CN101333338B

CN101333338B - Thermoplastic resin composition with stable conductivity

Info

Publication number: CN101333338B
Application number: CN2008101288966A
Authority: CN
Inventors: 井野庆一郎; 近藤史崇
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2007-06-25
Filing date: 2008-06-24
Publication date: 2012-06-13
Anticipated expiration: 2028-06-24
Also published as: JP2009001740A; CN101333338A

Abstract

The objective of the invention is to provide an electrical conductivity resin polymer which improves offset of electricity conductive performance. The invention provides an electrical conductivity resin compound which is characterized in that the compound contains A component of thermoplastic resin besides aromatic polyester resin, B component of nano carbon tubes and C component of aromatic polyester resin, wherein relative to 100 portions by weight of A component of thermoplastic resin besides aromatic polyester resin, the compound contains 0.1-15 portions by weight of B component, 0.1-4 portions by weight of C component.

Description

The thermoplastic resin composition of stable conductivity

Technical field

The present invention relates to a kind of resin combination that contains thermoplastic resin and carbon nanotube.More particularly, relate to a kind of have the good deformation characteristic that thermoplastic resin has and the resin combination of excellent electric conductivity.

Background technology

About being filled with the plastics composite of carbon nanotube (carbon nanotube), to have developed at present a lot, part is by practical application.As the characteristic of this matrix material, known have the pollution that causes by particle less, few, the surface finishing of exhaust and gloss is good, good fluidity, warping phenomenon is few, recycling property good and can keep (with reference to the non-patent literatures 1) such as physical propertiess of resin material.

By the resin combination that thermoplastic resin and carbon nanotube (below, abbreviate " CNT " sometimes as) constitute, in the formed body that obtains through pressure forming or extrusion moulding etc., CNT is about 2wt%, can access sufficient electroconductibility.But shear action when the content of CNT is low, is difficult to obtain the sufficient electroconductibility as the formed body that obtains through pressure forming or extrusion moulding etc. in the formed body that the forming method of molten resin obtains through like the moulding of injection molding etc. the time.In addition, the velocity of shear of the molten resin when electroconductibility exists with ... injection molding promptly depends on injection speed, particularly, exists the problem of the electroconductibility step-down of the formed body that the high injection speed that accelerates through velocity of shear obtains.Therefore, in order to obtain having the injection molded article of uniform conductive property, need in pressure forming or extrusion moulding, bring into play the CNT of the CNT amount of electroconductibility, thereby can diminish the deformation characteristic that resin had originally.

Before this, though a lot of to the opinion of the resin combination formed by thermoplastic resin and CNT,, all it is hard to tell sufficient opinion having been arranged like the dependent deviation of improving conductivity of the injection speed of electroconductibility.

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 polycarbonate resin by HYPERION company at present as the CNT of base resin.And, also put down in writing HYPERION company in the document and only sold the parent sizing material at present, never carried out the monomeric sale of CNT.

Also have, in 187 pages table 3 of non-patent literature 1, show the various characteristics of the thermoplastic resin that has mixed 3%CNT.And in 194～201 pages of above-mentioned non-patent literature 1, the HIPERSITE W1000 series that oiling electronics (strain) is made is as the compound material of CNT in thermoplastic resin, and this series is put down in writing.

In thermoplastic resin, cooperated CNT, and the resin combination 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 through with biaxial extruder the parent sizing material that is combined with CNT in the polycarbonate resin and polycarbonate resin being carried out melting mixing.In patent documentation 1; Record with the protofibril (carbon nanotube) of nest like (so-called BN type) and compare, the fibriilar poly carbonate resin composition that is combined with pectination has better shock-resistance, therefore; The complexing degree is more little, the content that the mechanical properties of compsn becomes better.But patent documentation 1 does not disclose the useful opinion about the conductivity deviation of improving resin combination.

Further; As the resin combination that in thermoplastic resin, has cooperated CNT; Known have a following compsn; Promptly in thermoplastic resin, cooperated by the resin combination of the BN type CNT of HYPERION manufactured and by the moulding article of this resin combination moulding, these moulding article have been pulverized and the operation of reshaping and the moulding article (with reference to patent documentation 2) that obtain repeatedly.Same compsn also is disclosed in patent documentation 3,4 and 5.

Moreover, about parent sizing material (master batch), think that the weight-average molecular weight of polycarbonate resin parent sizing material of HYPERION manufactured is 19500 (with reference to patent documentations 6).And, known have in viscosity-average molecular weight is about 15000 polycarbonate resin cooperated resin combination (with reference to patent documentation 7) by the BN type CNT of HYPERION manufactured.

As stated, though many resin combinations that is made up of thermoplastic resin and CNT are disclosed the not open relevant scheme of improving the conductivity deviation 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

Summary of the invention

As stated; So far; In containing the thermoplastic resin composition of carbon nanotube, can express high conductivity and improve and do not known that like the technical problem of the dependent conductivity deviation of the injection speed of electroconductibility its solution is not disclosed yet by people.

Thus, the objective of the invention is to, provide a kind of and have high conductivity and improved conductive resin composition like the dependent conductivity deviation of the injection speed of electroconductibility.The inventor etc., the result who has carried out wholwe-hearted research finds in the thermoplastic resin beyond the aromatic polyester resins, to cooperate the resin combination of carbon nanotube and a spot of aromatic polyester resins can realize above-mentioned purpose, thereby has accomplished the present invention.

