CN101280100A

CN101280100A - Conductive resin compound

Info

Publication number: CN101280100A
Application number: CNA2008100911540A
Authority: CN
Inventors: 井野庆一郎; 近藤史崇
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2007-04-05
Filing date: 2008-04-07
Publication date: 2008-10-08
Anticipated expiration: 2028-04-07
Also published as: CN101280100B; JP5154820B2; JP2008255230A

Abstract

The purposes of the present invention is providing a electroconductivity polycarbonate composition which is provided with high conductivity, and providing deformation characteristic to obtain improved product. The present invention provides a electroconductive resin composition, which is characterized in that, polycarbonate resin (A ingredient ) relative to 100 weight portion, containing 0.1-15 wt% electroconductivity carbon compounds (B ingredient ) and 0.01-1 wt% ache modified polyolefins genus wax (C ingredient ).

Description

Conductive resin composition

Technical field

The present invention relates to a kind of conductive resin composition that contains polycarbonate resin and conductive carbon compound.In more detail, the present invention relates to the good deformation characteristic that has without detriment to polycarbonate resin and the superior resin combination of electroconductibility.

Background technology

About containing the matrix material of conductive carbon compound and thermoplastic resin, to have developed at present a lot, part is by practical application.Also comprise polycarbonate resin in this thermoplastic resin.Particularly, as the conductive carbon compound, the feature that has cooperated the matrix material of carbon nanotube (carbon nanotube) be the pollution that causes by particle less, few, the surface finishing of exhaust and gloss is good, good fluidity, warping phenomenon is few, recirculation good and (please refer to non-patent literature 1) such as physical propertiess that can keep resin material.

Particularly, good recirculation is to bring the minimizing of carrying capacity of environment and the validity feature that cost reduces.But, exist the relatively poor shortcoming of deformation characteristic in the resin combination that constitutes by polycarbonate resin (below, abbreviate " PC " sometimes as) and carbon nanotube (below, abbreviate " CNT " sometimes as) as tension fracture elongation rate etc.The bad reduction that causes secondary processing behaviours such as tapping screw (セ Le Off Star プ) strength characteristics and thermal flexure processing of deformation characteristic.The bad phenomenon of the deformation characteristic vitrifying tansition temperature at PC easily is high more, and is perhaps obvious more when high more to the toughness reguirements of PC.

Before this, though a lot of to the opinion of the resin combination formed by PC and CNT,, it is hard to tell that all the improvement to present deformation characteristic as tension fracture elongation rate etc. has had sufficient opinion.

According to 185 pages table 1 of non-patent literature 1, sell with parent sizing material (master the batch) (name of product: MB6015-00) of PC by HYPERION society at present as the CNT of base resin.And, also put down in writing HYPERION society in the document and only sold the parent sizing material at present, never carry out the monomeric sale of pot CNT.

Also have, in 187 pages table 3 of non-patent literature 1, show the various characteristics of the PC that has mixed 3%CNT.And, in 194～201 pages of non-patent literature 1,, introduced the HIPERSITE W1000 series of making by oiling electronics (strain) as the material that in the thermoplastic resin that with PC is representative, has added CNT.

In PC, cooperated CNT, and the polymer composition that satisfies specific shock strength and volume specific resistance has been known (with reference to patent documentation 1).More particularly, said composition is to make by with biaxial extruder the parent sizing material that is combined with CNT among the PC and PC being carried out melting mixing.According to patent documentation 1, to compare with the protofibril (carbon nanotube) of nest like (so-called BN type), the fibriilar poly carbonate resin composition that is combined with pectination has better shock-resistance.Therefore, the complexing degree is more little, and the mechanical properties of composition becomes better, and this is known.But patent documentation 1 does not disclose the improvement situation about the deformation characteristic of resin combination.

Further, about cooperated the resin combination of CNT in PC, following item is disclosed.

Disclose the resin combination that in PC, cooperated the BN type CNT that makes by HYPERION company, moulding thus the moulding product, these moulding product are pulverized and the operation of reshaping and the moulding product (with reference to patent documentation 2) that obtain repeatedly.Same composition also is disclosed in patent documentation 3,4 and 5.

Moreover the weight-average molecular weight that also discloses the PC parent sizing material of HYPERION company manufacturing about parent sizing material (master batch) is 19500 (with reference to patent documentations 6).The resin combination (with reference to patent documentation 7) that has cooperated the BN type CNT that is made by HYPERION company in viscosity-average molecular weight is about 15000 PC is also disclosed.

And, the resin combination of being made up of fine carbon fiber and PC is disclosed, wherein, fine carbon fiber is synthetic by toluene by the CVD method, and has the multilayered structure (with reference to patent documentation 8) of non-graphite.As mentioned above, though many resin combinations that is made of PC and CNT are disclosed the not open relevant scheme of improving the deformation characteristic of resin combination.

Non-patent literature 1: the synthetic evaluation of carbon nanotube, practicability and nano-dispersed mixture control technology, (strain) technical intelligence association, distribution on February 26th, 2003.

The flat 8-508534 communique of the special table of patent documentation 1:JP

Patent documentation 2:JP spy opens the 2001-310994 communique

Patent documentation 3:JP spy opens the 2002-175723 communique

Patent documentation 4:JP spy opens the 2002-275276 communique

Patent documentation 5:JP spy opens the 2003-082115 communique

Patent documentation 6:JP spy opens the 2002-214928 communique

Patent documentation 7:JP spy opens the 2000-044815 communique

Patent documentation 8:WO2004/070095 trumpeter volume

Summary of the invention

As mentioned above, so far, improve the conductive carbon compound, the technical problem of deformation characteristic of poly carbonate resin composition that particularly comprises carbon nanotube is not by known to the people, and its solution is not disclosed yet.Thus, order of the present invention is to provide a kind of conductive polycarbonate resin combination that has high conductivity and improved deformation characteristic.The inventor etc., the result who has carried out wholwe-hearted research finds to have cooperated the resin combination of conductive carbon compound and acid modified polyolefin class wax can reach above-mentioned technical problem in polycarbonate resin, thereby has finished the present invention.

Above-mentioned purpose of the present invention, can realize in the following manner:

(1). a kind of conductive resin composition is provided, it is characterized in that, polycarbonate resin (A composition) with respect to 100 weight parts, the conductive carbon compound (B composition) that contains 0.1～15 weight part reaches (C) the acid modified polyolefin class wax (C composition) of 0.01～1 weight part, wherein, acid modified polyolefin class wax (C composition) is preferably the acid modified polyolefin wax with carboxyl and/or carboxylic acid anhydride, more preferably contains the multipolymer of maleic anhydride and alpha-olefin.

(2). as (1) described conductive resin composition, it is characterized in that, polycarbonate resin (A composition) with respect to 100 weight parts, the Phosphorus stablizer (D composition) that contains 0.0001～2 weight part, wherein, being the Phosphorus stablizer of phosphate compound and/or person's bi-ester of phosphite more than the 50 weight % in the described Phosphorus stablizer (D composition) of 100 weight % preferably, is the Phosphorus stablizer of trialkyl phosphates more than the 50 weight % in the described Phosphorus stablizer (D composition) of 100 weight % more preferably.

(3). as (1) or (2) described conductive resin composition, it is characterized in that, conductive carbon compound (B composition) is carbon black or carbon nanotube, being preferably dibutyl phthalate is 100ml/100g～1 to oil mass, and the carbon black of 000ml/100g or diameter are that 0.7nm～100nm and aspect ratio are the carbon nanotube more than 5.

Resin combination of the present invention by cooperating conductive carbon compound and specific acid modified polyolefin class wax, has good electroconductibility and improved melting heat stability.

Embodiment

The present invention is described in more detail below.

(A composition: polycarbonate resin)

The polycarbonate resin that uses as the A composition is reacted binary phenol and carbonic ether presoma to acquisition in the present invention.As reaction method, can enumerate the solid phase ester-interchange method of interface polycondensation, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.

Representative in the binary phenol of Shi Yonging here, can exemplify quinhydrones, Resorcinol, 4,4 '-bis-phenol, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-(are commonly referred to as dihydroxyphenyl propane, below abbreviate " BPA " sometimes as), 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) pentanes of 2-, 4,4 '-(to the phenylene diisopropylidene) diphenol, 4,4 '-(metaphenylene diisopropylidene) diphenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) oxide compound, two (4-hydroxy phenyl) sulfide, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxy-3-methyl phenyl) sulfide, 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc.Preferred binary phenol is two (4-hydroxy phenyl) paraffinic hydrocarbonss, wherein, considers from the aspect of toughness or excellent in deformation characteristics, and preferred especially dihydroxyphenyl propane, and by general.

Among the present invention, except general dihydroxyphenyl propane class polycarbonate, can also use as the A composition by the special polycarbonate that other binary phenol is made as polycarbonate.

