JP2010067448A - Manufacturing method of conductor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a conductor in which the conductor in which conductivity is improved can be obtained. <P>SOLUTION: In the manufacturing method of the electric conductor, a process in which a conductive compound containing water-soluble conductive polymer having sulfonic acid group and/or carboxyl group (A), basic compound (B), and a solvent (C) is coated on a base material to form a coated film, and a process in which the coated film is heat-treated under 125 to 180&deg;C are carried out sequentially. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for manufacturing a conductor.

As a conductive polymer, doped polyaniline is well known. As a production method thereof, a method of polymerizing an acidic group-substituted aniline such as a sulfonic acid group-substituted aniline or a carboxy group-substituted aniline in a solution containing a basic compound (for example, Patent Documents 1 and 2) has been proposed. These methods have the advantage that a high molecular weight polymer can be produced, contrary to the conventional theory that anilines having a sulfonic acid group or a carboxy group are difficult to polymerize by themselves and it is difficult to obtain a high molecular weight polymer. Have. Moreover, the conductive polymer obtained by this method exhibits excellent dissolution in any acidic to alkaline aqueous solution.
However, this method does not completely suppress side reactions and by-product formation of oligomer components that are considered to be based on this, and this impedes impurity contamination into the conductive polymer and improvement in conductivity. ing. Further, there is a problem that the impurity removal process becomes complicated due to the mixing of impurities.

In order to solve these problems, when an acidic group-substituted aniline is polymerized in a solution containing a basic compound, a solution containing the acidic group-substituted aniline and the basic compound in a solution of an oxidizing agent as a polymerization catalyst. There has been proposed a method capable of suppressing the generated impurities by dropping (see Patent Document 3). In this method, formation of oligomer components can be suppressed, and an acidic group-substituted aniline conductive polymer having high purity and high conductivity can be obtained.
JP-A-7-196791 JP 7-324132 A JP 2000-219739 A

However, even in the above method, the improvement in conductivity is insufficient, and further improvement is required.
This invention is made | formed in view of the said situation, Comprising: It aims at providing the manufacturing method of the conductor from which the conductor with improved electroconductivity is obtained.

As a result of intensive studies, the inventor has found that the basic compound contained in the conductive composition containing a conductive polymer having a sulfonic acid group and / or a carboxy group forms a salt with the conductive polymer, and the conductive It has been found that self-doping of the polymer is inhibited and the original conductivity is inhibited. And it discovered that this basic compound was fully removed by heating this electroconductive composition at specific temperature, and the electroconductivity of the conductor obtained was improved greatly, and completed this invention.
That is, in the present invention, a conductive composition containing a water-soluble conductive polymer (A) having a sulfonic acid group and / or a carboxy group, a basic compound (B), and a solvent (C) is applied to a substrate and applied. It is the manufacturing method of the conductor which performs the process of forming a film | membrane, and the process of heat-processing with respect to the said coating film at 125-180 degreeC sequentially.

  According to the method for producing a conductor of the present invention, a conductor having improved conductivity can be obtained.

<Conductive composition>
The conductive composition used in the present invention comprises a water-soluble conductive polymer (A) having a sulfonic acid group and / or a carboxy group (hereinafter referred to as component (A)), a basic compound (B) (hereinafter referred to as component). (B)), and a solvent (C).

(Ingredient (A))
“Water-soluble” in component (A) means that it is uniformly dissolved in water at 25 ° C. by about 0.1 g or more.
The component (A) has a sulfonic acid group (—SO ₃ H) and / or a carboxy group (—COOH). In the component (A), each of the sulfonic acid group and the carboxy group may be contained in an acid state (—SO ₃ H, —COOH), or in an ionic state (—SO ₃ ^— , —COO ⁻ ). It may be included.
The component (A) has at least one repeating unit selected from the group consisting of repeating units represented by the following general formulas (1) to (3) (hereinafter referred to as repeating unit (a1)). preferable.

