JP2007254730A - Electroconductive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive composition easily miscible with conventional resin solutions, which is stably dispersed and emulsified in a solvent giving only low load to the environment in a drying process. <P>SOLUTION: The electrical conductive composition comprises an ion pair of a polyanion (b) doped in a π-conjugated type electroconductive polymer (a) with a basic organic compound (c) which is dispersed in a solvent containing an organic solvent. By using the electrical conductive composition of the present invention, a transparent electroconductive film being remarkably excellent in transparency and resistance characteristics can be produced. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive composition, and more particularly to a conductive composition that is stably dispersed and emulsified in an organic solvent, and the conductive composition is capable of forming a uniform coating film. The coating film has very good permeability and resistance characteristics. Various antistatic agents, batteries, anticorrosive paints, EMI shields, chemical sensors, display elements, non-linear materials, anticorrosive agents, adhesives, fibers, antistatic paints, It can be applied to conductive paints, anticorrosion paints, electrodeposition paints, plating primers, cathodic protection, and battery storage capacity improvement.

  There is a growing recognition that the various performances of electronics and optical products are enhanced by the inclusion of conductive polymers. Examples of such objects include antistatic coating agents and antistatic films as well as various electronic implementations.

  Since electronics and optical products are required to have extremely high water resistance and smoothness, it is expected that studies with general-purpose organic solvent systems will continue. Since it cannot be sufficiently dissolved or dispersed, it has insufficient conductivity, insufficient transparency, low stability, and difficult processing conditions.

  For example, a conductive primer composition for electrostatic coating mainly comprising a water-soluble aniline-based conductive polymer having a sulfonic acid group and / or a carboxyl group disclosed in Patent Document 1, and electrostatic coating using the composition The method can be applied by a simple method, has excellent conductivity, and is excellent in terms of electrostatic coating effect. However, since the conductive polymer used in the present invention is water-soluble, it does not have sufficient water resistance as an antistatic film, and when a water-based base coat is used as an overcoat, the color of the conductive polymer is When mixed with a base coat and mixed with a general-purpose solvent-based resin, there is a problem in that it cannot be dissolved or sufficiently dispersible.

  Furthermore, the solvent exchange method for replacing water in a thiophene mixture disclosed in Patent Document 2 provides a method for efficiently replacing part or all of water with at least one other solvent using a Baytron ™ formulation as thiophene. is doing. However, low alcohol acetamide, lower alcohols containing diol and triol, pyrrolidone, low alkyl pyrrolidone, high alkyl pyrrolidone, low alkyl sulfoxide and mixtures thereof as solvents other than water, and glycol or glycerin as preferred lower alcohols are suitable. Low alkyl sulfoxides include dimethyl sulfoxide (DMSO), particularly preferred solvents include dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP), and acetonitrile, benzonitrile, methyl acetate, dichloromethane, diethyl ether. , Dimethoxyethane, N, N-dimethylformamide, nitrobenzene, nitromethane, propionitrile and propylene carbonate, dichloromethane and dibromine Such as methane are mentioned.

Moreover, in patent document 3 and patent document 4, the electroconductive composition which has favorable electroconductivity, transparency, stability, hydrolysis resistance, and a processing characteristic is reported. However, the composition used in the invention is obtained as a water-saturated colloidal dispersion of conductive polymer and is supplied in a significant amount of water solvent. Although attempts have been made to select one or more solvents for the composition used in the present invention and develop a solvent exchange method, N-methylpyrrolidone, pyrrolidone, caprolactam, N-methylcaprolactam, N -Octyl pyrrolidone, other protic solvents such as methanol, ethanol and isopropanol as lower alcohols, and mixtures of water with lower alcohols and other water miscible organic solvents such as acetone. Since the solvents as described above are too polar, the invention is applied to resins that use industrially general-purpose solvents such as ethyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), toluene, cyclohexylanone and the like as solvents. If the composition used in the above is added, the solubility and dispersibility of the composition used in the present invention are remarkably lowered, and a uniform and transparent coating film cannot be formed, and the boiling point of the solvent is too high. The type of base material that can be applied is limited, and the range of application is limited, and there is a problem with the cost of the drying process. In addition, some solvents contain halogen-based solvents that adversely affect the environment. Not suitable for.
Japanese Patent Laid-Open No. 10-147748 JP-T-2004-532292 Japanese Patent Laid-Open No. 7-90060 Japanese Patent Laid-Open No. 8-48858

  An object of the present invention is to provide a conductive composition that can be easily mixed with a general-purpose resin solution and that is stably dispersed and emulsified in a solvent that is not easily burdened with the environment in the drying step. By using the conductive composition of the present invention, it is possible to generate a uniform transparent conductive film having very excellent transmittance and resistance characteristics.

  The present invention relates to a conductive composition obtained by dispersing an ion pair of a polyanion (b) doped in a π-conjugated conductive polymer (a) and a basic organic compound (c) in a solvent containing an organic solvent. Related to things.

  Furthermore, this invention relates to the said electrically conductive composition whose solvent is the range of organic solvent: water = 50: 50-100: 0 by weight ratio.

  Furthermore, it is related with the said electroconductive composition formed by containing a binder polymer (d).

  In the present invention, the π-conjugated conductive polymer (a) is at least one selected from the group consisting of the following general formulas (1), (2), (3), (4), and (5). It is related with the said electrically conductive composition which has the above repeating unit.

  General formula (1)

（上記式中、Ｒ₁およびＲ₂は一緒になって−ＯＣＨ₂Ｏ−、−ＯＣ₂Ｈ₄Ｏ−、−ＯＣ₃Ｈ₆Ｏ−、−ＯＣ₄Ｈ₈Ｏ−、或いは相互に独立して、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₄ＳＯ₃ ^-、−Ｒ₄ＳＯ₃Ｈ、−ＯＣＨ₃、−ＯＣ₂Ｈ₅、−ＯＣ₃Ｈ₇、−ＯＣ₄Ｈ₉、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₃）₂、−ＮＨＣＯＲ₃、−ＯＨ、−Ｏ^-、−ＳＲ₃、−ＯＲ₃、−ＯＣＯＲ₃、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₄ＣＯＯＨ、−ＣＯＯＲ₃、−ＣＯＲ₃、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₃は炭素数１〜２４の、アルキル基、アリール基またはアラルキル基で、Ｒ₄は炭素数１〜２４の、アルキレン基、アリーレン基またはアラルキレン基である。）

(In the above formula, R ₁ and R ₂ together represent —OCH ₂ O—, —OC ₂ H ₄ O—, —OC ₃ H ₆ O—, —OC ₄ H ₈ O—, or independently of each other. H, —SO ₃ ⁻ , —SO ₃ H, —R ₄ SO ₃ ⁻ , —R ₄ SO ₃ H, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OC ₄ H ₉ , _{-CH 3, -C 2 H 5,} -F, -Cl, -Br, -I, -N (R 3) 2, -NHCOR 3, -OH, -O -, -SR 3, -OR 3, - OCOR ₃ , —NO ₂ , —COOH, —R ₄ COOH, —COOR ₃ , —COR ₃ , —CHO and —CN, wherein R ₃ is an alkyl group having 1 to 24 carbon atoms. An aryl group or an aralkyl group, and R ₄ is an alkylene group, an arylene group or an aralkylene group having 1 to 24 carbon atoms.)

  General formula (2)

（上記式中、Ｒ₅およびＲ₆は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₇ＳＯ₃ ^-、−Ｒ₇ＳＯ₃Ｈ、−ＯＣＨ₃、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₈）₂、−ＮＨＣＯＲ₈、−ＯＨ，−Ｏ^-、−ＳＲ₈、−ＯＲ₈、−ＯＣＯＲ₈、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₇ＣＯＯＨ、−ＣＯＯＲ₈、−ＣＯＲ₈、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₇は炭素数１〜２４の、アルキレン基、アリーレン基またはアラルキレン基で、Ｒ₈は炭素数１〜２４の、アルキル基、アリール基またはアラルキル基である。）

(In the above formula, R ₅ and R ₆ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₇ SO ₃ ⁻ , —R ₇ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 8) 2, -NHCOR 8, -OH, -O -, -SR 8, -OR 8, -OCOR 8, -NO ₂ , —COOH, —R ₇ COOH, —COOR ₈ , —COR ₈ , —CHO and —CN, wherein R ₇ is an alkylene group, arylene group or aralkylene having 1 to 24 carbon atoms. R ₈ is an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms.)