For example, as part or all of binary phenol composition, use 4,4 '-(metaphenylene diisopropylidene) diphenol (below, abbreviate " BPM " sometimes as), 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane (below, abbreviate " Bis-TMC " sometimes as), 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, the polycarbonate (homopolymer or multipolymer) of two (4-hydroxy-3-methyl phenyl) fluorenes of 9-(below, abbreviate " BCF " sometimes as) is suitable for the dimensional change or the shape stability of suction are required on the strict purposes.Binary phenol beyond these BPA, preferred 5 moles of the binary phenol composition weight that constitutes this polycarbonate of using especially preferably use 10 moles more than the % more than the %.

Particularly, when requiring to have high rigidity and good hydrolytic resistance, the A composition that preferably constitutes resin combination is the Copolycarbonate of following (1)～(3).

(1) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, the BPM composition is 20～80 moles of % (40～75 moles of % more preferably, 45～65 moles of % more preferably), and the BCF composition is the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %);

(2) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, the BPA composition is 10～95 moles of % (50～90 moles of % more preferably, 60～85 moles of % more preferably) and the BCF composition be the Copolycarbonate of 5～90 moles of % (more preferably 10～50 moles of %, more preferably 15～40 moles of %);

(3) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, the BPM composition is 20～80 moles of % (40～75 moles of % more preferably, 45～65 moles of % more preferably) and the Bis-TMC composition be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %).

These special polycarbonate both can use separately, also can two or morely suitably mix and use.In addition, also these can be mixed use with general bisphenol A polycarbonate.

About the manufacture method and the characteristic of these special polycarbonate, for example open flat 6-172508 communique, spy and open that flat 8-27370 communique, spy are opened the 2001-55435 communique and special opening in the 2002-117580 communique etc. has detailed record the spy.

Moreover, in above-mentioned various polycarbonate, by multipolymer composition etc. is adjusted, water-intake rate and Tg (vitrifying tansition temperature) are limited in the following scope, the hydrolytic resistance of its polymkeric substance self is good, and the low bendability after moulding is also very good, therefore is specially adapted to the field that shape stability is had relatively high expectations.

(i) water-intake rate is 0.05～0.15%, is preferably 0.06～0.13%, and Tg is 120～180 ℃ a polycarbonate; Or

(ii) Tg is 160～250 ℃, is preferably 170～230 ℃, and water-intake rate is 0.10～0.30%, is preferably 0.13～0.30%, more preferably 0.14～0.27% polycarbonate.

Here, the water-intake rate of polycarbonate is according to ISO62-1980, is that 45mm, thickness are the discoideus test piece of 3.0mm is flooded 24 hours in 23 ℃ water after with diameter, measures its moisture content and the numerical value that obtains.In addition, Tg (vitrifying tansition temperature) is according to JIS K7121, measures and the numerical value of acquisition with differential scanning heat instrument (DSC).

As the carbonic ether presoma, use carboxylic acid halides (Carbonyl halide), carbonic diester or haloformate (Ha ロホ Le メ one ト) etc., specifically exemplify, can enumerate the halo dicarboxylic acid esters of phosgene (Phosgene), diphenyl carbonate or binary phenol etc.

When by interface polycondensation, when utilizing above-mentioned binary phenol and carbonic ether presoma to make polycarbonate, also can use catalyzer, terminal terminator, antioxidant etc. as required, wherein antioxidant is in order to prevent the oxidation of binary phenol.And polycarbonate resin of the present invention comprises: with the branched polycarbonate of copolymerization in addition of the multifunctional aromatics more than the three-functionality-degree; With two functionality carboxylic acids of aromatic series or aliphatics (comprising ester ring type) the polyestercarbonate resin of copolymerization in addition; With two functionality alcohol (the comprising ester ring type) Copolycarbonate of copolymerization in addition; And with this two functionality carboxylic acid and the two functionality alcohol polycarbonate resin of copolymerization in addition.And, also can be with the two or more blended mixtures in addition in the polycarbonate resin of above acquisition.

Branched polycarbonate resin can improve the fusion tension force of resin combination of the present invention, can improve forming process in extrusion moulding, foaming and the blow molding according to this characteristic.The result can obtain by the excellent more moulding product of the dimensional precision of above method of forming making.

As the multifunctional aromatics more than the three-functionality-degree that is used for this branched polycarbonate resin, preferably can exemplify 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 2, two (2-hydroxy-5-methyl base benzyl)-4-methylphenol and the 4-{4-[1 of 6-, two (4-hydroxy phenyl) ethane of 1-] benzene }-α, triphenols such as α-Er Jiajibianji phenol.As other multifunctional aromatics, can exemplify Phloroglucinol, Gen Pi Portugal phenol, four (4-hydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) ketone, 1, the sour muriate of two (4, the 4-dihydroxyl trityl group) benzene of 4-, trimellitic acid, Pyromellitic Acid, benzophenone tetracarboxylic acid (Benzophenone tetracarboxylic) and these materials.Wherein, preferred 1,1,1-three (4-hydroxy phenyl) ethane and 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, preferred especially 1,1,1-three (4-hydroxy phenyl) ethane.

100 moles of % from binary phenol deutero-structural unit with from this summation of multifunctional aromatics deutero-structural unit, being 0.03～1 mole of %, being preferably 0.07～0.7 mole of %, being preferably 0.1～0.4 mole of % especially in the branched polycarbonate from multifunctional aromatics deutero-structural unit.

And this branched structure unit not only can be from multifunctional aromatics deutero-structural unit, can also be the side reaction during as melting state transesterification reaction, is not using deutero-structural unit under the situation of multifunctional aromatics.Moreover the ratio of this branched structure can be passed through ¹H-NMR measures and calculates.

Two functionality carboxylic acids of preferred aliphat are alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, can preferably enumerate straight chain saturated aliphatic dicarboxylic acids such as sebacic acid (Decanedioic acid), 12 diacid, 14 diacid, 18 diacid and octadecane dicarboxylic acid; And the ester ring type dicarboxylic acid of cyclohexane dicarboxylic acid etc.As two functionality alcohol, be preferably the ester ring type glycol, for example can enumerate cyclohexanedimethanol, cyclohexane diol and tristane dimethanol etc.

Can also use the polyorganosiloxane units polycarbonate-poly organo alkyl copolymer of copolymerization in addition.

Reaction formation as ring-opening polymerization method of interfacial polymerization, the solid phase ester-interchange method that dissolves ester-interchange method, carbonic ether prepolymer and the cyclic carbonate compound of the manufacture method of polycarbonate resin etc. has been disclosed on various documents and the patent gazette etc.

When making resin combination of the present invention, the viscosity-average molecular weight of polycarbonate resin (M) is not particularly limited, but is preferably 1 * 10 ⁴～5 * 10 ⁴, more preferably 1.4 * 10 ⁴～3 * 10 ⁴, more preferably 1.4 * 10 ⁴～2.4 * 10 ⁴

Be lower than 1 * 10 in viscosity-average molecular weight ⁴Polycarbonate resin in, can't obtain sufficient toughness or anti-crackle in the practical application sometimes.On the other hand, surpass 5 * 10 by viscosity-average molecular weight ⁴The resin combination that obtains of polycarbonate resin, generally need higher forming process temperature or the special forming method of needs, so versatility is relatively poor.High forming process temperature causes the reduction of the deformation characteristic of resin combination easily.

Moreover above-mentioned polycarbonate resin also can obtain by viscosity-average molecular weight is mixed at the polycarbonate resin beyond the above-mentioned scope.Particularly, has the above-mentioned value (5 * 10 of surpassing ⁴) the polycarbonate resin of viscosity-average molecular weight, can improve the fusion tension force of resin combination of the present invention, according to this characteristic, can improve the forming process in extrusion moulding, foaming and the blow molding.It is better than above-mentioned branched polycarbonate that this improves effect.

As more preferred form, also can use the A composition is 7 * 10 by viscosity-average molecular weight ⁴～2 * 10 ⁶Polycarbonate resin (A-3-1 composition) and viscosity-average molecular weight be 1 * 10 ⁴～3 * 10 ⁴Polycarbonate resin (A-3-2 composition) form, and its viscosity-average molecular weight is 1.6 * 10 ⁴～3.5 * 10 ⁴Polycarbonate resin (A-3 composition) (hereinafter referred to as " polycarbonate resin of pbz polymer amount composition ").

In the polycarbonate resin (A-3 composition) of this pbz polymer amount composition, the molecular weight of A-3-1 composition is preferably 7 * 10 ⁴～3 * 10 ⁵, more preferably 8 * 10 ⁴～2 * 10 ⁵, more preferably 1 * 10 ⁵～2 * 10 ⁵, be preferably 1 * 10 especially ⁵～1.6 * 10 ⁵And the molecular weight of A-3-2 composition is preferably 1 * 10 ⁴～2.5 * 10 ⁴, more preferably 1.1 * 10 ⁴～2.4 * 10 ⁴, more preferably 1.2 * 10 ⁴～2.4 * 10 ⁴, be preferably 1.2 * 10 especially ⁴～2.3 * 10 ⁴

The polycarbonate resin (A-3 composition) that contains high molecular weight components can be by being mixed above-mentioned A-3-1 composition and A-3-2 composition with various ratios, and it is adjusted into the molecular weight ranges that satisfies regulation and obtains.In the A-3 of 100 weight %, preferred A-3-1 composition is that 2～40 weight % and A-3-2 composition are 60～98 weight %, and more preferably the A-3-1 composition is that 5～20 weight % and A-3-2 composition are 80～95 weight %.Usually, the molecular weight of polycarbonate resin is the scope 2～3.Therefore, preferred A-3-1 composition of the present invention and A-3-2 composition also satisfy the scope of this molecular weight distribution.Moreover this molecular weight distribution can represent the ratio (Mw/Mn) of number-average molecular weight (Mn) with measure the weight-average molecular weight of calculating (Mw) by GPC (gel permeation chromatography), and this Mn and Mw is based on the polystyrene standard conversion and obtains.

