JP2013036013A - Composition for forming organic conductive film and the organic conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a conductive film, formable of an organic conductive film excellent in electrical conductivity, heat resistance, and light resistance.SOLUTION: The composition for forming an organic conductive film includes: [A] a conjugated polymer and [B] a copolymer including a structural unit (I) represented by formula (1), wherein Ris methylene, 2-12C alkylene, a 4-20C divalent alicyclic group, phenylene, or naphthylene; and Ris hydroxy, carboxy, sulfo, phosphono, or a salt of any one of these groups.

Description

  The present invention relates to a composition for forming an organic conductive film and an organic conductive film.

  Indium tin oxide (ITO) conductive films are widely used as electrode materials for liquid crystal displays, organic electroluminescence elements and the like. The ITO conductive film is generally formed by forming a metal material on a substrate by a vacuum deposition method, a sputtering method, or the like.

  In recent years, indium, which is the main component of ITO, is a rare metal, so the problem of resource depletion has become serious. On the other hand, a conductive polymer is known as a conductive material replacing indium. As a composition containing this conductive polymer, polythiophene doped with a polyanion has been developed (see JP-A-2005-350622 and JP-A-2009-238394). Such a composition is advantageous because it is relatively inexpensive and can form an organic conductive film on a large-area substrate by coating regardless of the vapor deposition method.

  However, a conventional conductive polymer is difficult to disperse in a solvent, and a coating film formed from a composition containing the conductive polymer has poor uniformity. Moreover, the electrical conductivity, heat resistance, and light resistance of the formed organic conductive film are not fully satisfactory.

  Under such circumstances, development of a conductive film forming composition capable of forming an organic conductive film excellent in conductivity, heat resistance and light resistance is desired.

JP-A-2005-350622 JP 2009-238394 A

  This invention is made | formed based on the above situations, The objective is providing the composition for electrically conductive film formation which can form the organic electrically conductive film which is excellent in electrical conductivity, heat resistance, and light resistance. is there.

（式（１）中、Ｒ^１は、メチレン基、炭素数２〜１２のアルキレン基、炭素数４〜２０の２価の脂環式基、フェニレン基又はナフチレン基である。Ｒ^２は、水酸基、カルボキシル基、スルホ基、ホスホノ基又はこれらの基の塩である。） The invention made to solve the above problems is
[A] a conjugated polymer, and [B] a copolymer containing at least the structural unit (I) represented by the following formula (1) (hereinafter also referred to as “[B] copolymer”)
Is a composition for forming an organic conductive film.

(In Formula (1), R ¹ is a methylene group, an alkylene group having 2 to 12 carbon atoms, a divalent alicyclic group having 4 to 20 carbon atoms, a phenylene group, or a naphthylene group. R ² is a hydroxyl group. , Carboxyl group, sulfo group, phosphono group or a salt of these groups.)

  The [B] copolymer contained in the composition for forming an organic conductive film functions as an excellent dopant because it has the structural unit (I) having the specific structure, and is a polymer having conductivity [A]. By doping a conjugated polymer, the conductivity of the [A] conjugated polymer can be dramatically improved. As a result, the organic conductive film formed from the composition for forming an organic conductive film has excellent conductivity, heat resistance, and light resistance, and can be suitably used for a display element, a touch panel, and the like.

  [A] The conjugated polymer is polyaniline, polypyrrole, polythiophene, poly (N-alkylpyrrole), poly (3-alkylthiophene) or poly (3-alkoxythiophene, poly (3,4-alkylenedioxythiophene). Preferably, it is poly (3,4-ethylenedioxythiophene), and these specific compounds are formed because they have more excellent conductivity and polymerizability as conjugated polymers. The organic conductive film is excellent in conductivity, heat resistance and light resistance.

（式（２）中、Ｒ^３は、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基である。ｎは、０〜４の整数である。但し、Ｒ^３が複数の場合、複数のＲ^３は同一であっても異なっていてもよい。） [B] The copolymer is preferably a copolymer further comprising a structural unit (II) represented by the following formula (2).

(In Formula (2), R ³ is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. N is an integer of 0 to 4. However, when R ³ is plural. The plurality of R ³ may be the same or different.)

  [B] When the copolymer further includes the structural unit (II), it can be a dopant having further excellent conductivity, and the conductivity of the formed organic conductive film can be further improved.

  [B] The content of the structural unit (I) in the copolymer is preferably 10 mol% or more. By making the content rate of structural unit (I) into the said specific range, the electrical conductivity, heat resistance, and light resistance of the organic electrically conductive film formed can be improved more.

  The composition for forming an organic conductive film includes [C] methanol, ethanol, isopropanol, propylene carbonate, N-methylpyrrolidone, N, N-dimethylformamide, dimethylacetamide, cyclohexanone, acetone, toluene, methyl ethyl ketone, methyl isobutyl ketone, dimethyl. It is preferable to further contain at least one solvent selected from the group consisting of sulfoxide, ethylene glycol and propylene glycol (hereinafter also referred to as “[C] solvent”). When the composition for forming an organic conductive film further contains the specific [C] solvent, the dispersibility and solubility of each component and the coating uniformity can be further improved. Moreover, the electrical conductivity of the formed organic conductive film can be further improved.

