JP5558661B2 - Conductive resin composition - Google Patents

Description

  The present invention relates to a novel polycarbonate resin composition. More specifically, the present invention relates to a conductive resin composition containing a polycarbonate resin and a conductive carbon compound. More specifically, the present invention relates to a resin composition excellent in conductivity that does not impair the good deformation characteristics of a polycarbonate resin.

  The polycarbonate resin is a polymer in which an aromatic or aliphatic dioxy compound is linked by a carbonic acid ester, and among them, a polycarbonate resin obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) (hereinafter “PC-”). A ”(sometimes referred to as“ A ”) is excellent in transparency and heat resistance, and has excellent mechanical properties such as impact resistance and is used in many fields.

  Polycarbonate resins are generally produced using raw materials obtained from petroleum resources. However, there is a concern about the exhaustion of petroleum resources, and there is a demand for production of polycarbonate resins using raw materials obtained from biological materials such as plants. ing.

  A typical example of a biomass material that uses biogenic materials as raw materials is polylactic acid. Among biomass plastics, it has relatively high heat resistance and mechanical properties, so its application is expanding to tableware, packaging materials, general merchandise, etc. However, the possibility as an industrial material has been studied. However, polylactic acid is insufficient in heat resistance when used as an industrial material, and when a molded product is obtained by injection molding with high productivity, the crystalline polymer has low crystallinity. There is a problem that moldability is inferior. From this point of view, considering the development of biomass materials into industrial materials, there is a demand for amorphous biomass materials such as polycarbonate resins.

  As a polycarbonate resin using a biogenic material as a raw material, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide in addition to a polylactic acid resin has been studied.

に示したエーテルジオールは、たとえば糖類およびでんぷんなどから容易に作られ、３種の立体異性体が知られているが、具体的には下記式（ｂ）

に示す、１，４：３，６ージアンヒドローＤーソルビトール（本明細書では以下「イソソルビド」と呼称する）、下記式（ｃ）

に示す、１，４：３，６ージアンヒドローＤーマンニトール（本明細書では以下「イソマンニド」と呼称する）、下記式（ｄ）

に示す、１，４：３，６ージアンヒドローＬーイジトール（本明細書では以下「イソイディッド」と呼称する）である。 For example, the following formula (a)

The ether diol shown in Fig. 2 is easily made from, for example, sugars and starch, and three stereoisomers are known. Specifically, the following formula (b)

1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”), represented by the following formula (c)

1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”), represented by the following formula (d):

1,4: 3,6-dianhydro-L-iditol (hereinafter referred to as “isoidid” in the present specification).

  Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. In particular, isosorbide homopolycarbonates are described in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2. Among these, Patent Document 1 reports a homopolycarbonate having a melting point of 203 ° C. using a melt transesterification method. In Non-Patent Document 1, a homopolycarbonate having a glass transition temperature of 166 ° C. is obtained in the melt transesterification method using zinc acetate as a catalyst, but the thermal decomposition temperature (5% weight loss temperature) is 283 ° C. Stability is not enough. In Non-Patent Document 2, homopolycarbonate is obtained by interfacial polymerization using bischloroformate of isosorbide, but the glass transition temperature is 144 ° C. and heat resistance (particularly heat resistance due to moisture absorption) is not sufficient. On the other hand, as an example of high heat resistance, Patent Document 2 reports a polycarbonate having a glass transition temperature of 170 ° C. or higher by differential calorimetry at a heating rate of 10 ° C./min. As for the polycarbonate resin, the resin composition which considered the development to an industrial material is not examined at all.

  Many proposals have already been made for thermoplastic resin compositions filled with conductive carbon compounds, and some of them have been put into practical use. Such thermoplastic resins also include polycarbonate resins. In particular, composite materials containing carbon nanotubes as conductive carbon compounds are characterized by low contamination by particles, low outgas, good surface finish and gloss, excellent fluidity, low warpage, and recycling. It is known that the resin material is excellent and that the physical properties of the resin material can be maintained (see Non-Patent Document 3).

Particularly excellent recyclability is a feature that is desired to be effectively used in reducing environmental burden and cost. However, a resin composition composed of a polycarbonate resin (hereinafter sometimes abbreviated as PC) and a carbon nanotube (hereinafter sometimes abbreviated as CNT) has a drawback that its deformation characteristics such as tensile elongation at break are inferior. Defects in deformation characteristics cause deterioration of secondary processing characteristics such as self-tapping strength characteristics and hot bending. Deterioration of deformation characteristics tends to become more prominent as the glass transition temperature of the PC is higher and as the toughness requirement for the PC is higher.
Conventionally, there are many knowledges of resin compositions composed of PC and CNT, but it is difficult to say that there is sufficient knowledge about improvement of deformation characteristics such as tensile elongation at break.

  According to Table 1 on page 185 of Non-Patent Document 3, it is known that Hyperion Corporation sells a CNT master batch (grade name: MB6015-00) using PC as a base resin. Further, it is described in the literature that Hyperion sells only a master batch and does not currently sell CNT alone.

  Further, Table 3 on page 187 of Document 3 shows various characteristics of PC containing 3% CNT. On pages 194 to 201 of the above-mentioned document 3, an introduction article of the series is described on the assumption that the HIPERSITE W1000 series manufactured by Yuka Denshi Co., Ltd. is a material in which CNT is combined with a thermoplastic resin such as PC. Has been.

  A polymer composition in which CNT is blended with PC and satisfies a specific impact strength and volume resistivity is known (see Patent Document 3). More specifically, such a composition is produced by melt-kneading a master batch in which CNT is blended with PC and PC with a twin screw extruder. According to this document, a polycarbonate resin composition containing comb fiber fibrils has better impact resistance and therefore entangled compared to bird nest fibrils (so-called BN type) fibrils (carbon nanotubes). It is known that the lower the degree, the better the mechanical properties of the composition. However, this document does not disclose useful knowledge regarding improvement of the deformation characteristics of the resin composition.

Furthermore, the following matters are known for resin compositions in which CNTs are blended with PC.
A resin composition in which BN type CNT manufactured by Hyperion Co., Ltd. is blended with PC, a molded product molded therefrom, and a molded product obtained by repeating operations of pulverizing and remolding the molded product are known (Patent Documents). 4). Similar compositions are also known in US Pat.

As for the master batch, there is a knowledge that the weight average molecular weight of the PC master batch manufactured by Hyperion is 19,500 (see Patent Document 8). A resin composition in which a PC having a viscosity average molecular weight of about 15,000 and a BN type CNT manufactured by Hyperion is blended is also known (see Patent Document 9).
Further, a resin composition composed of fine carbon fibers having a non-graphitic multilayer structure synthesized from toluene by a CVD method and PC is known (see Patent Document 10).
Although such a large number of resin compositions composed of PC and CNT have been disclosed, no method for improving the deformation characteristics of such a resin composition is described at all.

British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet Japanese Translation of National Publication No. 08-508534 JP 2001-310994 A JP 2002-175723 A JP 2002-275276 A Japanese Patent Laid-Open No. 2003-082115 Japanese Patent Laid-Open No. 2002-214928 JP 2000-044815 A WO2004 / 070095 pamphlet “Journal of Applied Polymer Science”, 2002, 86, p. 872-880. “Macromolecules”, 1996, Vol. 29, p. 8077-8082 Carbon Nanotube Synthesis / Evaluation, Practical Use, and Nano Dispersion / Formulation Control Technology Co., Ltd. Technical Information Association, issued February 26, 2003

  As described above, the technical problem of exhibiting the high conductivity of the conductive carbon compound, particularly the polycarbonate resin composition containing carbon nanotubes, and improving the deformation characteristics thereof is not yet known, and the solution method is also known. The current situation is not disclosed. Accordingly, an object of the present invention is to provide a conductive polycarbonate resin composition having high conductivity and improved deformation characteristics.

