JP5731974B2 - Conductive composition - Google Patents

Description

  The present invention relates to a conductive composition.

  As the conductive polymer, polyaniline or the like is a well-known material. In addition to its electrical characteristics, polyaniline has the advantage that it can be synthesized relatively easily from inexpensive aniline and exhibits excellent stability against air or the like in a state of conductivity.

As a method for producing polyaniline, a method of electrolytic oxidation polymerization or chemical oxidation polymerization of aniline or aniline derivatives is known.
Regarding electrolytic oxidation polymerization, Patent Document 1 and Patent Document 2 describe a method of polymerizing aniline on an electrode. In electrolytic oxidation polymerization, a film having excellent electrical characteristics and the like can be obtained. However, in general, the production cost is higher than that of chemical oxidative polymerization, it is not suitable for mass production, and it is difficult to obtain a molded article having a complicated shape.

On the other hand, in order to obtain a conductive polymer of aniline or an aniline derivative by chemical oxidative polymerization, in general, a dopant (doping agent) is added to polyaniline in a non-conductive base state (so-called emeraldine base state) to perform protonation. A process is required.
However, polyaniline in a nonconductive base state is not suitable for industrial production because it hardly dissolves in most organic solvents. Moreover, the conductive polyaniline (so-called emeraldine salt state) generated after the protonation is substantially insoluble and infusible, and it is difficult to easily manufacture a conductive composite material and a molded body thereof.

Under such circumstances, several proposals have been made as a method for improving the affinity of a polyaniline in a non-conductive base state and the conductivity of the conductive polyaniline after doping to an organic solvent.
For example, Non-Patent Document 1 describes that excellent electrical characteristics are exhibited by using a proton acid having affinity for an organic solvent, such as dodecylbenzene sulfonic acid and camphor sulfonic acid (CSA), as a dopant. ing.
Patent Document 3 describes a method in which polyaniline in a non-conductive base state is dissolved in m-cresol using, for example, adamantane sulfonic acid as a dopant.

Non-Patent Document 2, for example, in a special solvent (halogen-based strong acid) such as 2,2-dichloroacetic acid, using 2-acrylamido-2-methyl-propanesulfonic acid as a dopant and a non-conductive base state A method for doping polyaniline is described.
In Patent Document 4, for example, as in Patent Document 2, 2,2-dichloroacetic acid is used as a solvent, and di (2-ethylhexyl) ester of sulfosuccinic acid is used as a dopant to dope polyaniline in a non-conductive base state. A method is described.

On the other hand, Patent Document 5 reports that a doped polyaniline can be easily obtained by using an anionic surfactant as a dopant in a two-phase polymerization system of a solvent and water substantially immiscible with water. Has been.
However, it cannot be said that a molded article made of conductive polyaniline obtained by these methods is excellent in electrical characteristics such as electrical conductivity.

JP-A-62-230825 Japanese Patent Laid-Open No. 62-149724 JP-A-7-70312 JP 2003-183389 A International publication WO05 / 052058

Synthetic metals, 48, 1992, pp. 91-97. J. et al. Phys. : Condens. Matter, 10, 1998, 8293-8303.

  An object of this invention is to provide the electroconductive composition which gives the electroconductive molded object which has high electrical conductivity in view of the said present condition.

（式中、Ｒ_１は、式（Ｘ）中のベンゼン環へ電子を供与する働きを有する基である。）
２．少なくとも下記（ａ）〜（ｃ）を原料として用い、
下記フェノール性化合物（ｃ）と下記π共役系導電性高分子（ｂ）の重量比（フェノール性化合物［ｋｇ］／π共役系導電性高分子［ｋｇ］）が０．０１〜１０．０である導電性組成物。
（ａ）溶剤
（ｂ）前記溶剤に溶解する、ドーパントによりドープされたπ共役系導電性高分子
（ｃ）ＬＤ５０が５００［ｍｇ／ｋｇ］以上である、下記式（Ｘ）で表わされるフェノール性化合物

（式中、Ｒ_１は、式（Ｘ）中のベンゼン環へ電子を供与する働きを有する基である。）
３．溶剤、
前記溶剤に溶解した、ドーパントによりドープされたπ共役系導電性高分子、及び
下記式（２）で表わされるフェノール性化合物を含み、
前記フェノール性化合物と前記π共役系導電性高分子の重量比（フェノール性化合物［ｋｇ］／π共役系導電性高分子［ｋｇ］）が、０．０１〜１０．０である導電性組成物。

（式中、Ｒ_２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。）
４．少なくとも下記（ａ）〜（ｃ）を原料として用い、
下記フェノール性化合物（ｃ）と下記π共役系導電性高分子（ｂ）の重量比（フェノール性化合物［ｋｇ］／π共役系導電性高分子［ｋｇ］）が０．０１〜１０．０である導電性組成物。
（ａ）溶剤
（ｂ）前記溶剤に溶解する、ドーパントによりドープされたπ共役系導電性高分子
（ｃ）下記式（２）で表わされるフェノール性化合物