  The present invention preferably includes an organic conductive film formed from the composition for forming an organic conductive film. An organic conductive film formed from the composition for forming an organic conductive film is excellent in conductivity, heat resistance, and light resistance.

  The “conjugated polymer” in this specification is a polymer having a structure in which carbon-carbon double bonds and single bonds are alternately bonded.

  As described above, the present invention can provide a composition for forming a conductive film capable of forming an organic conductive film having excellent conductivity, heat resistance and light resistance. Therefore, the said composition for organic conductive film formation is suitable as a formation material of the organic conductive film used for a display element, a touch panel, etc.

<Composition for forming organic conductive film>
The composition for forming an organic conductive film of the present invention contains [A] a conjugated polymer and a [B] copolymer. Moreover, the said composition for organic conductive film formation may contain a [C] solvent as a suitable component. Furthermore, the composition for forming an organic conductive film may contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A] Conjugated polymer>
[A] The conjugated polymer is a polymer having a structure in which carbon-carbon double bonds and single bonds are alternately developed as described above. , A conjugated polymer derived from a π bond.

[A] Examples of the conjugated polymer include polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene, poly (p-phenylene), polyfluorene, polyazulene, poly (p-phenylene sulfide), polyisothianaphthene, poly (p -Phenylene vinylene), poly (2,5-thienylene vinylene), poly (N-alkylpyrrole), poly (3-alkylthiophene), poly (3-alkoxythiophene), poly (3,4-alkylenedioxythiophene) );
Double-chain conjugated polymers such as polyperinaphthalene;
Metal phthalocyanine polymers;
Other conjugated polymers such as poly (p-xylylene) and bipoly [α- (5,5′-bithiophenediyl) benzylidene] can be mentioned.

  Among these, [A] conjugated polymers include polyaniline, polypyrrole, polythiophene, poly (N-alkylpyrrole), poly (3-alkylthiophene), poly (3-alkoxythiophene, poly (3,4-alkylenediene). Oxythiophene) is preferred, and poly (3,4-ethylenedioxythiophene) is more preferred, since these specific compounds have even more excellent conductivity and polymerizability as conjugated polymers, The film is superior in conductivity, heat resistance and light resistance.

<[A] Method for synthesizing conjugated polymer>
[A] As a method for synthesizing the conjugated polymer, a known method can be applied. For example, the method described in Patent Document 1 can be mentioned. From the viewpoint of improving electrical conductivity, it is preferable to polymerize a compound that gives a [A] conjugated polymer by an oxidation polymerization method in the presence of a [B] copolymer described later.

  As the oxidant for the oxidative polymerization method, a known oxidant can be used. For example, peroxodisulfuric acid, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, inorganic ferric oxide salt, Organic ferric oxide, ferric chloride, ferric sulfate, ferric nitrate, cupric chloride, hydrogen peroxide, potassium permanganate, potassium dichromate, boron trifluoride, aluminum chloride, peroxy Examples thereof include alkali borate salts, silver oxide, cesium oxide, hydrogen peroxide, ozone, benzoyl peroxide, oxygen, and hydrates of the above metal salts.

  The amount of the oxidizing agent to be used is preferably 0.1 molar equivalent to 20 molar equivalents, and more preferably 1 molar equivalent to 10 molar equivalents, with respect to 1 mole of the compound giving the [A] conjugated polymer.

  The solvent used for the polymerization reaction is an aqueous solvent, preferably water. Water-soluble organic solvents such as methanol, ethanol, isopropanol, propylene carbonate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, cyclohexanone, acetone, toluene, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, ethylene glycol, propylene glycol methanol Can also be used by adding to water. By adding such a water-soluble organic solvent, the molecular weight of the [A] conjugated polymer can be increased and the conductivity can be improved.

<[B] Copolymer>
[B] The copolymer is a copolymer containing at least the structural unit (I) represented by the above formula (1). [B] The copolymer is preferably a copolymer further comprising the structural unit (II) represented by the above formula (2). In addition, the [B] copolymer may contain 2 or more types of each structural unit. Hereinafter, each structural unit will be described in detail.

[Structural unit (I)]
In the above formula (1), ^{R 1} is a methylene group, an alkylene group having 2 to 12 carbon atoms, a divalent alicyclic group having 4 to 20 carbon atoms, a phenylene group or a naphthylene group. R ² is a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group or a salt of these groups.

Examples of the alkylene group having 2 to 12 carbon atoms represented by R ¹ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group.

Examples of the divalent alicyclic group having 4 to 20 carbon atoms represented by R ¹ include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group.

