JP2019112499A - Composition, conductive film, method for producing conductive film, and capacitor - Google Patents

Abstract

To provide a composition that can form a conductive film having excellent heat resistance.SOLUTION: A composition contains (a) a conductive polymer, (b) silica, and (c) a phenolic compound.SELECTED DRAWING: None

Description

  The present invention relates to a composition, a conductive film, a method of manufacturing a conductive film, and a capacitor.

  The conductive polymer is used as a conductive ink for a solid electrolyte of a capacitor, an electromagnetic wave absorbing coating agent, an antistatic coating agent, an electrolytic plating base material, a circuit wiring application and the like. For example, Patent Document 1 discloses a coating liquid for forming a transparent conductive coating film, which contains a conductive polymer, a binder containing silica as a main component, and a solvent.

  In addition to its electrical properties, polyaniline, which is a type of conductive polymer, has the advantage of being able to be synthesized relatively easily from inexpensive aniline and showing excellent stability against oxygen etc. in the state of exhibiting conductivity. For example, highly conductive polyaniline can be easily prepared by the method described in Patent Document 2.

Unexamined-Japanese-Patent No. 2017-88695 International Publication No. 2012/102017 brochure

  In recent years, a capacitor using a conductive polymer has been widely used for in-vehicle use and the like, but conventional conductive polymer-containing compositions have failed to exhibit sufficient heat resistance. An object of the present invention is to provide a composition capable of forming a conductive film excellent in heat resistance.

According to the present invention, the following composition and the like are provided.
1. (A) conductive polymer,
A composition comprising (b) silica and (c) a phenolic compound.
2. The composition according to 1, wherein the content of the component (b) is 0.1 to 60 parts by mass with respect to 100 parts by mass of the component (a).
3. The composition as described in 1 or 2 whose content of the said component (b) is 0.1 mass% or more and less than 10 mass% in a total solid.
4. A composition comprising (a) a conductive polymer and (b) silica, wherein the content of the component (b) is 0.1% by mass or more and less than 10% by mass in the total solid content.
5. (D) The composition according to any one of 1 to 4 further comprising a solvent.
6. The composition according to any one of 1 to 5, wherein the component (a) is one or more selected from the group consisting of polyaniline, polyaniline derivative, polythiophene, polythiophene derivative, polypyrrole and polypyrrole derivative.
7. The composition according to any one of 1 to 6, wherein the component (a) is a polyaniline complex comprising polyaniline and a proton donor, wherein the polyaniline is doped with the proton donor.
8. 7. The composition according to 7, wherein the proton donor is sulfonic acid or sulfonic acid salt.
9. 8. The composition according to 8, wherein the sulfonic acid or the sulfonic acid salt is a sulfosuccinic acid derivative represented by the following formula (III):
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III)
(In formula (III),
M is a hydrogen atom, an organic radical or an inorganic radical,
m is the valence of M,
R ¹² and R ¹³ are each independently a hydrocarbon group or a group represented by — (R ¹⁴ O) _r —R ¹⁵ , R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is hydrogen atom, a hydrocarbon group, or ^R ₁₆ 3 Si- group represented ^{by, R 16} is a hydrocarbon group, and three ^{R 16} may be the same or different, r is an integer of 1 or more. )
10. The composition according to any one of 1 to 9, further comprising (e) one or more selected from the group consisting of an acidic substance and a salt of the acidic substance.
11. And (f) an acid having a hydrophobic group, wherein the hydrophobic group is one or more selected from the group consisting of a linear alkyl group, a branched alkyl group, an alkylphenyl group, and an alkylnaphthyl group. 10. The composition according to any one of 10.
12. A conductive film comprising: (a) a conductive polymer, and (b) silica, wherein the content of the component (b) is 0.1% by mass or more and less than 10% by mass.
13. The conductive film according to 12, further comprising (e) one or more selected from the group consisting of an acidic substance and a salt of the acidic substance.
14. (A) conductive polymer,
A conductive film comprising one or more selected from the group consisting of (b) silica, and (e) an acidic substance and a salt of an acidic substance.
15. The electroconductive film as described in 13 or 14 containing 2 or more types of the said component (e).
The composition according to any one of 16.1 to 11 is applied and dried to form a coating,
The manufacturing method of the conductive film which dips and dries the said coating film in the solution containing 1 or more selected from the group which consists of an acidic substance and the salt of an acidic substance.
17. A capacitor including the conductive film according to any one of 17.12 to 15.

  ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the electroconductive film which is excellent in heat resistance can be provided.

It is a transmission type microscope picture of organo silica sol "IPA-ST" used in the example. It is a figure which shows the upper surface of the glass substrate in which the indium tin oxide (ITO) electrode was formed in the surface. It is a figure which shows the upper surface of the glass substrate which shaved the conductive film and exposed the terminal of the ITO electrode on the surface. It is a transmission type microscope picture of organo silica sol "IPA-ST-ZL" used in the example. It is a transmission type microscope picture of organo silica sol "IPA-ST-UP" used in the example.

[First composition]
The first composition of the present invention comprises (a) a conductive polymer, (b) silica, and (c) a phenolic compound.
By containing the component (b), the first composition can form a conductive film excellent in heat resistance. Specifically, the conductive film obtained has a low rise in resistance value when it is left for a long time under high temperature conditions, and its stability is high. The component (b) does not necessarily have to be contained in a large amount, and even if it is a small amount, a large heat resistance improvement effect can be obtained. Moreover, it is possible to form the electroconductive film which has high electroconductivity by containing a component (c).
Each component will be described below. The component represented by each code may be simply referred to as "component (a)" or the like.

(Component (a): conductive polymer)
Examples of the conductive polymer include polyaniline, polythiophene, polypyrrole and derivatives thereof. These may or may not have a substituent. One of these may be used alone, or two or more of these may be used in combination.

As the conductive polymer, polyaniline is preferred.
The polyaniline preferably has a weight average molecular weight of 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more and 1,000,000 or less, still more preferably 40,000 or more. It is 1,000,000 or less, particularly preferably 52,000 or more and 1,000,000 or less.

