JP5710388B2 - Polyaniline conductive composition - Google Patents

Description

  The present invention relates to a conductive polymer composition containing polyaniline.

Conductive polymers are used for electrolytic capacitors, backup batteries for electronic devices, electrodes for lithium ion batteries used in mobile phones and notebook computers, and the like.
In addition to its electrical properties, polyaniline, a kind of conductive polymer, can be synthesized relatively easily from inexpensive aniline, and has the advantage of exhibiting excellent stability against oxygen and the like in a conductive state And having characteristics. In addition, highly conductive polyaniline can be easily obtained by the method described in Patent Document 1.
However, the conductive polyaniline composition described in Patent Document 1 cannot necessarily be said to have high heat resistance of the obtained molded product, and when left in an inert gas at 125 ° C. for 10 days, the resistance value is 40 times the initial value. Rise to the extent.

International Publication No. 2005/052058 Pamphlet

  An object of this invention is to provide the electroconductive composition with high heat resistance of the molded article obtained.

（式中、Ｍは水素原子、有機遊離基又は無機遊離基であり、ｍ’はＭの価数であり、Ｒ^１１２及びＲ^１１３は、それぞれ独立に、炭化水素基又は−（Ｒ^１１４Ｏ）ｒ−Ｒ^１１５基［ここで、Ｒ^１１４はそれぞれ独立に炭化水素基又はシリレン基であり、Ｒ^１１５は水素原子、炭化水素基又はＲ^１１６ _３Ｓｉ−基（ここで、Ｒ^１１６はそれぞれ独立に炭化水素基である）であり、ｒは１以上の整数である］である。）
６．前記（４）高分子化合物が、スルホン酸基、リン酸基、ホスホン酸基、カルボキシ基又は水酸基を有する高分子化合物である１〜５のいずれかに記載の導電性組成物。
７．前記（４）高分子化合物が、式（Ａ）及び（Ｂ）から選択される少なくとも１種の繰り返し単位と、式（Ｃ）の繰り返し単位を含む高分子化合物である、１〜５のいずれかに記載の導電性組成物。

（式中、Ｒ_ａ、Ｒ_ｂ、Ｒ_ｃは水素原子又は炭素数１〜６のアルキル基であり、Ｒ_ｄはアルキル基であり、Ａ₁ ^＋はナトリウムイオン、アンモニウムイオン、又は下記式で表されるイオンのいずれかである。

（式中、Ｒ’はそれぞれ水素原子、アルキル基、アルケニル基、アルキニル基、ヒドロキシルアルキル基である。アルキル基、アルケニル基、アルキニル基、ヒドロキシルアルキル基は直鎖でも、分岐していてもよく、Ｒ’は同一でも異なっていてもよい。））
８．前記（４）高分子化合物の酸価が１ｍｇ／ｇ以上である１〜７のいずれかに記載の導電性組成物。
９．前記（４）高分子化合物の重量平均分子量が２０００以上２０００００以下である１〜８のいずれかに記載の導電性高分子。
１０．前記含酸素有機溶剤が、炭素数１〜１２のアルコールである１〜９のいずれかに記載の導電性組成物。
１１．さらに低分子酸性化合物又はその塩を含む１〜１０のいずれかに記載の導電性組成物。
１２．前記低分子酸性化合物が、スルホン酸基、リン酸基、ホスホン酸基又はカルボキシ基を有する化合物である１１に記載の導電性組成物。
１３．前記低分子酸性化合物が、ナフタレンスルホン酸又はアルキルナフタレンスルホン酸である１１又は１２に記載の導電性組成物。
１４．１〜１３のいずれかに記載の導電性組成物を用いて製造されるコンデンサ。
１５．１〜１３のいずれかに記載の導電性組成物を用いて製造される導電性成形体。
１６．１〜１３のいずれかに記載の導電性組成物を、基材に塗布してなる表面導電性物品。
１７．１６に記載の表面導電性物品を用いて製造される導電性物品。
According to the present invention, the following conductive compositions and the like are provided.
1. (1) Protonated substituted or unsubstituted polyaniline (2) Phenolic compound (3) Oxygen-containing organic solvent (4) High molecular compound having acidic group or salt thereof
2. 2. The conductive composition according to 1, wherein the chlorine content of the protonated substituted or unsubstituted polyaniline is 0.6% by weight or less.
3. 3. The conductive composition according to 1 or 2, wherein the protonated substituted or unsubstituted polyaniline is a substituted or unsubstituted polyaniline protonated with an organic sulfonic acid or a salt thereof.
4). 4. The conductive composition according to 3, wherein the organic sulfonic acid or a salt thereof is a sulfosuccinic acid derivative.
5. The conductive composition according to 3 or 4, wherein the organic sulfonic acid or a salt thereof is represented by the following formula (III).

Wherein M is a hydrogen atom, an organic free radical or an inorganic free radical, m ′ is a valence of M, and R ¹¹² and R ¹¹³ are each independently a hydrocarbon group or — (R ¹¹⁴ O). r—R ¹¹⁵ group [wherein R ¹¹⁴ is each independently a hydrocarbon group or a silylene group, R ¹¹⁵ is a hydrogen atom, a hydrocarbon group, or an R ¹¹⁶ ₃ Si— group (where R ¹¹⁶ is independently Is a hydrocarbon group), and r is an integer of 1 or more.)
6). The conductive composition according to any one of 1 to 5, wherein the polymer compound (4) is a polymer compound having a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a carboxy group, or a hydroxyl group.
7). Any of 1 to 5, wherein the polymer compound (4) is a polymer compound containing at least one repeating unit selected from the formulas (A) and (B) and a repeating unit of the formula (C). The electroconductive composition as described in.

(In the formula, R _a , R _b , and R _c are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R _d is an alkyl group, and A ₁ ⁺ is a sodium ion, an ammonium ion, or the following formula: Any of the ions to be produced.

(In the formula, each R ′ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or a hydroxylalkyl group. The alkyl group, alkenyl group, alkynyl group, or hydroxylalkyl group may be linear or branched, R ′ may be the same or different.))
8). (4) The electrically conductive composition in any one of 1-7 whose acid value of a high molecular compound is 1 mg / g or more.
9. The conductive polymer according to any one of 1 to 8, wherein the polymer compound (4) has a weight average molecular weight of 2,000 to 200,000.
10. The conductive composition according to any one of 1 to 9, wherein the oxygen-containing organic solvent is an alcohol having 1 to 12 carbon atoms.
11. Furthermore, the electroconductive composition in any one of 1-10 containing a low molecular acidic compound or its salt.
12 12. The conductive composition according to 11, wherein the low molecular acid compound is a compound having a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, or a carboxy group.
13. The conductive composition according to 11 or 12, wherein the low molecular acid compound is naphthalenesulfonic acid or alkylnaphthalenesulfonic acid.
14. A capacitor manufactured using the conductive composition according to any one of 1 to 13.
The electroconductive molded object manufactured using the electroconductive composition in any one of 15.1-13.
16. A surface conductive article obtained by applying the conductive composition according to any one of 16.1 to 13 to a substrate.
A conductive article manufactured using the surface conductive article according to 17.16.

  ADVANTAGE OF THE INVENTION According to this invention, the electrically conductive composition with high heat resistance of the molded article obtained can be provided.

The conductive composition of the present invention comprises the following components.
(1) Protonated substituted or unsubstituted polyaniline (2) Phenolic compound (3) Oxygenated organic solvent (4) High molecular compound having acidic group or salt thereof The composition of the present invention comprises component (4) Thus, the heat resistance of the molded product obtained is increased.
Hereinafter, each component will be described.

1. Protonated substituted or unsubstituted polyaniline (component (1))
The protonated substituted or unsubstituted polyaniline contained in the conductive composition of the present invention is a complex (polyaniline complex) obtained by doping a substituted or unsubstituted polyaniline molecule with a proton donor.