  General formula (3)

（上記式中、Ｒ₉〜Ｒ₁₂は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₁₃ＳＯ₃ ^-、−Ｒ₁₃ＳＯ₃Ｈ、−ＯＣＨ₃、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₁₄）₂、−ＮＨＣＯＲ₁₄、−ＯＨ、−Ｏ^-、−ＳＲ₁₄、−ＯＲ₁₄、−ＯＣＯＲ₁₄、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₁₃ＣＯＯＨ、−ＣＯＯＲ₁₄、−ＣＯＲ₁₄、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₁₃は炭素数１〜２４の、アルキレン基、アリーレン基またはアラルキレン基で、Ｒ₁₄は炭素数１〜２４の、アルキル基、アリール基またはアラルキル基である。）

(In the above formula, R _{9 to} R ₁₂ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₁₃ SO ₃ ⁻ , —R ₁₃ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 14) 2, -NHCOR 14, -OH, -O -, -SR 14, -OR 14, -OCOR 14, -NO ₂ , —COOH, —R ₁₃ COOH, —COOR ₁₄ , —COR ₁₄ , —CHO and —CN, wherein R ₁₃ is an alkylene group, arylene group or aralkylene having 1 to 24 carbon atoms. R ₁₄ is an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms.)

  General formula (4)

（上記式中、Ｒ₁₅〜Ｒ₁₉は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₂₀ＳＯ₃ ^-、−Ｒ₂₀ＳＯ₃Ｈ、−ＯＣＨ₃、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₂₁）₂、−ＮＨＣＯＲ₂₁、−ＯＨ，−Ｏ^-、−ＳＲ₂₁、−ＯＲ₂₁、−ＯＣＯＲ₂₁、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₂₀ＣＯＯＨ、−ＣＯＯＲ₂₁、−ＣＯＲ₂₁、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₂₀は炭素数１〜２４の、アルキレン基、アリーレン基またはアラルキレン基で、Ｒ₂₁は炭素数１〜２４の、アルキル基、アリール基またはアラルキル基である。）

(In the above formula, R _{15 to} R ₁₉ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₂₀ SO ₃ ⁻ , —R ₂₀ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 21) 2, -NHCOR 21, -OH, -O -, -SR 21, -OR 21, -OCOR 21, -NO ₂ , —COOH, —R ₂₀ COOH, —COOR ₂₁ , —COR ₂₁ , —CHO and —CN, wherein R ₂₀ is an alkylene group, arylene group or aralkylene having 1 to 24 carbon atoms. R ₂₁ is an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms.)

  General formula (5)

（上記式中、Ｒ₂₂は−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₂₃ＳＯ₃ ^-、−Ｒ₂₃ＳＯ₃Ｈ、−ＣＯＯＨ及び−Ｒ₂₃ＣＯＯＨ からなる群より選ばれ、ここで、Ｒ₂₃は炭素数１〜２４の、アルキレン基、アリーレン基またはアラルキレン基である。）

(In the above formula, R ₂₂ is selected from the group consisting of —SO ₃ ⁻ , —SO ₃ H, —R ₂₃ SO ₃ ⁻ , —R ₂₃ SO ₃ H, —COOH, and —R ₂₃ COOH, ₂₃ is an alkylene group, an arylene group or an aralkylene group having 1 to 24 carbon atoms.

  Furthermore, the present invention provides a homopolymer obtained by radical polymerization of an ethylenically unsaturated monomer in which the polyanion (b) has a sulfonic acid group, a phosphoric acid group, a carboxyl group, or a salt-forming group of these and a basic compound. Or an ethylenically unsaturated monomer having a sulfonic acid group, a sulfonic acid group, a phosphoric acid group, a carboxyl group, or a salt-forming group of these with a basic compound, and another polymerizable ethylenically unsaturated monomer. The present invention relates to the conductive composition, which is a copolymer obtained by radical polymerization of a monomer.

  Furthermore, the present invention relates to the above conductive composition, wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene).

  Furthermore, this invention relates to the said electroconductive composition whose polyanion (b) is a polystyrene sulfonic acid.

  Furthermore, the present invention provides an organic compound represented by the following general formula (6), an organic compound containing a lactam group, a sugar, a sugar derivative, an alkylene glycol, an alcohol amine, a polyethylene glycol, a glycerin, a thiodiglycol, and dichloroacetic acid. In addition, the present invention relates to the above conductive composition containing at least one additive (e) selected from the group consisting of trifluoroacetic acid, trifluoroethanol, and metacresol.

  General formula (6)

（上記式中、ｎおよびｍは相互に独立して１〜２０の整数を表わし、Ｒ₂₄は炭素原子２〜２０個を有する、直鎖状、分枝鎖状もしくは環式アルキレン基、炭素原子６〜１４個を有する、置換されていてもよいアリーレン基またはピランもしくはフラン基を表わし、Ｘは−ＯＨまたは−ＮＹＺを表わし、Ｙ、Ｚは相互に独立して水素またはアルキル基を表わす。）

(In the above formula, n and m each independently represent an integer of 1 to 20, and R ₂₄ represents a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, carbon atoms. And represents an optionally substituted arylene group or pyran or furan group having 6 to 14 atoms, X represents —OH or —NYZ, and Y and Z each independently represent hydrogen or an alkyl group.

  Further, in the present invention, the additive (e) contains N-methylpyrrolidone, pyrrolidone, caprolactam, N-methylcaprolactam, N-octylpyrrolidone, sucrose, glucose, fructose, lactose, sorbitol, mannitol, 2-furancarboxylic acid, 3-furancarboxylic acid, ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethanolamine, triethanolamine, glycerin, di- or triethylene glycol, thiodiglycol, dichloroacetic acid, trifluoroacetic acid, tri The present invention relates to the conductive composition selected from the group consisting of fluoroethanol and metacresol.

  Furthermore, the present invention is characterized in that an ion pair of a polyanion (b) doped with a π-conjugated conductive polymer (a) and a basic organic compound (c) is dispersed in a solvent containing an organic solvent. The present invention relates to a method for producing the conductive composition.

  According to the present invention, a conductive composition that is stably dispersed and emulsified even in an organic solvent can be provided, and a transparent conductive film having excellent transparency and resistance characteristics can be provided from this composition.

  The π-conjugated conductive polymer (a) used in the present invention is at least one selected from the group consisting of the following general formulas (1), (2), (3), (4), and (5). Of repeating units.

  General formula (1)

（上記式中、Ｒ₁およびＲ₂は一緒になって−ＯＣＨ₂Ｏ−、−ＯＣ₂Ｈ₄Ｏ−、−ＯＣ₃Ｈ₆Ｏ−、−ＯＣ₄Ｈ₈Ｏ−、或いは相互に独立して、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₄ＳＯ₃ ^-、−Ｒ₄ＳＯ₃Ｈ、−ＯＣＨ₃、−ＯＣ₂Ｈ₅、−ＯＣ₃Ｈ₇、−ＯＣ₄Ｈ₉、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₃）₂、−ＮＨＣＯＲ₃、−ＯＨ、−Ｏ^-、−ＳＲ₃、−ＯＲ₃、−ＯＣＯＲ₃、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₄ＣＯＯＨ、−ＣＯＯＲ₃、−ＣＯＲ₃、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₃は炭素数１〜２４のアルキル基、炭素数１〜２４のアリール基または炭素数１〜２４のアラルキル基で、Ｒ₄は炭素数１〜２４のアルキレン基、炭素数１〜２４のアリーレン基または炭素数１〜２４のアラルキレン基である。）

(In the above formula, R ₁ and R ₂ together represent —OCH ₂ O—, —OC ₂ H ₄ O—, —OC ₃ H ₆ O—, —OC ₄ H ₈ O—, or independently of each other. H, —SO ₃ ⁻ , —SO ₃ H, —R ₄ SO ₃ ⁻ , —R ₄ SO ₃ H, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OC ₄ H ₉ , _{-CH 3, -C 2 H 5,} -F, -Cl, -Br, -I, -N (R 3) 2, -NHCOR 3, -OH, -O -, -SR 3, -OR 3, - _{OCOR 3, -NO 2, -COOH,} -R 4 COOH, -COOR 3, -COR 3, selected from the group consisting of -CHO, and -CN, wherein, R ₃ is an alkyl group having 1 to 24 carbon atoms, aralkyl groups aryl or 1 to 24 carbon atoms having 1 to 24 carbon atoms, R ₄ is 1-2 arylene group or a carbon number of 1 to 24 alkylene group, a carbon number of 1 to 24 carbon atoms It is an aralkylene group.)

  General formula (2)

（上記式中、Ｒ₅およびＲ₆は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₇ＳＯ₃ ^-、−Ｒ₇ＳＯ₃Ｈ、−ＯＣＨ₃、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₈）₂、−ＮＨＣＯＲ₈、−ＯＨ，−Ｏ^-、−ＳＲ₈、−ＯＲ₈、−ＯＣＯＲ₈、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₇ＣＯＯＨ、−ＣＯＯＲ₈、−ＣＯＲ₈、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₇は炭素数１〜２４のアルキレン基、炭素数１〜２４のアリーレン基または炭素数１〜２４のアラルキレン基で、Ｒ₈は炭素数１〜２４のアルキル基、炭素数１〜２４のアリール基または炭素数１〜２４のアラルキル基である。）

(In the above formula, R ₅ and R ₆ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₇ SO ₃ ⁻ , —R ₇ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 8) 2, -NHCOR 8, -OH, -O -, -SR 8, -OR 8, -OCOR 8, -NO ₂ , —COOH, —R ₇ COOH, —COOR ₈ , —COR ₈ , —CHO and —CN, wherein R ₇ is an alkylene group having 1 to 24 carbon atoms and 1 to 24 carbon atoms. R ₈ is an alkyl group having 1 to 24 carbon atoms, an aryl group having 1 to 24 carbon atoms, or an aralkyl group having 1 to 24 carbon atoms.)