  The weight average molecular weight of polyaniline is measured by the method described in the examples.

Polyaniline may or may not have a substituent, but is preferably unsubstituted polyaniline from the viewpoint of versatility and economy.
In the case of having a substituent, examples of the substituent include linear or branched hydrocarbon groups such as methyl, ethyl, hexyl and octyl; alkoxy groups such as methoxy and ethoxy; and aryloxy such as phenoxy And halogenated hydrocarbons such as trifluoromethyl group (—CF ₃ group) and the like.

In addition, it is preferable that the polyaniline is a polyaniline complex in which a proton donor is doped.
The fact that the proton donor is doped to polyaniline can be confirmed by ultraviolet / visible / near-infrared spectroscopy or X-ray photoelectron spectroscopy, and the proton donor is sufficient for generating a carrier in polyaniline. If it has acidity, it can be used without particular restrictions on the chemical structure.
By using the said polyaniline complex, since the solubility to a solvent improves, it is preferable.

The proton donor includes, for example, a Bronsted acid, or a salt thereof, preferably an organic acid, or a salt thereof (for example, a sulfonic acid or a sulfonic acid salt), more preferably represented by the following formula (I) Proton donors.
M (XAR _n ) _m (I)
In the above formula (I), M is a hydrogen atom, an organic free radical or an inorganic free radical.
As said organic free radical, a pyridinium group, an imidazolium group, an anilinium group etc. are mentioned, for example. Examples of the inorganic free radical include sodium, lithium, potassium, cesium, ammonium and the like.

X is an acidic group, for example, ^{_{-SO 3 -, -PO 3 2-,}} -PO 4 (OH) -, -OPO 3 2-, -OPO 2 (OH) -, -COO - , a group represented by etc. can be mentioned, -SO ₃ ^- group represented by are preferred.

A is a hydrocarbon group which may contain a substituent.
The hydrocarbon group is, for example, a linear or branched alkyl group having 1 to 24 carbon atoms; alkenyl group; cycloalkyl group which may contain a substituent such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, menthyl and the like An aryl group containing an aromatic ring which may contain a substituent such as bicyclohexyl, norbornyl, adamantyl or the like, which may be condensed, or a substituted or unsubstituted cycloalkyl, such as phenyl, tosyl, thiophenyl, pyrrolinyl, pyridinyl or furanyl; Groups such as naphthyl, anthracenyl, fluorenyl, 1,2,3,4-tetrahydronaphthyl, indanyl, quinolinyl, indinyl and the like, optionally condensed diaryl or polyaryl groups; alkylaryl groups etc., corresponding to (n + 1) A group of values It is.

Each R independently represents a substituent represented by -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ , -CO (COR ¹ ), or -CO (COOR ¹ ).
R ¹ is a hydrocarbon group which may include a four or more substituents carbon atoms, a silyl group, alkylsilyl ^group, - (R _{2 O)} groups represented by x -R ^3, or - (OSiR ³ _{2) x} It is a group represented by —OR ³ (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more).
Examples of the hydrocarbon group of R ¹ include linear or branched butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group, eicosanyl group and the like.
n is an integer of 2 or more. m is the valence of M.

The organic protic acid represented by the formula (I) or a salt thereof is preferably a dialkylbenzenesulfonic acid, a dialkyl naphthalenesulfonic acid, a sulfophthalic acid ester, or an organic protic acid represented by the following formula (II) or a salt thereof .
M (XCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ ) _p (II)

In the above formula (II), M and X are the same as in formula (I).
p is the valence of M.

R ⁴ and R ⁵ each independently represent a hydrogen atom, a hydrocarbon group or a group represented by R ⁸ ₃ Si— (wherein R ⁸ is a hydrocarbon group, and three R ^{8 s} are the same or different) May be
The hydrocarbon group of R ⁴ and R ^5, straight-chain or branched alkyl group having 1 to 24 carbon atoms; include alkyl aryl group; an aryl group containing an aromatic ring.
The hydrocarbon group of R ^{8 is the same as} the hydrocarbon group of R ⁴ and R ⁵ .

R ⁶ and R ⁷ each independently represent a hydrocarbon group or a group represented by — (R ⁹ O) _q —R ¹⁰ [wherein, R ⁹ is a hydrocarbon group or a silylene group, and R ¹⁰ is hydrogen] An atom, a hydrocarbon group or a group represented by R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, and three R ¹¹ may be the same or different), and q is an integer of 1 or more Yes].
As a hydrocarbon group of R ⁶ and R ⁷ , a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 4 or more carbon atoms; an aryl group containing an aromatic ring; an alkylaryl group and the like can be mentioned.
Specific examples of the hydrocarbon group of R ⁶ and R ⁷ include linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group and the like.

As a hydrocarbon group of R ⁹ , a linear or branched alkylene group having 1 to 24 carbon atoms; an arylene group including an aromatic ring; an alkyl arylene group; an aryl alkylene group and the like.
^The hydrocarbon group of ^{R 10} and ^{R 11,} is the same as in the case of ^{R 4} and ^{R 5.} q is preferably an integer of 1 to 10.

Specific examples of the organic protic acid or its salt represented by the formula (II) in the case where R ⁶ and R ⁷ are a group represented by-(R ⁹ O) _n -R ¹⁰ are represented by the following formula Acid can be mentioned.
(Wherein, X is a group represented by —SO ₃ , etc.)

The compound (organic protic acid or a salt thereof) represented by the above formula (II) is preferably a sulfosuccinic acid derivative represented by the following formula (III).
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III)
In the above formula (III), M and m are the same as the above formula (I).

R ¹² and R ¹³ each independently represent a hydrocarbon group or a group represented by — (R ¹⁴ O) _r —R ¹⁵ [wherein, R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is hydrogen] An atom, a hydrocarbon group or a group represented by R ¹⁶ ₃ Si— (wherein, R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different), and r is 1 or more Is an integer].

