JPH02255770A - New electronic conductive polymer and electroconductive material using thereof - Google Patents

Abstract

PURPOSE:To obtain electronic conductive polymer suitable as antistatic material, etc., for plastics having excellent electronic conductivity, mechanical strength and processability containing electronic conductive site comprising aniline-based compound or thiophene-based compound, etc., in side chain. CONSTITUTION:The aimed electronic conductive polymer is a (co)polymer composed of repeating unit expressed by formula I or formula II [A is polymer of main chain part (e.g. vinyl polymer); L is bifunctional bonding group; D is aniline-based compound] having electronic conductive site one or more aniline- based compound, thiophene-based compound or pyrrole-based compound in side chain as repeating unit. Said electronic conductive polymer is laminated with polymeric solid electrolyte to afford the aimed electroconductive material.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to antistatic materials for plastics, and in the fields of electrical and electronic industries, such as electrodes or electrolyte materials for batteries, capacitors, 74-cell devices, and electrochromic devices. Alternatively, it can be applied as a wide range of conductive materials such as planar heating elements and electromagnetic shielding materials.

[Conventional technology]

In recent years, organic polymer materials with electronic conductivity have been considered for application as batteries and various functional devices.

For example, polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polyphenylene acetylene, polyacetylene, etc. are promising, and West German Patent No. 3,223,
No. 544, No. 3,318,856, No. 3,318.8
No. 57, No. 3,325,892, No. 3.338904
No. 3,421,296, JP-A-58-18743
No. 2, No. 59-43060, No. 112583, No. 58-209864, No. 59-207933,
No. 60-120722, No. 60-67527, No. 6
No. 2-225518, No. 62-53328, No. 63-
No. 199726, No. 60-223817, No. 6i-8
No. 3221.

It is described in No. 59-31565 and the like. Although these polymers have excellent electronic conductivity, they have drawbacks such as poor mechanical strength and poor solubility in solvents, and poor moldability. A polymer with excellent electronic conductivity has been desired.

As conductive materials, these electron-conducting polymers and electrolytes are used in combination as layers, but in order to fully function as a device or pantry, electrons and ions must be exchanged at the interface between the two. need to be replaced promptly.

As an electrolyte, polymer solid electrolytes are superior in terms of no leakage, high mechanical strength, and high flexibility of laminated materials, and various reports have been made.

Conductive electronic materials that combine such polymer solid electrolytes and electronically conductive polymers include POLYMER,
1981, vol 22) November, 145
An organic battery combining polyacetylene and a solid electrolyte has been proposed on pages 4 to 1455, but the polyacetylene film produced by this addition polymerization has poor oxidation stability and is resistant to oxidation at the interface with the solid polymer electrolyte. There were problems such as insufficient contact and poor conductivity, and slow response speed as a device material.

Furthermore, JP-A No. 62-98577 describes a laminate conductive material in which an electrolytically polymerized polymer having a conjugated double bond in its main chain and a solid polymer electrolyte are combined. There were problems such as insufficient adhesion at the interface between the solid polymer electrolyte and the solid polymer electrolyte, resulting in high interfacial resistance1, poor conductivity, and poor mechanical strength.

In addition, as a compound aiming to achieve both mechanical strength and conductivity, compounds having a repeating unit of a carbazole group in the side chain, such as 6CH-CH, τ--- --- Dimension CH-cHz A7
has been studied, but its conductivity is 10-4 to 10-'
The S/cm was insufficient.

[Problem to be solved by the invention]

The first object of the present invention is to have excellent electronic conductivity and mechanical strength. The object of the present invention is to provide an electronically conductive polymer with excellent moldability.

The second object of the present invention is to provide an electronically conductive polymer and solid polymer electrolyte that, when combined with a solid polymer electrolyte, has low resistance at the contact interface, excellent electrical conductivity, and has a fast response speed as a device material. The object of the present invention is to provide a conductive material for a laminate with a laminate.

[Means for Solving the Problems] The above object could be achieved by the following electron conductive polymer and a conductive material formed by laminating the electron conductive polymer and a solid polymer electrolyte.

That is, an electron conductive polymer characterized by having an electron conductive moiety made of at least one of an aniline compound, a thiophene compound, or a virol compound in a side chain as a repeating unit, and the electron conductive polymer and the polymer. This was achieved using a conductive material made by laminating a molecular solid electrolyte.