  General formula (3)

（上記式中、Ｒ₉〜Ｒ₁₂は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₁₃ＳＯ₃ ^-、−Ｒ₁₃ＳＯ₃Ｈ、−ＯＣＨ₃、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₁₄）₂、−ＮＨＣＯＲ₁₄、−ＯＨ、−Ｏ^-、−ＳＲ₁₄、−ＯＲ₁₄、−ＯＣＯＲ₁₄、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₁₃ＣＯＯＨ、−ＣＯＯＲ₁₄、−ＣＯＲ₁₄、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₁₃は炭素数１〜２４のアルキレン基、炭素数１〜２４のアリーレン基または炭素数１〜２４のアラルキレン基で、Ｒ₁₄は炭素数１〜２４のアルキル基、炭素数１〜２４のアリール基または炭素数１〜２４のアラルキル基である。）

(In the above formula, R _{9 to} R ₁₂ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₁₃ SO ₃ ⁻ , —R ₁₃ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 14) 2, -NHCOR 14, -OH, -O -, -SR 14, -OR 14, -OCOR 14, -NO ₂ , —COOH, —R ₁₃ COOH, —COOR ₁₄ , —COR ₁₄ , —CHO and —CN, wherein R ₁₃ is an alkylene group having 1 to 24 carbon atoms and 1 to 24 carbon atoms. R ₁₄ is an alkyl group having 1 to 24 carbon atoms, an aryl group having 1 to 24 carbon atoms, or an aralkyl group having 1 to 24 carbon atoms.)

  General formula (4)

（上記式中、Ｒ₁₅〜Ｒ₁₉は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₂₀ＳＯ₃ ^-、−Ｒ₂₀ＳＯ₃Ｈ、−ＯＣＨ₃、−ＣＨ₃、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ₂₁）₂、−ＮＨＣＯＲ₂₁、−ＯＨ，−Ｏ^-、−ＳＲ₂₁、−ＯＲ₂₁、−ＯＣＯＲ₂₁、−ＮＯ₂、−ＣＯＯＨ、−Ｒ₂₀ＣＯＯＨ、−ＣＯＯＲ₂₁、−ＣＯＲ₂₁、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｒ₂₀は炭素数１〜２４のアルキレン基、炭素数１〜２４のアリーレン基または炭素数１〜２４のアラルキレン基で、Ｒ₂₁は炭素数１〜２４のアルキル基、炭素数１〜２４のアリール基または炭素数１〜２４のアラルキル基である。）

(In the above formula, R _{15 to} R ₁₉ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₂₀ SO ₃ ⁻ , —R ₂₀ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 21) 2, -NHCOR 21, -OH, -O -, -SR 21, -OR 21, -OCOR 21, -NO ₂ , —COOH, —R ₂₀ COOH, —COOR ₂₁ , —COR ₂₁ , —CHO and —CN, wherein R ₂₀ is an alkylene group having 1 to 24 carbon atoms and 1 to 24 carbon atoms. R ₂₁ is an alkyl group having 1 to 24 carbon atoms, an aryl group having 1 to 24 carbon atoms, or an aralkyl group having 1 to 24 carbon atoms.)

  General formula (5)

（上記式中、Ｒ₂₂は−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−Ｒ₂₃ＳＯ₃ ^-、−Ｒ₂₃ＳＯ₃Ｈ、−ＣＯＯＨ及び−Ｒ₂₃ＣＯＯＨ からなる群より選ばれ、ここで、Ｒ₂₃は炭素数１〜２４のアルキレン基、炭素数１〜２４のアリーレン基または炭素数１〜２４のアラルキレン基である。）

(In the above formula, R ₂₂ is selected from the group consisting of —SO ₃ ⁻ , —SO ₃ H, —R ₂₃ SO ₃ ⁻ , —R ₂₃ SO ₃ H, —COOH, and —R ₂₃ COOH, ₂₃ is an alkylene group having 1 to 24 carbon atoms, an arylene group having 1 to 24 carbon atoms, or an aralkylene group having 1 to 24 carbon atoms.

  The π-conjugated conductive polymer (a) used in the present invention is formed by polymerizing a monomer having a structure represented by the general formulas (1) to (5). As the monomer, preferably 3-thiophenecarboxamide, 3-thiophenmalonic acid, 3-thiophenemethanol, 3-thiopheneethanol, 3,4-ethylenedioxythiophene, 3-thiophenealdehyde, 3-hexylthiophene, 3 -Butylthiophene, 3-dodecylthiophene, 3-docosylthiophene, 3-thiophenecarboxylic acid, 3-thiopheneacetonitrile, 3-thiophenecarboxaldehyde, 3-thiopheneacetyl chloride, 3-thiopheneboronic acid, 3-thiophenecarboxyl chloride, 3-thiopheneethane sulfonate, 3-thiophene butane sulfonate, pyrrole, aniline, sodium aniline-2,5-disulfonate, aminobenzene sulfonic acid, ortho-anisidine, meta-ani Gin, ortho-anisidine hydrochloride, meta-anisidine hydrochloride, carbazole, 3- (N-carbazoyl) propyne, etc. can be used, and these monomers can be used alone or in combination of two or more. be able to.

  Next, examples of the acid group-containing monomer constituting the polyanion (b) used in the present invention include functional groups such as a sulfonic acid group, a phosphoric acid group, a carboxyl group, or a salt-forming group of these and a basic compound. Although it will not specifically limit if it is a monomer containing a group, What contains strong acid groups, such as a sulfonic acid group and a phosphoric acid group, can be used preferably.

  Examples of the monomer containing a sulfonic acid group include styrene sulfonic acid, allyloxybenzene sulfonic acid, methallyloxybenzene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, and 4-sulfonic acid butyl. Examples include methacrylate, isoprene sulfonic acid, sulfobutyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sulfoethyl methacrylate, and the like. These monomers can be used alone or in combination of two or more, and can also be used in the form of a salt-forming group neutralized with a base such as ammonia, triethylamine or sodium hydroxide. Furthermore, after polymerizing the resin, it is also preferable to sulfonate with a sulfonating agent such as sulfuric acid, fuming sulfuric acid, sulfamic acid and the like.

  Examples of the monomer containing a phosphoric acid group include 3-chloro-2-acid phosphoxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, and mono (2-hydroxyethyl acrylate). Acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate, mono (2-hydroxypropyl methacrylate) acid phosphate, mono (3-hydroxypropyl acrylate) acid phosphate, mono (3 -Hydroxypropyl methacrylate) acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate Such as over doors and the like. These monomers can be used alone or in combination of two or more, and can also be used in the form of a salt-forming group neutralized with a base such as ammonia, triethylamine or sodium hydroxide.

  Examples of the monomer containing a carboxyl group include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; ethylenically unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, and itaconic acid; Examples thereof include acid anhydrides thereof; partially esterified products of ethylenically unsaturated polyvalent carboxylic acids such as methyl maleate and methyl itaconate; and the like. These monomers can be used alone or in combination of two or more, and can be used in the form of a salt-forming group neutralized with a base such as ammonia, triethylamine or sodium hydroxide.

  As other monomers copolymerizable with the acid group-containing monomer, known compounds can be used without any limitation. For example, conjugated diene monomers such as 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene; styrene, α-methylstyrene, p-methylstyrene, etc. Aromatic vinyl monomers; ethylenically unsaturated carboxylic acid alkyl ester monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; Ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide; ethylenically unsaturated carboxylic acids such as hydroxyalkyl (meth) acrylate and glycerin di (meth) acrylate Acid hydroxyalkyl ester monomer; vinyl carboxylate such as vinyl acetate Ester monomers; (meth) acrylonitrile, N- vinylpyrrolidone, (meth) acryloyl morpholine, cyclohexyl maleimide, isopropyl maleimide, and (meth) glycidyl acrylate. These can be used alone or in combination of two or more.

  The polyanion (b) can be obtained by radical polymerization of the above monomer using an initiator.

  Furthermore, the polyanion (b) used in the present invention may be a water-soluble phosphoric acid ester produced by esterifying at least part of the terminal epoxy group of the epoxy resin with a phosphorus-containing acid.

  The weight average molecular weight of the polyanion (b) is preferably in the range of 1,000 to 2,000,000, more preferably in the range of 2,000 to 500,000.

  Furthermore, when the conductive composition according to the present invention requires extremely high permeability and conductivity, poly (3,4-ethylenedioxythiophene) is used for the π-conjugated conductive polymer (a). More preferably, polystyrene sulfonic acid is used for the polyanion (b).