In addition,, can enumerate (1) respectively polymerization A-3-1 composition and A-3-2 composition independently as the preparation method of A-3 composition, and with they blended methods in addition; (2) utilize with disclosed method in the flat 5-306336 communique of TOHKEMY be representative, based on the method that the aromatic polycarbonate resin of a plurality of polymkeric substance peak values of expression in the graph of molecular weight distribution of GPC method is made in same system, make this aromatic polycarbonate resin satisfy the making method of condition of the A-1 composition of benzene invention; And (3) will be by the aromatic polycarbonate resin and A-3-1 composition of making separately and/or A-3-2 composition blended method etc. of manufacture method (2) acquisition.

Viscosity-average molecular weight described in the present invention can be calculated according to following method.At first, from the solution that under 20 ℃, the 0.7g polycarbonate is dissolved in the 100ml methylene dichloride and obtains, use Ostwald viscometer, obtain specific viscosity (η by following formula _Sp):

Specific viscosity (η _Sp)=(t-t ₀)/t ₀

[t ₀Be the second number that methylene dichloride falls, t is the second number that sample solution falls]

Utilize the viscosity ratio (η that is obtained _Sp), calculate viscosity-average molecular weight M by following formula:

η _Sp/ c=[η]+0.45 * [η] ²C (wherein, [η] is limiting viscosity)

[η]＝1.23×10 ^-4M ^0.83

C＝0.7

Moreover the viscosity-average molecular weight of resin combination of the present invention is calculated in accordance with the following methods.That is, the methylene dichloride of said composition with its 20～30 times of weight mixed the solubilized composition in the dissolved composition.Take this solvent components by diatomite filtration.Afterwards, removal obtains the solvent in the solution.Thorough drying is removed the solid behind the solvent, and acquisition is dissolved in the solid of the composition of methylene dichloride.From this 0.7g solid is dissolved in the solution of methylene dichloride, obtain specific viscosity under 20 ℃ with method same as described above, utilize than this viscosity to calculate viscosity-average molecular weight M same as described abovely.

(B composition: the conductive carbon compound)

The conductive carbon compound that uses as the B composition in the present invention, be preferably carbon black or carbon nanotube, more preferably to give oil mass (below, abbreviate the DBP oil number sometimes as) be that 0.7nm～100nm and aspect ratio are the carbon nanotube more than 5 for the carbon black of 100ml/100g～1000ml/100g or diameter to dibutyl phthalate.

The carbon nanotube that uses as the B composition in the present invention is that the graphite linings of tubular is layered in the fibrous material to axial radiation direction.

Manufacture method to carbon nanotube is not particularly limited.Can adopt with arc discharge method, laser evaporation method, chemical Vapor deposition process (CVD method) and catalytic chemical vapor deposition technique (CCVD method) etc. be representative, as the manufacture method known method of carbon nanotube.

As the arc discharge method in the manufacture method of carbon nanotube, can be illustrated in the anode that constitutes by the carbon dioxide process carbon electrode that is arranged in the container and by and this anode is opposed and carry out arc-over between the negative electrode that carbon dioxide process carbon electrode that be provided with constitutes, and reclaim the method that is created on the stores on container inner wall and the electrode.

As the laser evaporation method in the preparation method for carbon nano-tube, but illustration utilizes laser pulse that the mixture of carbon and more than one period of element Table VIII group 4 transition metal is gasified, by this mixed gas being condensed upon the method for making in the device.As this VIII group 4 transition metal, for example can enumerate iron, nickel and cobalt.

Chemical Vapor deposition process (CVD method) as carbon nanotube, but illustration with at least a transition metal or its compound as catalyzer, to contain the compound of VI family element in the periodic table of elements and have organic compound as the VI family element of the organic compound of carbon source or the periodic table of elements, together be directed in the Reaktionsofen with the carrier gas that constitutes by hydrogen, methane or rare gas element, carry out the synthetic method by chemical Vapor deposition process.In this CVD method, also can adopt the catalytic chemical vapor deposition technique (CCVD method) that transition-metal catalyst is loaded on carrier and use.Wherein, preferably can be low-cost and carry out mass-produced CVD method and CCVD method.

When by CVD method and CCVD manufactured carbon nanotube, roughly all adopt the method for directly synthesizing, the method that reaches the catalyst residue in the cleaning carbon nanotube as the carbon nanotube of this ash residue amount.Catalyst residue becomes the source of ash residue.Certainly, also can further reduce the ash residue amount by the few carbon nanotube of ash residue amount that is obtained among the former is cleaned.

In above-mentioned the former synthetic method, the catalytic amount by controlling when synthetic can obtain carbon nanotube.That is, control is to the catalytic amount of the hydrocarbons of importing.We can say that it is more favourable to carry out carbon nanotube synthetic CCVD method with catalytic amount still less.But this method also exists in practicality and is difficult to problem that catalyzer and carrier thereof are stably acted on.In the CVD method, the hydrocarbons amount and the catalytic amount that offer Reaktionsofen are adjusted, so that ash residue is below the 3 weight %.In addition, in washing out method, use acidic cpd, basic cpd and supercutical fluid etc., clean the catalyst residue in the carbon nanotube.This cleaning both can be carried out after carbon nanotube synthetic, perhaps also can carry out in the thick finished product stage before high-temperature heat treatment.Reducing the ash residue amount by washing out method is the comparison difficulty, and is related to the increase of the cost of carbon nanotube.Therefore, preferable methods is the method for directly synthesizing as the carbon nanotube of this ash residue amount.

Below, above-mentioned CVD method and CCVD method as the preferred method of synthesizing carbon nanotubes are described.

(synthesis material of carbon nanotube)

As the synthesis material of carbon nanotube, can use hydrocarbons, contain the compound of periodic table of elements group vib element, the mixture of these materials etc.As hydrocarbons, preferred fragrance same clan hydrocarbons.As the aromatic series hydrocarbons, can exemplify the alkyl substituted benzene of benzene, toluene and dimethylbenzene etc.; Chlorobenzene, dichlorobenzene (adjacent--and santochlor), the benzene halide of trichlorobenzene, bromobenzene and dibromobenzene etc.; The alkyl displacement naphthalene compound of naphthalene, methylnaphthalene, dimethylnaphthalene etc. etc.

As the above-mentioned compound that contains periodictable group vib element, preferred oxygen or sulphur, preferred especially oxygen containing organic compound.As oxygenatedchemicals, preferred carbon monoxide, carbonic acid gas, alcohols, ketone, phenols, ethers, aldehydes, organic acid and ester class.Specifically, can enumerate the derivative etc. of methyl alcohol, ethanol, propyl alcohol, hexalin, acetone, butanone, methyl phenyl ketone, pimelinketone, phenol, cresols, formaldehyde, acetaldehyde, formic acid, acetic acid, propionic acid, oxalic acid, Succinic Acid, hexanodioic acid, dme, diethyl ether, diox, ritalin, vinyl acetic monomer and above material.And,, can enumerate the derivative of hydrogen sulfide, dithiocarbonic anhydride, sulfurous gas, sulphur, mercaptan, thioether, thiophene-based and these materials as the compound that contains sulphur.These oxygenatedchemicalss or sulfocompound both can use separately, also can mix two or more uses.

(synthetic catalyst of carbon nanotube)

Catalyzer during as synthesizing carbon nanotubes uses the ultramicron of being made up of transition metal.As transition metal, can exemplify iron, cobalt, nickel, yttrium, titanium, vanadium, manganese, chromium, copper, niobium, molybdenum, palladium, tungsten and platinum etc.Wherein, preferably from iron, nickel, and molybdenum at least a element selected.These metals can use with monomeric form, also can use with the form of the compound that comprises these metals.As metallic compound, preferably have organic compounds, mineral compound or its combination.As organic compound, can exemplify ferrocene, nickelocene, dicyclopentadienylcobalt, iron carbonyl and acetone iron (アセト Na one ト iron) etc.And,, can be any form in oxide compound, nitrate, vitriol and the muriate etc. as mineral compound.Also can make up two or more metals and use.Can obtain better catalyst effect by combination.Particularly organometallic compound provides catalyzer owing to easily make the gasification of this compound to Reaktionsofen, therefore is applicable to the CVD method.

The micropartical of above-mentioned metal or metallic compound both can directly use, and also these microparticals can be carried on inorganic carrier and use.As inorganic carrier, can enumerate aluminum oxide, zeolite, carbon, magnesium oxide, calcium oxide and aluminum phosphate etc.The particularly preferred high zeolite of thermotolerance.Preferably be used for the porous nickel of load in inorganic carrier, this aperture is preferably about 1nm.