The weight average molecular weight (hereinafter referred to as molecular weight) of the polyaniline molecule is preferably 20,000 or more. If the molecular weight is less than 20,000, the strength and stretchability of the conductive article obtained from the composition may be reduced. Preferably it is 20,000-500,000, More preferably, it is 50,000-300,000. Molecular weight distribution is 1.5-10.0 or less. A smaller molecular weight distribution is preferable from the viewpoint of conductivity, but a wider molecular weight distribution may be preferable from the viewpoint of solubility in solvents and moldability.
In this specification, molecular weight and molecular weight distribution are measured in terms of polystyrene by gel permeation chromatography (GPC).

The substituted or unsubstituted polyaniline molecule of the polyaniline complex is preferably unsubstituted polyaniline from the viewpoint of versatility and economy.
Examples of the substituent of the substituted polyaniline molecule include linear or branched hydrocarbon groups such as methyl group, ethyl group, hexyl group and octyl group; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group A halogenated hydrocarbon such as a trifluoromethyl group (—CF ₃ group);

The substituted or unsubstituted polyaniline molecule is preferably a polyaniline molecule obtained by polymerization in the presence of an acid containing no chlorine atom. The acid containing no chlorine atom is, for example, an acid composed of atoms belonging to Group 1 to Group 16 and Group 18, and examples thereof include polyaniline molecules obtained by polymerization in the presence of phosphoric acid.
The polyaniline molecule obtained in the presence of an acid containing no chlorine atom can lower the chlorine content of the polyaniline complex.
The chlorine content of the polyaniline complex is preferably 0.6% by weight or less. More preferably, it is 0.1 weight% or less, More preferably, it is 0.04 weight% or less, Most preferably, it is 0.0001 weight% or less.
When the chlorine content of the polyaniline complex is more than 0.6% by weight, the metal part that comes into contact with the polyaniline complex may be corroded.
The chlorine content can be measured by combustion-ion chromatography.

It can be confirmed by ultraviolet / visible / near-infrared spectroscopy or X-ray photoelectron spectroscopy that the proton donor of the polyaniline complex is doped into a substituted or unsubstituted polyaniline molecule. Can be used without particular chemical structural limitation as long as the polyaniline molecule has sufficient acidity to generate carriers.
Examples of the proton donor include a Bronsted acid or a salt thereof, preferably an organic acid or a salt thereof. Examples of organic acids include organic sulfonic acids.

The proton donor is more preferably a proton donor represented by the following formula (I).
M (XARn) m (I)
M in the formula (I) is a hydrogen atom, an organic radical or an inorganic radical.
Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group. Examples of the inorganic free radical include sodium, lithium, potassium, cesium, ammonium, calcium, magnesium, and iron.
X in the formula (I) is an anionic group, for example, —SO ₃ ^— group, —PO ₃ ^{2 —} group, —PO ₄ (OH) ^{2 —} , —OPO ₃ ^{2 —} group, —OPO ₂ (OH) ^—. group, -COO ^- group, and preferably -SO ₃ ^- is a group.

A in formula (I) (the definition of A in M (XARn) m) is a substituted or unsubstituted hydrocarbon group.
The hydrocarbon group is a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.
Examples of the chain saturated aliphatic hydrocarbon include a linear or branched alkyl group. Examples of the cyclic saturated aliphatic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Here, the cyclic saturated aliphatic hydrocarbon group may be a condensation of a plurality of cyclic saturated aliphatic hydrocarbon groups. Examples thereof include a norbornyl group, an adamantyl group, and a condensed adamantyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the chain unsaturated aliphatic hydrocarbon include a linear or branched alkenyl group.
Here, when A is a substituted hydrocarbon group, the substituent is alkyl group, cycloalkyl group, vinyl group, allyl group, aryl group, alkoxy group, halogen group, hydroxy group, amino group, imino group, nitro group. Group, silyl group or ester group.
A is the corresponding n + 1 valent residue of these substituents.

R in the formula (I) is bonded to A, and is independently -H, -R ¹⁰¹ , -OR ¹⁰¹ , -COR ¹⁰¹ , -COOR ¹⁰¹ ,-(C = O)-(COR ¹⁰¹ ). Or-(C = O)-(COOR ¹⁰¹ ), wherein R ¹⁰¹ is a hydrocarbon group, silyl group, alkylsilyl group,-(R ¹⁰² O) x-R ¹⁰³ group, which may contain a substituent, or _{^{- (OSiR 103 2) x-}} oR 103 (R 102 are each independently an alkylene ^{group, R 103} are each independently a hydrocarbon group, x is a is an integer of 1 or more) is.
Examples of the hydrocarbon group for R ¹⁰¹ include a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a pentadecyl group, and an eicosanyl group. These groups may be linear or branched. Examples of the branched octyl group include a 2-ethylhexyl group. The substituent of the hydrocarbon group is, for example, an alkyl group, a cycloalkyl group, a vinyl group, an allyl group, an aryl group, an alkoxy group, a halogen group, a hydroxy group, an amino group, an imino group, a nitro group, or an ester group. . The hydrocarbon group for R ¹⁰³ is the same as R ¹⁰¹ .
N in the formula (I) is an integer of 1 or more, and m in the formula (I) is a valence of M / a valence of X.

（式中、Ｍ、ｍ及びＸは、式（Ｉ）と同様である。Ｘは、−ＳＯ_３ ⁻基が好ましい。） As the compound represented by the formula (I), dialkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid, or a compound containing two or more ester bonds is preferable.
The compound containing two or more ester bonds is more preferably a sulfophthalic acid ester or a compound represented by the following formula (II).

(In the formula, M, m and X are the same as those in formula (I). X is preferably a —SO ₃ ^— group.)

R ¹⁰⁴ and two R ^{105 in} formula (II) are each independently a hydrogen atom, a hydrocarbon group or an R ¹⁰⁸ ₃ Si— group (where R ¹⁰⁸ is a hydrocarbon group, and three R ¹⁰⁸ are the same Or they may be different).
Examples of the hydrocarbon group when R ¹⁰⁴ and R ¹⁰⁵ are hydrocarbon groups include a linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group containing an aromatic ring, and an alkylaryl group.
The hydrocarbon group for R ¹⁰⁸ is the same as that for R ¹⁰⁴ and R ¹⁰⁵ .

R ¹⁰⁶ and R ^{107 in} formula (II) are each independently a hydrocarbon group or — (R ¹⁰⁹ O) _q —R ¹¹⁰ group [wherein R ¹⁰⁹ is a hydrocarbon group or a silylene group, and R ¹¹⁰ is A hydrogen atom, a hydrocarbon group, or R ¹¹¹ ₃ Si— (R ¹¹¹ is a hydrocarbon group, three R ¹¹¹ may be the same or different), and q is an integer of 1 or more]. .
When R ¹⁰⁶ and R ¹⁰⁷ are hydrocarbon groups, the hydrocarbon group is 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, or alkylaryl. Specific examples of the hydrocarbon group when R ¹⁰⁶ and R ¹⁰⁷ are hydrocarbon groups include, for example, a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group Etc. Examples of the branched octyl group include a 2-ethylhexyl group.

In R ¹⁰⁶ and R ¹⁰⁷ , when R ¹⁰⁹ is a hydrocarbon group, the hydrocarbon group is a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, an aryl An alkylene group and the like; The hydrocarbon group in R ¹⁰⁶ and R ¹⁰⁷ when R ¹¹⁰ and R ¹¹¹ are hydrocarbon groups is the same as in R ¹⁰⁴ and R ¹⁰⁵ , and q is 1 to 10. preferable.

（式中、Ｘは式（Ｉ）と同様である。） Specific examples of the compound represented by the formula (II) when R ¹⁰⁶ and R ¹⁰⁷ are — (R ¹⁰⁹ O) n—R ¹¹⁰ group include two compounds represented by the following formulae.