（式中、Ｒ_２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。）
５．前記フェノール性化合物（ｃ）のＬＤ５０が５００［ｍｇ／ｋｇ］以上である３又は４に記載の導電性組成物。
６．前記ドープされたπ共役系導電性高分子が、プロトネーションされた置換もしくは非置換ポリアニリン、プロトネーションされた置換もしくは非置換ポリピロール、又はプロトネーションされた置換もしくは非置換ポリチオフェンのいずれかである１〜５のいずれかに記載の導電性組成物。
７．前記π共役系導電性高分子のドーパントが有機スルホン酸である１〜６のいずれかに記載の導電性組成物。
８．前記π共役系導電性高分子のドーパントが、下記（ＸＸ）で表されるコハクスルホン酸類である１〜７のいずれかに記載の導電性組成物。
Ｍ（Ｏ_３ＳＣＨ（ＣＨ_２ＣＯＯＲ^１２）ＣＯＯＲ^１３）_ｍ （ＸＸ）
（式（ＸＸ）において、
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^１２及びＲ^１３は、それぞれ独立して炭化水素基又は−（Ｒ^１４Ｏ）_ｒ−Ｒ^１５で表される基であり、Ｒ^１４は炭化水素基又はシリレン基であり、Ｒ^１５は水素原子、炭化水素基又はＲ^１６ _３Ｓｉ−で表される基であり、Ｒ^１６は炭化水素基であり、３つのＲ^１６は同一又は異なっていてもよく、ｒは１以上の整数である。）
９．前記フェノール性化合物と前記溶剤の重量比（フェノール性化合物［ｋｇ］／溶剤［ｋｇ］）が、０．０００４以上０．７５以下である１〜８のいずれかに記載の導電性組成物。
１０．基材、及び
前記基材上に積層された１〜９のいずれかに記載の導電性組成物から製造された導電層を含む導電性積層体。
１１．前記基材が樹脂フィルムである１０に記載の導電性積層体。
１２．１０又は１１に記載の導電性積層体を成形して得られる導電性物品。
１３．１〜９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。
１４．１〜９のいずれかに記載の導電性組成物を成形してなる導電性フィルム。
１５．１〜９のいずれかに記載の導電性組成物を成形してなる導電性膜。
１６．１〜９のいずれかに記載の導電性組成物と基材を混合してなる導電性物品。
１７．π共役系導電性高分子、及び
下記式（１）で表わされるフェノール性化合物を含み、
前記フェノール性化合物と前記π共役系導電性高分子の重量比（フェノール性化合物／π共役系導電性高分子）が、０．０１〜１０．０であり、
前記π共役系導電性高分子が、プロトネーションされた置換もしくは非置換ポリアニリンであり、
前記π共役系導電性高分子が、有機スルホン酸でドープされている導電性組成物。

（式中、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。）According to the present invention, the following conductive compositions and the like are provided.
1. solvent,
A π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and a phenolic compound represented by the following formula (X) having an LD50 of 500 [mg / kg] or more,
Conductive composition having a weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π-conjugated conductive polymer [kg]) of 0.01 to 10.0. .

(In the formula, R ₁ is a group having a function of donating electrons to the benzene ring in formula (X).)
2. At least the following (a) to (c) are used as raw materials,
The weight ratio of the following phenolic compound (c) and the following π-conjugated conductive polymer (b) (phenolic compound [kg] / π-conjugated conductive polymer [kg]) is 0.01 to 10.0. A conductive composition.
(A) Solvent (b) A phenolic compound represented by the following formula (X) having a π-conjugated conductive polymer (c) LD50 of 500 [mg / kg] or more, which is dissolved in the solvent and is doped with a dopant. Compound

(In the formula, R ₁ is a group having a function of donating electrons to the benzene ring in formula (X).)
3. solvent,
A π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and a phenolic compound represented by the following formula (2):
Conductive composition having a weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π-conjugated conductive polymer [kg]) of 0.01 to 10.0. .

(In the formula, R ₂ is an alkyl group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms.)
4). At least the following (a) to (c) are used as raw materials,
The weight ratio of the following phenolic compound (c) and the following π-conjugated conductive polymer (b) (phenolic compound [kg] / π-conjugated conductive polymer [kg]) is 0.01 to 10.0. A conductive composition.
(A) Solvent (b) A π-conjugated conductive polymer doped with a dopant and dissolved in the solvent (c) A phenolic compound represented by the following formula (2)