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

(1) a kind of resin combination is provided; It is characterized in that; With respect to the thermoplastic resin (A composition) beyond the aromatic polyester resins of 100 weight parts; Contain the carbon nanotube (B composition) of 0.1～15 weight part and the aromatic polyester resins (C composition) of 0.1～4 weight part; Wherein, aromatic polyester resins (C composition) is preferably and is selected from least a in the group of being made up of liquid-crystal polyester resin, polybutylene terephthalate resin, PBN resin and pet resin.

(2) like (1) described resin combination; It is characterized in that,, contain the Phosphorus stablizer (D composition) of 0.0001～2 weight part with respect to the polycarbonate resin (A composition) of 100 weight parts; Wherein, 50 weight % in the preferred said Phosphorus stablizer (D composition) are above is trialkyl phosphates.

Like (1) or (2) described resin combination, it is characterized in that (3) diameter of said carbon nanotube (B composition) is that 0.7nm～100nm and aspect ratio are more than 5.

(4) like each described resin combination in (1)～(3), it is characterized in that, said aromatic polyester resins be contain by to the Para Hydroxy Benzoic Acid repeat units derived with by the liquid-crystal polyester resin of 6-hydroxyl-2-naphthoic acid repeat units derived.

Embodiment

Illustrate in greater detail the present invention below.

(A composition: the thermoplastic resin beyond the aromatic polyester resins)

The thermoplastic resin that uses as the A composition in the present invention, preferred use particularly are applied to the framework of electronic machine or the aromatic polyester resins thermoplastic resin in addition of internal mechanism parts.As this thermoplastic resin; For example, can enumerate the thermoplastic elastomer etc. of acrylic resin, phenylethylene resin series, modified polyphenylene ether resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, polyphenylene sulfide, polyarylate resin, polyester based elastomers, polyamide-based elastomerics, acrylic elastomer etc.Preferred especially, can enumerate two or more their mixtures of AS resin, ABS resin, polycarbonate resin and this.

As thermoplastic resin more suitably, can enumerate preferably contain the above polycarbonate resin of 50 weight %, more preferably contain the above polycarbonate resin of 60 weight %, further preferably contain the above polycarbonate resin of 70 weight %, the thermoplastic resin that most preferably in fact only constitutes by polycarbonate resin.

This polycarbonate resin reacts binary phenol and carbonic ether presoma to acquisition.As an example of reaction method, can enumerate the solid phase ester-interchange method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.

Representative in the binary phenol that here uses, the quinhydrones of can giving an example, Resorcinol, 4,4 '-bis-phenol, 1; Two (4-hydroxy phenyl) ethane, 2 of 1-, two (4-hydroxy phenyl) propane of 2-(be commonly referred to as dihydroxyphenyl propane, below abbreviate " BPA " sometimes as), 2; Two (the 4-hydroxy-3-methyl phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) butane, 1 of 2-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes, 1 of 1-; 1-bis(4-hydroxyphenyl) cyclohexane, 1; Two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane, 2; Two (4-hydroxy phenyl) pentanes, 4 of 2-; 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 binary phenol composition part or all, use 4; 4 '-(metaphenylene diisopropylidene) diphenol (below, abbreviate " BPM " sometimes as), 1,1-bis(4-hydroxyphenyl) cyclohexane, 1; Two (the 4-hydroxy phenyls)-3,3 of 1-, the 5-trimethyl-cyclohexane (below; Sometimes abbreviate " Bis-TMC " 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 total amount 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; Further be preferably 45～65 moles of %); And the BCF composition is the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of % further are 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; Further be preferably 60～85 moles of %) and the BCF composition be the Copolycarbonate of 5～90 moles of % (more preferably 10～50 moles of % further are 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; Further be preferably 45～65 moles of %) and the Bis-TMC composition be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of % further are preferably 35～55 moles of %).

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

About the method for manufacture and the characteristic of these special polycarbonate, for example in the flat 6-172508 communique of TOHKEMY, TOHKEMY flat 8-27370 communique, TOHKEMY 2001-55435 communique and TOHKEMY 2002-117580 communique etc., detailed record is arranged.

Moreover; In above-mentioned various polycarbonate; Through multipolymer composition etc. is adjusted, water-intake rate and Tg (vitrifying tansition temperatures) are adjusted at the polycarbonate in the following scope, the hydrolytic resistance of its polymkeric substance self is good; And the low toughness 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 temperatures) is according to JIS K7121, measures and the numerical value of acquisition with differential scanning heat appearance (DSC).