(Wherein X is the same as in formula (I).)

（式中、Ｍは、式（Ｉ）と同様である。ｍ’は、Ｍの価数である。） The compound represented by the above formula (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III).

(In the formula, M is the same as in formula (I). M ′ is the valence of M.)

R ¹¹² and R ^{113 in} the formula (III) are each independently a hydrocarbon group or — (R ¹¹⁴ O) r—R ¹¹⁵ group [wherein R ¹¹⁴ is each independently a hydrocarbon group or a silylene group; R ¹¹⁵ is a hydrogen atom, a hydrocarbon group, or an R ¹¹⁶ ₃ Si— group (wherein R ¹¹⁶ is each independently a hydrocarbon group), and r is an integer of 1 or more.

The hydrocarbon group when R ¹¹² and R ¹¹³ are hydrocarbon groups is the same as R ¹⁰⁶ and R ¹⁰⁷ .
In R ¹¹² and R ¹¹³ , the hydrocarbon group in the case where R ¹¹⁴ is a hydrocarbon group is the same as R ¹⁰⁹ described above. In R ¹¹² and R ¹¹³ , the hydrocarbon group in the case where R ¹¹⁵ and R ¹¹⁶ are hydrocarbon groups is the same as R ¹⁰⁴ and R ¹⁰⁵ described above.
r is preferably from 1 to 10.

Specific examples when R ¹¹² and R ¹¹³ are — (R ¹¹⁴ O) q—R ¹¹⁵ groups are the same as — (R ¹⁰⁹ O) n—R ¹¹⁰ in R ¹⁰⁶ and R ¹⁰⁷ .
The hydrocarbon group for R ¹¹² and R ¹¹³ is the same as R ¹⁰⁶ and R ¹⁰⁷ , and a butyl group, a hexyl group, a 2-ethylhexyl group, a decyl group, and the like are preferable.

  It is known that by changing the structure of the proton donor, the conductivity of the polyaniline complex and the solubility in a solvent can be controlled (Japanese Patent No. 338466). In the present invention, an optimum proton donor can be selected depending on the required characteristics for each application.

The doping rate of the proton donor with respect to the polyaniline molecule is preferably 0.35 or more and 0.65 or less, more preferably 0.42 or more and 0.60 or less, and further preferably 0.43 or more and 0.57 or less. Yes, and particularly preferably 0.44 or more and 0.55 or less. When the dope rate is less than 0.35, the solubility of the polyaniline complex in the organic solvent may not be increased.
The doping rate is defined by (number of moles of proton donor doped in polyaniline molecule) / (number of moles of monomer unit of polyaniline). For example, a polyaniline complex containing an unsubstituted polyaniline and a proton donor having a doping ratio of 0.5 means that one proton donor is doped with respect to two polyaniline monomer unit molecules.
The dope rate can be calculated if the number of moles of the proton donor in the polyaniline complex and the monomer unit of the polyaniline molecule can be measured. For example, when the proton donor is an organic sulfonic acid, the number of moles of sulfur atoms derived from the proton donor and the number of moles of nitrogen atoms derived from the monomer unit of polyaniline are determined by organic elemental analysis, and the ratio of these values is determined. The dope rate can be calculated by taking However, the calculation method of the dope rate is not limited to the means.

The polyaniline complex preferably contains an unsubstituted polyaniline molecule and a sulfonic acid that is a proton donor and satisfies the following formula (5).
0.42 ≦ S ₅ / N ₅ ≦ 0.60 (5)
(In the formula, 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 number of moles of nitrogen and sulfur atoms is a value measured by, for example, an organic elemental analysis method. )

The polyaniline complex is preferably dissolved in the composition.
Here, “dissolved” means that the polyaniline complex is uniformly dissolved in molecular units in the composition. For example, the polyaniline complex is dissolved in the composition and centrifuged in a centrifuge. Even when force (1000 G, 30 minutes) is applied, it can be confirmed that a concentration gradient of the polyaniline complex does not occur in the composition.
When a composition containing a dissolved polyaniline complex is formed, a uniform polyaniline complex film having no grain boundary can be obtained.

The polyaniline complex may or may not further contain phosphorus.
When the polyaniline complex contains phosphorus, the phosphorus content is, for example, not less than 10 ppm by weight and not more than 5000 ppm by weight. Moreover, phosphorus content is 2000 weight ppm or less, 500 weight ppm or less, and 250 weight ppm or less, for example.
The phosphorus content can be measured by ICP emission spectrometry.
Moreover, it is preferable that a polyaniline composite does not contain a Group 12 element (for example, zinc) as an impurity.

  The polyaniline complex can be produced by a known method (for example, polymerization of aniline in the presence of hydrochloric acid), but preferably contains a proton donor, phosphoric acid, and an emulsifier different from the proton donor. It is produced by chemical oxidative polymerization of substituted or unsubstituted aniline in a solution having a phase.

Here, the “solution having two liquid phases” means a state in which two liquid phases that are incompatible with each other exist in the solution. For example, it means a state in which a “high polarity solvent phase” and a “low polarity solvent phase” exist in the solution.
Further, “a solution having two liquid phases” includes a state in which one liquid phase is a continuous phase and the other liquid phase is a dispersed phase. For example, a state where the “high polarity solvent phase” is a continuous phase and the “low polarity solvent phase” is a dispersed phase, and the “low polarity solvent phase” is a continuous phase and the “high polarity solvent phase” is a dispersed phase. Is included.
As a highly polar solvent used for the manufacturing method of the said polyaniline composite_body | complex, water is preferable and aromatic hydrocarbons, such as toluene and xylene, are preferable as a low polarity solvent, for example.

（式中、Ｍ、Ｘ、Ａ、Ｒ、Ｒ^１０４、Ｒ^１０５、Ｒ^１０６、Ｒ^１０７、Ｒ^１１２、Ｒ^１１３、ｎ、ｍ及びｍ’は、ポリアニリン複合体のプロトン供与体で説明した通りである。） The proton donor is preferably a compound represented by the following formula (I), more preferably a compound represented by the following formula (II), and further preferably a compound represented by the following formula (III).

(Wherein M, X, A, R, R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹¹² , R ¹¹³ , n, m and m ′ are as described for the proton donor of the polyaniline complex. is there.)

  The emulsifier can be either an ionic emulsifier whose hydrophilic part is ionic or a nonionic emulsifier whose non-ionic hydrophilic part is used, or a mixture of one or more emulsifiers. May be used.

Examples of the ionic emulsifier include a cationic emulsifier, an anionic emulsifier, and a zwitter emulsifier.
Specific examples of the anionic emulsifier (anionic emulsifier) include fatty acids, disproportionated rosin soaps, higher alcohol esters, polyoxyethylene alkyl ether phosphates, alkenyl succinic acids, sarcosinates, and salts thereof.
Specific examples of the cationic emulsifier (cationic emulsifier) include alkyl dimethyl benzyl ammonium salt and alkyl trimethyl ammonium salt.
Specific examples of the zwitterionic emulsifier (both ion emulsifier) include alkyl betaine type, alkyl amide betaine type, amino acid type, and amine oxide type.
Specific examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polypropylene glycol polyethylene glycol ether, polyoxyethylene glycerol borate fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.

Of the above emulsifiers, anionic emulsifiers and nonionic emulsifiers are preferred.
As the anionic emulsifier, an anionic emulsifier having a phosphate ester structure is more preferable. Further, as the nonionic emulsifier, a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure is more preferable.

The amount of the proton donor used is preferably 0.1 to 0.5 mol, more preferably 0.3 to 0.45 mol, and still more preferably 0.35 to 0.005 mol per mol of the aniline monomer. 4 mol.
When the amount of the proton donor used is larger than the above range, for example, there is a possibility that the “high-polar solvent phase” and the “low-polar solvent phase” cannot be separated after completion of the polymerization.

