JP5582189B2 - Photosensitive conductive film, method for forming conductive film, and method for forming conductive pattern - Google Patents

Description

  The present invention relates to a photosensitive conductive film, a method for forming a conductive film, and a method for forming a conductive pattern, and in particular, an electrode wiring provided in a device such as a flat panel display such as a liquid crystal display element, a touch screen, a solar cell, or an organic EL. The present invention relates to a method for forming a conductive pattern.

  Among large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices, those equipped with a liquid crystal display element and a touch screen are widely used. In liquid crystal display elements and touch screens, transparent conductive films are used where transparency is required, such as transparent electrodes. The same applies to solar cells.

  Known materials that can form a transparent conductive film include ITO (Indium-Tin-Oxide), indium oxide, tin oxide, and the like. These materials show high transmittance with respect to visible light, and have become mainstream as materials for forming transparent electrodes such as substrates for liquid crystal display elements.

  In a liquid crystal display device, a part of a wiring, a pixel electrode, a terminal, or the like may be formed using a transparent conductive film. In this case, the transparent conductive film needs to have a predetermined shape. As a method for patterning the transparent conductive film, a method is used in which after forming the transparent conductive film, a resist pattern is formed thereon by photolithography, and the conductive film is patterned by wet etching. As an etching solution, a mixed solution composed of two solutions of hydrochloric acid and ferric chloride is often used for an ITO film or an indium oxide film.

  On the other hand, it has been studied to form a transparent conductive film using a material other than ITO. For example, in Patent Document 1 below, a conductive and transparent cured film is formed by applying a radiation curable conductive composition containing an organic conductive polymer such as polythiophene or polyaniline to a substrate surface and curing the composition. A method of forming is disclosed. Patent Document 2 below discloses a method of applying a resist material such as diazosulfonium on a support, further applying a thiophene organic conductive material thereon, and then forming a conductive pattern by exposure and development. Is disclosed.

JP 2005-170996 A JP-T-2004-504893

  Incidentally, an ITO film or a tin oxide film is generally formed by a sputtering method, but the properties of the film are likely to change depending on the difference in sputtering method, sputtering power, gas pressure, substrate temperature, type of atmospheric gas, and the like. Differences in the film quality of the transparent conductive film due to variations in sputtering conditions cause variations in the etching rate when the film is wet-etched, resulting in patterning defects in the transparent conductive film, which tends to reduce product yield. For this reason, the method using ITO or the like requires a long time for sputtering, resist formation, etching, and cost, and is a heavy burden in terms of cost. In addition, it is difficult for such a method to obtain patterning accuracy uniformity.

  On the other hand, the formation of a conductive pattern using an organic conductive material has the following problems. Patent Document 1 does not disclose the formation of a conductive pattern. It is conceivable to perform patterning by etching using a mask. However, since there is no appropriate etching solution, it is necessary to process using plasma etching or laser.

  Patent Document 2 discloses a method in which a liquid obtained by mixing a photosensitive material of an organic conductive material and a diazo compound is applied to a support and patterning, and a photosensitive material is further provided between the support and a layer made of the organic conductive material and the photosensitive material. A method of arranging has been proposed. However, in these methods, the adhesiveness between the conductive pattern and the substrate when a conductive pattern is to be provided on a desired substrate is not considered, and surface treatment of the substrate is necessary.

  The present invention has been made in view of the above-described problems of the prior art, and on a substrate, the adhesiveness with the substrate is sufficient, and a conductive pattern containing an organic conductive material is easily formed with sufficient resolution. It is an object of the present invention to provide a photosensitive conductive film that can be performed, a method for forming a conductive film using the photosensitive conductive film, and a method for forming a conductive pattern.

  In order to solve the above problems, the present invention provides a photosensitive conductive film having a structure in which a support, a conductive layer containing an organic conductive material, and a photosensitive resin layer are laminated in this order.

