JP5423416B2 - Conductive composition, conductive film using the same, and laminate having the conductive film - Google Patents

Description

  The present invention relates to a conductive composition, and the conductive composition has a very high uniformity of a coating film and can form a film having high conductivity. Utilizing these characteristics, it can be suitably used as a transparent electrode for touch panels, organic electroluminescence panels, inorganic electroluminescence panels, liquid crystal panels, and the like.

  Conventionally, as transparent electrode materials, development has been performed mainly on inorganic oxide materials such as indium oxide, tin oxide, and zinc oxide. Among them, ITO (tin-doped indium oxide), which is a mixed fired body of indium oxide and tin oxide, is generally used because of its high conductivity.

  In recent years, FTO (fluorine-doped tin oxide), IZO (indium oxide and zinc oxide mixed fired body), and the like have been developed for solar cells and organic electroluminescence elements.

  These transparent electrodes centered on inorganic oxides are formed using a dry film forming method such as a vacuum deposition method, a sputtering method, plasma, or an ion plating method. Since processes such as high-temperature film formation and high-temperature firing are required, glass is mainly used as a base material.

  When glass is used as a base material, it cannot be bent, cracked, or heavy, which is a problem when mobile applications are assumed.

  On the other hand, technology development in the area called “printable electronics” has been actively carried out in recent years. Production of expensive electronic parts that have been produced using expensive equipment and complicated processes by using printing methods that are low in process waste, have high material utilization efficiency, and are low in cost and are environmentally friendly That's it. It is said that this makes it possible to produce electronic components at low cost and high throughput. Furthermore, since a low temperature process can be used, a plastic film can be used for the base material. Thereby, a flexible electrically conductive film can be created. However, there is a problem that the reliability and performance of electronic components are sacrificed.

  Although it is possible to produce a conductive film made of an inorganic oxide on a plastic film by the above-mentioned dry process, due to its nature, cracks and the like are generated at the time of bending, and its flexibility is greatly lost. However, a conductive film using a conductive polymer as a conductive agent has flexibility in the film itself, can greatly suppress the occurrence of cracks and the like, and can produce a conductive film excellent in flexibility. . For this reason, there is an urgent need to develop a conductive ink suitable for the printing method (wet film formation method).

JP 2006-152203 A JP 2009-070789 A

Nikkei Electronics, August 10, 2009, 89 pages

  The present invention provides a conductive composition that is excellent in transparency, conductivity, and flexibility, can be applied and formed on a plastic substrate, and can provide a uniform coating film. Is an issue.

The present invention includes a conductive polymer (A), a dopant (B), and a compound (C) represented by the following general formula [1], and the total amount of conductive polymer (A) and dopant (B) is 100. The present invention relates to a conductive composition comprising 1 to 100 parts by weight of a compound (C) represented by the following general formula [1] with respect to parts by weight.
General formula [1]
R ¹ —Si (OR ² ) ₃
(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group, a methoxy group, or an ethoxy group, and R ² represents a methyl group or an ethyl group.)

  In the present invention, the conductive polymer (A) is characterized in that at least one selected from the group consisting of thiophene, aniline, pyrrole, and derivatives thereof is used as a monomer component. It relates to a conductive composition.

  The present invention also relates to the above conductive composition, wherein the conductive polymer (A) is poly (3,4-ethylenedioxythiophene).

  In addition, the present invention relates to the above conductive composition, wherein the dopant (B) is a compound having a sulfo group or an alkali metal salt thereof.

  In addition, the present invention relates to the conductive composition, wherein the dopant (B) is obtained by a reaction between a resin (B1) having a hydroxyl group and sultone (B2).

  Moreover, this invention relates to the electrically conductive film formed from the said electrically conductive composition.

  Moreover, this invention relates to the laminated body which has a base material and the said electrically conductive film.

  By carrying out the present invention, a conductive composition that is excellent in transparency, conductivity, and flexibility, can be applied to a plastic substrate, and can provide a uniform coating film. Can be provided.

First, the conductive polymer (A) of the present invention will be described.
The conductive polymer in the present invention means a polymer having a π-conjugated system spread throughout. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylene vinylenes, polyacetylenes, polyphenylenes, polyacenes, polythienylene vinylenes, and copolymers thereof.

