CN110128891A

CN110128891A - The manufacturing method of electroconductive polymer dispersion liquid and its manufacturing method and conductive membrane

Info

Publication number: CN110128891A
Application number: CN201910096092.0A
Authority: CN
Inventors: 松林总
Original assignee: Shin Etsu Polymer Co Ltd
Current assignee: Shin Etsu Polymer Co Ltd; Shin Etsu Chemical Co Ltd
Priority date: 2018-02-02
Filing date: 2019-01-31
Publication date: 2019-08-16
Anticipated expiration: 2039-01-31
Also published as: JP2019131768A; TWI706992B; TW201934660A; CN110128891B; JP7049125B2

Abstract

Electroconductive polymer dispersion liquid of the invention contains: the conductive composite body comprising pi-conjugated electroconductive polymer and polyanion, specific acrylate compounds and decentralized medium with holo-fluorine polyester.

Description

The manufacture of electroconductive polymer dispersion liquid and its manufacturing method and conductive membrane Method

Technical field

The present invention relates to a kind of electroconductive polymer dispersion liquid and its manufacturing method comprising pi-conjugated electroconductive polymer, And the manufacturing method of conductive membrane.

This application claims based on 2 2nd, 2018 Japanese patent application 2018-017409 priority in Japanese publication, And its contents are hereby incorporated herein by reference.

Background technique

It is used to requiring the purposes of antistatic in the conductive membrane that the surface of plastic basis material is formed with conductive layer, such as The packaging or container of electronic component, the packaging of food or container etc..

As conductive material contained by the conductive layer, from electric conductivity and transparent excellent and stable conductivity and independent of From the perspective of humidity, pi-conjugated electroconductive polymer is used sometimes.

As the manufacturing method of conductive membrane, such as known there are as below methods: will include pi-conjugated electroconductive polymer and poly- yin The conductive composite body of ion is dispersed in water, and obtains electroconductive polymer dispersion liquid, applies above-mentioned electric conductivity to film substrate High molecular dispersion liquid, it is dry, conductive layer is formed, conductive membrane (patent document 1) is obtained.

The conductive layer of conductive membrane sometimes requires that soil resistance.As the method for improving soil resistance, it is known that following method: in conduction In property high molecular dispersion liquid, other than the conductive composite body comprising pi-conjugated electroconductive polymer and polyanion, also cooperate Silicone modified acrylic resin (patent document 2).

Existing technical literature

Patent document

Patent document 1: International Publication No. 2015/108001

Patent document 2: Japanese Unexamined Patent Publication 2008-156452 bulletin

Summary of the invention

Problems to be solved by the invention

But in electroconductive polymer dispersion liquid disclosed in patent document 2, electric conductivity cannot be formed and soil resistance is equal Conductive layer excellent enough.That is, in electroconductive polymer dispersion liquid disclosed in patent document 2, when in order to improve soil resistance And when increasing the amount of silicone modified acrylic resin, there is the trend of electric conductivity reduction, is reduced when in order to improve electric conductivity When the amount of silicone modified acrylic resin, there is the trend of soil resistance reduction.

The object of the present invention is to provide a kind of conductions for being able to easily form the excellent conductive layer of electric conductivity and soil resistance Property high molecular dispersion liquid and its manufacturing method.The present invention also aims to, a kind of manufacturing method of conductive membrane is provided, The conductive membrane for having the excellent conductive layer of electric conductivity and soil resistance can be easily manufactured.

A technical solution to solve project

The present invention includes mode below.

[1] a kind of electroconductive polymer dispersion liquid, contains: conductive composite body, it includes pi-conjugated electroconductive polymer and Polyanion；Acrylate compounds are indicated by following formula (1), and have holo-fluorine polyester；And decentralized medium.

[changing 1]

X¹-[Z-Rf-Z-X²]_V-Z-Rf-Z-X¹ (1)

In formula (1), Rf is that the molecular weight of divalent is 500 or more 30000 holo-fluorine polyesters below, can contain branch in Rf； X¹Group to be indicated by following formula (2) independently of one another；X²Group to be indicated by following formula (5) independently of one another；Z is divalent Organic group, oxygen atom, nitrogen-atoms, fluorine atom can be contained, and cyclic structure, unsaturated bond can be contained；V is 0 or more 5 or less Integer.

[changing 2]

(in formula (2), a and c are separately 0 or more 4 integer below, and b is 1 or more 4 integer below, and a+b + c is 2,3 or 4；R¹Group to be indicated by following formula (3) independently of one another；R²Contain acrylic acid for what is indicated by following formula (4) The group of the group of base or the acrylic replaced containing α；Q¹And Q²It is independently of one another carbon atom number is 3 or more 20 below 2 The linker of valence, the linker of the divalent may include ehter bond, ester bond, amido bond, urethane bond, and can wherein contain ring Shape structure or branch, Q¹And Q²It can be mutually the same also different)

[changing 3]

-(C₄H₈O)_d(C₃H₆O)_e(C₂H₄O)_f(CH₂O)_gR³ (3)

(in formula (3), in R¹Molecular weight be 30 or more 600 or less range in, d, e, f, g are 0 or more independently of one another 20 integers below, the arrangement of each repetitive unit can be random；R³It is 1 or more 10 saturated hydrocarbyl below for carbon atom number Or unsaturated alkyl)

[changing 4]

(in formula (4), R⁴It is independently of one another hydrogen atom, fluorine atom, methyl or trifluoromethyl；R⁵For carbon atom number be 1 with The linker of the linker of upper 18 divalent below or trivalent, the divalent or trivalent may include at least one in ehter bond and ester bond Person；N is integer 1 or 2)

[changing 5]

(in formula (5), R¹、R²、Q¹、Q²It is identical as formula (2)；H, i, j are separately 0 or more 3 integer below, and h+ I+j is 1 or more 3 any one value below, and the arrangement of repetitive unit can be random.)

[2] the electroconductive polymer dispersion liquid according to [1], wherein in the formula (1) of the acrylate compounds Rf contains 1 or more 500 repetitive units that are below, being indicated by following formula (6).

-C_iF_2iO- (6)

(i independently is 1 or more 6 integer below in each unit.)

[3] the electroconductive polymer dispersion liquid according to [1] or [2], wherein in the formula (1) of the acrylate compounds Rf be selected from by following formula (7)~(9) any one indicate group.

[changing 6]

(in formula (7), Y is F or CF independently of one another₃Base；R is 2 or more 6 integers below；M, n be separately 0 with Upper 200 integer below, and m+n is 2 or more 200 or less；S is 0 or more 6 integer below；Each repetitive unit can randomly key It closes)

[changing 7]

-C_jF_2j(OCF₂CF₂CF₂)_kOC_jF_2j- (8)

(in formula (8), j is 1 or more 3 integer below；K is 1 or more 200 integer below)

[changing 8]

(in formula (9), Y is F or CF₃Base；J is 1 or more 3 integer below；M, n is separately 0 or more 200 or less Integer, and m+n be 2 or more 200 or less；Each repetitive unit can be randomly bonded)

[4] the electroconductive polymer dispersion liquid according to any one of [1]~[3], wherein the acrylate chemical combination Z in the formula (1) of object is any one group in following formula (10)~(14).

[changing 9]

-CH₂-O-CH₂- (14)

[5] the electroconductive polymer dispersion liquid according to any one of [1]~[4], wherein the acrylate chemical combination Q in the formula (2) of object¹And Q²It is independently of one another any one group in following formula (15)~(20).

[changing 10]

-CH₂CH₂CH₂- (15)

-CH₂CH₂CH₂-O-CH₂CH₂- (16)

-CH₂CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂- (17)

-CH₂CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂- (18)

-CH₂CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂- (19)

[6] the electroconductive polymer dispersion liquid according to any one of [1]~[5], wherein the acrylate chemical combination R in the formula (2) of object²For any one group in following formula (21)~(24).

[changing 11]

[7] the electroconductive polymer dispersion liquid according to any one of [1]~[6], wherein the acrylate chemical combination R in the formula (2) of object¹For the group indicated by following formula (25).

[changing 12]

-(C₂H₄O)_p(C₃H₆O)_qCH₃ (25)

(in formula (25), p, q are separately 0 or more 20 integer below, and p+q is 1 or more 40 hereinafter, Asia in formula Propyl can be the propylidene of branch, and each repetitive unit can be randomly bonded)

[8] the electroconductive polymer dispersion liquid according to any one of [1]~[7], wherein the decentralized medium is to have Solvent.

[9] the electroconductive polymer dispersion liquid according to any one of [1]~[8], wherein the anion of the polyanion A part of group is bonded with amine compounds.

[10] the electroconductive polymer dispersion liquid according to any one of [1]~[8], wherein the polyanion yin from A part of subbase group is bonded with epoxide.

[11] a kind of manufacturing method of electroconductive polymer dispersion liquid is produced from it electroconductive polymer described in [9] point Dispersion liquid, the manufacturing method of the electroconductive polymer dispersion liquid are included to comprising pi-conjugated electroconductive polymer and polyanion Conductive composite body aqueous dispersions in add amine compounds, make the conductive composite body that the work to form precipitate be precipitated Sequence；The process for recycling the precipitate；And acrylate compounds and organic are added into the precipitate of recycling The process of solvent.

[12] a kind of manufacturing method of electroconductive polymer dispersion liquid, is produced from it electroconductive polymer dispersion liquid described in [9], The manufacturing method of the electroconductive polymer dispersion liquid is included leading comprising pi-conjugated electroconductive polymer and polyanion The aqueous dispersions of electrical complex are freeze-dried the process for obtaining freeze-drying body；And amination is added into the freeze-drying body The process for closing object, the acrylate compounds and organic solvent.