  Examples of the monomer that gives the structural unit (I) include N-substituted maleimide compounds. As the N-substituted maleimide compound, a compound having a hydroxyl group, a carboxyl group, a sulfo group, or a phosphono group is preferable. Specific examples include N- (2-hydroxyethyl) maleimide, N- (4-hydroxybutyl) maleimide, N- (6-hydroxyhexyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (4 -Hydroxycyclohexyl) maleimide, N-ethanoic acid maleimide, N-pentanoic acid maleimide, N-hexanoic acid maleimide, N-octanoic acid maleimide, N- (4-carboxyphenyl) maleimide, N- (ethanesulfonic acid) maleimide, N -(Butanesulfonic acid) maleimide, N- (hexanesulfonic acid) maleimide, N- (octanesulfonic acid) maleimide, N- (ethanephosphonic acid) maleimide, N- (butanephosphonic acid) maleimide, N- (hexanephosphonic acid) ) Maleimide, N- (octanephosphonic acid) male Bromide, N-(4-sulfophenyl) maleimide, and the like.

  [B] The content of the structural unit (I) in the copolymer is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 80 mol%, based on all structural units. By making the content rate of structural unit (I) into the said specific range, the electrical conductivity, heat resistance, and light resistance of the organic electrically conductive film formed can be improved more.

[Structural unit (II)]
[B] The copolymer is preferably a copolymer further comprising the structural unit (II) represented by the above formula (2). [B] When the copolymer further includes the structural unit (II), it can be a dopant having further excellent conductivity, and the conductivity of the formed organic conductive film can be further improved.

In the above formula (2), ^{R 3} is an alkyl group or an alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. n is an integer of 0-4. However, if R ³ is plural, the plurality of R ³ may be be the same or different.

As a C1-C12 alkyl group represented by said R < ³ >, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group etc. are mentioned, for example.

As a C1-C12 alkoxy group represented by said R < ³ >, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

  Examples of the monomer that gives the structural unit (II) include 4-vinylbenzenesulfonic acid, 2-methyl-4-vinylbenzenesulfonic acid, 2-ethyl-4-vinylbenzenesulfonic acid, and 2,3-dimethyl-4. -Vinylbenzenesulfonic acid, 2,3-diethyl-4-vinylbenzenesulfonic acid, etc. are mentioned.

  [B] The content of the structural unit (II) in the copolymer is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 80 mol%, based on all structural units. By making the content rate of structural unit (II) into the said specific range, the electrical conductivity of the organic electrically conductive film formed can be improved more.

<[B] Copolymer Synthesis Method>
[B] As a method for synthesizing the copolymer, for example, a monomer that gives each structural unit is polymerized in a solvent using a radical polymerization initiator, or a salt of the monomer that gives each structural unit is polymerized. And can be synthesized by ion exchange using an ion exchange resin.

  The salt of the monomer is preferably a salt with a metal, and the metal is preferably sodium, potassium, lithium, iron or copper.

  The radical polymerization initiator is appropriately selected according to the type of monomer used. For example, ammonium persulfate, sodium persulfate, potassium persulfate, 2,2′-azobisisobutyronitrile, 2, 2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl Examples include azo compounds such as -2,2'-azobis (2-methylpropionate) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).

  Of these, ammonium persulfate, 2,2'-azobisisobutyronitrile, and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferable. A radical polymerization initiator can be used individually or in mixture of 2 or more types. The amount of the radical polymerization initiator used is usually 0.1% by mass to 50% by mass, preferably 0.1% by mass to 20% by mass with respect to 100% by mass of the monomer.

  Examples of the solvent used in the polymerization reaction include water, alcohols, ethers, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether. Examples include propionates, aromatic hydrocarbons, ketones, and other esters.

  [B] The weight average molecular weight (Mw) of the copolymer is preferably 2,000 to 300,000, more preferably 10,000 to 200,000. [B] By setting Mw of the copolymer within the specific range, the hardness or the like of the composition for forming an organic conductive film can be increased. In addition, Mw of the polymer in this specification is a polyethylene glycol conversion weight average molecular weight measured by gel permeation chromatography (GPC) method under the following conditions.

Apparatus: GPC chromatograph Waters 2695 manufactured by Waters Corporation (TSKgel α-M 1 manufactured by Tosoh Corporation)
Detector: Waters 2414
Flow rate: 1.0 mL / min Elution solvent: 0.1 M NaCl aqueous solution / acetonitrile = 80/20 (v / v)
Column temperature: 40 ° C

  The content ratio of the [A] conjugated polymer and the [B] copolymer in the composition for forming an organic conductive film is preferably 1:10 to 1: 1, more preferably 1: 6 to 1: 2 ([A] conjugated polymer: [B] copolymer) (molar ratio).

<Other optional components>
In addition to the [A] conjugated polymer, the [B] copolymer, and the [C] solvent described later, the organic conductive film forming composition [D] is necessary as long as the effects of the present invention are not impaired. A polymerizable unsaturated compound, [E] radiation sensitive polymerization initiator, etc. can be contained. Each of these optional components may be used alone or in combination of two or more. Hereinafter, each optional component will be described in detail.