The hydrocarbon groups of R ¹² and R ¹³ are the same as the hydrocarbon groups of R ⁶ and R ⁷ .
The hydrocarbon group of R ^{14 is the same as} the hydrocarbon group of R ⁹ . ^Further, the hydrocarbon group of ^{R 15} and ^{R 16} are the same as the hydrocarbon group of ^{R 4} and ^{R 5.}
r is preferably an integer of 1 to 10.

Specific examples of the organic protic acid or a salt thereof represented by the formula (III) when R ¹² and R ¹³ are a group represented by-(R ¹⁴ O) _r -R ¹⁵ are R ⁶ and R ⁷ It is the same as the organic protic acid or its salt represented by Formula (II) when it is group represented by-(R _< ⁹ _> O) _n- R _< ¹⁰ _> .
Hydrocarbon groups of R ¹² and ^{R 13} are the same as the hydrocarbon groups ^{R 6} and ^{R 7,} a butyl group, a hexyl group, a 2-ethylhexyl group, decyl group and the like are preferable.

The doping ratio of the proton donor to polyaniline is preferably 0.30 to 0.65, more preferably 0.32 to 0.60, and still more preferably 0.33 to 0.57. And particularly preferably 0.34 or more and 0.55 or less. If the doping rate is 0.30 or more, the solubility of the polyaniline complex in the organic solvent is sufficiently high.
The doping rate is defined by (the number of moles of a proton donor doped to polyaniline) / (the number of moles of monomer units of polyaniline). For example, a doping ratio of 0.5 for a polyaniline complex containing unsubstituted polyaniline and a proton donor means that one proton donor is doped to two monomer unit molecules of polyaniline.
The doping rate can be calculated if the number of moles of the proton donor and the monomer unit of polyaniline in the polyaniline complex can be measured. For example, when the proton donor is an organic sulfonic acid, the number of moles of sulfur atom derived from the proton donor and the number of moles of nitrogen atom derived from the monomer unit of polyaniline are quantified by organic elemental analysis and the ratio of these values The doping rate can be calculated by taking.

The polyaniline complex preferably contains unsubstituted polyaniline and sulfonic acid which is a proton donor, and satisfies the following formula (5).
0.32 ≦ S ₅ / N ₅ ≦ 0.60 (5)
(Wherein, S ₅ is the total number of moles of sulfur atoms contained in the polyaniline complex, and N ₅ is the total number of moles of nitrogen atoms contained in the polyaniline complex. The above-mentioned moles of nitrogen atoms and sulfur atoms The number is a value measured by organic elemental analysis.)

(Component (b): silica)
And "silica" to be used in the present invention means a silicon oxide containing silicon (Si) and oxygen (O), in not only the compounds represented by SiO _X such as SiO _2, siloxane bond (-O-Si Also included are oligomers or polymers comprising -O-). In addition, it may be a hydrate or an anhydride.

The silica is preferably in the form of particles, and the particles may be in the form of beads.
The average particle size of the silica particles is preferably 1 to 200 nm. Colloidal silica particles (colloidal silica) may be used.

  The average particle size of the silica particles is determined by calculating the specific surface area by the BET method and converting the specific surface area. The specific surface area is calculated by the BET method under the conditions described in JIS Z8830 (2013).

  Commercial products of silica include "Organo silica sol" series ("IPA-ST", "IPA-ST-ZL", "IPA-ST-UP", etc.) and "Snowtex" series manufactured by Nissan Chemical Co., Ltd. It can be mentioned.

The content of the component (b) is preferably 0.1 to 60 parts by mass, and may be 0.1 to 40 parts by mass with respect to 100 parts by mass of the component (a).
In addition, the content of the component (b) may be 0.1% by mass or more, or 0.3% by mass or more in the total solids in the first composition, and less than 10% by mass in the total solids , 9.5 mass% or less, or 5.0 mass% or less. The content of the component (b) is 0.1% by mass or more and less than 10% by mass, 0.1 to 9.5% by mass, or 0.1 to 5.0% by mass in the total solid content in the first composition. It is good also as mass%.
The solid content in the first composition is usually components (a), (b) and (e).

(Component (c): phenolic compound)
By using a phenolic compound, the conductivity can be improved, and the solubility in alcohol can be improved.
The phenolic compound is not particularly limited, and is a compound represented by ArOH (wherein Ar is an aryl group or a substituted aryl group). Specifically, phenol, o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol, o-, m- or p-butylphenol, o -, M- or p-chlorophenol, substituted phenols such as salicylic acid, hydroxybenzoic acid and hydroxynaphthalene; polyhydric phenolic compounds such as catechol and resorcinol; and polymers such as phenol resin, polyphenol and poly (hydroxystyrene) A compound etc. can be illustrated.

Moreover, the phenolic compound represented by following formula (3) can be used.
(Wherein n is an integer of 1 to 5).
R represents an alkyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, It is a C7-C20 alkylaryl group or a C7-C20 arylalkyl group. )

The above R will be described below.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, tertiary amyl and the like.
As an alkenyl group, the substituent which has an unsaturated bond in the molecule | numerator of the alkyl group mentioned above is mentioned.
Examples of the cycloalkyl group include cyclopentane and cyclohexane.
Examples of the alkylthio group include methylthio, ethylthio and the like.
The aryl group includes phenyl, naphthyl and the like.
Examples of the alkylaryl group and the arylalkyl group include substituents obtained by combining the above-mentioned alkyl group and aryl group.
Of these groups, R is preferably methyl or ethyl.

  The content of the component (c) is preferably 10 to 5000 parts by mass, and more preferably 10 to 2000 parts by mass with respect to 100 parts by mass of the component (a).

(Component (d): solvent)
The first composition preferably comprises a solvent. The solvent is not particularly limited as long as it dissolves the component (a), but an organic solvent is preferable. The organic solvent may be a water-soluble organic solvent or an organic solvent substantially immiscible with water (water-immiscible organic solvent).