The introduction method of catalyzer can adopt independent gasification process, mixes the method for back gasification with the carbon raw material, with the method for carrier gases dilute or be dissolved in the carbon raw material with any method in the method for liquid input etc.

(reaction conditions when carbon nanotube is synthetic)

During synthesizing carbon nanotubes, preferred reaction conditions is as follows: (a) about the residence time in the stove, the residence time of the carbon that is calculated by material budget is preferably 2～10 seconds, more preferably 5～10 seconds; (b) temperature is preferably 1000～1350 ℃, more preferably 1100～1250 ℃ in the stove; When (C) putting into catalyzer and material carbon compound in the stove, preferably be preheated to 300～450 ℃, more preferably be preheated to 330～400 ℃ scope, thereby drop into the gas shape; (d) carbon concentration in the furnace gas preferably is controlled at 1～20 capacity %, more preferably is controlled at 3～10 capacity %, further preferably is controlled at the scope of 5～9 capacity %; (e) lower limit set of preferred furnace pressure is about 98kPa, and the upper limit is set at 200kPa; (f) in the weight summation of carbon weight in above-mentioned synthesis material and the transition metal in the above-mentioned synthetic catalyst, transition metal weight is below the 3 weight %, be preferably 0.1～3 weight %, more preferably 0.1～0.8 weight %, more preferably 0.2～0.7 weight %.Moreover the lower limit of above-mentioned furnace pressure is essentially 98kPa, means as long as then there is not special problem in atmospheric environment.

And, by the carbon nanotube that obtains under the as above condition is carried out high-temperature heat treatment, thereby separate adsorbed hydrocarbons, and under higher temperature, heat-treat, promote crystalline to form thus.Preferably, finally obtain carbon nanotube by this pyroprocessing.

(g) carbon nanotube of the thick product of conduct that will obtain by the condition of above-mentioned (a)～(f) preferably at 1100～1500 ℃, is more preferably heat-treated 1300～1450 ℃ scope, isolates hydrocarbons; (h), at 2000～3000 ℃, preferably carry out high-temperature heat treatment, thereby promote crystalline to form 2500～3000 ℃ scope as next step.The condition of above-mentioned by satisfying (a)～(h) can stably be made carbon nanotube of the present invention with lower cost.

(about the constitutional features of carbon nanotube)

The number of plies that preferred carbon nanotube is a graphite linings is 1 layer, 2 layers or surpasses 2 layers multilayer.Be preferably the multilayer that surpasses more than 2 layers especially.The fiber of carbon nanotube directly is preferably 0.7～100nm, more preferably 7～100nm, more preferably 15～90nm.The aspect ratio of carbon nanotube is preferably more than 5, more preferably more than 100.Aspect ratio can be by with scanning electron microscope multiplying power 3～100,000 times measured length and diameter, and calculates its ratio and obtain.Moreover linear measure is to implement by the following method.At first, this view image is read in the ccd video camera as image data.Then use image analysis apparatus, this image data that obtains is calculated staple length.In addition, measuring radical is more than 5000.And the mensuration of diameter is finished by the following method.At first, in the image that obtains by electron microscope observation, randomly draw the carbon nanotube that to measure diameter, at position finding diameter near central part.In addition, if the cross section is non-circular, then with its maximum value as diameter.Calculate number average diameter from the measured value of obtaining.Nearest electron microscope possesses the function of calculating the length on this observation image, so this diameter also can calculate with comparalive ease.Measuring radical is more than 1000.

Distance in the carbon nanotube between the graphite linings (interlamellar spacing) can be the scope of 3.354～3.44nm, also can be the scope that surpasses 3.44nm.The upper limit of interlamellar spacing is preferably 3.65nm, more preferably 3.6nm.This interlamellar spacing preferably surpasses 3.44nm.Therefore, carbon nanotube of the present invention can so-called greying index be positive number and the carbon nanotube that has graphite-structure in fact both, also can be that the greying index is negative and the carbon nanotube with non-graphite multilayered structure.More preferably the greying index is the non-graphite multilayered structure of negative.

Carbon nanotube both can be that each layer of its graphite linings has the carbon nanotube of concentric structure in fact with respect to cylinder axis, also can be the carbon nanotube that the interval of this layer changes on fabric integer.The more preferably latter that on fabric integer, changes of interval of layer in the present invention.In addition, also can be the stacked structure of graphite linings to fibre axis inclination certain angle.In this case, its angle of inclination preferably is the scope of 25～35 degree with respect to medullary ray.

The carbon nanotube that the chirality (chirality) that preferred carbon nanotube is each layer makes up randomly, and, also can be in graphite linings, to have non-six-membered carbon ring structure.

The carbon black that uses as the B composition in the present invention can be enumerated known section qin carbon black, acetylene carbon black, oven process carbon black, dim, pyrolytic carbon black, channel black, cylinder carbon black (roll black), dish method carbon black etc.In these carbon blacks, preferred especially section qin carbon black, acetylene carbon black, oven process carbon black.

The dibutyl phthalate oil number of carbon black is preferably 100ml/100g～1000ml/100g, and more preferably 350ml/100g～600ml/100g is not particularly limited on raw material and manufacture method etc.Dibutyl phthalate oil number described here is the value of measuring according to the method for stipulating among the ASTM D2414-79, and its oil number is big more, and electroconductibility is just high more.In the electrical conductivity Carbon black of oil number less than 100ml/100g of dibutyl phthalate, must cooperate in a large number in order to obtain sufficient electroconductibility, its result can damage the physical strength of forming process and moulding resin, and is therefore not preferred.When the A composition was 100 weight parts, the content of conductive carbon compound (B composition) was 0.1～15 weight part, is preferably 1～12 weight part, more preferably 2～10 weight parts.If less than 0.1 weight part, poorly conductive then, if greater than 15 weight parts, the physical strength of forming process and resin combination can damaged, and is therefore not preferred.

(C composition: acid modified polyolefin class wax)

As the acid modified polyolefin wax of C composition of the present invention, be that to have with carboxyl, acid anhydride, sulfonic group, sulfino, phosphorous acid base and phosphonate group be the acid modified polyolefin class wax of the acidic-group of representative.

Preferred C composition of the present invention for having at least a acid modified polyolefin class wax in the above-mentioned illustrative acidic-group, is preferably the acid modified polyolefin class wax with carboxyl and/or acid anhydride especially.In acid modified polyolefin class wax, the concentration of this acidic-group is preferably the scope of 0.05～10meq/g, more preferably the scope of 0.1～6meq/g, the more preferably scope of 0.5～4meq/g.

As olefines wax, can enumerate paraffin, Microcrystalline Wax, Fischer-Tropsch process (Fischer-Tropsch) paraffin and the alpha-olefinic polymer etc. of paraffin class.

As in this acid modified polyolefin class wax in conjunction with the method for carboxyl class, can enumerate monomer and 'alpha '-olefin monomers polymeric method that (a) will have carboxyl; (b) with above-mentioned lubricant and compound or monomer combines or the method for copolymerization etc. with carboxyl.

In above-mentioned (a) method, except the radical polymerization of solution polymerization, emulsion polymerization, suspension polymerization, block polymerization etc., can also adopt living polymerization.And, also can adopt after forming macromonomer and carry out the polymeric method.The form of multipolymer can also be used alternating copolymer, segmented copolymer, tapered copolymer various forms of multipolymers such as (tapered copolymer) except nothing is returned multipolymer.In above-mentioned (b) method, can adopt as required and in acid modified polyolefin class wax, to add superoxide or 2,3-dimethyl-2, the free radical generating agent of 3-diphenyl butane (being commonly referred to as diisopropylbenzene(DIPB)) etc., and at high temperature react or the method for copolymerization.This method is to heat and the formation reaction active site method that compound of reaction or monomer are reacted at this active site in acid modified polyolefin class wax.As the additive method of the required active site of formation reaction, irradiation or the mechanochemical method that can enumerate by radioactive rays or electron rays etc. apply methods such as external force.And, but can also enumerate prior monomer methods in acid modified polyolefin class wax by the required active site of copolymerization preparation formation reaction.As being used for the reactive activity point, can enumerate unsaturated link(age) and peroxidation key etc., and as the method that obtains active site, can enumerate with TEMPO is the nitroxyl free radical polymerization of representative.

As above-mentioned compound or monomer with carboxyl, but exemplified by acrylic, methacrylic acid, toxilic acid, fumaric acid, maleic anhydride and citraconic anhydride etc., preferred especially maleic anhydride.

More preferably adopt in acid modified polyolefin class wax as the C composition, contain the carboxyl series lubricant agent with respect to 1g, with the carboxyl class preferably contain 0.05～10meq/g scope, more preferably contain 0.1～6meq/g scope, further preferably contain the olefines wax that contains the carboxyl class of 0.5～4meq/g scope.And the molecular weight of olefines wax is preferably 1 * 10 ³～1 * 10 ⁴, more preferably 5 * 10 ³～1 * 10 ⁴In addition, this molecular weight is to be the weight-average molecular weight that benchmark calculates with the working curve that obtained by the polystyrene standard among the GPC (gel permeation chromatography).