In formula (1), R ^{1 to} R ² each independently represent —H, —SO ₃ ^— , —SO ₃ H, —R ¹¹ SO ₃ ^— , —R ¹¹ SO ₃ H, —OCH ₃ , —CH. ^{_{3, -C 2 H 5, -F}} , -Cl, -Br, -I, -N (R 12) 2, -NHCOR 12, -OH, -O -, -SR 12, -OR 12, -OCOR 12 , —NO ₂ , —COOH, —R ¹¹ COOH, —COOR ¹² , —COR ¹² , —CHO or —CN, wherein R ¹¹ is an alkylene group having 1 to 24 carbon atoms or an arylene group having 1 to 24 carbon atoms. or an aralkylene group having 1 to 24 carbon ^{atoms, R 12} is an alkyl group, an aralkyl group an aryl group or a 1 to 24 carbon atoms having 1 to 24 carbon atoms having 1 to 24 carbon atoms, ^{R 1} and ^{R 2} At least one of _the, ^-SO 3 _-, -S _{^{3 H, -R 11 SO 3 -}} , a _-R 11 SO 3 H, -COOH or ^-R 11 COOH.

In formula (2), R ^{3 to} R ⁶ each independently represent —H, —SO ₃ ^— , —SO ₃ H, —R ¹¹ SO ₃ ^— , —R ¹¹ SO ₃ H, —OCH ₃ , —CH. ^{_{3, -C 2 H 5, -F}} , -Cl, -Br, -I, -N (R 12) 2, -NHCOR 12, -OH, -O -, -SR 12, -OR 12, -OCOR 12 , —NO ₂ , —COOH, —R ¹¹ COOH, —COOR ¹² , —COR ¹² , —CHO or —CN, wherein R ¹¹ is an alkylene group having 1 to 24 carbon atoms or an arylene group having 1 to 24 carbon atoms. or an aralkylene group having 1 to 24 carbon ^{atoms, R 12} is an alkyl group, an aralkyl group an aryl group or a 1 to 24 carbon atoms having 1 to 24 carbon atoms having 1 to 24 carbon ^atoms, R 3 to R ⁶ At least one of _the, ^-SO 3 _-, ^{-SO H,} -R ₁₁ ^SO 3 ^-, a _-R 11 SO 3 H, -COOH or ^-R 11 COOH.

In formula (3), R ^{7 to} R ¹⁰ each independently represent —H, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. , Hydroxyl group, nitro group, -F, -Cl, -Br or -I, and at least one of R ^{7 to} R ¹⁰ is an acidic group.
Here, the “acidic group” represents a sulfonic acid group or a carboxy group. That is, in formula (3), at least one of R ^{7 to} R ¹⁰ is —SO ₃ ^— , —SO ₃ H, —COOH, or —COO ^— .
In terms of easy production, any one of R ^{7 to} R ¹⁰ is a linear or branched alkoxy group having 1 to 4 carbon atoms, and any one of them is —SO ₃ ^— or —SO ₃ H. And the remainder being H is preferred.

In the component (A), the proportion of the repeating unit (a1) is preferably 20 to 100 mol%, more preferably 50 to 100 mol%, of all repeating units (100 mol%) constituting the component (A). 100 mol% is more preferable.
The component (A) preferably has 10 or more repeating units (a1) in one molecule.

5000-1 million are preferable and, as for the mass average molecular weight of a component (A), 5000-20000 are more preferable. When the mass average molecular weight of the component (A) is 5000 or more, the conductivity, film formability and film strength are excellent. If the mass average molecular weight of a component (A) is 1 million or less, it is excellent in the solubility to a solvent.
The mass average molecular weight of the component (A) is a mass average molecular weight (in terms of polyethylene glycol) measured by gel permeation chromatography (GPC).

(Ingredient (B))
The component (B) is used when oxidative polymerization of a monomer as a raw material of the component (A) such as an acidic group-substituted aniline in a solution. It remains and is contained in the conductive composition. As a component (B), the basic compound of the said patent document 3 is mentioned, for example. In the present invention, the component (B) is particularly preferably an amine.
In the present invention, the component (B) is preferably a basic compound having a pKa at 25 ° C. of 10 or less in that it easily evaporates from the conductive composition during the heat treatment in the next step. The pKa is more preferably 8 or less. The pKa is preferably 4 or more, more preferably 5 or more, from the viewpoint of the solubility of the component (A).
As the pKa, a numerical value described in “Chemical Handbook Basics II” (edited by the Chemical Society of Japan, Maruzen, issued on September 25, 1966) can be used.

  Specific examples of basic compounds having a pKa of 10 or less include 2-aminoethanol (pKa = 9.5), diethanolamine (pKa = 9.0), triethanolamine (pKa = 7.7), trimethylamine (pKa = 9.8), α-picoline (pKa = 6.2), β-picoline (pKa = 5.5), γ-picoline (pKa = 6.0), pyridine (pKa = 5.2), benzylamine ( pKa = 9.4), methoxyethylamine (9.2), aminopyridine (6.7), ethylenediamine (6.84) and the like. Any one of these amines may be used alone, or two or more thereof may be mixed and used.