[13] a kind of manufacturing method of electroconductive polymer dispersion liquid is produced from it the dispersion of electroconductive polymer described in [10] Liquid, the manufacturing method of the electroconductive polymer dispersion liquid are included to comprising pi-conjugated electroconductive polymer and polyanion Epoxide is added in the aqueous dispersions of conductive composite body, makes the conductive composite body that the work to form precipitate be precipitated Sequence；The process for recycling the precipitate；And acrylate compounds and organic are added into the precipitate of recycling The process of solvent.

[14] a kind of manufacturing method of conductive membrane, wherein to any one of film substrate coating claim [1]~[10] The electroconductive polymer dispersion liquid.

[15] manufacturing method of the conductive membrane according to [14], wherein

To after film substrate applying conductive high molecular dispersion liquid, it is dried, irradiates active energy beam.

Invention effect

Electroconductive polymer dispersion liquid according to the present invention can be readily formed the excellent conduction of electric conductivity and soil resistance Layer.

The electroconductive polymer dispersion can be easily manufactured in the manufacturing method of electroconductive polymer dispersion liquid according to the present invention Liquid.

The manufacturing method of conductive membrane according to the present invention can be easily manufactured and have that electric conductivity and soil resistance are excellent to be led The conductive membrane of electric layer.

Specific embodiment

< electroconductive polymer dispersion liquid >

One mode of electroconductive polymer dispersion liquid of the invention is illustrated.

The acrylate chemical combination that the electroconductive polymer dispersion liquid of the method contains conductive composite body, indicated by previously described formula (1) Object (hereinafter referred to as " acrylate compounds (A) ") and decentralized medium.

(conductive composite body)

Conductive composite body in the method includes pi-conjugated electroconductive polymer and polyanion.

In this mode, since aforementioned polyanion and aforementioned pi-conjugated electroconductive polymer are coordinated, the anion base of polyanion Group is doped in pi-conjugated electroconductive polymer, therefore forms conductive conductive composite body.

In polyanion, and not all anionic group is all doped in pi-conjugated electroconductive polymer, also has remaining yin Ionic group.In this mode, it is preferred that at least part of aforementioned remaining anionic group and amine compounds and ring At least one of oxygen compound reacts and is bonded.If remaining anionic group and amine compounds and epoxide At least one of react, then the charge of remaining anionic group is neutralized, therefore conductive composite body can be made hydrophobic Change.The conductive composite body of hydrophobization and the compatibility of acrylate compounds (A) are excellent.

[pi-conjugated electroconductive polymer]

As pi-conjugated electroconductive polymer, as long as organic polymer that main chain is made of pi-conjugated system and having of the invention Effect is not particularly limited, such as can enumerate: multi-metal polypyrrole electroconductive polymer, gathers polythiophene class electroconductive polymer Acetylene class electroconductive polymer, polyhenylene class electroconductive polymer, polyphenylene vinylene class electroconductive polymer, polyaniline compound are led Electrical macromolecule, polyacene class electroconductive polymer, Polythienylenevinylethermoelectric class electroconductive polymer and their copolymer Deng.From the viewpoint of aerial stability, preferably multi-metal polypyrrole electroconductive polymer, polythiophene class and polyaniline compound Electroconductive polymer, from the viewpoint of the transparency, more preferable polythiophene class electroconductive polymer.

As polythiophene class electroconductive polymer, can enumerate: polythiophene, poly- (3 methyl thiophene), poly- (3- ethylthiophene), Poly- (3- propyl thiophene), poly- (3- butyl thiophene), poly- (3- heptyl thiophene), poly- (3- octyl thiophene), gather poly- (3- hexyl thiophene) (3- decylthiophene), poly- (3- dodecylthiophene), poly- (3- octadecyl thiophene), poly- (3 bromo thiophene), poly- (3- chlorothiophene), Poly- (3- iodothiophen), poly- (3- cyano thiophene), poly- (3- tolylthiophene), poly- (3,4- thioxene), poly- (3,4- dibutyl thiophene Pheno), poly- (3- hydroxy thiophene), poly- (3- methoxythiophene), poly- (3- ethoxythiophene), poly- (3- butoxy thiophene), it is poly- (3- oneself Oxygroup thiophene), poly- (3- oxygroup in heptan thiophene), poly- (3- octyloxy thiophene), poly- (3- decyloxy thiophene), poly- (3- dodecyloxy Thiophene), poly- (3- octadecane epoxide thiophene), poly- (3,4- dihydroxy thiophene), poly- (3,4- dimethoxy-thiophene), poly- (3,4- bis- Ethoxythiophene), poly- (3,4- dipropoxy thiophene), poly- (3,4- dibutoxy thiophene), poly- (bis- hexyloxy thiophene of 3,4-), poly- (3,4- oxygroup thiophene in bis- heptan), poly- (bis- octyloxy thiophene of 3,4-), poly- (bis- decyloxy thiophene of 3,4-), poly- (bis- (dodecane of 3,4- Oxygroup) thiophene), poly- (3,4- ethyldioxythiophene), poly- (3,4- popylenedioxythiphene), poly- (3,4- butylidene dioxy thiophene Pheno), poly- (3- methyl -4- methoxythiophene), poly- (3- methyl -4- ethoxythiophene), poly- (3- carboxy thiophene), poly- (3- methyl - 4- carboxy thiophene), poly- (3- methyl -4- carboxyethyl thiophene), poly- (3- methyl -4- carboxylic butyl thiophene).

As multi-metal polypyrrole electroconductive polymer, can enumerate: polypyrrole, poly- (3- methylpyrrole), gathers poly- (N- methylpyrrole) (3- N-ethyl pyrrole N), poly- (3- n-propyl pyrroles), poly- (3- octyl pyrroles), poly- (3- decyl pyrroles), gather poly- (3- butyl pyrroles) (3- dodecyl pyrroles), poly- (3,4- dimethyl pyrrole), poly- (3,4- dibutyl pyrroles), poly- (3- carboxy pyrrole), poly- (3- first Base -4- carboxy pyrrole), poly- (3- methyl -4- carboxyethyl pyrroles), poly- (3- methyl -4- carboxylic butyl pyrroles), poly- (3- hydroxyl pyrrole Cough up), poly- (3- methoxypyrrole), poly- (3- ethyoxyl pyrroles), poly- (3- butoxy pyrroles), poly- (3- hexyloxy pyrroles), poly- (3- Methyl -4- hexyloxy pyrroles).

As polyaniline compound electroconductive polymer, can enumerate: polyaniline, poly- (3- isobutyl-aniline), gathers poly- (2-aminotoluene) (2- anilinesulfonic acid), poly- (3- anilinesulfonic acid).

It is particularly preferably poly- from the viewpoint of electric conductivity, the transparency, heat resistance among above-mentioned pi-conjugated electroconductive polymer (3,4- ethyldioxythiophene).

The pi-conjugated electroconductive polymer that conductive composite body is included can be a kind, can also be two or more.

[polyanion]

Polyanion refers to polymer in the molecule with 2 or more monomeric units with anionic group.The poly- yin The anionic group of ion plays pi-conjugated electroconductive polymer the function as dopant, makes pi-conjugated electroconductive polymer Electric conductivity enhancing.

As the anionic group of polyanion, preferably sulfonic group or carboxyl.

As the concrete example of such polyanion, can enumerate: polystyrolsulfon acid, polyvinylsulfonic acid, polyallyl sulfonic acid, With sulfonic polyacrylate, have sulfonic polymethacrylates (for example, poly- (2- acrylamide -2- methyl-prop Sulfonic acid), polymethylacrylic acid Sulfoethyl esters, poly- (methacrylic acid -4- sulfo group butyl ester), polymethyl acyloxybenzenesulfonic acids), Polyisoprene sulfonic acid etc. has sulfonic macromolecule or polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic Acid, polyacrylic acid, polymethylacrylic acid, poly- (2- acrylamide -2- methylpropane carboxylic acid), polyisoprene carboxylic acid etc. have carboxylic The macromolecule of base.The homopolymer that can be these substances can also be wherein copolymer of more than two kinds.

Among these polyanions, from the viewpoint of it can further improve electric conductivity, preferably there is sulfonic macromolecule, more It is preferred that polystyrolsulfon acid.

Aforementioned polyanion can be used alone a kind, can also be used in combination of two or more.

The matter average molecular weight of polyanion is preferably 20,000 or more 100 ten thousand hereinafter, more preferably 100,000 or more 50 ten thousand or less.Poly- yin The matter average molecular weight of ion are as follows: measure elution time using gel permeation chromatography (GPC), be based on the polyphenyl as known to molecular weight The molecular weight for the quality criteria that the molecular weight that ethylene standard substance is previously obtained is found out relative to the calibration curve of elution time.

When a part and at least one of amine compounds and epoxide of the anionic group of polyanion occur When reacting and being bonded, hydrophobic substituent can be formed.Using at least one of amine compounds and epoxide poly- yin from Hydrophobic substituent is formed on son, the hydrophobicity of conductive composite body improves as a result,.Aforementioned bonding can be covalent bond, ion Any one in key, coordinate bond or hydrogen bond.

