CN101514257A

CN101514257A - Electroconductive resin molding material

Info

Publication number: CN101514257A
Application number: CNA2009100082034A
Authority: CN
Inventors: 今村公一; 山中克浩; 鹿岛启一
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2008-02-19
Filing date: 2009-02-19
Publication date: 2009-08-26
Also published as: JP2009197056A

Abstract

The objective of the present invention is to provide an electroconductive resin molding material with high conductivity and electroconductivity deviation with improved electroconductivity injection speed dependency. The present invention provides an electroconductive resin molding material, including filamentary thermal plasticity polymer (A ingredient); electroconductivity filling agent (B ingredient); and large cyclic oligomer (C ingredient), wherein, the total weight of A ingredient, B ingredient and C ingredient is 100%, the A ingredient is 5-98.9 weight%, B ingredient is 0.1-50 weight%, C ingredient is 1-45 weight%.

Description

Electroconductive resin molding material

Technical field

The electroconductive resin molding product, the manufacture method of this molding material and the cooperation enriched material that can be used for making molding material that the present invention relates to a kind of electroconductive resin molding material, form by this molding material, wherein, this electroconductive resin molding material comprises strand of hot thermoplastic polymer, electroconductibility weighting agent and big cyclic oligomer.In more detail, molding material of the present invention, the injection speed dependency of the electroconductibility that occurs in the time of can reducing injection moulding and obtain the moulding product can be applicable to multiple use and various moulding product shape.

Background technology

In recent years, in the synthetic resin that constitutes electric and electronic,, begun to seek it and had good electrical conductivity along with its high development.As one of method of giving synthetic resin electroconductibility, the method that cooperates the electroconductibility weighting agent in resin material is arranged.In the method, in order to reduce the bad influence of electroconductibility weighting agent to resin, for example high specific gravityization, forming process deterioration and outward appearance deterioration etc. have begun to continue the content that research reduces the electroconductibility weighting agent.For example, the conductive carbon nano material of carbon nanotube (below, abbreviate " CNT " sometimes as) etc. is even knownly can be used as the electroconductibility weighting agent that low levels also can obtain good electrical conductivity.

But, in the prior art,, have the dependent problem of injection speed of following injection-molded article from the electroconductive resin molding material of thermoplastic resin and the formation of conductive carbon nano material.Promptly, although the content of this electroconductibility weighting agent can be brought into play sufficient electroconductibility in applying pressure moulding or extrusion moulding etc. from the moulding product that this molding material obtains, but adopt injection moulding etc. in moulding the time formed body that the forming method of molten resin effect shearing force is obtained, can not bring into play same electroconductibility, and this injection speed high conductivity is low more more.Therefore, in order to obtain the formed body that on any position of formed body, all has uniform conductive, need be in pressure forming or the extrusion moulding electroconductibility weighting agent of amount of electroconductibility weighting agent of the necessary electroconductibility of performance, consequently, relatively damage the characteristic that resin has, and damaged the effect of this electroconductibility weighting agent of being expected.

As using a spot of electroconductibility weighting agent to obtain one of method of better electroconductibility, known have, and with two kinds of immiscible mixed with resin, forms island structure, contains the method (with reference to patent documentation 1～5) of conductive material in these marine facies.This method, thus can think 1 mutually in condensing conductive material improve its concentration, thus, improve the contact probability between the electroconductibility weighting agent, form and conduct circuit phase (referring to patent documentation 1)., also disclose, for example, the size that makes this island phase is less than threshold value for this reason, and then volume resistance increases (referring to patent documentation 2).That is, provided in the good composition of intermiscibility can not improved electroconductibility enlightenment.

On the other hand, known a kind of composition, it contains the reticulated structure of the nanofiber of the polymkeric substance that obtains from big cyclic oligomer and loose combination, and wherein CNT is dispersed in the matrix, demonstrates specific electric conductivity (referring to patent documentation 6).More specifically, disclose in the document, melting mixing big ring-type polybutylene terephthalate oligopolymer and CNT then, add tin compound catalyst, by stirring under higher temperature, obtain polybutylene terephthalate/CNT matrix material.

Further, known a kind of manufacture method, it is manufactured on the polybutylene terephthalate is the dispersion of the filler particles of dispersed clay etc. in the polymkeric substance of representative, wherein, comprising: the operation that forms the masterbatch of the big cyclic oligomer that contains 10 these filler particles of weight % at least; Polymkeric substance is mixed with this masterbatch, in this big cyclic oligomer and mixture of polymers, disperse the operation (referring to patent documentation 7) of filler particles.But, in the document,, only limit to disclose by big ring-type mutual-phenenyl two acid bromide two alcohol ester's oligopolymer polymeric polybutylene terephthalate as the matrix polymer of this manufacture method.In addition, also disclose in the document, in the melting mixing of polyethylene terephthalate, big ring-type terephthalic acid butyleneglycol oligopolymer and organized clay, big ring-type mutual-phenenyl two acid bromide two alcohol ester oligopolymer is insufficient to the conversion of polymkeric substance, therefore, can not be shaped to test film.That is, do not express this manufacture method in the document and can be effective to polybutylene terephthalate matrix resin in addition.

Known, form mobile excellent homogenizing mixture (referring to patent documentation 8) by big cyclic oligomer usually with physical mixture and this mixture of the other strand of hot thermoplastic polymer of different structural unit with other.For example, in this patent documentation, disclosed the single transparent film mutually that obtains by the big ring-type polybutylene terephthalate oligopolymer and the solution casting method of bisphenol-a polycarbonate.

In addition, known a kind of resin combination, it also further contains Phosphorus stablizer (referring to patent documentation 9) for be combined with the resin combination of the CNT of ash residue below specified quantitative in polycarbonate.

Patent documentation 1:JP spy opens clear 62-004749 communique

The special table of patent documentation 2:JP 2002-544308 communique

Patent documentation 3:JP spy opens flat 01-263156 communique

Patent documentation 4:JP spy opens flat 02-1113068 communique

Patent documentation 5:JP spy opens the 2006-083195 communique

The special table of patent documentation 6:JP 2006-511652 communique

Patent documentation 7:WO2006/028541 brochure

Patent documentation 8:JP spy opens flat 06-016949 communique

Patent documentation 9:JP spy opens the 2006-306960 communique

Summary of the invention

As mentioned above, contain the electroconductibility weighting agent particularly CNT be in the electroconductive resin molding material of conductive carbon nano material of representative, have the technical task of the electroconductibility deviation of injection speed dependency of obtaining high conductivity and improving electroconductibility etc.Though there is above-mentioned problem, present situation is, this problem is also not known, and its solution is not open yet.Therefore, the objective of the invention is, a kind of electroconductive resin molding material that solves this problem is provided, it can access high conductivity and improve the electroconductibility deviation of the injection speed dependency etc. of electroconductibility.

In order to reach this purpose, the inventor etc. have carried out concentrated research, consequently be surprised to find, in the time can providing big cyclic oligomer with the mixed uniformly homogenizing mixture of thermoplastic resin to be engaged among the thermoplastic resin composition, good electrical conductivity can be brought into play and the injection speed dependency of electroconductibility can be improved, wherein, this thermoplastic resin composition to contain the electroconductibility weighting agent particularly be the conductive carbon nano material of representative with CNT.This electroconductibility modification method of the present invention is the opposite method of method with the immiscible composition of cooperation of the prior art.More surprised is, confirm not exist under the situation of electroconductibility weighting agent during the dispersion state of the electroconductibility weighting agent in the conductive resin composition of confirming to obtain, although cooperate the big cyclic oligomer that homogenizing mixture can be provided, also formed tangible phase separation structure.Though it is indeterminate to form the mechanism of this phase structure, as can be known, electroconductibility is improved and the result that improves the dependent mechanism of action of injection speed of electroconductibility is by this phase structure, identical with the method for the immiscible composition of cooperation of the prior art.The inventor etc. based on this discovery, further advance research, have finished the present invention.

The purpose of the invention described above can be reached by following (1).

(1) electroconductive resin molding material, it comprises:

Strand of hot thermoplastic polymer (A composition); Electroconductibility weighting agent (B composition); And big cyclic oligomer (C composition),

Wherein, when A composition, B composition and C composition added up to 100 weight %, the A composition was 5～98.9 weight %, and the B composition is 0.1～50 weight %, and the C composition is 1～45 weight %.

Herein, " wire " of A composition is the word that uses for clearly distinguishing as the big cyclic oligomer of C composition, is not to have got rid of the polymkeric substance that contains branched-chain component.That is, the A composition, comprise single linear chain thermoplastic polymer, have any in the thermoplastic polymer of side chain.Have in the thermoplastic polymer of side chain and also can contain graftomer.In addition, in the entire infrastructure unit, the branched structure unit is preferably 5 moles below the %, more preferably 3 moles below the %.

In addition, in the electroconductive resin molding material of the present invention, the structural unit of preferred C composition is different with the structural unit of A composition.That is, preferred A composition is a principal constituent with the different polymkeric substance of the polymkeric substance that generates with polymerization by the C composition.Preferred each components in proportions is, when the total amount of A composition～C composition is 100 weight %, the A composition is that 50～94.5 weight %, B composition are that 0.5～15 weight % and C composition are 5～35 weight %, being preferably the A composition is that 58～89 weight %, B composition are that 1～12 weight % and C composition are 10～30 weight %, more preferably the A composition is that 60～83 weight %, B composition are that 2～10 weight % and C composition are 15～30 weight %, and being preferably the A composition especially is that 65～80 weight %, B composition are that 2～5 weight % and C composition are 18～30 weight %.B composition and C composition are lower than the following of above-mentioned scope prescribes a time limit, and can not obtain sufficient good electrical conductivity and substantially improve the injection speed dependency.In addition, B composition and C composition surpass going up in limited time of above-mentioned scope, may damage the thermotolerance of resin molding material and the physical strength of moulding product respectively.

Of the present invention one of preferred embodiment, be (2) electroconductive resin molding material, it is above-mentioned (1) described electroconductive resin molding material, wherein, in the resin combination that cooperates after 80 weight part A compositions and 20 weight part C compositions carry out melting mixing, the C composition is to be used to make this resin combination to form the composition of homogenizing mixture.The structural unit of preferred this C composition, same as described above, different with the structural unit of A composition.The present invention is opposite with the understanding of prior art, and it is included in the unexistent feature of the prior art that obtains good electrical conductivity under this embodiment, consequently, compares with the immiscible composition of cooperation of the prior art, can reach more good electrical conductivity.

Of the present inventionly one of preferred embodiment be (3) electroconductive resin molding material, it is the described electroconductive resin molding materials in above-mentioned (1)～(2), and wherein, the C composition is big cyclic polyester oligopolymer.Big cyclic polyester oligopolymer obtains easily, and with the consistency height that is suitable for strand of hot thermoplastic polymer of the present invention, thereby preferred.Poly-(the dicarboxylic acid alkylidene group diester) oligopolymer of particularly preferred big ring-type is as the C composition.

Of the present inventionly one of preferred embodiment be (4) electroconductive resin molding material, it is the described electroconductive resin molding materials in above-mentioned (1)～(3), and wherein, the B composition is to be the electroconductibility weighting agent of principal constituent with the conductive carbon material.Electroconductibility weighting agent as B composition of the present invention comprises conductive carbon material, metallic substance and metal oxide materials and electric conductive polymer etc., preferred especially conductive carbon material.Conductive carbon material can satisfy low-gravity and good electroconductibility.Wherein, be that the electroconductibility weighting agent of principal constituent is as the B composition preferably with the conductive carbon nano material.The electroconductibility injection speed dependency of this material is also big, can bring into play effect of the present invention better.In addition, should " principal constituent " be meant in the B composition of 100 weight % and contain more than the 50 weight %, be preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 90 weight %.

Conductive carbon material comprises the conductive carbon nano material of conductive carbon black, graphite and CNT etc.In addition, conductive carbon nano material as the B composition, can enumerate, the diameter that is rolled into tubular by the graphene film of monolithic be individual layer CNT, tubular about several nm graphene film with the axle right angle orientation on the end of multi-layer C NT (many walls CNT), individual layer CNT of lamination seal into cone shape carbon nanotube (CNH) and form carbon nanotube (CNH) aggregate of the globular aggregate about diameter 100nm etc. by this carbon nanotube (CNH).Further, the conductive carbon nano material comprises the carbon onion (Carbon Onion) of the six membered ring assortment structure with carbon, imports soccerballene or the Nano capsule and Cabbeen (carbine) the class material etc. of five-membered ring in the six membered ring assortment structure of carbon.In addition, among the present invention, these conductive carbon nano materials can be the independent bodies of above-mentioned kind, also two or more mixtures.Wherein, especially preferably be principal constituent with the carbon nanotube.

