the terminal carboxyl group amount is less than 5 eq / t, the heat resistance and impact resistance are liable to decrease, and when it exceeds 50 eq / t, the moist heat resistance and thermal stability tend to be insufficient.

  Further, as the thermoplastic polyester resin as the component B of the present invention, not only virgin raw materials but also thermoplastic polyester resins regenerated from used products, so-called material recycled thermoplastic polyester resins can be used. . Spent products include mainly containers, films, sheets, fibers, etc., but more suitable are containers such as PET bottles. In addition, as the recycled thermoplastic polyester resin, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

(C) Conductive agent (C component)
Conductive carbon black and / or hollow carbon fibrils are used as the conductive agent (hereinafter sometimes abbreviated as C component) which is the C component of the present invention.

The conductive carbon black which is component C of the present invention is generally a carbon black having a large specific surface area and a developed secondary aggregate (structure), preferably a specific surface area (BET nitrogen adsorption method) of 150 to 1000 m. ^{It is in} the range of ² / g, and more preferably in the range of 200 to 900 m ² / g. When the specific surface area exceeds 1000 m ² / g, the fluidity and appearance of the resulting resin composition tend to deteriorate. When the specific surface area is less than 150 m ² / g, the conductivity may be difficult to be exhibited. Further, dibutyl phthalate (DBP) absorption number of conductive carbon black in the range of 100~450cm ³ / 100g are preferred, those in the range of 150~400cm ³ / 100g is, conductivity and impact resistance balance More preferable in terms. In the present invention, BET equation nitrogen adsorption method specific surface area ^(unit: m 2 / g), DBP absorption ^(unit: cm 3 / 100g) are those measured according to JIS K6217.

  Examples of such preferable conductive carbon black include a furnace method conductive carbon black in which raw material hydrocarbons are thermally decomposed by the combustion heat of crude oil or gas to generate carbon black, and a ketjen obtained by a heavy oil gasification process. Examples thereof include black and acetylene black obtained by thermally decomposing acetylene gas. For example, Ketjen Black EC manufactured by Lion Corporation, Printex L6 and Printex XE2 manufactured by Degussa are commercially available.

  Further, the hollow carbon fibril which is the C component of the present invention has an outer region composed of an essentially continuous multi-layer of regularly arranged carbon atoms, and an inner hollow region. They are essentially cylindrical fibrils that are arranged substantially concentrically. Further, it is preferable that the regularly arranged carbon atoms in the outer region are graphite-like and the hollow region has a diameter in the range of 2 to 20 nm. Such a component C is described in detail in Japanese Patent Publication No. 62-5000943, US Pat. No. 4,663,230, and the like. As described in detail in the latter U.S. patent specification, the hollow carbon fibril is produced by, for example, transition metal-containing particles such as iron, cobalt, and nickel-containing particles on an alumina support, carbon monoxide, Examples include a method in which a carbon-containing gas such as hydrocarbon is contacted at a high temperature of 850 to 1200 ° C., and carbon generated by pyrolysis is grown into a fiber starting from a transition metal. The hollow carbon fibril of component C is sold by, for example, Hyperion Catharsis under the trade name of graphite fibril and can be easily obtained.

As the conductive agent as the component C of the present invention, conductive carbon black is preferable from the viewpoint of fluidity, and hollow carbon fibrils are preferable from the viewpoint of impact resistance, but a balance of physical properties such as conductivity and impact resistance. more preferred in terms of dibutyl phthalate (DBP) absorption of the is a conductive carbon black 150~400cm ³ / 100g.

(D) Phosphorus compound (component D)
Phosphorus compounds represented by the following general formula (I) and / or phosphorous acid represented by the following general formula (II) as phosphorus compounds of the D component (hereinafter sometimes abbreviated as D component) Although it is an ester, the phosphoric acid ester represented by the general formula (I) is more effective in stabilizing the conductivity during residence.