In addition, the detailed analysis of conductive composite body may be not easy to carry out, but speculate by the anionic group of polyanion with The reaction of amine compounds is formed by-HNR¹R²R³The hydrophobic substituent of expression.Aforementioned R¹、R²、R³For from aftermentioned amination Close the substituent group of object.For example, R¹、R²、R³In at least one be alkyl (at least one of hydrogen atom of the alkyl can also be by alkane Base, aryl, hydroxyl etc. replace).R¹、R²、R³In non-alkyl be hydrogen atom.

Speculate through the anionic group of polyanion and reacting for epoxide, is formed by-CH₂CHOHR⁴What is indicated is hydrophobic Property substituent group.Aforementioned R⁴For from the substituent group of aftermentioned epoxide.For example, R⁴It is alkyl (in the hydrogen atom of the alkyl At least one can also be replaced by alkyl, aryl, hydroxyl etc.).

The oxygen atoms bond of aforementioned hydrophobic substituent and anionic group.

Amine compounds are at least one kind of in the group being made of primary amine, secondary amine and tertiary amine.Amine compounds can be used alone It a kind, can also be used in combination of two or more.

As primary amine, such as aniline, toluidines, benzylamine, ethanol amine can be enumerated etc..

As secondary amine, such as diethanol amine, dimethylamine, diethylamine, di-n-propylamine, diphenylamines, dibenzylamine, dinaphthylamine can be enumerated etc..

As tertiary amine, such as triethanolamine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, trihexylamine, trioctylamine, three can be enumerated Aniline, tribenzylamine, three naphthylamines etc..

It is excellent from the viewpoint of the electroconductive polymer dispersion liquid that the method can be easily manufactured among amine compound Select tertiary amine, at least one of more preferable tri-n-butylamine and trioctylamine.

Epoxide is the compound in 1 molecule with 1 or more epoxy group.From preventing cohesion or gelation From the point of view of viewpoint, epoxide is preferably the compound in 1 molecule with 1 epoxy group.

Epoxide can be used alone a kind, can also be used in combination of two or more.

As the monofunctional epoxy compound in 1 molecule with 1 epoxy group, such as can enumerate: propylene oxide, 2, 3- epoxy butane, epoxy iso-butane, 1,2- epoxy butane, 1,2- oxepane, 1,2- oxepane, 1,2- epoxypentane, 1, 2- octylene oxide, 1,2- decamethylene, 1,3- butadiene monoxide, the 1,2- epoxy tetradecane, glycidyl methyl ether, 1, 2- epoxy octadecane, 1,2- epoxyhexadecane, ethyl ether, glycidyl isopropyl ether, tertiary butyl glycidyl Ether, 1,2- epoxy eicosane, 2- (chloromethyl) -1,2 epoxy prapane, glycidol, epoxychloropropane, epoxy bromopropane, butyl Glycidol ether, 1,2- oxepane, 1,2- epoxy -9- decane, 2- (chloromethyl) -1,2- epoxy butane, the contracting of 2- ethylhexyl Water glycerin ether, 1,2- epoxy -1H, 1H, 2H, 2H, 3H, 3H- trifluorobutane, allyl glycidyl ether, four cyano ethylene oxide, Glycidyl butyrate, 1,2- epoxy cyclooctane, glycidyl methacrylate, 1,2- epoxy cyclododecane, 1- methyl-1, 2- 7-oxa-bicyclo[4.1.0,1,2- epoxy cyclopentadecane, 1,2- cyclopentane epoxide, 1,2- 7-oxa-bicyclo[4.1.0,1,2- epoxy -1H, 1H, 17 fluorine butane of 2H, 2H, 3H, 3H-, 3,4- epoxy tetrahydrofuran, stearic acid glycidyl ester, 3- glycidyloxypropyl Ice drops in trimethoxy silane, Epoxysuccinic acid, glycidyl phenyl ether, oxidation isophorone, alpha-oxidation firpene, 2,3- epoxy Piece alkene, benzyl glycidyl ether, diethoxy (3- glycidyloxypropyl) methyl-monosilane, 3- [2- (perfluoro hexyl) Ethyoxyl] -1,2 epoxy prapane, 1,1,1,3,5,5,5- seven methyl -3- (3- glycidoxypropyl) trisiloxanes, 9, Bis- (the 4- glycidyl oxygroup benzene of 12 carbon diene of 10- epoxy -1,5- ring, 4- p t butylbenzoic acid ethylene oxidic ester, 2,2- Base) propane, 2- tert-butyl -2- [2- (4- chlorphenyl)] ethyl ethylene oxide, styrene oxide, glycidyl trityl Ether, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- phenyl propylene oxide, -5 α of cholesterol, 6 α-epoxides, oxygen Change talan, p-methyl benzenesulfonic acid ethylene oxidic ester, 3- methyl -3- ethyl phenylglycidate, N- propyl-N- (2,3- ring Oxygen propyl group) n-perfluoro-octyl sulfonamide, (2S, 3S) -1,2- epoxy -3- (tertbutyloxycarbonylamino) -4- phenyl butane, 3- nitre Base benzene sulfonic acid ((R)-ethylene oxidic ester, 3- nitrobenzene-sulfonic acid-ethylene oxidic ester, parithenolide, N- glycidyl neighbour benzene two Carboximide, endrin, dieldrite, 4- propylene oxide oxygroup carbazole, 7,7- dimethyl octanoic acid oxiranylmethylester, 1,2- Epoxy -4- vinyl cyclohexane, C₁₂,C₁₃Mix higher alcohol glycidol ether etc..

, with the multi-functional epoxy compound of 2 or more epoxy groups, such as can be enumerated as in 1 molecule: 1,6- oneself Hexanediol diglycidyl ether, 1,2,7,8- diepoxyoctane, neopentylglycol diglycidyl ether, 4- butanediol 2-glycidyl Ether, 1,2:3,4- butane diepoxide, 1,2- cyclohexane dicarboxylic acid 2-glycidyl ester, isocyanuric acid three-glycidyl ester, new penta Hexanediol diglycidyl ether, 1,2:3,4- butane diepoxide, polyethyleneglycol diglycidylether, ethylene glycol diglycidylether, Diethylene glycol diglycidyl glycerin ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol two shrink sweet Oily ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three hydroxyl first Base propane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid 2-glycidyl ester, glycerol bunching Water glycerin ether, diglycerol polyglycidyl ether, polyglycereol polyglycidyl ether, D-sorbite class polyglycidyl ether, epoxy second Alkane laruyl alcohol glycidol ether etc..

The content ratio of polyanion in conductive composite body is excellent relative to pi-conjugated 100 mass parts of electroconductive polymer The range of 1 mass parts or more, 1000 below the mass is selected as, more than more preferably 10 mass parts, 700 below the mass, into one Step is preferably 100 mass parts or more, 500 range below the mass.If the content ratio of polyanion aforementioned minimum value with On, then there is the tendency of the doping effect enhancing to pi-conjugated electroconductive polymer, electric conductivity becomes higher.On the other hand, if it is poly- The content of anion is in aforementioned upper limit value hereinafter, then can sufficiently contain pi-conjugated electroconductive polymer, thus ensuring that adequately leading Electrically.

(acrylate compounds (A))

Acrylate compounds (A) are acrylate chemical combination indicated by previously described formula (1), with holo-fluorine polyester in the method Object.

In formula (1), Rf be divalent, molecular weight be 500 or more 30000 holo-fluorine polyesters below, branch can be contained in Rf.

Rf preferably includes that the perfluoropolyether of the divalent of 1 or more 500 repetitive units below, by following formula (6) expression is residual Base.

-C_iF_2iO- (6)

I in formula (6) independently is 1 or more 6 integer below in each unit.

Rf is more preferably the perfluoropolyether residue indicated by any one in previously described formula (7)~(9).

In formula (7), Y is separately F or CF₃Base.R is 2 or more 6 integers below, and m, n are separately 0 or more 200 integers below, and m+n is 2 or more 200 or less.S is 0 or more 6 integer below.Each repetitive unit can be randomly bonded.

In formula (8), j is 1 or more 3 integer below, and k is 1 or more 200 integer below.

In formula (9), Y is F or CF₃Base.J is 1 or more 3 integer below, and m, n are separately 0 or more 200 below whole Number, and m+n is 2 or more 200 or less.Each repetitive unit can be randomly bonded.

In formula (1), X¹Group to be indicated by previously described formula (2) independently of one another.

In formula (2), a and c are separately 0 or more 4 integer below, and b is 1 or more 4 integer below, and a+b+c For any one in 2,3,4.

In formula (2), Q¹And Q²Be independently of one another carbon atom number be 3 or more 20 it is below may include ehter bond, ester bond, Amido bond, urethane bond divalent linker, wherein cyclic structure, branch, Q can be contained¹And Q²It can be mutually the same It is different.

As Q¹And Q², any one group preferably in previously described formula (15)~(20) independently of one another.

R¹Group to be indicated by previously described formula (3) independently of one another.

In formula (3), in R¹Molecular weight be 30 or more 600 or less, preferably 60 or more 300 or less range in, d, e, f, g It is independently of one another 0 or more 20 integer below, preferably 1 or more 10 integer below.The arrangement of each repetitive unit can be Random.

R in formula (3)³It is 1 or more 10 saturated hydrocarbyl or unsaturated alkyl below for carbon atom number.

As saturated hydrocarbyl or unsaturated alkyl, such as can enumerate: methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, 2- ethylhexyl, cyclohexyl, phenyl, benzyl, allyl, cyclobutenyl, styryl etc..Among these, preferably methyl or ethyl.

Aforementioned R¹Among, preferably by the group represented by previously described formula (25).

