JP2008255230A - Electroconductive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive polycarbonate resin composition having excellent electroconductivity and giving moldings improved in deformation characteristics. <P>SOLUTION: The electroconductive polycarbonate resin composition comprises, based on (A) 100 pts.wt. of a polycarbonate resin (component A), (B) 0.1-15 pts.wt. of an electroconductive carbon compound (component B) and (C) 0.01-1 pt.wt. of an acid modification polyolefin-based wax (component C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  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.

  Many proposals have already been made for thermoplastic resin composite materials 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 it has excellent properties and that the physical properties of the resin material can be maintained (see Non-Patent Document 1).

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 1, 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 1 shows various characteristics of PC containing 3% CNT. On pages 194 to 201 of the above-mentioned document 1, 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 1). 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). 2). 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 6). A resin composition in which a PC having a viscosity average molecular weight of about 15,000 is blended with a BN type CNT manufactured by Hyperion is also known (see Patent Document 7).
Further, a resin composition composed of fine carbon fibers synthesized from toluene by a CVD method and having a non-graphitic multilayer structure and PC is known (see Patent Document 8).
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.

Carbon Nanotube Synthesis / Evaluation, Practical Use, and Nano Dispersion / Formulation Control Technology Co., Ltd. Technical Information Association, issued February 26, 2003 JP-T 8-508534 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

  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. Therefore, 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, the present inventors have found that a conductive polycarbonate resin composition in which a conductive carbon compound and a maleic anhydride copolymer are blended with a polycarbonate resin can achieve the above-mentioned problems, and the present invention has been completed. It came to do.

  According to the present invention, the above problems are (1) 0.1 to 50 parts by weight of conductive carbon compound (component B) and acid-modified polyolefin wax (C) with respect to 100 parts by weight of polycarbonate resin (component A). Component), preferably a polyolefin wax having a carboxyl group and / or a carboxyl anhydride, more preferably 0.01 to 1 part by weight of a copolymer of maleic anhydride and α-olefin. This is achieved by the conductive polycarbonate resin composition.

  One of the preferred embodiments of the present invention is (2) 0.0001 to 2 parts by weight of a phosphorus stabilizer (D component) per 100 parts by weight of the polycarbonate resin (component A), preferably 50% by weight in 100% by weight. % Or more of a phosphorus stabilizer which is a phosphate compound and / or a phosphite compound, and more preferably 50% by weight or more of the phosphorus stabilizer is a trialkyl phosphate. It is a composition.

  One of the preferred embodiments of the present invention is that (3) the conductive carbon compound (component B) is carbon black or carbon nanotubes, preferably carbon black having a dibutyl phthalate oil supply amount of 100 ml / 100 g to 1000 ml / 100 g, or a diameter. 3. The resin composition according to any one of the above constitutions (1) to (2), which is a carbon nanotube having a ratio of 0.7 to 100 nm and an aspect ratio of 5 or more.

Details of the present invention will be described below.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of excellent toughness and deformation characteristics, and is widely used.

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

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

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

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

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

  In producing a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention includes a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. , A copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained.

  Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6- Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1 , 1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1- Trisphenol such as bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol is preferably exemplified. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is 0 in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. 0.03 to 1 mol%, preferably 0.07 to 0.7 mol%, particularly preferably 0.1 to 0.4 mol%.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  Reaction formats such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patents. This is a well-known method in gazettes.

In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10 ^4. a to 3 × 10 ^4, more preferably from ^{1.4 × 10 4 ~2.4 × 10 4} .

A polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ may not provide practically sufficient toughness and crack resistance. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ generally has a low versatility because it generally requires a high molding temperature or requires a special molding method. A high molding temperature tends to cause a decrease in deformation characteristics of the resin composition.

The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above value (5 × 10 ⁴ ) increases the melt tension of the resin composition of the present invention, and molding in extrusion molding, foam molding and blow molding based on such characteristics. Processability can be improved. Such an improvement effect is even better than the branched polycarbonate.

As a more suitable aspect, the A component is a polycarbonate resin (A-3-1 component) having a viscosity average molecular weight of 7 × 10 ⁴ to 2 × 10 ^{6, and} a polycarbonate resin having a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ Polycarbonate resin (A-3 component) consisting of (A-3-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter, “high molecular weight component-containing polycarbonate resin”) May also be used).