  These conductive polymers may introduce a functional group such as an alkyl group, an alkoxyl group, a carboxyl group, a hydroxyl group, or a sulfo group as a substituent for the purpose of improving conductivity and compatibility with the binder resin. .

As a specific example of the conductive polymer (A),
Poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-heptyl) Thiophene), poly (3-octylthiophene), poly (3- (2-ethylhexyl) thiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-fluorothiophene), poly (3-chlorothiophene), poly (3-bromothiophene), poly (3-iodothiophene), poly (3,4-dibromothiophene) , Poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3-biphenylthio) Phen), poly (3-carboxythiophene), poly (3-sulfonylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene) , Poly (3-hexyloxythiophene), poly (3-octyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3- (2-ethylhexyl) oxythiophene), Poly (3-methyl-4-methoxythiophene), poly (3,4-ethylenedioxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl- 4-carboxythiophene) or poly (3-methyl-4-carbo) Phenoxyethyl thiophene), poly (3-methyl-4-carboxybutyl thiophene) polythiophenes such as;
Poly (pyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-propylpyrrole), poly (3-butylpyrrole), poly (3-hexylpyrrole), poly (3-heptyl) Pyrrole), poly (3-octylpyrrole), poly (3- (2-ethylhexyl) pyrrole), poly (3-dodecylpyrrole), poly (3-octadecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-fluoropyrrole), poly (3-chloropyrrole), poly (3-bromopyrrole), poly (3-iodopyrrole), poly (3,4-dibromopyrrole) , Poly (3-cyanopyrrole), poly (3-phenylpyrrole), poly (3-biphenylpyrrole), poly (3-carboxypyrrole) Poly (3-sulfonylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-octyloxypyrrole), poly (3-dodecyloxypyrrole), poly (3-octadecyloxypyrrole), poly (3- (2-ethylhexyl) oxypyrrole), poly (3-methyl-4-methoxypyrrole) , Poly (ethylenedioxypyrrole), poly (3-methyl-4-ethoxypyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyl) Ethylpyrrole), polypyrroles such as poly (3-methyl-4-carboxybutylpyrrole); It is,
And polyanilines such as polyaniline, methylpolyaniline, dimethylpolyaniline, hexylpolyaniline, dihexylpolyaniline, methoxypolyaniline, ethoxypolyaniline, hexyloxypolyaniline; and the like. Moreover, these can be used individually or in combination of 2 or more types.
Among the above compounds, poly (3,4-ethylenedioxythiophene) is preferably used.

Next, the dopant (B) will be described.
In general, it is known that a conductive polymer increases carrier density and improves conductivity by doping. The dopant used for doping can be classified into a donor dopant and an acceptor dopant depending on the type of carrier to be doped.

As a specific example of the donor dopant,
Alkali metals such as lithium, sodium or potassium;
Alkaline earth metals such as calcium or magnesium; or
Examples include, but are not limited to, quaternary ammonium cations such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, ethyldiisopropylammonium, methyltriethylammonium, trioctylmethylammonium, or ammonium salts such as cetyltrimethylammonium. Not. Moreover, these can be used individually or in combination of 2 or more types.

As a specific example of the acceptor dopant,
Halogen compounds such as chlorine, bromine, iodine, ICI, ICl ₃ , IBr, or IF;
Inorganic protonic acids such as HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, or ClSO ₃ H;
Formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, sebacic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid Or organic carboxylic acids such as triphenylacetic acid;
Methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 2-bromoethanesulfonic acid , Trifluoromethanesulfonic acid, ligninsulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-aminopropanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid , Propylbenzenesulfonic acid, butylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadeci Benzenesulfonic acid, camphorsulfonic acid, 2,4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, butylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, Or an organic sulfonic acid such as naphthalenesulfonic acid formalin polycondensate;
Tetracyanoethylene (TCNE), tetracyanoethylene oxide, tetracyanobenzene, tetracyanoquinodimethane (TCNQ), fluorinated tetracyanoquinodimethane (F4-TCNQ), 2,3-dichloro-5,6-dicyano- electron-deficient organic compounds such as p-benzoquinone (DDQ), chloranil, or tetracyanoazanaphthalene; Lewis acids such as PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ , or SO ₃ ; ,
Examples include, but are not limited to, transition metal compounds such as FeCl ₃ , FeOCl, TiCl ₄ , AlCl ₃ , ZrCl ₄ , HfCl ₄ , TaCl ₅ , MoCl ₅ , WF ₆ , or WCl ₆ . Moreover, these can be used individually or in combination of 2 or more types.