The electron conductive polymer of the present invention will be explained in more detail.

The number of electron conductive moieties made of at least one of an aniline compound, a thiophene compound, or a virole compound, which are repeating units of the side chain, may be one type or two or more types. Furthermore, the repeating units of the electron conductive portions may be linked by a linking group.

A preferable electron conductive polymer of the present invention is a polymer or copolymer having at least a repeating unit represented by the following general formula (1) or (II).

(A?L (1) BeD) - I8toHere, A represents a polymer in the main chain portion, L represents a divalent linking group, D is an aniline compound, a thiophene compound, or virol. Represents a system compound.

The compound D contains a bond with L.

The main chain portion of A may be any polymer, for example, vinyl polymer, polyether, polysulfonamide,
polypeptide, polyamide, polyester, polyurea,
Examples include polyurethane, polyacid anhydride, polysulfone, polyazine, polyamine, polyheterocycle, polyketone, polyimine, polysulfide, phenol resin, and the like.

The basic monomers forming vinyl polymers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (
methacrylic acid), esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-
ethyl fuxyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylate lyl, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid. Examples include, but are not limited to, acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine.

Specific examples of polyether include: CH3 CH.

Specific examples of polypeptides include: ÷NHCH-CO←, +NHCHCO→-1H3 Specific examples of polyamide include: Specific examples of polysulfonamide include.

Specific examples of polyurethane include: Specific examples of polyester include: CH3 CH.

can be mentioned.

CH3 Specific examples of polyacid anhydrides include: Specific examples of polyurea include: It will be done.

A specific example of polysulfone is On the body side, It will be done.

A specific example of voriazine is Can be mentioned.

polyamine, Polyketoni and polyheterocyclic components etc.

Specific examples of polyimine and polysulfide include: CH.

It will be done.

The above specific example is Shunsuke Murahashi et al., Synthetic Polymer ■, 1975 (
It may be the one listed in Breakfast Bookstore).

Specific examples of phenolic resins include those described in Arata Murakami, Phenol Resins (published in 1981), such as '-C8HIff.

The electron conductive portion is connected to the main chain polymer by a linking group represented by the above general formula.

Specifically, L is (x++, r, -xg + -Tf-, h-Xi seven,
It is expressed as +z÷, and Jl, Jz, and Js may be the same or different, and -o --s --co---so,
-RI R1 10CO--Coo--CON--3o□NN-Co
--N-sow --N-R"--N-R"-N--
N-Co-N R'R'R'
Examples include RN-3o□-N--NGO□--0CON-. R1 represents a hydrogen atom, an optionally substituted alkyl group, or a phenyl group.

R2 represents an alkylene group having 1 to 4 carbon atoms.

R3 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. J, ,J, ,J, is preferably
-co --so□--CONH3OJHNHCo
NHSot 0=-N)ICONH--5-
-Co□--OCO--NllCO2-1 and -〇C0
It is NH-.

-NHCO□-5 and -0C0NH-.

X, , X, and X3 may be the same or different and each represents an optionally substituted alkylene group, arylene group, or aralkylene group, preferably having 1 to 1 carbon atoms.
4 alkylene group, an arylene group having 6 to 9 carbon atoms, and a substituted arylene group.

pSg, , r and S represent 0 or 1.

The electron conductive moiety represented by the above general formula represents an aniline compound, a thiophene compound, or a pyrrole compound. These may be substituted with aniline, thiophene, pyrrole, or each with an arbitrary substituent.

Examples of this substituent include halogen atom, nitro group, cyano group, alkyl group, alkoxy group, -NHCOR',
-NH30□R4SOR', -so□R' -CO
R', -CON.

/5otN, , an amino group (which may be further substituted with an alkyl group), a hydroxyl group, and a group that forms a hydroxyl group by hydrolysis. R4 represents an alkyl group, a phenyl group, or an aralkyl group.

R5 and R6 may be the same or different and represent a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. Furthermore, two substituents may be condensed to form a carbocycle or a heterocycle.

Furthermore, the alkyl group, alkoxy group, phenyl group, and aralkyl group in the above-exemplified substituents may be further substituted, and examples of the substituent include a hydroxyl group, a nitro group, an alkoxy group having 1 to 4 carbon atoms, / N) IsOtR' N) IcR' 5
Examples include OzN\a -CON/-5OJ7-COR', a halogen atom, a cyano group, and an amino group (which may be further substituted with an alkyl group).