  As a result of intensive studies aimed at achieving the above object, the present inventors have found that the above-mentioned problem is a conductive polycarbonate resin composition in which a specific polycarbonate resin is blended with a conductive carbon compound and optionally a maleic anhydride copolymer. The present invention has been completed.

（上記式（５）において、「−Ｘ ^１ 」は下記式（２）で示される基である。）

（上記式（２）において、Ｒ^１は水素原子または炭素原子数１〜１０のアルキル基であり、Ｒ^２は炭素原子数４〜１０のアルキル基であり、Ｒ^３は水素原子または炭素原子数１〜１０のアルキル基である。）
２．ポリカーボネート樹脂（Ａ成分）１００重量部に対して、酸変性ポリオレフィン系ワックス（Ｄ成分）０．０１〜１重量部を含有してなる前項１記載の導電性ポリカーボネート樹脂組成物、
３．上記式（１）で表されるカーボネート構成単位は、イソソルビド（１，４：３，６ージアンヒドローＤーソルビトール）由来のカーボネート構成単位である前項１記載の導電性ポリカーボネート樹脂組成物、
４．導電性炭素化合物（Ｂ成分）は、カーボンブラックまたはカーボンナノチューブである前項１記載の導電性ポリカーボネート樹脂組成物、
５．導電性炭素化合物（Ｂ成分）は、ジブチルフタレート吸油量が１００ｍｌ／１００ｇ〜１０００ｍｌ／１００ｇであるカーボンブラックまたは直径０．７ｎｍ〜１００ｎｍであり、かつアスペクト比が５以上であるカーボンナノチューブである前項４記載の導電性ポリカーボネート樹脂組成物、
６．リン系熱安定剤（Ｃ成分）は、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る前項１記載の導電性ポリカーボネート樹脂組成物、および
７．前項１記載の導電性ポリカーボネート樹脂組成物から形成された成形品、
が提供される。 That is, according to the present invention,
1. With respect to 100 parts by weight of a polycarbonate resin (component A) containing a carbonate structural unit represented by the following formula (1), 0.1 to 15 parts by weight of a conductive carbon compound (component B), and the following formula (5) A conductive polycarbonate resin composition comprising 0.001 to 0.5 parts by weight of a phosphorus-based heat stabilizer (component C), which is a compound represented by

(In the above formula (5), “—X ¹ ” is a group represented by the following formula (2).)

(In the above formula (2), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 4 to 10 carbon atoms, and R ³ is a hydrogen atom or the number of carbon atoms. 1 to 10 alkyl groups .)
2. The conductive polycarbonate resin composition according to item 1 above, comprising 0.01 to 1 part by weight of an acid-modified polyolefin wax (D component) with respect to 100 parts by weight of the polycarbonate resin (A component);
3 . The conductive polycarbonate resin composition according to item 1, wherein the carbonate structural unit represented by the formula (1) is a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol).
4 . The conductive polycarbonate resin composition according to item 1, wherein the conductive carbon compound (component B) is carbon black or carbon nanotubes,
5 . Conductive carbon compound (B component), preceding dibutyl phthalate absorption oil amount is carbon black or diameter 0.7nm~100nm a 100ml / 100g~1000ml / 100g, and a carbon nanotube is aspect ratio of 5 or more 4 conductive polycarbonate resin composition according,
6 . The conductive polycarbonate resin composition according to item 1, wherein the phosphorus-based heat stabilizer (component C) is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite , and
7 . A molded article formed from the conductive polycarbonate resin composition according to the preceding item 1,
Is provided.

Details of the present invention will be described below.
The polycarbonate resin (component A) used in the present invention is a polycarbonate resin containing a carbonate constituent unit represented by the formula (1), and the constituent unit represented by the formula (1) is 60 mol in all carbonate constituent units. % Or more is preferable, 70 mol% or more is more preferable, 80 mol% or more is further more preferable, and 90 mol% or more is particularly preferable. Most preferably, it is a homopolycarbonate resin consisting only of the carbonate structural unit of the formula (1).

The polycarbonate resin (component A) used in the present invention is a polycarbonate resin containing a carbonate constituent unit of the above formula (1), and the lower limit of the specific viscosity at 20 ° C. of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride is 0. .20 or more, more preferably 0.22 or more, and the upper limit is preferably 0.50 or less, more preferably 0.45 or less, and still more preferably 0.37 or less. When the specific viscosity is lower than 0.20, it becomes difficult to give the molded product obtained from the polycarbonate resin composition of the present invention sufficient mechanical strength. On the other hand, if the specific viscosity is higher than 0.50, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for molding becomes higher than the decomposition temperature, which is not preferable. Further, the polycarbonate resin (component A) used in the present invention has a melt viscosity measured with a capillary rheometer at 250 ° C. in a range of 0.4 × 10 ^{3 to} 3.0 × 10 ³ Pa · s at a shear rate of 600 sec ^-1. It is preferable that it is in the range of 0.4 × 10 ^{3 to} 2.4 × 10 ³ Pa · s, and still more preferably 0.4 × 10 ^{3 to} 1.8 × 10 ³ Pa · s. It is. When the melt viscosity is within this range, the mechanical strength is excellent, and when molding using the polycarbonate resin composition of the present invention, silver is not generated during molding, which is good.

  The lower limit of the glass transition temperature (Tg) of the polycarbonate resin (component A) used in the present invention is preferably 145 ° C. or higher, more preferably 148 ° C. or higher, and the upper limit is preferably 165 ° C. or lower, more preferably 163 It is below ℃. When the Tg is less than 145 ° C., the heat resistance (particularly heat resistance due to moisture absorption) is poor, and when it exceeds 165 ° C., the melt fluidity during molding using the polycarbonate resin composition of the present invention is poor. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.

  Further, the lower limit of the 5% weight loss temperature of the polycarbonate resin (component A) used in the present invention is preferably 300 ° C. or higher, more preferably 330 ° C. or higher, further preferably 350 ° C. or higher, and the upper limit is It is preferably 400 ° C. or lower, more preferably 390 ° C. or lower, and further preferably 380 ° C. or lower. It is preferable that the 5% weight loss temperature is in the above range since there is almost no decomposition of the resin when molding using the polycarbonate resin composition of the present invention. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).

で表されるエーテルジオールおよび炭酸ジエステルとから溶融重合法により製造することができる。エーテルジオールとしては、具体的には下記式（ｂ）、（ｃ）および（ｄ）

で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。 The polycarbonate resin (component A) used in the present invention has the following formula (a):

It can manufacture with the melt polymerization method from the ether diol and carbonic acid diester represented by these. As the ether diol, specifically, the following formulas (b), (c) and (d)

And isosorbide, isomannide, and isoidide represented by the formula:

  These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.

  In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .

（式中 ｍは１〜１０の整数）
で表される脂肪族ジオールが好ましく用いられる。具体的にはエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールなどの直鎖状ジオール類や、シクロヘキサンジオール、シクロヘキサンジメタノールなどの脂環式アルキレン類などが挙げられ、中でも１，３−プロパンジオール、１，４−ブタンジオール、ヘキサンジオール、およびシクロヘキサンジメタノールが好ましい。また上記式（１）で表されるエーテルジオールおよび上記式（６）で表されるジオールに加えて他のジオール残基を含むことも好ましい。その他のジオールとしてはジメタノールベンゼン、ジエタノールベンゼンなどの芳香族ジオール、ビスフェノール類などを挙げることができる。 The polycarbonate resin (component A) used in the present invention may be copolymerized with aliphatic diols or aromatic bisphenols as long as the properties are not impaired. Such aliphatic diol includes the following formula (6):

(Where m is an integer from 1 to 10)
An aliphatic diol represented by the formula is preferably used. Specifically, linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, etc. Among these, 1,3-propanediol, 1,4-butanediol, hexanediol, and cyclohexanedimethanol are preferable. In addition to the ether diol represented by the above formula (1) and the diol represented by the above formula (6), it is also preferable to include other diol residues. Examples of other diols include aromatic diols such as dimethanolbenzene and diethanolbenzene, and bisphenols.