Of the present invention one of preferred embodiment, be (5) electroconductive resin molding material, it is the described electroconductive resin molding materials in above-mentioned (1)～(4), wherein, the A composition is to be selected from least a as principal constituent in the group of being made up of polycarbonate, polyarylester, poly-naphthalic acid alkylidene group diester and polyphenylene ether.The thermoplastic polymer that this is suitable is high heat resistance and full-bodied polymkeric substance, and is big with the injection speed dependency of electroconductive resin molding material, therefore, can bring into play effect of the present invention better.Wherein, optimization polycarbonate.Should " principal constituent " be meant in the A composition of 100 weight % and contain more than the 50 weight %, be preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 90 weight %.In addition, the polymkeric substance beyond the principal constituent can comprise above-mentioned suitable polymers polymkeric substance in addition.As above-mentioned prior art, the polymkeric substance of other of formation micro phase separation structure that also can be by further cooperating low intermiscibility further improves electroconductibility.

Of the present inventionly one of preferred embodiment be (6) synthetic resin, wherein, by obtaining with the described electroconductive resin molding material of the injection speed injection moulding of 40mm/ more than second above-mentioned (1)～(5).The present invention carries out injection moulding by like this high injection speed, also can obtain to have good electrical conductivity and improve the dependent electroconductive resin molding product of injection speed of electroconductibility.

The surface resistivity of the moulding product that electroconductive resin molding material of the present invention is made is preferably 10 ¹²～10 ^-1Ω, more preferably 10 ¹⁰～10 ^-1Ω.Half fading period that preferred electroconductive resin molding material, the electrostatic charging that satisfies the moulding product that this resin combination makes discharge in (ESD) testing of characteristic is less than 20 seconds.This ESD testing of characteristic is one of index of electroconductibility, is to use the test film of the level and smooth flat board of 0.05 μ m to measure.For satisfying this ESD characteristic, preferably utilize CNT as the electroconductibility weighting agent.

In the feature of electroconductive resin molding material of the present invention, there are its injection moulding product can bring into play the dependent aspect of injection speed that reduces above-mentioned electroconductibility.The upper limit of the injection speed of embodiments of the present invention (6) can be made as 800mm/ second aptly, is preferably 400mm/ second, 300mm/ second more preferably, more preferably 100mm/ second.In addition, in this embodiment (6), identical in the preferred implementation of A composition, B composition and C composition and above-mentioned embodiment (2)～(5).

The present invention also provides another kind of embodiment, promptly, (7) manufacture method of electroconductive resin molding product, when it makes the electroconductive resin molding product in that electroconductive resin molding material is carried out injection moulding, can suppress the reduction of the electroconductibility that the increase because of injection speed causes, wherein, use electroconductive resin molding material, this electroconductive resin molding material comprises:

Wherein, when A composition, B composition and C composition added up to 100 weight %, the A composition was 5～98.9 weight %, and the B composition is 0.1～50 weight %, and the C composition is 1～45 weight %.In this embodiment (7), identical in the preferred implementation of A composition, B composition and C composition and above-mentioned (2)～(5).

The present invention also provides another kind of embodiment, promptly, (8) manufacture method of electroconductive resin molding material, it is the manufacture method of the electroconductive resin molding material described in above-mentioned (1)～(5), wherein, to cooperate with enriched material to be engaged in A composition or A composition and the C composition, this cooperation comprises with enriched material:

Wherein, when A composition, B composition and C composition added up to 100 weight %, the A composition was 0～98 weight %, and the B composition is 1～60 weight %, and the C composition is 1～99 weight %.Mix in the manufacturing of resin molding material of various raw materials at needs, usually, the operation of the B composition difficulty that is easy to become.Utilize enriched material can improve this aspect.The melt viscosity of C composition is extremely low, and has good thermostability.Therefore, have preferably as the characteristic of cooperations high temperature process and the engineering plastics that melt viscosity is high with the matrix reagent of enriched material, wherein, at least a polymkeric substance of engineering plastics for selecting in the group of forming by polycarbonate, polyarylester, poly-naphthalic acid alkylidene group diester and polyphenylene ether.

According to above-mentioned (8), the present invention also further provides (9) to cooperate and uses enriched material, and it comprises:

Wherein, when A composition, B composition and C composition added up to 100 weight %, the A composition was 0～98 weight %, and the B composition is 1～60 weight %, and the C composition is 1～99 weight %.The cooperation of above-mentioned (8) and (9) preferred each components in proportions in the enriched material, be A composition～C composition with respect to total 100 weight %, the A composition is 1～88 weight %, the B composition is that 2～30 weight % and C composition are 10～80 weight %, more preferably the A composition is 10～80 weight %, and the B composition is that 5～20 weight % and C composition are 20～70 weight %.Than the cooperation enriched material that is only become to be grouped into by B composition and C, the cooperation enriched material that A composition, B composition and C one-tenth are grouped into can reduce the injection speed dependency of conductivity, thereby, more preferably also contain the A composition.In addition, in above-mentioned (8) and (9), A composition, B composition and C composition preferred embodiment with above-mentioned (2)～(5) in identical.

Description of drawings

Fig. 1 is the photo of the infiltration type electron microscope of the section parallel with thickness direction that cut out in the square plate moulding product of moulding when injection speed is 50mm/sec of embodiment 1.Cut out the position in other photo also much at one.

Fig. 2 is the photo of the infiltration type electron microscope of the section parallel with thickness direction that cut out in the square plate moulding product of moulding when injection speed is 50mm/sec of embodiment 3.

Fig. 3 is the photo of the infiltration type electron microscope of the section parallel with thickness direction that cut out in the square plate moulding product of moulding when injection speed is 50mm/sec of comparative example 3.

Embodiment

Describe the present invention below in detail.

(A composition: the strand of hot thermoplastic polymer)

Strand of hot thermoplastic polymer as A composition of the present invention, can enumerate the various catenanes polymkeric substance and the multipolymer of polyethylene (the various multipolymers that comprise LLDPE etc.) and polypropylene (the polymer-modified and multipolymer that comprises maleic anhydride modified and various graft modifications etc.) etc.In addition, also can enumerate the styrenic polymer of polystyrene, acrylonitritrile-styrene resin, maleic anhydride-styrene copolymers, copolymer of methyl methacrylatestyrene, vinylbenzene-isobutylene copolymers and phenyl methyl acrylic styrene copolymer etc.In addition, also can enumerate polymethylmethacrylate and multipolymer thereof, polymeric amide.In addition, also can enumerate aliphatic polyester, polycarbonate, polyarylester, polyphenylene ether, urethane, polysulfones, polyethersulfone, cyclic polyolefin, polyetherimide, polyamide-imide, polyimide, PABM and the polyether-ether-ketone etc. of the aromatic polyester, poly(lactic acid) etc. of poly terephthalic acid alkylidene group diester and poly-naphthalic acid alkylidene group diester etc.Preferred A composition, as mentioned above, for to be selected from least a resin in the group that polycarbonate, polyarylester, poly-naphthalic acid alkylidene group diester and polyphenylene ether formed as the polymkeric substance of principal constituent.Special optimization polycarbonate.Should " principal constituent " be meant in the A composition of 100 weight % and contain more than the 50 weight %.Polymkeric substance beyond the above-mentioned suitable polymers in the A composition of 100 weight %, also can contain below the 50 weight %.Above-mentioned suitable polymers in the A composition of 100 weight %, is preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, is preferably especially more than the 90 weight %.

With respect to the polymkeric substance of the principal constituent among the present invention,, also can further improve the electroconductibility of composition by cooperate forming other polymkeric substance of micro phase separation structure.So long as the polycarbonate of proper A composition, the polymkeric substance of other beyond the polycarbonate nearly all forms micro phase separation structure, preferred alkenes base polymer, aliphatic polyester, styrene copolymer, aromatic polyester and acrylic polymers.

(polycarbonate)

Be particularly suitable for the polycarbonate of A composition of the present invention, can use itself the known polycarbonate that uses in the various moulding product of prior art.That is, be the polycarbonate that divalent phenol and/or aliphatics and/or ester ring type two functionality alcohol are obtained with the reaction of carbonic ether precursor.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.In the situation of interfacial polycondensation, use the end-capping reagent of monovalence phenols usually.As mentioned above, also outside the phenol of the polycarbonate of A composition or divalence or alcohols repolymerization the branched polycarbonate of trifunctional composition is arranged, further, the also copolymerization polycarbonate that forms of copolymerization aliphatic dicarboxylic acid or aromatic dicarboxylic acid, organopolysiloxane composition and vinyl monomer.

Suitable polycarbonate with the structural unit that comprises divalent phenol is with following formula (i) expression

In the formula (i), A represents to be selected from by the key arbitrarily in organic residue, singly-bound or the following formula (i-4) of at least a divalence in following formula (i-1)～(i-3) and the group that (i-5) formed.S and t represent 0 or 1～4 integer respectively independently.R ₁₃And R ₁₄Represent halogen atom or organic residue of from the group that forms by the aralkoxy of the aryloxy of the aralkyl of the aryl of the cycloalkyloxy of the cycloalkyl of the alkoxyl group of the alkyl of carbonatoms 1～10, carbonatoms 1～10, carbonatoms 6～20, carbonatoms 6～20, carbonatoms 6～10, carbonatoms 7～20, carbonatoms 6～10, carbonatoms 7～20, selecting respectively independently.

In the formula (i-1), R ₁₅, R ₁₆, R ₁₇And R ₁₈Represent independently that respectively hydrogen atom, halogen atom or carbonatoms are 1～3 alkyl.

In the formula (i-2), R ₁₉And R ₂₀Represent independently that respectively hydrogen atom, halogen atom or carbonatoms are 1～3 alkyl.

In the formula (i-3), u is 4～11 integer, these a plurality of R ₂₁And R ₂₂Expression is selected from the group that hydrogen atom, halogen atom or carbonatoms are 1～3 alkyl independently respectively.

In the formula (i-5), R ₂₃And R ₂₄Expression is selected from the group that hydrogen atom, halogen atom or carbonatoms are 1～10 alkyl independently respectively.

Next, the specific examples of above-mentioned formula (i) is described according to the specific examples of the dihydroxy compound of this structural unit of deriving.

Compound when being singly-bound as the A in the formula (i) can enumerate 4,4 '-xenol and 4,4 '-two (2, the 6-dimethyl) biphenol etc.

Compound when being (i-1) as A, can enumerate α, α '-two (4-hydroxy phenyl)-adjacent diisopropyl benzene, α, α '-two (4-hydroxy phenyl)-diisopropyl benzene (being commonly referred to " bis-phenol M ") and α, α '-two (4-hydroxy phenyl)-to diisopropyl benzene etc.

Compound when being (i-2) as A can enumerate 9, two (4-hydroxy phenyl) fluorenes, 9 of 9-, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc.

Compound when being (i-3) as A, can enumerate 1,1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (the 4-hydroxy-3-methyl phenyl) hexanaphthenes, 1 of 1-, two (4-the hydroxy phenyl)-4-normenthanes and 1 of 1-, two (3-cyclohexyl-4-hydroxy phenyl) hexanaphthenes of 1-etc.

As A is any compound during group in (i-4), can enumerate 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl ether, 4,4 '-dihydroxy-diphenyl sulfone, 2,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxyl diphenyl sulfide, 3,3 '-dimethyl-4,4 '-dihydroxyl diphenyl sulfide and two (3,5-dimethyl-4-hydroxy phenyl) sulfone etc.

Compound when being (i-5) as A, can enumerate 1, two (4-hydroxy phenyl) methane of 1-, 2,4 '-dihydroxyl ditan, two (2-hydroxy phenyl) methane, two (4-hydroxy phenyl) methane, two (4-hydroxyl-5-nitrophenyl) methane, two (4-hydroxyls-2,6-dimethyl-3-p-methoxy-phenyl) methane, two (4-hydroxy phenyl) cyclohexyl-methane, two (4-hydroxy phenyl) ditan, 1, two (4-hydroxy phenyl) ethane of 1-, 1, two (4-hydroxyl-2-the phenyl)-1-diphenylphosphino ethanes of 1-, 1, two (4-hydroxyl-2-chloro-phenyl-) ethane of 1-, 2, two (4-hydroxy phenyl) propane (being commonly referred to " dihydroxyphenyl propane ") of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane (being commonly referred to " bisphenol-c ") of 2-, 2, two (3-phenyl-4-hydroxy phenyl) propane of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxyl-3-ethylphenyl) propane of 2-, 2, two (4-hydroxyl-3-isopropyl phenyl) propane of 2-, 2, two (3-tert-butyl-hydroxy phenyl) propane of 2-, 2, two (3-bromo-4-hydroxy phenyl) propane of 2-, 2,2-two (3,5-two bromos-4-hydroxy phenyl) propane, 2, two (4-the hydroxy phenyl)-1-phenyl-propanes of 2-, 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) pentanes of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 4, two (4-hydroxy phenyl) heptane of 4-, 2, two (4-hydroxy phenyl) octanes of 2-, 1, two (4-hydroxy phenyl) decane of 1-, 1, two (3-methyl-4-hydroxy phenyl) decane and 1 of 1-, two (2,3-dimethyl-4-hydroxy phenyl) decane of 1-etc.