(In the formula, R ₂ is an alkyl group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms.)
5. The conductive composition according to 3 or 4, wherein the phenolic compound (c) has an LD50 of 500 [mg / kg] or more.
6). The doped π-conjugated conductive polymer is any one of a protonated substituted or unsubstituted polyaniline, a protonated substituted or unsubstituted polypyrrole, or a protonated substituted or unsubstituted polythiophene. The electrically conductive composition in any one of 5.
7). The conductive composition according to any one of 1 to 6, wherein the dopant of the π-conjugated conductive polymer is an organic sulfonic acid.
8). The conductive composition according to any one of 1 to 7, wherein the dopant of the π-conjugated conductive polymer is a succinic sulfonic acid represented by the following (XX).
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (XX)
(In Formula (XX),
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 a hydrogen atom. , A hydrocarbon group or a group represented by R ¹⁶ ₃ Si—, R ¹⁶ is a hydrocarbon group, three R ¹⁶ may be the same or different, and r is an integer of 1 or more. )
9. The electrically conductive composition in any one of 1-8 whose weight ratio (phenolic compound [kg] / solvent [kg]) of the said phenolic compound and the said solvent is 0.0004 or more and 0.75 or less.
10. The electroconductive laminated body containing the base material and the electroconductive layer manufactured from the electroconductive composition in any one of 1-9 laminated | stacked on the said base material.
11. The conductive laminate according to 10, wherein the substrate is a resin film.
12. A conductive article obtained by molding the conductive laminate according to 10.10 or 11.
13. A capacitor manufactured using the conductive composition according to any one of 1 to 9.
The electroconductive film formed by shape | molding the electroconductive composition in any one of 14.1-9.
15. A conductive film formed by molding the conductive composition according to any one of 1 to 9.
16. A conductive article obtained by mixing the conductive composition according to any one of 1 to 9 and a base material.
17. a π-conjugated conductive polymer, and a phenolic compound represented by the following formula (1):
The weight ratio of the phenolic compound and the π-conjugated conductive polymer (phenolic compound / π-conjugated conductive polymer) is 0.01 to 10.0,
The π-conjugated conductive polymer is a protonated substituted or unsubstituted polyaniline,
A conductive composition in which the π-conjugated conductive polymer is doped with an organic sulfonic acid.

(In the formula, R is an alkyl group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms.)

  ADVANTAGE OF THE INVENTION According to this invention, the electroconductive composition which gives the electroconductive molded object which has high electrical conductivity can be obtained.

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 (pi) conjugate polymer thin film and exposed the terminal of the ITO electrode on the surface. It is a figure which shows the upper surface of the glass substrate which shaved the electroconductive polyaniline thin film and exposed the terminal of the ITO electrode on the surface.

（式中、Ｒ_１は、式（Ｘ）中のベンゼン環へ電子を供与する働きを有する基である。）The first conductive composition of the present invention includes a solvent, a π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and an LD50 of 500 [mg / kg] or more. A phenolic compound represented by (X) is included.
The weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π-conjugated conductive polymer [kg]) is 0.01 to 10.0.

(In the formula, R ₁ is a group having a function of donating electrons to the benzene ring in formula (X).)

  In the present invention, the doped π-conjugated conductive polymer is dissolved in the solvent in the composition in the composition. Here, being dissolved means that the π-conjugated conductive polymer is uniformly dissolved in a solvent in molecular units. Thereby, when the conductive composition is dried, a uniform π-conjugated conductive polymer film having no grain boundary is obtained.

The LD50 is a half-lethal dose. When 50 chemicals are administered to 50 rats (taken by mouth), half of the rats die during the test period. The dose at which 50% dies is expressed as the amount per body weight (mg / kg).
In practice, a dose-mortality graph is drawn from animal experiment data to determine the dose (LD50) corresponding to 50% mortality.

Although it means LD50 disclosed in the Tokyo Chemical Industry Co., Ltd. product safety data sheet, the substances not disclosed in the Tokyo Chemical Industry Co., Ltd. product safety data sheet are determined by the measurement method.
The LD50 of the phenolic compound is 500 [mg / kg] or more. LD50 is 30000 [mg / kg] or less, for example.

The group having a function of donating electrons is a group having a function of donating electrons to the benzene ring in formula (X) and increasing the electron density in the benzene ring. Examples thereof include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups, alkoxy groups such as methoxy groups, ethoxy groups, and propoxy groups, and aryloxy groups such as phenoxy groups.
Here, the LD50 of the phenolic compound represented by the formula (X) is 500 [mg / kg] or more. Examples of compounds having an LD50 of 500 [mg / kg] or more and LD50 values thereof include, for example, the LD50 value of 3-methoxyphenol is 597, the LD50 value of 4-methoxyphenol is 1,600, and the LD50 value of t-amylphenol. The value of is 1830, and the value of LD50 of 3-phenoxyphenol is 5000.

（式中、Ｒ_１は、式（Ｘ）中のベンゼン環へ電子を供与する働きを有する基である。）The second conductive composition of the present invention is manufactured using at least the following (a) to (c) as raw materials.
The weight ratio of the following phenolic compound (c) and the following π-conjugated conductive polymer (b) (phenolic compound [kg] / π-conjugated conductive polymer [kg]) is 0.01 to 10.0. is there.
(A) Solvent (b) A phenolic compound represented by the following formula (X) having a π-conjugated conductive polymer (c) LD50 of 500 [mg / kg] or more, which is dissolved in the solvent and is doped with a dopant. Compound

(In the formula, R ₁ is a group having a function of donating electrons to the benzene ring in formula (X).)