で表されるヒドロキシ化合物が好ましく用いられる。 In addition, the polycarbonate resin (component A) used in the present invention can introduce a terminal group as long as its properties are not impaired. Such end groups can be introduced by adding the corresponding hydroxy compound during polymerization. As a hydroxy compound, following formula (7) or (8)

A hydroxy compound represented by the formula is preferably used.

であり、好ましくは炭素原子数４〜２０のアルキル基、炭素原子数４〜２０のパーフルオロアルキル基、または上記式（９）であり、特に炭素原子数８〜２０のアルキル基、または上記式（９）が好ましい。Ｙは単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも一種の結合が好ましいが、より好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合であり、なかでも単結合、エステル結合が好ましい。ａは１〜５の整数であり、好ましくは１〜３の整数であり、特に１が好ましい。 In the above formulas (7) and (8), R ⁴ represents an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( 9)

Preferably, it is an alkyl group having 4 to 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the above formula (9), particularly an alkyl group having 8 to 20 carbon atoms, or the above formula. (9) is preferred. Y is preferably at least one bond selected from the group consisting of a single bond, ether bond, thioether bond, ester bond, amino bond and amide bond, more preferably selected from the group consisting of a single bond, ether bond and ester bond. It is at least one kind of bond, and among them, a single bond and an ester bond are preferable. a is an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is particularly preferable.

In the above formula (9), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, It is at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably each independently a carbon atom. And at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, and particularly at least one group selected from the group consisting of a methyl group and a phenyl group, respectively. Is preferred. b is an integer of 0 to 3, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is particularly preferable. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50.

  Since the polycarbonate resin (component A) used in the present invention has a carbonate structural unit in the main chain structure using raw materials obtained from renewable resources such as plants, these hydroxy compounds are also derived from renewable resources such as plants. The obtained raw material is preferable. Examples of hydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.

  The polycarbonate resin (component A) used in the present invention is a mixture of a bishydroxy compound containing an ether diol represented by the formula (a) and a carbonic acid diester, and the alcohol or phenol produced by the transesterification reaction is decompressed at high temperature. It can be obtained by carrying out a melt polymerization which is distilled under.

  The reaction temperature is preferably as low as possible in order to suppress decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 270 ° C.

In the initial stage of the reaction, ether diol and carbonic acid diester are heated at normal pressure and pre-reacted, and then gradually reduced in pressure, and the system is changed to 1.3 × 10 ^{−3 to} 1.3 × 10 ^{− in the} late stage of the reaction. A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about ⁵ MPa is preferred. The reaction time is usually about 1 to 4 hours.

  A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, alkali metal compounds such as sodium salt or potassium salt of dihydric phenol, calcium hydroxide, barium hydroxide, magnesium hydroxide. And alkaline earth metal compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, nitrogen-containing basic compounds such as trimethylamine and triethylamine. These may be used alone or in combination of two or more. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination.

The amount of these polymerization catalysts used is preferably in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁴ equivalents, relative to 1 mol of the carbonic acid diester component. Chosen by The reaction system is preferably maintained in an atmosphere of a gas inert to raw materials such as nitrogen, reaction mixture, and reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, you may add additives, such as antioxidant, as needed.

  Examples of the carbonic acid diester used for the production of the polycarbonate resin (component A) used in the present invention include esters such as optionally substituted aryl groups having 6 to 20 carbon atoms, aralkyl groups, or alkyl groups having 1 to 18 carbon atoms. It is done. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (p-butylphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. preferable.

  The carbonic acid diester is preferably used in a molar ratio of 1.05 to 0.97, more preferably in a ratio of 1.03 to 0.97, and more preferably 1.03 to 0.007. More preferably, the ratio is 99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid ester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. Even when the molar ratio of carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.

  A catalyst deactivator can also be added to the polycarbonate resin (component A) obtained by the above production method. As the catalyst deactivator, known catalyst deactivators are effectively used. Among them, ammonium salts and phosphonium salts of sulfonic acid are preferable, and further, dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is preferable. The salts of paratoluenesulfonic acid such as the above-mentioned salts and paratoluenesulfonic acid tetrabutylammonium salt are preferred. As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, para Octyl toluenesulfonate, phenyl p-toluenesulfonate and the like are preferably used, and among them, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used. These catalyst deactivators are used in an amount of 0.5 to 50 mol, preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. It can be used in a proportion, more preferably in a proportion of 0.8 to 5 mol.

Conductive carbon compound used in the present invention (B component), carbon black or carbon nanotubes is preferably, (sometimes hereinafter abbreviated as DBP oil absorption.) Dibutyl phthalate absorption oil amount is 100ml / 100g~1000ml / 100g Carbon black or a carbon nanotube having a diameter of 0.7 nm to 100 nm and an aspect ratio of 5 or more is more preferable.
The carbon nanotube used as the B component in the present invention is a fibrous substance having a structure in which cylindrical graphene sheets are laminated in the radial direction with respect to the axial direction.

  The method for producing the carbon nanotube of the present invention is not particularly limited. A known method can be used as a method for producing carbon nanotubes represented by arc discharge method, laser evaporation method, chemical vapor deposition method (CVD method), catalytic chemical vapor deposition method (CCVD method) and the like.

  As the arc discharge method in the carbon nanotube production method of the present invention, arc discharge is performed between an anode made of a carbon electrode arranged in a container and a cathode made of a carbon electrode arranged to face the anode, and the inner wall of the container and the electrode A method for recovering the deposit generated in the above is suitably exemplified.

  As a laser evaporation method in the method for producing a carbon nanotube of the present invention, a method for producing a mixture of carbon and one or more kinds of transition metal of group VIII of the periodic table by vaporizing with a laser pulse and aggregating the mixed gas in the apparatus Is preferably exemplified. As such a group VIII transition metal, for example, iron, nickel, and cobalt are preferably exemplified.

  As a chemical vapor deposition method (CVD method) of the carbon nanotube of the present invention, a compound containing a group VI element of the periodic table using at least one transition metal or a compound thereof as a catalyst, and an organic compound serving as a carbon source Alternatively, a method in which an organic compound having a group VI element in the periodic table is introduced into a reaction furnace together with a carrier gas composed of hydrogen, methane, or an inert gas, and synthesized by chemical vapor deposition is preferably exemplified. The Such a CVD method may be a catalytic chemical vapor deposition method (CCVD method) in which a transition metal catalyst is supported on a support. Among these, a CVD method and a CCVD method that can be mass-produced at low cost are preferable.

  When the carbon nanotubes of the present invention are produced using the CVD method and the CCVD method, a method of synthesizing carbon nanotubes that directly becomes the amount of ashing residue and a method of cleaning catalyst residues in the carbon nanotubes are roughly used. Is done. The catalyst residue is a source of ash residue. Of course, the amount of ashing residue may be further reduced by washing the carbon nanotubes obtained by the former method and having a small amount of ashing residue.