<[D] polymerizable unsaturated compound>
[D] The polymerizable unsaturated compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond. For example, ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full Orange (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl (meth) a Relate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- ( In addition to (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, etc., linear alkylene groups and alicyclic structures, and two or more isocyanate groups A urethane (meth) acrylate compound obtained by reacting a compound having a compound with a compound having one or more hydroxyl groups in the molecule and having 3 to 5 (meth) acryloyloxy groups, etc. It is below.

[D] Examples of commercially available polymerizable unsaturated compounds include Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M-8060, M-8100, M-8100, M-8530, M-8560, M-9050, Aronix TO-1450, TO-1382 (above, Toagosei Co., Ltd.) );
KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (above, Nippon Kayaku Co., Ltd.);
Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.);
As a urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.);
KAYARAD DPHA-40H, UX-5000 (Nippon Kayaku Co., Ltd.);
UN-9000H (Negami Kogyo Co.);
Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309, M M-310, M-315 (above, Toagosei Co., Ltd.);
KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301 UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.);
Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P (Negami Industrial Co., Ltd.);
SH-500B biscoat 260, 312 and 335HP (above, Osaka Organic Chemical Industry Co., Ltd.).

  [D] The polymerizable unsaturated compound is preferably a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group. The content of the [D] polymerizable unsaturated compound in the composition for forming an organic conductive film is preferably 10 parts by mass to 150 parts by mass with respect to 100 parts by mass of the [A] conjugated polymer, and 15 parts by mass. -100 mass parts is more preferable. [D] By making the content rate of a polymerizable unsaturated compound into the said specific range, the said composition for organic conductive film formation can form the organic conductive film which has sufficient hardness.

<[E] Radiation sensitive polymerization initiator>
The [E] radiation-sensitive polymerization initiator contained in the composition for forming an organic conductive film is a component that generates an active species capable of initiating polymerization of the [D] polymerizable unsaturated compound in response to radiation. Examples of such [E] radiation sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like.

  Examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9- Ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-oneoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- Ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1 -[9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4 -(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Of these, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6 -(2-Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl). ) -1- (4-Morpholin-4-yl-phenyl) -butan-1-one is more preferred.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′. -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bi Examples include imidazole. Among these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is more preferred.

  [E] A commercially available product may be used as the radiation-sensitive polymerization initiator. For example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, 2- (4-Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Irgacure 379), ethanone-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02), 1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01), bis (2 , 4,6 Trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819) (above, Ciba Specialty Chemicals) And the like.

  The content of the [E] radiation-sensitive polymerization initiator in the composition for forming an organic conductive film is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the [A] conjugated polymer, 1 mass part-5 mass parts are more preferable. [E] By making the content rate of a radiation sensitive polymerization initiator into the said specific range, the said composition for organic conductive film formation can form the organic conductive film which has sufficient hardness.

<Method for Preparing Composition for Forming Organic Conductive Film>
The composition for forming an organic conductive film is prepared by mixing other optional components at a predetermined ratio as needed in addition to the [A] conjugated polymer and the [B] copolymer. The composition for forming an organic conductive film is preferably used in a solution state after being dissolved in a [C] solvent.

  [C] The solvent used in the preparation of the composition for forming an organic conductive film is not particularly limited as long as each component is uniformly dissolved or dispersed and does not react with each component. From the viewpoint of solubility, coating uniformity, etc., methanol, ethanol, isopropanol, propylene carbonate, N-methylpyrrolidone, N, N-dimethylformamide, dimethylacetamide, cyclohexanone, acetone, toluene, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, It is preferable to contain at least one solvent selected from the group consisting of ethylene glycol and propylene glycol. When the composition for forming an organic conductive film further contains the specific [C] solvent, the dispersibility and solubility of each component and the coating uniformity can be further improved. Moreover, the electrical conductivity of the formed organic conductive film can be further improved.

<Method for forming organic conductive film>
The present invention preferably includes an organic conductive film formed from the composition for forming an organic conductive film. An organic conductive film formed from the composition for forming an organic conductive film is excellent in conductivity, heat resistance, and light resistance.

The method for forming the organic conductive film of the present invention includes:
(1) It has the process of apply | coating the said composition for organic electrically conductive film formation to a board | substrate, and forming a coating film, and (2) The process of baking the said coating film. Hereinafter, each process is explained in full detail.

[Step (1)]
This step is a step of applying the organic conductive film forming composition to a substrate to form a coating film. Examples of the substrate include resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide. The substrate may be subjected to a surface hydrophilization treatment using an ultraviolet surface modification device or the like in advance.

  Examples of the coating method of the composition for forming an organic conductive film include a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, and an inkjet coating method. An appropriate method can be adopted.