R'+ has the same meaning as R4. RI+ and R9 may be the same or different and have the same meaning as R5.

Specific examples of D are shown below, but of course the invention is not limited to these.

H, C-C-CH.

L Preferred are aniline, thiophene, and virol.

The compound of the present invention may have a repeating unit of any monomer in addition to the repeating unit represented by the general formula (1> or (II)) for the purpose of increasing mechanical strength or improving solubility.

As the above repeating unit, A in the general formula (+)
Repeating units forming the main base corresponding to, for example, vinyl polymers, polyethers, polysulfonamides, polypeptides, polyamides, polyesters, polyureas, polyurethanes, polyanhydrides, polysulfones, polyazines,
polyamine, polyheterocycle, polyketone, polyimine,
Examples include polysulfide and phenolic resin.

Specific examples include those listed above as specific examples of A.

The repeating unit having an electron conductive moiety in its side chain consisting of at least one of the aniline compound, thiophene compound, or pyrrole compound of the present invention is:
It may be present in any proportion in the polymer. Preferably 1~
It is 20%.

Specific examples of the electron conductive polymer of the present invention will be shown, but the invention is not limited thereto.

Compound (1) CH2 + CH, C → 1- -(-C)1. CH → 7- Compound (If) CH3 x/y=1/9.2 n=13 Average n number Compound (m) CH.

+C)I IC±r ＋CH□C1l→Bottom- +cutco tencho= Compound (V) L +CLC±r C1l.

+CHtC1l)y (CLCH)-compound (TV
) −←CH, CII→1− COoC) IxCtl+0OCCtl14CONIIC
Hi-←cnzcH← 0OCaL Compound (Vl) CHl CH3 x/y・1/21 n-60 (average 0 losses) X/V wealth 1/20 n=65 (average number of n) Compound (■) Compound (■) Compound (Kari) L 1,000C11,C-)? 1+Cl12CH÷7 Compound (Xi) H2 x/y 1/10 21 (average n number) Compound (IX) (Jl x/y/z=50/42/8 CI+□ Compound (X mouth) H3 x/y = 1/25 70 (average n number) The synthesis method for obtaining the electron conductive polymer of the present invention may be a commonly used synthesis method, such as a known polymerization method, a chemical oxidation polymerization method, or an electrolytic oxidation polymerization method. , C-C coupling reaction, etc. can be used.

For example, after polymerizing the main chain so that the electron conductive site is present in the side chain, chemical oxidation polymerization, electrolytic oxidation polymerization, C
The compound of the present invention can be obtained by polymerizing the electron-conductive site by -C coupling reaction or the like. At this time, polymerization may be performed at different electron conductive sites, and the polymerization at the electron conductive sites may be carried out by chemical oxidation polymerization, electrolytic oxidation polymerization, C-
A side chain having a repeating unit of an electron-conducting moiety may be introduced into the main chain polymer by a polymer reaction after the C coupling reaction. The main chain may be polymerized using a hexamer whose electron-conductive site has been polymerized by -C coupling reaction or the like. At this time, the monomer used to polymerize the electron conductive site may be homopolymerized, or it may be copolymerized with any other monomer.

The above chemical oxidative polymerization method can be carried out in water or any organic solvent (
Dissolving or dispersing the monomer compound in the solution (which may contain water),
This is carried out by gradually adding a catalyst (oxidizing agent) solution at 60°C to -20°C (preferably 20°C to 0°C). In this case, an aqueous dispersion of the polymer can be obtained by using an appropriate dispersant or surfactant, which is preferable because it has excellent moldability.

The above electrolytic oxidation polymerization method involves dissolving or dispersing the monomer compound and the conductive salt in water or an organic solvent that can dissolve the conductive salt, and immersing the positive and negative electrodes at 80°C to -20°C. (preferably at 30'C to 0C) by a constant voltage method, a constant potential method, or a constant current method. Preferably, a constant voltage method is used.

The above C-C coupling reaction is mainly applied to thiophene compounds (it may also be applied to aniline compounds and pyrrole compounds), and a Grignard reagent or a metal halide is applied to a halogenated thiophene compound. can be obtained.

Specifically, 5ynthesis Metal, 26
．． 267 (1988) etc. Further, the compound of the present invention may be doped with an arbitrary dopant (for example, a halogen or a salt used during the polymerization).