In such a high molecular weight component-containing polycarbonate resin (A-3 component), the molecular weight of the A-3-1 component is preferably 7 × 10 ^{4 to} 3 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ⁵ , preferably ^{1 × 10 5 ~2 × 10 5} , particularly preferably ^{1 × 10 5 ~1.6 × 10 5} . The molecular weight of the A-3-2 component is preferably 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 × 10 ^4. to 2.4 × 10 ^4, particularly preferably ^{1.2 × 10 4 ~2.3 × 10 4} .

  The high molecular weight component-containing polycarbonate resin (component A-3) can be obtained by mixing the components A-3-1 and A-3-2 in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight and the A-3-2 component is 60 to 98% by weight, more preferably the A-3-1 component is 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually, the molecular weight distribution of the polycarbonate resin is in the range of 2-3. Therefore, it is preferable that the A-3-1 component and the A-3-2 component of the present invention satisfy the molecular weight distribution range. The molecular weight distribution is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC (gel permeation chromatography) measurement. And Mw is based on standard polystyrene conversion.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method for producing the composition so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by the production method (the production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., the specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The calculation of the viscosity average molecular weight in the resin composition of the present invention is performed as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

(B component: conductive carbon compound)
Carbon black or carbon nanotube is preferable as the conductive carbon compound used as the component B in the present invention, and carbon black having a dibutyl phthalate oil supply amount (hereinafter sometimes referred to as DBP oil absorption amount) of 100 ml / 100 g to 1000 ml / 100 g. 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 a liquid state 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. Moreover, the structure where the lamination | stacking of the graphene sheet inclined by a fixed angle with respect to the fiber axis may be sufficient. 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.

(C component: acid-modified polyolefin wax)
The acid-modified polyolefin wax that is component C of the present invention is an acid-modified polyolefin 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. System wax.
A preferred embodiment of the component C of the present invention 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 preferably as component C, in the acid-modified polyolefin wax, the carboxyl group is preferably in the range of 0.05 to 10 meq / g, more preferably 0.1 to 6 meq / g, per 1 g of the carboxyl group-containing lubricant. It is a carboxyl group-containing olefin wax that is contained in the range of g, more preferably 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 as the component C, 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. Is 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 (component C) is 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 based on 100 parts by weight of the polycarbonate resin (component A). -0.5 parts by weight. If the content of the acid-modified polyolefin wax (component C) is within this range, a molded article having good electrical conductivity can be obtained while maintaining high melting heat stability.

(D component: phosphorus stabilizer)
The resin composition of the present invention preferably further contains a phosphorus stabilizer. Such phosphorus stabilizers greatly improve the thermal stability during production or molding. As a result, mechanical properties, hue, and molding stability are improved. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, and phosphonic acid, triorganophosphate compound, and acid phosphate compound are preferable, and 50% by weight or more of the 100% by weight is phosphate compound and / or phosphite compound. More preferably, the phosphorus stabilizer is more preferably 50% by weight or more of 100% by weight of a trialkyl phosphate and / or acid phosphate compound, and more than 50% by weight of 100% by weight of A phosphorus stabilizer which is an alkyl phosphate is most preferably used.

  The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.

  Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphate is preferable. The carbon number of the alkyl group of such a trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

  Examples of the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like. Among these, long-chain dialkyl acid phosphates having 10 or more, more preferably 14 to 22 carbon atoms in the alkyl group are effective in improving thermal stability, and are preferred because the acid phosphate itself has high stability.

  Other phosphite compounds include, for example, trialkyl phosphites such as tridecyl phosphite, dialkyl monoaryl phosphites such as didecyl monophenyl phosphite, monoalkyl diaryl phosphites such as monobutyl diphenyl phosphite, triphenyl phosphite. Triaryl phosphites such as phyto and tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite , Bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Erythritol phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di Illustrative are cyclic phosphites such as -tert-butylphenyl) phosphite.

  Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite. Tetrakis (2,4-di-tert More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. An example of the tertiary phosphine is triphenylphosphine.

  The content of the phosphorus stabilizer is preferably 0.0001 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 0, based on 100 parts by weight of the polycarbonate resin (component A). .5 parts by weight.

(Other ingredients)
In the resin composition of the present invention, various additives, reinforcing agents, and other polymers that are usually blended in a polycarbonate resin can be further blended.

(Other polymers and elastomers)
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, and polymethyl methacrylate.

  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 polyester, 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.