  According to the photosensitive conductive film of the present invention, by having the above configuration, the photosensitive conductive film is attached so that the photosensitive resin layer is in close contact with the substrate, and is exposed and developed in a simple process. And a desired conductive pattern having sufficient transparency can be easily formed.

  In addition, according to the photosensitive conductive film of the present invention, the photosensitive conductive film is attached on the substrate so that the photosensitive resin layer is in close contact, and is exposed to light so that sufficient transparency and good for the base material are obtained. It is possible to form a conductive film having both excellent adhesiveness.

  In the photosensitive conductive film of the present invention, the organic conductive material is preferably a polymer of a thiophene derivative from the viewpoints of transparency and conductivity.

  Further, from the viewpoint of further improving the patterning property of the conductive film and the adhesion to the substrate, the photosensitive resin layer comprises a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. It is preferable that it consists of the photosensitive resin composition to contain.

  In the photosensitive conductive film of the present invention, a protective film may be further laminated on the side opposite to the conductive layer side of the photosensitive resin layer in terms of preventing foreign matter adhesion and scratches during the period from manufacture to use. preferable. This protective film can be removed when the photosensitive conductive film is used.

  In the present invention, the photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a base material, and at least the photosensitive resin layer and the conductive layer are laminated in this order on the base material. The conductive resin layer is exposed, and a method for forming a conductive film is provided.

  According to the method for forming a conductive film of the present invention, a photosensitive resin layer and a conductive layer are provided on a base material in this order by attaching the photosensitive resin layer of the photosensitive conductive film of the present invention to the base material. With a simple process of exposing, a conductive film made of the conductive layer can be easily formed on the substrate. This conductive film is sufficiently bonded onto the base material when the photosensitive resin layer is cured by exposure.

  In the present invention, the photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a substrate, and at least the photosensitive resin layer and the conductive layer are laminated in this order on the substrate, and the laminated photosensitive property Provided is a method for forming a conductive pattern, which comprises exposing and developing a resin layer.

  According to the method for forming a conductive pattern of the present invention, a photosensitive resin layer and a conductive layer are provided on a base material in this order by attaching the photosensitive resin layer of the photosensitive conductive film of the present invention to the base material. A conductive pattern obtained by patterning the conductive layer on a substrate can be easily formed by a simple process of exposure and development. This conductive pattern is sufficiently adhered onto the substrate by curing the photosensitive resin layer by exposure.

  The present invention also provides a conductive film substrate comprising a substrate and a conductive film formed on the substrate by the conductive film formation method of the present invention.

  The present invention also provides a conductive film substrate comprising a substrate and a conductive pattern formed on the substrate by the conductive pattern forming method of the present invention.

  According to the present invention, a photosensitive conductive film that has sufficient adhesion to a substrate on a substrate and that can easily form a conductive pattern containing an organic conductive material with sufficient resolution, and A conductive film forming method and a conductive pattern forming method using the same can be provided.

It is a schematic cross section which shows one Embodiment of the photosensitive conductive film of this invention. It is a schematic cross section for demonstrating one Embodiment of the formation method of the conductive pattern of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” or “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” or “methacryloyl” corresponding thereto.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive conductive film of the present invention. A photosensitive conductive film 10 shown in FIG. 1 is formed by laminating a film-like support 1, a conductive layer 2 containing an organic conductive material, a photosensitive resin layer 3, and a protective film 4 in this order.

  Hereinafter, each of the film-like support (hereinafter sometimes referred to as “film support”), the conductive layer, the photosensitive resin layer, and the protective film constituting the photosensitive conductive film 10 according to the present embodiment will be described in detail. To do.

  The film support 1 is preferably a transparent support film. Transparent here means having transparency to the exposure light beam in the exposure step after transfer to the substrate, and in this embodiment, it is preferable to have transparency in the ultraviolet (300 to 400 nm) region.