In formula (25), p, q are separately 0 or more 20 integer below, and p+q is 1 or more 40 or less.Asia in formula (25) Propyl can be the propylidene of branch.Each repetitive unit can be randomly bonded.

R²For any one in the acrylic replaced with acrylic or α that is indicated by previously described formula (4), carbon it is former Subnumber is the organic group of 1 or more 20 monovalence below.

In formula (4), R⁴It is independently of one another any one in hydrogen atom, fluorine atom, methyl or trifluoromethyl, wherein excellent Select hydrogen atom or methyl.

R in formula (4)⁵It is the linker of 1 or more 18 divalent below or trivalent for carbon atom number, wherein ehter bond and ester can be contained At least one of key.

N in formula (4) is integer 1 or 2.

As R², any one group preferably in previously described formula (21)~(24) preferably has ethylidene among these groups Group.

In formula (2), in the case where a > 1, R¹With Q¹It is preferred combination it is as follows.It is preferred that R¹For hydrogen atom, methyl, second Base, propyl, any one in butyl, with Q¹For any one in methylene, ethylidene, propylidene, butylidene, hexylidene Combination.

In formula (2), in the case where b > 1, R²With Q²It is preferred combination it is as follows.It is preferred that R²For hydrogen atom, methyl, ethyl, Any one in propyl, butyl, with Q²For any one in methylene, ethylidene, propylidene, butylidene, hexylidene Combination.

In formula (2), in the case where c > 1, preferred Q²For in methylene, ethylidene, propylidene, butylidene, hexylidene Any one.

In formula (2), in the case where a > 1, b > 1, preferably make aforementioned preferred R¹With Q¹Combination and aforementioned preferred R²With Q²Combination be further combined obtained by compound.

In formula (2), in the case where a > 1, c > 1, preferably make aforementioned preferred R¹With Q¹Combination and aforementioned preferred Q²Into Compound obtained by the combination of one step.

In formula (2), in the case where b > 1, c > 1, preferably make aforementioned preferred R²With Q²Combination and aforementioned preferred Q²Into Compound obtained by the combination of one step.

In formula (2), in the case where a > 1, b > 1, c > 1, preferably make aforementioned preferred R¹With Q¹Combination, it is aforementioned preferably R²With Q²Combination and aforementioned preferred Q²Compound obtained by being further combined.

In formula (1), X²Group to be indicated by previously described formula (5) independently of one another.

In formula (5), R¹、R²、Q¹、Q²It is identical as formula (2).

H, i, j in formula (5) are separately 0 or more 3 integer below, and h+i+j is any one value in 1,2,3. The arrangement of repetitive unit can be random.)

In formula (1), Z is the organic group of divalent, can contain oxygen atom, nitrogen-atoms, fluorine atom.In addition, Z can have ring Shape structure, unsaturated bond, v are 0 or more 5 integer below.

As long as Z does not interfere the polymerization of acrylic, structure is not particularly limited.

As preferred Z, any one group in previously described formula (10)~(14) can be enumerated.

As the preferred example of Z, the group indicated by any one in following formula (26)~(33) can be enumerated.As more Preferred Z can enumerate the group by following formula (28) or formula (29) expression.

[changing 13]

-CH₂-CH₂- (26)

-CH₂-O-CH₂- (28)

Acrylate compounds can be used alone a kind, can also be used in combination of two or more.

The synthetic method of acrylate compounds (A) is for example on the books in Japanese Unexamined Patent Publication 2010-285501 bulletin.

In the electroconductive polymer dispersion liquid of the method, the content of acrylate compounds (A) is compound relative to electric conductivity 100 mass parts of body be preferably 0.01 mass parts or more 10000 below the mass, more than more preferably 0.05 mass parts 5000 mass Part hereinafter, more than further preferably 0.1 mass parts 1000 below the mass.If the content of acrylate compounds (A) is preceding Lower limit value or more is stated, then the soil resistance of conductive layer can be made further to be promoted, if can ensure that adequately more than aforementioned minimum value Electric conductivity.

(other acrylate compounds)

The electroconductive polymer dispersion liquid of the method contains other acrylic acid in addition to foregoing acrylates compound (A) Ester compounds (hereinafter referred to as " acrylate compounds (B) ").Acrylate compounds (B) can be the propylene comprising fluorine atom Ester compound can also be not fluorine-containing acrylate compounds.From being easy to get, can easily improve the hardness of conductive layer Viewpoint is set out, preferably not fluorine-containing acrylate compounds.

As not fluorine-containing acrylate compounds (B), such as more than 2 functions that can be listed below 6 functions (first below Base) acyclic compound: urethane acrylate (urethane acrylate), 1,6-HD two (methyl) propylene Acid esters, neopentyl glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, isocyanuric acid ethylene-oxide-modified two (methyl) acrylate, isocyanuric acid ethylene-oxide-modified three (methyl) acrylate, trimethylolpropane tris (methyl) propylene Acid esters, pentaerythrite three (methyl) acrylate, glycerol three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphoric acid Ester, hydrogen phthalate-(2,2,2- tri--(methyl) acryloyloxymethyl) ethyl ester, glycerol three (methyl) acrylate, season penta Tetrol four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate, D-sorbite six (methyl) acrylate etc..

In addition, not fluorine-containing acrylate compounds (B) are also possible to: making aforementioned (methyl) acyclic compound and epoxy compound Epoxy acrylate obtained by object reaction imports copolymer obtained by (methyl) acryloyl group to the side chain of acrylate copolymer Deng.

Acrylate compounds (B) can be used alone a kind, can also be used in combination of two or more.

Among foregoing acrylates compound (B), from acrylate compounds (A) reactivity it is excellent, can be easily From the perspective of the hardness for improving conductive layer, preferred urethane acrylate.

Urethane acrylate can be enumerated: making the polyisocyanates with 2 or more isocyanate group and have hydroxyl Compound obtained by (methyl) acrylate reactions；(methyl) for making the polyester of polyisocyanates and terminal diol and there is hydroxyl Compound obtained by acrylate reactions；So that polyalcohol and excessive di-isocyanate reaction is obtained polyisocyanates, keeps this more Isocyanates and compound obtained by (methyl) acrylate reactions with hydroxyl etc..

Among urethane acrylate, preferably make selected from 2- ethoxy (methyl) acrylate, 2- hydroxyl -3- acryloyl-oxy (methyl) acrylate with hydroxyl of base-methacryloxy propane and pentaerythritol triacrylate be selected from Hexamethylene diisocyanate, isophorone diisocyanate, toluene di-isocyanate(TDI) and '-diphenylmethane diisocyanate Urethane acrylate obtained by polyisocyanates reacts.

In the case where the electroconductive polymer dispersion liquid of the method includes acrylate compounds (B), acroleic acid esterification Close the content of object (B) relative to 100 mass parts of acrylate compounds (A) be preferably 0.1 mass parts or more, 10000 mass parts with Under, it is more than more preferably 0.5 mass parts that 5000 below the mass, more than further preferably 1.0 mass parts 3000 mass parts with Under.If the content of acrylate compounds (B) more than aforementioned minimum value, can sufficiently be reacted with acrylate compounds (A), Improve the hardness of conductive layer.If acrylate compounds (B) content in aforementioned upper limit value hereinafter, if can ensure that leading for conductive layer Electrically.

(decentralized medium)

In the electroconductive polymer dispersion liquid of the method, in the case where conductive composite body is hydrophobic, it is preferable to use having Principal component of the solvent as decentralized medium.But decentralized medium can not be only organic solvent, can also contain water.

As organic solvent, it is preferable to use alcohols solvent, ketone from the viewpoint of it can improve the dispersibility of conductive composite body Solvent, esters solvent more preferably use at least one of ketones solvent and alcohols solvent.In addition, organic solvent is preferably Not fluorine-containing solvent.

It as alcohols solvent, such as can enumerate: methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol (also known as isopropanol), 2- methyl -2- third Alcohol, n-butyl alcohol, 2- butanol, 2- methyl-1-propyl alcohol, allyl alcohol, propylene glycol monomethyl ether, glycol monoethyl ether etc..

It as ketones solvent, such as can enumerate: metacetone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl Ketone, methyl Isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol etc..

It as esters solvent, such as can enumerate: ethyl acetate, propyl acetate, butyl acetate etc..

Specifically, when electroconductive polymer dispersion liquid is set as 100 mass %, in electroconductive polymer dispersion liquid The content of organic solvent is preferably 50 mass % or more and less than 100 mass %, more preferably 80 mass % or more and less than 100 Quality %, further preferably 90 mass % or more and less than 100 mass %.Electroconductive polymer dispersion liquid can be entirely free of Water.

It is said conductive relative to the gross mass of electroconductive polymer dispersion liquid in the electroconductive polymer dispersion liquid of the method The content of complex is for example preferably 0.1 mass % or more, 20 mass % hereinafter, more preferably 0.5 mass % or more, 10 mass % Hereinafter, further preferably 1.0 mass % or more, 5.0 mass % or less.

(highly conductive agent)

In order to promote the electric conductivity of conductive layer further, electroconductive polymer dispersion liquid also may include highly conductive agent.Herein, Pi-conjugated electroconductive polymer above-mentioned, polyanion, amine compounds, epoxide, acrylate compounds (A), acrylic acid Ester compounds (B) and organic solvent are not classified as highly conductive agent.