  Furthermore, a polyanion can be mentioned as an acceptor type dopant. The polyanion is a general term for polymer compounds having the aforementioned carboxylic acid and sulfonic acid units.

  Specific examples of polyanions include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 4-sulfobutyl methacrylate, methallyloxybenzene sulfonic acid, allyloxybenzene sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, Alternatively, a homopolymer or copolymer such as acrylamide-t-butylsulfonic acid, or a sodium salt or potassium salt thereof may be used. Examples of these commercially available products include, but are not limited to, Goseiran L-3288, L-0301, or L-0302 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Moreover, these can be used individually or in combination of 2 or more types.

  In the present invention, a compound having a sulfo group or an alkali metal salt thereof is preferably used as the dopant (B).

  A dopant having a sulfo group can also be obtained by reacting a hydroxyl group-containing resin (B1) and sultone (B2). At this time, the resin (B1) having a hydroxyl group is, for example, polymerized with an ethylenically unsaturated monomer having a hydroxyl group, or after polymerizing an ethylenically unsaturated monomer having a protected hydroxyl group, It is obtained by deprotecting a part. Moreover, you may copolymerize with ethylenically unsaturated monomers other than the above-mentioned ethylenically unsaturated monomer at the time of superposition | polymerization.

As a specific example of an ethylenically unsaturated monomer having a hydroxyl group,
2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, ethyl-α- (hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, 2-hydroxy (Meth) acrylates such as -3-phenoxypropyl (meth) acrylate or p-hydroxyphenylethyl (meth) acrylate; or
Vinyl alcohol, 1-hydroxy-3-butene, 1-hydroxy-4-pentene, 1-hydroxy-5-hexene, 1-hydroxy-7-octene, 1-hydroxy-9-decene, or 1-hydroxy-3- Examples include, but are not limited to, hydroxyl group-containing olefins such as methyl-3-butene.
As the ethylenically unsaturated monomer having a protected hydroxyl group, the hydroxyl group in the above-mentioned ethylenically unsaturated monomer having a hydroxyl group is an acetyl group, a benzoyl group, a benzyl group, a paramethoxybenzyl group, a methoxymethyl group. , Triethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, or an ethylenically unsaturated monomer protected with a trityl group, and the like, but is not limited thereto.
As specific examples of the copolymerizable ethylenically unsaturated monomer other than the ethylenically unsaturated monomer having a hydroxyl group and the ethylenically unsaturated monomer having a protected hydroxyl group,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo- (5,2,1,0,2.6) -decanyl (meth) acrylate, or tricyclo- (5, 2,1,0,2.6) -aliphatic (meth) acrylates such as decanyloxyethyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, or rosin acrylate;
(Meth) acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) acrylic acid or α- (hydroxymethyl) methacrylic acid and other ethylenic unsaturated Monomer;
Glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxybutyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate , 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, α-ethylacryl Acid glycidyl, allyl glycidyl ether, crotonyl glycidyl ale, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, o-Vinylbenzylglyce Jyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethyl Styrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyloxymethylstyrene, etc. Is preferred Is glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, oxetane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2- Methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, 1,4-dioxaspiro [4,5] deca-2-yl) methyl (meth) acrylate, 2-methacryloyloxy-γ-butyrolactone, 3- Heterocyclic (meth) acrylates such as methacryloyloxy-γ-butyrolactone or N- (meth) acryloyloxyethyl hexahydrophthalimide;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate;
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutyl (meth) acrylamide, t-butyl N-substituted (meth) acrylamides such as (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine;
(Meth) acrylates having an amino group such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
And nitriles such as (meth) acrylonitrile; or
Examples thereof include polymerizable oligomers such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, or one-end methacryloylated polyethylene glycol.