  Examples of the transparent support film include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate film, polypropylene film, and polycarbonate film. Among these, it is preferable to use a polyethylene terephthalate film from the viewpoint of transparency and heat resistance. These polymer films were removed when developing the photosensitive resin layer 3 later or to expose the formed conductive film, and thus were subjected to a surface treatment that would make removal impossible. It must not be a thing or a material.

  The thickness of the support film is preferably 5 to 300 μm, and more preferably 20 to 300 μm. When the thickness of the support film is less than 5 μm, the mechanical strength decreases, and when the conductive film is formed, when the photosensitive resin layer is formed, or when the support film is peeled off before the development of the photosensitive resin layer In addition, the support film tends to be easily broken. On the other hand, when the thickness exceeds 300 μm, the resolution tends to decrease when the actinic ray is irradiated to the photosensitive resin layer through the support film, and the price tends to increase. It is in.

  Examples of the organic conductive material contained in the conductive layer 2 include a polymer of thiophene or a thiophene derivative and a polymer of aniline or an aniline derivative. Specifically, polyethylenedioxythiophene, polyhexylthiophene, polyaniline and the like can be used. Moreover, it is possible to use commercially available products such as “Clevios P” (trade name, manufactured by HC Starck Co., Ltd.) and “Sepulzida OC-U1” (trade name, manufactured by Shin-Etsu Polymer Co., Ltd.). it can.

  The organic conductive material included in the conductive layer 2 is preferably a material that can form a pattern by light irradiation. In addition, the organic conductive material may be contained in the conductive layer 2 in combination with a material capable of forming a pattern by light irradiation as long as the effect of the present invention is obtained.

  Examples of the polymer of thiophene or a thiophene derivative include a polymer having a repeating unit that can be represented by the following formula (1).

In Formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, or an alkoxy having 1 to 20 carbon atoms. Group, an arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 nuclear carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 40 nuclear carbon atoms, and adjacent substituents They may be bonded to each other to form a ring. In addition, as a terminal group of a polymer, a hydrogen atom or a substituted or unsubstituted monovalent group is mentioned, respectively.

In R ₁ and R ₂ of the above formula (1), examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n- Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- Hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl Group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 3,5-tetramethylcyclohexyl group and the like. Among these, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group are preferable. N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group N-octadecyl group, neopentyl group, 1-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, and 3,5-tetramethylcyclohexyl group Can be mentioned.

  Examples of the haloalkyl group having 1 to 20 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group. Of these, a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group are preferable.

  Examples of the alkoxy group having 1 to 20 carbon atoms include those represented by -OY, wherein Y is the same as described for the alkyl group, and preferred examples are also the same.

  Examples of the arylamino group having 6 to 40 carbon atoms include a diphenylamino group or the like, or a phenyl group, a naphthyl group, an anthracenyl group, a triphenylenyl group, a fluoranthenyl group, a biphenyl having a diphenylamino group or an amino group as a substituent. Groups and the like. Of these, a phenyl group and a naphthyl group having a diphenylamino group or an amino group as a substituent are preferable.

  Examples of the aryl group having 6 to 40 nuclear carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a triphenylenyl group. Examples of the substituent include a methyl group, an ethyl group, a cyclohexyl group, an isopropyl group, a butyl group, and a phenyl group. Of these, a substituted or unsubstituted phenyl group, naphthyl group, and biphenyl group are preferable.