（式中、Ｒ_２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 third conductive composition of the present invention includes a solvent, a π-conjugated conductive polymer doped with a dopant dissolved in the solvent, a phenolic compound represented by the following formula (2), including.
The weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π-conjugated conductive polymer [kg]) is 0.01 to 10.0.

(In the formula, R ₂ is an alkyl group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms.)

（式中、Ｒ_２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 4th electroconductive composition of this invention is manufactured using at least following (a)-(c) as a raw material.
The weight ratio of the following phenolic compound (c) and the following π-conjugated conductive polymer (b) (phenolic compound [kg] / π-conjugated conductive polymer [kg]) is 0.01 to 10.0. is there.
(A) Solvent (b) A π-conjugated conductive polymer doped with a dopant and dissolved in the solvent (c) A phenolic compound represented by the following formula (2)

(In the formula, R ₂ is an alkyl group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms.)

  The LD50 of the phenolic compound (c) in the third and fourth conductive compositions is preferably 500 [mg / kg] or more. LD50 is 30000 [mg / kg] or less, for example.

（式中、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 fifth conductive composition of the present invention comprises a phenolic compound represented by the following formula (1) and a π-conjugated conductive polymer.
The weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound / π-conjugated conductive polymer) is 0.01 to 10.0, and the π-conjugated conductive polymer is A substituted or unsubstituted polyaniline that is protonated, and the π-conjugated conductive polymer is doped with an organic sulfonic acid.

(In the formula, R is an alkyl group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms.)

  By using the phenolic compound, a conductive composition having high electrical conductivity can be obtained. In addition, the above compounds are not toxic and have no odor. Therefore, unlike m-cresol and the like, it is suitable for industrial production of conductive compositions.

R in the formula (1), and for _{R 2} of formula (2), the alkyl group having 1 to 20 carbon atoms, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl and the like.
Examples of the alkenyl group include those 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.
Of these groups, a methyl or ethyl group is preferred.

-R ₁ in the formula (X), -OR in formula (1), the substitution position of -OR ₂ in formula (2) based on the phenolic hydroxyl group, meta, or is preferably in the para position. Thereby, the steric hindrance of the phenolic hydroxyl group is reduced, and a composition having higher conductivity can be obtained.

  In the first to fifth conductive compositions, the weight ratio of the phenolic compound to the solvent (phenolic compound [kg] / solvent [kg]) is preferably 0.0004 or more and 0.75 or less. . More preferably, it is 0.002 or more and 0.45 or less.

The π-conjugated conductive polymer contained in the first to fifth conductive compositions of the present invention preferably has a weight average molecular weight of 1,000 or more, more preferably 1,000 to 1,000,000. It is.
Specific examples of the π-conjugated conductive polymer include substituted or unsubstituted polyaniline, polypyrrole, polythiophene, poly (p-phenylene), poly (p-phenylene vinylene), and derivatives thereof.

The π-conjugated conductive polymer is doped with a dopant that is an electron-accepting substance such as Bronsted acid or Lewis acid.
Here, there is a doping rate with respect to the degree of doping. The doping rate is generally defined by (number of moles of dopant molecules doped in conductive polymer) / (monomer unit of conductive polymer). When the doped π-conjugated conductive polymer is a polyaniline complex, a dopant doping rate a of 0.5 means that one molecule of dopant is doped per two molecules of nitrogen. Preferably, however, the conductivity is highest at this value and in the vicinity thereof.

Here, when the π-conjugated conductive polymer contains a nitrogen atom and the dopant is a sulfonic acid, the composition of the present invention preferably satisfies the formula (XXX).
0.2 ≦ S ₁ / N ₁ ≦ 0.7 (XXX)
(S ₁ is the total number of moles of sulfur atoms of the π-conjugated conductive polymer doped with the dopant contained in the composition, and N ₁ is the π-conjugated system doped with the dopant contained in the composition. (The total number of moles of nitrogen atoms in the conductive polymer.)

Moreover, it is preferable that the electrical conductivity of the molded body of π-conjugated conductive polymer doped with a dopant is 0.01 S / cm or more. Conductivity is measured by the 4-terminal method. Here, a molded object can be obtained as follows.
“500 mg of π-conjugated conductive polymer doped with a dopant” is dissolved in 10 g of toluene to prepare a solution for measuring conductivity. As shown in FIG. 1, 1 ml of a conductivity measuring solution is applied to the upper surface of a glass substrate 1 on which an indium tin oxide (ITO) electrode 2 is formed by patterning. Specifically, it is applied by spin coating.