O = P (OH) _n (OR) _3-n (n is an integer of 0 to 2) (I)
In the formula, R is an alkyl group or an aryl group, and may be the same or different. Specifically, an alkyl group having about 1 to 30 carbon atoms, or phenyl group, nonylphenyl group, stearylphenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-butyl-methylphenyl Group, tolyl group and the like. Phosphoric acid where n is 3 has no conductivity stabilizing effect, and even when R does not contain an alkyl group or aryl group, there is no conductivity stabilizing effect. R is preferably an alkyl group having 2 to 25 carbon atoms, and n = 1 and / or 2.

式中、Ｒ'はアルキル基またはアリール基であり、それぞれ同一であっても異なっていても良い。上記一般式（II）を満たす亜リン酸エステルの好ましい具体例としては、ジステアリルペンタエリスリトールジホスファイト、ジノニルペンタエリスリトールジホスファイト、ビスノニルフェニルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−イソプロピルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト等が挙げられ、好ましくはジステアリルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイトであり、より好ましくはジステアリルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイトである。

In the formula, R ′ is an alkyl group or an aryl group, and may be the same or different. Preferable specific examples of the phosphite satisfying the general formula (II) include distearyl pentaerythritol diphosphite, dinonylpentaerythritol diphosphite, bisnonylphenylpentaerythritol 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, bis (2,6-di-tert-butyl-4-isopropylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, etc. Preferably Thealyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite And more preferably distearyl pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

(E) Rubber polymer (E component)
The conductive thermoplastic resin composition according to the present invention must contain the component A, component B, component C and component D, but for the purpose of improving the impact resistance of the resin composition, It is preferable to contain a rubbery polymer (hereinafter sometimes abbreviated as E component) as the E component. Here, the rubbery polymer means a rubbery polymer having a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, or a monomer copolymerizable with the rubbery polymer as necessary. A polymer obtained by copolymerizing components.

  The rubbery polymer of component E used in the present invention is not particularly limited as long as it is generally blended in a polycarbonate resin composition and can improve the mechanical properties.

  Examples of rubber-like polymers include polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, acrylic / butadiene rubbers, etc.), copolymers of ethylene and α-olefins ( Ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer, etc.), copolymer of ethylene and unsaturated carboxylic acid ester (ethylene / methacrylate copolymer, ethylene / butyl acrylate copolymer) Etc.), copolymers of ethylene and aliphatic vinyl compounds, terpolymers of ethylene, propylene and nonconjugated dienes, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl acrylate), butyl acrylate / 2-ethylhexyl acrylate Polymers), silicone Rubber (polyorganosiloxane rubber; consisting of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber IPN type composite rubber etc.) and the like.

  Preferred examples of the monomer component copolymerized with such a rubbery polymer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. . As other monomer components, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; maleic acid, maleic anhydride, Examples thereof include α, β-unsaturated carboxylic acid compounds such as phthalic acid, itaconic acid and anhydrides thereof.

  Specific examples of the rubber polymer include polybutadiene rubber, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), and styrene-ethylene / butylene-styrene block copolymer (SEBS). Styrene-ethylene / propylene-styrene block copolymer (SEPS), acrylonitrile-butadiene-styrene polymer (ABS), acrylonitrile-styrene-acrylic rubber polymer (ASA), acrylonitrile-ethylenepropylene rubber-styrene polymer (AES) And the like.

For improving the impact resistance of the conductive thermoplastic resin composition of the present invention, a core / shell type graft copolymer type is more preferable. Among these, at least one kind selected from acrylic acid ester, methacrylic acid ester, and aromatic vinyl compound around at least one rubbery polymer core layer selected from butadiene-containing rubber, butyl acrylate-containing rubber, and silicone rubber. A core / shell type graft copolymer comprising a shell layer formed by polymerizing monomers is particularly preferred. More specifically, methyl methacrylate-butadiene-styrene polymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl methacrylate-acrylic rubber polymer ( MA), methyl methacrylate-acrylic rubber-styrene polymer (MAS), methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, methyl methacrylate- (acrylic silicone IPN rubber) A polymer etc. can be mentioned.
Such rubbery polymers can be used alone or in combination of two or more.