(Solvent (C))
The solvent (C) is not particularly limited as long as it can dissolve the component (A) and the component (B), and examples thereof include water or a mixed solvent of water and a water-soluble organic solvent.
When a mixed solvent is used, the mixing ratio of water and the water-soluble organic solvent is not particularly limited and is arbitrary, but usually a mixed solvent of water: water-soluble organic solvent = 1: 100 to 100: 1 is preferably used. It is done.
The water-soluble organic solvent is not particularly limited as long as it is mixed with water. Specific examples of water-soluble organic solvents include water, alcohols such as methanol, ethanol, isopropanol, propanol, and butanol, ketones such as acetone and ethyl isobutyl ketone, and ethylene glycols such as ethylene glycol and ethylene glycol methyl ether. , Propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether, amides such as dimethylformamide and dimethylacetamide, pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone And the like. Among these, alcohols, acetone, acetonitrile, dimethylformamide, dimethylacetamide and the like are preferable, and alcohols are particularly preferable. As alcohols, methanol, ethanol, isopropanol and the like are preferably used.
As the solvent (C), water or a mixed solvent of water and alcohols is particularly preferable. Moreover, it is preferable that this mixed solvent contains 50 mass% or more of water.

  A known additive can be arbitrarily mixed in the conductive composition. As the additive, those that improve the coating property to a substrate, film-forming property, film-forming property, adhesion, etc. are preferable. For example, nonionic surfactants, anionic surfactants, cationic surfactants, Examples thereof include water-soluble polymers and emulsion polymers.

In the conductive composition, for example, a monomer that is polymerized to give component (A) is polymerized (oxidative polymerization) using an oxidizing agent in the presence of component (B), and the resulting product is solvent (C ).
For example, the water-soluble conductive polymer having a repeating unit represented by the general formula (3) can be obtained by polymerizing a compound (acid group-substituted aniline) represented by the following general formula (3a).

Wherein ^{(3a), R} 17 ~R ²⁰ are each independently, -H, a linear or branched alkyl group having 1 to 24 carbon atoms, straight-chain or branched alkoxy group having 1 to 24 carbon atoms, acidic groups , Hydroxyl group, nitro group, -F, -Cl, -Br or -I, and at least one of R ^{17 to} R ²⁰ is an acidic group. The acidic group is the same as the acidic group in the formula (3).

Examples of the acidic group-substituted aniline include a sulfonic acid group-substituted aniline having a sulfonic acid group as an acidic group, and a carboxy group-substituted aniline having a carboxy group as an acidic group.
A typical example of the sulfonic acid group-substituted aniline is an aminobenzenesulfonic acid derivative. Representative examples of the carboxy group-substituted aniline include aminobenzoic acid derivatives. Of these, aminobenzenesulfonic acid derivatives tend to have higher conductivity than aminobenzoic acid derivatives, while aminobenzoic acid derivatives tend to be more soluble than aminobenzenesulfonic acid derivatives. These derivatives can also be used by mixing at an arbitrary ratio according to the purpose.

  Examples of sulfone group-substituted anilines include o-, m- or p-aminobenzenesulfonic acid, aniline-2,6-disulfonic acid, aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, and aniline-2. Aminobenzenesulfonic acids such as 1,4-disulfonic acid and aniline-3,4-disulfonic acid; methylaminobenzenesulfonic acid, ethylaminobenzenesulfonic acid, n-propylaminobenzenesulfonic acid, iso-propylaminobenzenesulfonic acid, n -Alkyl group-substituted aminobenzenesulfonic acids such as butylaminobenzenesulfonic acid, sec-butylaminobenzenesulfonic acid, t-butylaminobenzenesulfonic acid; methoxyaminobenzenesulfonic acid, ethoxyaminobenzenesulfonic acid, propoxyaminobenzenesulfone Alkoxy group-substituted aminobenzenesulfonic acids such as acids; Hydroxy group-substituted aminobenzenesulfonic acids; Nitro group-substituted aminobenzenesulfonic acids; Halogen-substituted aminobenzenes such as fluoroaminobenzenesulfonic acid, chloroaminobenzenesulfonic acid, and bromoaminobenzenesulfonic acid Sulfonic acids; and the like. Of these, aminobenzene sulfonic acids, alkyl group-substituted aminobenzene sulfonic acids, alkoxy group-substituted aminobenzene sulfonic acids, hydroxy group-substituted aminobenzene sulfonic acids and the like are preferred in practice. These sulfonic acid group-substituted anilines may be used alone or in a mixture of two or more at any ratio.