[Step (2)]
This step is a step of baking the coating film formed in the above step (1) with an appropriate heating device such as an oven to form an organic conductive film. As a baking temperature, 50 to 200 degreeC is preferable. The firing time is preferably 30 seconds to 10 minutes.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly to this Example.

<[B] Synthesis of monomer giving copolymer>
[Synthesis Example 1]
In a three-necked flask equipped with a reflux condenser and a thermometer, 10 g of glycine (Wako Pure Chemical Industries, 133 mmol), 13.06 g of maleic anhydride (Wako Pure Chemical Industries, 133 mmol) and 380 mL of acetic acid (Wako Pure Chemical) Kogyo Co., Ltd.) was added, stirred for 15 hours at room temperature in the atmosphere using a magnetic stirrer, and then heated to reflux for 8 hours. After distilling off acetic acid under reduced pressure, impurities were separated by silica gel column chromatography and recrystallized, whereby N-ethanoic acid maleimide (b-1) represented by the following formula (11.5 g, yield 56%) Got. The compound was identified by proton nuclear magnetic resonance spectroscopy.

¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) = 8.70 (1H, bs, CO ₂ H ), 6.79 (2H, s, 2 × C H ), 4.32 (2H, s, CH ₂₎

[Synthesis Example 2]
N-pentanoic acid maleimide (b-2) represented by the following formula was obtained in the same manner as in Synthesis Example 1 except that 5-aminovaleric acid was used instead of glycine.

[Synthesis Example 3]
N- (4-carboxyphenyl) maleimide (b-3) represented by the following formula was obtained in the same manner as in Synthesis Example 1 except that 4-aminobenzoic acid was used instead of glycine.

[Synthesis Example 4]
N- (ethanesulfonic acid) maleimide (b-4) represented by the following formula was obtained in the same manner as in Synthesis Example 1 except that 2-aminoethanesulfonic acid was used instead of glycine.

[Synthesis Example 5]
N- (4-sulfophenyl) maleimide sodium salt (b-5) represented by the following formula was prepared in the same manner as in Synthesis Example 1 except that 4-aminobenzenesulfonic acid sodium salt was used instead of glycine. Obtained.

<Synthesis of [B] copolymer>
[Synthesis Example 6]
A 300 mL separable flask is charged with 20.3 g of sodium styrenesulfonate (98.5 mmol, Tosoh Organic Chemical Co., Ltd.), 1.4 g of ammonium persulfate (5.9 mmol, Wako Pure Chemical Industries, Ltd.) and 161.4 g of ultrapure water. After bubbling with nitrogen gas for 10 minutes, the temperature was raised to 75 ° C. with stirring. After reaching 75 ° C., a solution obtained by dissolving 6.6 g (42.2 mmol) of the compound (b-1) giving the structural unit (I) in 80.7 g of ultrapure water was gradually added under a nitrogen atmosphere. . Thereafter, stirring was continued at 75 ° C. for 5 hours. This was passed through a cation exchange resin (Organo Corporation, IR-120H) to produce the structural unit (II) to obtain a solution of the copolymer (B-1). Mw of the copolymer (B-1) was 68,000, and the solid content concentration was 8.5%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 30: 70 (mol%). ^{For the 13} C-NMR analysis, a nuclear magnetic resonance apparatus (manufactured by JEOL, JNM-ECX400) was used.

[Synthesis Example 7]
In a 300 mL separable flask, 15.4 g (74.6 mmol) of sodium styrenesulfonate, 0.54 g (2.4 mmol) of ammonium persulfate and 161.4 g of ultrapure water were put, and after bubbling with nitrogen gas for 10 minutes, The temperature was raised to 75 ° C. with stirring. After reaching 75 ° C., a solution prepared by dissolving 11.6 g (74.6 mmol) of the compound (b-1) giving the structural unit (I) in 80.8 g of ultrapure water was gradually added under a nitrogen atmosphere. . Thereafter, stirring was continued at 75 ° C. for 5 hours. It cooled to room temperature and obtained the solution of the copolymer (B-2). Mw of the copolymer (B-2) was 107,000, and the solid content concentration was 9.4%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 50: 50 (mol%).

[Synthesis Example 8]
Except that 11.1 g (53.6 mmol) of sodium styrenesulfonate, 1.08 g (4.8 mmol) of ammonium persulfate and 15.9 g (80.4 mmol) of the compound (b-2) giving the structural unit (I) were used. By operating in the same manner as in Synthesis Example 6, a solution of copolymer (B-3) was obtained. Mw of the copolymer (B-3) was 98,000, and the solid content concentration was 8.1%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 60: 40 (mol%).

[Synthesis Example 9]
Except for using 3.1 g (12.8 mmol) of the compound (b-3) giving 23.8 g (115.4 mmol) of sodium styrenesulfonate, 1.35 g (5.9 mmol) of ammonium persulfate and the structural unit (I). By operating in the same manner as in Synthesis Example 6, a solution of copolymer (B-4) was obtained. Mw of the copolymer (B-4) was 145,000, and the solid content concentration was 7.6%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 10: 90 (mol%).