  Examples of the substituted or unsubstituted heterocyclic group having 2 to 40 carbon atoms include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 1-imidazolyl group, and 2-imidazolyl. Group, 1-pyrazolyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 2-imidazopyridinyl group, 3-Imidazopyridinyl group, 5-Imidazopyridinyl group, 6-Imidazopyridinyl group, 7-Imidazopyridinyl group, 8-Imidazopyridinyl group, 3-Pyridinyl group, 4-Pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5 -Isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7- Quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6 Isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9- Carbazolyl group, β-carbolin-1-yl, β-carbolin-3-yl, β-carbolin-4-yl, β-carbolin-5-yl, β-carbolin-6-yl, β-carbolin-7-yl Β-carbolin-6-yl, β-carbolin-9-yl, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6 -Phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1- Cridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthroline-3-yl group, 1,7-phenanthroline -4-yl group, 1,7-phenanthroline-5-yl group, 1,7-phenanthroline-6-yl group, 1,7-phenanthroline-8-yl group, 1,7-phenanthroline-9-yl group, 1,7-phenanthroline-10-yl group, 1,8-phenanthroline-2-yl group, 1,8-phenanthroline-3-yl group, 1,8-phenanthroline-4-yl group, 1,8-phenanthroline- 5-yl group, 1,8-phenanthroline-6-yl group, 1,8-phenanthroline-7-yl group, 1,8-phenanthroline-9-yl group, 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2-yl group, 1,9-phenanthroline-3-yl group, 1,9-phenanthroline-4-yl group, 1,9-phenanthroline- 5-yl group, 1,9-phenanthroline-6-yl group, 1,9-phenanthroline-7-yl group, 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-yl group, 1 , 10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-4-yl group, 1,10-phenanthroline-5-yl group, 2,9-phenanthroline-1 -Yl group, 2,9-phenanthroline-3-yl group, 2,9-phenanthroline-4-yl group, 2,9-phenanthroline-5-yl group, 2,9- Enanthroline-6-yl group, 2,9-phenanthroline-7-yl group, 2,9-phenanthroline-8-yl group, 2,9-phenanthroline-10-yl group, 2,8-phenanthroline-1-yl group 2,8-phenanthroline-3-yl group, 2,8-phenanthroline-4-yl group, 2,8-phenanthroline-5-yl group, 2,8-phenanthroline-6-yl group, 2,8-phenanthroline -7-yl group, 2,8-phenanthroline-9-yl group, 2,8-phenanthroline-10-yl group, 2,7-phenanthroline-1-yl group, 2,7-phenanthroline-3-yl group, 2,7-phenanthroline-4-yl group, 2,7-phenanthroline-5-yl group, 2,7-phenanthroline-6-yl group, 2,7-phenanthroline 8-yl group, 2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3 -Phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group Group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl Group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl group, 3-methyl group, Tilpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group, 3 -(2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group, 4-t-butyl-3-indolyl group, 1-dibenzofuranyl group 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 4-dibenzothiopheny Group, 1-silafluorenyl group, 2-silafluorenyl group, 3-silafluorenyl group, 4-silafluorenyl group, 1-germafluorenyl group, 2-germafluorenyl group, 3-germafluorenyl group, and 4-germa A fluorenyl group etc. are mentioned.

  Among these, 2-pyridinyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 2-imidazopyr Zinyl group, 3-Imidazopyridinyl group, 5-Imidazopyridinyl group, 6-Imidazopyridinyl group, 7-Imidazopyridinyl group, 8-Imidazopyridinyl group, 3-Pyridinyl group, 4 -Pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3 -Isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzo Furanyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 4-dibenzothiophenyl group, 1-silafluorenyl group, 2-silafluorenyl group, 3-silafluorenyl group, 4-silafluorenyl Group, 1-germafluorenyl group, 2-germafluorenyl group, 3-germafluorenyl group, 4-germafluorenyl group.

  Examples of the substituent include a methyl group, an ethyl group, a cyclohexyl group, an isopropyl group, a butyl group, and a phenyl group.

R ₁ and R ₂ may be bonded to each other to form a ring. As the ring, for example, a dioxane ring, a benzene ring, a cyclohexyl ring, and a naphthyl ring are preferable.

Y ₁ and Y _{2 in} formula (1) are preferably each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 nuclear carbon atoms, or a substituted or unsubstituted group. A heterocyclic group having 2 to 40 nuclear carbon atoms. Examples of the alkyl group, aryl group, or heterocyclic group include the same groups as R ₁ and R ₂ .