  The π-conjugated conductive polymer (a) used in the present invention undergoes oxidative polymerization at a temperature of 0 to 100 ° C. in an aqueous medium, preferably using an oxidizing agent and / or oxygen or air in an aqueous polyanion (b) solution. It can be obtained by doing.

  The molar ratio (b / a) between the polyanion (b) and the π-conjugated conductive polymer (a) used in the present invention is preferably 1 to 80, more preferably 2 to 40. When the molar ratio (b / a) between the polyanion (b) and the π-conjugated conductive polymer (a) is less than 1, the π-conjugated conductive polymer (a) and the polyanion (b) are dissolved in water. Or may not be dispersed, and if it is greater than 80, the conductivity efficiency may be reduced.

  Next, the basic organic compound (c) used in the present invention will be described. The basic organic compound (c) forms an ion pair with the polyanion (b) doped in the π-conjugated conductive polymer (a) and is used for stable dispersion in the organic solvent. Here, the term “dope” refers to a compound (dopant) that can transfer electrons between the polymer chain of the conductive polymer and the charge transfer interaction, and can assist the movement between the carrier chains. It is impregnated or forced. In the present invention, the anion group remaining in the polyanion (b) doped in the π-conjugated conductive polymer (a) is further made into an ion pair with the cation group in the basic organic compound (c), so that For example, the π-conjugated conductive polymer (a) doped with the polyanion (b), which can be dispersed only in water, can be stably dispersed even in a solvent.

  As the basic organic compound (c), a known amine compound (c1), a cationic emulsifier (c2), a basic resin (c3), or the like is used. Examples of the amine compound (c1) used in the present invention include N-methyloctylamine, methylbenzylamine, N-methylaniline, dimethylamine, diethylamine, diethanolamine, N-methylethanolamine, di-n-propylamine, and diisopropyl. Examples include amine, methyl-isopropanolamine, dibutylamine, di-2-ethylhexylamine and the like. Examples of the primary amine include aminoethylethanolamine, 3-amino-1-propanol, isopropylamine, monoethylamine, 2-ethylhexylamine, t-butylamine, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, etc. are mentioned.

  Furthermore, examples of the cationic emulsifier (c2) used in the present invention include hydrochlorides of primary amines such as monomethylamine, monoethylamine and stearylamine, and hydrochlorides of secondary amines such as dimethylamine, diethylamine and distearylamine. , Tertiary amine hydrochlorides such as trimethylamine, triethylamine, stearyldimethylamine, quaternary ammonium salts such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, monoethanolamine, diethanolamine, triethanolamine, etc. Ethanolamine hydrochlorides, polyethylenepolyamine hydrochlorides such as ethylenediamine and diethylenetriamine, etc., which can be used alone or in combination. The

  Although there is no restriction | limiting in the usage-amount of an amine compound (c1) and a cationic emulsifier (c2), 1-100,000 weight% is added based on the sum total of (pi) conjugated polymer (a) and a polyanion (b). Is preferably added in the range of 10 to 10,000% by weight.

Furthermore, as an example of the basic resin (c3) used in the present invention, it is composed of a polyester-based, acrylic-based, or urethane-based polymer copolymer disclosed in Patent Documents 5 to 8, and has a weight average molecular weight. The thing of 1,000-1,000,000 is mentioned. If the weight average molecular weight of the basic resin (c3) is less than 1,000, sufficient steric hindrance may not be obtained, and the dispersion effect may be reduced. Conversely, even if the weight average molecular weight is greater than 1,000,000, Aggregation may occur. The amine value of the basic resin (c3) is preferably 5 to 200 mgKOH / g. If it is less than 5 mgKOH / g, the interaction with the polyanion (b) doped in the π-conjugated conductive polymer (a) tends to be insufficient, and a sufficient dispersion effect may not be obtained. On the other hand, when the amine value of the basic resin (c3) exceeds 200 mgKOH / g, the steric hindrance layer is reduced as compared with the affinity part for the polyanion (b) doped in the π-conjugated conductive polymer (a). The dispersion effect may be insufficient. Examples of such basic resin (c3) include Solsperse 17000, Solsperse 20000, Solsperse 24000, Solsperse 32000 (manufactured by Geneca Corporation), Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperkk-163, Disperkk-163, Disperk 2000, Disperbyk-2001 (manufactured by Big Chemie), Addisper PB711, Addisper PB821, Addisper PB822, Addisper PB824 (made by Ajinomoto Co., Inc.), Epomin 006, Epomin 012, Epomin 018 (made by Nippon Shokubai Co., Ltd.), EFKA4046, EFKA4300, EFKA4300 , EFKA4510 (EFKA Corporation ), DISPARLON DA-400 N (manufactured by Kusumoto Chemicals Chemical Co.), etc., and can be used alone or in combination. In particular, Addisper PB821, Addisper PB822, and Addisper PB824 are preferable in terms of dispersibility and conductivity during use. Although there is no restriction | limiting in the usage-amount of basic resin (c3), 1-100,000 weight% based on the sum total of (pi) conjugated system conductive polymer (a) and a polyanion (b), Preferably it is 10-10. It is preferably added in the range of 1,000% by weight.
(Patent Document 5) JP-A-60-166318 (Patent Document 6) JP-A-61-174939 (Patent Document 7) JP-A-46-7294 (Patent Document 8) JP-A-09-169821 Gazette

  Furthermore, when solvent resistance is required for the dried coating film containing the π-conjugated conductive polymer (a) doped with the polyanion (b), a basic organic compound having a photocuring function is preferable. When using the basic organic compound which has a photocuring function, the basic resin which has an ethylenically unsaturated group is preferable, and what has 2 or more is especially preferable. Examples of ethylenically unsaturated groups include (meth) acryloyl groups, vinyl groups, allyl groups, vinyloxy groups, (meth) acryloylphenyl groups, vinylphenyl groups, vinyloxyphenyl groups, allylphenyl groups, maleic acid groups, itaconic acid groups, etc. Is mentioned.

  In the present invention, when the polyanion (b) doped in the π-conjugated conductive polymer (a) is dispersed in a solvent containing an organic solvent, the basic organic compound (c) is an amine compound (c1), The cationic emulsifier (c2) and the basic resin (c3) can be used alone or in combination. Although there is no restriction | limiting in the usage-amount, it is 1-100,000 weight% as a basic organic compound (c) based on the sum total of (pi) conjugated system conductive polymer (a) and a polyanion (b), Preferably it is 10- It is preferable to add in the range of 10,000% by weight.

  The organic solvent used in the present invention is not particularly limited, and various liquid media such as alcohols, ketones, esters, ethers, cellosolves, aromatic hydrocarbons, aliphatic hydrocarbons, Can be used alone or in combination. In order to disperse the π-conjugated conductive polymer (a) doped with the polyanion (b) in a solvent containing an organic solvent, the solubility in water is finite, and the boiling point from the cost of the drying step Is less than 200 ° C., and is preferably a non-halogen organic solvent in consideration of the influence on the environment. For example, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, butyl acetate, xylene, propylene glycol monomethyl ether acetate, Isooctane and the like are preferable. If a solvent having infinite solubility in water is used, the π-conjugated conductive polymer (a) doped with the polyanion (b) cannot be dispersed, and the resin or general-purpose solvent dissolved in the general-purpose solvent When added to the dispersed pigment solution, a shock occurs, and when it is formed into a coating film, a coating film with low permeability may be formed.

  The mixing ratio of the organic solvent and water in the present invention is preferably in a range of weight ratio of organic solvent: water = 50: 50 to 100: 0, more preferably 75:25 to 100: 0, and 90:10 to 100: 0 is particularly preferred. When the amount of water is larger than organic solvent: water = 50: 50, when added to a resin solution dissolved in a general-purpose solvent, the storage stability of the resin is lowered, or a pigment or the like is dispersed in the general-purpose solvent. When added to the system, the pigment may aggregate or the composition may not be applied uniformly.

  When the π-conjugated conductive polymer (a) doped with the polyanion (b) is dispersed in a solvent containing an organic solvent using the basic organic compound (c), an emulsifier may be used. Good. The emulsifier used in the present invention may be any one as long as the average particle diameter of the π-conjugated conductive polymer (a) doped with the polyanion (b) can be 10 μm or less, preferably 5 μm or less. Various models may be used. Examples of the emulsifier that can be used in the present invention include an ultrasonic homogenizer, a homomixer, a milder, an attritor, a (ultra) high pressure homogenizer, and a colloid mill.

  Here, the average particle diameter referred to in the present invention is the measurement of the particle diameter of the π-conjugated conductive polymer (a) doped with the polyanion (b) in a solvent containing an organic solvent by a dynamic light scattering method. In this case, the cumulative volume average diameter is a value measured with a Zetasizer Nano-ZS particle size measuring device manufactured by MALBERN INSTRUMENTS, for example.