(F) Inorganic filler (F component)
The conductive thermoplastic resin composition according to the present invention must contain the A component, the B component, the C component, and the D component, but the dimensional stability, rigidity, and heat resistance of the resin composition can be improved. For the purpose of improvement, an inorganic filler other than the C component (hereinafter sometimes abbreviated as F component) can be further contained as the F component. Typical examples include magnesium silicates such as talc, clay, mica, graphite, sericite, montmorillonite, plate calcium carbonate, plate alumina, glass flakes, wollastonite, etc., calcium moss, zonotrite, calcium titanate. , Aluminum borate, acicular calcium carbonate, acicular titanium oxide, tetrapotted zinc oxide, glass fiber, carbon fiber, and the like. Of these, talc, mica, wollastonite, and kaolin are preferable in terms of balance of physical properties such as rigidity and impact resistance, and surface appearance, and talc and wollastonite are particularly preferable.

  The inorganic filler may be left untreated, but in order to increase the affinity with the resin component or to suppress deterioration of the resin, an inorganic surface treatment agent, a derivative such as a higher fatty acid or an ester salt thereof, silane A surface treatment with a coupling agent or the like may be performed.

In the conductive thermoplastic resin composition of the present invention, the blending ratio of the A component to the D component constituting this is as follows:
(Component A) Aromatic polycarbonate 10 to 95 parts by weight (Component B) Thermoplastic polyester 5 to 90 parts by weight
(C component) Conductive agent 0.01 to 10 parts by weight (D component) Phosphorous compound 0.01 to 5 parts by weight.

  The content ratio of the A component and the B component is 10 to 95 parts by weight, preferably 51 to 80 parts by weight, and the B component is 5 to 90 parts by weight, in a total of 100 parts by weight of the A and B components. Preferably it is 20-49 weight part. If the A component is less than 10 parts by weight, the impact property and the dimensional stability are inferior, and if it exceeds 95 parts by weight, the conductivity is hardly exhibited. The content ratio of component C is 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total of component A and component B. . When the C component is less than 0.1 part by weight, the conductivity of the resin composition is insufficient, and when the C component exceeds 10 parts by weight, the fluidity, impact resistance, and appearance of the resin composition are deteriorated.

  The content ratio of component D is 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.02 to 0 parts, based on 100 parts by weight of the total of component A and component B. 8 parts by weight. Even if the D component is less than 0.01 parts by weight or more than 5 parts by weight, the stability of conductivity during residence is inferior. About D component, there exists an optimal range with respect to stabilization of the electroconductivity at the time of residence.

  In the present invention, the content in the case of using the above rubbery polymer (E component) is preferably 0.5 to 30 parts by weight, more preferably 100 parts by weight in total of the A component and the B component. 1 to 20 parts by weight. If it is less than 0.5 part by weight, the expected impact resistance improvement effect is small, and if it is 30 parts by weight or more, heat resistance and rigidity may be lowered.

  In the present invention, the content in the case of using the above-mentioned inorganic filler (F component) is preferably 0.5 to 50 parts by weight, more preferably 1 to 100 parts by weight in total of the A component and the B component. ~ 40 parts by weight. If it is less than 0.5 parts by weight, the expected effect of improving rigidity and dimensional stability is small, and if it is 50 parts by weight or more, impact resistance, appearance, etc. are lowered.

  The conductive thermoplastic resin composition according to the present invention may contain other resins as long as the effects of the present invention are not impaired. Examples of other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polystyrene, acrylonitrile-styrene copolymers, etc. And other resins such as styrene resins, polymethacrylate resins, phenol resins, and epoxy resins.

  Furthermore, the conductive thermoplastic resin composition of the present invention may contain other various resin additives in addition to the above components, as long as the effects of the present invention are not impaired. Various resin additives include flame retardants, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, plasticizers, mold release agents, lubricants, compatibilizers, foaming agents, dyes and pigments, and one or two of them. More than one seed may be added.