  As the polythiophene or polythiophene derivative represented by the formula (1), commercially available products or those synthesized by a known method can be used. The molecular weight of the polythiophene or polythiophene derivative is generally in the range of 1,000 to 100,000 as the number average molecular weight. When the molecular weight is smaller than this, sufficient conductivity based on the π-electron conjugated system is not exhibited. On the other hand, when the molecular weight is too large, the film becomes viscous and difficult to form a thin film. Repeat units are bonded to adjacent repeat units in a head-tail, head-head or tail-tail manner to form a polymer. If the alkyl group or alkoxy group substituted at the 3-position of the thiophene ring is too long, the steric structure of the molecule may be disturbed and the mobility may be impaired. preferable.

  The conductive layer 2 is, for example, a conductive layer forming dispersion obtained by adding the above-described organic conductive material to the film support 1 with water and / or an organic solvent, and if necessary, a dispersion stabilizer such as a surfactant. After coating, it can be formed by drying. The coating can be performed by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. The drying can be performed at 30 to 150 ° C. for about 1 to 30 minutes using a hot air convection dryer or the like.

  The thickness of the conductive layer 2 varies depending on the use of the conductive film or conductive pattern formed using the photosensitive conductive film of the present invention and the required conductivity, but is preferably 1 μm or less, and 0.01 μm to 0 μm. More preferably, it is 0.5 μm, particularly preferably 0.01 μm to 0.3 μm. When the thickness of the conductive layer 2 is 1 μm or less, it becomes easy to ensure light transmission.

  The photosensitive resin layer 3 is preferably composed of a photosensitive resin composition containing a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.

  Examples of the binder polymer include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, and phenol resin. From the viewpoint of excellent alkali developability, it is preferable to use an acrylic resin. These can be used individually by 1 type or in combination of 2 or more types.

  The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyl toluene, α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl, and the like. -Ethers of vinyl alcohol such as n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, ( (Meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acryl Acid, α-chloro ( T) Acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and the like, Examples include fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

  Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (2), and compounds in which the alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like.

In General Formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and These structural isomers are mentioned.

  Examples of the compound represented by the general formula (2) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) ) Acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) ) Acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester. These can be used individually by 1 type or in combination of 2 or more types.

  Moreover, it is preferable that the binder polymer used by this invention has a carboxyl group from a viewpoint of making alkali developability more favorable. Such a binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid as described above is preferable.

  The ratio of the carboxyl group of the binder polymer is 12 to 50% by mass from the viewpoint of balancing alkali developability and alkali resistance as the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used. It is preferable that it is 12-40 mass%, It is especially preferable that it is 15-30 mass%, It is very preferable that it is 15-25 mass%. When the ratio of the polymerizable monomer having a carboxyl group is less than 12% by mass, the alkali developability tends to be inferior, and when it exceeds 50% by mass, the alkali resistance tends to be inferior.

  The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 40000 to 150,000, from the viewpoint of balancing the mechanical strength and alkali developability. When the weight average molecular weight is less than 20000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long. In addition, the weight average molecular weight in this invention is a value measured by the gel permeation chromatography method (GPC), and converted with the analytical curve created using standard polystyrene.

  These binder polymers are used individually by 1 type or in combination of 2 or more types. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. A binder polymer is mentioned.

  Next, the photopolymerizable compound having an ethylenically unsaturated bond will be described. Examples of the photopolymerizable compound having an ethylenically unsaturated bond include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, 2,2-bis (4-((meth) acryloxy). Polyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane Such as bisphenol A (meth) acrylate compounds, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, γ-chloro- β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl- β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate, (meth) acrylic acid alkyl ester, and the like. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, having 2 to 14 ethylene groups and 2 to 14 propylene groups, polypropylene polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxy Tetramethylolmethane (meta) such as citri (meth) acrylate, trimethylolpropane (meth) acrylate such as trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, etc. ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytri (meth) acrylate, etc., pentaerythritol (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Dipentaerythritol (meth) such as (meth) acrylate and dipentaerythritol alkoxypenta (meth) acrylate Acrylate, and the like.