  The binder polymer (d) used in the present invention is not particularly limited as long as it can be dissolved or dispersed in a solvent. For example, petroleum resin, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, Unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate acidic group-containing urethane resin, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin, drying oil, synthetic drying oil, Examples thereof include styrene-modified maleic acid, polyamide resin, chlorinated polypropylene, butyral resin, and vinylidene chloride resin.

  When using the compound which has a photocuring function as a binder polymer (d), the compound which has an ethylenically unsaturated group is preferable, and what has 2 or more is especially preferable. Examples of ethylenically unsaturated groups include (meth) acryloyl groups, vinyl groups, allyl groups, vinyloxy groups, (meth) acryloylphenyl groups, vinylphenyl groups, vinyloxyphenyl groups, allylphenyl groups, maleic acid groups, itaconic acid groups, etc. Is mentioned. When a compound having a photocuring function is used as the binder polymer (d), a photopolymerization initiator can be added. The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used. These are not limited to the above compounds, and any compounds can be used as long as they have the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination, and the amount used is not limited, but is preferably added in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the dry weight of the binder polymer (d). Moreover, a well-known organic amine can also be added as a sensitizer.

  In order to further increase the conductivity, the conductive composition according to the present invention includes an organic compound represented by the following general formula (6), an organic compound containing a lactam group, a sugar, a sugar derivative, an alkylene glycol, an alcohol amine, It may contain at least one or more additives (e) selected from the group consisting of polyethylene glycols, glycerin, thiodiglycol, dichloroacetic acid, trifluoroacetic acid, trifluoroethanol, and metacresol. The additive (e) is a conductive composition obtained by dispersing an ion pair of a polyanion (b) doped in a π-conjugated conductive polymer (a) and a basic organic compound (c) in an organic solvent. 100% by weight or less, preferably 50% by weight or less can be added. An additive (e) that is preferably soluble in water is used. Additives exceeding 100% by weight with respect to a conductive composition obtained by dispersing a polyanion (b) doped in a π-conjugated conductive polymer (a) and an ion pair of a basic organic compound in an organic solvent When (e) is added, the drying process may be lengthened, and the properties of the resin to be blended may be adversely affected.

  General formula (6)

（上記式中、ｎおよびｍは相互に独立して１〜２０の整数を表わし、Ｒ₂₄は炭素原子２〜２０個を有する、直鎖状、分枝鎖状もしくは環式アルキレン基、炭素原子６〜１４個を有する場合により置換されていてもよいアリーレン基または炭素原子６〜１４個を有するピラン基もしくは炭素原子６〜１４個を有するフラン基を表わし、そしてＸは−ＯＨまたは−ＮＹＺを表わし、ここでＹ、Ｚは相互に独立して水素または炭素原子１〜１０個を有するアルキル基を表わす。）

(In the above formula, n and m each independently represent an integer of 1 to 20, and R ₂₄ represents a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, carbon atoms. Represents an optionally substituted arylene group having 6 to 14 or a pyran group having 6 to 14 carbon atoms or a furan group having 6 to 14 carbon atoms, and X represents —OH or —NYZ. Y and Z are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.)

  Particularly suitable organic compounds corresponding to additive (e) are N-methylpyrrolidone, pyrrolidone, caprolactam, N-methylcaprolactam, N-octylpyrrolidone, sucrose, glucose, fructose, lactose, sorbitol, mannitol, 2- Furancarboxylic acid, 3-furancarboxylic acid, 1,3-propanediol, 1,4-butanediol, diethanolamine, triethanolamine, ethylene glycol, glycerin, di- or triethylene glycol, thiodiglycol, dichloroacetic acid, tri It is a mixture selected from the group consisting of fluoroacetic acid, trifluoroethanol, and metacresol.

  In addition, the solvent-stable composition of the present invention includes, as optional components within a range not to impair the purpose, and further include a solvent, a dye, an antioxidant, a polymerization inhibitor, a leveling agent, a humectant, a viscosity modifier, an antiseptic, and an antibacterial agent. An agent, an anti-blocking agent, an ultraviolet absorber, an infrared absorber, an electromagnetic shielding agent, a spherical filler, etc. can be added.

  When a photosensitive resin is not included in the conductive composition of the present invention, a transparent conductive film can be obtained by natural or forced drying after coating on a substrate. When the conductive composition of the present invention contains a photosensitive resin, it may be subjected to radiation curing by natural or forced drying after coating on the base material, or natural or forced after radiation curing following coating. Although forced drying may be carried out, it is preferable to perform radiation curing after natural or forced drying. In the case of curing with an electron beam, it is preferable to perform radiation curing after natural or forced drying in order to prevent curing inhibition by water or reduction of the strength of the coating film due to residual organic solvent. The timing of radiation curing may be simultaneous with coating or after coating. It can be cured by a known radiation curing method to obtain a cured product, and as the active energy ray, an electron beam, ultraviolet rays, or visible light of 400 to 500 nm can be used.

  A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp or a xenon mercury lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated can be set in a timely manner within a range of 5 to 2000 mJ, but is preferably within a range of 50 to 1000 mJ that can be easily managed in the process.

  Further, these ultraviolet rays or electron beams can be used in combination with heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  The conductive composition of the present invention can be applied to an organic or inorganic substrate. Examples of suitable inorganic substrates are glass, oxides or oxidizable or non-oxidizable ceramics such as aluminum oxide, silicon nitride. Examples of suitable organic substrates are pure organic polymers, copolymers or mixtures thereof such as polystyrene, polycarbonate, polyacrylate, polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyamide, polyimide, optionally glass fiber reinforced. And epoxy resins, cellulose derivatives such as cellulose triacetate, polyolefins such as polyethylene and polypropylene.

  The conductive composition of the present invention is capable of forming a uniform coating film, and the formed coating film has very excellent permeability and resistance characteristics, and various antistatic agents, batteries, anticorrosion paints, EMI shields. , Optical coating agent, chemical sensor, display element, non-linear material, anticorrosive agent, adhesive, fiber, antistatic paint, conductive paint, anticorrosion paint, electrodeposition paint, plating primer, cathodic protection Can do.

  The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. % Is based on weight unless otherwise specified.

  The evaluation methods in the examples are shown below. The surface resistance value of the transparent conductive film obtained from the conductive composition of the present invention was determined by applying the conductive composition to the substrate and drying the surface of the transparent conductive film after applying the conductive composition to the substrate. ("R8340A", manufactured by Advantest Corporation) (Ω).

  The total light transmittance of the transparent conductive film obtained from the conductive composition of the present invention was determined by applying a haze meter (“NDH2000”, Nippon Denshoku Industries Co., Ltd.) Measured using a product manufactured by Co., Ltd.

  The HAZE of the transparent conductive film obtained from the conductive composition of the present invention was coated with a conductive composition on a base material and then dried, and then a haze meter (“NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.). ).

  The ratio of the organic solvent to water in the conductive composition of the present invention was determined by quantifying the organic solvent using a gas chromatograph (“GC-17A” manufactured by Shimadzu Corporation).

  The molecular weight of the polyanion was measured using a gel permeation chromatograph (GPC: “HLC-8220GPC” manufactured by Tosoh Corporation).

  A PET film having a wet film thickness of 100 μm was used as the substrate used for the evaluation.

(Synthesis Example 1) <Synthesis of Binder Polymer (d)>
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) Company: KAYARAD PET-30) 250.0 parts, hydroquinone 0.16 parts, methyl ethyl ketone (MEK) 141.2 parts were charged, and the temperature was raised to 60 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 90 ° C. for 6 hours. 77.3 parts by company) and 33.9 parts of methyl ethyl ketone (MEK) were added. Then, 2.65 parts of dimethylbenzylamine was added as a catalyst, stirred at 90 ° C. for 8 hours, cooled to room temperature, and multifunctional ( A methyl ethyl ketone (MEK) solution of the binder polymer (d), which is a meth) acrylate compound, was obtained. The obtained binder polymer (d) solution was transparent light yellow and had a solid content of 70%. The obtained binder polymer (d) had a number average molecular weight (Mn) 870 and a weight average molecular weight (Mw) 2,830.

Example 1
As a π-conjugated conductive polymer (a) doped with a polyanion (b), poly (3,4-ethylenedioxythiophene) synthesized in the presence of an aqueous polystyrenesulfonic acid solution was used. C. BAYTRON PAG manufactured by Starck was used. BAYTRON P AG had a solvent of water and an NV of 1.2%, and a molar ratio of styrenesulfonic acid: 3,4-ethylenedioxythiophene = 2.5: 1.0.

  To a solution of 10 g of distearyldimethylammonium chloride dissolved in 100 g of toluene, 100 g of BAYTRON PAG was added and stirred at room temperature for 1 hour using a disper to obtain an emulsion.