  In the former synthesis method, the carbon nanotube of the present invention can be obtained by controlling the amount of catalyst during synthesis. That is, the catalyst amount for the hydrocarbon to be introduced is controlled. A CCVD method capable of synthesizing carbon nanotubes with a smaller amount of catalyst is advantageous. However, in this method, it is still difficult to make the catalyst and its support act stably in practical use. In the CVD method, the amount of hydrocarbons supplied to the reaction furnace and the amount of catalyst are adjusted so that the ashing residue is 3% by weight or less. On the other hand, in the cleaning method, the catalyst residue in the carbon nanotube is cleaned using an acidic compound, an alkaline compound, a supercritical fluid, or the like. Such washing may be performed after the synthesis of the carbon nanotubes or at the stage of the raw product before the high temperature heat treatment. It is relatively difficult to reduce the amount of ash residue by the cleaning method, which leads to an increase in the cost of carbon nanotubes. Therefore, a preferred method is a method of directly synthesizing carbon nanotubes that will be the amount of such ashing residue.

  Hereinafter, the CVD method and the CCVD method, which are preferable methods for synthesizing the carbon nanotubes of the present invention, will be described.

(Carbon nanotube synthesis raw material)
As a synthetic raw material for carbon nanotubes, hydrocarbons, compounds containing Group VIB elements of the periodic table, mixtures thereof, and the like can be used. The hydrocarbon is preferably an aromatic hydrocarbon. Aromatic hydrocarbons include halogenated alkyl group-substituted benzenes such as benzene, toluene and xylene, chlorobenzene, dichlorobenzene (o-, m- and p-dichlorobenzene), trichlorobenzene, bromobenzene and dibromobenzene. Examples include benzene, naphthalene, and alkyl group-substituted naphthalene compounds such as methylnaphthalene and dimethylnaphthalene.

  As a compound containing the said VIB group element of a periodic table, the thing containing oxygen or sulfur is preferable, and the organic compound containing oxygen is especially preferable. As the oxygen-containing compound, carbon monoxide, carbon dioxide, alcohols, ketones, phenols, ethers, aldehydes, organic acids, and esters are preferable. Specifically, methanol, ethanol, propanol, cyclohexanol, acetone, methyl ethyl ketone, acetophenone, cyclohexanone, phenol, cresol, formaldehyde, acetaldehyde, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, adipic acid, dimethyl ether, diethyl ether , Dioxane, methyl acetate, ethyl acetate, and derivatives thereof. Examples of the compound containing sulfur include hydrogen sulfide, carbon disulfide, sulfur dioxide, sulfur, thiol, thioether, thiophenes, and derivatives thereof. These oxygen-containing compounds or sulfur-containing compounds may be used alone or in combination of two or more.

(Carbon nanotube synthesis catalyst)
As a catalyst for the synthesis of the carbon nanotube, ultrafine particles made of a transition metal are used. Examples of the transition metal include iron, cobalt, nickel, yttrium, titanium, vanadium, manganese, chromium, copper, niobium, molybdenum, palladium, tungsten, and platinum. Among these, at least one element selected from iron, nickel, and molybdenum is preferable. These metals may be used alone or as a compound containing these metals. As the metal compound, an organic compound, an inorganic compound, or a combination thereof is preferable. Examples of the organic compound include ferrocene, nickel sen, cobalt cene, iron carbonyl, and acetonate iron. In addition, the inorganic compound may be in any form such as oxide, nitrate, sulfate, and chloride. Two or more metals may be used in combination. Depending on the combination, a larger catalytic effect can be obtained. In particular, an organometallic compound is preferably used in a CVD method because it is easy to gasify the compound and supply a catalyst into the reaction furnace.

The fine particles of the metal or metal compound may be used as they are, but these fine particles may be supported on an inorganic carrier. As the inorganic carrier, alumina, zeolite, carbon, magnesia, calcia, aluminophosphate and the like are preferable. In particular, zeolite with high heat resistance is preferable. The pores are preferably uniform for supporting the inorganic carrier, and the pore diameter is preferably around 1 nm.
As a method of introducing the catalyst, any method such as a method of gasifying alone, a method of gasifying after mixing with a carbon raw material, a method of diluting with a carrier gas, or a method of dissolving in a carbon raw material and charging in liquid But you can.

(Reaction conditions for carbon nanotube synthesis)
When synthesizing the carbon nanotube of the present invention, more preferable reaction conditions are as follows. (A) Regarding the residence time in the furnace, the residence time of carbon calculated from the mass balance is preferably 2 to 10 seconds, more preferably 5 to 10 seconds. (B) The furnace temperature is preferably 1,000 to 1,350 ° C, more preferably 1,100 to 1250 ° C. (C) The catalyst and the raw material carbon compound are charged into the furnace preferably in a gaseous state by preheating in the range of 300 to 450 ° C., more preferably 330 to 400 ° C. (D) The carbon concentration in the furnace gas is preferably controlled in the range of 1 to 20% by volume, more preferably 3 to 10% by volume, and still more preferably 5 to 9% by volume. (E) The pressure in the furnace is preferably about 98 kPa as the lower limit and the upper limit as 200 kPa. (F) In the total of the weight of carbon in the synthetic raw material and the weight of the transition metal in the synthetic catalyst, the weight of the transition metal is 3% by weight or less, preferably 0.1 to 3% by weight, more preferably Is 0.1 to 0.8% by weight, more preferably 0.2 to 0.7% by weight. The lower limit of the pressure in the furnace is basically 98 kPa, which means that there is no particular problem if the atmosphere is in atmospheric pressure.

  Further, the carbon nanotubes obtained under the above conditions are subjected to high-temperature heat treatment to separate adsorbed hydrocarbons, and further heat-treated at a higher temperature to promote crystal development. It is preferable to obtain a final carbon nanotube by such a high temperature treatment.

  (G) The raw carbon nanotubes obtained under the conditions (a) to (f) are preferably heat-treated in the range of 1,100 to 1,500 ° C., more preferably 1,300 to 1,450 ° C. And the hydrocarbons are separated. (H) As the next step, high-temperature heat treatment is promoted in the range of 2,000 to 3,000 ° C., preferably 2,500 to 3,000 ° C., to promote crystal development. By satisfying the above conditions (a) to (h), the carbon nanotube of the present invention can be stably produced at a relatively low cost.

(Structural characteristics of carbon nanotubes)
The carbon nanotubes of the present invention may have one, two, or more than two layers of graphene sheets. In particular, a plurality of layers exceeding two layers are preferred. The fiber diameter of the carbon nanotube of the present invention is preferably 0.7 to 100 nm, more preferably 7 to 100 nm, and still more preferably 15 to 90 nm. The aspect ratio of the carbon nanotube of the present invention is preferably 5 or more, more preferably 100 or more. The aspect ratio can be determined from the ratio of length and diameter measured at a scanning electron microscope magnification of 3 to 100,000. The length is measured by the following method. First, the observation image is taken into the CCD camera as image data. Next, the fiber length of the obtained image data is calculated using an image analyzer. The number of measurement is 5000 or more. The diameter is measured by the following method. First, carbon nanotubes whose diameter is to be measured are randomly extracted from an image obtained by observation with an electron microscope, and the diameter is measured near the center. If the cross section is not a circle, the maximum value is the diameter. The number average diameter is calculated from the measured values obtained. Since recent electron microscopes have a function of calculating the length on the observation screen, the diameter can be calculated relatively easily. The number of measurement is 1,000 or more.

  The distance (interlayer distance) between the graphene sheets in the carbon nanotubes of the present invention may be in the range of 3.354 to 3.44 nm, or may be in the range exceeding 3.44 nm. The upper limit of the interlayer distance is preferably 3.65 nm, more preferably 3.6 nm. Such interlayer distance is preferably more than 3.44 nm. Therefore, the carbon nanotube of the present invention may have a so-called graphitization index having a positive value and a substantially graphite structure, or a graphitization index having a negative value and a non-graphitic multilayer structure. Good. More preferred is a non-graphitic multilayer structure having a negative graphitization index.