Here, the application by spin coating is performed in a nitrogen atmosphere. In addition, the rotation time of the glass substrate after dropping the conductivity measuring solution on the glass substrate by spin coating is 15 seconds. Moreover, the glass substrate rotation speed of the spin coating method is 500 rpm.
Thereafter, the glass substrate is dried to form a π-conjugated polymer thin film. Here, the drying is performed in a nitrogen atmosphere. The drying time is 5 minutes. The drying temperature is 80 ° C.

Here, the molded product refers to a molded product itself of a π-conjugated conductive polymer formed on a glass substrate. The conductivity is obtained as follows, for example.
After drying the π-conjugated polymer thin film, as shown in FIG. 2, the portion of the π-conjugated polymer thin film 3 covering the terminal of the ITO electrode is scraped off in a nitrogen atmosphere to expose the terminal of the ITO electrode on the surface. Using the ITO electrode terminal exposed on the surface, the conductivity is measured by a 4-terminal method using a resistivity meter manufactured by Mitsubishi Chemical Corporation.

  In the present invention, the doped π-conjugated conducting polymer is either a protonated substituted or unsubstituted polyaniline, a protonated substituted or unsubstituted polypyrrole, or a protonated substituted or unsubstituted polythiophene. In particular, a protonated substituted or unsubstituted polyaniline is preferred.

  When the π-conjugated conductive polymer is polyaniline, the weight average molecular weight of polyaniline is preferably 20,000 or more, more preferably 50,000 or more. If the weight molecular weight of polyaniline is less than 20,000, the strength and stretchability of the conductive article obtained from the composition may be reduced.

Moreover, molecular weight distribution is 1.5-10.0 or less, for example. From the viewpoint of electrical conductivity, a smaller molecular weight distribution is preferable, but from the viewpoint of solubility in a solvent and moldability, a wider molecular weight distribution may be preferable.
The molecular weight and molecular weight distribution can be measured by gel permeation chromatograph (GPC).

Examples of the substituent of the substituted polyaniline include linear or branched hydrocarbon groups such as methyl group, ethyl group, hexyl group and octyl group; alkoxyl groups such as methoxy group and phenoxy group; aryloxy group; CF ₃ group and the like And halogen-containing hydrocarbon groups.

The dopant preferably used in the present invention is an organic sulfonic acid, and can be used without any particular chemical structure limitation as long as the π-conjugated conductive polymer has sufficient acidity to generate carriers. Examples include alkyl sulfonic acids such as methane sulfonic acid and ethane sulfonic acid, aromatic sulfonic acids such as paratoluene sulfonic acid, dodecylbenzene sulfonic acid, isopropyl naphthalene sulfonic acid, and succinic sulfonic acids. A salt of these acids (such as a sodium salt) may be used.
It is known that by changing the structure of these dopants, the conductivity of the π-conjugated conductive polymer and the solubility in a solvent can be controlled (Japanese Patent No. 338466). In the present invention, an optimum dopant can be selected according to required characteristics for each application.

The π-conjugated conductive polymer is preferably doped with succinic sulfonic acids represented by the following (XX).
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (XX)
(In Formula (XX), M is a hydrogen atom, an organic free radical or an inorganic free radical, m is a valence of M, and R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) a group represented by _r- R ¹⁵ , R ¹⁴ is a hydrocarbon group or a silylene group, R ¹⁵ is a hydrogen atom, a hydrocarbon group or a group represented by R ¹⁶ ₃ Si—, R ¹⁶ is a hydrocarbon group, three R ¹⁶ may be the same or different, and r is an integer of 1 or more.)

In the conductive composition of the present invention, the weight ratio of the above-described phenolic compound to the π-conjugated conductive polymer (phenolic compound / π-conjugated conductive polymer) is 0.01 to 10.0, That is, it is 0.01 or more and 10.0 or less. If it is less than 0.01, the effect obtained by adding the phenolic compound may not be sufficiently exhibited. On the other hand, if it exceeds 10.0, the strength of the film obtained from the composition may be lowered. If it is this range, although a composition ratio can be arbitrarily set according to the required characteristic for every use, 0.05-5.0 are preferable from a viewpoint of the balance of electroconductivity and film | membrane intensity | strength.
In the conductive composition of the present invention, the weight ratio of the above-described phenolic compound to the π-conjugated conductive polymer is, for example, 2.5 or more and 5.0 or less, 2.5 or more and 4.0 or less. .

The composition of the present invention contains a solvent in addition to the above-described phenolic compound and π-conjugated conductive polymer. The solvent may be an inorganic solvent or an organic solvent, and is preferably an organic solvent. By containing an organic solvent, for example, a coating material for forming a conductive film can be obtained.
The organic solvent may be an organic solvent that is substantially immiscible with water (a water-immiscible organic solvent) or a water-soluble organic solvent.