  The use concentration of phosphoric acid is 0.3 to 6 mol / L, more preferably 1 to 4 mol / L, still more preferably 1 to 2 mol / L with respect to the highly polar solvent.

The amount of the emulsifier used is preferably 0.001 to 0.1 mol, more preferably 0.002 to 0.02 mol, and still more preferably 0.003 to 0.01 mol with respect to 1 mol of the aniline monomer. is there.
When the amount of the emulsifier used is larger than the above range, the “high polar solvent phase” and the “low polar solvent phase” may not be separated after the completion of the polymerization.

Oxidizing agents used for chemical oxidative polymerization include peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide; ammonium dichromate, ammonium perchlorate, potassium iron (III) sulfate, trichloride Iron (III), manganese dioxide, iodic acid, potassium permanganate, iron paratoluenesulfonate, etc. can be used, and persulfates such as ammonium persulfate are preferred.
These oxidizing agents may be used alone or in combination of two or more.

The amount of the oxidizing agent used is preferably 0.05 to 1.8 mol, more preferably 0.8 to 1.6 mol, still more preferably 1.2 to 1.4 mol, relative to 1 mol of the aniline monomer. It is. A sufficient degree of polymerization can be obtained by setting the amount of the oxidizing agent used within the above range. Further, since aniline is sufficiently polymerized, it is easy to recover the liquid separation, and there is no possibility that the solubility of the polymer is lowered.
The polymerization temperature is usually −5 to 60 ° C., preferably −5 to 40 ° C. The polymerization temperature may be changed during the polymerization reaction. Side reactions can be avoided when the polymerization temperature is within this range.

Specifically, the polyaniline complex can be produced by the following method.
A solution in which a proton donor and an emulsifier are dissolved in toluene is placed in a separable flask placed in a stream of an inert atmosphere such as nitrogen, and a substituted or unsubstituted aniline is further added to this solution. Thereafter, phosphoric acid containing no chlorine as an impurity is added to the solution, and the solution temperature is cooled.
Stirring is performed after cooling the internal temperature of the solution. A solution in which ammonium persulfate is dissolved in phosphoric acid is dropped using a dropping funnel and reacted. Thereafter, the solution temperature is raised and the reaction is continued. After completion of the reaction, the aqueous phase separated into two phases by standing is separated. Toluene is added to the organic phase side and washed with phosphoric acid and ion-exchanged water to obtain a polyaniline complex (protonated polyaniline) toluene solution.
Some insolubles contained in the obtained complex solution are removed, and a toluene solution of the polyaniline complex is recovered. The solution is transferred to an evaporator, heated and decompressed to evaporate and remove volatile components, whereby a polyaniline complex is obtained.

2. Phenolic compounds (component (2))
The phenolic compound contained in the conductive composition of the present invention is not particularly limited as long as it is a compound having a phenolic hydroxyl group. The compound having a phenolic hydroxyl group is a polymer compound composed of a compound having one phenolic hydroxyl group, a compound having a plurality of phenolic hydroxyl groups, and a repeating unit having one or more phenolic hydroxyl groups.

（式中、ｎは１〜５の整数であり、好ましくは１〜３であり、より好ましくは１である。
Ｒは、炭素数１〜２０のアルキル基、アルケニル基、シクロアルキル基、アリール基、アルキルアリール基又はアリールアルキル基である。） The compound having one phenolic hydroxyl group is preferably a compound represented by the following formulas (A), (B) and (C).

(In formula, n is an integer of 1-5, Preferably it is 1-3, More preferably, it is 1.
R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group. )

  In the phenolic compound represented by the formula (A), the substitution position of -OR is preferably a meta position or a para position with respect to the phenolic hydroxyl group. By making the substitution position of —OR the meta position or the para position, the steric hindrance of the phenolic hydroxyl group is reduced, and the conductivity of the composition can be further increased.

  Specific examples of the phenolic compound represented by the formula (A) include methoxyphenol, ethoxyphenol, propoxyphenol, isopropoxyphenol, butyloxyphenol, isobutyloxyphenol, and tertiary butyloxyphenol.

（式中、ｎは０〜７の整数であり、好ましくは０〜３であり、より好ましくは１である。
Ｒは、それぞれ炭素数１〜２０のアルキル基、アルケニル基、アルキルチオ基、炭素数３〜１０のシクロアルキル基、炭素数６〜２０のアリール基、アルキルアリール基又はアリールアルキル基である。）

(In formula, n is an integer of 0-7, Preferably it is 0-3, More preferably, it is 1.
R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. )

  Specific examples of the phenolic compound represented by the formula (B) include hydroxynaphthalene.

（式中、ｎは１〜５の整数であり、好ましくは１〜３であり、より好ましくは１である。
Ｒは、それぞれ炭素数１〜２０のアルキル基、アルケニル基、アルキルチオ基、炭素数３〜１０のシクロアルキル基、炭素数６〜２０のアリール基、アルキルアリール基又はアリールアルキル基である。）

(In formula, n is an integer of 1-5, Preferably it is 1-3, More preferably, it is 1.
R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. )

  Specific examples of the compound represented by the formula (C) include o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol, o-, m. -Or p-butylphenol, o-, m- or p-amylphenol.

Regarding R in formulas (A), (B), and (C), examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary butyl.
Examples of the alkenyl group include groups having an unsaturated bond in the molecule of the alkyl group described above.
Examples of the cycloalkyl group include cyclopentane and cyclohexane.
Examples of the aryl group include phenyl and naphthyl.
Examples of the alkylaryl group and the arylalkyl group include groups obtained by combining the above-described alkyl group and aryl group.

（式中、Ｒは炭化水素基、ヘテロ原子含有炭化水素基、ハロゲン原子、カルボン酸基、アミノ基、ＳＨ基、スルホン酸基、又は水酸基であり、複数のＲはそれぞれ互いに同一であっても異なっていてもよい。ｎは０〜６の整数である。） Although the example of the compound which has one said phenolic hydroxyl group was shown, a phenol, o-, m- or p-chlorophenol, a salicylic acid, hydroxybenzoic acid is mentioned as a specific example of substituted phenols. Specific examples of the compound having a plurality of phenolic hydroxyl groups include catechol, resorcinol, and a compound represented by the following formula (D).

(In the formula, R is a hydrocarbon group, a hetero atom-containing hydrocarbon group, a halogen atom, a carboxylic acid group, an amino group, an SH group, a sulfonic acid group, or a hydroxyl group. May be different, n is an integer from 0 to 6.)

The phenolic compound represented by the formula (D) preferably has two or more hydroxyl groups that are not adjacent to each other.
Specific examples of the phenolic compound represented by the formula (D) include 1,6 naphthalenediol, 2,6 naphthalenediol, and 2,7 naphthalenediol.

  Specific examples of the polymer compound composed of a repeating unit having one or more phenolic hydroxyl groups include phenol resin, polyphenol, and poly (hydroxystyrene).

The content of the phenolic compound in the composition is preferably such that the molar concentration of the phenolic compound relative to 1 g of the polyaniline complex is 0.01 [mmol / g] or more and 100 [mol / g] or less, more preferably 0. 05 [mmol / g] or more and 1 [mol / g] or less, more preferably 0.1 [mmol / g] or more and 500 [mmol / g] or less, particularly preferably 0.2 [mmol / g] or more and 80 [mmol] / G] is in the following range.
When there is too little content of a phenolic compound, there exists a possibility that the electrical conductivity improvement effect may not be acquired. On the other hand, when there is too much content of a phenolic compound, there exists a possibility that film quality may worsen. In addition, a large amount of heat, time, and other labor are required to volatilize and remove, which increases costs.