Highly conductive agent be preferably selected from by carbohydrate, nitrogenous aromatic ring compounds, the compound with 2 or more hydroxyls, Compound with 1 or more hydroxyl and 1 or more carboxyl, the compound with amide groups, with the chemical combination of imide At least one kind of compound of the group of object, lactam compound composition.

Highly conductive agent contained by electroconductive polymer dispersion liquid can be a kind, can also be two or more.

The content ratio of highly conductive agent is preferably 1 mass parts or more, 10000 mass relative to 100 mass parts of conductive composite body Part hereinafter, more than more preferably 10 mass parts 5000 below the mass, more than further preferably 100 mass parts 2500 mass parts Below.If the content ratio of highly conductive agent more than aforementioned minimum value, can give full play to the addition because of highly conductive agent Caused electric conductivity promotes effect, if in aforementioned upper limit value hereinafter, if can prevent from drawing because pi-conjugated electroconductive polymer concentration reduces The reduction of the electric conductivity risen.

(additive)

It also may include other well known additives in electroconductive polymer dispersion liquid.

As additive, as long as effect of the invention can be obtained, it is not particularly limited, such as usable polymerization initiator, Surfactant, inorganic conductive agent, defoaming agent, coupling agent, antioxidant, ultraviolet absorbing agent etc..Wherein, additive includes removing Pi-conjugated electroconductive polymer above-mentioned, polyanion, amine compounds, epoxide, acrylate compounds (A), acrylic acid Compound other than ester compounds (B), organic solvent and highly conductive agent.

As polymerization initiator, Photoepolymerizationinitiater initiater, thermal polymerization can be enumerated.Foregoing acrylates compound (A) and When foregoing acrylates compound (B) is irradiated in the presence of Photoepolymerizationinitiater initiater with active energy beam, it may occur however that freely Base polymerize and solidifies.

As surfactant, the surfactant of non-ionic, anionic, cationic can be enumerated, but is stablized from saving From the perspective of property, preferably non-ionic surfactant.In addition, the polymerization species table such as polyvinylpyrrolidone can also be added Face activating agent.

As inorganic conductive agent, metal ion class, conductive carbon etc. can be enumerated.In addition, metal ion can be by keeping metal salt molten It is generated in Xie Yushui.

As defoaming agent, silicone resin, dimethyl silicone polymer, silicone oil etc. can be enumerated.

As coupling agent, the silane coupling agent etc. with vinyl or amino can be enumerated.

As antioxidant, phenol antioxidant, amine antioxidants, phosphorus antioxidants, sulphur class antioxidant, sugar can be enumerated Class etc..

It as ultraviolet absorbing agent, can enumerate: Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorbent, water Poplar esters of gallic acid ultraviolet absorbing agent, cyanoacrylate ultraviolet absorbent, oxanilide class ultraviolet absorbing agent, hindered amine Class ultraviolet absorbing agent, benzoates ultraviolet absorbing agent etc..

In the case where electroconductive polymer dispersion liquid contains above-mentioned additive, content ratio is fitted according to the type of additive Work as decision, such as 100 mass parts of solid component relative to conductive composite body can be set as 0.001 mass parts or more, 5 mass parts Range below.

(manufacturing method of electroconductive polymer dispersion liquid)

Electroconductive polymer dispersion liquid used in the method can be manufactured by following methods (a) or (b).

(a) method with the following process: to the conductive composite body comprising pi-conjugated electroconductive polymer and polyanion At least one of amine compounds and epoxide are added in aqueous dispersions, and aforesaid conductive sex camplex is made to be precipitated to form analysis The process of object out；The process for recycling aforementioned precipitate；And foregoing acrylates chemical combination is added into the aforementioned precipitate of recycling The process of object (A) and organic solvent.

(b) method with the following process: make the conductive composite body comprising pi-conjugated electroconductive polymer and polyanion Aqueous dispersions are freeze-dried the process for obtaining freeze-drying body；And amine compounds and ring are added into aforementioned freeze-drying body The process of at least one of oxygen compound, foregoing acrylates compound (A) and organic solvent.

Preceding method (a) and (b) used in conductive composite body aqueous dispersions, be containing comprising pi-conjugated conduction The aqueous dispersions of the conductive composite body and water of property macromolecule and polyanion.Aforementioned aqueous dispersions may include organic molten Agent, but due to conductive composite body not yet hydrophobization at this time, go out from the viewpoint for the dispersibility for improving conductive composite body Hair, the content of preferable organic solvent are less.Specifically, the content of the organic solvent in aforementioned aqueous dispersions is preferably 0 matter 50 mass % of % or more is measured hereinafter, more preferably 0 mass % or more, 30 mass % is hereinafter, further preferably 0 mass % or more 10 mass % or less.

The method of aqueous dispersions as manufacture conductive composite body, such as can enumerate: in the aqueous solution of polyanion Make to form the method that the monomer of pi-conjugated electroconductive polymer carries out chemical oxidising polymerisation.

In addition, the electric conductivity comprising pi-conjugated electroconductive polymer and polyanion can be used in the aqueous dispersions of conductive composite body The commercially available aqueous dispersions of complex.

In afore mentioned chemical oxidation polymerization, well known catalyst can be used.Such as catalyst and oxidant can be used.As urging Agent, such as the transistion metal compounds such as iron chloride, ferric sulfate, ferric nitrate, copper chloride can be enumerated etc..As oxidant, such as The persulfates such as ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate can be enumerated.It is original that oxidant can be such that the catalyst being reduced returns The state of oxidation.

The solid component concentration of conductive composite body contained in the aqueous dispersions of conductive composite body is relative to aqueous dispersions Gross mass is preferably 0.1 mass % or more, 10 mass % hereinafter, more preferably 0.3 mass % or more, 5 mass % or less.

In method (a), at least one of amine compounds and epoxide are being added to aforementioned aqueous dispersions In the case of, at least one of amine compounds and epoxide add to the polyanion for constituting aforesaid conductive sex camplex In a part of anionic group, be specifically not involved on the anionic group of the doping of pi-conjugated electroconductive polymer, Aforementioned anionic group disappears.Conductive composite body is hydrophobic as a result,.

Wherein, at least one of amine compounds and epoxide can not add to whole being not involved in pi-conjugated and lead On the anionic group of electrically high molecular doping, the anionic group for being not involved in doping can remaining a part.

For the conductive composite body being hydrophobic due to that cannot disperse in water system decentralized medium, being precipitated is precipitate.

In the case where adding amine compounds, the additive amount of amine compounds is excellent relative to 100 mass parts of conductive composite body It is selected as 1 mass parts or more 100000 below the mass, more than more preferably 10 mass parts 50000 below the mass, further excellent It is selected as 50 mass parts or more 10000 below the mass.If the additive amount of amine compounds more than aforementioned minimum value, can make conduction The hydrophobicity of sex camplex is sufficiently promoted, if in aforementioned upper limit value hereinafter, if can prevent the electric conductivity of conductive layer from reducing.

In the case where adding epoxide, the additive amount of epoxide is relative to 100 mass of conductive composite body More than part preferably 10 mass parts 10000 below the mass, and more than more preferably 100 mass parts 5000 below the mass, into one It is more than step preferably 200 mass parts that 500 below the mass.If the additive amount of epoxide, can more than aforementioned minimum value Promote the hydrophobicity of conductive composite body sufficiently, if in aforementioned upper limit value hereinafter, if can prevent the electric conductivity of conductive layer from reducing.

When conductive composite body is precipitated, organic solvent can be added.As the organic solvent added when being precipitated, can enumerate Alcohol solvent, ketone solvent, esters solvent.The organic solvent added when precipitation can be used alone a kind, can also be used in combination of two or more.

Before adding at least one of amine compounds and epoxide into electroconductive polymer aqueous dispersions, During addition or after addition, in order to promote reaction that can be heated.

It is separated in the process of recycling precipitate in method (a), such as well known to usable filtering, precipitating, extraction etc. Method.Preferably filtering is, it is preferable to use filter opening size is to be able to use in formation conductive composite body among these separation methods The filter for the degree that polyanion passes through together with filtrate is filtered.According to the filter method, in the same of separation precipitate When, the remaining polyanion of not formed conductive composite body can be made to remain on filtrate side, make precipitate and it is remaining it is poly- yin from Son separates.By removing remaining polyanion, the electric conductivity of precipitate can be improved.

As filter used in filtering, the preferably filter paper used in chemical analysis field.As such filter paper, Such as the filter paper etc. of Edk company (ADVANTEC CO., LTD.) system can be enumerated, retaining partial size is 7 μm.Herein, filter paper Retain the benchmark that partial size is filter opening size, it is natural according to barium sulfate of JIS P3801 (filter paper (chemical analysis use)) defined etc. Leakage partial size when filtering is sought.The reservation partial size of filter paper can for example be set as 2 μm or more 20 μm or less.It is remaining poly- from that can make Anion-permeable and be easy to carry out from the perspective of separation, which is preferably 5 μm or more 10 μm or less.

Being added in acrylate compounds (A) and the process of organic solvent into precipitate in method (a), preferably After being added to acrylate compounds (A) and organic solvent into precipitate, to including precipitate and acrylate The organic solvent of compound (A) implements decentralized processing.

, it is preferable to use dispersion machine in decentralized processing.As dispersion machine, such as homogenizer, high-pressure homogenizer, ball mill can be enumerated Deng.Among dispersion machine, from the viewpoint of can be improved precipitate to the dispersibility of organic solvent, preferred high-pressure homogenizer.