The carbon nanotube of the present invention may be one in which each layer of the graphene sheet has a substantially concentric structure with respect to the cylinder axis, or the interval between the sheets may vary over the entire fiber. More preferably in the present invention, the latter sheet spacing varies across the fiber. Further, a structure in which the stack of graphene sheets is inclined at a certain angle with respect to the fiber axis may be employed. In such a case, the inclination angle is preferably in the range of 25 to 35 degrees with respect to the center line.
The carbon nanotubes of the present invention are preferably those in which the chirality of each layer is randomly combined, and a carbon ring structure that is not a six-membered ring may exist in the graphene sheet.

  Examples of the carbon black used as the component B in the present invention include conventionally known ketjen black, acetylene black, furnace black, lamp black, thermal black, channel black, roll black, disk black and the like. Among these carbon blacks, ketjen black, acetylene black, and furnace black are particularly preferable.

  The carbon black of the present invention preferably has a dibutyl phthalate oil absorption of 100 ml / 100 g to 1000 ml / 100 g, more preferably 350 ml / 100 g to 600 ml / 100 g, and there are no particular restrictions on the raw materials and production method. The dibutyl phthalate oil absorption here is a value measured according to the method defined in ASTM D2414-79, and the higher this oil absorption, the higher the electrical conductivity. Conductive carbon black having a dibutyl phthalate oil absorption of less than 100 ml / 100 g is preferable because a large amount of blending is required to obtain sufficient electrical conductivity, and as a result, molding processability and mechanical strength of the molded resin are impaired. Absent.

  The content of the conductive carbon compound (component B) is 0.1 to 15 parts by weight, preferably 1 to 12 parts by weight, and more preferably 2 to 10 parts by weight when the component A is 100 parts by weight. If it is less than 0.1 part by weight, the electrical conductivity is inferior, and if it exceeds 15 parts by weight, the moldability and the mechanical strength of the resin composition are impaired, which is not preferable.

Phosphorus-based heat stabilizer used in the present invention component (C) is a phosphorus-based heat stabilizer containing a structure represented by the following formula (2).

In the above formula (2), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom, a methyl group, or an isopropyl group. , An isobutyl group, a tert-butyl group, or a tert-pentyl group is preferable.

R ² is an alkyl group having 4 to 10 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms, and particularly preferably an isobutyl group, a tert-butyl group, a tert-pentyl group, or a cyclohexyl group.

R ³ is water atom or an alkyl group having 1 to 10 carbon atoms.

When the structure represented by the above formula (2) represents the "-X ^1" group, phosphorus-based heat stabilizer used in the present invention is a compound represented by the following formula (5).

  Preferred examples of the above formula (5) include bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (2-tert-pentylphenyl) pentaerythritol diphosphite, bis (2-cyclohexylphenyl) 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, bis (nonylphenyl) pentaerythritol diphosphite, especially bis (2,6-di-tert-butyl-4-methylphenyl) ) Pentaerythritol di Sufaito is preferable.

The compound of component C may be one type or a mixture of two or more types.
The amount of the phosphorus stabilizer (component C) used in the present invention is 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.5 parts by weight, with respect to 100 parts by weight of the polycarbonate resin. 005 to 0.3 parts by weight is more preferable, and 0.01 to 0.3 parts by weight is most preferable. When the phosphorus stabilizer is within this range, it is possible to suppress a decrease in molecular weight or a deterioration in hue when the polycarbonate resin composition of the present invention is molded.

  A hindered phenol heat stabilizer may be further added to the polycarbonate resin composition of the present invention. Examples of the hindered phenol heat stabilizer include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4. -Hydroxyalkyl ester (alkyl has 7 to 9 carbon atoms and has a side chain), ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9- Bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Lopionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2′-methylenebis (6-tert-butyl-4-methylphenol, 2,2 '-Isopropylidenebis (6-tert-butyl-4-methylphenol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- tert-pentyl-6- (3-tert-pentyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl methacrylate, 2-tert-pentyl-6- (3-tert-pentyl) 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-butylphenyl Acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-Di-tert-butylphenyl) ethyl] -4,6-di-tert-butylphenyl methacrylate and 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4 , 6-di-tert-pentylphenyl methacrylate and the like.

  The blending amount of the hindered phenol heat stabilizer is preferably 0.0005 to 0.1 parts by weight, more preferably 0.001 to 0.1 parts by weight, and more preferably 0.005 to 0.005 parts by weight with respect to 100 parts by weight of the polycarbonate resin. 1 part by weight is more preferable, and 0.01 to 0.1 part by weight is particularly preferable.

  It is preferable to add an acid-modified polyolefin wax (D component) to the polycarbonate resin composition of the present invention in order to obtain a molded article having good electrical conductivity while maintaining high melt heat stability. This acid-modified polyolefin wax is an acid-modified polyolefin wax having an acidic group represented by a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group.

  A preferred embodiment as the acid-modified polyolefin wax is an acid-modified polyolefin wax having at least one acidic group exemplified above, and particularly preferably an acid having a carboxyl group and / or a carboxylic anhydride group. It is a modified polyolefin wax. In the acid-modified polyolefin wax, the concentration of the acidic group is preferably in the range of 0.05 to 10 meq / g, more preferably in the range of 0.1 to 6 meq / g, and still more preferably in the range of 0.5 to 4 meq / g. It is.

  Examples of olefin waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and α-olefin polymer as paraffin waxes.

  Examples of a method for binding carboxyl groups to such acid-modified polyolefin wax include, for example, (a) a method of copolymerizing a monomer having a carboxyl group and an α-olefin monomer, and (b) the above lubricant. On the other hand, a method of bonding or copolymerizing a compound or monomer having a carboxyl group can be exemplified.

  In the method (a), a living polymerization method can be employed in addition to radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible. The form of the copolymer can be used as a copolymer of various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer in addition to the random copolymer. In the method (b), a radical generator such as peroxide or 2,3-dimethyl-2,3-diphenylbutane (commonly called “dicumyl”) is added to the acid-modified polyolefin wax as necessary, at a high temperature. It is possible to employ a method of reacting or copolymerizing with the above. Such a method is to thermally generate a reactive site in the acid-modified polyolefin wax and to react a compound or monomer that reacts with the active site. Other methods for generating active sites required for the reaction include methods such as irradiation with radiation and electron beams and application of external force by mechanochemical techniques. Furthermore, there may be mentioned a method in which a monomer that generates an active site required for the reaction is copolymerized in advance in the acid-modified polyolefin wax. Examples of active sites for the reaction include unsaturated bonds and peroxide bonds, and a method for obtaining active sites includes nitroxide-mediated radical polymerization represented by TEMPO.

  Examples of the compound or monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.

More preferred as the acid-modified polyolefin wax is that the carboxyl groups are preferably in the range of 0.05 to 10 meq / g, more preferably in the range of 0.1 to 6 meq / g, per gram of the carboxyl group-containing lubricant. More preferably, it is a carboxyl group-containing olefin wax contained in the range of 0.5 to 4 meq / g. Further molecular weight of the olefin wax is preferably ^{1 × 10 3 ~1 × 10 4} , more preferably ^{5 × 10 3 ~1 × 10 4} . This molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (gel permeation chromatography).

  As a more preferred embodiment of the acid-modified polyolefin wax, there can be mentioned a copolymer of an α-olefin and maleic anhydride, and the copolymer further satisfies the above carboxyl group content ratio and molecular weight. Those are particularly preferred. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

  The content of the acid-modified polyolefin wax is 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 part based on 100 parts by weight of the polycarbonate resin (component A). Parts by weight. If the content of the acid-modified polyolefin wax is within this range, it is possible to obtain a molded article having good electrical conductivity while maintaining high melting heat stability.