  The emulsion was allowed to stand at room temperature for 24 hours, and then a blue and transparent toluene layer was collected to obtain a conductive composition. The weight ratio of the organic solvent to water in the composition was 99.7: 0.3. The obtained conductive composition was coated on a PET film using a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. Furthermore, it was stored at 55% relative humidity for 1 hour.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁶ Ω (55% relative humidity);
Total light transmittance: 88%;
HAZE: 0.5

(Example 2)
The conductive composition obtained in Example 1 was diluted 3 times with toluene to obtain a conductive composition. The weight ratio of the organic solvent to water in the obtained composition was 99.9: 0.1. The obtained conductive composition was coated on a PET film using a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. Furthermore, it was stored at 55% relative humidity for 1 hour.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁷ Ω (relative humidity 55%);
Total light transmittance: 89%;
HAZE: 0.4

(Example 3)
100 g of BAYTRON PAG was added to a solution obtained by dissolving 16 g of Ajisper PB-821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) in 100 g of ethyl acetate, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition. The weight ratio of the organic solvent to water in the composition was 50.3: 49.7.

2 g of the obtained conductive composition, 1.4 g of the binder polymer (d) solution obtained in Synthesis Example 1, Irgacure 907 (manufactured by Ciba Specialty Chemicals) and Irgacure 184 (Ciba Special) as photopolymerization initiators Tea Chemicals) was added at 2.5% to the solid content of the binder polymer (d). This was diluted with ethylene glycol and methyl ethyl ketone (MEK) to prepare 20% ethylene glycol in the solvent and 20% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 2.0 × 10 ¹⁰ Ω (55% relative humidity);
Total light transmittance: 89%;
HAZE: 0.4

Example 4
100 g of BAYTRON PAG was added to a solution obtained by dissolving 16 g of Ajisper PB-821 in 100 g of MIBK, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition. The weight ratio of the organic solvent to water in the composition was 50.3: 49.3.

To 2 g of the obtained conductive composition, 1.4 g of the binder polymer (d) solution obtained in Synthesis Example 1, and Irgacure 907 and Irgacure 184 as photopolymerization initiators were respectively added to the solid content of the binder polymer (d). .5% added. This was diluted with ethylene glycol and methyl ethyl ketone (MEK) to prepare 20% ethylene glycol in the solvent and 20% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 5.0 × 10 ¹⁰ Ω (55% relative humidity);
Total light transmittance: 88%;
HAZE: 0.3

(Example 5)
100 g of BAYTRON PAG was added to a solution obtained by dissolving 16 g of Azisper PB-821 in 100 g of cyclohexanone, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition.

 1 g of UV curable resin UV1700B (manufactured by Nihon Gosei Co., Ltd.) was added as a binder polymer (d) to 2 g of the obtained conductive composition, water was removed with an evaporator, and a blue and transparent conductive composition was obtained. . The weight ratio of the organic solvent to water in the composition was 99.9: 0.1.

Irgacure 907 and Irgacure 184 were added to the conductive composition from which water was removed by an evaporator, as a photopolymerization initiator, 2.5% with respect to UV1700B, respectively. This was diluted with ethylene glycol and cyclohexanone to prepare 20% ethylene glycol in the solvent and 20% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored for 1 hour at a relative humidity of 55%.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁶ Ω (55% relative humidity);
Total light transmittance: 88%;
HAZE: 0.2

(Example 6)
100 g of BAYTRON PAG was added to a solution obtained by dissolving 16 g of Azisper PB-821 in 100 g of cyclohexanone, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition.

  1.4 g of the binder polymer (d) solution obtained in Synthesis Example 1 was added to 2 g of the obtained conductive composition, and water was removed with an evaporator to obtain a blue and transparent conductive composition. The weight ratio of the organic solvent to water in the composition was 99.9: 0.1.

Irgacure 907 and Irgacure 184 were added as 2.5% of the solid content of the binder polymer (d) as photopolymerization initiators to the conductive composition from which water was removed by an evaporator. This was diluted with ethylene glycol and cyclohexanone to prepare 20% ethylene glycol in the solvent and 20% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁶ Ω (55% relative humidity);
Total light transmittance: 88%;
HAZE: 0.2

(Example 7)
To a solution of 10 g of distearyldimethylammonium chloride dissolved in 100 g of toluene, 100 g of BAYTRON PAG was added and stirred at room temperature for 1 hour using a disper to obtain an emulsion.

  Water was removed from the emulsion using an evaporator to obtain a blue and transparent conductive composition. The weight ratio of the organic solvent to water in the composition was 100: 0.

After dissolving 10 g of Azisper PB-821 in 100 g of the above transparent conductive composition, 140 g of the binder polymer (d) solution obtained in Synthesis Example 1, and Irgacure 907 and Irgacure 184 as photopolymerization initiators of the binder polymer (d) 2.5% of each was added to the solid content. This was diluted with methyl isobutyl ketone (MIBK) to prepare a solid content of 20%. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁶ Ω (55% relative humidity);
Total light transmittance: 88%;
HAZE: 0.3

(Example 8)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube was charged with 500 g of sodium styrenesulfonate, 1000 g of water and 0.5 g of ammonium persulfate, and the air in the reaction vessel was replaced with nitrogen gas. The reaction solution was reacted at 80 ° C. for 8 hours in a nitrogen atmosphere with stirring. After completion of the reaction, 250 g of water was added to obtain an aqueous polystyrenesulfonic acid Na solution having a nonvolatile content concentration of 40% and a weight average molecular weight of 25,000.

  A reaction vessel equipped with a stirrer, a thermometer, and a cooling device was charged with 2.6 g of pyrrole and 100 g of water, stirred in an air atmosphere and confirmed that pyrrole was dissolved in water. 50 g was added, and the reaction solution was kept at 5 ° C., and 43.5 g of 10 wt% cupric chloride aqueous solution was dropped for 2 hours to react for a total of 8 hours. After completion of the reaction, 68.5 g of water was added to obtain an aqueous polypyrrole solution doped with polystyrene sulfonic acid having a nonvolatile content concentration of 10% and a molar ratio of styrene sulfonic acid: pyrrole = 2.5: 1.0.

  12 g of the conductive composition was added to a solution obtained by dissolving 16 g of Azisper PB-821 in 100 g of MEK, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition. The weight ratio of the organic solvent to water in the composition was 90.3: 9.7.

  1 g of polymethyl methacrylate (manufactured by Aldrich: weight average molecular weight 93,000) as a binder polymer (d) was dissolved in 3 g of MEK, and 1 g of the conductive composition was further added. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, dried at 100 ° C. for 2 minutes, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent black PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁹ Ω (55% relative humidity);
Total light transmittance: 87%;
HAZE: 0.7

Example 9
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube was charged with 500 g of sodium styrenesulfonate, 1000 g of water, and 0.4 g of ammonium persulfate, and the air in the reactor was replaced with nitrogen gas. The reaction solution was reacted at 80 ° C. for 8 hours in a nitrogen atmosphere with stirring. After completion of the reaction, 250 g of water was added to obtain an aqueous polystyrenesulfonic acid Na solution having a nonvolatile content of 40% and a weight average molecular weight of 33,000.

  A reaction vessel equipped with a stirrer, a thermometer and a cooling device was charged with 5.8 g of aniline hydrochloride and 100 g of water, stirred in an air atmosphere, and further added with 50 g of the above polystyrene sulfonate Na solution, and the reaction solution was brought to 5 ° C. Then, 44.2 g of 5 wt% ammonium persulfate aqueous solution was added dropwise for 2 hours and reacted for a total of 8 hours. After completion of the reaction, 64 g of water was added to obtain a polyaniline aqueous solution doped with polystyrene sulfonic acid having a nonvolatile content concentration of 10% and a molar ratio of styrene sulfonic acid: aniline = 2.0: 1.0.

  12 g of the conductive composition was added to a solution of 16 g of Azisper PB-821 dissolved in 100 g of ethyl acetate, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition. The weight ratio of the organic solvent to water in the composition was 90.3: 9.7.

  As a binder polymer (d), 1 g of polymethyl methacrylate (manufactured by Aldrich: weight average molecular weight 93,000) was dissolved in 3 g of ethyl acetate, and 1 g of the conductive composition was further added. This was diluted with metacresol and ethyl acetate to prepare 20% metacresol in the solvent and 15% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, dried at 100 ° C. for 2 minutes, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent green PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁸ Ω (55% relative humidity);
Total light transmittance: 87%;
HAZE: 0.6

(Example 10)
50.31 g of BAYTRON PAG was added to a solution prepared by dissolving 9.40 g of Azisper PB-821 in 56.67 g of ethyl acetate, and stirred at room temperature for 1 hour using a disper to obtain an emulsion. Water was removed from the emulsion using a rotary evaporator. If necessary, ethyl acetate was added appropriately. Finally, a conductive composition having a nonvolatile content of 15% was obtained. The weight ratio of the organic solvent to water in the composition was 100: 0.