As the multipolymer of can be further preferred alpha-olefin of C composition and maleic anhydride, particularly preferably in the multipolymer that satisfies above-mentioned carboxyl-content ratio and molecular weight requirement in this multipolymer.This multipolymer can be made by common melt polymerization that carries out under the free radical catalyst condition or mass polymerization.Here, it is 10～60 alpha-olefin that alpha-olefin can preferably be enumerated when carbonatoms is represented with mean value, be 16～60 alpha-olefin when more preferably carbonatoms is represented with mean value, further preferred carbonatoms is 25～55 alpha-olefin when representing with mean value.

With respect to the polycarbonate resin (A composition) of 100 weight parts, the content of acid modified polyolefin class wax (C composition) is 0.01～1 weight part, is preferably 0.05～1 weight part, more preferably 0.1～0.5 weight part.When the content of acid modified polyolefin class wax (C composition) is in this scope, can keep the high thermostability that dissolves, can obtain to have the moulding product of good electrical conductivity.

(D composition: Phosphorus stablizer)

Resin combination of the present invention further preferably contains Phosphorus stablizer.This Phosphorus stablizer can during fabrication or improve thermostability greatly when forming process.Its result can improve mechanical characteristics, color and luster and forming stability.As this Phosphorus stablizer, but illustration phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.Wherein, preferred especially phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids, three organophosphorus compoundss and phosphate ester acid compound, it more preferably in the Phosphorus stablizer of 100 weight % the Phosphorus stablizer of phosphate compound and/or person's bi-ester of phosphite, being the Phosphorus stablizer of trialkyl phosphates and/or person's phosphate ester acid compound more than 50% in the Phosphorus stablizer of 100 weight % preferably further, most preferably is the Phosphorus stablizer of trialkyl phosphates more than the 50 weight % in the Phosphorus stablizer of 100 weight %.

Moreover the organic radical in the phosphate ester acid compound comprises any kind in monosubstitution, double-basis replacement and their mixture.In the following illustrative compound corresponding, comprise any kind too with this compound.

As three organophosphorus compoundss, can the illustration trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, three (dodecyl) phosphoric acid ester, three Tryfac 5573s, three stearyl-phosphoric acid ester, Tritolyl Phosphate, triphenylphosphate, trichloro-benzene base phosphoric acid ester, diphenylmethyl phenyl phosphate ester, the adjacent xenyl phosphoric acid ester of phenylbenzene list and three butoxyethyl group phosphoric acid ester etc.Wherein, preferred trialkyl phosphates.The carbonatoms of the alkyl of this trialkyl phosphates is preferably 1～22, and more preferably 1～4.Particularly preferred trialkyl phosphates is a trimethyl phosphite 99.

As the phosphate ester acid compound, but illustration acid methyl orthophosphoric acid, acid phosphate ester, acid butyl phosphate, acid phosphoric acid (butoxyethyl group) ester, acid octyl phosphate, acid phosphoric acid ester in the last of the ten Heavenly stems, acid lauryl phosphate, acid phosphoric acid stearyl ester, acid phosphoric acid oil alkene ester, acid phosphoric acid mountain Yu ester, acid phosphoric acid phenylester, acid phosphoric acid nonyl phenylester, acid phosphoric acid cyclohexyl, acid phosphoric acid ethyl phenoxy, acid phosphoric acid alkoxyl group macrogol ester and dihydroxyphenyl propane phosphate ester acid etc.Wherein, because the carbonatoms of alkyl is 10 or more, more preferably 14～22 long-chain dialkyl group phosphate ester acid helps the raising of thermostability, and the stability of this phosphate ester acid self is high, therefore preferably.

As other bi-ester of phosphite, trialkyl phosphite that can illustration three decyl phosphorous acid esters etc.; The dialkyl group list aromatic yl phosphite of didecyl list phenyl phosphites etc.; The monoalkyl diaryl phosphorous acid ester of monobutyl phenylbenzene phosphorous acid ester etc.; The triarylphosphite of triphenyl phosphorous acid ester and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester etc.; Distearyl acyl group pentaerythritol diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, the 4-dicumylphenyl) pentaerythritol phosphite of pentaerythritol diphosphites and two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites etc.; 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester and 2, the cyclic phosphites of 2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester etc.

As phosphinate compound, but preferred illustration four (di-tert-butyl-phenyl)-diphenylene two phosphinates and two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-diphenylene two phosphinates and two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite ester.This phosphinate compound can have the bi-ester of phosphite and the usefulness of two above substituted aryls with abovementioned alkyl, and preferably adopts this mode.

As phosphonate compound, can illustration phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.As tertiary phosphine, can the illustration triphenylphosphine etc.

With the polycarbonate resin (A composition) of 100 weight parts during as benchmark, content 0.0001～2 weight part of preferred Phosphorus stablizer, more preferably 0.01～1 weight part, more preferably 0.05～0.5 weight part.

(other parts)

In resin combination of the present invention, can also cooperate various additives, reinforcer and other the polymkeric substance etc. that are engaged in usually in the polycarbonate.

(other polymkeric substance or elastomerics)

Resin combination of the present invention can also cooperate other polymkeric substance or elastomerics in keeping the scope of effect of the present invention.As the benchmark of this scope, with respect to the A composition of 100 weight parts, other polymkeric substance or elastomeric total amount are below 200 weight parts, are preferably below 100 weight parts, more preferably below 50 weight parts, are preferably especially below 30 weight parts.

As these other polymkeric substance, can the illustration polyphenylene oxide, the polyolefine of polyacetal, aromatic polyester, aliphatic polyester, polymeric amide, polyarylester (the brilliant polyarylester of amorphism, liquid crystal liquid crystal property polyarylester), polyether-ether-ketone, polyetherimide, polysulfones, polyethersulfone, polyphenylene sulfides, polyethylene, polypropylene, poly--4-methyl amyl-1 and cyclic polyolefin etc.; Acrylic polymers such as styrenic polymer, polymethylmethacrylate etc.

And, as elastomerics, but thermoplastic elastomers such as illustration olefin type elastomer, acrylic elastomer, polyester elastomer, polyamide-based elastomerics and polyurethanes elastomerics.Be further used as elastomerics, can also be illustrated in the rubber mass graft copolymer that combines grafted chain on the rubber matrix.This rubber matrix, for having caoutchouc elasticity, and its vitrifying tansition temperature be below 10 ℃, be preferably below-10 ℃, the polymkeric substance of the grafting trunk that becomes graft copolymer (グラ Off ト Dry) below more preferably-30 ℃.As this rubber matrix, but illustration polyhutadiene, polyisoprene; The multipolymer of the multipolymer of the random copolymers of styrene butadiene or segmented copolymer, acrylonitrile butadiene copolymer, alkyl acrylate or alkyl methacrylate and divinyl, ethene and alpha-olefin; The multipolymer of ethene and esters of unsaturated carboxylic acids; The multipolymer of ethene and aliphatic ethylene; The non-conjugated diene polymkeric substance of ethene and propylene, acrylic rubber and silicon class rubber etc.As the monomer of the grafted chain of derived rubber matter graft copolymer, but illustration aromatic ethylene compound, vinyl cyanide compound, acrylate and different methacrylic ester etc.As the object lesson of rubber mass graft copolymer, can enumerate SB (styrene butadiene) multipolymer, ABS (acrylonitrile-butadiene-styrene (ABS)) multipolymer, MBS (methyl methacrylate-butadiene-styrene) multipolymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene (ABS)) multipolymer, MB (methyl methacrylate-divinyl) multipolymer, ASA (acrylonitrile-styrene-acrylic rubber) multipolymer, AES (vinyl cyanide-ethylene propylene rubber-vinylbenzene) multipolymer, MA (methyl methacrylate-acrylic rubber) multipolymer, MAS (methyl methacrylate-acrylic rubber-vinylbenzene) multipolymer, methyl methacrylate-acrylate-butadiene rubber multipolymer, methyl methacrylate-vinylformic acid butadiene type rubber-styrene multipolymer and methyl methacrylate-(silicon Acrylote IPN rubber) multipolymer etc.In the rubber mass graft copolymer of 100 weight %, rubber matrix is more than the 40 weight %, is preferably more than the 50 weight %, more preferably the scope of 55～85 weight %.

In addition, as above-mentioned styrenic polymer, can illustration polystyrene (PS) (comprising syndiotactic polystyrene), AS (acrylonitrile-styrene) multipolymer, MS (methyl methacrylate-vinylbenzene) multipolymer and SMA (phenylethylene-maleic anhydride) multipolymer etc.Styrenic polymer can utilize in advance and carry out incorporate mixture with above-mentioned rubber mass graft copolymer.For example, as the commercially available AS multipolymer and the mixture of Acrylonitrile Butadiene, can utilize commercially available ABS resin.And this multipolymer comprises so-called transparent ABS resin.Styrenic polymer also can be by being the various functional group modification of representative with epoxy group(ing) and anhydride group etc.These styrenic polymers also can mix two or more uses.