  Carboxy group-substituted anilines include o-, m- or p-aminobenzenecarboxylic acid, aniline-2,6-dicarboxylic acid, aniline-2,5-dicarboxylic acid, aniline-3,5-dicarboxylic acid, aniline-2. Aminobenzene carboxylic acids such as 1,4-dicarboxylic acid and aniline-3,4-dicarboxylic acid; methylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid, n-propylaminobenzenecarboxylic acid, iso-propylaminobenzenecarboxylic acid, n Alkyl group-substituted aminobenzene carboxylic acids such as butylaminobenzene carboxylic acid, sec-butylaminobenzene carboxylic acid, t-butylaminobenzene carboxylic acid; methoxyaminobenzene carboxylic acid, ethoxyaminobenzene carboxylic acid, propoxyaminobenzene carboxylic acid Alkoxy group-substituted aminobenzene carboxylic acids such as acids; Hydroxy group-substituted aminobenzene carboxylic acids; Nitro group-substituted aminobenzene carboxylic acids; Halogen group substitution such as fluoroaminobenzene carboxylic acid, chloroaminobenzene carboxylic acid, bromoaminobenzene carboxylic acid, etc. Aminobenzene carboxylic acids; and the like. Of these, aminobenzene carboxylic acids, alkyl group-substituted aminobenzene carboxylic acids, alkoxy group-substituted aminobenzene carboxylic acids, hydroxy group-substituted aminobenzene carboxylic acids and the like are preferred in practice. These carboxy group-substituted anilines may be used alone or in a mixture of two or more at any ratio.

  In the above oxidative polymerization, the amount of the component (B) used is preferably 0.5 to 3 mol, preferably 0.5 to 2 mol with respect to 1 mol of the monomer, in that the conductivity of the component (A) to be obtained is improved. Is more preferable.

The oxidizing agent used for the oxidative polymerization is not particularly limited as long as the standard electrode potential is 0.6 V or more, but peroxodisulfuric acid such as peroxodisulfuric acid, ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate. And hydrogen peroxide are preferably used. Any one of these oxidizing agents may be used alone, or two or more thereof may be used in combination.
1-5 mol is preferable with respect to 1 mol of monomers, and, as for the usage-amount of an oxidizing agent, 1-3 mol is more preferable.

More specifically, as a polymerization method, a method in which a monomer solution is dropped into an oxidant solution, a method in which an oxidant solution is dropped into a monomer solution, and a reaction in which an oxidant solution and a monomer solution are simultaneously dropped into another reactor. A method is mentioned.
At this time, it is also effective to add a transition metal compound such as iron or copper as a catalyst.
The polymerization is preferably performed while stirring the inside of the polymerization system. Stirring is usually preferably performed at a stirring power of 0.01 to 5 kw / m ³ .
The reaction temperature during polymerization is preferably 50 ° C. or lower, more preferably −15 to 50 ° C., and further preferably −10 to 40 ° C. If the reaction temperature exceeds 50 ° C., the conductivity may decrease due to the progress of side reactions or the change in the redox structure of the main chain. Moreover, if it is less than -15 degreeC, reaction time may become long.

After polymerization, unreacted monomers are dissolved in the obtained reaction solution. Therefore, operation which isolate | separates a product from this reaction liquid is performed. As the separation device used at this time, vacuum filtration, pressure filtration, centrifugal separation, centrifugal filtration or the like is used, and it is particularly preferable to use a separation device such as centrifugal separation or centrifugal filtration because a high-purity one can be easily obtained. .
After separation, the product obtained may be purified. Purification can be carried out using a washing solvent, which includes alcohols such as methanol, ethanol, iso-propanol, n-propanol, t-butanol, acetone, acetonitrile, N, N-dimethylformamide, N- Methyl pyrrolidone, dimethyl sulfoxide, and the like are preferable because high-purity ones can be obtained. In particular, methanol, ethanol, iso-propanol, acetone, and acetonitrile are effective.