  Examples of water-immiscible organic solvents include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; halogen-containing solvents such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, and tetrachloroethane; ethyl acetate and the like And ester solvents. Among these, toluene, xylene, chloroform, trichloroethane, and ethyl acetate are preferable in that the solubility of the doped polyaniline is excellent.

  Examples of the water-soluble organic solvent include alcohols; ketones such as acetone and methyl ethyl ketone; polar ethers such as tetrahydrofuran and dioxane; and aprotic polar solvents such as N-methylpyrrolidone.

As the organic solvent, it is preferable to use a mixed organic solvent of a water-immiscible organic solvent and a water-soluble organic solvent in a mass ratio of 99 to 50: 1 to 50. Thereby, when storing the composition of this invention, generation | occurrence | production of a gel etc. may be prevented.
A low polar organic solvent can be used as the water-immiscible organic solvent of the mixed organic solvent. For example, toluene and chloroform are preferable. Moreover, as a water-soluble organic solvent of a mixed organic solvent, a highly polar organic solvent can be used. For example, methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran or diethyl ether are preferable.

  The ratio of the π-conjugated conductive polymer in the organic solvent is usually 900 g / L or less, preferably 0.01 to 300 g / L or less, depending on the type of the organic solvent. If the content of the π-conjugated conductive polymer is too large, the solution state cannot be maintained, the handling of the molded body becomes difficult, the uniformity of the molded body is impaired, and consequently the electrical properties of the molded body And mechanical strength and transparency are reduced. On the other hand, if the content of the π-conjugated conductive polymer 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.

The composition of the present invention may comprise, for example, 1% by weight or more, 15% by weight or more, 45% by weight or more, and 100% by weight of the above-described π-conjugated conductive polymer, phenolic compound, and solvent.
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 resins are added as, for example, a binder base material, a plasticizer, a matrix base material, etc., and specific examples thereof include, for example, polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrenes, polyesters, polyamides, polyacetals, polyethylenes. Examples include terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, and polyvinyl alcohol. A chlorinated polyolefin is preferred.
Moreover, you may use the precursor which can form thermosetting resins, such as an epoxy resin, a urethane resin, a phenol resin, with resin instead of resin.

  Inorganic materials are added for the purpose of, for example, improving strength, surface hardness, dimensional stability and other mechanical properties. Specific examples thereof include silica (silicon dioxide), titania (titanium oxide), alumina ( Aluminum oxide) and the like.

  The curing agent is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, and specific examples thereof include, for example, thermosetting agents such as phenol resins, acrylate monomers and photopolymerization. Examples thereof include a photo-curing agent using a property initiator.

  The plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength, and specific examples thereof include phthalic acid esters and phosphoric acid esters.

  The composition of the present invention can be prepared by a known method, for example, by the method disclosed in WO05 / 052058.

A conductive molded body is obtained from the composition of the present invention.
For example, a conductive laminate (surface conductive article) having a conductive film by applying the composition of the present invention to a substrate such as glass, a resin film, a sheet or a nonwoven fabric having a desired shape and removing the solvent. ) Can be manufactured.
For example, a conductive article can be obtained by processing the conductive laminate of the present invention into a desired shape by a known method such as vacuum forming or pressure forming. From the viewpoint of molding, the substrate is preferably a resin film or sheet.

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

  When drying the coating film, the coating film may be heated depending on the type of the solvent. For example, it is heated at a temperature of 250 ° C. or lower, preferably 50 to 200 ° C. under an air stream, and further heated under reduced pressure as necessary. The heating temperature and the heating time are not particularly limited and may be appropriately selected depending on the material to be used.

  For example, a conductive film can be manufactured by removing a solvent from the composition of this invention. When the molded product of the present invention is a film or a film, the thickness is usually 1 mm or less, preferably 10 nm to 50 μm. 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.

  Moreover, the composition of this invention is good also as a conductive article by mixing with a base material. Thermoplastics such as polyolefin such as polyethylene and polypropylene, chlorinated polyolefin, polystyrene, polyester, polyamide, polyacetal, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol Examples of the resin include thermosetting resins such as epoxy resins, phenol resins, and urethane resins.

  Furthermore, the composition of this invention can also be made into the self-supporting molded object which does not have a base material. 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.

Production Example 1
[Production of Polyaniline Complex 1]
1.8 g of AOT (sodium diisooctylsulfosuccinate) was dissolved in 50 mL of toluene, and the solution was put into a 500 mL separable flask placed under a nitrogen stream, and 1.8 mL of aniline was further added to this solution. Thereafter, 150 mL of 1N hydrochloric acid was added to the solution, and the solution temperature was cooled to 5 ° C.
When the internal temperature of the solution reached 5 ° C., a solution obtained by dissolving 3.6 g of ammonium persulfate in 50 mL of 1N hydrochloric acid was dropped over 2 hours using a dropping funnel. The reaction was carried out while maintaining the internal temperature of the solution at 5 ° C. for 18 hours from the start of dropping. Thereafter, 125 mL of toluene was added, the reaction temperature was raised to 25 ° C., and the reaction was continued for 4 hours.
Then, the aqueous phase side separated into two phases by standing was separated, and the toluene phase side was washed twice with 50 mL of ion-exchanged water and once with 50 mL of 1N hydrochloric acid to give a polyaniline complex (protonated polyaniline). ) A toluene solution was obtained.
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 1.25 g of a polyaniline complex.