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

When through interfacial polymerization, when utilizing above-mentioned binary phenol and carbonic ether presoma to make polycarbonate, also can use catalyzer, terminal terminator, inhibitor etc. as required, wherein inhibitor is used to prevent the oxidation of binary phenol.And polycarbonate resin of the present invention comprises: with the branched polycarbonate resin 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 the forming process property in extrusion moulding, foaming and the blow molding according to this characteristic.Consequently can obtain through the excellent more moulding article 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 give an example 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-methylphenols of 6-and 4-{4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, the triphenol of α-Er Jiajibianji phenol etc.As other multifunctional aromatics; Can give an example 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 resin 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 like 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 aliphatic are alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, can preferably enumerate straight chain saturated aliphatic dicarboxylic acids such as sebacic acid (sebacic acid), 12 diacid, 14 diacid, 18 diacid and octadecane dicarboxylic acid; And the ester ring type dicarboxylicacid 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 method for manufacture 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) does not receive special restriction, but is preferably 1 * 10 ⁴～5 * 10 ⁴, more preferably 1.4 * 10 ⁴～3 * 10 ⁴, further be 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 property 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 needs higher forming process temperature, or needs special forming method, 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 through 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 property 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) (below be sometimes 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, further be 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, further be 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 through mixing 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 composition 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 MWD.Moreover this MWD can use the weight-average molecular weight of calculating through GPC (GPC) mensuration (Mw) that the ratio (Mw/Mn) of number-average molecular weight (Mn) is represented, 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 method of mixing in addition; (2) utilizing with disclosed method in the flat 5-306336 communique of TOHKEMY is method representative, that will in same system, make based on the aromatic polycarbonate resin of a plurality of polymkeric substance peak values of expression in the graph of molecular weight distribution of GPC method, makes this aromatic polycarbonate resin satisfy the making method of condition of the A-1 composition of benzene invention; And (3) will be through the aromatic polycarbonate resin and A-3-1 composition of making separately and/or A-3-2 composition method of mixing etc. of method of manufacture (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 resin is dissolved in the 100ml methylene dichloride and obtains, use Ostwald viscometer, obtain specific viscosity (η through 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 specific viscosity (η that is obtained _Sp), calculate viscosity-average molecular weight M through 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 according to following method.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 through diatomite filtration.Afterwards, remove the solvent in the solution that obtains.Thorough drying is removed the solid behind the solvent, and acquisition is dissolved in the solid of the composition of methylene dichloride.From this solid of 0.7g is dissolved in the solution of 100ml methylene dichloride, obtain the specific viscosity under 20 ℃ with method same as described above, utilize this specific viscosity to calculate viscosity-average molecular weight M same as described abovely.

(B composition: carbon nanotube)

The carbon nanotube that uses as the B composition in the present invention, being preferably diameter 0.7nm～100nm and aspect ratio is the carbon nanotube more than 5.Carbon nanotube is that the graphite linings of tubular is layered in the fibrous material to axial radiation direction.

Method of manufacture to the carbon nanotube that uses among the present invention does not have special qualification.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 method for manufacture known method of carbon nanotube.

As arc discharge method, 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, 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, through 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.

As chemical Vapor deposition process (CVD method); But illustration with at least a transition metal or its compound as catalyzer; Compound that will contain the VI family element in the periodic table of elements and the organic cpds that has as the VI family element of the organic cpds 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 through chemical Vapor deposition process.In this CVD method, also can adopt transition-metal catalyst is loaded on carrier and the catalytic chemical vapor deposition technique (CCVD method) that uses.Wherein, preferably can be low-cost and carry out mass-produced CVD method and CCVD method.

When through 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 through the few carbon nanotube of ash residue amount that is obtained among the former is cleaned.

In above-mentioned the former compound method, the catalytic amount through controlling when synthetic can obtain carbon nanotube of the present invention.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 through 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, as the preferred method of synthesizing carbon nanotubes, above-mentioned CVD method and CCVD method 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 and their mixture etc.As hydrocarbons, be preferably fragrant same clan hydrocarbons.As fragrant same clan hydrocarbons, the alkyl substituted benzene of can give an example benzene, toluene and YLENE etc.; Chlorobenzene, dichlorobenzene (adjacent--and santochlor), the benzene halide of trichlorobenzene, bromobenzene and dibromobenzene etc.; The alkyl-substituted naphthaline compound of naphthalene, methylnaphthalene, dimethylnaphthalene etc. etc.

As the above-mentioned compound that contains periodic table of elements group vib element, preferably contain the compound of oxygen or sulphur, preferred especially oxygen containing organic cpds.As oxygenatedchemicals, preferred carbon monoxide, carbonic acid gas, alcohols, ketone, phenols, ethers, aldehydes, organic acid and ester class.Specifically, can enumerate the verivate etc. of methyl alcohol, ethanol, propyl alcohol, hexalin, acetone, methylethylketone, 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 verivate 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 can use the ultramicron that is made up of transition metal.As transition metal, can give an example 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 cpds, the ferrocene of can giving an example, nickelocene, dicyclopentadienylcobalt, iron carbonyl and acetone iron (アセト Na one ト iron) etc.And,, can be any form in oxide compound, nitrate salt, vitriol and the muriate etc. as mineral compound.Also can make up two or more metals and use.Can obtain better catalyst effect through combination.Particularly organometallic compound provides catalyzer owing to easily make this compound gasification in Reaktionsofen, therefore is applicable to the CVD method.

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

As the introduction method of catalyzer, thus can adopt independent gasification process, with the carbon raw materials mix after gasify method, 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 the carbon nanotube that uses among synthetic the present invention, preferred reaction conditions is following: (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 ℃ scope, 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; The weight of transition metal is below the 3 weight %; Be preferably 0.1～3 weight %, more preferably 0.1～0.8 weight % further is preferably 0.2～0.7 weight %.Moreover the lower limit of above-mentioned furnace pressure is essentially 98kPa, this means as long as in atmospheric environment, then there is not special problem.