In addition, divalent phenol as the formula of deriving (i) structural unit in addition, can enumerate 2, the 6-dihydroxy naphthlene, quinhydrones, Resorcinol, carbonatoms is the Resorcinol that 1～3 alkyl replaces, 3-(4-hydroxy phenyl)-1,1,3-trimethylammonium indane-5-alcohol, 1-(4-hydroxy phenyl)-1,3,3-trimethylammonium indane-5-alcohol, 6,6 '-dihydroxyl-3,3,3 ', 3 '-tetramethyl-spiral shell indane, the 1-methyl isophthalic acid, two (4-the hydroxy phenyl)-3-normenthanes of 3-, 1-methyl-2-(4-hydroxy phenyl)-3-[1-(4-hydroxy phenyl) sec.-propyl] hexanaphthene, 1, two (the 4-hydroxy phenyls)-1 of 6-, 6-hexane diketone and ethylene glycol bis (4-hydroxy phenyl) ether etc.

In the above-mentioned divalent phenol, the bis-phenol M of preferred formula (i-1) expression; 9 of formula (i-2) expression, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-; 1 of formula (i-3) expression, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy-3-methyl phenyl) hexanaphthenes, 1 of 1-, two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane; 3 of formula (i-4) expression, 3 '-dimethyl-4, dihydroxyphenyl propane, the bisphenol-c and 1 of 4 '-dihydroxyl diphenyl sulfide and formula (i-5) expression, two (4-hydroxy phenyl) silane of 1-.

Other details about this polycarbonate, for example, on the books in WO03/080728 book, the flat 6-172508 communique of TOHKEMY, the flat 8-27370 communique of TOHKEMY, TOHKEMY 2001-55435 communique and TOHKEMY 2002-117580 communique etc.

Among the present invention, two functionality alcohol as the structural unit of the polycarbonate of deriving more preferably use the ester ring type glycol, for example, can enumerate cyclohexanedimethanol, cyclohexane diol, three ring (5.2.1.0 ^2.6) decane dimethanol, norbornane dimethanol, naphthane-2,6-dimethanol, spiral shell ethylene glycol, 1,4-two dehydration-D-sorbitols, 3,6-two dehydration-D-sorbitols, 1,4-two dehydration-D-N.F,USP MANNITOL, 3,6-two dehydration-D-N.F,USP MANNITOL and 1,4-two dehydration-L-iditols, 3,6-two dehydration-L-iditols etc.

Further, as A composition of the present invention, also can use the polycarbonate-poly organo alkyl copolymer of copolymerization polyorganosiloxane units.As polycarbonate-poly organo alkyl copolymer, preferably can enumerate the multipolymer of organopolysiloxane part of the structural unit of the polycarbonate part of structural unit of the useful following formula of intramolecularly (ii-1) expression and following (ii-2) expression.

In the formula (ii-1), Z two functionality alcohol of the unitary divalent phenol of polycarbonate part-structure and/or aliphatics and/or ester ring type this residue of divalent-Z-when being expressed as HO-Z-OH that represents to derive.R ₁, R ₂, R ₃, and R ₄The expression carbonatoms is 1～6 alkyl or phenyl, and is identical or different, is preferably methyl.R ₅Expression is preferably adjacent propenyl phenol residue, para hydroxybenzene ethene residue, 4-propenyl-2-methoxyphenol residue and isopropenyl phenol residue from the organic residue of the divalence of aliphatics or aromatics, preferred especially adjacent propenyl phenol residue.In addition, n represents the polymerization degree of the structural unit in the bracket, and this structural unit also can be the mixture more than 2 kinds.The scope of this n is, its mean value is 1～500, is preferably 5～200, more preferably 10～70, more preferably 15～30.In addition, the higher limit of the n of each composition is preferably 500, and more preferably 200, more preferably 70.

As the multifunctional aromatics more than the three-functionality-degree that uses in the branched polycarbonate, can enumerate 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 the benzyl)-4-methylphenols of 6-, 4-{4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, the triphenol of α-Er Jiajibianji phenol etc.Wherein, preferred 1,1,1-three (4-hydroxy phenyl) ethane.In the total amount of divalent component deutero-structural unit with other is among 100 moles of %, by this multifunctional aromatics deutero-structural unit, be preferably 0.03～1 mole of %, more preferably 0.07～0.7 mole of %, be preferably 0.1～0.4 mole of % especially.

In addition, the branched structure unit is not only from multifunctional aromatics and is derived, and does not also use multifunctional aromatics as the side reaction of melt transesterification process etc. and derives.About the unitary content of this branched structure, can pass through ¹H-NMR measures and calculates.

As the polycarbonate of A composition, comprise the polyestercarbonate of two functionality carboxylic acids of copolymerization aromatic series or aliphatics (comprising ester ring type).Aliphatic two functionality carboxylic acids are preferably alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, preferably can enumerate direct-connected saturated aliphatic dicarboxylic acids such as sebacic acid (sebacic acid), dodecanedioic acid (Dodecandioic acid), tetradecane diacid, octadecane diacid and octadecane dicarboxylic acid; And the ester ring type dicarboxylic acid of cyclohexane dicarboxylic acid etc.

The viscosity-average molecular weight of polycarbonate (M) 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 ⁴Be lower than 1.0 * 10 in viscosity-average molecular weight ⁴Polycarbonate resin in, can't obtain sufficient toughness or fracture-resistant in the practicality sometimes.On the other hand, surpass 5 * 10 by viscosity-average molecular weight ⁴The resin combination that obtains of polycarbonate resin, generally need the special forming method of high mold temperature or needs, so versatility is poor.And also owing to the increase of melt viscosity, the injection speed dependency also uprises easily.

In addition, 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 scope (5 * 10 of surpassing ⁴) the polycarbonate resin of viscosity-average molecular weight, can improve the fusion tension force of resin combination.Based on this characteristic, can improve the forming process in extrusion moulding, foaming and the blow molding.It is more excellent than above-mentioned branched polycarbonate that this improves effect.

As preferred embodiment, it is 7 * 10 that the A composition also can use by viscosity-average molecular weight ⁴～2 * 10 ⁶Polycarbonate and viscosity-average molecular weight be 1 * 10 ⁴～3 * 10 ⁴Polycarbonate resin form, its viscosity-average molecular weight is 1.6 * 10 ⁴～3.5 * 10 ⁴Polycarbonate resin (below, be also referred to as " polycarbonate resin of pbz polymer amount composition " sometimes).The polycarbonate resin of pbz polymer amount composition can be by being mixed above-mentioned each composition with various ratios, and it is adjusted into the molecular weight ranges that satisfies regulation and obtains.

The viscosity-average molecular weight of polycarbonate 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 drippage number second of methylene dichloride, drippage number second that t is sample solution];

According to resulting specific viscosity (η _Sp), calculate viscosity-average molecular weight (M) by following formula:

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

[η]＝1.23×10 ^-4M ^0.83

c＝0.7

In the electroconductive resin molding material of the present invention, the calculating of the viscosity-average molecular weight of resin (M) is to carry out according to following method.That is, said composition is mixed with 20～30 times methylene dichloride of its weight, make the solvable composition dissolving in the composition.Obtain this solvable composition by diatomite filtration.Then, the solvent in the removal gained solution.Solid behind the removal solvent is carried out sufficient drying, obtain to be dissolved in the solids component of methylene dichloride.The solution that obtains from this solid of 0.7g is dissolved in the 100ml methylene dichloride, obtain specific viscosity under 20 ℃ with above-mentioned same operation, and, obtain viscosity-average molecular weight (M) with above-mentioned same operation from this specific viscosity.

(poly-naphthalic acid alkylidene group diester)

The poly-naphthalic acid alkylidene group diester of the suitable polymers as the A composition of the present invention (poly-naphthalene dicarboxylic acids alkylidene group diester) is with 2, and the 6-naphthalene dicarboxylic acids is main sour composition, be the polyester that main pure composition forms with alkyl diol.Principal constituent herein is meant the ratio that 80 moles of % are above, is preferably the above ratio of 85 moles of %.Therefore, but also sour composition, pure composition and the oxygen acid composition of following other of 20 moles of % of copolymerization, or contain the polyester that forms by this composition as mixture.Herein 2,6-naphthalene dicarboxylic acids composition is meant from 2, the repeating unit of 6-naphthalene dicarboxylic acids.Can be by 2,6-naphthalene dicarboxylic acids and ester thereof formation property derivative imports in the polymkeric substance.In addition, other sour composition also can import in the polymkeric substance by this acid self or its ester formation property derivative.As this ester formation property derivative, can enumerate lower alkyl esters, phenylester and acid anhydrides etc.

Among the present invention, more suitably poly-naphthalic acid alkylidene group diester is preferably PEN (below, abbreviate " PEN " as) and PBN (below, abbreviate " PBN " as).This PEN and PBN, as mentioned above, PEN can contain 2, the composition beyond 6-naphthalene dicarboxylic acids composition and the glycol component, PBN can contain 2, the composition beyond 6-naphthalene dicarboxylic acids composition and the butyleneglycol composition.In 100 moles of % dicarboxylic acid composition total amounts or diol component total amount, this other composition is preferably 15 moles below the %, more preferably 12 moles below the %.Herein, this 2, the dicarboxylic acid composition beyond the 6-naphthalene dicarboxylic acids composition is preferably iso-phthalic acid composition and/or terephthalic acid composition.Beyond these, for example, also can utilize 2, the 7-naphthalene dicarboxylic acids, the tert.-butylbenzene dioctyl phthalate, hexichol oxidative ethane dicarboxylic acid, diphenyldicarboxylic acid, the biphenoxyl ethane dicarboxylic acid, the sulfobenzide dicarboxylic acid, the diphenyl ether dicarboxylic acid, the phenylmethane dicarboxylic acid, the diphenylketone dicarboxylic acid, and the aromatic dicarboxylic acid of diphenyl sulfide dicarboxylic acid etc., oxalic acid, succsinic acid, arabic acid, the aliphatic dicarboxylic acid of sebacic acid and dodecanedicarboxylic acid etc., six hydrogen terephthalic acids, the naphthane dicarboxylic acid, and the alicyclic dicarboxylic acid of tetraline dicarboxylic acid etc., and ester that should acid forms property derivative deutero-acid composition.

Pure composition beyond the ethylene glycol that also can contain among the PEN can be enumerated propylene glycol, 1, the fatty alcohol of 4-butyleneglycol, 1,3 butylene glycol, pentanediol, hexylene glycol, neopentyl glycol and Diethylene Glycol etc.; The alicyclic diol of cyclohexanedimethanol and tristane dimethanol etc.; The divalent phenol of dihydroxyphenyl propane, Resorcinol, quinhydrones and dihydroxyl phenylbenzene etc.; Aromatic alcohols such as the alkylidene group oxygen affixture of dihydroxyphenyl propane etc.; Polyoxyethylene glycol and poly-1, the fluorenes deutero-alcohol composition of the polyalcohols of 4-butyleneglycol etc. and two hydroxyl-oxethyl phenyl fluorenes etc.Reduce crystallinity and when stretching, can reach and consider that in 100 moles of % diol component total amounts, particularly this Diethylene Glycol composition preferably contains 2～5 moles of % aspect the sufficient stretch orientation from appropriateness.In PBN, can contain 1 in ethylene glycol and the mentioned component, the composition beyond the 4-butyleneglycol.

In addition, contain oxygen M-nitro benzoic acid composition and hydroxy diphenyl carboxylic acid composition etc. as gathering the oxygen acid composition that can contain in the naphthalic acid alkylidene group diester, can enumerating.

Further, in the scope of not damaging purpose of the present invention, poly-naphthalic acid alkylidene group diester can contain three-functionality-degree above sour composition or pure composition.Can enumerate the trimellitic acid composition as the sour composition more than the three-functionality-degree, can enumerate by glycerol, trimethyl propane and tetramethylolmethane deutero-to become to grade as the pure composition more than the three-functionality-degree.In 100 moles of % of each constituent, the composition that three-functionality-degree is above is preferably 2 moles below the %, more preferably 1 mole below the %.

Poly-naphthalic acid alkylidene group diester, its limiting viscosity of measuring in 25 ℃ ortho chloro phenol solvent is preferably more than the 0.55dl/g, more preferably more than the 0.6dl/g.On the other hand, limiting viscosity is preferably below the 1.3dl/g, more preferably below the 1.2dl/g.

The polymerization of poly-naphthalic acid alkylidene group diester can be adopted known various polymerization processs in the prior art.As the one example, can enumerate following method, promptly, aklylene glycol, 2 with ethylene glycol etc., the dimethyl esters of 6-naphthalene dicarboxylic acids and copolymer composition (terephthalic acid dimethyl esters etc.) carry out transesterify when boiling off methyl alcohol, under reduced pressure carry out polycondensation then.Among the present invention, particularly, preferably carry out solid state polymerization in order further to improve limiting viscosity.As transesterification catalyst, can enumerate calcium acetate or magnesium acetate etc.As transesterification catalyst, in addition, also can enumerate acetate, monocarboxylate, alcoholate and the oxide compound etc. of magnesium, manganese, calcium and zinc etc.In addition, the phosphorus compound that preferably adds trimethyl phosphate etc. after transesterification reaction makes this transesterification catalyst inactivation.As polymerisation catalysts, can use germanium compound, titanium compound and antimony compounds etc.For example, can enumerate germanium dioxide, hydroxide germanium, germanium alkylol cpd, four titanium butoxide, tetraisopropoxy titanium and titanous oxalate etc.