  In the resin composition of the present invention, other polymers and elastomers can be further blended within a range in which the effects of the present invention are exhibited. As a guideline of such a range, the total amount of other polymers and elastomers based on 100 parts by weight of the component A is 200 parts by weight or less, preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight. It is as follows.

  Such other polymers include polyphenylene ether, polyacetal, aromatic polyester, aliphatic polyester, polyamide, polyarylate (amorphous polyarylate, liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyether Examples include sulfone, polyphenylene sulfide, polyolefins such as polyethylene, polypropylene, poly-4-methylpentene-1, and cyclic polyolefin, acrylic polymers such as styrene polymers, polymethyl methacrylate, and the like.

  Examples of the elastomer include thermoplastic elastomers such as olefin elastomers, acrylic elastomers, polyester elastomers, polyamide elastomers, and polyurethane elastomers. Further, a rubbery graft copolymer in which a graft chain is bonded to a rubber substrate is also preferably exemplified as an elastomer. The rubber substrate is a polymer that has rubber elasticity and has a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower, which becomes a graft trunk of the graft polymer. Examples of the rubber substrate include polybutadiene, polyisoprene, styrene-butadiene random copolymer or block copolymer, acrylonitrile-butadiene copolymer, alkyl acrylate ester or copolymer of methacrylic acid alkyl ester and butadiene. Copolymer of ethylene and α-olefin, copolymer of ethylene and unsaturated carboxylic acid ester, copolymer of ethylene and aliphatic vinyl, ethylene, propylene and non-conjugated diene terpolymer, acrylic rubber, Examples thereof include silicone rubber. Preferred examples of the monomer for deriving the graft chain of the rubbery graft copolymer include aromatic vinyl compounds, vinyl cyanide compounds, acrylic acid esters, and methacrylic acid esters. Specific examples of the rubbery graft copolymer include SB (styrene-butadiene) polymer, ABS (acrylonitrile-butadiene-styrene) polymer, MBS (methyl methacrylate-butadiene-styrene) polymer, MABS (methyl methacrylate-acrylonitrile). -Butadiene-styrene) polymer, MB (methyl methacrylate-butadiene) polymer, ASA (acrylonitrile-styrene-acrylic rubber) polymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) polymer, MA (methyl methacrylate-acrylic rubber) ) Polymer, MAS (methyl methacrylate-acrylic rubber-styrene) polymer, methyl methacrylate-acrylic / butadiene rubber copolymer, methyl methacrylate-acrylic / butadiene rubber-steel Emissions copolymers, and methyl methacrylate - and the like (acrylic silicone IPN rubber) polymer. The rubber substrate is more than 40% by weight in 100% by weight of the rubbery graft copolymer, preferably 50% by weight or more, and more preferably in the range of 55 to 85% by weight.

  Examples of the styrenic polymer include polystyrene (PS) (including syndiotactic polystyrene), AS (acrylonitrile-styrene) copolymer, MS (methyl methacrylate-styrene) copolymer, and SMA (styrene-maleic anhydride). ) Copolymers and the like are exemplified. As the styrenic polymer, a mixture previously integrated with the rubber-like graft copolymer can be used. For example, a commercially available ABS resin can be used as a mixture of a commercially available AS copolymer and ABS copolymer. Such a copolymer includes a so-called transparent ABS resin. The styrenic polymer may be modified with various functional groups typified by epoxy groups and acid anhydride groups. These styrenic polymers can be used in combination of two or more.

  As aromatic polyesters, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene-2,6-naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1, In addition to 2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene terephthalate copolymerized with 1,4-cyclohexanedimethanol (so-called PET-G), polyethylene isophthalate / terephthalate, polybutylene terephthalate / Copolyesters such as isophthalate can also be used. Of these, PET, PBT, PEN and PBN are preferred. Two or more of the above aromatic polyesters can be mixed. These aromatic polyesters are copolymerized polyesters obtained by copolymerizing units derived from other aromatic dicarboxylic acids or units derived from other glycols in an amount of 50 mol% or less, preferably 1 to 30 mol%. May be. Although there is no restriction | limiting in particular about the molecular weight of aromatic polyester, The intrinsic viscosity measured at 35 degreeC by using o-chlorophenol as a solvent is 0.4-1.2, Preferably it is 0.5-1.15.

Various well-known fillers can be mix | blended with the resin composition of this invention as a reinforcement filler. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including a rod shape, a needle shape, or a shape whose axis extends in a plurality of directions), and the plate-like filler has a plate shape (surface) (Including those having irregularities and those having a curved plate). The granular filler is a filler having a shape other than these including an indefinite shape.
The fiber-like and plate-like shapes are often clear from the observation of the shape of the filler. For example, a difference from a so-called indeterminate shape can be said to be a fiber-like or plate-like one having an aspect ratio of 3 or more.

  As plate-like fillers, glass-flake, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and these fillers are coated with different materials such as metals and metal oxides. A material etc. are illustrated preferably. The particle size is preferably in the range of 0.1 to 300 μm. The particle size is about 10 μm in terms of 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 of 10-50 μm, laser diffraction -The value by the median diameter (D50) of the particle size distribution measured by the scattering method is referred to, and in the region of 50 to 300 μm, the value is by the vibration sieving method. Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane, titanate, aluminate, and zirconate, and olefin resin, styrene resin, acrylic resin, polyester resin. It may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins and urethane resins, higher fatty acid esters, and the like.

The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is preferably 13 μm, more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm.
The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is determined by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ashing residue collected after ashing with a crucible. It is a value calculated from an image observed with an electron microscope.

  Examples of the fibrous filler include glass fiber, glass milled fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker, and aluminum borate whisker. Fibers such as calcium carbonate whisker, titanium oxide whisker, wollastonite, zonotlite, palygorskite (attapulgite), and sepiolite, and other fibers such as heat-resistant organic fibers such as aramid fibers, polyimide fibers, and polybenzthiazole fibers Examples thereof include fibrous heat-resistant organic fillers, and fibrous fillers whose surfaces are coated with different materials such as metals and metal oxides. Examples of the filler whose surface is coated with a different material include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The surface coating method of different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition methods, ion plating methods, CVD methods ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned.

Here, the fibrous filler means a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is a value in the resin composition. The fibrous filler may be surface-treated with various coupling agents in the same manner as the plate-like filler, may be converged with various resins, and may be granulated by compression.
The content of the filler is 200 parts by weight or less, preferably 100 parts by weight or less, more preferably 50 parts by weight or less, particularly preferably 30 parts by weight or less based on 100 parts by weight of the component A.

  A release agent can be blended in the resin composition of the present invention as necessary. The resin composition of the present invention often requires high dimensional accuracy. Therefore, the resin composition is preferably excellent in releasability. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, and beeswax. Such a release agent is preferably 0.005 to 2% by weight in 100% by weight of the resin composition.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). In the fatty acid ester, the acid value is preferably 20 or less (can take substantially 0), the hydroxyl value is in the range of 0.1 to 30, and the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  Since the resin composition of the present invention may be used in a high heat atmosphere, the hydrolysis resistance of the resin composition of the present invention may be required. In such a case, a compound conventionally known as a hydrolysis improver for polycarbonate resin can be blended within a range not impairing the object of the present invention. Examples of such compounds include epoxy compounds, oxetane compounds, silane compounds, and phosphonic acid compounds, with epoxy compounds and oxetane compounds being particularly preferred. Examples of the epoxy compound include an alicyclic epoxy compound represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, and a silicon atom-containing epoxy represented by 3-glycidylpropoxy-triethoxysilane. The compound is preferably exemplified. Such a hydrolysis improver is preferably 1% by weight or less in 100% by weight of the resin composition.