High-pressure homogenizer can for example enumerate have to carry out decentralized processing liquid to be treated pressurize high pressure generating unit, carry out The device of the opposite impact portions of dispersion, orifice part or slit portion.As high pressure generating unit, high pressure well known to plunger pump etc. is used Pump.As the specific example of high-pressure homogenizer, such as can enumerate: the trade name nanometer of YOSHIDA KIKAI CO., LTD. are super High pressure homogenizer (nanomizer), the trade name of Microfluidics Corp. (マイ Network ロ Off Le イディス Network) system are micro- Jet homogenizer (Microfluidizer), Sugino Machine Co., Ltd. (Sugino Machine Limited) make ULTIMAIZER etc..

In freeze-drying in method (b), the moisture in the aqueous dispersions of conductive composite body is freezed, carries out vacuum It is dry.Freeze-drying body is obtained as a result,.

Temperature when freeze-drying is preferably set to -60~60 DEG C, is more preferably set as -40~40 DEG C.If being freeze-dried temperature preceding State lower limit value or more, then be easy carry out temperature adjustment, if in aforementioned upper limit value hereinafter, if can easily make conductive composite body Aqueous dispersions freeze-drying.

At least one of amine compounds and epoxide, acrylate compounds are added into freeze-drying body (A) and when organic solvent, their order of addition is not particularly limited.

It is preferred that adding at least one of amine compounds and epoxide, acrylate compounds into freeze-drying body (A) and after organic solvent, implement decentralized processing.If implementing decentralized processing, can make in electroconductive polymer dispersion liquid The dispersibility of conductive composite body is promoted.Decentralized processing is identical as the decentralized processing in method (a).

In method (a) and method (b), acrylate compounds (B), highly conductive agent and additive can suitably add Add, is preferably added together with organic solvent.

(function and effect)

The electroconductive polymer dispersion liquid of the method is in addition to conductive composite body also comprising the acrylic acid with holo-fluorine polyester Ester compounds (A).The acrylate compounds (A) are due to having the double bond that may occur from being polymerize by base, in conductive layer shape Cheng Shike occurs polymerization and solidifies.

The solidfied material of acrylate compounds (A) is fluororesin.

In general, fluororesin water repellency and oil repellent are high, soil resistance is excellent.Acrylate compounds (A) in the method Solidfied material there is extra high water repellency and oil repellent, soil resistance is especially excellent.

It is played in conductive layer by conductive composite body in addition, the solidfied material of the acrylate compounds in the method is difficult to damage Electric conductivity.Therefore, the excellent electric conductivity of the conductive layer formed by the electroconductive polymer dispersion liquid of the method.

In addition, the parent of acrylate compounds (A) and not fluorine-containing acrylate compounds (B) and not fluorine-containing organic solvent It is excellent with property, not fluorine-containing acrylate compounds (B) and not fluorine-containing organic solvent are difficult to separate, are easy to use.

In turn, acrylate compounds (A) can be by being irradiated in the presence of Photoepolymerizationinitiater initiater with active energy beam To solidify.

< conductive membrane >

One mode of the manufacturing method of conductive membrane of the invention is illustrated.

Conductive membrane in the method has film substrate and is formed on the face of at least side of aforementioned film substrate Conductive layer.

It as the resin of composition film substrate, such as can enumerate: polyolefin-based resins, ethylene-vinyl acetate c tree Rouge, ethylene methyl methacrylate copolymer resins, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate Ester, polybutylene terephthalate (PBT), polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, Polyarylate, styrenic elastomer, polyester elastomer, polyether sulfone, polyetherimide, polyether-ether-ketone, polyphenylene sulfide, polyamides are sub- Amine, Triafol T, cellulose acetate propionate etc..It as polyolefin-based resins, can enumerate: polyethylene, polypropylene, ethylene-α Olefin-copolymerization resin, propylene-alpha olefin copolymer resins etc..

In addition, film substrate can be unstretched film substrate, the film substrate of stretching can also be.

As the average thickness of film substrate, preferably 10 μm or more 500 μm hereinafter, more preferably 20 μm or more 200 μm Below.If the average thickness of film substrate does not allow easy fracture more than aforementioned minimum value, if in aforementioned upper limit value hereinafter, if It can ensure that the sufficient flexibility as film.

The thickness of film substrate is the thickness used more than at optical microscopy or determination of electron microscopy any 10, by the measured value Value obtained by carrying out averagely.

Conductive layer in the method is the electroconductive polymer dispersion liquid for applying foregoing manner and the layer that is formed.Therefore, originally Conductive layer in mode includes at least the solidfied material of aforesaid conductive sex camplex and foregoing acrylates compound (A).

Conductive layer in the case where electroconductive polymer dispersion liquid also contains foregoing acrylates compound (B), in the method Solidfied material comprising foregoing acrylates compound (B) and foregoing acrylates compound (A) and foregoing acrylates chemical combination The solidfied material of object (B).

In addition, the case where also containing at least one of highly conductive agent and additive in electroconductive polymer dispersion liquid Under, conductive layer also contains at least one of highly conductive agent and additive.

As the average thickness of aforesaid conductive layer, preferably 10nm or more 20000nm hereinafter, more preferably 20nm or more 10000nm is hereinafter, further preferably 30nm or more 5000nm or less.If the average thickness of conductive layer aforementioned minimum value with On, then can give full play to high conductivity and soil resistance, if in aforementioned upper limit value hereinafter, if can easily form conductive layer.

The thickness of conductive layer be with the thickness more than at optical microscopy or determination of electron microscopy any 10, by the measured value into It is worth obtained by row is average.

Conductive layer applies said conductive high molecular dispersion liquid on the face by at least side in film substrate come shape At.

It as the method for coating electroconductive polymer dispersion liquid, such as can be used: using gravure coater, roll coater, curtain Flow coating machine, spin coater, metering bar coater, reverse coating machine, kiss coater, jet flow coating machine, bar type coating Machine, air knife coater, scraper coating machine (knife coater), Wiper blade type coating machine (blade coater), curtain coating apply The method of the coating machines such as cloth machine, silk screen coating machine, it is spraying using air atomizer, airless sprayer, rotor damping sprayer etc. Dipping methods such as spray method, the dipping (dip) of device etc..

Among above-mentioned, from the viewpoint of it can easily apply electroconductive polymer dispersion liquid, metering bar coater is used sometimes. Among metering bar coater, according to type, applied thickness is different, various types of to be labeled with model in commercially available metering bar coater, should Model is bigger, then can apply thicker.

It is preferred that the electroconductive polymer dispersion liquid of coating is dried after being coated with electroconductive polymer dispersion liquid.

As the drying means, heat drying, vacuum drying etc. can be enumerated.As heat drying, for example, can be used Hot-blast Heating, The usual ways such as infrared heating.

Using heat drying, heating temperature is usually 50 DEG C or more 150 DEG C of ranges below, preferably 60 DEG C with Upper 130 DEG C hereinafter, in more preferably 70 DEG C or more 120 DEG C or less of range.Herein, heating temperature is the setting temperature of drying device Degree.

In addition, drying time is preferably 5 minutes or more from the viewpoint of sufficiently removal decentralized medium.

Acrylate compounds contained by electroconductive polymer dispersion liquid (A) in the presence of Photoepolymerizationinitiater initiater by using Active energy beam is irradiated to solidify.Therefore, in the case where electroconductive polymer dispersion liquid includes Photoepolymerizationinitiater initiater, It can be irradiated after the electroconductive polymer dispersion liquid of coating is dry with active energy beam.

As active energy beam, ultraviolet light, electron beam, visible light etc. can be enumerated.As the light source of ultraviolet light, such as can be used The light sources such as ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp.

Illumination is preferably 100mW/cm in ultraviolet light irradiation²More than.If illumination is less than 100mW/cm², then active energy beam is solid The adhesive component for the property changed solidifies insufficient sometimes.In addition, accumulative light quantity is preferably 50mJ/cm²More than.If accumulative deficiency in light quantity 50mJ/cm², then it is crosslinked sometimes insufficient.In addition, the illumination, accumulative light quantity in this specification are to use TOPCON UVR-T1 (the industrial UV detector of CORPORATION；Optical receiver: UD-T36；Measure wave-length coverage: 300nm or more 390nm or less；Wavelength of peak sensitivity: about 355nm) be measured obtained by value.

In the manufacturing method of the conductive membrane of the method, disperse as the electroconductive polymer for being applied to film substrate Liquid uses the dispersion liquid in addition to conductive composite body also including foregoing acrylates compound (A).Therefore, by electric conductivity height The electric conductivity and soil resistance for the conductive layer that molecular dispersions are formed are excellent enough.

Therefore, according to the manufacturing method of the conductive membrane of the method, it can be easily manufactured and have electric conductivity and soil resistance all The conductive membrane of conductive layer excellent enough.

[embodiment]

(Production Example 1)

The sodium styrene sulfonate that 206g is dissolved in the ion exchange water of 1000ml, was added dropwise with 20 minutes while stirring at 80 DEG C It is dissolved in the oxidizing agent solution of the 1.14g ammonium persulfate in the water of 10ml in advance, stirs the solution 12 hours.

Into the obtained solution containing sodium styrene sulfonate, addition is diluted to the sulfuric acid 1000ml of 10 mass %, uses ultrafiltration Remove the solvent of the 1000ml of the solution containing polystyrolsulfon acid.The ion exchange water of 2000ml is added into residual liquid, The solvent that about 2000ml is removed with ultrafiltration, washes polystyrolsulfon acid.It repeats the ultrafiltration 3 times.

Decompression removes the water in obtained solution, obtains the polystyrolsulfon acid of colourless solid-like.