(polyarylester)

Below, the polyarylester of A composition of the present invention is described.Polyarylate resin of the present invention is resultant by aromatic dicarboxylic acid or derivatives thereof and divalent phenol or derivatives thereof.As the aromatic dicarboxylic acid that is used for the polyarylester preparation,, can use separately also can mix more than 2 kinds and use so long as can provide the polymkeric substance that satisfies with the divalent phenol reaction to get final product.

As preferred aromatic dicarboxylic acid composition, can enumerate terephthalic acid and isophthalic acid.In addition, also these mixture.

Object lesson as the divalent phenol composition, can enumerate 2, two (4-hydroxy phenyl) propane of 2-, 2, two (the 4-hydroxyls-3 of 2-, 5-dibromo-benzene base) propane, 2, two (4-hydroxyl-3, the 5-dichloro-phenyl) propane of 2-, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl diphenylketone, 4,4 '-dihydroxyl ditan, 2,2 '-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane, 1, two (4-hydroxy phenyl) ethane of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 4,4 '-dihydroxyl phenylbenzene, quinhydrones etc.These divalent phenol compositions are para-isomeride, also can use other isomer, also can be in the xylenol composition further and spent glycol, propylene glycol, neopentyl glycol etc.

As preferred polyarylester in above-mentioned, can enumerate the aromatic dicarboxylic acid composition and be terephthalic acid and isophthalic acid, the divalent phenol composition is 2, the polyarylester of two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) of 2-.The ratio of terephthalic acid and isophthalic acid is preferably terephthalic acid/isophthalic acid=9/1～1/9 (mol ratio), particularly considers preferred 7/3～3/7 from melt processable, performance balance aspect.

As other the polyarylester of representative, can enumerate the aromatic dicarboxylic acid composition is terephthalic acid, and the divalent phenol composition is the polyarylester of dihydroxyphenyl propane and quinhydrones.The ratio of this dihydroxyphenyl propane and quinhydrones is preferably dihydroxyphenyl propane/quinhydrones=50/50～70/30 (mol ratio), and more preferably 55/45～70/30, more preferably 60/40～70/30.

The viscosity-average molecular weight of the polyarylester among the present invention from physical properties and extrude the processibility aspect and consider, is preferably about 7000～100000 scope.In addition, polyarylester can be by any polymerization process in interface polycondensation and the ester-interchange method.

(polyphenylene ether)

As the polyphenylene ether (hereinafter to be referred as " PPE ") of A composition of the present invention, be polymkeric substance or multipolymer with nucleophilic substitution phenol of phenylene ether structure.Further, PPE of the present invention is included in the polymeric blends that contains styrenic polymer in this polymkeric substance or the multipolymer.This polymeric blends (so-called modification polyphenylene ether), because it is obtain easily, more general than polyphenylene ether itself.

Typical example as the polymkeric substance of nucleophilic substitution phenol with phenylene ether structure, can enumerate poly-(2,6-dimethyl-1, the 4-phenylene) ether, poly-(2-methyl-6-ethyl-1, the 4-phenylene) ether, poly-(2,6-diethyl-1, the 4-phenylene) ether, poly-(2-ethyl-6-n-propyl-1, the 4-phenylene) ether, poly-(2,6-di-1,4-phenylene) ether, poly-(2-methyl-6-normal-butyl-1, the 4-phenylene) ether, poly-(2-methyl-6-sec.-propyl-1, the 4-phenylene) ether, poly-(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly-(2-methyl-6-chloroethyl-1,4-phenylene) ether etc.Wherein, especially preferably poly-(2,6-dimethyl-1,4-phenylene) ether.

Typical example as the multipolymer of nucleophilic substitution phenol with phenylene ether structure, can enumerate 2,6-xylenol and 2,3, the multipolymer of 6-pseudocuminol, 2, the multipolymer of 6-xylenol and adjacent Resorcinol or 2,6-xylenol and 2,3, the multipolymer of 6-pseudocuminol and adjacent Resorcinol etc.

The manufacture method of above-mentioned PPE has no particular limits, can be according to the method for record in No. 4788277 specification sheets of United States Patent (USP) (the clear 64-33131 of TOHKEMY number), and in the presence of dibutylamine, oxidative coupling polymerization 2 and making.

The molecular weight of PPE and molecular weight distribution can be various situations.As molecular weight, preferably the reducing viscosity when 30 ℃ of 0.5g/dl chloroformic solutions is 0.20～0.70dl/g, more preferably 0.30～0.55dl/g.

In addition, in PPE of the present invention, in the scope of not violating purpose of the present invention, also can contain other various phenylene ether units that in the polyphenylene ether resin, can exist of the prior art as part-structure.As the example of the motion of a small amount of coexistence, can enumerate 2-(dialkyl amino ylmethyl)-6-methylphenylene ether unit of in the clear 63-301222 communique of TOHKEMY, putting down in writing or 2-(positive alkyl-positive phenyl amino methyl)-6-methylphenylene ether unit etc.In addition, also can contain in the resinoid main chain of polyphenylene ether in conjunction with a small amount of phenoquinone etc.

Among the PPE of the present invention, have the polymkeric substance of nucleophilic substitution phenol of phenylene ether structure or multipolymer (below, only be called " PPE polymkeric substance ") with the ratio of styrenic polymer, in adding up to 100 weight %, the PPE polymkeric substance is at least more than the 20 weight %, preferred PPE polymkeric substance is more than the 30 weight %, and more preferably the PPE polymkeric substance is 30～80 weight %.

As styrenic polymer, the styrene monomer that uses, beyond vinylbenzene, can enumerate o-methyl styrene, p-methylstyrene, a vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, to the nucleophilic alkyl-substituted styrene of t-butyl styrene etc.; The polymkeric substance of the alpha-alkyl substituted phenylethylene of alpha-methyl styrene, Alpha-Methyl-p-methylstyrene etc. etc., and in these compounds more than a kind with other at least a above multipolymer of vinyl compound, or the multipolymer more than 2 kinds in these compounds.As can with the monomer of this styrene monomer copolymerization, can enumerate the methyl acrylic ester of methyl methacrylate, Jia Jibingxisuanyizhi etc.; The unsaturated nitrile compound class of vinyl cyanide, methacrylonitrile etc.; The acid anhydrides of maleic anhydride etc. etc.As styrenic polymer, preferred polystyrene (comprising syndiotactic polystyrene).

(B composition: the electroconductibility weighting agent)

As mentioned above, B composition of the present invention comprises conductive carbon material, metallic substance and metal oxide materials and electric conductive polymer etc., and preferred especially conductive carbon material is a principal constituent.This conductive carbon material comprises the conductive carbon nano-tube material of conductive carbon black, graphite and carbon nanotube etc., especially preferably is principal constituent with the carbon nanotube.

(conductive carbon black)

Conductive carbon black is with the non-fibrous carbon weighting agent of carbon as principal constituent.Particularly, be carbon black, graphite, soccerballene.From physical strength and prevent that the static aspect from considering preferred carbon black, graphite.As carbon black, consider that from the electroconductibility aspect preferred DBP oil number is the carbon black of 100ml/100g～500ml/100g.This carbon black, normally acetylene black, Ketjen black (Ketjenblack).Particularly, can enumerate the デ Application カ Block ラ Star Network of electrochemical industry (strain) manufacturing, バ Le カ Application XC-72 and BP-2000, ライオ Application (strain) manufacturing Ketjen black EC-300JD and the Ketjen black EC-600JD etc. that キヤボ Star ト society makes.

(graphite)

As graphite, can utilize the mineral substance name to be called the natural graphite of graphite or various synthetic graphite.As natural graphite, can utilize in amorphous graphite, flaky graphite (being also referred to as the vein graphite (VeinGraphite) of blocky graphite) and the flaky graphite (Flake Graphite) any.In addition, synthetic graphite, be thermal treatment decolorizing carbon and manually carry out the graphite of orientation of the small graphite crystallization of irregular assortment, outside the synthetic graphite that is used in usually in the carbon material, also comprise kish (Kishgraphite), decompose graphite and thermolysis graphite etc.Usually the synthetic graphite that uses in the carbon material is that main raw material is made by graphitization processing with petroleum coke or coal class pitch coke normally.Graphite of the present invention by flaky graphite being imposed the processing that oxygen is treated to representative, also can contain the graphite of crossing as the expanded graphite or the expansion process of heat-swellable.Further, the graphite that uses among the present invention also can carry out pulverization process by the mechanical crushing method of planetary ball mill, beater grinder and friction pulverizer etc.Among the present invention, the median size of graphite is preferably below the 100 μ m, more preferably below the 50 μ m, more preferably below the 10 μ m.The lower limit of median size is preferably 1 μ m.The median size of graphite can be tried to achieve by the laser diffraction and scattering method.

The fixed carbon content of graphite is preferably more than the 80 weight %, more preferably more than the 90 weight %, more preferably more than the 98 weight %.In addition, the volatile component of graphite is preferably below the 3 weight %, more preferably below the 1.5 weight %, more preferably below the 1 weight %.In addition, the surface of graphite in the scope of the characteristic of not damaging composition of the present invention, in order to increase the affinity with thermoplastic resin, can implement also that epoxy finishes, urethanum are handled, silane coupling agent is handled and the surface treatment of oxide treatment etc.

(conductive carbon nano material)

As the conductive carbon nano material, as mentioned above, comprise individual layer CNT, multi-layer C NT, carbon nanotube (CNH) and carbon nanotube (CNH) aggregate etc., wherein preferred CNT.

CNT, the diameter that can be rolled into tubular for the graphene film of monolithic be individual layer CNT about several nm and tubular graphene film with the meet at right angles multi-layer C NT (many walls CNT) of lamination on the direction of axle, consider preferred multi-layer C NT from the injection speed dependency aspect that can further reduce composition.Further, the preferred mode of CNT is that its ash residue is below the 3 weight %, is preferably 0.1～3 weight %, more preferably 0.1～0.8 weight %, more preferably 0.2～0.7 weight % as described in the above-mentioned patent documentation 8.

This ash residue contains at least a element of selecting at least from the group of being made of iron, nickel and molybdenum as principal constituent.Be somebody's turn to do " containing at least a element of from the group of forming by iron, nickel and molybdenum, selecting as principal constituent at least ", be meant that the total ratio of iron, nickel and molybdenum element is more than the 70 weight % the part by weight of each element that peak intensity that the ash residue measured from fluorescent X-ray obtains is calculated.This total ratio is preferably more than the 80 weight %, more preferably more than the 90 weight %.

Measure the operation of the weight ratio of the element calculate from fluorescent X-ray, can calculate based on lubber-line usually, amount of element and peak intensity that this lubber-line is obtained from the standard substance of each element are calculated.In recent years, being built-in with in the fluorescent X-ray determinator can quantitative program, can directly be obtained the weight ratio of element by this device.As this device, can enumerate the MESA-500 type that (strain) hole field makes manufacturing, the fluorescent X-ray that can be used for ash residue is aptly measured.This algorithm can be undertaken by the underlying parameter method in the MESA-500 type.

Do not limit the manufacture method of CNT is special.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 CNT.Wherein, preferably can low-cost mass-produced CVD method and CCVD method

(manufacture method of CNT)

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

As chemical Vapor deposition process (CVD method), but illustration with at least a transition metal or its compound as catalyzer, to have as the organic compound of carbon source and carrier gas and together be directed in the Reaktionsofen, carry out the synthetic method by chemical Vapor deposition process by hydrogen, methane or intert-gas configuration.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, be preferably aluminum oxide, zeolite, carbon, magnesium oxide, calcium oxide and phosphalugel etc. as the inorganic carrier in the CCVD method.The particularly preferred high zeolite of thermotolerance.Be used in this inorganic carrier carrying the hole of holding, be preferably uniformly, and its aperture be about 1nm.

Use CVD method and CCVD method, when making the CNT of the further minimizing of ash residue, have the amount of adjustment initial stage catalyzer method, by The high temperature anneal distillation as the method for the metal particle of catalyzer, make and remove groove by magnet and remove as the method for the metal particle of catalyzer and the method etc. of cleaning the catalyst residue among the CNT, these methods can be used separately, but preferably combination is used.Catalyst residue becomes the ash residue source.Consider that from the aspect that helps reducing the ash residue amount preferred use can be carried out synthetic CCVD method by catalytic amount still less, still, this method also exists in industrial practicality and is difficult to problem that catalyzer and carrier thereof are stably acted on.Therefore, more practical is to use above-mentioned method to reduce the ash residue amount in the CVD method.