The water-soluble organic solvent may be a protic polar solvent or an aprotic polar solvent, such as isopropyl alcohol, 1-butanol, 2-butanol, 2-pentanol, benzyl alcohol, alkoxy alcohol (eg 1-methoxy-2-propanol) Alcohols such as 3-methoxy-1-butanol) Ketones such as acetone; Ethers such as tetrahydrofuran, dioxane, ethylene glycol mono-tert-butyl ether and the like; aprotic polar solvents such as N methyl pyrrolidone etc. .
Examples of water-immiscible organic solvents include hydrocarbon solvents such as hexane, benzene, toluene, xylene, ethylbenzene and tetralin; halogen-containing solvents such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane and tetrachloroethane; acetic acid Ester solvents such as ethyl, isobutyl acetate and n-butyl acetate; ketones solvents such as methyl isobutyl ketone (MIBK), methyl ethyl ketone, cyclopentanone and cyclohexanone; and ether solvents such as cyclopentyl methyl ether. Moreover, you may use the iso paraffin type solvent which contains 1 type, or 2 or more types of iso paraffin as a hydrocarbon type solvent.

Among these, toluene, xylene, methyl isobutyl ketone, chloroform, trichloroethane and ethyl acetate are preferable in that the solubility of the component (a) is excellent.
Among the component (a), the polyaniline complex can be dissolved even if the solvent is an alcohol such as isopropyl alcohol, 1-butanol, 2-butanol, 2-pentanol, benzyl alcohol or alkoxy alcohol. Alcohol is preferable from the viewpoint of environmental load reduction compared with aromatics such as toluene.

When an organic solvent is used as the solvent, generation of gel or the like during storage can be achieved by using a mixed organic solvent in which a water immiscible organic solvent and a water-soluble organic solvent are mixed at 99 to 1: 1 to 99 (mass ratio). It is preferable because it can be prevented and stored for a long time.
A low polarity organic solvent can be used as the water immiscible organic solvent of the mixed organic solvent, and the low polarity organic solvent is preferably a hydrocarbon solvent such as hexane or toluene; a halogen-containing solvent such as chloroform; an isoparaffinic solvent.
As the water-soluble organic solvent of the mixed organic solvent, a highly polar organic solvent can be used. For example, methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 3-methoxy- Alcohols such as 1-butanol; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Ethers such as tetrahydrofuran, diethyl ether and ethylene glycol mono-tert-butyl ether are preferable.
The mixed organic solvent may contain one or more water immiscible organic solvents, and may contain one or more water soluble organic solvents.

(Component (e): acidic substance and / or salt of acidic substance)
The first composition may comprise one or more selected from the group consisting of acidic substances and salts of acidic substances. The said component is normally used as a heat resistant stabilizer, and the heat resistance of a conductive film can further be improved.

  The acidic substance may be either an organic acid which is an acid of an organic compound or an inorganic acid which is an acid of an inorganic compound, preferably an organic acid. The acidic substance is preferably an organic acid containing one or more sulfonic acid groups.

The organic acid having a sulfonic acid group is preferably a cyclic, linear or branched alkylsulfonic acid, substituted or unsubstituted aromatic sulfonic acid, or polysulfonic acid having one or more sulfonic acid groups.
As said alkylsulfonic acid, methanesulfonic acid, ethanesulfonic acid, di 2-ethylhexyl sulfosuccinic acid is mentioned, for example. Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
As said aromatic sulfonic acid, a C6-C20 thing is mentioned, For example, the sulfonic acid which has a benzene ring, the sulfonic acid which has a naphthalene frame, and the sulfonic acid which has an anthracene frame are mentioned. Moreover, as said aromatic sulfonic acid, substituted or unsubstituted benzenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and substituted or unsubstituted anthracenesulfonic acid are mentioned.

  The substituent is selected, for example, from the group consisting of an alkyl group (for example, those having 1 to 20 carbon atoms), an alkoxy group (for example, those having 1 to 20 carbon atoms), a hydroxy group, a nitro group, a carboxy group, and an acyl group. And one or more substituents.

Specifically, as the aromatic sulfonic acid, a compound represented by the following formula (4) or (5) may be mentioned.
(In the formula (4), l is 1 or more, m is an integer of 0 or more and 5 or less, n is an integer of 0 or more and 5 or less. When one of m or n is 0, the other is 1 or more Is)
(In the formula (5), q is 1 or more, p is an integer of 0 or more and 7 or less, and R is each independently an alkyl group having 1 to 20 carbon atoms, a carboxy group, a hydroxy group, a nitro group, a cyano group And amino groups.)

1 is preferably 1 to 3. m is preferably 1 to 3. n is preferably 0-3.
As for q, 1-3 are preferable. p is preferably 0-3. R is preferably an alkyl group having 1 to 20 carbon atoms, a carboxy group or a hydroxyl group.

  As an aromatic sulfonic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, 5-sulfosalicylic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 2-hydroxy-6-naphthalenesulfonic acid, p-phenolsulfonic acid , Toluenesulfonic acid, p-xylene-2-sulfonic acid, 4,4'-biphenyldisulfonic acid, dibenzofuran-2-sulfonic acid, flavianic acid, (+)-10-camphorsulfonic acid, monoisopropylnaphthalenesulfonic acid, 1 -Pyrene sulfonic acid etc. are mentioned. Among these, 4-sulfophthalic acid, 5-sulfosalicylic acid, 5-sulfoisophthalic acid, 2-naphthalenesulfonic acid, dibenzofuran-2-sulfonic acid, flavianic acid, 2-hydroxy-6-naphthalene from the viewpoint of heat resistance improvement. Sulfonic acid and 1-pyrene sulfonic acid are preferred.

As salts of acidic substances, salts of the compounds listed above can be mentioned. Examples of salt counter ions include sodium, lithium, potassium, cesium, ammonium, calcium, barium and the like.
Component (e) may be a hydrate.

  The content of the component (e) is preferably 0.1 to 1000 parts by mass, more preferably 1 to 100 parts by mass, still more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (a) It is.