3.33 g of this conductive composition, 3.57 g of binder polymer (d) prepared in Synthesis Example 1, 0.70 g of ethylene glycol, 1.80 g of ethyl acetate, and 20% ethyl acetate solution of Irgacure 184 as a photopolymerization initiator A conductive composition having a nonvolatile content of 30% was obtained by blending 0.75 g. This composition was applied onto a PET film using a bar coater # 10 and dried in an oven at 100 ° C. for 2 minutes. A metal halide lamp was used for this to irradiate with 400 mJ / cm ² of ultraviolet rays to produce a conductive film. The conductive film was measured for surface resistance, haze, and total light transmittance.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 3.5 × 10 ⁷ Ω (55% relative humidity);
Total light transmittance: 87.9%;
HAZE: 0.9

(Example 11)
50.31 g of BAYTRON PAG was added to a solution prepared by dissolving 9.40 g of Azisper PB-822 in 56.67 g of ethyl acetate, and stirred at room temperature for 1 hour using a disper to obtain an emulsion. A portion of water was removed from the emulsion using a rotary evaporator. If necessary, ethyl acetate was added appropriately. Finally, a conductive composition having a nonvolatile content of 15% was obtained. The weight ratio of the organic solvent to water in the composition was 76:24.

3.33 g of this conductive composition, 3.57 g of binder polymer (d) prepared in Synthesis Example 1, 0.70 g of ethylene glycol, 1.80 g of ethyl acetate, and 20% ethyl acetate solution of Irgacure 184 as a photopolymerization initiator A conductive composition having a nonvolatile content of 30% was obtained by blending 0.75 g. This composition was applied onto a PET film using a bar coater # 10 and dried in an oven at 100 ° C. for 2 minutes. A metal halide lamp was used for this to irradiate with 400 mJ / cm ² of ultraviolet rays to produce a conductive film. The conductive film was measured for surface resistance, haze, and total light transmittance.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 3.5 × 10 ⁹ Ω (55% relative humidity);
Total light transmittance: 86.9%;
HAZE: 0.9

(Example 12)
50.31 g of BAYTRON PAG was added to a solution prepared by dissolving 9.40 g of Azisper PB-824 in 56.67 g of ethyl acetate, and stirred at room temperature for 1 hour using a disper to obtain an emulsion. A portion of water was removed from the emulsion using a rotary evaporator. If necessary, ethyl acetate was added appropriately. Finally, a conductive composition having a nonvolatile content of 15% was obtained. The weight ratio of the organic solvent to water in the composition was 95: 5.

3.33 g of this conductive composition, 3.57 g of binder polymer (d) prepared in Synthesis Example 1, 0.70 g of ethylene glycol, 1.80 g of ethyl acetate, and 20% ethyl acetate solution of Irgacure 184 as a photopolymerization initiator A conductive composition having a nonvolatile content of 30% was obtained by blending 0.75 g. This composition was applied onto a PET film using a bar coater # 10 and dried in an oven at 100 ° C. for 2 minutes. A metal halide lamp was used for this to irradiate with 400 mJ / cm ² of ultraviolet rays to produce a conductive film. The conductive film was measured for surface resistance, haze, and total light transmittance.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.5 × 10 ⁷ Ω (relative humidity 55%);
Total light transmittance: 87.9%;
HAZE: 0.7

(Synthesis Example 2) <Synthesis of Basic Organic Compound (c)>
In a 4-neck flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 12.16 g of 12-hydroxystearic acid (manufactured by Ito Oil Co., Ltd.), caprolactone (manufactured by Daicel Chemical Industries, Ltd .: Plaxel M) 87. 72 g and 0.088 g of tetrabutyl titanate (manufactured by Matsumoto Pharmaceutical Co., Ltd .: Orgatics TA-25) were charged, the temperature was raised to 160 ° C. while blowing nitrogen gas, and the reaction was allowed to proceed for 5 hours. Then, it cooled to 100 degreeC, 30.00g of 20% aqueous solution of polyallylamine was added, and it heated up, and removed the water in a reaction liquid. The temperature was raised to 120 ° C. and reacted for 2 hours. Next, 105.97 g of cyclohexanone was added to obtain a cyclohexanone solution of the basic resin (c3). The solid content was 50%, the number average molecular weight (Mn) was 1,564, the weight average molecular weight (Mw) was 6,609, and the amine value was 8.907 mgKOH / g.

(Synthesis Example 3) <Synthesis of Basic Organic Compound (c)>
In a 4-neck flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 12.17 g of 12-hydroxystearic acid (manufactured by Ito Oil Co., Ltd.), caprolactone (manufactured by Daicel Chemical Industries, Ltd .: Plaxel M) 87. 79 g of tetrabutyl titanate (manufactured by Matsumoto Pharmaceutical Co., Ltd .: ORGATICS TA-25) 0.088 g was charged, the temperature was raised to 160 ° C. while blowing nitrogen gas, and the mixture was reacted for 5 hours. Then, it cooled to 100 degreeC, 60.55g of 20% aqueous solution of polyallylamine was added, and it heated up, and removed the water in a reaction liquid. The temperature was raised to 140 ° C. and reacted for 2 hours. Next, 112.06 g of cyclohexanone was added to obtain a cyclohexanone solution of the basic resin (c3). The solid content was 50%, the number average molecular weight (Mn) was 1,538, the weight average molecular weight (Mw) was 5,556, and the amine value was 11.055 KOH / g.

(Example 13)
Add 50.31 g of BAYTRON PAG to a solution obtained by dissolving 18.80 g of the basic resin solution obtained in Synthesis Example 2 in 47.27 g of cyclohexanone, and stir at room temperature for 1 hour using a disper to obtain an emulsion. It was. Water was removed from the emulsion using a rotary evaporator. If necessary, ethyl acetate was added appropriately. Finally, a conductive composition having a nonvolatile content of 15% was obtained. The weight ratio of the organic solvent to water in the composition was 100: 0.

3.33 g of this conductive composition, 3.57 g of binder polymer (d) prepared in Synthesis Example 1, 0.70 g of ethylene glycol, 1.80 g of ethyl acetate, and 20% ethyl acetate solution of Irgacure 184 as a photopolymerization initiator A conductive composition having a nonvolatile content of 30% was obtained by blending 0.75 g. This composition was applied onto a PET film using a bar coater # 10 and dried in an oven at 100 ° C. for 2 minutes. A metal halide lamp was used for this to irradiate with 400 mJ / cm ² of ultraviolet rays to produce a conductive film. The conductive film was measured for surface resistance, haze, and total light transmittance.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 2.1 × 10 ⁷ Ω (relative humidity 55%);
Total light transmittance: 87.9%;
HAZE: 0.7

(Example 14)
Add 50.31 g of BAYTRON P AG to a solution obtained by dissolving 18.80 g of the basic resin solution obtained in Synthesis Example 3 in 47.27 g of cyclohexanone, and stir at room temperature for 1 hour using a disper to obtain an emulsion. It was. Water was removed from the emulsion using a rotary evaporator. If necessary, ethyl acetate was added appropriately. Finally, a conductive composition having a nonvolatile content of 15% was obtained. The weight ratio of the organic solvent to water in the composition was 100: 0.

3.33 g of this conductive composition, 3.57 g of binder polymer (d) prepared in Synthesis Example 1, 0.70 g of ethylene glycol, 1.80 g of ethyl acetate, and 20% ethyl acetate solution of Irgacure 184 as a photopolymerization initiator A conductive composition having a nonvolatile content of 30% was obtained by blending 0.75 g. This composition was applied onto a PET film using a bar coater # 10 and dried in an oven at 100 ° C. for 2 minutes. A metal halide lamp was used for this to irradiate with 400 mJ / cm ² of ultraviolet rays to produce a conductive film. The conductive film was measured for surface resistance, haze, and total light transmittance.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated material were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 2.0 × 10 ⁷ Ω (55% relative humidity);
Total light transmittance: 87.7%;
HAZE: 0.9

(Example 15)
100 g of BAYTRON PAG was added to a solution of 16 g of Azisper PB-822 dissolved in 100 g of cyclohexanone, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition.

 1 g of UV curable resin DA-721 (manufactured by Nagase ChemteX Corporation) is added as a binder polymer (d) to 2 g of the obtained conductive composition, water is removed by an evaporator, and the blue transparent conductive composition Got. The weight ratio of the organic solvent to water in the composition was 99.9: 0.1.

Irgacure 907 and Irgacure 184 were added to the conductive composition from which water was removed by an evaporator, respectively, as photopolymerization initiators with respect to DA-721. This was diluted with diethylene glycol and cyclohexanone to prepare 20% diethylene glycol in the solvent and 20% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored for 1 hour at a relative humidity of 55%.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.8 × 10 ⁸ Ω (55% relative humidity);
Total light transmittance: 87%;
HAZE: 0.7

(Example 16)
100 g of BAYTRON PAG was added to a solution of 16 g of Azisper PB-822 dissolved in 100 g of cyclohexanone, and stirred at room temperature for 1 hour using a disper to obtain a conductive composition.

 1 g of UV curable resin DA-911M (manufactured by Nagase ChemteX Corporation) is added as a binder polymer (d) to 2 g of the obtained conductive composition, water is removed with an evaporator, and the blue transparent conductive composition Got. The weight ratio of the organic solvent to water in the composition was 99.9: 0.1.