As aromatic polyester, except using polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, poly-2,6-(ethylene naphthalate) (PEN), PBN (PEN), PBN (PBN), poly-1, two (phenoxy group) alkyl-4 of 2-, outside 4 '-dicarboxylic acid glycol ester etc., can also use polyethylene terephthalate (so-called PET-G) with the 1,4 cyclohexane dimethanol copolymerization, polyethylene glycol isophthalate/polyethylene terephthalate, the polyester copolymer of polybutylene terephthalate/polyethylene glycol isophthalate etc.Wherein, preferred PET, PBT, PEN and PBN.Above-mentioned aromatic polyester can use in two or more mixing.In addition, these aromatic polyesters also can be with from the unit of other aromatic dicarboxylic acids or from other the unit of glycol 50 moles of scopes below the %, preferably at the scope of 1～30 mole of % polyester copolymer of copolymerization in addition.Molecular weight to aromatic polyester has no particular limits, but with ortho chloro phenol as solvent, and be 0.4～1.2 35 ℃ of intrinsic viscosities of measuring down, be preferably 0.5～1.15.

(packing material)

Can cooperate in the resin combination of the present invention as strengthening weighting agent by known various packing materials.As this packing material, can use various fibrous packing materials, tabular packing material, reach granular packing material.Here, the shape of fibrous packing material is fibrous (comprising the shape that bar-shaped arbitrarily, needle-like or its axial a plurality of directions are extended), being shaped as of tabular packing material tabular (comprising has concavo-convex, plate that shapes such as knee are arranged on its surface).Granular packing material is to comprise packing material erose, except that above shape.

Above-mentioned fibrous and tabular etc. shape can determine by visual inspection as a rule, still, for example as and so-called difference between irregularly shaped, aspect ratio be more than 3 just be called fibrous or tabular etc.

As tabular packing material, preferably can the illustration sheet glass, talcum, mica, kaolin, tinsel, carbon plate and graphite, and on the surface of these weighting agents, be coated with the tabular packing material etc. of foreign material such as metal or metal oxide for example.Its particle diameter is preferably the scope of 0.1～300 μ m.This particle diameter, zone at less than 10 μ m, be meant the value of the mid-diameter (D50) of the size distribution of measuring by the X ray penetrant method of one of liquid phase settling process, and in the zone of 10～50 μ m, then refer to value by the mid-diameter (D50) of the size distribution of laser diffraction, scattering method, in addition, in 50～300 μ m zones, then refer to the diameter value of measuring by the oscillatory type sieve method.This particle diameter is the particle diameter in the resin combination.Tabular packing material, can be that coupler by various silicane, metatitanic acid salt, aluminate class and zirconic acid salt etc. carries out surface-treated weighting agent, can also be to carry out boundling by various resins such as olefine kind resin, styrene resin, acrylic resin, polyester resin, redix and polyurethanes resin or high-grade aliphatic ester etc. to handle, perhaps carry out the granulation thing that overdraft is handled.

Fibrous packing material, its Fibre diameter is preferably the scope of 0.1～20 μ m.The upper limit of Fibre diameter is preferably 13 μ m, more preferably 10 μ m.On the other hand, the lower limit of Fibre diameter is preferably 1 μ m.

Here said Fibre diameter is meant the number average Fibre diameter.This number average Fibre diameter is by utilizing sem observation that the moulding product are dissolved in solvent or decompose the residue that obtains behind the resin, and the ash residue obtained and value that the image calculation that obtains is come out with basic cpd after crucible carries out ashing.

As this fibrous packing material, but illustration is with fibrous inorganic filling materials such as glass fibre, glass milled fiber, carbon fiber, carbon milled fiber, steel fiber, asbestos, rock wool, ceramic fiber, slag staple fibre, potassium titanate crystal whisker, boron whisker, aluminium borate whisker, calcium carbonate crystal whisker, titanium oxide whisker, wollastonite, xonotlite, polygorskite (attapulgite) and sepiolites; Kevlar, polyimide fiber and polybenzothiozole fiber etc. be the fibrous heat-resisting organic filler material of representative with the heatproof organic fiber; And the fibrous packing material of the foreign material of metal or metal oxide etc. for example of on the surface of these packing materials, being covered etc.As at the surface-coated packing material of foreign material, but illustration metallic coating glass fibre, metallic coating sheet glass, titania coating sheet glass and metallic coating carbon fiber etc.As the surface method that is covered with foreign material, be not particularly limited, can enumerate various as is well known electrochemical plating (for example, metallide, plated by electroless plating, fusion plating etc.), vacuum vapour deposition, ion plating, CVD method (for example hot CVD, MOCVD, plasma CVD etc.), PVD method and sputtering method etc.

Here, fibrous packing material be meant aspect ratio be more than 3, be preferably more than 5, the more preferably fibrous packing material more than 10.Be limited to about 10000 on the aspect ratio, be preferably 200.The aspect ratio of this packing material is the value in resin combination.Fibrous packing material can with above-mentioned tabular packing material similarly, by surface-treated, also can be carried out boundling and be handled by various resins etc. by various couplers, can also be by processed compressed and granulationization.

When being benchmark with the A composition of 100 weight parts, the content of this packing material is below 200 weight parts, is preferably below 100 weight parts, more preferably below 50 weight parts, is preferably especially below 30 weight parts.

(releasing agent)

In the resin combination among the present invention, can cooperate remover as required.As a rule, require the resin combination among the present invention to have high dimensional accuracy.Therefore, the preferred resin composition has good release property.As this releasing agent, can use known releasing agent.For example, can enumerate polyunsaturated fatty acid ester, unsaturated fatty acid ester, polyalkenes wax (polyethylene wax, 1-alkene polybutadiene homopolymer etc. also can use sour modification etc. by the compound modified wax that contains functional group), silicon compound, fluorine cpd (with the fluorocarbon oil of poly-fluoroalkyl ether), paraffin and beeswax etc. as representative.In the resin combination of 100 weight %, preferably the use level of this remover is 0.005～2 weight %.

Fatty acid ester of the present invention can be any kind in part ester and the full ester (full ester).In lipid acid, preferred acid number be (can get 0 in fact) below 20, hydroxyl value is that 0.1～30 scope, iodine number are (can get 0 in fact) below 10.These characteristics can be obtained according to the method for regulation among the JIS K 0070.

(Hinered phenols stablizer and other antioxidant)

The Hinered phenols stablizer has the resistant to heat aging effect that prevents resin combination.Owing under hot environment, use resin combination of the present invention sometimes, therefore, be particularly suitable for cooperating the Hinered phenols stablizer in this case.As the Hinered phenols stablizer, but illustration octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, 3,9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] undecane, N, N '-hexa-methylene two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene and four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These all are easy to obtain.Wherein, preferred octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester.

And, also can use above-mentioned Hinered phenols stablizer other antioxidants in addition.As these other antioxidant; for example can enumerate with 3-hydroxyl-5; the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol is lactone stablizer (detailed content of this stablizer has been recorded in the flat 7-233160 communique of TOHKEMY), tetramethylolmethane four (3-thiohydracrylic acid fat), tetramethylolmethane four (3-dodecyl thiopropionate) and the glycerol-sulfur-bearing class stablizer such as 3-octadecanoyl thiopropionate of representative.Above-mentioned Hinered phenols stablizer both may be used singly or in combination of two or more and used.With respect to the resin combination of 100 weight %, the content of these stablizers is preferably 0.0001～1 weight %, more preferably 0.005～0.5 weight %.

(hydrolysis activator)

Because resin combination of the present invention is utilized under hot environment sometimes, therefore, requires it is carried out the improvement of hydrolytic resistance sometimes.In this case, can be in the scope of not damaging the object of the invention, cooperate hydrolysis activator as polycarbonate resin by known compound.As this compound, can the illustration epoxy compounds, trimethylene oxide (オキセ Application) compound, silane compound and phosphinic acid compounds etc., preferred especially epoxy compounds and trimethylene oxide cyclic cpds.As epoxy compounds, but illustration with 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters are the alicyclic epoxy compound of representative and are the epoxy compounds of the silicon atoms of representative with 3-glycidyl propoxy--three ethoxy silane.In the resin combination of 100 weight %, the content of this hydrolysis activator is preferably below the 1 weight %.

(UV light absorber)

When requiring resin combination of the present invention to have the improvement of weathering resistance or ultraviolet-absorbing, preferably cooperate UV light absorber.As UV light absorber, but illustration benzophenone compound, benzotriazole compound, hydroxyphenyltriazinuv compounds, cyclic imide base ester compound and cyanoacrylate compound etc.More particularly; but illustration 2-(2H-benzotriazole-2-yl)-p-cresol; 2-(2H-benzotriazole-2-yl)-4-(1; 1; 3; the 3-tetramethyl butyl) phenol; 2-(2H-benzotriazole-2-yl)-4; two (1-methyl isophthalic acid-phenylethyl) phenol of 6-; 2-[5-chloro (2H)-benzotriazole-2-yl]-4-methyl-6-tert butyl phenol; 2; 2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(1,1,3; the 3-tetramethyl butyl) phenol]; 2-(4; 6-phenylbenzene-1,3,5-triazines-2-yl)-and the 5-[(hexyl) oxygen] phenol; 2; 2 '-TOPOT 2,2 (3; 1-benzoxazine-4-ketone) and 1,3-two-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen]-2; 2-pair-{ [(2-cyano group-3,3-diphenylprop enoyl-) oxygen] methyl } propane etc.Further, also can use with the photostabilizer for the hindered amines of representative such as two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate.In the resin combination of 100 weight %, preferably the use level of this UV light absorber, photostabilizer is 0.01～5 weight %.