Catalysts that can be used in chemical oxidative polymerization methods include:
For example, chlorides such as ferric chloride and cupric chloride, sulfates such as ferric sulfate and cupric sulfate, metal oxides such as lead dioxide and manganese dioxide, potassium persulfate, ammonium persulfate, and peroxide. Examples include peroxides such as hydrogen, quinones such as benzoquinone, halogens such as iodine and bromine, and potassium ferricyanide. Specific examples of these are JP-A Nos. 63-213518, 63-193926, 62-116665, 62-104832, and 6
No. 3-215717, No. 63-69823, No. 63-
It is also described in No. 101415, No. 60-58430, etc. The amount of catalyst varies depending on the characteristics of the monomer compound and the catalyst used, but can be used in a molar ratio of catalyst/monomer compound in the range of 0.01 to 10.

Electrode materials that can be used in the electrolytic oxidation polymerization method include metal electrodes (eg, Au%PL, NisCu).

Sn, Zu), carbon electrodes (e.g. glassy carbon), metal oxide electrodes (e.g. SnO2) In2O2
) etc. Further, it is preferable to use a separate reference electrode.

! Conductive salts that can be used in the deoxidative polymerization method include alkali metal cations (Li", Na"K1, etc.)
, NO'", Noz"" cations, onium cations (EtaN", Bu4N", BusP"", etc.) and negative ions (BF, -AsFa-, AsPh-, 5bFa-
,5bCj! *-, PF&Cl0a-, AIFa-, ^
IF4-, NtFa"-1Zrh"-1Tip, z-
1BroC1,. t-5HSO,-,SO,”-,Cj
! -, Br, l", I-), sulfonic acid anion CCH3CbHaSOs-, C, HsSOz-1
CFsSOs-polystyrene sulfonic acid, etc.),
HCOOLi.

Examples include salts containing carboxylic acid anions such as sodium polyacrylate, chlorides such as FeCl s, and organic amine salts such as pyridine hydrochloride.

Examples of solvents that can be used in the chemical oxidative polymerization method and the electrolytic oxidative polymerization method include organic solvents (e.g., acetonitrile, dimethyl sulfuric acid, N,N-dimethylacetamide, N,
N-dimethylformamide, dimethyl sulfoxide,
sulfuran, formamide, dimethoxyethane, propylene carbonate, dioxane, methanol, ethanol, T-butyl lactone, nitrobenzene, tetrahydrofuran, nitromethane, etc.), water, or a mixture of both.

In addition, conductive compounds that may be added and polymerized during chemical oxidative polymerization or electrolytic oxidative polymerization include:
Inorganic acids (e.g. HCl, HtSO□, nczo,
, BP, ), organic acids (e.g. sulfonic acids such as toluenesulfonic acid, trifluoromethylsulfonic acid, polystyrene sulfonic acid, carboxylic acids such as formic acid, acetic acid, polyacrylic acid), organic bases (e.g. pyridine, triethanolamine). At the time of chemical oxidative polymerization, the above-mentioned conductive salt may be added.

As the dispersant, cationic, anionic, nonionic, betaine polymers and surfactants (emulsifiers) can be used. Specific examples of these include polyvinyl alcohol, polyethylene oxide, polypropylene oxide, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, dextrin, polyvinylpyrrolidone, sodium polystyrene sulfonate, polyacrylic acid, polyacrylamide, gelatin, collagen, tertiary or quaternary Polymers having ammonium salt sites, polymers having oxonium salt sites, polymers having sulfonium salt sites, long chain alkyl compounds having quaternary ammonium salt sites, higher fatty acid alkali salts (for example, CI (+JzsCOONa
), alkyl sulfates (e.g. sodium lauryl sulfate),
Alkyl sulfonates (e.g. sodium lauryl sulfonate), alkylaryl sulfonates (e.g. sodium dodecylbenzenesulfonate), sulfosuccinate ester salts, higher amine halogenates, alkylpyridinium halides (e.g. dodecylpyridinium chloride) ,
Quaternary ammonium salts (e.g. trimethylammonium chloride), polyethylene glycol alkyl ethers,
Examples include polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride, and amino acids.

When using a dispersant, the amount is 1 to 300% based on the monomer.
It is used in weight percent, preferably from 5 to 200 weight percent. When using a surfactant, it should be 0.01 to 70%
It is used at 50% by weight, preferably from 0.1 to 20% by weight.