Irgacure 907 and Irgacure 184 as photopolymerization initiators were added to the conductive composition from which water was removed by an evaporator, respectively, at 2.5% with respect to DA-911M. This was diluted with thiodiglycol and cyclohexanone so that 5% of thiodiglycol was contained in the solvent and the solid content was 20%. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored for 1 hour at a relative humidity of 55%.

  As a result, a transparent light blue PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 3.0 × 10 ⁷ Ω (55% relative humidity);
Total light transmittance: 87%;
HAZE: 0.7

(Comparative Example 1)
Only BAYTRON P AG was applied to a PET film so that the dry film thickness was 5 μm, dried at 100 ° C. for 2 minutes, and stored for 1 hour at 55% relative humidity.

  As a result, a light blue PRT film coated product having no surface gloss was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.0 × 10 ⁶ Ω (55% relative humidity);
Total light transmittance: 74%;
HAZE: 43.4

(Comparative Example 2)
When 1.4 g of the binder polymer (d) solution obtained in Synthesis Example 1 was added to 2 g of BAYTRON P AG, a blue agglomerate was generated and coating could not be performed uniformly.

(Comparative Example 3)
When the physical properties of a PET film having a wet film thickness of 100 μm as a substrate were measured in the same manner as in Example 1, the following results were obtained.

Surface resistance (R _OB ) of PET film: 1.0 × 10 ¹⁵ Ω (relative humidity 55%);
Total light transmittance: 89%;
HAZE: 0.3

(Comparative Example 4)
Irgacure 907 and Irgacure 184 as photopolymerization initiators were added to 1.4 g of the binder polymer (d) solution obtained in Synthesis Example 1 at 2.5% based on the solid content of the binder polymer (d). This was diluted with ethylene glycol and cyclohexanone to prepare 20% ethylene glycol in the solvent and 20% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. This was irradiated with ultraviolet rays of 400 mJ / cm ² with a metal halide lamp to prepare a coated product, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 2.0 × 10 ¹⁴ Ω (relative humidity 55%);
Total light transmittance: 89%;
HAZE: 0.2

(Comparative Example 5)
As the binder polymer (d), 1 g of polymethyl methacrylate (manufactured by Aldrich: weight average molecular weight 93,000) was dissolved in 3 g of ethyl acetate. This was diluted with metacresol and ethyl acetate to prepare 20% metacresol in the solvent and 15% solid content. This solution was applied to a PET film with a bar coater so that the dry film thickness was 5 μm, dried at 100 ° C. for 2 minutes, and stored at 55% relative humidity for 1 hour.

  As a result, a transparent PET film coated product was obtained. When the physical properties of the coated product were measured in the same manner as in Example 1, the following results were obtained.

Film surface resistance (R _OB ): 1.5 × 10 ¹⁴ Ω (55% relative humidity);
Total light transmittance: 89%;
HAZE: 0.4

  The conductive compositions of Examples 1 to 16 were able to obtain a conductive coating film having a low surface resistance, and a coating film having excellent transparency with low haze. On the other hand, the compositions of Comparative Examples 1 to 5 could not achieve both conductivity and transparency.

Claims (10)

  A conductive composition obtained by dispersing an ion pair of a polyanion (b) doped into a π-conjugated conductive polymer (a) and a basic organic compound (c) in a solvent containing an organic solvent.   The conductive composition according to claim 1, wherein the solvent has a weight ratio of organic solvent: water = 50: 50 to 100: 0.   The conductive composition according to claim 1 or 2, further comprising a binder polymer (d). The π-conjugated conductive polymer (a) has at least one or more repeating units selected from the group consisting of the following general formulas (1), (2), (3), (4), and (5). The electrically conductive composition in any one of Claims 1-3 which have.
General formula (1)

(In the above formula, R ₁ and R ₂ together represent —OCH ₂ O—, —OC ₂ H ₄ O—, —OC ₃ H ₆ O—, —OC ₄ H ₈ O—, or independently of each other. H, —SO ₃ ⁻ , —SO ₃ H, —R ₄ SO ₃ ⁻ , —R ₄ SO ₃ H, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OC ₄ H ₉ , _{-CH 3, -C 2 H 5,} -F, -Cl, -Br, -I, -N (R 3) 2, -NHCOR 3, -OH, -O -, -SR 3, -OR 3, - OCOR ₃ , —NO ₂ , —COOH, —R ₄ COOH, —COOR ₃ , —COR ₃ , —CHO and —CN, wherein R ₃ is an alkyl group having 1 to 24 carbon atoms. An aryl group or an aralkyl group, and R ₄ is an alkylene group, an arylene group or an aralkylene group having 1 to 24 carbon atoms.)
General formula (2)

(In the above formula, R ₅ and R ₆ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₇ SO ₃ ⁻ , —R ₇ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 8) 2, -NHCOR 8, -OH, -O -, -SR 8, -OR 8, -OCOR 8, -NO ₂ , —COOH, —R ₇ COOH, —COOR ₈ , —COR ₈ , —CHO and —CN, wherein R ₇ is an alkylene group, arylene group or aralkylene having 1 to 24 carbon atoms. R ₈ is an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms.)
General formula (3)

(In the above formula, R _{9 to} R ₁₂ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₁₃ SO ₃ ⁻ , —R ₁₃ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 14) 2, -NHCOR 14, -OH, -O -, -SR 14, -OR 14, -OCOR 14, -NO ₂ , —COOH, —R ₁₃ COOH, —COOR ₁₄ , —COR ₁₄ , —CHO and —CN, wherein R ₁₃ is an alkylene group, arylene group or aralkylene having 1 to 24 carbon atoms. R ₁₄ is an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms.)
General formula (4)

(In the above formula, R _{15 to} R ₁₉ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ₂₀ SO ₃ ⁻ , —R ₂₀ SO ₃ H, —OCH ₃ , —CH ₃ , — _{C 2 H 5, -F, -Cl} , -Br, -I, -N (R 21) 2, -NHCOR 21, -OH, -O -, -SR 21, -OR 21, -OCOR 21, -NO ₂ , —COOH, —R ₂₀ COOH, —COOR ₂₁ , —COR ₂₁ , —CHO and —CN, wherein R ₂₀ is an alkylene group, arylene group or aralkylene having 1 to 24 carbon atoms. R ₂₁ is an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms.)
General formula (5)

(In the above formula, R ₂₂ is selected from the group consisting of —SO ₃ ⁻ , —SO ₃ H, —R ₂₃ SO ₃ ⁻ , —R ₂₃ SO ₃ H, —COOH, and —R ₂₃ COOH, ₂₃ is an alkylene group, an arylene group or an aralkylene group having 1 to 24 carbon atoms.   The polyanion (b) is a homopolymer obtained by radical polymerization of an ethylenically unsaturated monomer having a sulfonic acid group, a phosphoric acid group, a carboxyl group, or a salt-forming group of these and a basic compound, or these sulfone Radicals of an ethylenically unsaturated monomer having an acid group, a sulfonate group, a phosphate group, a carboxyl group, or a salt-forming group of these with a basic compound, and another polymerizable ethylenically unsaturated monomer The conductive composition according to claim 1, which is a copolymer obtained by polymerization.   The conductive composition according to claim 1, wherein the π-conjugated conductive polymer (a) is poly (3,4-ethylenedioxythiophene).   The conductive composition according to any one of claims 1 to 6, wherein the polyanion (b) is polystyrene sulfonic acid. Furthermore, organic compounds represented by the following general formula (6), organic compounds containing a lactam group, sugars, sugar derivatives, alkylene glycols, alcohol amines, polyethylene glycols, glycerin, thiodiglycol, dichloroacetic acid, trifluoro The electrically conductive composition according to any one of claims 1 to 7, comprising at least one or more additives (e) selected from the group consisting of acetic acid, trifluoroethanol, and metacresol.
General formula (6)

(In the above formula, n and m each independently represent an integer of 1 to 20, and R ₂₄ represents a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, carbon atoms. And represents an optionally substituted arylene group or pyran or furan group having 6 to 14 atoms, X represents —OH or —NYZ, and Y and Z each independently represent hydrogen or an alkyl group.   Additive (e) is N-methylpyrrolidone, pyrrolidone, caprolactam, N-methylcaprolactam, N-octylpyrrolidone, sucrose, glucose, fructose, lactose, sorbitol, mannitol, 2-furancarboxylic acid, 3-furancarboxylic acid , Ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethanolamine, triethanolamine, glycerin, di- or triethylene glycol, thiodiglycol, dichloroacetic acid, trifluoroacetic acid, trifluoroethanol, and meta The conductive composition according to claim 1, which is selected from the group consisting of cresol.    Conductive composition characterized by dispersing ion pair of polyanion (b) doped with π-conjugated conductive polymer (a) and basic organic compound (c) in a solvent containing an organic solvent Manufacturing method.