In addition,
Α-olefins such as ethylene, propylene, 1-butene, isobutene, or 1-hexene;
Styrenes such as styrene, α-methylstyrene, p-hydroxystyrene, p-vinylbenzoic acid, chloromethylstyrene, vinyltoluene, or indene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Examples thereof include N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide.

  Polymerization of an ethylenically unsaturated monomer having a hydroxyl group or polymerization of an ethylenically unsaturated monomer having a protected hydroxyl group can be carried out by a known method. That is, it can be carried out by optionally mixing an ethylenically unsaturated monomer with a polymerization initiator and heating. The polymerization temperature is 40 to 150 ° C, preferably 50 to 120 ° C.

In the polymerization, 0.001 to 15 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, an azo compound or an organic peroxide can be used.
Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like.
Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide.
These polymerization initiators can be used alone or in combination of two or more.

  During the polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. 0.001 to 15 parts by weight of a chain transfer agent can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer.

The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used.
For example,
Octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Mercaptans such as octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, or butylthioglycolate;
Disulfides such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, or tetrabutylthiuram disulfide;
Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide, or ethylene bromide;
Secondary alcohols such as isopropanol or glycerin;
Phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, or salts thereof (sodium hydrogen sulfite) , Potassium oxide bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and the like; or allyl alcohol, 2-ethylhexyl thioglycolate, α- Examples thereof include methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, and anisole. These may be used alone or in combination of two or more.

  In the polymerization, an organic solvent can be used as a polymerization solvent. Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, or diethoxydiethylene glycol, but are not particularly limited thereto. It is not something. These polymerization solvents may be used as a mixture of two or more kinds, but are preferably used for final use.

  Specific examples of sultone (B2) include, but are not limited to, propane sultone, butane sultone, pentane sultone, 1,8-naphthalene sultone, and the like.

  Next, the compound (C) will be described. The compound (C) preferably contains 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the conductive polymer (A) and the dopant (B). When the amount is less than 1 part by weight, the coating film is repelled and a uniform coating film cannot be obtained. Moreover, when more than 100 weight part, not only the flexibility of a coating film is impaired but electroconductivity also falls.

  Specific examples of the compound (C) include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, phenyltrimethoxysilane, benzyltrimethoxysilane, Tetramethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, or tetraethoxysilane Although it is mentioned, it is not limited to these. Moreover, these can be used individually or in combination of 2 or more types.

The conductive composition of the present invention may contain a silane compound other than the compound (C). For example,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, or vinyltrimethoxysilane;
(meth) acryloxysilanes such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, or γ- (meth) acryloxypropyldimethoxymethylsilane;
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3, 4-epoxycyclohexyl) epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-glycidoxypropyltriethoxysilane;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, or N-phenyl-γ-aminopropyltriethoxysilane; or
and thiosilanes such as γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane;

  The conductive composition of the present invention may contain a solvent depending on the purpose such as forming a coating film thereof. The solvent used at this time is not particularly limited as long as it is a solvent that can dissolve or disperse the conductive composition of the present invention, but water; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. (Poly) alkylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate Ether acetates; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene Glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono -N-propyl ether, dipropylene glycol (Poly) alkylene glycol monoalkyl ethers such as ethyl mono-n-butyl ether, tripropylene glycol monomethyl ether, or tripropylene glycol monoethyl ether; ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, propion Butyl acid, ethyl butyrate, isopropyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropyl Ethyl pionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion Acid methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-methoxy-2-methyl Esters such as ethyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate or ethyl 2-oxobutanoate; aromatic carbonization such as toluene or xylene Hydrogens; or - methylpyrrolidone, or N, and the like can be given amides such as N- dimethylacetamide. These solvents can be used alone or in admixture of two or more.

  Next, a method for forming a conductive film using the prepared conductive composition will be described. A wet film forming method is mainly used for forming the conductive film. Specifically, there are methods using various means such as spin coating, spraying, roller coating, gravure coating, die coating, comma coating, roll coating, curtain coating, or bar coating. These methods can be appropriately used depending on the thickness, viscosity, and the like to be applied.