(Component (f): acid having a hydrophobic group)
The first composition may comprise an acid having a hydrophobic group. The component is generally used as a permeability enhancer, and the first composition can be more penetrated into the object (eg, a capacitor).

  Examples of the hydrophobic group include linear alkyl groups, branched alkyl groups, alkylphenyl groups and alkylnaphthyl groups. The carbon number of the alkyl group included in the linear alkyl group, the alkyl group of the branched alkyl group, and the alkylphenyl group and the alkylnaphthyl group is preferably 2 to 20.

Examples of the component (f) include alkyl carboxylic acids, phosphoric monoesters, phosphoric acid diesters, alkyl benzene carboxylic acids, alkyl benzene phosphonic acids and the like. The alkylbenzenecarboxylic acid is a compound represented by R-Ph-COOH, and the alkylbenzenephosphonic acid is a compound represented by R-Ph-PO (OH) ₂ (wherein R represents an alkyl group, Ph represents a phenyl group).
The carbon number of the alkyl group of alkyl carboxylic acid, alkyl benzene carboxylic acid and alkyl benzene phosphonic acid is preferably 2 to 20. The phosphoric monoester and phosphoric diester are preferably esters obtained from phosphoric acid and an alcohol having 2 to 20 carbon atoms.

  Specific examples of the component (f) include propionic acid, DL-2-methylbutyric acid, 2-methylvaleric acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, myristic acid, monomethyl phosphate, Dimethyl phosphate, a mixture of monomethyl phosphate and dimethyl phosphate, monoethyl phosphate, diethyl phosphate, a mixture of monoethyl phosphate and diethyl phosphate, monoisopropyl phosphate, diisopropyl phosphate, monoisopropyl phosphate and diisopropyl phosphate Mixture, monobutyl phosphate, dibutyl phosphate, mixture of monobutyl phosphate and dibutyl phosphate, mono (2-ethylhexyl) phosphate, di (2-ethylhexyl) phosphate, mono (2-ethylhexyl) phosphate and diphosphate Mixtures of (2-ethylhexyl) and the like can be mentioned.

  The content of the component (f) is preferably 20 to 900 parts by mass with respect to 100 parts by mass of the component (a).

The first composition may also consist essentially of one or more components selected from the group consisting of components (a), (b) and (c) and optionally (d) to (f) Good. In this case, unavoidable impurities may be included.
For example, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more of the first composition % By mass
Components (a) to (c),
Components (a) to (d),
Component (a) to (e) or component (a) to (f) may be used.

[Second composition]
The second composition of the present invention comprises (a) a conductive polymer and (b) silica, and the content of component (b) is 0.1% by mass or more and less than 10% by mass in the total solid content. It is.
The second composition can form a conductive film excellent in heat resistance by containing the component (b). The resulting conductive film has a low rise in resistance value when it is left for a long time under high temperature conditions, and has high stability. Although the content of the component (b) is small in the second composition, a large heat resistance improvement effect can be obtained nevertheless. In addition, since the amount of the component (b) is small, the conductivity of the conductive film can be maintained higher.

Components (a) and (b) are as described for the first composition. The content of the component (b) may be 0.1% by mass or more, or 0.3% by mass or more in the total solid content, and 9.5% by mass or less in the total solid content, or 5.0% by mass It may be% or less. Content of a component (b) is good also as 0.1-9.5 mass% or 0.1-5.0 mass% in a total solid.
The second composition may include one or more components selected from the components (c) to (f) described above.

The second composition may consist essentially of one or more components selected from the group consisting of components (a) and (b) and optionally components (c) to (f). In this case, unavoidable impurities may be included.
For example, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more of the second composition % By mass
Components (a) and (b),
Components (a) to (c),
The components (a) to (d), or the components (a) to (e), or the components (a) to (f) may be used.

  The first composition and the second composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") can be prepared by known methods, for example, WO 2005-052058. It can be prepared by the method disclosed in

[Conductive film]
The composition of the present invention can be applied onto a substrate and dried to form a conductive film. The composition of the present invention may be applied to a substrate having a desired shape, such as glass, resin film, sheet, non-woven fabric, etc., to form a conductive laminate.
The thickness of the conductive film is usually 1 mm or less, preferably 10 nm to 50 μm.

  As a method of applying the composition, a known method such as cast method, spray method, dip coating method, doctor blade method, bar code method, spin coating method, electro spinning method, screen printing, gravure printing method may be used. it can.

  Moreover, you may provide the process of immersing said conductive film (coating film) in the solution containing the said component (e), and drying. As a component (e) in this case, the sulfonate represented by the said Formula (4) or its salt is preferable.

The solution to be immersed may contain a solvent.
The solvent is not particularly limited as long as the component (e) is dissolved, and water, alcohol solvents, ketone solvents, ether solvents, ester solvents and the like can be mentioned. You may mix and use 1 type or 2 types or more.

  As a solvent, specifically, methanol, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 1-ethoxy-2-propanol Ethyl acetate, butyl acetate, MIBK, methyl ethyl ketone (MEK), ethylene glycol monotert butyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether and the like.

10-1200 mass parts is preferable with respect to 1 mass part of compositions obtained by removing a solvent, as for content of the component (e) in the solution to immerse, 30-700 mass parts is more preferable, and 70-400. Parts by weight are more preferred.
If the amount is more than 1200 parts by mass, the amount of the acidic substance in the coating film is excessive to cause deterioration of the polyaniline main chain, which may lower the conductivity.

  Moreover, 0.1 weight%-10 weight% are preferable in the solution to be immersed, 0.3 weight%-6 weight% are more preferable, and 0.7 weight%-3.5 weight% are components (e). More preferable.

A dip method etc. are mentioned as an immersion method.
The immersion time is preferably 1 minute or more, and more preferably 3 minutes or more and 200 minutes or less. The immersion temperature is preferably 5 ° C to 50 ° C.
Drying after immersion is preferably performed using an oven, a hot plate or the like.
80-200 degreeC is preferable and 100-170 degreeC of a drying temperature is more preferable.
The drying time is preferably 1 to 180 minutes, and more preferably 3 to 60 minutes. If necessary, heating may be performed under reduced pressure. The drying temperature and the drying time are not particularly limited, and may be appropriately selected according to the material to be used.