3. Oxygenated organic solvent (component (3))
Examples of the oxygen-containing organic solvent include ester solvents such as ethyl acetate, isobutyl acetate and n-butyl acetate, methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, 2-pentanol, benzyl alcohol, 2- Alcohols such as methoxyethanol and 2-ethoxyethanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, polar ethers such as tetrahydrofuran, dioxane, diethyl ether and cyclopentyl methyl ether, N-methylpyrrolidone and the like And aprotic polar solvents.
Component (1) and the phenolic compound are soluble in alcohols such as isopropyl alcohol, 2-butanol, 2-pentanol, and benzyl alcohol. Alcohol is preferable from the viewpoint of reducing environmental burden unlike toluene.
Among these, a C1-C12 alcohol is preferable and a C1-C6 alcohol is more preferable.

  The proportion of component (1) in the oxygen-containing organic solvent is usually 0.2 g / g or less, preferably 0.01 to 0.1 g / g or less, depending on the type of organic solvent. If the content of component (1) is too large, the solution state cannot be maintained, and handling during molding becomes difficult, the uniformity of the molded body is impaired, and consequently the electrical properties and mechanical properties of the molded body are impaired. Reduces strength and transparency. On the other hand, when the content of the component (1) is too small, only a very thin film can be produced when the film is formed by the method described later, which may make it difficult to produce a uniform conductive film.

4). Polymer compound having acidic group or salt thereof (component (4))
The high molecular compound having an acidic group or a salt thereof is a compound having a repeating structure in one molecule, and at least one of the repeating structures is an acidic group (or a group constituting a salt with other ions). ), A compound having a plurality of acidic groups (or groups constituting a salt with other ions) in one molecule.
The acidic group contained in the polymer compound is not particularly limited, and examples thereof include a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a carboxy group, and a hydroxyl group. A carboxy group is preferred.
Further, the structure of the polymer compound is not particularly limited, and examples thereof include polystyrene, polyvinyl, and (meth) acrylic polymers. The weight average molecular weight of the component (4) (measured in terms of polystyrene by GPC as in the case of the weight average molecular weight of the polyaniline) is preferably from 1,000 to 300,000, more preferably from 2,000 to 200,000.
These polymer compounds form a solid component together with polyaniline when the composition of the present application is dried to form a thin film or the like. By adjusting the amount of the polymer compound in the composition, the volume of the thin film after drying can be adjusted.

  Examples of the polymer compound having an acidic group or a salt thereof include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyphosphoric acid (trade name: polyphosmer), polyacrylic acid, polystyrene acrylic acid copolymer (trade name: alfone), and the like. Examples include sodium salts, ammonium salts, and amine salts of acids.

  The polymer compound having an acidic group or a salt thereof is preferably a compound having two or more different repeating structures in one molecule, and at least one of these repeating structures having a carboxy group.

（式（Ａ），（Ｂ）中、Ｒ_ａ、Ｒ_ｂは水素原子又は炭素数１〜６のアルキル基であり、Ａ₁ ^＋はナトリウムイオン、アンモニウムイオン、又は下記の構造式で表されるイオンのいずれかである。

式中、Ｒ’はそれぞれ水素原子、アルキル基、アルケニル基、アルキニル基、ヒドロキシルアルキル基である。アルキル基、アルケニル基、アルキニル基、ヒドロキシルアルキル基は直鎖でも、分岐していてもよく、Ｒ’は同一でも異なっていてもよい。）
The high molecular compound which has an acidic group or its salt can contain the repeating unit of the following formula (A), the repeating unit of the following formula (B), or both as a repeating unit which has an acidic group or its salt, for example. Two or more repeating units of the formula (A) and the repeating unit of the formula (B) may be included.

(In the formulas (A) and (B), R _a and R _b are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A ₁ ⁺ is represented by a sodium ion, an ammonium ion, or the following structural formula. One of the ions.

In the formula, R ′ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or a hydroxylalkyl group, respectively. The alkyl group, alkenyl group, alkynyl group and hydroxylalkyl group may be linear or branched, and R ′ may be the same or different. )

（式（Ｃ）中、Ｒ_ｃは水素原子又は炭素数１〜６のアルキル基であり、Ｒ_ｄはアルキル基である。）
Furthermore, as another repeating unit, for example, a repeating unit of the following formula (C) can be included. Two or more repeating units of formula (C) can also be included.

(In formula (C), R _c is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R _d is an alkyl group.)

  Examples of the polymer compound include compounds comprising or consisting of at least one repeating unit selected from formulas (A) and (B) and a repeating unit of formula (C).

（式（１）中、Ｒ_１はそれぞれ水素原子又はメチル基であり、Ｒ_２はアルキル基であり、Ａ_２ ^＋は下記式のいずれかで表される構造のイオンであり、Ｘ，Ｙ，Ｚは繰り返し数である。）

Examples of the polymer compound having such an acidic group or a salt thereof include a compound represented by the following formula (1).

(In the formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group, A ₂ ⁺ is an ion having a structure represented by any of the following formulas, and X, Y, Z is the number of repetitions.)

  The alkyl group in the formulas (A) to (C) and (1) may be linear or branched.

  It is preferable that 1-100 mass parts of component (4) is contained with respect to 100 mass parts of component (1). More preferably, the component (4) is contained in an amount of 1 to 80 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (1).

  The acid value of the polymer compound having an acidic group is preferably 1 mg / g or more. More preferably, they are 1 mg / g or more and 1000 mg / g or less, More preferably, they are 1 mg / g or more and 800 mg / g or less, More preferably, they are 1 mg / g or more and 600 mg / g or less, Most preferably, they are 2 mg / g or more and 600 mg / g or less. .

  Here, the acid value is represented by the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the polymer compound.

The composition of this invention can contain a low molecular acidic compound or its salt (component (5)) other than the said components (1)-(4). By including the component (5), the heat resistance of the composition can be further increased. In addition, the molecular weight of a component (5) is 1500 or less.
A low molecular acid compound or a salt thereof (low molecular heat stabilizer) is an acidic substance or a salt of an acidic substance, and the acidic substance is either an organic acid (an acid of an organic compound) or an inorganic acid (an acid of an inorganic compound). But you can. In addition, the conductive composition of the present invention may contain a plurality of low molecular heat resistance stabilizers.

  When the composition of the present invention contains only an acidic substance as a low molecular heat resistance stabilizer, preferably the acidic substance is a compound different from the proton donor of the polyaniline complex, and the composition of the present invention is an acidic substance. In the case where only the salt of is included, the salt of the acidic substance is preferably a compound different from the proton donor of the polyaniline complex. In the case where the composition of the present invention contains both an acidic substance and an acidic substance salt as a low molecular heat resistance stabilizer, preferably at least one of the acidic substance and the acidic substance salt is a proton donor. And a different compound.

  When the composition of the present invention contains only an acidic substance as a low molecular heat resistance stabilizer, the acidic substance is preferably different from the phenolic compound. In the case where the composition of the present invention contains only a salt of an acidic substance as a low molecular heat resistance stabilizer, preferably the salt of the acidic substance is different from the phenolic compound. Further, when the composition of the present invention contains both an acidic substance and an acidic substance salt as a low molecular heat resistance stabilizer, preferably at least one of the acidic substance and the acidic substance salt is phenolic. Different from compound.

  The acidic substance that is a low-molecular heat-resistant stabilizer is preferably an organic acid, more preferably an organic acid having one or more sulfonic acid groups, carboxy groups, phosphoric acid groups, or phosphonic acid groups, and more preferably, An organic acid having one or more sulfonic acid groups.