In addition, as a base material for forming the conductive composition of the present invention, a plastic film such as polyethylene, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polypropylene, polyimide, polycarbonate, or cellulose triacetate, Alternatively, glass or the like can be used.
A laminated body can be obtained by forming a conductive film on a substrate using the conductive composition of the present invention.

  In general, various treatments can be performed on the surface of the base material for the purpose of improving the adhesion between the base material and the conductive film. Specific examples include UV ozone treatment, corona treatment, plasma treatment, and easy adhesion treatment.

  Hereinafter, the present invention will be described more specifically by way of examples. In the examples, “parts” means “parts by weight”, and “%” means “% by weight”. “Mn” represents a number average molecular weight.

[Synthesis Example 1]
In 100 mL deionized water, add 0.56 g 3,4-ethylenedioxythiophene, 2 g polystyrene sulfonic acid (Mn 40,000), 0.27 g ammonium persulfate and 2.5 mg iron (III) sulfate, By stirring at room temperature for 24 hours, an aqueous dispersion of resin (1) was obtained (solid content: 2.8%).

[Synthesis Example 2]
An aqueous dispersion of resin (2) was obtained in the same manner as in Synthesis Example 1 except that dodecylbenzenesulfonic acid was used instead of polystyrenesulfonic acid (solid content: 2.8%).

[Synthesis Example 3]
An aqueous dispersion of resin (3) was obtained in the same manner as in Synthesis Example 1 except that pyrrole was used instead of 3,4-ethylenedioxythiophene (solid content 2.8%).

[Synthesis Example 4]
An aqueous dispersion of resin (4) was obtained in the same manner as in Synthesis Example 3 except that sodium p-toluenesulfonate was used instead of polystyrenesulfonic acid (solid content: 2.8%).

[Synthesis Example 5]
An aqueous dispersion of resin (5) was obtained in the same manner as in Synthesis Example 2 except that aniline was used instead of 3,4-ethylenedioxythiophene (solid content 2.8%).

[Synthesis Example 6]
An aqueous dispersion of resin (6) was obtained in the same manner as in Synthesis Example 5 except that AOT (sodium bis (2-ethylhexyl) sulfosuccinate) was used instead of dodecylbenzenesulfonic acid (solid content 2. 8%).

[Synthesis Example 7]
10 g of polyvinyl alcohol (PVA102 manufactured by Kuraray Co., Ltd.) was dissolved in 200 g of dimethyl sulfoxide. At room temperature, 10 g of propane sultone was added and further stirred for 24 hours. Then, the dopant (7) was obtained as a white solid by adding to 500 g of methanol and collecting the precipitate by filtration.
An aqueous dispersion of resin (7) was obtained in the same manner as in Synthesis Example 1 except that dopant (7) was used instead of polystyrene sulfonic acid (solid content: 2.8%).

[Synthesis Example 8]
An aqueous dispersion of resin (8) was obtained in the same manner as in Synthesis Example 7 except that polyvinyl alcohol (Pura120, manufactured by Kuraray Co., Ltd.) was used instead of polyvinyl alcohol (PVA102, manufactured by Kuraray Co., Ltd.) (solid content 2 .8%).

[Synthesis Example 9]
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 200 parts of water, 20 parts of 2-hydroxyethylacrylamide and 0.1 part of 2-mercaptoethanol, and the temperature was raised to 60 ° C. After replacing the inside of the reaction vessel with nitrogen, 0.05 part of ammonium persulfate was added, and then the polymerization was continued for 3 hours at the same temperature for polymerization. After cooling to room temperature, water was removed to obtain poly (2-hydroxyethylacrylamide).
An aqueous dispersion of resin (9) was obtained in the same manner as in Synthesis Example 7 except that poly (2-hydroxyethylacrylamide) was used instead of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA102) (solid content 2. 8%).

[Example 1]
After the mixture was stirred and mixed with the composition shown in Table 1, it was applied onto untreated or easy adhesion treated PET using a bar coater (# 14). Table 2 shows the results of measuring the total light transmittance, the bendability test, the repellency of the coating film, and the change in conductivity after drying at 80 ° C. for 2 minutes.