(Filler)
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 is performed. -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 obtained by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ash 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, zonotolite, palygorskite (attapulgite), sepiolite, and other inorganic heat-resistant fibers such as aramid fiber, polyimide fiber and polybenzthiazole fiber 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.

(Release agent)
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.

(Hindered phenol stabilizers and other antioxidants)
The hindered phenol stabilizer is effective in preventing the heat aging of the resin composition. Since the resin composition of the present invention may be used in a high heat atmosphere, it is particularly preferably blended in such a case. Hindered phenol stabilizers include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′- Methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N'-hexamethylenebis- (3,5- -Tert-butyl-4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis [methylene -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used.

  In addition, antioxidants other than the hindered phenol stabilizers can be used. Examples of such other antioxidants include lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Are described in JP-A-7-233160), and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthio And sulfur-containing stabilizers such as propionate. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types. The content of these stabilizers is preferably 0.0001 to 1% by weight, more preferably 0.005 to 0.5% by weight, in 100% by weight of the resin composition.

(Hydrolysis improver)
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 that does not impair 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.

(UV absorber)
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 − ), And 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane 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.

(Antistatic agent)
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.

(Other additional ingredients)
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.

(Manufacture of resin composition)
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 of supplying the B component to the C component, the optional 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.

(Preferable production method of resin composition)
As described above, according to the present invention, per 100 parts by weight of component A, 0.1 to 15 parts by weight of component B, 0.01 to 1 part by weight of component C, and optionally 0.0001 to 2 parts by weight of component D, A manufacturing method characterized by mixing the above 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 250 to 320 ° C, more preferably 270 to 310 ° C, and the screw rotation speed is preferably set to 60 to 500 rpm, more preferably 70 to 200 rpm.

(About a molded article made of the resin composition of the present invention)
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 melt heat stability by blending a conductive carbon compound and a specific acid-modified polyolefin wax. 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.

(II) Production of Resin Composition and Molded Product A resin composition having a content ratio shown in the table was prepared as follows. In addition, in the content rate of a table | surface description, the net amount of the carbon nanotube was described about B-1 component. The description will be made according to the symbols in the following table. The components described in the table 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: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 22,500 (Panlite L-1225WP (trade name) manufactured by Teijin Chemicals Ltd.)
(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: Conductive carbon black (Ketjen Black International Co., Ltd. Ketjen Black EC-600JD (trade name)) with dibutyl phthalate oil supply of 495 ml / 100 g
(C component: modified polyolefin wax)
C-1: Olefin wax by copolymerization of α-olefin and maleic anhydride (Mitsubishi Chemical Corporation; Diacarna 30M (trade name))
(D component: phosphorus stabilizer)
D-1: Trimethyl phosphate (TMP (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)
D-2: Distearyl pentaerythritol diphosphite (Adeka Stub PEP-8 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.)

  As is clear from the above table, according to the present invention, the resin composition comprising PC and CNT can be improved in deformation characteristics such as tensile elongation at break, and thus has both these characteristics and good electrical conductivity. You can see that things have been achieved.

Claims (8)

  (A) 0.1 to 15 parts by weight of conductive carbon compound (B component) and (C) acid-modified polyolefin wax (C component) with respect to 100 parts by weight of polycarbonate resin (A component) A conductive polycarbonate resin composition comprising 01 to 1 part by weight.   The conductive polycarbonate resin composition according to claim 1, comprising 0.0001 to 2 parts by weight of (D) a phosphorus stabilizer (D component) per 100 parts by weight of component A.   The conductive polycarbonate resin composition according to claim 1, wherein the component B is carbon black or carbon nanotube.   The conductive polycarbonate according to claim 3, wherein the B component is carbon black having a dibutyl phthalate oil supply amount of 100 ml / 100 g to 1000 ml / 100 g or a carbon nanotube having a diameter of 0.7 nm to 100 nm and an aspect ratio of 5 or more. Resin composition.   The conductive polycarbonate resin composition according to claim 1, wherein the component C is a polyolefin-based wax having a carboxyl group and / or a carboxyl anhydride.   The conductive polycarbonate resin composition according to claim 1, wherein component C is a copolymer of maleic anhydride and α-olefin.   The conductive polycarbonate resin composition according to any one of claims 2 to 6, wherein the D component is a phosphorus stabilizer in which 50% by weight or more thereof is a phosphate compound and / or a phosphite compound.   The conductive polycarbonate resin composition according to claim 7, wherein the D component is a phosphorus-based stabilizer in which 50% by weight or more thereof is a trialkyl phosphate.