And, through 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, obtain final carbon nanotube through this pyroprocessing.

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

(about the constitutional features of carbon nanotube)

The carbon nanotube that uses among the present invention, the number of plies of its graphite linings can or surpass 2 layers multilayer for 1 layer, 2 layers.Be preferably the multilayer that surpasses more than 2 layers especially.The Fibre diameter of carbon nanotube is preferably 0.7～100nm, and more preferably 7～100nm further is preferably 15～90nm.The aspect ratio of carbon nanotube of the present invention is preferably more than 5, more preferably more than 100.Aspect ratio, can through with scanning electron microscope with multiplying power 3～100,000 times measured length and diameter, and calculate its ratio and obtain.Moreover linear measure is to implement through 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 accomplished through following method.At first, in the image that obtains through electron microscope observation, randomly draw the carbon nanotube that to measure diameter, at position finding diameter near central part.In addition, if when the cross section is non-circular, then with its peak 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 that uses among the present invention 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 both can be that so-called greying index is positive number and the carbon nanotube that has graphite-structure in fact, also can be that the greying index is negative and the carbon nanotube with non-graphite property multilayered structure.More preferably the greying index is the non-graphite property multilayered structure of negative.In addition, about the greying index, can be with reference to the WO2004/070095 pph.

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 range upon range of 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.

When the A composition was 100 weight parts, the content of carbon nanotube (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 property and resin combination can damaged, and is therefore not preferred.

(C composition: aromatic polyester resins)

One example of the aromatic polyester resins that uses among the present invention is made up of aromatic dicarboxylic acid composition and diol component.

As the aromatic dicarboxylic acid composition, preferred terephthalic acid or 2,6-naphthalene dicarboxylic acids.As diol component, but the alkylene alcohol of illustration terepthaloyl moietie, tetramethylene glycol, Ucar 35 etc.

The aromatic dicarboxylic acid composition can come from aromatic dicarboxylic acid or its ester formation property verivate.Diol component can come from glycol or its ester formation property verivate.

As this aromatic polyester resins, preferred polyethylene terephthalate, mutual-phenenyl two acid bromide two alcohol ester and PBN.

Aromatic polyester resins also can be the material that replaces the part of its dicarboxylicacid composition and/or diol component with copolymer composition.As this copolymer composition, for example, can enumerate m-phthalic acid, phthalic acid; The halogeno-benzene dioctyl phthalate of tetrabromo-benzene dioctyl phthalate, tetrabromo terephthalic acid etc.; The alkyl substituted benzene dioctyl phthalate of methyl m-phthalic acid etc.; 2,7-naphthalene dicarboxylic acids, 1, the naphthalene dicarboxylic acids of 5-naphthalene dicarboxylic acids etc.; 4,4'-diphenyldicarboxylic acids, 3, the diphenyldicarboxylic acid of 4 '-diphenyldicarboxylic acid etc.; 4, the aromatic dicarboxylic acid of 4 '-biphenoxyl ethane dicarboxylicacid etc.; The aliphatic dicarboxylic acid or the alicyclic dicarboxylic acid of succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, ten carbon dicarboxylicacid, cyclohexane dicarboxylic acid etc.; The aliphatic diol or the alicyclic diol of trimethylene, tetramethylene glycol, hexamethylene glycol, dimethyltrimethylene glycol, 1,4 cyclohexane dimethanol etc.; The dihydroxy-benzene of quinhydrones, Resorcinol etc.; The bis-phenol of 2,2 '-two (hydroxy phenyl) propane, 2,2 '-two (4-hydroxy phenyl) sulfone etc.; The aromatic series family glycol such as ether glycol that obtain by the glycol of bisphenols and terepthaloyl moietie etc.; Polyoxy for the polyoxy of tetramethylene glycol etc. for aklylene glycol; Oxo carboxylic acids such as ε-oxo caproic acid Para Hydroxy Benzoic Acid, hydroxyl-oxethyl TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. etc.

These copolymer compositions can use one or more.When the copolymer composition copolymerization, its ratio is preferably 20 moles below the % with respect to dicarboxylicacid composition total amount (oxo carboxylic acid with its half the be that carboxylic acid calculates), more preferably 10 moles below the %.

This aromatic polyester resins; Also can be with respect to dicarboxylicacid composition total amount; With 1.0 moles of branched-chain component copolymerizations below the %, preferred copolymerization below 0.5 mole, the more preferably material of copolymerization below 0.3 mole; Wherein, This branched-chain component is the acid that ester that acid or Pyromellitic Acid etc. that ester that tricarballylic acid, three decane tricarboxylic acid, benzene tricarboxylic acid etc. have a three-functionality-degree forms ability have four functionality forms ability, and perhaps ester with three-functionality-degree or four functionality such as USP Kosher, TriMethylolPropane(TMP), tetramethylolmethane forms the alcohol of ability.