[Example 2] to [Example 10], [Comparative Example 1] to [Comparative Example 4]
After stirring and mixing the mixture with the composition shown in Table 1, the results of measuring the total light transmittance, the bendability test, the repellency of the coating film, and the conductivity in the same manner as in Example 1 are shown in Table 2.

PhSi (OEt) ₃ : Phenyltriethoxysilane EtSi (OEt) ₃ : Ethyltriethoxysilane PhCH ₂ Si (OMe) ₃ : Benzyltrimethoxysilane EtOSi (OEt) ₃ : Tetraethoxysilane SiHexSi (OEt) ₃ : n- hexyltriethoxysilane MeOSi _(OMe) 3: tetramethoxysilane PrSi _(OMe) 3: n- propyltrimethoxysilane MeSi _(OMe) 3: methyltrimethoxysilane _{C 8 H 17 Si (OEt)} 3: n- octyltriethoxysilane Silane

  In the table, the “foldability test” is a test in which the dried coating film is bent 180 degrees together with the base material to return it to the original state. ○: No excitement or peeling, △: Partial excitement , Peeled off, x: evaluated as completely peeled. The “coating repellency” means the number of cissings when the coated and dried coatings are randomly cut out to 10 × 10 cm. Depending on the number of cissings, ◎: 0, ○: 1 to Three, Δ: 4-6, x: 7 or more, or evaluated that it was totally repelled and did not form a coating film. Further, “change in conductivity” refers to the relative value of the surface resistance value of the coating film in the example when the surface resistance value of the coating film to which the compound (C) is not added is 100.

  In Table 2, from the comparison of Examples 1 to 10 and Comparative Example 1, by using the compound (C), it was strong against bending of the base material, and repelling could be greatly suppressed. A coating film having electrical conductivity can also be provided.

  In Comparative Example 2, since the amount of the compound (C) added was too small, a larger number of repellency of the coating film was observed as compared with Example 1.

  In Comparative Example 3, since the amount of the compound (C) added was too large, the bending property was poor as compared with Example 1, and the conductivity was also greatly deteriorated. In addition, it was found that the coating liquid at this time produced a white precipitate after one day and the stability of the coating liquid was low.

  In Comparative Example 4, a silane compound having an alkyl group having 8 carbon atoms is used instead of the compound (C), but the bending property, the repellency of the coating film, and the conductivity are deteriorated as compared with the Example. It has become.

  The conductive composition according to the present invention can be used as a transparent conductive film to organic electroluminescence, solar cells, touch panels, liquid crystal panels, electronic paper, etc., and heat ray reflective glass, electromagnetic wave shields, antistatic films, It is excellent in transparency, conductivity, and flexibility, and can be applied and formed on a plastic substrate. Furthermore, a uniform coating film can be formed.

Claims (7)

100 parts by weight of the total amount of the conductive polymer (A) and the dopant (B) including the conductive polymer (A), the dopant (B), and the compound (C) represented by the following general formula [1] In contrast, a conductive composition comprising 1 to 100 parts by weight of the compound (C) represented by the following general formula [1].
General formula [1]
R ¹ —Si (OR ² ) ₃
(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group, a methoxy group, or an ethoxy group, and R ² represents a methyl group or an ethyl group.) Conductive polymer (A) is, claims thiophene, aniline, pyrrole, and selected from the group consisting of their derivatives, characterized in that obtained by polymerizing at least one monomer component 1. The conductive composition according to 1. The conductive composition according to claim 1 or 2, wherein the conductive polymer (A) is poly (3,4-ethylenedioxythiophene). The conductive composition according to any one of claims 1 to 3, wherein the dopant (B) is a compound having a sulfo group or an alkali metal salt thereof. The conductive composition according to any one of claims 1 to 4 , wherein the dopant (B) is obtained by a reaction between a resin (B1) having a hydroxyl group and a sultone (B2). A conductive film formed from the conductive composition according to claim 1. The laminated body which has a base material and the electrically conductive film of Claim 6.