  When the resin composition of the present invention is required to have improved weather resistance or ultraviolet absorption, it is preferable to incorporate an ultraviolet absorber. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers. More specifically, for example, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl) Butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6-tert-butylphenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,2′-p-phenylenebis (3,1-benzoxazine-4 ON), 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane and the like Is exemplified. Further, hindered amine light stabilizers typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like Can also be used. The content of the ultraviolet absorber and light stabilizer is preferably 0.01 to 5% by weight in 100% by weight of the resin composition.

  An antistatic agent can be used in combination with the resin composition of the present invention. Examples of such antistatic agents include polyether ester amide, glycerin monostearate, naphthalene sulfonate formaldehyde highly condensed alkali (earth) metal salt, alkali dodecyl benzene sulfonate metal (earth) metal salt, ammonium dodecyl benzene sulfonate. Examples thereof include salts, phosphonium salts of dodecylbenzenesulfonic acid, maleic anhydride monoglyceride, and maleic anhydride diglyceride. The content of the antistatic agent is preferably 0.5 to 20% by weight in 100% by weight of the resin composition.

  In addition to the above, the resin composition of the present invention includes a sliding agent (for example, PTFE particles and high molecular weight polyethylene particles), a colorant (for example, pigments and dyes such as carbon black and titanium oxide), an inorganic phosphor ( For example, phosphors having aluminate as a mother crystal), inorganic or organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorbers (ATO fine particles, ITO fine particles, lanthanum boride) Fine particles, tungsten boride fine particles, phthalocyanine metal complexes, etc.), photochromic agents, fluorescent whitening agents, and the like.

  In the production of the resin composition of the present invention, the production method is not particularly limited. However, it is preferable to melt knead components A to D and other components using a twin screw extruder.

  A typical example of the twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. In addition, melt kneaders such as FCM (manufactured by Farrel, trade name), Ko-Kneader (manufactured by Buss, trade name), and DSM (manufactured by Krauss-Maffei, trade name) can also be given as specific examples. Among the above, the type represented by ZSK is more preferable. In such a ZSK type twin screw extruder, the screw is a fully meshed type, and the screw includes various screw segments having different lengths and pitches, and various kneading disks having different widths (and corresponding kneading segments). It consists of

  A more preferable embodiment in the twin screw extruder is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw having a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of the screw length (L) to the diameter (D) in the twin screw extruder is preferably 20 to 50, more preferably 28 to 42. When L / D is large, uniform dispersion is likely to be achieved, whereas when it is too large, decomposition of the resin is likely to occur due to thermal degradation. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. Further, water, an organic solvent, a supercritical fluid, or the like may be added in order to enhance the dispersibility of the carbon nanotubes or to remove impurities in the resin composition as much as possible. Further, it is possible to remove a foreign substance from the resin composition by installing a screen for removing foreign substances mixed in the extrusion raw material in the zone in front of the extruder die part. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  The method for supplying the B component, optional C component, D component and other additives (simply referred to as “additive” in the following examples) to the extruder is not particularly limited, but the following methods are typically exemplified. . (I) A method of supplying the additive into the extruder independently of the polycarbonate resin. (Ii) A method in which the additive and the polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to the extruder. (Iii) A method of melt-kneading an additive and a polycarbonate resin in advance to form a master pellet.

  One of the methods (ii) is a method in which all necessary raw materials are premixed and supplied to the extruder. Another method is a method in which a master agent containing a high concentration of additives is prepared, and the master agent is separately or further premixed with the remaining polycarbonate resin or the like and then supplied to the extruder. The master agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Other premixing means include, for example, a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. A high-speed stirring type mixer such as a Henschel mixer is preferable. Yet another premixing method is, for example, a method in which a polycarbonate resin and an additive are uniformly dispersed in a solvent and then the solvent is removed.

  The resin extruded from the twin-screw extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. Furthermore, when it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  As described above, according to the present invention, 0.1 to 15 parts by weight of B component and optionally 0.001 to 0.5 parts by weight of C component and 0.01 to 1 part by weight of D component per 100 parts by weight of A component A manufacturing method characterized by mixing the parts is provided. The details of the A component, the B component, the C component, and the D component used in the production method are as described above. For such mixing, as explained in the method for producing a resin composition, a vent type twin screw extruder can be most suitably used.

  In such melt kneading, the cylinder temperature is preferably set to 220 to 320 ° C., more preferably 240 to 300 ° C., and the screw rotation speed is preferably set to 60 to 500 rpm, more preferably 70 to 200 rpm.

  The resin composition of the present invention obtained as described above can usually produce various products by injection molding the pellets produced as described above. Further, the resin composition melt-kneaded by a twin screw extruder can be directly formed into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.

  In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-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. More preferable are injection compression molding and injection press molding which can be molded at a low injection speed.

  Moreover, the resin composition of this invention can also be used in the form of various profile extrusion-molded articles, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Moreover, you may make the resin composition of this invention into a molded article by rotational molding or blow molding.

  Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary resins can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  The resin composition of the present invention has excellent conductivity and improved melting by blending a specific polycarbonate resin with a conductive carbon compound, a specific phosphorus stabilizer and a specific acid-modified polyolefin wax as desired. It has thermal stability. With such characteristics, the resin composition can cope with a wide range of molding conditions, and the molding is excellent in crack resistance, so that a conductive material applicable to a wide range of applications can be provided. Such applications include, for example, personal computers, notebook computers, game machines (home game machines, arcade game machines, pachinko machines, slot machines, etc.), display devices (LCD, organic EL, electronic paper, plasma display, projectors, etc.) The power transmission component (represented by the housing of the dielectric coil power transmission device) is exemplified. Examples of such applications include printers, copiers, scanners, and fax machines (including these multifunction machines). Examples of such applications include precision equipment such as VTR cameras, optical film cameras, digital still cameras, camera lens units, security devices, and mobile phones. In particular, the resin composition of the present invention is suitably used for a housing, a cover, and a frame of a digital image information processing apparatus such as a camera barrel or a digital camera.

  In addition, the resin composition of the present invention can be used for medical devices such as massage machines and hyperoxia treatment devices; home video appliances such as image recorders (so-called DVD recorders), audio devices, and electronic musical instruments; pachinko machines, slot machines, etc. It is also suitable for parts such as game machines; and home robots equipped with precision sensors.