The aromatic polyester resins that uses among the present invention; Be Wholly aromatic polyester resin, Wholly aromatic polyester amide resins; Said Wholly aromatic polyester resin, Wholly aromatic polyester amide resins have the unit from following compound, and this compound is one or more compounds that are selected from the group of being made up of aromatic hydroxy-carboxylic, aromatic series azanol, aromatic diamine.More particularly, can enumerate (1) mainly by one or more the synthetic aromatic polyester resins of compound that is selected from the group of forming by aromatic hydroxy-carboxylic and verivate thereof; (2) mainly by following a, b, the synthetic aromatic polyester resins of c compound; Wherein, A is one or more the compound that is selected from the group of being made up of aromatic hydroxy-carboxylic and verivate thereof; B is one or more compounds that are selected from the group of being made up of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and verivate thereof, and c is one or more the compound that is selected from the group of being made up of aromatic diol, alicyclic diol, aliphatic diol and verivate thereof; (3) mainly by following a, b, the synthetic aromatic polyester amide resins of c compound; Wherein, A is one or more the compound that is selected from the group of being made up of aromatic hydroxy-carboxylic and verivate thereof; B is one or more the compound that is selected from the group of being made up of aromatic series azanol, aromatic diamine and verivate thereof, and c is one or more the compound that is selected from the group of being made up of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and verivate thereof; (4) mainly by following a, b, c, the synthetic aromatic polyester amide resins of d compound; Wherein, A is one or more the compound that is selected from the group of being made up of aromatic hydroxy-carboxylic and verivate thereof; B is one or more the compound that is selected from the group of being made up of aromatic series azanol, aromatic diamine and verivate thereof; C is one or more compounds that are selected from the group of being made up of aromatic dicarboxylic acid, alicyclic dicarboxylic acid and verivate thereof, and d is one or more the compound that is selected from the group of being made up of aromatic diol, alicyclic diol, aliphatic diol and verivate thereof.Preferably (1) is mainly by one or more the synthetic aromatic polyester resins of compound that is selected from the group of being made up of aromatic hydroxy-carboxylic and verivate thereof.

And, as required, can and use molecular weight regulator in the said structure composition.

As the preferred example of synthesizing the middle particular compound of using of aromatic polyester resins of the present invention, can enumerate 2,6-naphthalene dicarboxylic acids, 2,6-dihydroxy naphthlene, 1, the naphthalene compound of 4-dihydroxy naphthlene and 6-hydroxyl-2-naphthoic acid etc.; 4,4'-diphenyldicarboxylic acids, 4, the biphenol compound of 4 '-dihydroxybiphenyl etc.; Benzene compound and their substitution in ring benzene compound (substituting group is selected from chlorine, bromine, methyl, phenyl, 1-phenylethyl) thereof to the para-orientation of Para Hydroxy Benzoic Acid, terephthalic acid, quinhydrones, PARA AMINOPHENOL and P-pHENYLENE dI AMINE etc.; The substituted benzene compound in position between m-phthalic acid, Resorcinol etc.; And with formula (1), (2) perhaps (3) expression compound.Wherein, be preferably and contain to the Para Hydroxy Benzoic Acid repeat units derived and from the liquid-crystal polyester resin of 6-hydroxyl-2-naphthoic acid repeat units derived.As both ratio of mixture, preferably the former is the scope of 90～50 moles of %, the scope of 80～65 moles of % more preferably, and the preferred latter is the scope of 10～50 moles of %, the scope of 20～35 moles of % more preferably.

(wherein, X be selected from by carbonatoms be 1～4 alkylene base and alkylidene ,-O-,-SO-,-SO ₂-,-S-and-group in the group that CO-formed; Y is selected from by-(CH ₂) _n-(n=1～4) ,-O (CH ₂) _nGroup in the group that O-(n=1～4) is formed.)

Further, preferred above-mentioned Wholly aromatic polyester resin, Wholly aromatic polyester amide resins is liquid-crystal polyester resin.

Liquid-crystal polyester resin is meant the thermotropic liquid crystal vibrin, has the character that its polymer molecular chain is arranged to certain orientation under molten state.And the form of this ordered state, can be nematic, stratose type, cholesterol type and dish-like in arbitrary form, also can be to present two or more spread patterns.And, as the structure of liquid-crystal polyester resin, can be the arbitrary structures in backbone chain type, side chain type and the upright and outspoken main chain curved side chain etc., but be preferably the main chain type liquid crystalline polyester resin.

The form of above-mentioned ordered state, i.e. the character of anisotropy fusion phase can be confirmed through having utilized polarisation detection method crossed nicols, common.More particularly, the affirmation of anisotropy fusion phase, through using the Leitz polarizing microscope, will carry fusion sample on the hot platform of Leitz (hotstage) under nitrogen environment with 40 times multiplying power observation and implement.When checking between the crossed nicols, even liquid-crystal polyester resin is the fusion stationary state, polarisation also can see through, and demonstrates optical anisotropy.

In addition, except the said structure composition, can also there be the unit of a part from the polyalkylene terephthalate that does not show anisotropic fusion phase in the liquid-crystal polyester resin that uses among the present invention in same molecular chain.The carbonatoms of the alkyl of this moment is 2～4.

To the basic method of manufacture of the liquid-crystal polyester resin that adopts among the present invention, do not do special qualification, can make according to the polycondensation method of known liquid-crystal polyester resin.And, when under 60 ℃, being dissolved in Pentafluorophenol with the concentration of 0.1 weight % above-mentioned liquid-crystal polyester resin, show about 2.0dI/g, the logarithm viscosity of about 2.0～10.0dI/g (IV value) for example usually at least.