Although there is no restriction | limiting in particular in the preparation method of the electroconductive thermoplastic resin composition of this invention, From an industrial viewpoint, the melt-kneading method is preferable. As a typical method of melt kneading, there is a use of a melt kneader generally used for thermoplastic resins. For example, a single-screw extruder, a multi-screw extruder, a Banbury mixer, a roll, a Brabender plastogram, and the like can be mentioned. After melt-kneading with a melt-kneader, the mixture is granulated. Specifically, the A component, the B component, the C component and the D component, and if necessary, the E component and the F component are mixed in advance, and the mixture is put into a melt kneader and melt kneaded to obtain a resin composition. There is a way to get it.
Among these, from the viewpoint of the conductivity of the composition, components other than the component C are mixed in advance, and the mixture is introduced into the upstream portion of the melt kneader and melt kneaded. A method of obtaining a resin composition by adding component C and melt-kneading is more preferred.
In addition, when the F component is an inorganic filler that is easily broken by melt-kneading, a component other than the C component and the F component is added to the upstream portion at once, and the C component and the F component are added all at once or separately after the middle stream Is preferable from the viewpoint of electrical conductivity and mechanical properties.
Further, an intermediate composition obtained by melt-kneading C component with at least a part of A component in advance is blended with the remainder of A component, B component, D component and E component, F component if necessary, and melt-kneaded. Obtaining a resin composition is also a preferable method from the viewpoint of conductivity. Also in this case, when the F component is an inorganic filler that is easily broken by melt-kneading, a method of adding all components other than the F component to the upstream portion and adding the F component after the middle stream is preferable in terms of mechanical properties.

  In addition, the above A component to D component are added to a suitable solvent, for example, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and derivatives thereof, regardless of the melting / kneading method, It is also possible to prepare the conductive thermoplastic resin composition of the present invention by a solution mixing method in which dissolved components or dissolved components and insoluble components are mixed in a suspended state.

  The method for producing a molded product from the conductive thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally employed for thermoplastic resins, that is, an injection molding method, an injection compression molding method, a hollow method, and the like. A molding method, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a laminate molding method, a press molding method, and the like can be employed.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these ranges. In the following examples and comparative examples, the blending amount means parts by weight.

In obtaining each resin composition of Examples and Comparative Examples, the following raw materials were prepared.
<A component>
PC-1: Bisphenol A type aromatic polycarbonate, “Iupilon S-3000FN” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 22,500.
PC-2: Bisphenol A type aromatic polycarbonate, “Iupilon H-4000FN” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 15,500.

<B component>
PET-1: Polyethylene terephthalate resin, “Novapex GS400” manufactured by Mitsubishi Chemical Corporation, dissolved in a one-to-one (weight ratio) mixture of phenol and tetrachloroethane at a temperature of 30 ° C. Intrinsic viscosity is 0.70 dl / g.
PET-2: Polyethylene terephthalate resin, “Dianite PA500D25” manufactured by Mitsubishi Rayon Co., Ltd., dissolved in a one-to-one (weight ratio) mixture of phenol and tetrachloroethane at a temperature of 30 ° C. and measured at a concentration of 1% by weight Inherent viscosity of 0.76 dl / g.
PET-3: Polyethylene terephthalate resin, “Dianite PA200D25” manufactured by Mitsubishi Rayon Co., Ltd., dissolved in a one-to-one (weight ratio) mixture of phenol and tetrachloroethane at a temperature of 30 ° C. and measured at a concentration of 1% by weight Inherent viscosity of 1.09 dl / g.
PBT-1: Polybutylene terephthalate resin, “Novaduran 5008” manufactured by Mitsubishi Engineering Plastics Co., Ltd., dissolved in a one-to-one (weight ratio) mixture of phenol and tetrachloroethane at a temperature of 30 ° C. to a concentration of 1% by weight. The intrinsic viscosity measured in this way was 0.85 dl / g.