(Production Example 2)

The 3,4- ethyldioxythiophene of 14.2g and the polystyrolsulfon acid for the 36.7g for obtaining Production Example 1 are dissolved in Solution obtained by the ion exchange water of 2000ml mixes at 20 DEG C.For thus obtained mixed solution, it is maintained at 20 on one side It DEG C is stirred, is slowly added the ammonium persulfate of the 29.64g dissolved in the ion exchange water of 200ml and the sulphur of 8.0g on one side The oxidation catalyst solution of sour iron, stirring are allowed to react for 3 hours.

The ion exchange water that 2000ml is added into obtained reaction solution, the solvent of about 2000ml is removed with ultrafiltration.Repeating should Operation 3 times.Then, into obtained solution, the sulfuric acid for being diluted to 10 mass % of 200ml and the ion exchange of 2000ml are added Water removes the solvent of about 2000ml with ultrafiltration.The ion exchange water that 2000ml is added into residual liquid, is removed with ultrafiltration The solvent of about 2000ml is washed poly- (3,4- ethyldioxythiophene) (PEDOT-PSS) that polystyrolsulfon acid adulterates. It repeats the operation 8 times, obtains the PEDOT-PSS aqueous dispersions that solid component concentration is 1.2 mass %.

(Production Example 3)

Make the 3,4- ethyldioxythiophene of 2.5g and the polystyrolsulfon acid of the Production Example 1 of 12.5g is dissolved in 500ml Ion exchange water obtained by solution mixed at 30 DEG C.

Thus obtained mixed solution is maintained at 30 DEG C, is stirred on one side, is slowly added the ion exchange water in 44.35ml on one side The oxidation catalyst solution of the ferric sulfate of the ammonium persulfate and 0.15g of the 5.5g of middle dissolution, stirring are allowed to react for 8 hours.As a result, Obtain poly- (3,4- ethyldioxythiophene) aqueous dispersions (the PEDOT-PSS moisture of the polystyrolsulfon acid doping of 2.7 mass % Dispersion liquid).

The mixed liquor that trioctylamine 53.0g and isopropanol 500g are added into aforementioned PEDOT-PSS aqueous dispersions 565.0g, makes The trioctylamine addition product of PEDOT-PSS is precipitated.For the trioctylamine addition product of the PEDOT-PSS of precipitation, divided by filtering From after being washed with water 100g, being washed with acetone 100g, take out the trioctylamine addition product of the PEDOT-PSS of solid 18.8g。

The isopropanol that 3760g is added into obtained solid, carries out decentralized processing with high-pressure homogenizer, obtains electroconductive polymer Dispersion liquid.

(Production Example 4)

The PEDOT-PSS aqueous dispersions 1000g obtained by Production Example 2 is freeze-dried, the freeze-drying body of 12g is obtained.

Foregoing freeze hirudo leech 5.0g and tri-n-butylamine 1.4g is added in isopropanol 1000g, is carried out at dispersion with high-pressure homogenizer Reason, obtains electroconductive polymer dispersion liquid.

(Production Example 5)

Methanol 300g and epoxide (Kyoeisha is added into the PEDOT-PSS aqueous dispersions 100g obtained by Production Example 2 Chemical Co., Ltd. EPOLIGHT M-1230, C₁₂,C₁₃Mix higher alcohol glycidol ether) 25g, add at 60 DEG C Thermal agitation 4 hours.At this point, since the epoxy group of aforementioned epoxy compound is reacted with the sulfonic group of PSS, free sulfonic acid Base disappears, and the water dispersible of PEDOT-PSS reduces, and PEDOT-PSS is precipitated.For thus obtained precipitate, by filter into Row recycling.Aforementioned precipitate 1.575g is added to the methyl ethyl ketone of 315g, decentralized processing is carried out with high-pressure homogenizer, obtains Electroconductive polymer dispersion liquid.

(Production Example 6)

Into the PEDOT-PSS aqueous dispersions 100g obtained by Production Example 2, methanol 300g and epoxy butane 25g is added, at 60 DEG C Lower heating stirring 4 hours.At this point, since the epoxy group of epoxy butane is reacted with the sulfonic group of PSS, free sulfonic group It disappears, the water dispersible of PEDOT-PSS reduces, and PEDOT-PSS is precipitated.For thus obtained precipitate, carried out by filtering Recycling.Aforementioned precipitate 1.45g is added to the methyl ethyl ketone of 290g, decentralized processing is carried out with high-pressure homogenizer, is led Electrical high molecular dispersion liquid.

(Production Example 7)

Under dry nitrogen atmosphere, in the 2000ml three-necked flask for having reflux unit and agitating device, put by following formula (34) what is indicated has α-unsaturated bond perfluoropolyether 500g, hexafluoro meta-xylene 700g and tetramethyl two ends Cyclotetrasiloxane 361g is heated to 90 DEG C while stirring.Chloroplatinic acid/vinylsiloxane is put into thus obtained mixture The toluene solution 0.442g of complex compound (as platinum monomer, contains 1.1 × 10^-6Mole), shape of the temperature at 90 DEG C or more in maintaining Continue stirring 4 hours under state.Pass through¹After H-NMR confirms that the allyl of raw material disappears, vacuum distillation removes solvent and excess Tetramethyl-ring tetrasiloxane, carry out active carbon processing.The colorless and transparent liquid indicated by following formula (35) is obtained as a result, The compound 498g (compound I) of perfluoro-polyether.

[changing 14]

[changing 15]

Under dry air atmosphere, between two compound (I) 50.0g mixing 2- allyl ethoxy-ethanol 7.05g, hexafluoro Toluene 50.0g and chloroplatinic acid/vinylsiloxane complex compound toluene solution 0.0442g (as platinum monomer, containing 1.1 × 10^-7Mole), it is stirred 4 hours at 100 DEG C.With¹After H-NMR and IR confirmation Si-H base disappears, vacuum distillation removal solvent And excessive 2- allyl ethoxy-ethanol, carry out active carbon processing.It obtains indicating faint yellow by following formula (36) as a result, The compound 55.2g (compound II) of the perfluoro-polyether of bright liquid.

[changing 16]

Under dry air atmosphere, to compound (II) 50.0g mixing tetrahydrofuran 50.0g and acryloyl-oxyethyl Isocyanates 9.00g is heated to 50 DEG C.Dioctyltin laurate 0.05g is added into thus obtained mixture, at 50 DEG C Stirring 24 hours.After heating, vacuum distillation removal is carried out at 80 DEG C, 2Torr.Flaxen paste is obtained as a result, Matter 58.7g (compound III).By¹The result of H-NMR and IR is confirmed as acrylate compounds shown in following formula (37).

[changing 17]

(Production Example 8)

In addition to different using the compound 11.9g and acryloyl-oxyethyl indicated by following formula (38) to compound (I) 50g Cyanate 7.05g is replaced other than 2- allyl ethoxy-ethanol, is obtained by following formula (39) table with the step identical as Production Example 7 The acrylate compounds 56.1g (compound IV) shown.

[changing 18]

[changing 19]

(Production Example 9)

Under dry nitrogen atmosphere, it is packed into the three-necked flask for the 100ml for having reflux unit and agitating device by following formula (40) the fluorine-containing annular siloxane 50.0g and toluene 20.0g indicated, is heated to 90 DEG C while stirring.It is mixed to thus obtained It closes 1 hour in object and the polyoxyethylene methallyl ether 9.75g and chloroplatinic acid/vinyl silicon indicated by following formula (41) is added dropwise The toluene solution 0.0110g of oxygen alkane complex compound (as platinum monomer, contains 2.73 × 10^-8Mole) mixed solution, at 90 DEG C Stirring obtains reaction solution in 12 hours.

In addition, being packed into allyl alcohol in the 100ml three-necked flask for having reflux unit and agitating device under dry nitrogen atmosphere 16.9g is heated to 90 DEG C, into obtained mixed liquor through 3 hours be added dropwise temporarily be cooled to room temperature reaction solution above-mentioned it Afterwards, it is stirred 16 hours at 90 DEG C.In obtained solution, unreacted allyl alcohol is carried out 2 hours at 100 DEG C, 6Torr Vacuum distillation removal, obtain compound (V).

Under dry air atmosphere, to obtain compound (V) 60.0g mixing acrylic acid 2- ethyl isocyanate 7.01g, laurel Sour dioctyl tin 0.010g stirs 12 hours at 25 DEG C, obtains the acrylic acid with average composition shown in following formula (42) Ester compounds (compound VI).In addition, the RF in formula (42) is identical as the RF in formula (40).

[changing 20]

(in formula (40), RF is group as shown below.)

[changing 21]

CH₂=CH-CH₂-O-(CH₂CH₂O)_4.5CH₃ (41)

[changing 22]

(embodiment 1)

Following substances are mixed: the electroconductive polymer dispersion liquid 40g of Production Example 3, Production Example 7 are indicated by previously described formula (37) Acrylate compounds 1.4g, urethane acrylate (Negami chemical industrial co., ltd ART RESIN UN904M, solid component concentration are 80 mass %, methyl ethyl ketone solution) 45.5g, Photoepolymerizationinitiater initiater (BASF public affairs Take charge of IRGACURE 184 processed) 1.5g and diacetone alcohol 11.6g, obtain electroconductive polymer dispersion liquid.