Aromatic polyester resins can cooperate one or more uses.Optimization aromatic vibrin (C composition) is for being selected from least a in the group of being made up of liquid-crystal polyester resin, polybutylene terephthalate resin, PBN resin and pet resin.

When (A) composition was 100 weight parts, the content of aromatic polyester resins (C composition) was 0.1～4 weight part, is preferably 0.2～2 weight part, more preferably 0.5～1 weight part.If less than 0.1 weight part then can not obtain sufficient electroconductibility.If surpass 4 weight parts, then when injection speed is fast, can not obtain sufficient electroconductibility, thereby not preferred.

(D composition: Phosphorus stablizer)

Resin combination of the present invention preferably further contains Phosphorus stablizer.This Phosphorus stablizer can improve during fabrication or the thermostability when forming process greatly.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.More preferably being the Phosphorus stablizer of trialkyl phosphates and/or person's phosphate ester acid compound more than the 50 weight % in the Phosphorus stablizer of 100 weight %, is the Phosphorus stablizer of trialkyl phosphates more than 50% in the Phosphorus stablizer of 100 weight % preferably further.

Moreover the organic radical in the phosphate ester acid compound comprises any kind in monosubstitution, double-basis replacement and their mixture.Below corresponding, in the illustrative compound, 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) SULPHOSUCCINIC ACID ESTER, three Tryfac 5573s, three stearyl-SULPHOSUCCINIC ACID ESTERs, Tritolyl Phosphate, triphenylphosphate, trichloro-benzene base SULPHOSUCCINIC ACID ESTER, diphenylmethyl phenyl phosphate ester, the adjacent xenyl SULPHOSUCCINIC ACID ESTER of phenylbenzene list and three butoxyethyl group SULPHOSUCCINIC ACID ESTERs etc.Wherein, preferred trialkyl phosphates.The carbonatoms of the alkyl of this trialkyl phosphates is preferably 1～22, and more preferably 1～4.Preferred especially 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 acid long-chain dialkyl phosphate 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.

During as benchmark, the content of preferred Phosphorus stablizer is 0.0001～2 weight part with the thermoplastic resin (A composition) beyond the aromatic polyester resins of 100 weight parts, and more preferably 0.01～1 weight part further is preferably 0.05～0.5 weight part.

(other compositions)

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 thermoplastic resin.

(packing material)

In the resin combination of the present invention, can cooperate 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 shape can confirm through visual inspection as a rule, still, for example conduct and so-called difference between irregularly shaped, be aspect ratio be more than 3 just be called fibrous or tabular.

As tabular packing material, preferably can the illustration sheet glass, talcum, mica, kaolin, tinsel, carbon plate and graphite, and on the surface of these packing materials, be coated with the tabular packing material etc. of foreign material such as metal or MOX for example.Its particle diameter is preferably the scope of 0.1～300 μ m.This particle diameter; In the zone of less than 10 μ m, be meant the value of the mid-diameter (D50) of the size distribution that the X ray penetrant method through one of liquid phase settling process is measured, and in the zone of 10～50 μ m; Then refer to value through the mid-diameter (D50) of the size distribution of laser diffraction, scattering method; In addition, in 50～300 μ m zone, then refer to the diameter value of measuring through 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 packing material; Can also be to carry out boundling by various resins such as olefine kind resin, styrene resin, acrylics, 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, be by utilize sem to the moulding article are dissolved in solvent or with basic cpd decompose the residue that obtains behind the resin, and the ash residue of after crucible carries out ashing, obtaining observe and value that the image calculation that obtains is come out.

As this fibrous packing material, but illustration is with the fibrous inorganic filling material of spun glass, glass milled fiber, thomel, 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 sepiolite etc.; 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 MOX 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 spun glass, metallic coating sheet glass, titania coating sheet glass and metallic coating thomel etc.As method with foreign material lining surface; Not special the qualification; Can enumerate like known various plating method (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 fibrous packing material more than 10 more preferably.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 likewise, by surface-treated, also can be carried out boundling and handled by various resins etc. by various couplers, can also be through processed compressed and by 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 compsn 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 polymers etc. also can use sour modification etc. by the compound modified wax that contains functional group), silicon compound, fluorine cpd (being fluorocarbon oil of representative etc.), paraffin and beeswax etc. to gather fluoroalkyl ether.In the resin combination of 100 weight %, preferably the use level of this remover is 0.005～2 weight %.