[Synthesis Example 10]
Except that 2.7 g (13.1 mmol) of sodium styrenesulfonate, 1.1 g (4.8 mmol) of ammonium persulfate and 24.2 g (117.9 mmol) of compound (b-4) giving structural unit (I) were used. By operating in the same manner as in Synthesis Example 6, a solution of the copolymer (B-5) was obtained. Mw of the copolymer (B-5) was 52,000, and the solid content concentration was 8.1%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 90: 10 (mol%).

[Synthesis Example 11]
Except for using 9.0 g (43.6 mmol) of sodium styrenesulfonate, 0.26 g (1.2 mmol) of ammonium persulfate and 18.0 g (65.4 mmol) of the compound (b-5) giving the structural unit (I). The solution of copolymer (B-6) was obtained in the same manner as in Synthesis Example 6. Mw of the copolymer (B-6) was 181,000, and the solid content concentration was 7.9%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 60: 40 (mol%).

[Synthesis Example 12]
Into a 300 mL separable flask, 26.8 g (130.8 mmol) of the compound (b-4) that gives the structural unit (I), 1.61 g (7.1 mmol) of ammonium persulfate and 241.6 g of ultrapure water were placed for 10 minutes. After bubbling with nitrogen gas, the temperature was raised to 75 ° C. with stirring. Thereafter, stirring was continued at 75 ° C. for 5 hours. This was passed through a cation exchange resin to obtain a solution of a copolymer (B-7). Mw of the copolymer (B-7) was 43,000, and the solid content concentration was 6.9%.

[Synthesis Example 13]
In a 300 mL separable flask, 14.0 g (67.8 mmol) of sodium styrenesulfonate, 2.38 g of sodium methallylsulfonate (Asahi Kasei Finechem, 15.1 mmol), 1.08 g (4.8 mmol) of ammonium persulfate and ultra After putting 161.4 g of pure water and bubbling with nitrogen gas for 10 minutes, the temperature was raised to 75 ° C. while stirring. After reaching 75 ° C., a solution prepared by dissolving 10.5 g (67.8 mmol) of the compound (b-1) giving the structural unit (I) in 80.7 g of ultrapure water was gradually added under a nitrogen atmosphere. . Thereafter, stirring was continued at 75 ° C. for 5 hours. This was passed through a cation exchange resin to obtain a solution of a copolymer (B-8). Mw of the copolymer (B-8) was 28,000, and the solid content concentration was 9.2%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 45: 55 (mol%).

[Synthesis Example 14]
A 300 mL separable flask was charged with 10.2 g (49.5 mmol) of sodium styrenesulfonate, 0.81 g (3.5 mmol) of ammonium persulfate and 161.4 g of ultrapure water, and after bubbling with nitrogen gas for 10 minutes, stirring was performed. The temperature was raised to 75 ° C. After reaching 75 ° C., 10.5 g (67.8 mmol) of the compound (b-1) giving the structural unit (I) and 26.8 g (130.8 mmol) of the compound (b-5) were added to 80.7 g of ultrapure water. The solution dissolved in was gradually added under a nitrogen atmosphere. Thereafter, stirring was continued at 75 ° C. for 5 hours. This was passed through a cation exchange resin to obtain a solution of a copolymer (B-9). Mw of the copolymer (B-9) was 195,000, and the solid content concentration was 8.6%. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II) = 60: 40 (mol%).

[Synthesis Example 15]
A 300 mL separable flask is charged with 18.0 g (86.6 mmol) of 2-acrylamido-2-methylpropanesulfonic acid, 0.72 g (3.1 mmol) of ammonium persulfate and 251.3 g of ultrapure water for 10 minutes with nitrogen gas. And then heated to 75 ° C. with stirring. Thereafter, stirring was continued at 75 ° C. for 5 hours. This was passed through a cation exchange resin to obtain a solution of a copolymer (CB-1). Mw of the copolymer (CB-1) was 114,000, and the solid content concentration was 6.7%.

[Synthesis Example 16]
In a 300 mL separable flask, 17.3 g (82.6 mmol) of sodium styrenesulfonate, 9.87 g (55.1 mmol) of N-cyclohexylmaleimide, 1.08 g (6.6 mmol) of azobisisobutyronitrile and propylene glycol After putting 242.3 g of monomethyl ether and bubbling with nitrogen gas for 10 minutes, the temperature was raised to 75 ° C. with stirring. Thereafter, stirring was continued at 75 ° C. for 5 hours. After the solvent was distilled off, it was dissolved in ultrapure water so that the solid content concentration was 6% by mass, and this was passed through a cation exchange resin to obtain a solution of a copolymer (CB-2). The Mw of the copolymer (CB-2) was 69,000, and the solid content concentration was 5.2%.