Production Example 2
[Production of Polyaniline Complex 2]
(1) Synthesis of sodium 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonate 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) ester (manufactured by Tokyo Chemical Industry Co., Ltd.) under an argon gas stream 80 g and 900 mL of isopropyl alcohol were charged, and a solution of 42.3 g of sodium hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) in 660 mL of water was added. The solution was heated to reflux temperature and stirred at 80-83 ° C. for 16 hours. During this time, 1.66 g of 2,2′-azobis (isobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) was added every hour from the start of reflux to 1 to 5 hours later, then 9 hours and 10 hours later. did. The reaction solution was cooled to room temperature and then concentrated under reduced pressure. The concentrated residue was dissolved in 1 L of an ethyl acetate / hexane mixed solution, 250 g of silica gel was added and stirred, and the solution was separated by filtration.
Further, extraction was performed twice from silica gel with 1 L of ethyl acetate / hexane solution, and the filtrates were combined and concentrated under reduced pressure. This concentrated solution was purified by column chromatography (silica gel 1500 g, developing solvent: ethyl acetate / hexane), and the purified product was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure, whereby 3,4-bis [(2- Ethylhexyl) oxycarbonyl] sodium cyclohexanesulfonate (Na salt of compound A represented by the following formula) was obtained 52.4 g.

(2) Production of polyaniline complex In production example 1, 2.0 g of sodium 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonate synthesized in (1) above was used instead of 1.8 g of AOT. In the same manner as in Production Example 1, 1.32 g of a polyaniline complex was obtained.

Example 1
0.1 g of polyaniline complex 1 obtained in Production Example 1 was redissolved in toluene to prepare a 5% by weight solution. 0.02 g of 4-methoxyphenol (LD50 = 1600 mg / kg) was added thereto, and the mixture was stirred and mixed at room temperature for 30 minutes. This solution was formed into a film by a spin coat method, formed on an ITO (indium tin oxide) substrate by a spin coat method, and the intrinsic conductivity was measured by a four-terminal method.

  Specifically, about 1 ml of this solution was applied on the upper surface of the glass substrate 1 on which the ITO electrode 2 was formed by patterning as shown in FIG. Here, application by spin coating was performed in a nitrogen atmosphere. Moreover, the glass substrate rotation time after dripping this solution on the glass substrate of the spin coat method was 15 seconds. The glass substrate rotation speed in the spin coating method was 500 rpm. Thereafter, the glass substrate was dried to form a conductive polyaniline thin film. Here, drying was performed in a nitrogen atmosphere. The drying time was 5 minutes. The drying temperature was 80 ° C.

  After the conductive polyaniline thin film was dried, as shown in FIG. 3, the portion of the conductive polyaniline thin film 4 covering the ITO electrode terminal was scraped off under a nitrogen atmosphere to expose the ITO electrode terminal on the surface. Using the ITO electrode terminal exposed on the surface, the intrinsic conductivity was measured using a Lorester GP (Mitsubishi Chemical Co., Ltd .; resistivity meter by the four-terminal method).

Example 2
A film was formed in the same manner as in Example 1 except that the amount of 4-methoxyphenol added was 0.4 g, and the intrinsic conductivity was measured.

Example 3
A film was formed in the same manner as in Example 1 except that the amount of 4-methoxyphenol added was 0.001 g, and the intrinsic conductivity was measured.

Example 4
A film was formed in the same manner as in Example 1 except that the amount of 4-methoxyphenol added was 1.0 g, and the intrinsic conductivity was measured.

Example 5
A film was formed in the same manner as in Example 1 except that 0.02 g of 3-methoxyphenol (LD50 = 597 mg / kg) was used instead of 4-methoxyphenol, and the intrinsic conductivity was measured.

Example 6
A film was formed in the same manner as in Example 3 except that 0.4 g of 3-methoxyphenol was used, and the intrinsic conductivity was measured.

Reference example 1
A film was formed in the same manner as in Example 1 except that 0.02 g of 3-phenoxyphenol (LD50 = 5000 mg / kg) was used instead of 4-methoxyphenol, and the intrinsic conductivity was measured.

Reference example 2
A film was formed in the same manner as in Example 5 except that 0.4 g of 3-phenoxyphenol was used, and the intrinsic conductivity was measured.

Example 7
0.1 g of polyaniline complex 2 obtained in Production Example 2 was redissolved in toluene to prepare a 5 wt% solution. 0.02g 4-methoxyphenol was added here, and it stirred and mixed at room temperature for 30 minutes. This solution was formed into a film by a spin coat method, formed on an ITO (indium tin oxide) substrate by a spin coat method, and the intrinsic conductivity was measured by a four-terminal method.