The method of above-mentioned The high temperature anneal is the preferred CNT that generates attitude (as-grown), the method that metal particle remaining in the CNT as catalyzer is distilled outside CNT handled in 2400 ℃～3000 ℃ scope.But, only using this method, the metal ingredient of resolidification is with monomeric state or to remain among the CNT of B composition under the state of CNT surface attachment sometimes.Therefore, further reduce under the situation of ash residue preferably combination will be removed groove by the CNT that The high temperature anneal generates by magnet method at needs.By this method, remove metal particle as catalyzer, consequently reduced the ash residue amount.The preferred mode of this method is the method for removing groove by the magnet of the structure of configuration magnetite in cyclonic air flow, and the detailed situation of this method has been disclosed in the TOHKEMY 2006-327915 communique.

As the method for cleaning the catalyst residue among the CNT, use acidic cpd, basic cpd and supercutical fluid etc., clean the catalyst residue among the CNT.This cleaning both can be carried out after CNT synthetic, and perhaps the stage of generation attitude that also can be before high-temperature heat treatment carries out.But, reduce the ash residue amount by washing out method, low in industrial efficient, and be related to the increase of the cost of carbon nanotube.Therefore, preferable methods is, as mentioned above, and the method for The high temperature anneal, or combination The high temperature anneal and the method for removing groove by magnet.Promptly, preferred B composition among the present invention, be by in 2400 ℃～3000 ℃ scope, handling the CNT that generates attitude (as-grown), from this generates the carbon nanotube of attitude, reduce the carbon nanotube of ash residue, thereby or make the magnet of the structure of this carbon nanotube by in cyclonic air flow, having disposed magnetite remove the carbon nanotube that groove further reduces ash residue.The latter's method has reduced the amount of ash residue, but causes cost to increase, and can consider above-mentioned aspect as one feels fit and utilizes.

Preferred CNT among the present invention, the CNT of the CVD manufactured of the operation of following by comprising (i)～(iii), the preferably CNT that makes by the method that also comprises operation (iv).That is, (i) carbon source is heated to 300～450 ℃ temperature, in rare gas element and/or hydrogen environment, is supplied to Reaktionsofen, in gas phase, make its thermolysis under 1000～1350 ℃, obtain the operation of first intermediate with catalyzer; (ii) this intermediate is carried out sintering and removes unreacted raw material and tar ingredients at least in rare gas element in 800～1250 ℃ scope, obtain the operation of second intermediate; And (iii) this second intermediate is further carried out The high temperature anneal under 1500～3000 ℃, obtain the operation of carbon nanotube.Further, comprise also as required that (iv) the carbon nanotube that will obtain removes groove by the magnet of the structure by disposing magnetite in cyclonic air flow, remove the operation of metal particle.

As above-mentioned carbon source, can exemplify aromatic hydrocarbonss such as benzene, toluene and dimethylbenzene; The alcohols of carbon monoxide and ethanol etc., wherein, optimization aromatic hydrocarbon, more preferably toluene and dimethylbenzene.Further, as carbon source, preferably use the different two or more at least compound of decomposition temperature., use two or more compounds herein, comprise the situation that contains the different two or more carbon compound of decomposition temperature by the pyrolysis process in system.For example, toluene or dimethylbenzene carry out the reaction of dehydrogenation alkylation etc., become the different two or more carbon compound of decomposition temperature.Therefore, using two or more compounds, might not be to use two or more material organic compounds.

Environmental gas in the above-mentioned operation (i) can utilize the rare gas element or the hydrogen of argon, helium, xenon etc., especially preferably has the reducing environment of hydrogen.

As catalyzer, can use the compound of transition metal and this transition metal, as this transition metal, can exemplify iron, nickel, cobalt, copper and molybdenum etc.As transistion metal compound, can enumerate ferrocene and acetic acid metal-salt etc., preferred especially ferrocene.Outside this catalyzer, more preferably and be used as the sulphur of promotor or the sulfur compound of thiophene and iron sulphide etc.Transistion metal compound is decomposed to form atoms metal in Reaktionsofen, next, form former subgroup, and further growth forms the metal particle that works as catalyzer.As the introduction method of catalyzer, thereby can adopt independent gasification process, mix 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.

Reaktionsofen in the above-mentioned operation preferably can adopt known various Reaktionsofens in the CVD method, is preferably the tubular Reaktionsofen.This Reaktionsofen, have usually with material mixed gas import in the Reaktionsofen distributing nozzle with the heating unit of this Reaktionsofen internal heating.More preferably, this Reaktionsofen has the concentration distribution that makes in the Reaktionsofen and the temperature distribution uniforming device with respect to the orthogonal directions homogenizing of axis.As this uniforming device, preferably, make the device of this mixed gas flow turbulization near the introducing port of distributing nozzle by the impact portions that makes the mixed gas collision is set.This Reaktionsofen, as shown in TOHKEMY 2007-146316 communique, wall forms noncrystalline carbon-coating within it, can easily remove and makes the carbonaceous fouling effectively, thereby be preferred.

The residence time of the carbon that the material budget in Reaktionsofen calculates is preferably 2～10 seconds, more preferably 5～10 seconds.Temperature is preferably 1000～1350 ℃, more preferably 1100～1250 ℃ in the stove of Reaktionsofen.When 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.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 %.The lower limit set of preferred furnace pressure is about 98kPa, and the upper limit is set at 200kPa, more preferably is set at above 98kPa and below 110kPa.In the summation of the carbon weight in above-mentioned synthesis material and the weight of 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 %, more preferably 0.2～0.7 weight %.

As carrier gas, can utilize rare gas and the hydrogen and the nitrogen etc. of argon, xenon and helium etc.In these the carrier gas, use hydrogen to form the yield that reducing environment can increase CNT, thus preferred.

First intermediate that obtains in the above-mentioned operation (i) is to give birth to the burning state, and defective is many, comprises unreacting material, CNT carbide, tar component and catalyst metal in addition.Operation (ii) in, unreacting material or tar component are removed in volatilization effectively from this first intermediate.Can obtain the high CNT of purity thus.As this operation (ii), in the inert gas environment of the rare gas of argon etc. and nitrogen etc., 800～1200 ℃ of heating down.Be preferably 10～60 minutes heat-up time.

Above-mentioned operation (iii), be by with second intermediate at 2400～3600 ℃, be preferably and under 2500～2700 ℃, carry out anneal, make the sheet combination respectively of the patch shape of the carbon atom formation in first intermediate, form the operation of the layer of a plurality of Graphene sheets.Preferred this operation is also carried out in rare gas element, particularly carries out in rare gas.Also can in inert gas environment add the CO (carbon monoxide converter) gas of reducing gas or trace in order to protect the structure of matter this moment.

Next, CNT generates mutually the closely state of aggregation of complexing usually.From this aspect, also be same in by the CNT of above-mentioned operation manufacturing.Thus, CNT in order further to improve the dispersion in matrix polymer, can carry out fragmentation by common the whole bag of tricks and handle (sectionalization processing).Preferably in the CNT that above-mentioned operation (i) is (iii) made, also carry out same fragmentation and handle.Detailed situation for suitable fragmentation is handled has been disclosed in the TOHKEMY 2007-204857 communique.In addition, this fragmentation is handled, and also can use in first intermediate, second intermediate or the anneal product any.

(constitutional features of CNT)

The CNT that uses among the present invention, the number of plies of graphene film 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 CNT of the present invention is preferably 0.7～100nm, more preferably 7～100nm, more preferably 15～90nm.The aspect ratio of CNT of the present invention is preferably more than 5, more preferably more than 100.Aspect ratio, can by 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 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 when 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 that uses among the present invention between the graphene film (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.Preferred this interlamellar spacing surpasses 3.44nm.Therefore, CNT of the present invention both can be that so-called greying index is the carbon nanotube that has graphite-structure in fact of positive number, also can be that the greying index is the carbon nanotube of the non-graphite multilayered structure of having of negative.More preferably the greying index is the non-graphite multilayered structure of negative.In addition, about the greying index, can be with reference to the WO2004/070095 brochure.

CNT among the present invention both can be that each layer of its graphene film 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 sheet changes on fabric integer.The more preferably latter that on fabric integer, changes of the interval of sheet in the present invention.In addition, also can be the stacked structure of graphene film 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 graphene film, to have non-hexavalent carbocyclic ring structure.

(C composition)

As the big cyclic oligomer of C composition of the present invention, comprise big cyclic polycarbonates oligopolymer, big cyclic polyester oligopolymer, big ring-type pi oligopolymer, big cyclic polyether-Ya oligoamide and big ring-type polyphenylene ether oligomer.Wherein, be preferably big cyclic polyester oligopolymer and big cyclic polycarbonates oligopolymer, more preferably big cyclic polyester oligopolymer.This big cyclic polyester oligopolymer comprises in poly-(the dicarboxylic acid alkylidene group diester) oligopolymer of big ring-type polyarylester oligopolymer and big ring-type any.This big cyclic oligomer can be the oligopolymer that is made of different structural units, also can be the mixture of the different big cyclic oligomer more than 2 kinds of structural unit.

Suitable big ring-type of the present invention is gathered (dicarboxylic acid alkylidene group diester) oligopolymer, is the big cyclic oligomer that comprises the structural unit of (iii) representing with following formula.

In the formula, R ₇Represent independently that respectively alkylidene group, ring alkylidene group, list or polyoxy are for alkylidene group; X represents divalence aromatic series or non-ring type group respectively independently.

Preferred X be between position or contraposition bonded monocyclic aromatic series or non-ring type group.More preferably, X is the monocyclic aromatic series or the non-ring type group of carbonatoms 6～10.Preferred R ₇Be that carbonatoms is that 2～8 alkylidene group or list or polyoxy are for alkylidene group.In the preferred C composition, above-mentioned formula unit (iii), be by terephthalic acid 1,4-butanediol ester, terephthalic acid 1,3-butanediol ester, terephthalic acid 1,4-hexamethylene dimethylene ester, ethylene glycol terephthalate, ethylene-2, the big cyclic oligomer that 6-naphthalene dicarboxylic acids ester forms, or by 2 kinds or the big cyclic oligomer that forms more than it of this big cyclic oligomer.

Among the present invention, big cyclic oligomer is to cooperate above-mentioned strand of hot thermoplastic polymers of 80 weight parts (A composition) and the big cyclic oligomer of 20 weight parts (C composition) to carry out giving mixed uniformly material in the resin combination of melting mixing.

Big cyclic oligomer, its mean polymerisation degree is 2～30, more preferably 2～10.This mean polymerisation degree can be calculated by big cyclic oligomer is applied in the high-speed liquid chromatography (HPLC).Under this situation, separate the oligopolymer of each polymerization degree, in advance the amount of making and with the detection line of the corresponding peak area of amount.

The manufacture method of big cyclic oligomer is not particularly limited, can be by the known method manufacturing.

Manufacture method as big cyclic polycarbonates oligopolymer, usually undertaken by following manner, that is,, under the thin solution that the concentration with the reactive material of this reaction mixture reduces, make its reaction with bischloroformates compound, alkali metal hydroxide and the tertiary amines of basic correspondence.Further, in order to improve this reaction efficiency, for example can use the reaction under the disclosed simulation diluting condition in the flat 02-001733 communique of TOHKEMY.The derive divalent phenol of structural unit of big cyclic polycarbonates oligopolymer of C composition and two functional alcohol of aliphatics and ester ring type can be used the material identical with the material of putting down in writing in the polycarbonate of above-mentioned A composition.Further preferred embodiment also with above-mentioned in record identical, but can especially preferably use divalent phenol.Big cyclic polycarbonates oligopolymer can be the oligopolymer that comprises the structural unit of selecting more than 2 kinds from this group.

The manufacturing of big cyclic polyester oligopolymer also can utilize known method.As this method, basically, after forming straight chain shape polyester oligomer, this oligopolymer contact cyclization catalyst is made its reaction, generate big cyclic polyester oligopolymer.As this cyclization catalyst, but illustration, the four titan-alkoxide acid esters of tetra isopropyl titanate and tetrabutyl titanate ester etc. and the organo-tin compound of monobutyl hydroxyl tin-oxide and dibutyl tin oxide etc. etc.

Further, as the solvent that uses in the cyclization, can enumerate alpha-methyl-naphthalene and neighbour, or the hydrocarbon of p-terphenyl etc.With respect to resulting polymkeric substance, the addition of cyclization catalyst is considered from the speed of response and the economy aspect of cyclization, calculates with weight metal, is preferably 0.01 weight %～2 weight %, more preferably 0.1 weight %～1 weight %.

Other manufacture method comprises by lytic enzyme making straight chain shape polyester oligomer or this oligopolymer and the reaction of glycols compound, generates the method for big cyclic polyester oligopolymer.As this method, for example, open by TOHKEMY 2004-248564 communique.Also comprise, when making straight chain shape polyester oligomer contact cyclization catalyst, use the mesoporous material (mesoporous) that supports this catalyzer, generate the method for big cyclic polyester oligopolymer.This uses the detailed situation of the method for mesoporous material, and is open by TOHKEMY 2003-082081 communique.