As mentioned above, the component (e) may be added to the composition of the present invention or may be included in the conductive film obtained from the composition. Component (e) may be added to the composition, and the conductive film obtained from the composition may further contain component (e).
That is, the conductive film of the present invention comprises a component (e) added before film formation (hereinafter sometimes referred to as component (e1)) and a component (e) added after film formation (hereinafter, component And (e2) may be included. Components (e1) and (e2) may be the same or different. When different, for example, the component (e1) is a compound represented by the above formula (5), and the component (e2) is a compound represented by the above formula (4).

  Specific examples of the conductive film of the present invention include the following first conductive film and second conductive film (hereinafter sometimes referred to as “the conductive film of the present invention”).

The first conductive film contains (a) a conductive polymer and (b) silica, and the content of the component (b) is 0.1% by mass or more and 10% by mass with respect to the component (a) Less than. The first conductive film may contain the component (e) described above (one or more selected from components (e1) and (e2)).
The first conductive film may consist essentially of components (a) and (b) and optional component (e). In this case, unavoidable impurities may be included.
For example, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more of the first conductive film 100 mass%,
Component (a) and (b), or Component (a), (b) and (e)
It may be

The second conductive film is one or more selected from the group consisting of (a) a conductive polymer, (b) silica, and (e) an acidic substance and a salt of an acidic substance (components (e1) and (e2) And one or more selected from
The second conductive film may consist essentially of components (a), (b) and (e). In this case, unavoidable impurities may be included.
For example, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.5 mass% or more, 99.9 mass% or more of the second conductive film, or 100 mass%,
Components (a), (b) and (e)
It may be

  As mentioned above, the conductive film of the present invention may contain the components (e1) and (e2), that is, may contain two or more components (e).

The components of the first conductive film and the second conductive film are as described in the composition of the present invention.
Moreover, the components (a) to (f) described above are different from one another.

[Capacitor]
The compositions of the invention can be used to make capacitors. Specifically as a capacitor | condenser, an electrolytic capacitor, an electric double layer capacitor, etc. are mentioned, As a electrolytic capacitor, a solid electrolytic capacitor is mentioned.
In the case of producing a solid electrolytic capacitor, for example, the step of impregnating the composition of the present invention with an anode body including the anode of a solid electrolytic capacitor and a dielectric, and drying is performed to form a conductive film on the anode body. . That is, the solid electrolytic capacitor contains the conductive film of the present invention.

Production Example 1 (Production of Polyaniline Complex)
In a 1,000-ml separable flask, 32.4 g of "neocoal SWC" (sodium diisooctyl sulfosuccinate, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 13.3 g of aniline, "Sorbon T-20" (polyoxyethylene sorbitan fatty acid ester structure 0.9 g of Toion Chemical Industries, Ltd. (manufactured by Toho Chemical Industry Co., Ltd.) was added and dissolved in 320.4 g of toluene. Thereto, 450 g of an 8.4% by mass aqueous phosphoric acid solution was added, the reaction solution having two liquid phases of toluene and water was stirred, and the internal temperature of the reaction solution was cooled to 5 ° C. When the internal temperature of the reaction solution reached 5 ° C., a solution of 39.3 g of APS (ammonium persulfate) dissolved in 90.2 g of an 8.4% by mass aqueous phosphoric acid solution was added to a dropping funnel while stirring the reaction solution. It was used dropwise over 1 hour. After completion of the dropwise addition, the solution was further stirred for 8 hours while keeping the solution temperature at 5 ° C. (total reaction time 9 hours). After the stirring was stopped, the contents were transferred to a separatory funnel, and the aqueous phase and the toluene phase were separated by settling. After separation, the organic layer was washed once with 180.3 g of 1 M aqueous phosphoric acid solution and five times with 328.0 g of ion-exchanged water to obtain a toluene solution of polyaniline complex. This solution is no. The solution was filtered through a filter paper No. 2 to remove insolubles, and a toluene solution of polyaniline complex soluble in toluene was recovered. The solution was transferred to an evaporator, heated in a water bath at 60 ° C., and the volatile component was evaporated by evaporation under reduced pressure to obtain polyaniline complex 1 (protonated polyaniline). The weight average molecular weight of the polyaniline of the polyaniline complex 1 was 73,000.

The weight average molecular weight of polyaniline was measured as follows.
0.25 g of the polyaniline complex was dissolved in 5 g of toluene, and 10 mL of a 1 M aqueous solution of sodium hydroxide was added and stirred for 15 minutes, followed by suction filtration. The obtained residue is washed three times with 10 mL of toluene, three times with 10 mL of ion-exchanged water, and three times with 10 mL of methanol, the obtained solid is dried under reduced pressure, and the weight average molecular weight of the obtained polyaniline is gel permeation It measured by the chromatograph (GPC).
The GPC measurement was performed using a GPC column ("Shodex KF-806M" manufactured by Showa Denko KK, two) under the following measurement conditions.
Solvent: NMP containing 0.01 M LiBr
Flow rate: 0.70 ml / min Column temperature: 60 ° C.
Injection volume: 100 μL
UV detection wavelength: 270 nm
The weight average molecular weight obtained by the above method is a polystyrene (PS) conversion value.

  In addition, the doping ratio of the proton donor to polyaniline was 0.40.

Production Example 2 (Production of Polyaniline Complex)
The same reaction as in Production Example 1 is performed except that the cooling temperature of the temperature of the reaction solution is -5 ° C and the 8.4 mass% phosphoric acid aqueous solution is changed to a 17 mass% phosphoric acid aqueous solution, and polyaniline complex 2 (protonation) The obtained polyaniline) was obtained. The weight-average molecular weight of polyaniline of Polyaniline Complex 2 was measured in the same manner as in Production Example 1 to be 106,000.
In addition, the doping ratio of the proton donor to polyaniline was 0.36.