<C component>
C-1: conductive carbon black, Lion Corporation, Ltd., "Ketchen Black EC", BET equation nitrogen adsorption method specific surface area of 800 m ² / g, a dibutylphthalate (DBP) absorption of 360 cm ^3/100 g.
PC / C-2: Hollow carbon fibrils, “PC / 15BN” manufactured by Hyperion Catalysis, Inc., 85% polycarbonate, 15 nm outer diameter, 5 nm inner diameter, 100 to 10,000 nm long hollow carbon fibrils (graphite fibril BN) 15 And a masterbatch with
<Other than C component>
Conductive agent for comparative example:
C-3: Carbon fiber, “Pyrofil chopped FTR06U” manufactured by Mitsubishi Rayon Co., Ltd.

<D component>
D-1: Chemical formula: O = P (OH) _{n ′} (OC ₁₈ H ₃₇ ) _{3-n ′} (mixture of n ′ = 1 and 2), “ADK STAB AX-71” manufactured by Asahi Denka Kogyo Co., Ltd.
D-2: Distearyl pentaerythritol diphosphite, “ADK STAB PEP-8” manufactured by Asahi Denka Kogyo Co., Ltd.
<Other than D component>
Phosphorus compound for comparative example:
D-3: Phosphorous acid, manufactured by Wako Pure Chemical Industries, Ltd. D-4: Sodium dihydrogen phosphate, manufactured by Wako Pure Chemical Industries, Ltd.

<E component>
Rubber polymer: Core / shell type graft copolymer consisting of polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell), “Paralloid EXL2603” manufactured by Rohm and Haas Japan Co., Ltd.
<F component>
F-1: Compression talc, “UPN HST0.5” manufactured by Hayashi Kasei Co., Ltd.
F-2: Wollastonite “PH330” manufactured by Kawatetsu Mining Co., Ltd.

[Preparation of composition]
(1) Examples 1-5, Examples 7-12, and Comparative Examples 1-7
When adding the A component, the B component, the D component, and the E component and the F component, the E component and the F component are uniformly mixed with a tumbler mixer in the ratios shown in Tables 1 and 2, and then a twin screw extruder ( Using Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12), the cylinder temperature is 260 ° C. and the screw rotation speed is 200 rpm. Were fed to the extruder at the ratios shown in Tables 1 and 2 and melt kneaded to prepare resin composition pellets.
(2) Example 6
After the A component, B component, C component, and D component were uniformly mixed with a tumbler mixer in the ratios shown in Table 1, a twin-screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12) ) Was fed from the barrel 1 to the extruder at a cylinder temperature of 260 ° C. and a screw rotation speed of 200 rpm, and melt-kneaded to prepare resin composition pellets.
(3) Examples 13 and 14
A component, B component, D component and E component were uniformly mixed with a tumbler mixer in the proportions shown in Table 2, and then a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12). ) Is fed to the extruder from the barrel 1 at a cylinder temperature of 260 ° C. and a screw speed of 200 rpm, melted and kneaded, and further fed from the barrel 7 to the extruder at a ratio shown in Table 2 at the ratio shown in Table 2. Then, the mixture was melt-kneaded to produce resin composition pellets.

[Preparation of test piece]
The pellets obtained by the above method are dried at 120 ° C. for 4 hours or more and then injection molded using an injection molding machine (Toshiba IS150) under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. A piece and a 100 mmφ disk-shaped molded product (thickness 3 mm) were prepared. In normal molding, molding was performed in 1 minute per cycle (ordinary molded product), and in retention molding, molding was performed in 5 minutes per cycle, and evaluation was performed on molded products after 5 shots (residual molded product).