In the product obtained as described above, the component (A) and the component (B) are present in the form of a salt. Therefore, the electroconductive composition used for this invention is obtained by melt | dissolving this in a solvent (C).
In the conductive composition, the content of the component (A) is preferably 0.5 to 10 parts by mass and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the solvent (C). When the content is 0.5 parts by mass or more, sufficient conductivity is obtained, and when it is 10 parts by mass or less, the viscosity of the conductive composition can be prevented from becoming too high, and the handling is easy. .
In the conductive composition, the content of the component (B) is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A). The solubility of a component (A) improves that this content is 1 mass part or more, and electroconductivity improves that it is 30 mass parts or less.

In the present invention, the conductor is obtained by sequentially performing a step of applying the conductive composition to a substrate to form a coating film, and a step of heat-treating the coating film at 125 to 180 ° C. To manufacture.
The base material on which the conductive composition is applied is not particularly limited, and polymer compounds, wood, paper materials, ceramics, and films or glass plates thereof are used. For example, as a base material made of a polymer compound, polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyamide, polyimide, polyaramid, polyphenylene sulfide, Examples thereof include polymer films containing any one or more of polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, and the like. Since these polymer films form a conductive film made of the conductive composition on at least one surface thereof, the film surface is subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the conductive film. Is preferably applied.

  As a method for coating the conductive composition, a method generally used for coating a paint can be used. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fan ten coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc. A spraying method such as coating or a dipping method such as dip is used.

As for the heat processing with respect to the said coating film, 125-180 degreeC is preferable.
When the temperature of the heat treatment is 125 ° C. or higher, the heat treatment can volatilize the component (A) and the component (B) forming a salt, and a conductor exhibiting high conductivity is obtained. It is done. On the other hand, when the temperature is lower than 125 ° C., the volatilization of the component (B) from the conductive composition is not sufficient and the conductivity is not sufficiently exhibited. When this temperature exceeds 180 degreeC, a decomposition | disassembly of a component (A) will arise and there exists a possibility of generating acidic gas.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[Production Example 1 (Production of polymer powder (1))]
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 30 ml of water: acetonitrile = 5: 5 solution of N, N-dimethylaniline at a concentration of 4 mol / l at 0 ° C. (120 mmol of N, N-dimethylaniline). The solution was dropped into 100 ml of a water: acetonitrile 5: 5 solution containing 100 mmol of ammonium sulfate under cooling. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered with a centrifugal filter, washed with methyl alcohol and dried to obtain 12 g of polymer powder (1).

[Production Example 2 (Production of polymer powder (2))]
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 30 ml of water: acetonitrile 3: 7 solution of pyridine at a concentration of 4 mol / l at 0 ° C. (120 mmol of pyridine), and water: acetonitrile 3: 7 solution containing 100 mmol of ammonium peroxodisulfate. It was dripped in 100 ml under cooling. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered off with a centrifugal filter, washed with methyl alcohol and dried to obtain 16 g of polymer powder (2).

[Production Example 3 (Production of polymer powder (3))]
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 30 ml of water: acetonitrile 3: 7 solution of α-picoline at a concentration of 4 mol / l at 0 ° C. (120 mmol of α-picoline), and water containing 100 mmol of ammonium peroxodisulfate: acetonitrile The solution was dropped into 100 ml of 3: 7 solution under cooling. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered off with a centrifugal filter, washed with methyl alcohol and dried to obtain 16 g of polymer powder (3).

[Production Example 4 (Production of polymer powder (4))]
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 30 ml of water: acetonitrile 3: 7 solution of triethanolamine at a concentration of 4 mol / l at 0 ° C. (120 mmol of triethanolamine), and water containing 100 mmol of ammonium peroxodisulfate: acetonitrile The solution was added dropwise to 100 ml of a 7: 3 solution under cooling. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered with a centrifugal filter, washed with methyl alcohol and dried to obtain 12 g of polymer powder (4).

[Production Example 5 (Production of polymer powder (5))]
100 mmol of 2-aminoanisole-4-sulfonic acid is dissolved in 30 ml of water: acetonitrile 3: 7 solution of diethanolamine at a concentration of 4 mol / l at 0 ° C. (120 mmol of diethanolamine), and water: acetonitrile 7: 3 solution containing 100 mmol of ammonium peroxodisulfate It was dripped in 100 ml under cooling. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered off with a centrifugal filter, washed with methyl alcohol and dried to obtain 11 g of polymer powder (5).