(D composition: Phosphorus stablizer)

Preferably further contain Phosphorus stablizer in the electroconductive resin molding material of the present invention.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.Moreover the organic radical in the phosphate ester acid compound comprises any kind in single replacement, two 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 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, more preferably 0.01～1 weight part, more preferably 0.05～0.5 weight part with the A composition～C composition of total amount 100 weight parts.In addition, the C composition, preferably having 50 weight % above among its 100 weight % is trialkylphosphate and/or phosphate ester acid compound, having 50 weight % above among preferred especially its 100 weight % is trialkylphosphate.

(other composition)

In the electroconductive resin molding material of the present invention, can further add common various additives that in resin, cooperate and reinforcer etc.

(cross-linked polymer)

In the electroconductive resin molding material of the present invention, beyond linear polymer, but also compound rubber matter polymkeric substance is the cross-linked polymer of representative.Target value as the use level of this polymkeric substance is, the total amount with respect to the A composition～C composition of 100 weight parts is preferably 0.1～50 weight part, more preferably 0.5～30 weight part, more preferably 1～15 weight part.This rubber polymer preferably in rubber matrix in conjunction with the rubber mass graft copolymer of grafted chain.This rubber matrix is to have the polymkeric substance that caoutchouc elasticity becomes the cadre of graftomer, and its second-order transition temperature is preferably below-10 ℃ below 10 ℃, more preferably-30 ℃ below.As this rubber matrix, for example, but illustration, the multipolymer of the multipolymer of the multipolymer of the multipolymer of the random copolymers of polyhutadiene, polyisoprene, styrene butadiene or segmented copolymer, acrylonitrile butadiene copolymer, alkyl acrylate or alkyl methacrylate and divinyl, ethene and alpha-olefin, ethene and esters of unsaturated carboxylic acids, ethene and fatty acid ethylene, ethene and propylene and non-conjugated diene heteropolymer ( one Port リマ one), acrylic rubber and silicon class rubber etc.As derived rubber matter graft copolymer the branch chain monomer, can enumerate aromatic ethylene compound, vinyl cyanide compound, acrylate and methacrylic ester etc. aptly.Object lesson as the rubber mass graft copolymer, can enumerate SB multipolymer (styrene butadiene), Acrylonitrile Butadiene (acronitrile-butadiene-styrene), MBS multipolymer (MMB methyl methacrylate butadiene vinylbenzene), MABS multipolymer (methyl methacrylate acronitrile-butadiene-styrene), MB multipolymer (MMB methyl methacrylate butadiene), ASA multipolymer (vinyl cyanide styrene-acrylonitrile copolymer base rubber), AES multipolymer (vinyl cyanide ethylene propylene rubber vinylbenzene), MA multipolymer (methyl methacrylate acrylic rubber), MAS multipolymer (methyl methacrylate acrylic rubber vinylbenzene), methyl methacrylate-acrylate-butadiene rubber multipolymer, methyl methacrylate-acrylate-butadiene rubber-styrol copolymer and methyl methacrylate-(vinylformic acid silicone IPN rubber) multipolymer etc.In rubber mass graft copolymer 100 weight %, rubber matrix is preferably more than the 50 weight %, more preferably 55～85 weight %.

(packing material)

In the electroconductive resin molding material of the present invention, beyond the B composition, 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 determine by visual inspection as a rule, still, for example as 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 and on the surface of these packing materials, be coated with the tabular packing material etc. of foreign material.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, the value that then refers to the mid-diameter (D50) of the size distribution measured by the laser diffraction and 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 electroconductive resin molding material.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, 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, be by utilize scanning electronic microscope to the moulding product 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 glass fibre, glass milled fiber, potassium titanate crystal whisker, boron whisker, aluminium borate whisker, calcium carbonate crystal whisker, titanium oxide whisker, wollastonite, xonotlite, polygorskite (attapulgite) and sepiolite etc.; The heatproof organic fiber of Kevlar, polyimide fiber and polybenzothiozole fiber etc. is the fibrous heat-resisting organic filler material of representative; And the fibrous packing material of the foreign material that on the surface of these packing materials, is covered 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 electroconductive resin molding material.Fibrous packing material can similarly carry out surface treatment by various couplers with above-mentioned tabular packing material, also can carry out boundling by various resins etc. and handle, can also be by processed compressed and granulation.

With 100 weight parts the A composition～when the C composition was benchmark, the content of this packing material was preferably 0.1～200 weight part, 1～100 weight part more preferably, more preferably 3～50 weight parts are preferably 5～30 weight parts especially.

(releasing agent)

In the electroconductive resin molding material of the present invention, can cooperate releasing agent as required.Electroconductive resin molding material of the present invention requires to have high dimensional precision mostly.Therefore, preferred electroconductive resin molding material has excellent release property.Can use known releasing agent as this releasing agent.For example, can enumerate polyunsaturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (for example, polyethylene wax and 1-olefin polymerization thing etc.Also can use the compound of the functional group by containing aerobic modification etc. and the material of modification), silicone compounds, fluorine cpd (being the fluorocarbon oil of representative for example), paraffin and beeswax etc. with poly-fluoroalkyl ether.With respect to total 100 weight parts of A composition～C composition, this releasing agent is preferably 0.005～2 weight part.

Fatty acid ester of the present invention can also can be complete ester (full ester) for part ester (ester of partial esterification).Acid value in the fatty acid ester of the present invention is preferably (desirable in fact 0) below 20.In addition, the hydroxyl valency in the fatty acid ester is preferably 0.1～30.Further, the iodine value in the fatty acid ester is preferably (desirable in fact 0) below 10.These characteristics can be by trying to achieve with the method for JIS K 0070 regulation.

(fire retardant)

Electroconductive resin molding material of the present invention needs to improve its flame retardant resistance sometimes.In this case, cooperate fire retardant, flame retardant and drippage to prevent agent.As above-mentioned fire retardant, can enumerate various halogen based flame retardants, organophosphate based flame retardant, mineral-type fire retardant, organic alkali metal salt (alkaline-earth metal salt) fire retardant, silicone fire retardant and phosphazene flame retardant etc.

As the halogen based flame retardant, can enumerate tetrabromo-bisphenol, tetrabromo-bisphenol oligopolymer, brominated bisphenol based epoxy resin, brominated bisphenol class phenoxy resin, brominated bisphenol class polycarbonate, brominated Polystyrene, bromination crosslinked polystyrene, bromination polyphenylene ether, poly-two bromo phenylene ethers, ten bromo diphenyloxides are for the bis-phenol condenses and contain halophosphate.

As the organophosphate based flame retardant, but illustration, the phosplate compound of triphenyl etc., Resorcinol two (two (2, the 6-xylyl) phosphoric acid ester), the condensed phosphoric acid esters of dihydroxyphenyl propane two (diphenyl phosphoester) and dihydroxyphenyl propane two (two (2, the 6-xylyl) phosphoric acid ester) and tetramethylolmethane phenylbenzene bisphosphate etc.

As the mineral-type fire retardant, but illustration, the mineral-type phosphoric acid salt of polyphosphoric acid ammonium salt, aluminum phosphate and zirconium phosphate etc.; The metal oxide of the hydrate of the inorganic metal compound of aluminium hydroxide and magnesium hydroxide etc. and zinc borate, methyl-boron-dihydroxide zinc, magnesium oxide, molybdenum oxide, zirconium white, stannic oxide and weisspiessglanz etc.

As organic alkali metal salt (alkaline-earth metal salt) fire retardant, but illustration, potassium perfluorobutane sulfonate, perfluorinated butane sodium sulfonate, perfluorinated butane sulfonic acid caesium, phenylbenzene sulphur generation-3-potassium sulfonate, phenylbenzene sulphur generation-3,3 '-disulfonic acid potassium and sodium formalin condenses etc.

As the silicone fire retardant, can utilize, improve the known silane compound or the silicone compounds of the flame retardant resistance of polycarbonate resin.For example, but illustration, high density contain the silicone compounds of aryl, the silane that contains aryl and alkoxyl group or silicone compounds, contain the silane compound of Si-H group (particularly high density contains aryl) or the multipolymer of silicone compounds and organo-siloxane and polycarbonate resin etc.

In addition, as phosphazene flame retardant, but illustration, benzene oxygen phosphonitrile oligopolymer or ring-type benzene phosphine oxide nitrile oligopolymer.

As flame retardant, can enumerate sodium antimonate and ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.Prevent agent as drippage, but illustration has the tetrafluoroethylene that fibril forms ability.In order to improve the dispersiveness of tetrafluoroethylene in the electroconductibility electroconductive resin molding material, form when cooperating this tetrafluoroethylene can be dispersion liquid, the dispersion liquid polymkeric substance mixture of cohesion or dispersion liquid or the solid and be the premixture of the inorganic filler with sliding of representative with the talcum altogether with other.

With respect to the A composition～C composition of 100 weight parts, the use level of fire retardant is preferably 0.01～20 weight part.With respect to the A composition～C composition of 100 weight parts, the use level of flame retardant is preferably 0.01～10 weight part.With respect to the A composition～C composition of 100 weight parts, drippage prevents the use level of agent (having the net content that fibril forms the tetrafluoroethylene of ability), is preferably 0.01～2 weight part.

(Hinered phenols stablizer and other antioxidant)

The Hinered phenols stablizer has the resistant to heat aging effect that prevents electroconductive resin molding material.Electroconductive resin molding material of the present invention uses under high thermal environment sometimes, is particularly suitable for cooperating the Hinered phenols stablizer under this environment.As this Hinered phenols stablizer, for example can enumerate 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-two (3 methy 6 tert 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 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These all are easy to obtain.Wherein, preferably use octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester.

In the electroconductive resin molding material of the present invention, except above-mentioned Hinered phenols stablizer, can also use other antioxidant.As this other antioxidant, can enumerate, for example, 3-hydroxyl-5, the resultant of reaction of 7-di-t-butyl furans-2-ketone and o-Xylol are the sulfur-bearing class stablizer of the lactone stablizer of representative (details of this stablizer is documented in the flat 7-233160 communique of TOHKEMY) and tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerol-3-stearyl thiopropionate etc.Above-mentioned Hinered phenols stablizer can use use more than 2 kinds also capable of being combined separately.With respect to the total amount as A composition～C composition of 100 weight parts, the usage quantity of these stablizers is preferably 0.0001～1 weight part, more preferably 0.005～0.5 weight part.

(hydrolysis modifying agent)

Electroconductive resin molding material of the present invention will use in high thermal environment sometimes, so require to improve its hydrolytic resistance sometimes.Under this situation, in the scope of not damaging the object of the invention, can cooperate as the hydrolysis modifying agent in the poly-carbon ester resin and known in the prior art compound.As this compound, can enumerate epoxy compounds, oxetane compound, silane compound and phosphinic acid compounds etc.Particularly preferably be epoxy compounds and oxetane compound.As epoxy compounds, preferably can enumerate with 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters be representative the alicyclic epoxy compound, and be the epoxy compounds that contains Siliciumatom of representative with 3-glycidyl propoxy--triethoxyl silane.With respect to the A composition～C composition of 100 weight parts, the content of this hydrolysis modifying agent is preferably 0.005～1 weight part.

(flow ability modifying agent)

Electroconductive resin molding material of the present invention, most dimensional stabilitys that require height.Sometimes require good flowability in this case.In this case, it is resultful cooperating flow ability modifying agent.Therefore, in the scope of not damaging purpose of the present invention, can cooperate as flow ability modifying agent and known in the prior art compound.As this flow ability modifying agent, for example, (for example can enumerate fluidizer, can enumerate phosphoric acid ester, the phosphoric acid ester oligopolymer, the phosphonitrile oligopolymer, fatty acid ester, aliphatic polyester, and aliphatic polycarbonate etc.), the wire oligopolymer (for example, can enumerate polymerization from vinylbenzene, oligopolymer that at least a composition of selecting in vinyl cyanide and the polymethylmethacrylate forms and polycarbonate oligomer etc.), and lubricant (for example, can be enumerated mineral oil, synthetic oil, high-grade aliphatic ester, higher fatty acid amides, organopolysiloxane, olefines wax, polyalkylene glycol and fluorocarbon oil etc.) etc.Herein, oligopolymer is that mean polymerisation degree is 2～30 to be preferably 2～10 polymkeric substance.

A composition～C composition with respect to 100 weight parts, the content of above-mentioned fluidizer is preferably 0.5～20 weight part, the thermoplastic resin or the thermoplastic resin oligopolymer of other of above-mentioned high rigidity and high workability are preferably 0.5～30 weight part, liquid crystalline polymers is preferably 0.5～30 weight part, upright and outspoken type molecule is preferably 0.1～15 weight part, and lubricant is preferably 0.1～10 weight part.

(UV light absorber)

Electroconductive resin molding material of the present invention requires to improve its weathering resistance or ultraviolet-absorbing sometimes, under this situation, preferably is combined with UV light absorber.As UV light absorber, can enumerate particularly as the known benzophenone compound of UV light absorber, benzotriazole compound, hydroxyphenyltriazinuv compounds, cyclic imide base ester compound, cyanoacrylate compound etc.More specifically; for example can enumerate 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-chlorine (2H)-benzotriazole-2-yl]-4-methyl-6-tert butyl phenol and 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); 1,3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen]-2; 2-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] methylpropane etc.Further, also can use with two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate etc. and be the hindered amine light stabilizer of representative.With respect to the A composition～C composition of 100 weight parts, the usage quantity of this UV light absorber, photostabilizer is preferably 0.01～5 weight part.