Example 1
(Preparation of composition)
A mixed solvent A was prepared by stirring and mixing 43.5 g of isopropyl alcohol, 43.5 g of p-tert-amylphenol and 13 g of hexane until uniform. 11 g of polyaniline complex 1 was dissolved in 89 g of mixed solvent A to obtain an 11 mass% polyaniline complex solution. In this solution, 0.95 g of 2-naphthalenesulfonic acid hydrate, and organosilica sol “IPA-ST” (manufactured by Nissan Chemical Industries, Ltd., colloidal silica, dispersion medium is isopropyl alcohol, solid content is 30% by mass, BET method The composition was prepared by adding 0.183 g of an average particle diameter of 11 nm converted from the obtained specific surface area, and a transmission type photomicrograph shown in FIG. The ratio of colloidal silica (component (b)) to the polyaniline complex 1 (component (a)) and the ratio of colloidal silica (component (b)) in the total solid content are shown in Table 1.

(Production of conductive film)
About 1 ml of the above composition was applied to the upper surface of the glass substrate 1 on the surface of which the ITO electrode 2 was formed by patterning, as shown in FIG. Coating was performed by spin coating under a nitrogen atmosphere. The rotation time of the glass substrate 1 after dropping the composition was 15 seconds, and the rotation speed of the glass substrate 1 was 2000 rpm. Thereafter, the glass substrate 1 was dried to form a conductive film. The drying temperature was 150 ° C., and the drying time was 5 minutes.

(Evaluation of conductive film (conductivity))
As shown in FIG. 3, the portion of the obtained conductive film 5 covering the terminal of the ITO electrode was scraped off in the air atmosphere to expose the terminal of the ITO electrode 2 on the surface. Using the terminals exposed on the surface, the resistance (initial resistance R0) and the conductivity of the conductive film were measured by a resistivity meter “Lorestar GP” (manufactured by Mitsubishi Chemical Corporation) according to a four-terminal method. The conductivity was 37 S / cm.

(Evaluation of conductive film (heat resistance))
The conductive film obtained in (Production of conductive film) was left as it is under a nitrogen atmosphere at 145 ° C. for a predetermined time (elapsed days shown in Table 1) as it is with a glass substrate. After the conductive film was returned to room temperature after a predetermined time elapsed, the resistance R was measured in the same manner as the initial resistance R0. The ratio of R to R0 (R / R0) is shown in Table 1. From the ratio (R / R0), the rate of increase in resistance of the conductive film, that is, the degree of deterioration with time can be known.

Example 2
A composition and a conductive film were prepared and evaluated in the same manner as in Example 1 except that the addition amount of organosilica sol "IPA-ST" was changed to 0.367 g. The conductivity of the conductive film was 42 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 3
A composition and a conductive film were prepared and evaluated in the same manner as in Example 1 except that the amount of the organosilica sol "IPA-ST" added was changed to 3.67 g. The conductivity of the conductive film was 46 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 4
A composition and a conductive film were prepared and evaluated in the same manner as in Example 1 except that the amount of organosilica sol "IPA-ST" added was changed to 11 g. The conductivity of the conductive film was 36 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 5
Organosilica sol “IPA-ST” is organosilica sol “IPA-ST-ZL” (manufactured by Nissan Chemical Industries, Ltd., colloidal silica, dispersion medium is isopropyl alcohol, solid content is 30% by mass, specific surface area obtained by BET method converted The composition and the conductive film were prepared and evaluated in the same manner as in Example 1 except that the average particle diameter was 70 to 100 nm and the transmission type photomicrograph was shown in FIG. The conductivity of the conductive film was 36 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 6
A composition and a conductive film were prepared and evaluated in the same manner as in Example 5 except that the addition amount of organosilica sol “IPA-ST-ZL” was changed to 0.367 g. The conductivity of the conductive film was 40 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 7
A composition and a conductive film were prepared and evaluated in the same manner as in Example 5 except that the amount of the organosilica sol “IPA-ST-ZL” was changed to 3.67 g. The conductivity of the conductive film was 40 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 8
A composition and a conductive film were prepared and evaluated in the same manner as in Example 5 except that the amount of the organosilica sol "IPA-ST-ZL" added was changed to 11 g. The conductivity of the conductive film was 40 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 9
Organosilica sol "IPA-ST" organosilica sol "IPA-ST-UP" (Nissan Chemical Industry Co., Ltd., dispersion medium is isopropyl alcohol, solid content 15% by mass, average converted from specific surface area obtained by BET method) The composition and the conductive film were prepared and evaluated in the same manner as in Example 1 except that the particle diameter was 9 to 15 nm and the transmission type photomicrograph was changed to 0.367 g). The conductivity of the conductive film was 41 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 10
A composition and a conductive film were prepared and evaluated in the same manner as in Example 9 except that the addition amount of organosilica sol “IPA-ST-UP” was changed to 0.733 g. The conductivity of the conductive film was 40 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 11
A composition and a conductive film were prepared and evaluated in the same manner as in Example 9 except that the amount of the organosilica sol “IPA-ST-UP” was changed to 7.33 g. The conductivity of the conductive film was 40 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 12
A composition and a conductive film were prepared and evaluated in the same manner as in Example 9 except that the amount of the organosilica sol “IPA-ST-UP” added was changed to 22 g. The conductivity of the conductive film was 40 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 13
A composition and a conductive film were prepared and evaluated in the same manner as in Example 9 except that the addition amount of organosilica sol “IPA-ST-UP” was changed to 36.7 g. The conductivity of the conductive film was 37 S / cm. The heat resistance evaluation results are shown in Table 1.

Comparative Example 1
The composition and the conductive film were prepared and evaluated in the same manner as in Example 1 except that the organosilica sol “IPA-ST” was not added. The conductivity of the conductive film was 42 S / cm. The heat resistance evaluation results are shown in Table 1.