[Synthesis Example 17]
In a 300 mL separable flask, 9.7 g (144.2 mmol) of methacrylonitrile, 17.2 g (96.1 mmol) of N-cyclohexylmaleimide, 1.08 g (6.6 mmol) of azobisisobutyronitrile and propylene glycol monomethyl After putting 242.0 g of ether and bubbling with nitrogen gas for 10 minutes, the temperature was raised to 75 ° C. with stirring. Thereafter, stirring was continued at 75 ° C. for 5 hours. After the solvent was distilled off, it was dissolved in ultrapure water so as to have a solid content concentration of 6% by mass, and this was passed through a cation exchange resin to obtain a solution of a copolymer (CB-3). Mw of the copolymer (CB-3) was 131,000, and the solid content concentration was 4.9%.

<Preparation of composition for forming organic conductive film>
The detail of each component used for preparation of the composition for organic electrically conductive film formation as an Example and a comparative example is shown below.

<[A] Compound giving conjugated polymer>
a-1: 3,4-ethylenedioxythiophene (Aldrich)
a-2: 3-hexylthiophene (Tokyo Chemical Industry Co., Ltd.)
a-3: Aniline (Wako Pure Chemical Industries)
a-4: Pyrrole (Wako Pure Chemical Industries, Ltd.)

<Components corresponding to [B] copolymer>
CB-4: Polystyrene sulfonic acid (Aldrich)
<[C] solvent>
C-1: Dimethyl sulfoxide C-2: N, N-dimethylformamide C-3: Ethylene glycol

[Example 1]
In a 250 mL separable flask, 0.91 g of compound (a-1) as a compound that gives [A] conjugated polymer, (B-1) aqueous solution (solid content concentration 8.5 as a [B] copolymer) %) 57.3 g and ultrapure water 125.0 g were added, and after bubbling with nitrogen gas for 10 minutes, 3.4 g of sodium persulfate (Wako Pure Chemical Industries, Ltd.) and ferric sulfate / n hydrate (Wako Pure) Yakugyo Co., Ltd.) A solution prepared by dissolving 0.91 g in 62.5 g of ultrapure water was gradually added under a nitrogen atmosphere. After stirring at room temperature for 24 hours, the inorganic salt component was removed by passing through a cation exchange resin (organo, IR-120H) and an anion exchange resin (organo, IRA-400OH). The solution was diluted with ultrapure water so that the concentration became 1.2% to obtain a dispersion. (C-1) 5 mass% as a [C] solvent was added with respect to this dispersion whole quantity, and the composition for organic electrically conductive film formation was prepared.

[Examples 2 to 13 and Comparative Examples 1 to 4]
Each composition for forming an organic conductive film was prepared in the same manner as in Example 1 except that each type and amount of each component shown in Table 1 were contained. Table 1 shows the molar ratio of the content of the [A] conjugated polymer and the [B] copolymer contained in the organic conductive film forming composition as a result.

[Example 14]
In a 300 mL separable flask, 1.10 g of compound (a-2) as a compound that gives [A] conjugated polymer, aqueous solution of copolymer (B-2) (solid content concentration: 9.4%) 76.9 g and 125.0 g of ultrapure water were added, and after bubbling with nitrogen gas for 10 minutes, 3.4 g of sodium persulfate (Wako Pure Chemical Industries, Ltd.) and ferric sulfate / n hydrate (Wako Pure Chemical Industries, Ltd.) A solution prepared by dissolving 0.91 g in 62.5 g of ultrapure water was gradually added under a nitrogen atmosphere. After stirring at room temperature for 24 hours, the inorganic salt component was removed by passing through a cation exchange resin (organo, IR-120H) and an anion exchange resin (organo, IRA-400OH). Dilution with ultrapure water to a concentration of 1.2% gave a dispersion. A dispersion was obtained. (C-1) 5 mass% as a [C] solvent was added with respect to this dispersion whole quantity, and the composition for organic electrically conductive film formation was prepared.

[Example 15]
In a 300 mL separable flask, 40 mL of 0.5 M hydrochloric acid was added, and 0.59 g of the compound (a-3) as a compound giving a [A] conjugated polymer was gradually added dropwise, followed by stirring for 1 hour. Into this, 49.1 g of an aqueous solution of copolymer (B-2) (solid content concentration: 9.4%) and 99.5 g of ultrapure water were put, and after bubbling with nitrogen gas for 10 minutes, sodium persulfate (sum) (Hikari Pure Chemical Industries, Ltd.) A solution dissolved in 2.0 g of ultrapure water (2.0 g) was gradually added under a nitrogen atmosphere. After stirring for 12 hours at room temperature, the inorganic salt component is removed by passing through the cation exchange resin and anion exchange resin, and diluted with ultrapure water to a solid content concentration of 1.2%. A dispersion was obtained. (C-1) 5 mass% as a [C] solvent was added with respect to this dispersion whole quantity, and the composition for organic electrically conductive film formation was prepared.