(static inhibitor)

In resin combination of the present invention, also can and use static inhibitor.As described static inhibitor, for example can enumerate polyether ester amides, glyceryl monostearate, the high condenses alkali of naphthalenesulfonateformaldehyde formaldehyde (alkali earths) metal-salt, Witco 1298 Soft Acid alkali (alkali earths) metal-salt, Witco 1298 Soft Acid amine salt, ten dialkyl benzene sulfonic acid phosphonium salts, maleic anhydride direactive glyceride and maleic anhydride two glyceryl ester etc.In the resin combination of 100 weight %, the content of described static inhibitor is preferably 0.5～20 weight %.

(other supplementary components)

Except above-mentioned, in the resin combination of the present invention, can also cooperate lubricant (for example PTFE particle and High molecular weight polyethylene particle etc.), tinting material (for example pigment of carbon black and titanium oxide etc. and dyestuff), mineral-type fluor (for example being the fluor of parent crystal) with aluminate, inorganic or organic antibacterial agent, photochemical catalysis class stain control agent (micropartical titanium oxide and micropartical zinc oxide etc.), infrared absorbent (ATO micropartical, the ITO micropartical, the lanthanum boride micropartical, tungsten boride micropartical and phthalocyanines metal complex etc.), photochromic agent and white dyes etc.

(manufacturing of resin combination)

When making resin combination of the present invention, its manufacture method is had no particular limits.But, preferably use biaxial extruder to A composition～D composition and other compositions melting mixing in addition.

As the example of the representative of biaxial extruder, can enumerate ZSK (trade(brand)name, Werner ﹠amp; Pfleiderer society makes).As the concrete example of same model, can enumerate TEX (trade(brand)name, (strain) JSW makes), TEM (trade(brand)name, toshiba machine (strain) is made), KTX (trade(brand)name, the manufacturing of (strain) Kobe Steel) etc.In addition, as object lesson, can also enumerate the melting mixing machine of FCM (trade(brand)name, Farrel society makes), Ko-Kneader (trade(brand)name, Buss society makes) and DSM (trade(brand)name, Krauss-Maffei society makes) etc.In above-mentioned, preferably be the model of representative with ZSK.In the biaxial extruder of described ZSK model, its screw rod is complete meshing type, and screw rod is made of length various screw portions and the different various kneading disks (perhaps suitable with it the mixing part of using) of width different with spacing.

In biaxial extruder, preferred mode is as described below.Promptly, the screw rod shape can adopt the screw-type screw rod (ネジス Network リユ one) of single thread, double thread and triple thread, preferably especially uses the transporting power of molten resin or shears all wide double thread screw rod of the two aspect scope of applications of mixing ability.In biaxial extruder, the ratio (L/D) of spiro rod length (L) and diameter (D) is preferably 20-50, more preferably 28-42.The L/D value is big more, and the uniform dispersion state of easy more formation when bullet is too big, then produces the decomposition of resin easily because of thermal ageing.Screw rod must have more than one mixing district, preferably has 1～3, and wherein, described mixing district is by kneading disk part (perhaps suitable with it the mixing part) formation that is used to improve mixing property.

As forcing machine, the preferred forcing machine that uses the venting port of the volatilization gas that has the moisture that can slough in the raw material or produce by the melting mixing resin.Preferably be provided with the moisture that will be produced and volatilization gas are discharged to the forcing machine outside effectively from venting port vacuum pump.In addition, in order to improve the dispersiveness of CNT (carbon nano-tube), perhaps, also can add water, organic solvent and supercutical fluid etc. in order to remove the impurity in the resin combination as far as possible.Further, the zone before forcing machine mould portion is provided with and is used to remove the filtering net of sneaking into extruding impurities in raw materials etc., impurity can be removed from resin combination thus.As described filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.

To with B composition～C composition, arbitrarily D composition and other additives (abbreviating additive as in the following example) there is no particular limitation to method that forcing machine is supplied with, but, can enumerate following method: the method that (i) additive and polycarbonate resin is fed to independently forcing machine respectively as its representative example; (ii) adopt the mixing machine of super mixing machine etc., in advance additive and polycarbonate resin powder are carried out pre-mixing after, resupply the method for forcing machine; (iii) in advance additive and polycarbonate resin are carried out melting mixing, make the method for host grain (マス one ペレ Star ト).

Aforesaid method is the method that resupplies forcing machine behind the required whole starting material of pre-mixing one of (ii).In addition, other method is to make the host (マス one drug) that high density ground is combined with additive, this host is further carried out pre-mixing individually or with remaining polycarbonate resin etc. after, the method for supply forcing machine.In addition, this host can be selected arbitrary shape Powdered and that this powder is compressed granulation etc.In addition,, for example can enumerate nauta mixer, V-mixer, Henschel mixer, chemomotive force device and extrude mixing machine etc., the mixing machine of the high-speed stirring type of preferred Henschel mixer etc. as other pre-blend approach.Further, the blending means that other are pre-for example is that polycarbonate resin and additive are dispersed in solvent and after disposing solution, remove the method for this solvent.

By the resin that biaxial extruder is extruded, can directly cut off and carry out granulating, perhaps form strand after, described strand is cut into particulate with tablets press.In addition, when needs reduce outsidely during as the influencing of dust etc., preferably purify the environmental gas around the forcing machine.Further, in described particulate is made, can be used on CD with the whole bag of tricks that has proposed in the polycarbonate resin, suitably carry out stricturization that particulate form distributes, minimizing, transportation that mistake is cut off thing (ミスカ Star ト thing) or the minimizing of the bubble (bubbles of vacuum) that the minimizing of the micro powder that produces when carrying and strand or granule interior produce.By these prescriptions, the ratio that can make the height circulationization of moulding and reduce the bad phenomenon generation of silver-colored spot etc.Coating of particles can be the general shape of cylindrical, corner post shape, sphere etc. in addition, but pref. cylindrical.The diameter of described cylinder is preferably 1～5mm, more preferably 1.5～4mm, further preferred 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, 2～5mm, more preferably 2.5～3.5 more preferably.

(preferable production process of resin combination)

As mentioned above,, can provide a kind of manufacture method, it is characterized in that,, mix B composition, the C composition of 0.01～1 weight part and the composition of D arbitrarily of 0.0001～2 weight part of 0.1～15 weight part with respect to the A composition of 100 weight parts according to the present invention.The detailed description of the A composition that utilizes in the described manufacture method, B composition, C composition and D composition as mentioned above.In the described mixing,, most preferably use the exhaust biaxial extruder as illustration in the manufacture method of resin combination.In described melting mixing, barrel temperature is preferably set to 250～320 ℃, more preferably is set at 270～310 ℃, and the screw rod revolution is preferably set to 60～500rpm, more preferably is set at 70～200rpm.

(about the moulding product that form by resin combination of the present invention)

The resin combination of the present invention that obtains as mentioned above can produce various products by the particle of making is as mentioned above carried out injection molding usually.And, also can be without granulation, with biaxial extruder directly with the resin manufacture slabbing behind the melting mixing, film like, special-shaped extrusion molding article, blowing (direct blow) moulding product and injection-molded article.In above-mentioned injection molding, not only can adopt common forming method, can also be according to purpose, suitably adopt injection compression molding, injection pressure moulding, air-auxiliary injection forming, foaming (comprising moulding), insert moulding by the injection of supercutical fluid, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, the injection moulding of heating cooling mould molding, dual-color forming, interlayer moulding and ultra-high speed injection molding etc. rapidly, thereby obtain the moulding product.The advantage of these various forming methods is all known.In addition, moulding can be selected any in cold runner mode and the hot runner mode.Even more preferably injection compression molding and injection pressure moulding that also can moulding under low injection speed.

In addition, resin combination of the present invention also can become forms such as various special-shaped extrusion molding articles, sheet, film like and be used by extrusion moulding.In addition, in sheet, film like moulding, can also use blow moulding, rolling process, casting etc.And, by implementing specific extension operation, also can be shaped to heat-shrinkable tube.In addition, also can resin combination of the present invention be manufactured the moulding product by rotoforming or blow molding etc.

And, to the moulding product that form by resin combination of the present invention, can carry out various surface treatments.In this said surface treatment, be meant that the surface at synthetic resin of evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (electric plating, plated by electroless plating, fusion plating etc.), application, coating, printing etc. forms the processing of new coating, can use the method that is generally used in the resin.As surface treatment, can enumerate the various surface treatments of hard coat, hydrophobic oleophobic coating, ultraviolet radiation absorption coating, infrared ray absorption coating, metallic coating (evaporation etc.) etc. particularly.