(static inhibitor)

In electroconductive resin molding material of the present invention, also can and use static inhibitor.As described static inhibitor, for example can enumerate 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.Further, as the A composition, also can contain polyether ester amides with antistatic property.In the A of 100 weight % composition～C composition, the content of described static inhibitor is preferably 0.5～20 weight part.

(other supplementary component)

Except above-mentioned, in the electroconductive resin molding material of the present invention, can also cooperate antiseize paste (for example PTFE particle and High molecular weight polyethylene particle etc.), tinting material, mineral-type fluor (for example being the fluor of parent crystal), inorganic or organic antibacterial agent, photocatalyst class stain control agent (particulate titanium dioxide and particulate oxide zinc etc.) etc. with aluminate.

(manufacturing of electroconductive resin molding material)

When making electroconductive resin molding material of the present invention, its manufacture method is had no particular limits.But,, therefore, preferably use biaxial extruder that A composition, B composition, C composition and other composition are carried out melting mixing because the dispersion of electroconductibility weighting agent needs excellent mixing behavior.

As the typical example 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, and more preferably 28～42.The L/D value is big more, the uniform dispersion state of easy more formation, but when too big, the then decomposition that produces resin because of thermal ageing easily.

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.In the nanometer fibrous weighting agent of CNT etc., consider the cut-out of the fiber in the mixing zone, be necessary to adopt suitable mixing plot structure.That is, consider to avoid the surplus in mixing shearing force load and be provided with.In addition, in the supply area and constricted zone of material, the structure of also considering Fast Compression can promote the cut-out of fiber, considers this aspect, is necessary the L/D that reduces compression ratio and elongate constricted zone.

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 molding material 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 molding material thus.As described filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.

To there is no particular limitation to the method for forcing machine supply with B composition, C composition and other additive (abbreviating " additive " in the following illustration as).Each additive can be supplied with in the dried back of mixing, and also can not do and mix and the direct forcing machine that independently is supplied to.Each additive is also made part or all melting mixing of A composition and additive or solution mixing system cooperation and is supplied to forcing machine with enriched material and with the form of this enriched material.In addition, even in dried mixing, also can temporarily make the host that high density cooperates additive, this host independently or with remaining polymkeric substance further is supplied to forcing machine after the pre-mixing.In addition, this host can select to make powder morphology and with in the form of this powders compression granulation etc. any.Premixed device for example can be enumerated Nautamixer, V-type mixing tank, Henschel mixing tank, chemomotive force device and extrude mixing tank etc.The high-speed stirring type mixing tank of wherein preferred Henschel mixing tank etc.Other pre-blend approach for example, is made the homodisperse solution in solvent with polymkeric substance and additive, then, removes the method for this solvent.

By the resin that forcing machine is extruded, can directly cut off granulation and also can form strand and cut off this strand with tablets press then and carry out granulation.Further, sometimes in order to reduce the influence of outside dust etc., preferably purify the environment around the forcing machine.When this granulation, can use CD with the various methods of having mentioned in the polycarbonate resin, carry out aptly, make coating of particles distribute narrow and smallization, reduce and shortly to cut thing, reduce the small powder that transports or take place when carrying and to reduce the bubble (bubbles of vacuum) that takes place in strand or granule interior.By this forming method, the bad generation ratio that can carry out the height circulationization of moulding and reduce silver-colored light etc.

Coating of particles can be the general shape of cylindrical, corner post shape, sphere etc., 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, more preferably 2～5mm, 2.5～3.5mm more preferably.

(cooperate and use enriched material)

Masterbatch (that is cooperation enriched material) is used in the cooperation of electroconductibility weighting agent (wherein, preferred CNT) in polymkeric substance more.This enriched material makes the compounding practice of electroconductibility weighting agent become easy.Therefore, from the particulate of above-mentioned electroconductive resin molding material of the present invention is made, as the raw material that is supplied to forcing machine, enriched material is used in cooperating that the part that can make the A composition in advance and B composition and C composition form, utilize this cooperation enriched material, consequently, can obtain having the moulding product of electroconductibility of the electroconductibility of electroconductibility and productivity excellence.Though its reason is also indeterminate, the cooperation enriched material that is formed by B composition and C composition only can not substantially improve the injection speed dependency of the electroconductibility molding material that obtains sometimes.In addition, cooperate with the A composition in the enriched material, that is, the strand of hot thermoplastic polymer can be the polymkeric substance different with this polymkeric substance.

Cooperate with in the enriched material at this, preferred A composition is a polycarbonate, and the B composition is CNT.This cooperates with the polycarbonate in the enriched material, and more preferably its divalent phenol composition is a dihydroxyphenyl propane.Further, be 17000～30000 preferably by cooperating viscosity-average molecular weight with the isolating A composition of enriched material.Viscosity-average molecular weight, more preferably 19000～28000, more preferably 20000～26000.Cooperation of the present invention is identical with the B composition with the content and the preferred implementation thereof of CNT in the enriched material and big cyclic oligomer.

Further, cooperation of the present invention is with in the enriched material, and is same with electroconductive resin molding material, preferably with respect to the A composition～C composition of 100 weight parts, cooperates the Phosphorus stablizer as the D composition of 0.0001～2 weight part.This use level is 0.01～1 weight part more preferably, more preferably 0.05～0.5 weight part.In addition, this cooperates uses in the enriched material, and also preferred D composition is among the 100 weight %, and having 50 weight % above is trialkylphosphate and/or phosphate ester acid compound, and among the particularly preferred 100 weight %, having 50 weight % above is trialkylphosphate.

Cooperate with in the enriched material, enriched material is used in the CNT cooperation, and preferably this enriched material 600 ℃ of following heat treated ash residue after 6 hours in air is below the 0.5 weight %.This ash residue is preferably 0.001～0.5 weight %, more preferably 0.005～0.2 weight %, more preferably 0.015～0.15 weight %.Enriched material is used in the CNT cooperation that is adjusted to above-mentioned ash residue amount, when the A composition is polycarbonate, can suppress the deterioration of its characteristic.Therefore, use the fracture-resistant or the dimensional precision of the electroconductive resin molding material of this enriched material manufacturing can further improve.

Cooperation enriched material of the present invention can the method identical with the manufacture method of above-mentioned electroconductive resin molding material be made, particularly the specified amount of the mixing A composition of preferred molten, B composition and C composition.This melting mixing can use pressurization kneader, Banbury mixing tank and various forcing machine etc.During this is mixing, also can adds water, organic solvent and supercutical fluid etc. and carry out, its situation with electroconductive resin molding material is identical.Cooperating with in the manufacturing of enriched material, behind the molten state mixing B composition and C composition with the C composition, can further add the A composition and carry out melting mixing.In addition,, also can the B composition be dispersed in water, organic solvent and the supercutical fluid etc., then, mix with other composition for the easier dispersion of carrying out the B composition.As the method beyond the melting mixing, also can mix solution and B composition or its dispersion liquid of A composition and/or C composition, obtain making the isolating mixture of solute.This mixes, and the super mixer that can use roll surface speed to surpass the high-shear type of 30m/s carries out.

Cooperation is used known method of cooling and cutting method with enriched material, makes particle shape or indefinite form.Coating of particles can be the general shape of cylindrical, corner post shape, sphere etc., but pref. cylindrical.The diameter of described cylinder is preferably 1～5mm, 1.5～4mm more preferably.On the other hand, the length of cylinder is preferably 1～30mm, 2～5mm more preferably.

(use and cooperate the method for making electroconductive resin molding material with enriched material)

As mentioned above, according to the present invention, provide the manufacture method of above-mentioned (8).The detailed situation of A composition～C composition that this method is utilized and cooperation usefulness enriched material as mentioned above.During this mixes, illustrated in the manufacture method as electroconductive resin molding material, most preferably utilize the exhaust biaxial extruder.

The manufacturing of this molding material, center housing temperature are preferably set to 250～320 ℃, more preferably are set at 270～310 ℃, and the screw rod revolution is preferably set to 60～500rpm, more preferably is set at 70～200rpm.In this melting mixing, can be from supplying with the method that cooperates the usefulness enriched material with the same supplying opening of the resin of raw material A composition, also can be from forcing machine midway to the method for this enriched material of molten resin supplying, also can be to cut apart the method for supplying with this enriched material from a plurality of supplying openings.

(the moulding product that electroconductive resin molding material of the present invention forms)

Electroconductive resin molding material of the present invention, the particle that will make as mentioned above carries out injection moulding and produces various moulding product usually.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 moulding product.

In this injection moulding, not only can adopt common forming method, can also be according to purpose, suitably adopt injection compression molding, injection pressure moulding, gas assistant injection molding, foaming (comprising the moulding of injecting), insert moulding by supercutical fluid, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, the injection molding method of heating cooling mould molding, dual-color forming, interlayer moulding and ultra-high speed injection moulding 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, electroconductive resin molding material of the present invention also can become forms such as various special-shaped extrusion molding articles, sheet and film like and be used by extrusion moulding.In addition, in sheet, film like moulding, can also use blow moulding, rolling process, casting method etc.And, by implementing specific stretched operation, also can be shaped to heat-shrinkable tube.In addition, also can electroconductive resin molding material of the present invention be manufactured the moulding product by rotoforming or blow molding etc.

To electroconductive resin molding product of the present invention, can carry out various surface treatments.In this said surface treatment, be meant that the top layer at synthetic resin of evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (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 for 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 etc. think the embodiments of the present invention of present the best, are the embodiments that has compiled the preferable range of above-mentioned each important document, for example, have put down in writing its typical example in the following embodiments.Certainly the present invention is not subjected to the restriction of these embodiments.

Embodiment

The present invention is described by the following examples.But the present invention is not limited to this.In addition, evaluation is to be undertaken by implementing following project.

(I) assessment item

(I-1) surface resistivity

With the injection speed of 10mm/sec and two kinds of injecting conditions of injection speed of 50mm/sec, the square plate of forming width 45mm * length 80mm * thickness 2mm.Take out the moulding product of the 2nd, 4,6,8,10 injection after purifying, it was placed 24 hours under the environment of 23 ℃ of temperature and relative humidity 50%, then, use numeral insulation meter (East Asia electric wave industry (strain) manufacturing) and low-resistivity meter (Mitsubishi Chemical's (strain) manufacturing) that these 5 square plates are measured surface resistivity, calculate its mean value.

(I-2) electrostatic charging discharge (ESD) characteristic

In the square plate that uses in the evaluation of above-mentioned (I-1), use injection speed to carry out the square plate of moulding as 50mm/sec, use electrified voltage determinator (シシ De static gas (strain) manufacturing) under the electrified voltage of 10kV, to make electric charge saturated to 5 square plates, measure the transformation period of electrified voltage then, calculate its mean value.In addition, 0 second souvenir in the table is meant and uses any sample also not reach saturation voltage.

(II) manufacturing of electroconductive resin molding material and moulding product

With the electroconductive resin molding material of following method manufacturing by the cooperation composition of proportions described in the table.In addition, explanation is to carry out according to the symbol in the following table.

According to the cooperation ratio (weight part) described in the table, each raw material described in the table is taken by weighing to the bag of polyethylene system, fully shake this bag by above-below direction and left and right directions, the raw material that will pack into is done equably and is mixed.This mixture is supplied to the aftermost the 1st of the exhaust biaxial extruder that screw diameter is 15mm (KZW15-25MG, テ Network ノベ Le (strain) is made) to be added in the inlet.Center housing temperature and die body temperature are 290 ℃ in embodiment 4 and comparative example 4, be 310 ℃ in embodiment 8 and comparative example 6, are 270 ℃ in other embodiment and comparative example.Screw speed is 250rpm, and extrusion capacity hourly is 2kg, and exhaust vacuum tightness is 3kPa.In addition, the structure of the mixing part of screw rod is the mixing district that has in the upstream side of exhaust position and downstream side by the kneading disk structure.The strand of extruding cools off in water-bath, then, cuts off granulation by tablets press.

The particle that obtains after dry 10 hours, is used injection moulding machine (J75EIII type, (strain) JSW system), the square plate moulding product of forming width 45mm * length 80mm * thickness 2mm with hot air dryer down at 90 ℃.Center housing temperature is 280 ℃ in embodiment 1～7,9 and comparative example 8, is 300 ℃ in embodiment 8, the comparative example 1～4 and 7, is 260 ℃ among the embodiment 10, is 320 ℃ in the comparative example 5, is 340 ℃ in the comparative example 6, and the die body temperature is 90 ℃.Injection speed is two kinds of 10mm/sec and 50mm/sec as mentioned above.