The organic acid having one or more sulfonic acid groups is preferably a cyclic, linear or branched alkyl sulfonic acid, substituted or unsubstituted aromatic sulfonic acid having one or more sulfonic acid groups.
Examples of the alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, and di-2-ethylhexylsulfosuccinic acid. The alkyl group here is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
Examples of the aromatic sulfonic acid include a sulfonic acid having a benzene ring, a sulfonic acid having a naphthalene skeleton, a sulfonic acid having an anthracene skeleton, a substituted or unsubstituted benzenesulfonic acid, a substituted or unsubstituted naphthalenesulfonic acid, and a substituted Alternatively, unsubstituted anthracene sulfonic acid may be mentioned, and naphthalene sulfonic acid is preferable. Specific examples include naphthalene sulfonic acid, dodecylbenzene sulfonic acid, and anthraquinone sulfonic acid.
Here, the substituent is, for example, a substituent selected from the group consisting of an alkyl group, an alkoxy group, a hydroxy group, a nitro group, a carboxy group, and an acyl group, and one or more substituents may be substituted.

The organic acid having one or more carboxy groups is preferably a cyclic, linear or branched alkyl carboxylic acid or substituted or unsubstituted aromatic carboxylic acid having one or more carboxy groups.
Examples of the alkyl carboxylic acid include undecylenic acid, cyclohexane carboxylic acid, and 2-ethylhexanoic acid. Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
Examples of the substituted or unsubstituted aromatic carboxylic acid include substituted or unsubstituted benzene carboxylic acid and naphthalene carboxylic acid. Here, the substituent is, for example, a substituent selected from the group consisting of a sulfonic acid group, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, and an acyl group, and one or more substituents may be substituted. Specific examples include salicylic acid, benzoic acid, naphthoic acid, and trimesic acid.

The organic acid having at least one phosphoric acid group or phosphonic acid group is preferably a cyclic, chain or branched alkylphosphoric acid or alkylphosphonic acid having at least one phosphoric acid group or phosphonic acid group; a substituted or unsubstituted aromatic Group phosphoric acid or aromatic phosphonic acid.
Examples of the alkyl phosphoric acid or alkylphosphonic acid include dodecyl phosphoric acid and bis (2-ethylhexyl) hydrogen phosphate. Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
Examples of the aromatic phosphoric acid and aromatic phosphonic acid include substituted or unsubstituted benzenesulfonic acid or phosphonic acid, and naphthalenesulfonic acid or phosphonic acid. Here, the substituent is, for example, a substituent selected from the group consisting of an alkyl group, an alkoxy group, a hydroxy group, a nitro group, a carboxy group, and an acyl group, and one or more substituents may be substituted. An example is phenylphosphonic acid.

Examples of the salt of the acidic substance contained in the composition of the present invention include the salt of the acidic substance.
The composition of the present invention may contain two or more acidic substances and / or salts of acidic substances which are low molecular heat resistance stabilizers. Specifically, the composition of the present invention may include different acidic substances and / or salts of different acidic substances.

When the proton donor of the polyaniline complex is a sulfonic acid and the composition contains only an acidic substance as a low molecular heat resistance stabilizer, the acidic substance is preferably the same or different sulfonic acid as the proton donor. . In the case where the composition contains only a salt of an acidic substance as a low molecular heat resistance stabilizer, the salt of the acidic substance is preferably the same or different sulfonic acid salt as the proton donor of the polyaniline complex. .
When the composition includes an acidic substance and a salt of the acidic substance as a low-molecular heat-resistant stabilizer, at least one of the acidic substance and the salt of the acidic substance is the same or different from the proton donor or a salt of the sulfonic acid It is preferable that

When the composition of the present invention contains only sulfonic acid as the low-molecular heat-resistant stabilizer, it is preferable to satisfy the formula (12), and the composition contains only the salt of sulfonic acid as the low-molecular heat-resistant stabilizer. In some cases, the formula (13) is preferably satisfied. When the composition contains a sulfonic acid and a sulfonic acid salt as a low-molecular heat-resistant stabilizer, the formula (14) is preferably satisfied.
0.01 ≦ S ₂ / N ₂ ≦ 0.5 (12)
0.01 ≦ S ₃ / N ₃ ≦ 0.5 (13)
0.01 ≦ S ₄ / N ₄ ≦ 0.5 (14)
(Wherein S ₂ is the total number of moles of sulfur atoms of all acidic substances contained in the composition, and N ₂ is the number of moles of nitrogen atoms in all polyaniline complexes contained in the composition. S ₃ is the total number of moles of sulfur atoms of the salts of all acidic substances contained in the composition, and N ₃ is the nitrogen of all the polyaniline complexes contained in the composition. Means the total number of moles of atoms, S ₄ is the total number of moles of sulfur atoms of all acidic substances and salts of acidic substances contained in the composition, and N ₄ is contained in the composition (It means the total number of moles of nitrogen atoms in all polyaniline complexes.)

When the composition of the present invention satisfies any of the above formulas (12), (13), or (14), the composition preferably further satisfies the following formula (11).
0.36 ≦ S ₁ / N ₁ ≦ 1.15 (11)
(Here, S ₁ is the number of moles of sulfur atoms contained in the composition, and N ₁ is the number of moles of nitrogen atoms contained in the composition.)

When the composition of this invention contains only an acidic substance, it is preferable that the acidity (pKa) of the said acidic substance is 5.0 or less. The lower limit of the acidity is not particularly limited. For example, when an acid substance having an acidity of −4.0 or less is included, the polyaniline complex may be deteriorated.
When the composition of this invention contains only the salt of an acidic substance, it is preferable that the acidity of the salt of the said acidic substance is 5.0 or less. About the minimum of acidity, it is the same as that of the said acidic substance.
When the composition of the present invention includes both an acidic substance and an acidic substance salt, at least one of the acidic substance salts having an acidity of 5.0 or less and an acidity of 5.0 or less is included. It is preferable to satisfy. The lower limit of acidity is the same as described above.

Acidity (pKa) is defined by computational chemistry methods. A. Journal of Physical Chemistry 1995, Vol. 99, p. 50, which calculates the charge density on the surface of a molecule by quantum chemical calculation developed by Klamt et al. The method described in 2224 is used.
Specifically, using “TURBOMOLE Version 6.1” (manufactured by COSMO logic), the structure is optimized using TZVP as a basis function, and the COSMO-RS method calculation is performed using this structure using “COSMO therm version C2”. .1 Release 01.10 "(manufactured by COSMO logic).
Here, the pKa is calculated by inputting the conditions of 25 ° C. in an aqueous solvent, the chemical formula of the molecule, and the chemical formula of the deprotonated molecule in “COSMO thermion C2.1 Release 01.10”. be able to.

  In the composition of the present invention, the content of the low molecular acid compound or a salt thereof is preferably 1 to 1000 parts by mass, more preferably 1 to 100, and still more preferably 1 with respect to 100 parts by mass of the component (1). -50 mass parts.

In the composition of the present invention, for example, 15% by weight or more, 50% by weight or more, 70% by weight or more, and 100% by weight may be composed of components (1) to (4) or components (1) to (5).
In addition to these components, the composition of the present invention may contain other resins, inorganic materials, curing agents, plasticizers and the like as long as the effects of the present invention are not impaired.

Other resin is added as a binder base material, a plasticizer, and a matrix base material, for example.
Specific examples of other resins include, for example, polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, polyester, polyamide, polyacetal, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, Examples thereof include polymethacrylic acid ester and polyvinyl alcohol.
Further, instead of the above resin, together with the resin, a thermosetting resin such as an epoxy resin, a urethane resin, or a phenol resin, or a precursor capable of forming these thermosetting resins may be included.

The inorganic material is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, or improving electrical properties such as conductivity.
Specific examples of the inorganic material include, for example, silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), Sn-containing In ₂ O ₃ (ITO), Zn-containing In ₂ O ₃ , and In ₂ O ₃ . Examples include co-substituted compounds (oxides in which tetravalent elements and divalent elements are substituted with trivalent In), Sb-containing SnO ₂ (ATO), ZnO, Al-containing ZnO (AZO), and Ga-containing ZnO (GZO). .