Comparative Example 1
A film was formed in the same manner as in Example 1 except that 4-methoxyphenol was not added, and the intrinsic conductivity was measured.

Comparative Example 2
A film was formed in the same manner as in Example 1 except that the amount of 4-methoxyphenol added was 0.0005 g, and the intrinsic conductivity was measured.

Comparative Example 3
A film was formed in the same manner as in Example 1 except that the amount of 4-methoxyphenol added was 2.0 g. However, the film itself was extremely fragile and the conductivity could not be measured.

Comparative Example 4
A film was formed in the same manner as in Example 1 except that 0.4 g of m-cresol (LD50 = 242 mg / kg) was added instead of 4-methoxyphenol, and the intrinsic conductivity was measured.
Table 1 shows the measurement results of the compositions and intrinsic conductivities of the conductive compositions of Examples and Comparative Examples described above.

  The conductive composition of the present invention is used in the field of power electronics and optoelectronics. Electrostatic and antistatic materials, transparent electrodes and conductive film materials, electroluminescent element materials, circuit materials, electromagnetic wave shielding materials, capacitor dielectrics and It can be used for electrolytes, solar cell and secondary battery electrode materials, fuel cell separator materials, etc., plating bases, rust inhibitors, and the like.

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The entire contents of the documents described in this specification are incorporated herein by reference.

Claims (15)

solvent,
A π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and a phenolic compound represented by the following formula (2):
The dopant is one or more selected from succinic sulfonic acids and alkylsulfonic acids,
Conductive composition having a weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π-conjugated conductive polymer [kg]) of 0.01 to 10.0. .

(Wherein, _{R 2} is an alkyl group, an alkenyl group, or a cycloalkyl group having 1 to 20 carbon atoms.) At least the following (a) to (c) are used as raw materials,
The weight ratio of the following phenolic compound (c) and the following π-conjugated conductive polymer (b) (phenolic compound [kg] / π-conjugated conductive polymer [kg]) is 0.01 to 10.0. A conductive composition.
(A) Solvent (b) A π-conjugated conductive polymer doped with a dopant that dissolves in the solvent , wherein the dopant is one or more selected from succinic sulfonic acids and alkylsulfonic acids. Conjugated conductive polymer (c) Phenolic compound represented by the following formula (2)

(Wherein, _{R 2} is an alkyl group, an alkenyl group, or a cycloalkyl group having 1 to 20 carbon atoms.) 3. The conductive composition according to claim 1, wherein the phenolic compound (c) has an LD50 of 500 [mg / kg] or more. The doped π-conjugated conductive polymer is either a protonated substituted or unsubstituted polyaniline, a protonated substituted or unsubstituted polypyrrole, or a protonated substituted or unsubstituted polythiophene. The electrically conductive composition as described in any one of 1-3 . The conductive composition according to any one of claims 1 to 4 , wherein the alkylsulfonic acid is a compound represented by the following formula .

The conductive composition according to any one of claims 1 to 4 , wherein the succinic sulfonic acids are succinic sulfonic acids represented by the following (XX).
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (XX)
(In Formula (XX),
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 a hydrogen atom. , A hydrocarbon group or a group represented by R ¹⁶ ₃ Si—, R ¹⁶ is a hydrocarbon group, three R ¹⁶ may be the same or different, and r is an integer of 1 or more. ) The electrical conductivity according to any one of claims 1 to 6 , wherein a weight ratio of the phenolic compound to the solvent (phenolic compound [kg] / solvent [kg]) is 0.0004 or more and 0.75 or less. Composition. Substrate, and electroconductive laminate comprising a conductive layer made of a conductive composition according to any one of claims 1 to 7 which is laminated on the substrate. The conductive laminate according to claim 8 , wherein the substrate is a resin film. The electroconductive article obtained by shape | molding the electroconductive laminated body of Claim 8 or 9 . Capacitor produced using the conductive composition according to any one of claims 1-7. Conductive films obtained by molding a conductive composition according to any one of claims 1-7. Conductive films obtained by molding a conductive composition according to any one of claims 1-7. Conductive composition and the conductive article comprising a mixture of base material according to any one of claims 1-7. a π-conjugated conductive polymer, and a phenolic compound represented by the following formula (1):
The weight ratio of the phenolic compound and the π-conjugated conductive polymer (phenolic compound / π-conjugated conductive polymer) is 0.01 to 10.0,
The π-conjugated conductive polymer is a protonated substituted or unsubstituted polyaniline,
A conductive composition in which the π-conjugated conductive polymer is doped with one or more selected from succinic sulfonic acids and alkylsulfonic acids .

(Wherein, R is an alkyl group, an alkenyl group, or a cycloalkyl group having 1 to 20 carbon atoms.)

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