Fatty ester of the present invention can be any kind in part ester and the full ester (full ester).In fatty ester, preferred acid number be (can get 0 in fact) below 20, OH 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 inhibitor)

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 propenoate, 4; 4 '-butylidene-bis(3-methyl-6-t-butyl phenol), triethylene glycol-N-be two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, 3, and two { 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyls }-2 of 9-; 4,8,10-four oxaspiros [5; 5] undecane, N, N '-hexa-methylene is 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 other inhibitors beyond the above-mentioned Hinered phenols stablizer.As these other inhibitor; 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 USP Kosher-sulfur-bearing class stablizer such as 3-octadecanoyl thiopropionate of representative.Above-mentioned Hinered phenols stablizer both can use separately, also can make up 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 (オキセタ Application) compound, silane compound and phosphinic acid compounds etc., preferred especially epoxy compounds and oxetane compound.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 improvement or the ultraviolet-absorbing of weathering resistance, preferably cooperate UV light absorber.As UV light absorber, but illustration benzophenone compound, benzotriazole compound, hydroxyphenyltriazinuv compounds, cyclic aminocarbonyl ester compound and cyanoacrylate compound etc. as the known material of UV light absorber.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; 1,3,3-tetramethyl butyl) phenol], 2-(4; 6-phenylbenzene-1,3,5-triazines-2-yl)-5-[(hexyl) oxygen] phenol, 2; 2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone) and 1,3-pair-[(2-cyanic acid-3; 3-diphenylprop enoyl-) oxygen]-2,2-pair-{ [(2-cyanic acid-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 said 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 said 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 (the for example pigment of carbon black and titanium oxide etc. and dyestuff), mineral-type fluor (for example being the fluor of parent crystal), inorganic or organic antibacterial agent, photochemical catalysis class stain control agent (micropartical titanium oxide and micropartical zinc oxide etc.), infrared absorbent (ATO micropartical, ITO micropartical, lanthanum boride micropartical, tungsten boride micropartical and phthalocyanines metal complex etc.), photochromic agent and white dyes etc. with aluminate.

(manufacturing of resin combination)

When making resin combination of the present invention, its method of manufacture 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&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 said ZSK model, its screw rod is complete meshing type, and screw rod is made up 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 for being 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, and more preferably 28～42.The L/D value is big more, the uniform dispersion state of easier formation, but when too big, then produce the decomposition of resin easily because of thermal ageing.Screw rod must have more than one mixing district, preferably has 1～3, and wherein, said 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 moisture that is produced and volatilization gas are discharged to the outside vacuum pump of forcing machine from venting port effectively.In addition, in order to improve the dispersiveness of CNT, 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., can impurity be removed from resin combination thus.As said filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.

To with B composition～C composition, the method supplied with to forcing machine of D composition and other additives (abbreviating " additive " in the following example as) does not have special qualification arbitrarily; 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, process the method for host grain (マスタ 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 (マスタ 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 random shape Powdered and that this powder 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, other pre-blend approach for example are that polycarbonate resin and additive are dispersed in solvent and behind the obtain solution, remove the method for this solvent.

By the resin that biaxial extruder is extruded, can directly cut off and carry out prilling, perhaps form strand after, said strand is cut into particulate with tablets press.In addition, when needs reduce outsidely during like the influencing of dust etc., preferably purify the environmental gas around the forcing machine.Further; In said particulate is made; Can be used on CD with the whole bag of tricks that has proposed in the polycarbonate resin, suitably carry out the minimizing of the bubble (bubbles of vacuum) of the stricturization of particulate form distribution, the minimizing that mistake is cut off thing (ミスカ Star ト thing), the minimizing of transporting the micro powder that produces when perhaps carrying and strand or granule interior generation.Through 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 said cylinder be preferably 1～5mm, more preferably 1.5～4mm, further be preferably 2～3.3mm.On the other hand, the length of cylinder be preferably 1～30mm, more preferably 2～5mm, further be preferably 2.5～3.5mm.

(preferable production process of resin combination)

As stated,, a kind of method of manufacture can be provided, it is characterized in that,, mix B composition, the C composition of 0.1～4 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 in said method of manufacture, uses, B composition, C composition and D composition as stated.In the said mixing,, most preferably use the exhaust biaxial extruder like illustration in the method for manufacture of resin combination.

In said 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 article that form by resin combination of the present invention)

The resin combination of the present invention that obtains as stated can produce various products through the particle of making is as stated 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 article 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 through 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 article.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 injection compression molding and injection pressure moulding that more preferably 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 through extrusion moulding.In addition, in sheet, film like moulding, can also use blow moulding, rolling process, casting etc.And, through 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 article through rotoforming or blow molding etc.

And, to the moulding article 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 vapor deposition (physical vapor deposition, cvd 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, UVA coating, infra-red absorption coating, metallic coating (vapor deposition 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, its typical example is documented among the following embodiment.But the present invention is not limited to these embodiments.

Embodiment

Below, lift embodiment and further explain, 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 10mm/ second and 30mm/ second, shaping cycle are under the about 60 seconds condition, comes the gusset of forming width 45mm * length 80mm * thickness 2mm through 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 numeral insulation meter (East Asia electric wave industry (strain) is made) and ohmer (Mitsubishi Chemical's (strain) manufacturing), measure the surface resistivity of said 5 gussets, calculate its MV.In addition, 1.0 * 10 ¹³Surface resistivity below the Ω is set at well.

(I-2) 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 * thickness 4mm.With above-mentioned MV of likewise 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, explain 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 minor amounts of additives, then using super mixing machine to make additive level is the premixture of 10 weight %.Should a plurality of premixtures and remaining reinstating V-Mixer mixes.

With a screw diameter of 30mm vented twin-screw extruder (vent-type two-axis Extruder) (TEX-30XSST, Japan Steel Works (strain) manufacturing) will be V-type blender mixture supplied to the rearmost The first input port.This forcing machine has the mixing region through 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 through mixing zone and this mixing zone of continuing of kneading disk.The venting port length of this part is about 1.5D, thereby and in this part, 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 prilling 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 260 ℃, die temperature are that 60 ℃, injection speed are that 10mm/sec and 30mm/sec, 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 in the foregoing description and comparative example, use are described below.