[Evaluation methods]
(1) Fluidity (Q value)
Using a high load flow tester, the flow rate Q value (unit: cc / s) per unit time of the composition was measured under the conditions of 280 ° C. and a load of 160 kgf / cm ² to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. The higher the Q value, the better the fluidity.
(2) Impact resistance (Izod impact strength)
In accordance with ASTM D256, Izod impact strength (unit: J / m) was measured at 23 ° C. using a notched specimen having a thickness of 3.2 mm.
(3) Dimensional stability (linear expansion coefficient)
The linear expansion coefficient (unit: K ⁻¹ ) was measured according to ASTM D696. However, the measurement temperature range was 23 to 80 ° C.
(4) Appearance The surface appearance of the disk-shaped molded product was visually observed and evaluated as “◯” when there was no aggregate, and “X” when there was an aggregate or poor visibility.
(5) Conductivity (volume resistivity)
Cut both ends of a parallel part of ASTM No. 2 dumbbell test piece (thickness: 3.2 mm) to a length of 50 mm, apply silver paste to both end faces resulting from the cutting, and dry at room temperature. Then, the resistance value (RL: unit Ω) between the both end faces was measured, and the volume resistivity R (unit: Ωcm) was calculated from the following equation.
R = RL × AL / L
(In the formula, AL means the cross-sectional area of the test piece (unit: cm ² ), and L means the length of the test piece (unit: cm).)
Moreover, about the test piece, it measured about the normal molded product and the retention molded product, the change rate was computed by following Formula, and it described in Table 1 and Table 2.
(Volume resistance change rate) = (Volume resistivity of staying molded product) / (Volume resistivity of normal molded product)

[Description of Examples and Comparative Examples]
(1) Examples 1 to 14 are within the range specified in this patent, have little decrease in conductivity due to retention, and are excellent in appearance, fluidity, and impact resistance.
(2) Since Comparative Examples 1 to 5 do not add a phosphorus compound whose use is defined as a D component in this patent, the decrease in conductivity due to residence is large.
(3) Comparative Example 6 uses carbon fiber that is outside the range specified in this patent as the C component, and is blended in a relatively large amount in order to impart conductivity close to that of the example, but compared to the example. The conductivity was inferior, the fluidity of the composition was inferior, and the appearance was poor.
(4) In Comparative Example 7, since the amount of component C exceeds the range of this patent, the electrical conductivity is good and the change during residence is relatively small, but the fluidity and impact resistance of the composition The appearance was also poor.

Claims (7)

(A) Aromatic polycarbonate resin (component A) 10 to 95 parts by weight, and (B) thermoplastic polyester resin (component B) 5 to 90 parts by weight, for a total of 100 parts by weight,
(C) 0.1 to 10 parts by weight of a conductive agent (component C) composed of conductive carbon black and / or hollow carbon fibrils, and (D) a phosphate ester represented by the following general formula (I), and the following general A conductive thermoplastic resin composition comprising 0.01 to 5 parts by weight of a phosphorus compound (component D) which is at least one selected from the group consisting of phosphites represented by the formula (II).
O = P (OH) _n (OR) _3-n (n is an integer of 0 to 2) (I)
(In the formula, R is an alkyl group or an aryl group, and each may be the same or different.)

(In the formula, R ′ represents an alkyl group or an aryl group, which may be the same or different.) C component, the specific surface area (BET equation nitrogen adsorption method) is 150~1000m ² / g, a conductive carbon black (DBP) absorption amount is in the range of 100~450cm ³ / 100g, claim 1, wherein Conductive thermoplastic resin composition.   The electroconductive thermoplastic resin composition of Claim 1 or 2 whose A component is 51-80 weight part and B component is 20-49 weight part.   The C component is 0.5 to 5 parts by weight and the D component is 0.01 to 1 part by weight with respect to a total of 100 parts by weight of the A component and the B component. The conductive thermoplastic resin composition according to Item. The conductive thermoplastic resin composition according to any one of claims 1 to 4, wherein the component D is a phosphate represented by the following general formula (III).
O = P (OH) _{n ′} (OR) _{3-n ′} (n ^′ is an integer of 1 and / or 2) (III)
(In the formula, R is an alkyl group having 2 to 25 carbon atoms, which may be the same or different.)   Furthermore, (E) Rubber-like polymer (E component) contains 0.5-30 weight part with respect to a total of 100 weight part of A component and B component, As described in any one of Claims 1-5. The electrically conductive thermoplastic resin composition as described. Furthermore, the electroconductivity as described in any one of Claims 1-6 formed by containing 0.5-50 weight part of (F) inorganic filler (F component) with respect to a total of 100 weight part of A component and B component. Thermoplastic resin composition.