In addition, the resin composition of the present invention is used to transport various vehicle parts, batteries, power generation devices, circuit boards, integrated circuit molds, optical disk boards, disk cartridges, optical cards, IC memory cards, connectors, cable couplers, and electronic parts. Containers (IC magazine cases, silicon wafer containers, glass substrate storage containers, carrier tapes, etc.), antistatic or antistatic parts (e.g., charging rolls for electrophotographic photosensitive devices), and various mechanical parts (gears, turntables, It can be used for rotors and screws (including mechanical parts for micromachines).
Therefore, the resin composition of the present invention is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and the industrial effect exerted by the resin composition is extremely large.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated.
(I) Evaluation item (I-1) Surface resistivity A square plate having a width of 45 mm, a length of 80 mm, and a thickness of 2 mm, having a cylinder temperature of 300 ° C., a mold temperature of 80 ° C., a firing speed of 20 mm / sec, and a molding cycle of about 60 seconds. Molded by injection molding under conditions. The molded products of the second, fourth, sixth, eighth and tenth shots are extracted immediately after the purge, and left for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. Kogyo Co., Ltd.) and a resistivity meter (Mitsubishi Chemical Corporation) were used to measure the surface resistivity, and the average value was calculated. In addition, it can be said that surface resistivity is favorable in the case of 1.0 × 10 ¹⁴ Ω or less.
(I-2) Melting heat stability A square plate having a width of 45 mm, a length of 80 mm, and a thickness of 2 mm was molded by injection molding under the condition of a molding cycle of 30 seconds. The molded product was pulverized and the viscosity average molecular weight was measured by the method described in the text. On the other hand, it was molded by injection molding under conditions of a molding cycle of 600 seconds, and the viscosity average molecular weight after pulverization was measured in the same manner. The molecular weight at the molding cycle of 600 seconds when the molecular weight of the molded product at the molding cycle of 30 seconds was taken as 100% was expressed as a percentage and evaluated as the molecular weight retention rate. It can be said that the higher the molecular weight retention, the better the heat of fusion stability.
(I-3) Tensile rupture elongation The tensile rupture elongation was measured according to ISO527-1 and 527-2. The test shape was 175 mm long × 10 mm wide × 4 mm thick. The average value of five samples was calculated in the same manner as described above. The test speed was 5 mm / min.

Reference Example 1 Production of Polycarbonate Resin 7307 parts by weight (50 moles) of isosorbide and 10709 parts by weight (50 moles) of diphenyl carbonate were placed in a reactor, and 4.8 parts by weight of tetramethylammonium hydroxide as a polymerization catalyst (diphenyl carbonate component) 1 × 10 ⁻⁴ mol per 1 mol) and 5.0 × 10 ⁻³ parts by weight of sodium hydroxide (0.25 × 10 ⁻⁶ mol per 1 mol of diphenyl carbonate component) It was melted by heating to 180 ° C. at normal pressure.
Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while distilling off the produced phenol. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes.

Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 ⁻³ MPa for 10 minutes and 1.33 × 10 ⁻³ MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 ⁻⁵ MPa. , gradually heated up to 260 ° C., and finally 260 ° C., was allowed to react for 1 hour at 6.66 × 10 ^over 5 MPa. The polymer after the reaction was pelletized to obtain a pellet having a specific viscosity of 0.32. The pellet had a biogenic content of 85%, a glass transition temperature of 165 ° C., and a 5% weight loss temperature of 355 ° C. These values were measured by the following method.

Specific viscosity η _sp ; measured using an Ostwald viscometer (equipment name: RIGO AUTO VISOSIMETER TYPE VMR-0525 · PC) at a temperature of 20 ° C. with a pellet dissolved in methylene chloride at a concentration of about 0.7 g / dL. did. In addition, specific viscosity (eta) _sp was calculated | required from the following formula.
η _sp = t / t _o −1
t: sample solution flow time t _o of:; according ASTM D6866 05, radiocarbon concentrations flow time biogenic matter content of the solvent only; from biogenic matter content test with (percent modern carbon C14), biogenic matter content Was measured.
Glass transition temperature: Measured by DSC (model DSC2910) manufactured by TA Instruments using pellets.
5% weight loss temperature; measured by TGA (model TGA2950) manufactured by TA Instruments using pellets.

Examples 1 to 5 and Comparative Examples 1 to 2 Resin compositions and resin compositions having a content ratio described in Manufacturing Table 1 of molded products were prepared as follows. In addition, in the content rate of Table 1, about the B-1 component, the net amount of the carbon nanotube was described. The description will be made according to the symbols in the following table. The components described in Table 1 were mixed in a V-type blender to prepare a mixture. A small amount of additives other than PC was produced using a supermixer as a premix with a content of 10% by weight. The plurality of premixtures were mixed uniformly with the remaining PC using a V-type blender.

Using a vent type twin screw extruder (Nippon Steel Works TEX-30XSST) with a screw diameter of 30 mm, a mixture by a V-type blender was supplied to the first inlet at the rearmost part. Such an extruder has a kneading zone by a kneading disk between the first supply port and the second supply port, and a vent port opened immediately after that is provided. The length of the vent port was about 2D with respect to the screw diameter (D). A side feeder was installed after the vent port, and a kneading zone with a kneading disk and a subsequent vent port were further provided after the side feeder. The length of the vent port in this portion is about 1.5D, and the vacuum pressure is about 3 kPa in that portion using a vacuum pump. Extrusion was performed under the conditions of a cylinder temperature of 250 ° C. to 300 ° C. (raise almost uniformly from the barrel at the root of the screw to a die), a screw rotation speed of 180 rpm, and a discharge amount of 20 kg per hour. The extruded strand was cooled in a water bath, then cut with a pelletizer and pelletized.
The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours, and then using an injection molding machine, the cylinder temperature was 280 ° C., the mold temperature was 80 ° C., the firing speed was 20 mm / sec, and the molding. A test piece of the above-mentioned evaluation item was prepared under the condition of a cycle of about 60 seconds.

The raw materials used in the above examples and comparative examples are as follows.
(A component: polycarbonate resin)
A-1: The polycarbonate resin pellet produced in Reference Example 1 was dried at 100 ° C. for 24 hours before being charged into the extruder.
(B component: conductive carbon compound)
B-1: Concentrate for compounding carbon nanotubes having a carbon nanotube concentration of 15% by weight with a diameter of 20 nm and an aspect ratio of 5 or more (Carbon Nanotube Master MB6015-00 (trade name) manufactured by Hyperion)
B-2: dibutyl phthalate absorption oil amount of 495ml / 100g conductive carbon black (made by Ketjen Black International Co., Ltd. Ketchen black EC-600JD (trade name))
(C component: phosphorus stabilizer)
C-1: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Adeka Stub PEP-36)
(D component: modified polyolefin wax)
D-1: Olefin wax by copolymerization of α-olefin and maleic anhydride (Mitsubishi Chemical Corporation; Diacarna 30M (trade name))

  As is apparent from Table 1, according to the present invention, the deformation characteristics such as the tensile elongation at break of the resin composition composed of the polycarbonate resin and the carbon nanotube can be improved, so that both these characteristics and good electrical conductivity are combined. It can be seen that the resin composition has been achieved.

Claims (7)

With respect to 100 parts by weight of a polycarbonate resin (component A) containing a carbonate structural unit represented by the following formula (1), 0.1 to 15 parts by weight of a conductive carbon compound (component B), and the following formula (5) A conductive polycarbonate resin composition comprising 0.001 to 0.5 parts by weight of a phosphorus-based heat stabilizer (component C) which is a compound represented.

(In the above formula (5), “—X ¹ ” is a group represented by the following formula (2).)

(In the above formula (2), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 4 to 10 carbon atoms, and R ³ is a hydrogen atom or the number of carbon atoms. 1 to 10 alkyl groups .)   The conductive polycarbonate resin composition according to claim 1, comprising 0.01 to 1 part by weight of an acid-modified polyolefin wax (D component) with respect to 100 parts by weight of the polycarbonate resin (A component).   The conductive polycarbonate resin composition according to claim 1, wherein the carbonate constituent unit represented by the formula (1) is a carbonate constituent unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol).   The conductive polycarbonate resin composition according to claim 1, wherein the conductive carbon compound (component B) is carbon black or carbon nanotube. Conductive carbon compound (B component), wherein dibutyl phthalate absorption oil amount is carbon black or diameter 0.7nm~100nm a 100ml / 100g~1000ml / 100g, and a carbon nanotube is aspect ratio of 5 or more Item 5. A conductive polycarbonate resin composition according to Item 4 . The conductive polycarbonate resin composition according to claim 1, wherein the phosphorous heat stabilizer (component C) is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite .   A molded article formed from the conductive polycarbonate resin composition according to claim 1.