(A composition: the thermoplastic resin beyond the aromatic polyester resins)

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

A-2: the straight chain shape aromatic polycarbonate resin powder of viscosity-average molecular weight 20000 (パ Application ライト L-1225WX (trade(brand)name), Supreme Being people change into (strain) and make)

(B composition: carbon nanotube)

B-1: diameter 20nm, the aspect ratio carbon nanotube concentration more than 5 is that the carbon nanotube of 15 weight % cooperates with enriched material (carbon nanotube masterbatch MB6015-00 (trade(brand)name), Hyperion society makes)

B-2: diameter 15nm, the aspect ratio carbon nanotube concentration more than 5 is that the carbon nanotube of 8 weight % cooperates with enriched material (carbon nanotube masterbatch PC (T)-JCNT-08AK (trade(brand)name), (strain) ジエ system コ society makes)

(C composition: aromatic polyester resins)

C-1: Wholly aromatic polyester resin (Ltd makes for ベ Network トラ A-950RX (trade(brand)name), Polyplastics Co.)

C-2: polyethylene terephthalate (TR-4550BH (trade(brand)name), Supreme Being people change into (strain) and make)

C-3: polybutylene terephthalate (ジユラネ Star Network ス 300FP (trade(brand)name), WinTechPolymer Ltd. makes)

C-4: PBN (TQB-T (trade(brand)name), Supreme Being people change into (strain) and make)

(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 (アデカスタ Block PEP-8 (trade(brand)name), rising sun electrochemical industry (strain) is made)

The result is shown in table 1 and table 2.

Resin combination of the present invention even injection speed is 10mm/sec～30mm/sec, also has surface of good resistivity.

Result by table 1 and table 2 clearly can know; According to the present invention; The deformation characteristic of the tension fracture elongation rate etc. of the resin combination that forms by thermoplastic resin and carbon nanotube can be improved, thus, the resin combination of these characteristics and good electrical conductivity can be obtained having both.

Industrial applicibility

Resin combination of the present invention through in thermoplastic resin, cooperating carbon nanotube and a spot of aromatic polyester resins, has the melting heat stability of excellent electroconductibility and improvement.Through this characteristic, the condition of molding that resin combination can corresponding wide region, and the anti-crackle property of its moulding is excellent, so the conductive material applicable to the wide region purposes can be provided.As said purposes, for example can enumerate computingmachine, laptop computer, game machine (home-use game machine, business are with game machine, marble game machine and slot machine etc.), display unit (LCD, organic EL, Electronic Paper, plasma display and projector etc.), send electric parts (housing of ruhmkorff coil formula power transmission device is representative).In addition, can also give an example stamping machine, duplicating machine, scanning machine and facsimile recorder (compounding machine that contains them).As said purposes, can also enumerate VTR camera, optically thin membrane type camera, digital camera, camera precision instrument with lens unit, the criminal's of preventing device and mobile phone etc.Especially, resin combination of the present invention is suitable on framework, cover and the framework of digital image signal conditioning packages such as camera lens barrel, digital camera.

Further, resin combination of the present invention also is applicable to the medicine equipment of masseur or high oxygen therapy unit etc.; The household electronic products of video recorder (so-called DVD burner etc.), sound machine and electronic musical instrument etc.; The game device of Ball paddle device and slot machine game etc.; And carried on the parts of home-use robot etc. of sophisticated sensor.

In addition; Resin combination of the present invention can be used for casting mold, optic disc base board, cassette disk, light-card, IC storage card, junctor, cable coupler, the transporting with container (IC box for feeding odd, silicon wafer container, glass substrate accepting container and carrier band etc.), anti-electrostatic of electronic unit of various vehicle parts, battery, power generation assembly, circuit substrate, unicircuit and use perhaps and remove on electric parts (charged roller of electronic photo photosensitive device etc.) and the various mechanism part (gear, turntable, rotor and screw etc. contain micromachine and use mechanism part).

Therefore, resin combination of the present invention is exceedingly useful in the various industrial uses of OA mechanical field, electric and electronic mechanical field etc., and the industrial effect that it reached is very excellent.

Claims

1. conductive resin composition; It is characterized in that; Its contain as the polycarbonate resin of A composition, as the diameter of B composition be 0.7nm～100nm and aspect ratio be more than 5 carbon nanotube and as the aromatic polyester resins of C composition, wherein, with respect to the A composition of 100 weight parts; The B composition is 0.1～15 weight part, and the C composition is 0.1～4 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; It is characterized in that said C composition is at least a aromatic polyester resins that is selected from the group of being made up of liquid-crystal polyester resin, polybutylene terephthalate resin, PBN resin and pet resin.

4. conductive resin composition according to claim 2 is characterized in that, to be that 50 weight % of this D composition are above be the Phosphorus stablizer of trialkyl phosphates to said D composition.

5. conductive resin composition according to claim 1 is characterized in that, said C composition is to contain by to the Para Hydroxy Benzoic Acid repeat units derived and by the liquid-crystal polyester resin of 6-hydroxyl-2-naphthoic acid repeat units derived.