These aqueous dispersions may be used after being subjected to treatments such as dialysis and ultrafiltration.

The above-mentioned conductive compound may be added to these aqueous dispersions, or a polymer compound such as polyvinyl acetate polymer may be blended therein.

The electron conductive polymer of the present invention can be laminated with a solid polymer electrolyte and used as a conductive material such as a polymer battery.The electron conductive polymer of the present invention may form a plurality of layers. , may form a plurality of layers with known electronically conductive polymers, or may further have a laminated layer with a salt of a metal ion of group Xa or group nc of the periodic table. The electrolyte and the electronically conductive polymer of the present invention are in direct contact.

Polymer solid electrolytes for obtaining the laminated conductive material with the electron conductive polymer of the present invention include cation polymer anion polymer, polyacrylonitrile, polyalkylene oxide polymer (PEO, PPO, silicon compound containing PEO, phosphazene, etc.), polyvinyl Examples include combinations of alcohol and salt. Specific examples of these are JP-A-61-256573, JP-A-61-124001, JP-A-62-20263, JP-A-62-139266, JP-A-63.
-241066, 63-241026, 63-
No. 135477, No. 63-142061, No. 63-1
No. 30613, No. 60-23974, No. 63-136
No. 409, No. 63-193954, No. 63-1867
No. 66, No. 63-205364, Macromolecusis 21S648.

Examples of the salt constituting the solid polymer electrolyte include conductive salts used during polymerization in the chemical oxidation polymerization method and electrolytic polymerization method described above.

Preferably, it is a salt of a metal ion of group Ia or IIa of the periodic table, and more preferably a Li salt.

When the electronically conductive polymer obtained by the chemical oxidation polymerization method of the present invention is in the form of powder or lumps, the laminate conductive material is produced by pressing a film processed by compression molding onto a solid polymer electrolyte membrane. can do. Moreover, when the obtained electron conductive polymer is an aqueous dispersion, roller coating, spin cord, Giesser coating, dip coating,
Known coating methods such as spray coating, extrusion molding,
and a known drying method can be used.

In addition, it is also possible to apply a dissolved or melted polymer solid electrolyte onto an electron conductive polymer film formed on an electrode by electrolytic oxidation polymerization method or an electron conductive polymer film formed into a film by the above method. They may be laminated in close contact.

Synthesis examples of the compounds of the present invention are shown below, but the compounds of the present invention are not limited thereto.

Synthesis examples of the compounds of the present invention are shown below, but of course the compounds of the present invention are not limited thereto.

[Synthesis of Compound (1)] While stirring 0.1 mol of 2-bromo-4-2-hydroxyethoxymethylthiophene, 0.1 mol of pyridine, and 100 d of acetonitrile at 10°C or lower, 0.1 mol of methacryloyl chloride was added to 30 ml of methacryloyl chloride. Dropped in minutes. After stirring for 1 hour, 200 id of ethyl acetate and 200 m of water were added, and the ethyl acetate layer was extracted, concentrated, and purified by column.
Bromo-4-thienylmethoxyethyl methacrylate (
1-1) 22.1g was obtained.

10 g of (1-1), 30 g of n-butyl acrylate, 300 d of ethyl acetate, and 0.6 g of 2,2'-azobismethylisobutyrate were stirred at 80° C. for 5 hours under a nitrogen stream. After concentrating ethyl acetate, 1ffi of nitrobenzene and 1111.5 mol of trichloride were added, and 0.5 mol of 2-chlorothiophene was added dropwise over 1 hour at 100°C under a nitrogen stream.
After stirring at 0° C. for 6 hours, nitrobenzene was concentrated. To this, 500 ml of ethyl acetate was added and compound (1) was extracted with heating and purified using a Sephadec column to obtain 65 g of compound (I).

(1-1) From elemental analysis and NMR of compound (1), the composition of compound (1) is x/y=1/9°2)n=13
．． 2 (average n number) was obtained.