[Example 16]
In a 300 mL separable flask, 0.54 g of compound (a-4) as a compound that gives [A] conjugated polymer, aqueous solution of copolymer (B-2) (solid content concentration 9.4%) 61.5 g and 128.0 g of ultrapure water were added, and after bubbling with nitrogen gas for 10 minutes, it was cooled to −20 ° C. and stirred for 1 hour. A solution prepared by dissolving 3.8 g of sodium persulfate (Wako Pure Chemical Industries, Ltd.) in 40.5 g of ultrapure water was gradually added while maintaining the temperature at −20 ° C. in a nitrogen atmosphere. After stirring at −20 ° C. for 12 hours, the inorganic salt component is removed by passing through the cation exchange resin and anion exchange resin, and diluted with ultrapure water to a solid content concentration of 1.2%. To obtain a dispersion. (C-1) 5 mass% as a [C] solvent was added with respect to this dispersion whole quantity, and the composition for organic electrically conductive film formation was prepared.

<Evaluation>
Using the prepared composition for forming an organic conductive film, an organic conductive film was formed as follows, and the following evaluation was performed. The results are shown in Table 1. In addition, "-" in Table 1 indicates that measurement was impossible.

<Formation of organic conductive film>
A 50 μm-thick polyethylene terephthalate film (Toyobo Co., Ltd., A4100) was subjected to surface hydrophilization treatment (irradiation amount: 0.5 J / cm ² ) using an ultraviolet surface modification device (Sen Special Light Company). Next, each organic conductive film forming composition is dropped onto this film, spread using a bar coater (Tester Sangyo Co., Ltd., WET film thickness 22.9 μm), and baked in an oven (100 ° C. for 3 minutes). An organic conductive film was formed.

[Conductivity (S / cm)]
The electrical conductivity (S / cm) of each organic conductive film was measured using a resistivity meter Loresta MCP-T610 (Dia Instruments Co., Ltd.) by a four-terminal four-probe method (JIS-K7194 compliant). It was. The larger this value, the better the conductivity.

[Heat-resistant(%)]
Each organic conductive film was placed in an oven at 100 ° C., and the conductivity after 200 hours was measured. The electric conductivity maintenance rate was calculated from the result of the electric conductivity (%) measurement and the electric conductivity after heating before being put in the oven, and was defined as heat resistance (%). The larger this value, the better the heat resistance.

[Light resistance (%)]
Each organic conductive film was irradiated with ultrahigh pressure mercury lamp light (500 W) obtained by cutting light of 400 nm or less with a filter from a distance of 15 cm, and the conductivity after 50 hours was measured. The retention rate of conductivity was calculated from the result of the measurement of conductivity (%) before irradiation, that is, the conductivity after irradiation, and defined as light resistance (%). The larger this value, the better the light resistance.

  From the results of Table 1, it was found that the composition for forming an organic conductive film can form an organic conductive film having excellent conductivity, heat resistance, and light resistance.

  This invention can provide the composition for electrically conductive film formation which can form the organic electrically conductive film which is excellent in electrical conductivity, heat resistance, and light resistance. Therefore, the said composition for organic conductive film formation is suitable as a formation material of the organic conductive film used for a display element, a touch panel, etc.

Claims (7)

A composition for forming an organic conductive film, comprising: [A] a conjugated polymer; and [B] a copolymer containing at least the structural unit (I) represented by the following formula (1).

(In Formula (1), R ¹ is a methylene group, an alkylene group having 2 to 12 carbon atoms, a divalent alicyclic group having 4 to 20 carbon atoms, a phenylene group, or a naphthylene group. R ² is a hydroxyl group. , Carboxyl group, sulfo group, phosphono group or a salt of these groups.)   [A] The conjugated polymer is polyaniline, polypyrrole, polythiophene, poly (N-alkylpyrrole), poly (3-alkylthiophene) or poly (3-alkoxythiophene, poly (3,4-alkylenedioxythiophene). A composition for forming an organic conductive film according to claim 1.   [A] The composition for forming an organic conductive film according to claim 2, wherein the conjugated polymer is poly (3,4-ethylenedioxythiophene). [B] The composition for forming an organic conductive film according to claim 1, wherein the copolymer further comprises a structural unit (II) represented by the following formula (2): object.

(In Formula (2), R ³ is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. N is an integer of 0 to 4. However, when R ³ is plural. The plurality of R ³ may be the same or different.)   [B] The composition for forming an organic conductive film according to any one of claims 1 to 4, wherein the content of the structural unit (I) in the copolymer is 10 mol% or more. [C] Group consisting of methanol, ethanol, isopropanol, propylene carbonate, N-methylpyrrolidone, N, N-dimethylformamide, dimethylacetamide, cyclohexanone, acetone, toluene, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, ethylene glycol and propylene glycol The composition for forming an organic conductive film according to any one of claims 1 to 5, further comprising at least one solvent selected from the above.   The organic conductive film formed from the composition for organic conductive film formation of any one of Claims 1-6.