  The curing agent is added for the purpose of, for example, improving strength, surface hardness, dimensional stability, and other mechanical properties. Specific examples of the curing agent include a thermosetting agent such as a phenol resin, and a photocuring agent using an acrylate monomer and a photopolymerization initiator.

For example, the plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength.
Specific examples of the plasticizer include phthalic acid esters and phosphoric acid esters. Examples of the organic conductive material include carbon materials such as carbon black and carbon nanotubes, or conductive polymers other than the polyaniline obtained in the present invention.

The composition of the present invention can be prepared by mixing each component, and the method disclosed in Patent Document 1 can be referred to.
The mixing method of these components is not limited as long as a uniform composition can be obtained. For example, after preparing a solution by mixing the component (1), the component (2), and the component (3), the component ( 4) is added and dissolved to obtain a uniform conductive composition.

[Molded body]
From the polyaniline composition of the present invention, a molded product, a conductive laminate (surface conductive article), a conductive article, and a conductive film are obtained.
For example, a molded body can be obtained by drying the composition of the present invention and removing the solvent. The shape of the molded body may be any shape such as a plate shape, a rod shape, or a film shape. For example, a conductive laminate having a conductive film is produced by applying the composition of the present invention to a substrate such as glass, resin film, sheet or nonwoven fabric having a desired shape and removing the solvent. Can do. By processing the conductive laminate into a desired shape by a known method such as vacuum forming or pressure forming, a conductive article can be manufactured. From the viewpoint of molding, the substrate is preferably a resin film, a sheet, or a nonwoven fabric.

  The thickness of the conductive film (conductive film) of the present invention is usually 1 mm or less, preferably 10 nm or more and 50 μm or less. A film having a thickness in this range is advantageous in that it does not easily crack during film formation and has uniform electrical characteristics.

  As a method for applying the composition to the substrate, known methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a bar coating method, a spin coating method, an electrospinning method, screen printing, and a gravure printing method are used. Can be used.

The composition of the present invention can also be a self-supporting molded article having no substrate.
In the case of a self-supporting molded body, preferably, a molded body having a desired mechanical strength can be obtained when the composition contains the other resin described above.

[Capacitor]
A capacitor is obtained from the composition of the present invention.
Specific examples of the capacitor include an electrolytic capacitor and an electric double layer capacitor. Here, the electrolytic capacitor includes a solid electrolytic capacitor.
Moreover, a plating base agent or a rust preventive agent is obtained from the composition of the present invention.

Production Example 1
[Production of Pronated Polyaniline (Polyaniline Complex)]
Aerosol OT (sodium diisooctyl sulfosuccinate, which is a sulfosuccinic acid derivative, purity 75% or more, manufactured by Wako Pure Chemical Industries, Ltd.) 5.4 g (12 mmol), Phosphanol FP120 (manufactured by Toho Chemical Co., Ltd.) 0.66 g (0 .8 mmol) was stirred and dissolved in 100 mL of toluene, and placed in a 30 L glass reactor (with mechanical stirrer, jacket, thermometer and dropping funnel) placed under a nitrogen stream. To this solution, 3.7 g (40 mmol) of raw material aniline was added and dissolved by stirring. Stirring and cooling of the flask with the refrigerant was started, and 300 mL of 1M phosphoric acid was further added to the solution. While keeping the solution temperature at 5 ° C., a solution obtained by dissolving 7.3 g (32 mmol) of chemical ammonium persulfate in 100 mL of 1M phosphoric acid was dropped with a dropping funnel, and the dropping was completed in 2 hours. The aqueous phase (lower phase) separated into two phases by standing was withdrawn from the lower part of the reactor to obtain a crude polyaniline complex toluene solution.
After adding 100 mL of ion-exchanged water to the obtained complex solution and stirring, it was allowed to stand to separate the aqueous phase, and this operation was performed again. The complex solution was washed in the same manner with 100 mL of 1N phosphoric acid aqueous solution, allowed to stand, then the acidic aqueous solution was separated, and the toluene solution of the polyaniline complex was recovered. Some insoluble matter contained in the complex solution was removed with # 5C filter paper, and a toluene solution of the polyaniline complex was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate and remove volatile components to obtain 7 g of a polyaniline complex.

About the obtained polyaniline composite_body | complex, the elemental analysis result at the time of removing a volatile matter substantially is shown below. From the ratio of the nitrogen weight percent based on the aniline raw material and the sulfur weight percent based on the sulfosuccinate ester, the molar fraction of sulfosuccinate ester / aniline monomer unit in the composite is 0.48.
Carbon 60.2 wt%, Hydrogen: 7.8 wt%, Nitrogen: 4.6 wt%, Sulfur: 5.0 wt%
The weight average molecular weight of the polyaniline skeleton in this polyaniline complex was measured by GPC and found to be 114,000 g / mol.
Moreover, the chlorine content of the polyaniline composite prepared by this method was determined by an organic chlorine content-coulometric titration method, and it was confirmed that the chlorine content was 10 ppm by weight or less. Therefore, the chlorine content in the polyaniline complex is 10 ppm by weight or less.

Example 1
[Preparation of conductive polyaniline composition]
700 mg of the conductive polyaniline complex obtained in Production Example 1 was dissolved again in 4.65 g of isopropyl alcohol and 4.65 g of p-tert-amylphenol (Tokyo Chemical Industry) to prepare a uniform conductive polyaniline complex solution. To this composite solution, 300 mg of Alfon UC3080 (acrylic polymer having a carboxy group, manufactured by Toagosei Co., Ltd., acid value 230 mg / g, Mw = 14000) was added to obtain a uniform conductive polyaniline composition.

[Production of conductive polyaniline thin film]
About 1 ml of the obtained conductive polyaniline composition was spread on a 30 mm × 30 mm square glass substrate patterned with ITO under a nitrogen atmosphere and spin-coated at 1000 rpm for 15 seconds. This was dried at 150 ° C. for 5 minutes in a nitrogen atmosphere to form a transparent and homogeneous thin film on the glass substrate. The resistance of the thin film was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method), and the value was defined as an initial value (R ₀ ).

[Heat resistance test of conductive polyaniline thin film]
The thin film of the obtained conductive polyaniline composition was left as it was for a predetermined time in a nitrogen atmosphere and at 125 ° C. with the glass substrate. The resistance was measured in the same manner as the initial value (R ₀ ) after the temperature of the thin film was returned to room temperature after a predetermined time had elapsed. The ratio (R / R ₀ ) between the resistance value (R) and the initial value after the lapse of a predetermined time was calculated, and the deterioration with time (resistance increase rate) of the thin film was evaluated. The results are shown in Table 1. The values in the table indicate the ratio R / R ₀ between the resistance value R and the initial value R ₀ after a predetermined time.

Example 2
Uniform conductive polyaniline composition in the same manner as in Example 1 except that the addition amount of Alfon UC3080 (acrylic polymer having a carboxy group, manufactured by Toagosei Co., Ltd., acid value 230 mg / g, Mw = 14000) was changed to 500 mg. I got a thing.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 3
A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that the addition amount of Alfon UC3080 was changed to 100 mg.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 4
Uniform conductive polyaniline composition as in Example 1 except that Alfon UC3910 (acrylic polymer having a carboxy group, manufactured by Toagosei Co., Ltd., acid value 200 mg / g, Mw = 8500) is used instead of Alfon UC3080 I got a thing.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 5
Uniform conductive polyaniline composition as in Example 1 except that Alfon UC3920 (acrylic polymer having a carboxy group, manufactured by Toagosei Co., Ltd., acid value 240 mg / g, Mw = 15500) was used instead of Alfon UC3080 I got a thing.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

得られた導電性ポリアニリン組成物を用いて、実施例１と同様にして薄膜を形成し、得られた薄膜を評価した。結果を表１に示す。 Example 6
The same as in Example 1 except that 3 g of 10% isopropyl alcohol solution (manufactured by DAP, acid value 311 mg / g, Mw = 150,000) of polyphosmer PE201 of the following formula was added instead of adding 300 mg of Alfon UC3080 A conductive polyaniline composition was obtained.

Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 7
A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to Example 1.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 8
A uniform conductive polyaniline composition was obtained in the same manner as in Example 2 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to Example 2.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 9
A uniform conductive polyaniline composition was obtained in the same manner as in Example 3 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to Example 3.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 10
A uniform conductive polyaniline composition was obtained in the same manner as in Example 4 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to Example 4.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 11
A uniform conductive polyaniline composition was obtained in the same manner as in Example 5 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to Example 5.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 12
A uniform conductive polyaniline composition was obtained in the same manner as in Example 6 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to Example 6.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 13
LC8560 (acrylic polymer having a carboxy group, 35 wt% solution (solvent: ethyl acetate), manufactured by Toei Kasei Co., Ltd., acid value 2.2 mg / g, Mw = 80000) 0.28 g was used instead of Alfon UC3080 Obtained a uniform conductive polyaniline composition in the same manner as in Example 1.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 14
Except for using 0.26 g of YB7003 (acrylic polymer having a carboxy group, 38 wt% solution (solvent: ethyl acetate), manufactured by Toei Kasei Co., Ltd., acid value 2.4 mg / g, Mw = 50000) instead of Alfon UC3080 Obtained a uniform conductive polyaniline composition in the same manner as in Example 1.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 15
Instead of Alfon UC3080, PB7050 (acrylic polymer having a carboxy group, 38.5 wt% solution (solvent: ethyl acetate (60%) IPA (40%)), manufactured by Toei Kasei Co., Ltd., acid value 2.5 mg / g, Mw = 80000) A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that 0.26 g was used.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 16
0.25 g of Aniset L1000 (39.9 wt% solution (solvent: methanol), manufactured by Osaka Organic Chemical Industry Co., Ltd., acid value 5 mg / g, Mw = 80000) which is an acrylic polymer having a carboxy group instead of Alfon UC3080 A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that it was used.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 17
Aniset KB-100H which is an acrylic polymer having a carboxy group instead of Alfon UC3080 (40.8 wt% solution (solvent: methanol), manufactured by Osaka Organic Chemical Industry Co., Ltd., acid value 8 mg / g, Mw = 60000) A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that 24 g was used.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 18
Aniset KB-100H, which is an acrylic polymer having a carboxy group instead of Alfon UC3080, is not neutralized (54.8 wt% solution (solvent: methanol), manufactured by Osaka Organic Chemical Industry Co., Ltd., acid value 53 mg / g, Mw = 60000 ) A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that 0.18 g was used.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 19
Anisset NF-1000 (40.0 wt% solution (solvent: methanol), manufactured by Osaka Organic Chemical Industry Co., Ltd., acid value 5 mg / g, Mw = 80000), which is an acrylic polymer having a carboxy group instead of Alfon UC3080 A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that 25 g was used.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 20
Aniset HS-3000 (30.1 wt% solution (solvent: methanol), manufactured by Osaka Organic Chemical Industry Co., Ltd., acid value 3 mg / g, Mw = 60000), which is an acrylic polymer having a carboxy group instead of Alfon UC3080 A uniform conductive polyaniline composition was obtained in the same manner as in Example 1 except that 33 g was used.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 21
Uniform conductive polyaniline as in Example 1 except that 1 g of Neocryl B-818 (acrylic polymer having a carboxy group, Enomoto Kasei Co., Ltd., acid value 50 mg / g, Mw = 38000) was used instead of Alfon UC3080. A composition was obtained.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

Example 22
A uniform conductive polyaniline composition was obtained in the same manner as in Example 16 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to Example 16.

Example 23
A uniform conductive polyaniline composition was obtained in the same manner as in Example 17 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to Example 17.

Example 24
A uniform conductive polyaniline composition was obtained in the same manner as in Example 18 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to Example 18.

Example 25
A uniform conductive polyaniline composition was obtained in the same manner as in Example 19 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to Example 19.

Example 26
A uniform conductive polyaniline composition was obtained in the same manner as in Example 20 except that 47 mg of 2-naphthalenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to Example 20.

Comparative Example 1
A uniform conductive polyaniline composition was prepared in the same manner as in Example 1 except that Alfon UC3080 was not added.
Using the obtained conductive polyaniline composition, a thin film was formed in the same manner as in Example 1, and the obtained thin film was evaluated. The results are shown in Table 1.

  The molded body obtained from the composition of the present invention is used in the fields of power electronics and optoelectronics, for electrostatic and antistatic materials, transparent electrodes and conductive film materials, electroluminescent element materials, circuit materials, electromagnetic wave shielding materials, and capacitor materials. It can be used for dielectrics and electrolytes, electrode materials for solar cells and secondary batteries, fuel cell separator materials, etc., or for plating bases, rust inhibitors and the like.

Claims (15)

(1) Protonated substituted or unsubstituted polyaniline (2) Phenolic compound (3) Oxygenated organic solvent (4) At least one repeating unit selected from formulas (A) and (B), A conductive composition comprising a polymer compound which is an acrylic polymer containing a repeating unit of C) or an acrylic polymer having a phosphate group .

(Wherein a _{R a,} R _b, R _c is a hydrogen atom or a methyl group, the R _d is an alkyl group, A ₁ ⁺ is either ion represented by sodium ion, or the following formula.

(In the formula, each R ′ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or a hydroxylalkyl group. The alkyl group, alkenyl group, alkynyl group, or hydroxylalkyl group may be linear or branched, R ′ may be the same or different.))   The conductive composition according to claim 1, wherein the chlorine content of the protonated substituted or unsubstituted polyaniline is 0.6% by weight or less.   The conductive composition according to claim 1 or 2, wherein the protonated substituted or unsubstituted polyaniline is a substituted or unsubstituted polyaniline protonated with an organic sulfonic acid or a salt thereof.   The conductive composition according to claim 3, wherein the organic sulfonic acid or a salt thereof is a sulfosuccinic acid derivative. The conductive composition according to claim 3 or 4, wherein the organic sulfonic acid or a salt thereof is represented by the following formula (III).

Wherein M is a hydrogen atom, an organic free radical or an inorganic free radical, m ′ is a valence of M, and R ¹¹² and R ¹¹³ are each independently a hydrocarbon group or — (R ¹¹⁴ O). ^{r-R 115} group ^{[wherein, R 114} are each independently a hydrocarbon group or a silylene ^{group, R 115} is a hydrogen atom, a hydrocarbon group, or ^R ₁₁₆ 3 Si- groups ^{(wherein, R 116} are each independently Is a hydrocarbon group), and r is an integer of 1 or more.) The conductive composition according to any one of claims 1 to 5 , wherein the acid value of the polymer compound (4) is 1 mg / g or more. The conductive polymer according to any one of claims 1 to 6 , wherein the polymer compound (4) has a weight average molecular weight of 2,000 to 200,000. The conductive composition according to any one of claims 1 to 7 , wherein the oxygen-containing organic solvent is an alcohol having 1 to 12 carbon atoms. Furthermore, the electroconductive composition in any one of Claims 1-8 containing a low molecular acidic compound or its salt. The conductive composition according to claim 9 , wherein the low-molecular acid compound is a compound having a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, or a carboxy group. The conductive composition according to claim 9 or 10 , wherein the low molecular acid compound is naphthalenesulfonic acid or alkylnaphthalenesulfonic acid. Capacitor produced by using a conductive composition according to any one of claims 1 to 11. Conductive moldings produced using the conductive composition according to any one of claims 1 to 11. The conductive composition according to any one of claims 1 to 11 surface conductive article formed by applying to a substrate. Conductive article manufactured using the surface conductive article of claim 1 4.