It is thin that obtained electroconductive polymer dispersion liquid with the metering bar coater of No.6 is coated on polyethylene terephthalate On the face of the side of film (TORAY INDUSTRIES, INC. LUMILAR T-60), be allowed at 100 DEG C dry 1 minute it Afterwards, the ultraviolet light of 400mJ is irradiated.Make the electroconductive polymer applied on pet film point as a result, Dispersion liquid solidification, forms conductive layer, obtains conductive membrane.

(embodiment 2)

Other than the electroconductive polymer dispersion liquid of Production Example 3 is changed to the electroconductive polymer dispersion liquid of Production Example 4, with Embodiment 1 gets similarly conductive membrane.

(embodiment 3)

Other than the electroconductive polymer dispersion liquid of Production Example 3 is changed to the electroconductive polymer dispersion liquid of Production Example 5, with Embodiment 1 gets similarly conductive membrane.

(embodiment 4)

Other than the electroconductive polymer dispersion liquid of Production Example 3 is changed to the electroconductive polymer dispersion liquid of Production Example 6, with Embodiment 1 gets similarly conductive membrane.

(embodiment 5)

In addition to by Production Example 7 by the acrylate compounds that previously described formula (37) indicate be changed to Production Example 8 by previously described formula (39) other than the acrylate compounds indicated, conductive membrane is obtained similarly to Example 1.

(comparative example 1)

In addition to by Production Example 7 by the acrylate compounds that previously described formula (37) indicate be changed to Production Example 9 by previously described formula (42) other than the acrylate compounds indicated, conductive membrane is obtained similarly to Example 1.

(comparative example 2)

In addition to by Production Example 7 by the acrylate compounds that previously described formula (37) indicate be changed to trifluoroethyl methacrylate with Outside, conductive membrane is obtained similarly to Example 1.

< evaluates >

For the sheet resistance value of the conductive membrane of each embodiment, comparative example, using resistrivity meter, (Mitsubishi Chemical is analyzed (Mitsubishi Chemical Analytech) Hiresta processed), apply voltage be 10V, the item that application time is 10 seconds It is measured under part.Sheet resistance value is smaller, and electric conductivity is more excellent.

Each embodiment, comparative example conductive membrane in, with automatic contact angle meter DMs-200 (Kyowa Interface Science Co., Ltd. system) contact angle of water and the contact angle of oleic acid are measured.Contact angle is bigger, and soil resistance is more excellent It is different.

[table 1]

< result >

Has the conductive membrane of each embodiment of the conductive layer comprising acrylate compounds (A), sheet resistance value is small, water The contact angle of contact angle and oleic acid is big.

Conductive layer includes the acrylate compounds of Production Example 9 indicated by previously described formula (42) to replace acrylate compounds (A) conductive membrane of comparative example 1, sheet resistance value is big, and electric conductivity is low.

Conductive layer includes trifluoroethyl methacrylate to replace the conductive membrane of the comparative example 2 of acrylate compounds (A), The contact angle of water and the contact angle of oleic acid are small, and soil resistance is low.

These results indicate that the electric conductivity and soil resistance of the conductive layer formed by electroconductive polymer dispersion liquid of the invention are all It is excellent.

Claims

1. a kind of electroconductive polymer dispersion liquid, contains:

Conductive composite body, it includes pi-conjugated electroconductive polymer and polyanions；

Acrylate compounds are indicated by following formula (1), and have holo-fluorine polyester；And

Decentralized medium,

[changing 1]

X1-[Z-Rf-Z-X²]_V-Z-Rf-Z-X¹ (1)

In formula (1), Rf is that the molecular weight of divalent is 500 or more 30000 holo-fluorine polyesters below, can contain branch in Rf；X¹That This independently is the group indicated by following formula (2)；X²Group to be indicated by following formula (5) independently of one another；Z is divalent Organic group can contain oxygen atom, nitrogen-atoms, fluorine atom, and can contain cyclic structure, unsaturated bond；V is 0 or more 5 below Integer,

[changing 2]

In formula (2), a and c are separately 0 or more 4 integer below, and b is 1 or more 4 integer below, and a+b+c is 2,3 or 4；R¹Group to be indicated by following formula (3) independently of one another；R²For by following formula (4) indicate containing acrylic The group of group or the acrylic replaced containing α；Q¹And Q²It is independently of one another carbon atom number is 3 or more 20 divalents below Linker, the linker of the divalent may include ehter bond, ester bond, amido bond, urethane bond, and can wherein contain cyclic annular knot Structure or branch, Q¹And Q²Can be mutually the same also different,

[changing 3]

-(C₄H₈O)_d(C₃H₆O)_e(C₂H₄O)_f(CH₂O)_gR³ (3)

In formula (3), in R¹Molecular weight be 30 or more 600 or less range in, d, e, f, g are 0 or more 20 or less independently of one another Integer, the arrangement of each repetitive unit can be random；R³It is 1 or more 10 saturated hydrocarbyl below or insatiable hunger for carbon atom number And alkyl,

[changing 4]

In formula (4), R⁴It is independently of one another hydrogen atom, fluorine atom, methyl or trifluoromethyl；R⁵It is 1 or more 18 for carbon atom number The linker of the linker of divalent below or trivalent, the divalent or trivalent may include at least one of ehter bond and ester bond；N is Integer 1 or 2；

[changing 5]

In formula (5), R¹、R²、Q¹、Q²It is identical as formula (2)；H, i, j are separately 0 or more 3 integer below, and h+i+j is 1 Above 3 any one value below, the arrangement of repetitive unit can be random.

2. electroconductive polymer dispersion liquid according to claim 1, wherein

Rf in the formula (1) of the acrylate compounds contains 1 or more 500 weights that are below, being indicated by following formula (6) Multiple unit,

-C_iF_2iO-(6)

I independently is 1 or more 6 integer below in each unit.

3. electroconductive polymer dispersion liquid according to claim 1, wherein

Rf in the formula (1) of the acrylate compounds is selected from the base indicated by any one in following formula (7)~(9) Group,

[changing 6]

In formula (7), Y is F or CF independently of one another₃Base；R is 2 or more 6 integers below；M, n is separately 0 or more 200 Integer below, and m+n is 2 or more 200 or less；S is 0 or more 6 integer below；Each repetitive unit can be randomly bonded,

[changing 7]

In formula (8), j is 1 or more 3 integer below；K is 1 or more 200 integer below,

[changing 8]

In formula (9), Y is F or CF₃Base；J is 1 or more 3 integer below；M, n is separately 0 or more 200 integer below, And m+n is 2 or more 200 or less；Each repetitive unit can be randomly bonded.

4. electroconductive polymer dispersion liquid according to claim 1, wherein

Z in the formula (1) of the acrylate compounds is any one group in following formula (10)~(14):

[changing 9]

-CH₂-O-CH₂- (14)。

5. electroconductive polymer dispersion liquid according to claim 1, wherein

Q in the formula (2) of the acrylate compounds¹And Q²It is independently of one another any in following formula (15)~(20) One group:

[changing 10]

6. electroconductive polymer dispersion liquid according to claim 1, wherein

R in the formula (2) of the acrylate compounds²For any one group in following formula (21)~(24):

[changing 11]

7. electroconductive polymer dispersion liquid according to claim 1, wherein

R in the formula (2) of the acrylate compounds¹For the group indicated by following formula (25),

[changing 12]

-(C₂H₄O)_p(C₃H₆O)_qCH₃ (25)

In formula (25), p, q are separately 0 or more 20 integer below, and p+q is 1 or more 40 hereinafter, the propylidene in formula can To be the propylidene of branch, each repetitive unit can be randomly bonded.

8. electroconductive polymer dispersion liquid according to claim 1, wherein

The decentralized medium is organic solvent.

9. electroconductive polymer dispersion liquid described according to claim 1~any one of 8, wherein

A part of the anionic group of the polyanion is bonded with amine compounds.

10. electroconductive polymer dispersion liquid described according to claim 1~any one of 8, wherein

A part of the anionic group of the polyanion is bonded with epoxide.

11. a kind of manufacturing method of electroconductive polymer dispersion liquid is produced from it electroconductive polymer as claimed in claim 9 point The manufacturing method of dispersion liquid, the electroconductive polymer dispersion liquid includes

Amine compounds are added into the aqueous dispersions comprising pi-conjugated electroconductive polymer and the conductive composite body of polyanion Object makes the conductive composite body that the process to form precipitate be precipitated；

The process for recycling the precipitate；And

The process of the acrylate compounds and organic solvent is added into the precipitate of recycling.

12. a kind of manufacturing method of electroconductive polymer dispersion liquid is produced from it electroconductive polymer as claimed in claim 9 point The manufacturing method of dispersion liquid, the electroconductive polymer dispersion liquid includes

Aqueous dispersions comprising pi-conjugated electroconductive polymer and the conductive composite body of polyanion are freeze-dried to obtain cold Freeze the process of hirudo leech；And

The process of amine compounds, the acrylate compounds and organic solvent is added into the freeze-drying body.

13. a kind of manufacturing method of electroconductive polymer dispersion liquid, is produced from it electroconductive polymer described in any one of claim 10 The manufacturing method of dispersion liquid, the electroconductive polymer dispersion liquid includes

Epoxy compound is added into the aqueous dispersions comprising pi-conjugated electroconductive polymer and the conductive composite body of polyanion Object makes the conductive composite body that the process to form precipitate be precipitated；

The process for recycling the precipitate；And

14. a kind of manufacturing method of conductive membrane, wherein to described in any one of film substrate coating claim 1~10 Electroconductive polymer dispersion liquid.

15. the manufacturing method of conductive membrane according to claim 14, wherein