Example 14
(Preparation of composition)
5.6 g of polyaniline complex 2 was dissolved in 94.4 g of mixed solvent A to obtain a 5.6 mass% polyaniline complex solution. To this solution was added 0.42 g of 2-naphthalenesulfonic acid hydrate and 0.187 g of organosilica sol "IPA-ST" to prepare a composition.

(Production and evaluation of conductive film (conductivity))
The conductive film was manufactured by the same method as Example 1 using the obtained composition, and resistance and conductivity were measured. The conductivity was 120 S / cm.

(Evaluation of conductive film (heat resistance))
The heat resistance of the conductive film was evaluated in the same manner as in Example 1 except that the standing temperature was changed from 145 ° C. to 150 ° C. The results are shown in Table 2.

Example 15
A composition and a conductive film were prepared and evaluated in the same manner as in Example 14 except that the addition amount of organosilica sol “IPA-ST” was changed to 1.87 g. The conductivity of the conductive film was 118 S / cm. The heat resistance evaluation results are shown in Table 2.

Example 16
A composition and a conductive film were prepared and evaluated in the same manner as in Example 14 except that the amount of the organosilica sol "IPA-ST" added was changed to 5.6 g. The conductivity of the conductive film was 106 S / cm. The heat resistance evaluation results are shown in Table 2.

Comparative example 2
The composition and the conductive film were prepared and evaluated in the same manner as in Example 14 except that the organosilica sol “IPA-ST” was not added. The conductivity of the conductive film was 118 S / cm. The heat resistance evaluation results are shown in Table 2.

Example 17
(Immersion treatment of conductive film)
0.4 g of a 50% by mass aqueous solution of 4-sulfophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 19.6 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a uniform 1% by mass 4-sulfophthalic acid solution . The conductive film obtained by the same method as Example 14 was immersed in 10 g of this 4-sulfophthalic acid solution for 5 minutes. After immersion, drying was performed at 150 ° C. for 5 minutes.

(Evaluation of conductive film (conductivity and heat resistance))
The conductivity and heat resistance of the obtained conductive film were evaluated in the same manner as in Example 14. The conductivity was 327 S / cm. The heat resistance evaluation results are shown in Table 3.

Example 18
A composition and a conductive film were prepared and evaluated in the same manner as in Example 17 except that the addition amount of organosilica sol “IPA-ST” was changed to 1.87 g. The conductivity of the conductive film was 292 S / cm. The heat resistance evaluation results are shown in Table 3.

Comparative example 3
The composition and the conductive film were prepared and evaluated in the same manner as in Example 17 except that the organosilica sol “IPA-ST” was not added. The conductivity of the conductive film was 341 S / cm. The heat resistance evaluation results are shown in Table 3.

  The composition of the present invention can be used in the fields of power electronics and optoelectronics, electrostatic and antistatic materials, transparent electrodes and conductive film materials, materials of electroluminescent devices, circuit materials, electromagnetic shielding materials, dielectrics and electrolytes of capacitors, It can be used as an electrode material of a solar cell and a secondary battery, a fuel cell separator material, etc., or as a plating base, a rust inhibitor, etc.

1 glass substrate 2 ITO electrode 5 conductive film

Claims (17)

(A) conductive polymer,
A composition comprising (b) silica and (c) a phenolic compound.   The composition according to claim 1, wherein the content of the component (b) is 0.1 to 60 parts by mass with respect to 100 parts by mass of the component (a).   The composition according to claim 1 or 2, wherein the content of the component (b) is 0.1% by mass or more and less than 10% by mass in the total solid content. A composition comprising (a) a conductive polymer and (b) silica, wherein the content of the component (b) is 0.1% by mass or more and less than 10% by mass in the total solid content.   The composition according to any one of claims 1 to 4, further comprising (d) a solvent.   The composition according to any one of claims 1 to 5, wherein the component (a) is one or more selected from the group consisting of polyaniline, polyaniline derivative, polythiophene, polythiophene derivative, polypyrrole and polypyrrole derivative.   The composition according to any one of claims 1 to 6, wherein the component (a) is a polyaniline complex comprising polyaniline and a proton donor, wherein the polyaniline is doped with the proton donor.   The composition according to claim 7, wherein the proton donor is a sulfonic acid or a sulfonate. The composition according to claim 8, wherein the sulfonic acid or the sulfonic acid salt is a sulfosuccinic acid derivative represented by the following formula (III).
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III)
(In formula (III),
M is a hydrogen atom, an organic radical or an inorganic radical,
m is the valence of M,
R ¹² and R ¹³ are each independently a hydrocarbon group or a group represented by — (R ¹⁴ O) _r —R ¹⁵ , R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is hydrogen atom, a hydrocarbon group, or ^R ₁₆ 3 Si- group represented ^{by, R 16} is a hydrocarbon group, and three ^{R 16} may be the same or different, r is an integer of 1 or more. )   The composition according to any one of claims 1 to 9, further comprising (e) one or more selected from the group consisting of an acidic substance and a salt of the acidic substance.   And (f) an acid having a hydrophobic group, wherein the hydrophobic group is one or more selected from the group consisting of a linear alkyl group, a branched alkyl group, an alkylphenyl group, and an alkylnaphthyl group. The composition in any one of 1-10. A conductive film comprising: (a) a conductive polymer, and (b) silica, wherein the content of the component (b) is 0.1% by mass or more and less than 10% by mass.   The conductive film according to claim 12, further comprising (e) one or more selected from the group consisting of an acidic substance and a salt of the acidic substance. (A) conductive polymer,
A conductive film comprising one or more selected from the group consisting of (b) silica, and (e) an acidic substance and a salt of an acidic substance.   The electroconductive film of Claim 13 or 14 containing 2 or more types of the said component (e). The composition according to any one of claims 1 to 11 is applied and dried to form a coating,
The manufacturing method of the conductive film which dips and dries the said coating film in the solution containing 1 or more selected from the group which consists of an acidic substance and the salt of an acidic substance.   A capacitor comprising the conductive film according to any one of claims 12 to 15.