The inventor thinks preferred forms of the present invention, is the gathering of preferable range of above-mentioned each key element, for example, and with its typical example record in the following embodiments.But the present invention is not limited to these embodiments.

Embodiment

Below, be further detailed for embodiment, but the present invention is not limited to this.In addition, as evaluation, implemented following project.

(I) assessment item

(I-1) surface resistivity

At barrel temperature is that 300 ℃, die temperature are that 80 ℃, injection speed are that 20mm/ second and shaping cycle are under the about 60 seconds condition, comes the gusset of forming width 45mm * length 80mm * thickness 2mm by injection molding.Extract the 2nd, 4,6,8 and the 10th times the molding that begins after the washing out, and be that 23 ℃, relative humidity are under 50% the environment in temperature, place after 24 hours, with electronic isolation meter (East Asia electric wave industry (strain) manufacturing) and ohmer (Mitsubishi Chemical's (strain) manufacturing), measure the surface resistivity of described 5 gussets, calculate its mean value.In addition, 1.0 * 10 ¹⁴The following surface resistivity of Ω is set at well.

(I-2) melting heat stability

Under 30 seconds condition of shaping cycle, come the gusset of forming width 45mm * length 80mm * thickness 2mm with injection molding.Pulverize this moulding product, measure viscosity-average molecular weight with method described herein.On the other hand, by under 600 seconds condition of forming period, carrying out moulding, and use the same method and measure viscosity-average molecular weight after pulverizing by injection molding.Represent with described shaping cycle to be that the molecular weight of 30 seconds moulding product is 600 seconds a molecular weight as 100% o'clock forming period with per-cent, and estimate as the molecular weight conservation rate.Described molecular weight conservation rate is high more, illustrates that melting heat stability is good more.

(I-3) tension fracture elongation rate

Measure tension fracture elongation rate according to ISO527-1 and 527-2.Test piece is shaped as length 175mm * width 10mm * thick 4mm.With above-mentioned mean value of similarly calculating 5 kinds of samples.In addition, trial speed is that the 5mm/ branch is planted.

(II) manufacturing of resin combination and molding

In such a way, manufacturing is by the resin combination of the cooperation composition of proportions of record in the table.In addition, in the content ratio of in table, putting down in writing,, put down in writing the nt wt net weight of carbon CNT (carbon nano-tube) for the B-1 composition.In addition, illustrate according to the symbol in the following table and carry out.The composition of record in the table is obtained mixture with the V-Mixer mixing.In addition, about the minor amounts of additives beyond the PC, then making additive level with super mixing machine is the premixture of 10 weight %.Should a plurality of premixtures and PC one reinstate V-Mixer and mix.

With screw diameter is the exhaust biaxial extruder (ベ Application ト Shi Er Shaft Ya Chu Machine) (TEX-30XSST, JSW's (strain) makes) of 30mm, will be supplied to aftermost first input port by V-Mixer blended mixture.This forcing machine has the mixing region by kneading disk between first supplying opening to the second supplying opening, directly be provided with open venting port thereafter.The length of venting port is about 2D with respect to screw diameter (D).Behind this venting port, be provided with the side feeder, behind the side feeder, further be provided with venting port by mixing zone and this mixing zone of continuing of kneading disk.The venting port length of this part is about 1.5D, and uses vacuum pump that this part is decompressed to about 3kPa.Extrude is to be that 250～300 ℃ of (roughly rising equably from the cylinder of screw rod root to mould), screw rod revolutions are that 180rpm and extrusion capacity hourly are to carry out under the condition of 20kg at barrel temperature.After the monofilament of extruding cooled off in water-bath, cut off and carry out granulating with tablets press.

With the heated air circulation type drying machine under 120 ℃ to resulting granules after dry 5 hours, use injection moulding machine, be that 280 ℃, die temperature are that 80 ℃, injection speed are that 20mm/sec and shaping cycle are about under 60 seconds the condition all, make the test piece that above-mentioned assessment item is used at barrel temperature.

The starting material that use in the foregoing description and comparative example are as described below.

(A composition: polycarbonate resin)

A-1: the straight chain shape aromatic polycarbonate toner of viscosity-average molecular weight 22500 (パ Application ライト L-1225WP (trade(brand)name), Supreme Being people change into (strain) and make)

(B composition: the conductive carbon compound)

B-1: diameter 20nm, the aspect ratio CNT (carbon nano-tube) concentration more than 5 is that the carbon nanotube of 15 weight % mixes with enriched material (carbon nanotube マス one MB6015-00 (trade(brand)name), (manufacturing of Hyperion society)

B-2: dibutyl phthalate is the electrical conductivity Carbon black (KETJENBLACK EC-600JD (trade(brand)name), KETJENBLACK international society makes) of 495ml/100g to oil mass

(C composition: modified polyolefin class wax)

C-1: the polyolefins wax that the copolymerization by alpha-olefin and maleic anhydride obtains (ダイヤカ Le Na 30M (trade(brand)name), Mitsubishi Chemical's (strain) makes)

(D composition: Phosphorus stablizer)

D-1: trimethyl phosphite 99 (TMP (trade(brand)name), big eight chemical industry (strain) are made)

D-2: distearyl acyl group pentaerythritol diphosphites (アデカス Block PEP-8 (trade(brand)name), rising sun electrochemical industry (strain) is made)

Table 1

Table 1 (continuation)

By on show really as can be known, according to the present invention, can improve the deformation characteristic of the tension fracture elongation rate etc. of the resin combination that forms by PC and CNT, thus, can obtain having both the resin combination of these characteristics and good electrical conductivity.

Utilizability on the industry

Resin combination of the present invention can corresponding wide region condition of molding, and the anti-crackle of its moulding Excellence is so can provide conductive material applicable to the wide region purposes. As described purposes, example As enumerating computer, laptop computer, game machine (home-use game machine, business game machine, bullet Pearl game machine and slot machine etc.), display unit (LCD, organic EL, Electronic Paper, etc. from Sub-display and projector etc.), send electric parts (housing of line of induction ring type power transmission device is representative). In addition, can also exemplify printer, duplicator, scanning machine and facsimile machine (compounding machine that contains them). As described purposes, can also enumerate VTR camera, optically thin membrane type camera, digital camera, camera Precision instrument with lens unit, preventing device and mobile phone etc. Especially, resin group of the present invention Compound be suitable for the digital image information processors such as camera lens barrel, digital camera framework, cover and On the framework.

Further, resin combination of the present invention also is applicable to the medical treatment of massager or high oxygen therapy unit etc. Machine; The family expenses of video recorder (so-called DVD burner etc.), sound machine and electronic musical instrument etc. Electric equipment products; The game device of Ball paddle device and slot machine game etc.; And carried sophisticated sensor On the parts of home-use automatics etc.

In addition, resin combination of the present invention can be used in various vehicle parts, battery, TRT, The casting mold of circuit substrate, integrated circuit, optic disc base board, cartridge, light-card, IC storage card, connection Device, cable coupler, transporting of electronic unit are used container (IC box for feeding odd, silicon wafer container, glass-based Plate accepting container and belt carrier etc.), antistatic with or except electric parts (the electronic photo photosensitive device Charged roller etc.) and various mechanism part (gear, turntable, rotor and screw etc. contain micromachine Use mechanism part) on.

Therefore, resin combination of the present invention is in the various industry in OA mechanical field, electric mechanical field etc. Exceedingly useful in the purposes, its industrial effect that reaches is very excellent.

Claims

1. conductive resin composition, it is characterized in that, with respect to the polycarbonate resin as the A composition of 100 weight parts, contain the conductive carbon compound as the B composition of 0.1～15 weight part, and the acid modified polyolefin class wax as the C composition of 0.01～1 weight part.

2. conductive resin composition according to claim 1 is characterized in that, with respect to the A composition of 100 weight parts, contains the Phosphorus stablizer as the D composition of 0.0001～2 weight part.

3. conductive resin composition according to claim 1 and 2 is characterized in that, described B composition is carbon black or carbon nanotube.

4. conductive resin composition according to claim 3, it is characterized in that, described B composition is that dibutyl phthalate is the carbon black of 100ml/100g～1000ml/100g to oil mass, or diameter is that 0.7nm～100nm and aspect ratio are the carbon nanotube more than 5.

5. according to each described conductive resin composition in the claim 1～4, it is characterized in that described C composition is the acid modified polyolefin class wax with carboxyl and/or carboxylic acid anhydride.

6. according to each described conductive resin composition in the claim 1～5, it is characterized in that described C composition is the multipolymer of maleic anhydride and alpha-olefin.

7. according to each described conductive resin composition in the claim 2～6, it is characterized in that described D composition is the above Phosphorus stablizer for phosphate compound and/or person's bi-ester of phosphite of 50 weight % of this D composition.

8. conductive resin composition according to claim 7 is characterized in that, described D composition is that 50 weight % of this D composition are above is the Phosphorus stablizer of trialkyl phosphates.