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

(A composition)

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

PC-2: viscosity-average molecular weight is 28500 straight chain shape aromatic polycarbonate resin powder (パ Application ライト K-1285WQ (trade(brand)name), Supreme Being people change into (strain) and make)

PC-3: the vitrifying tansition temperature by following method manufacturing is that 171 ℃, water-intake rate are the heat resistant poly carbonic ether of 0.2 weight %

PAR: polyacrylate resin (U Port リマ one U-100 (trade(brand)name), ユニチカ (strain) makes)

PEN:2,92 moles of % of 6-naphthalene diformic acid dimethyl ester and 8 moles of % of dimethyl terephthalate (DMT) and ethylene glycol are according to usual method, carry out the polyethylene terephthalate (テオネ Star Network ス TN8770 (trade(brand)name), Supreme Being people change into (strain) and make) of the IV:0.70 of transesterification reaction and melt polymerization acquisition

PPE: polyphenylene ether resin (ザイロ Application 300H (trade(brand)name), Asahi Chemical Industry's industry (strain) is made)

(mixture of A composition and cross-linked polymer)

ABS: the ABS resin that accounts for all about 12 weight % with the polyhutadiene component content of continuous block polymerization manufacturing, this ABS resin forms (サ Application Star Network U T-61, Japanese エイア Application De エ Le (strain) is made) by free acrylonitritrile-styrene resin composition 80 weight % and acrylonitrile-styrene-butadiene graft copolymers composition 20 weight %

(manufacture method of PC-3)

Take into account adding ion exchanged water 19580 weight parts and 48.5 weight % aqueous sodium hydroxide solutions, 3850 weight parts in the reactor of agitator toward having temperature, toward wherein dissolving 9, two (4-hydroxyl-3 aminomethyl phenyl) fluorenes (being designated hereinafter simply as " BCF ") 1175 weight parts of 9-and dihydroxyphenyl propane (below abbreviate " BPA " as) 2835 weight parts and hydrosulphite 9 weight parts, then, add methylene dichloride 13210 weight parts, under 15 ℃, limit high degree of agitation ray flower was blown into phosgene 2000 weight parts in about 40 minutes, made its reaction.After phosgene is blown into end, rise to 28 ℃, add aqueous sodium hydroxide solution 640 weight parts of p-tert-butylphenol 94 weight parts and 48.5 weight %, make its emulsification, then, add triethylamine 6 weight parts, continue to stir 1 hour, reaction is finished.After ending, reaction separates organic phase, dilute with methylene dichloride, it is acid and wash to make hydrochloric acid after the washing, when the electric conductivity of water is almost identical with ion exchanged water, evaporate methylene dichloride with kneader, the mol ratio that obtains BCF and BPA is 20: 80 colourless powder 4080 weight parts.The viscosity-average molecular weight of this aromatic copolycarbonate powder is 20300.

(A composition and B mixture of ingredients)

CNT-1: the ash residue of carbon nanotube is 9 weight %, it is 1.3 weight % that carbon nanotube cooperates with the ash residue in the enriched material, fluorescent X-ray determinator (the MESA-500 type of these ash residue, the making manufacturing of (strain) hole field) part by weight of the element of calculating, iron is that 63 weight %, aluminium are that 28 weight % and nickel are 3 weight %, carbon nanotube concentration is 15 weight %, straight chain shape aromatic copolycarbonate cooperates with enriched material (carbon nanotube masterbatch MB6015-00, Ha イペリオ Application society makes) as the carbon nanotube of matrix composition

CNT-2: the ash residue of the carbon nanotube by following method manufacturing is 0.4 weight %, it is 0.1 weight % that carbon nanotube cooperates with the ash residue in the enriched material, fluorescent X-ray determinator (the MESA-500 type of these ash residue, the making manufacturing of (strain) hole field) part by weight of the element of calculating, iron is almost 100 weight %, and carbon nanotube concentration is the carbon nanotube cooperation enriched material of 5 weight %.

(manufacturing of the carbon nanotube of CNT-2)

Use have internal diameter 76mm, length 1500mm silicon carbide system the stove core barrel and can be from the longitudinal type Reaktionsofen of this stove core barrel of indirect heating.Drop into reaction raw materials from the top of tower of this Reaktionsofen, from the recovery still recovery resultant of reaction of bottom.Half of environment hydrogen supplied with raw material, and second half is independently supplied with from top of tower.Environment hydrogen recycles by the separator separation.Raw material is pre-mixed in toluene, and making ferrocene is that 1.6 weight % and thiophene are 1.6 weight %, is that 8 seconds speed is supplied with this liquid residence time in stove, and temperature is 1200 ℃ in the stove, makes its reaction.Furnace pressure is almost normal pressure, and the toluene concentration in the furnace gas is 7 capacity %.

The generation attitude that recovery obtains further is warming up to 1200 ℃, and separating treatment hydrocarbon 30 minutes then, carries out pyroprocessing under 2800 ℃, improves crystallinity.Final resultant is that external diameter is the carbon nanotube of about 60nm.

(cooperation of the CNT-2 manufacturing of enriched material)

With the above-mentioned carbon nanotube that obtains, methyl alcohol, water and methylcellulose gum with weight ratio 20: 20: 9: 1 mixes, and carries out granulation 15 minutes by tablets press (granulator), dry in 110 ℃ hot air dryer then, obtains the granulation thing of carbon nanotube.Above-mentioned PC-1 with respect to 100 weight parts, with this granulation thing of super mixing tank pre-mixing 18 weight parts and the trimethyl phosphate of 0.2 weight part, then, this premixture is supplied to the exhaust biaxial extruder that screw diameter is 15mm (KZW15-25MG, テ Network ノ Block Le (strain) make) to carry out melting mixing and obtains particle.Condition is identical with the manufacturing of resin combination.

(B composition)

CNT-3: the multilayer carbon nanotube C that Korea S CNT society makes _TUBE100 (buying) from (strain) field, temple

CB: conductive carbon black (DBP oil number 495ml/100g) (Ketjen black EC-600JD (trade(brand)name), ライオ Application (strain) is made)

(C composition)

CBT: polybutylene terephthalate cyclic oligomer (buying) from U.S. Cyclics Corporation

(B composition and C mixture of ingredients)

CNT-4: the CNT-3 of the above-mentioned B composition of the CBT of the above-mentioned C composition of 20 weight parts (83.3 weight %) and 4 weight parts (16.7 weight %) is added in the container, make with corresponding full-bodied magnetic stirrer and can stir this container contents.Tank immersion in 80 ℃ oil bath, was kept decompression state 1 hour by vacuum pump, and then, under this decompression state, oil bath is warming up to 200 ℃, fusion CBT, and the stirring of carrying out 2 hours obtains homogeneous substance.The homogeneous substance transfer that obtains is injected on the teflon still, and cooling curing is pulverized with pulverizer mill, makes B composition and C mixture of ingredients.

(A composition, B composition and C mixture of ingredients)

CNT-5: the PC-1 of the above-mentioned A composition of the CBT of the above-mentioned C composition of 20 weight parts and 6 weight parts is dissolved in the methylene dichloride of 130 weight parts, makes homogeneous solution, then, the evaporation methylene dichloride obtains their mixture.With the CNT-3 of the above-mentioned B composition of these mixture 26 weight parts and 4 weight parts, use screw rotor type kneader, by vacuum pump, under reduced pressure mixing 20 minutes, obtain mixing thing, should mixing thing pulverizing make mixture.

(D composition: Phosphorus stablizer)

TMP: trimethyl phosphate (big eight chemical industry (strain) are made for trimethyl phosphate, TMP (trade(brand)name))

AX71: list and stearic bicine diester base phosphate ester acid (アデカス Block A X-71 (trade(brand)name), rising sun electrochemical industry (strain) is made)

Use the molding material of the foregoing description 9, the preform of moulding wall thickness 5mm, height 7cm then, is heated to about 150 ℃ with quartz heater, injects in the mould, is blown into the pressurized air of about 3MPa, and obtaining the area multiplying power is about 12.5 times blow molded article.The surface resistivity of this formed body is 10E+2 Ω, obtains the moulding product of good electrical conductivity.

In addition, for the moulding product of the foregoing description 1 and 3,, as shown in Figures 1 and 2, can be observed the segregation structure of CNT by its section of infiltration type electron microscope observation.As can be known, because this clear and definite segregation structure has been reached good electrical conductivity and has been improved the injection speed dependency.Express the same observation photo in the comparative example 3 among Fig. 3, as can be known, compare with the situation of the embodiment 3 of Fig. 2, its segregation structure is indeterminate, and CNT is whole to be disperseed.On the other hand, because the big cyclic polyester and the polycarbonate of C composition mix equably, therefore, the expression of this segregation structure is complete unexpected result.In addition, use and same forcing machine and the shaper of embodiment, the PC-1:80 weight part and the CBT:20 weight part that use in the foregoing description are extruded the manufacturing particle under 280 ℃, use drying machine after dry 10 hours down at 90 ℃, this particle is obtained the thick level and smooth tabular moulding product of 2mm at 270 ℃ of center housing temperatures and 90 ℃ of compacted unders of die temperature, its mist degree is 0.6%, total light transmittance is 90%, confirms that CBT mixes fully with polycarbonate among the 20 weight %.This good intermiscibility is with disclosed consistent in the known document of prior art.

Industrial applicibility

Electroconductive resin molding material of the present invention is filled out by cooperate electric conductivity in thermoplastic polymer Fill agent and big cyclic oligomer, have excellent electric conductivity and particularly have the injection speed that has reduced and rely on The property. According to this characteristic, electroconductive resin molding material can be corresponding to the notes of the condition of molding of wide region Molded, consequently applicable to the products formed shape of broad purposes. As described purposes, for example can To enumerate computer, laptop computer, game machine (home-use game machine, business game machine, hoodle trip Play machine and slot machine etc.), (LCD, organic EL, Electronic Paper, plasma are aobvious for display unit Show device and projector etc.), send electric parts (housing of line of induction ring type power transmission device etc.). As the institute State purposes, can also exemplify printer, duplicator, scanning machine and facsimile machine and (comprise the compound of them Machine). As described purposes, can also enumerate VTR camera, optically thin membrane type camera, digital camera, The camera precision instrument of lens unit, preventing device and mobile phone etc. Especially, of the present invention leading Electrically resin combination is suitable for the frame of the digital image information processors such as camera lens barrel, digital camera On body, cover and the framework.

Further, electroconductive resin molding material of the present invention also is applicable to massager or high oxygen therapy The medicine equipment of device etc.; Video recorder (so-called DVD burner etc.), sound machine and electronics are happy The household electronic products of device etc.; The game device of Ball paddle device and slot machine game etc.; And carried essence On the parts of the home-use automatics of close sensor etc.

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

Therefore, electroconductive resin molding material of the present invention is at OA mechanical field, electric and electronic machinery neck Exceedingly useful in the various industrial uses in territory etc., its industrial effect that reaches is very excellent.

Claims

1. electroconductive resin molding material, it comprises:

Strand of hot thermoplastic polymer as the A composition;

Electroconductibility weighting agent as the B composition; And

As the big cyclic oligomer of C composition,

2. electroconductive resin molding material as claimed in claim 1, wherein, in the resin combination that the A composition of 80 weight parts and the C composition of 20 weight parts is cooperated and carry out melting mixing form, the C composition is to be used to make this resin combination to form the composition of homogenizing mixture.

3. electroconductive resin molding material as claimed in claim 1 or 2, wherein, the C composition is big cyclic polyester oligopolymer.

4. as each described electroconductive resin molding material in the claim 1～3, wherein, the B composition is a conductive carbon material.

5. as each described electroconductive resin molding material in the claim 1～4, wherein, the A composition is to be selected from least a as principal constituent in the group of being made up of polycarbonate, polyarylester, poly-naphthalic acid alkylidene group diester and polyphenylene ether.

6. electroconductive resin molding product, it obtains by with the speed of 40mm/ more than second each described electroconductive resin molding material in the claim 1～5 being carried out injection moulding.

7. the manufacture method of electroconductive resin molding product, when it makes the electroconductive resin molding product in that electroconductive resin molding material is carried out injection moulding, can suppress the reduction of the electroconductibility that the increase because of injection speed causes, it is characterized in that, use electroconductive resin molding material, this electroconductive resin molding material comprises:

Strand of hot thermoplastic polymer as the A composition;

Electroconductibility weighting agent as the B composition; And

As the big cyclic oligomer of C composition,

8. the manufacture method of an electroconductive resin molding material, it is the manufacture method of each described electroconductive resin molding material in the claim 1～5, wherein, will cooperate with enriched material to be engaged in A composition or A composition and the C mixture of ingredients, this cooperation comprises with enriched material:

Strand of hot thermoplastic polymer as the A composition;

Electroconductibility weighting agent as the B composition; And

As the big cyclic oligomer of C composition,

Wherein, when A composition, B composition and C composition added up to 100 weight %, the A composition was 0～98 weight %, and the B composition is 1～60 weight %, and the C composition is 1～99 weight %.

9. cooperation enriched material, it comprises:

Strand of hot thermoplastic polymer as the A composition;

Electroconductibility weighting agent as the B composition; And

As the big cyclic oligomer of C composition,