[Synthesis of comparative compound r]

According to compound (1), 0.1 mol of 2-chlorothiophene and 0.6 iron trichloride were added using 300 d of nitrobenzene as a solvent.
[Synthesis of Compound (If)] 0.5 mol of 2-aminoethyl methacrylate, 0.5 mol of p-chloronitrobenzene, and 250 id of N,N dimethylacetamide were mixed at 120°C under a nitrogen atmosphere for 2 hours. Stir for hours. Ethyl acetate (5°Od) and water (500ml) were added thereto, and the ethyl acetate layer was extracted and concentrated, then methanol (500ml) was added, and the mixture was reduced under pressure of H2 under a Pd--C catalyst. Pd
After removing the -C catalyst, methanol was concentrated, and the residue was purified using a silica gel column to obtain 71.1 g of 2-4-aminophenylaminoethyl methacrylate (U-1).

(U-1) 5g, n-butyl methacrylate 60g, ethyl acetate 300d and 2,2'-azobismethylisobutyrate 0.7g were stirred at 90°C for 5 hours under a nitrogen stream. After concentrating the reaction solution, It was purified using a Cadex column to obtain 45 g of copolymer (Il-2).

(II-2) 1.2 g, 7-1-rif 1, 8 g
, 47.5g of Liclo and 500g of acetonitrile
Electrolytic polymerization was carried out for 1 hour using a constant voltage method (3 V, 2 mA/cm") using PT plates for both the positive and negative electrodes while stirring m, to obtain a polymer precipitate on the negative electrode. Thereafter, the polymer precipitate was treated with methyl ethyl ketone. The mixture was extracted with heat, concentrated, and purified using a Sephadex column to obtain compound (If) 12.

(II-2), elemental analysis of compound (■) and NMR revealed that the composition of compound (n) was x/y-1/26, n=85
(average n number) was obtained.

[Comparative compound ■]

Aniline was electropolymerized according to compound (II) [constant voltage method (
3V, 2 mA/am'') was deposited on the negative electrode.

〔Example〕

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 Compound (1) of the present invention and comparative compound (1) were dissolved in ethyl acetate and N,N-dimethylformamide, respectively, and cast onto a PET film and a Teflon plate. The film cast on the Teflon plate was peeled off from the Teflon plate and then immersed in an IjCI O, aqueous solution.
Electrical conductivity was measured by our probe method.

The film cast on PET film is 1 as it is.
Scratch resistance test using a sapphire needle of -diameter The above results show that the compound of the present invention improves moldability and mechanical strength without lowering electrical conductivity.

Example 3 Compound (1) (II) of the present invention obtained in Example 1.2
and Comparative Compound (1) (It) (each about 30 μm thick) were laminated with a cast film (about 100 μm thick) of the polymer solid electrolyte shown below, and sandwiched between stainless steel plates to create a laminated material. Also, this laminated material has 1
A force of "kg/cm" was applied thereto and allowed to stand for one week. The results of measuring the electrical conductivity (Cafe-Cole plot method) of each are shown below.

The load applied by the needle when the film was destroyed and a scar remained was determined and was taken as the scratch strength.

The above results revealed that the compound of the present invention improves mechanical strength without lowering electrical conductivity.

Example 2 The same operation as in Example 1 was carried out using DMF as a solvent for each of the compound (n) of the present invention and the comparative compound (II). Comparative compound (II) solubilized only about 20% of the low molecular weight components and was significantly inferior in moldability.

The compound (n) of the present invention is soluble in DMF and other solvents (acetone, etc.) and can be said to have significantly superior moldability compared to the comparative compound @IJ (If).

(Polymer solid electrolyte film) A mixture of 1/2 was dissolved in a7tonitrile and cast on a Teflon plate.

The above results revealed that the laminated material of the present invention has low interfacial resistance, excellent conductivity, and excellent mechanical strength.

(Effects of the Invention) By carrying out the present invention, an electronically conductive polymer having excellent electronic conductivity, excellent mechanical strength, and excellent moldability can be obtained, and it can also be used as a solid polymer electrolyte. When combined, a conductive material with excellent conductivity can be obtained.

Patent applicant: Fuji Photo Film Co., Ltd. 1999 year/month day Display of incidents 1999 Patent Application No. 101OJ name of invention New electronically conductive polymers and secondary conductive materials using them person who makes corrections Relationship with the incident

Claims (2)

[Claims] (1) An electron-conductive polymer characterized by having an electron-conductive moiety made of at least one of an aniline-based compound, a thiophene-based compound, or a pyrrole-based compound as a repeating unit in a side chain. (2) An electrically conductive material comprising a laminate of an electronically conductive polymer and a solid polymer electrolyte according to claim (1).