[Production Example 6 (Production of polymer powder (6))]
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 30 ml of water: acetonitrile 3: 7 solution of triethylamine at a concentration of 4 mol / l at 0 ° C. (120 mmol of triethylamine), and water: acetonitrile 3: 7 solution containing 100 mmol of ammonium peroxodisulfate. It was dripped in 100 ml under cooling. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered with a centrifugal filter, washed with methyl alcohol and dried to obtain 17 g of polymer powder (1).

[Production Example 7 (Production of polymer powder (7))]
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 30 ml of water: acetonitrile = 5: 5 solution of diethylamine at a concentration of 4 mol / l at 0 ° C. (120 mmol of diethylamine), and water containing 100 mmol of ammonium peroxodisulfate: acetonitrile 5: 5 The solution was dropped into 100 ml of the solution under cooling. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered with a centrifugal filter, washed with methyl alcohol and dried to obtain 16 g of polymer powder (7).

[Preparation Examples 1 to 7]
(1. Preparation of conductive composition)
At room temperature, the polymer powders shown in Table 1 were dissolved in the solvent (C) in the blending amounts shown in Table 1 to prepare conductive compositions 1 to 7.
Moreover, in Table 1, the kind of component (B) used for manufacture of each polymer powder and its pKa are written together.

[Test Example 1 (Electrical conductivity evaluation)]
After spin coating application (500 rpm × 5 seconds + 2000 rpm × 60 seconds) of each of the conductive compositions 1 to a glass substrate, heat treatment was performed for 2 minutes at a temperature shown in Table 2 on a hot plate to obtain a film thickness of about A conductive film was obtained by forming a 0.1 μm conductive film.
The surface resistance value of the obtained conductor was measured by a two-terminal method (distance between electrodes 20 mm) using Hiresta MCP-HT260 (Mitsubishi Chemical Corporation). The results are shown in Table 2. Further, from the results, a graph was created with the temperature of the heat treatment (baking temperature) on the horizontal axis and the surface resistance value on the vertical axis. The graph is shown in FIG.
From these results, it was confirmed that when the baking temperature was 125 ° C. or higher, the surface resistance value of the obtained conductive film was drastically decreased and the conductivity was improved.

[Test Example 2 (Evaluation of Volatile State)]
For the conductive composition 2 (using pyridine as the component (B)) and the conductive composition 6 (using triethylamine as the component (B)), the following measurement was performed using a heat generation gas mass spectrometry (EGA-MS) method. Under the conditions, analysis of the volatile state of component (B) was performed. The results are shown in FIGS.
(Measurement condition)
Measurement temperature: 50 ° C. to 200 ° C. (heating rate 5 ° C./min)

FIG. 2 shows the result of observing the volatilization of typical ions (m / z) = 79 of pyridine (pka = 5.2, boiling point 115 ° C.) with respect to the conductive composition 2 by EGA-MS. FIG. 3 is a result of observing the volatilization of typical ions (m / z) = 86 of triethylamine (pka = 10.9, boiling point 90 ° C.) with respect to the conductive composition 6 by EGA-MS.
From these results, it was confirmed that pyridine in the conductive composition 2 began to evaporate from around 70 ° C., and most of the pyridine was removed in a temperature range of 125 to 180 ° C.
On the other hand, it was confirmed that triethylamine in the conductive composition 6 was less likely to volatilize than pyridine and was likely to remain in the conductive composition after heating.
From these results, it was shown that a basic compound having a pKa of 10 or less can be easily removed by heating at 125 to 180 ° C. as compared with a basic compound having a pKa of more than pKa10. Since the basic compound remaining in the conductor is considered to adversely affect the conductivity, a basic compound having a pKa of 10 or less is suitable as the component (B).

In Test Example 1, for conductive compositions 1 to 7, the horizontal axis represents the baking temperature (° C.), and the vertical axis represents the surface resistance value (Ω) of the conductor. In Test Example 2, the conductive composition 2 is the result of observing the volatilization of pyridine (pka = 5.2, boiling point 115 ° C.) by EGA-MS. In Test Example 2, the conductive composition 6 was observed by volatilization of triethylamine (pka = 10.9, boiling point 90 ° C.) by EGA-MS.

Claims (1)

  A step of applying a conductive composition containing a water-soluble conductive polymer (A) having a sulfonic acid group and / or a carboxy group, a basic compound (B), and a solvent (C) to a substrate to form a coating film And the manufacturing method of the conductor which performs sequentially the process of heat-processing with respect to the said coating film at 125-180 degreeC.

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