  Among the above, at least one selected from trimethylolpropane (meth) acrylate, tetramethylolmethane (meth) acrylate, pentaerythritol (meth) acrylate, and dipentaerythritol (meth) acrylate is excellent in transparency and adhesiveness. It is preferable to contain.

  Examples of the urethane monomer include a (meth) acryl monomer having a hydroxyl group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris [(meth) acryloxytetraethylene glycol isocyanate] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. “EO” represents ethylene oxide, and an EO-modified compound has a block structure of an ethylene oxide group. “PO” represents propylene oxide, and the PO-modified compound has a block structure of a propylene oxide group. Examples of the EO-modified urethane di (meth) acrylate include “UA-11” (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). Examples of the EO and PO-modified urethane di (meth) acrylate include “UA-13” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  The content ratio of the photopolymerizable compound is preferably 30 to 80 parts by mass, and more preferably 40 to 70 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. If this content is less than 30 parts by mass, the photocuring will be insufficient, and the curability of the transferred conductive film tends to be inadequate, and if it exceeds 80 parts by mass, storage becomes difficult when the film is wound as a film. Tend.

  Next, the photopolymerization initiator will be described. Examples of the photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4. '-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 Aromatic ketones such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone 1-chloroanthraquinone Quinones such as 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether Benzoin ether compounds such as benzoin, benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [ Oxime ester compounds such as 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), benzyl derivatives such as benzyldimethyl ketal, 2- (o- Chlorophenyl) -4,5-diphenylimidazo Dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9- Examples thereof include acridine derivatives such as phenylacridine and 1,7-bis (9,9′-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, and oxazole compounds. Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. Among these, from the viewpoint of transparency, aromatic ketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1,2-octanedione, 1- [4 An oxime ester compound such as — (phenylthio)-, 2- (o-benzoyloxime)] is more preferable. These are used alone or in combination of two or more.

  The content ratio of the photopolymerization initiator is preferably 0.1 to 30 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. If this content is less than 0.1 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 30 parts by mass, the absorption at the surface of the composition increases during exposure and the internal photocuring is insufficient. Tend to be.

  For the photosensitive resin layer 3, a plasticizer such as p-toluenesulfonamide, a filler, an antifoaming agent, a flame retardant, a stabilizer, an adhesion imparting agent, a leveling agent, a peeling accelerator, and an antioxidant, if necessary. Additives such as an agent, a fragrance, an imaging agent, and a thermal crosslinking agent can be contained alone or in combination of two or more. The addition amount of these additives is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

  The photosensitive resin layer 3 is formed on the transparent film support 1 on which the conductive layer 2 is formed, as required, methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, It is preferable to apply a solution of a photosensitive resin composition having a solid content of about 10 to 60% by mass dissolved in a solvent such as propylene glycol monomethyl ether or a mixed solvent thereof. However, in this case, the amount of the remaining organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less in order to prevent the organic solvent from diffusing in the subsequent step.

  The photosensitive resin composition can be applied by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. Moreover, drying can be performed at 70-150 degreeC for about 5 to 30 minutes.

  Although the thickness of the photosensitive resin layer 3 changes with uses, it is preferable that it is 1-50 micrometers in thickness after drying, it is more preferable that it is 1-20 micrometers, and it is especially preferable that it is 1-10 micrometers. If the thickness is less than 1 μm, coating tends to be difficult industrially. If the thickness exceeds 50 μm, the sensitivity due to the decrease in light transmission tends to be insufficient, and the photocurability of the photosensitive resin layer tends to be reduced. Moreover, it is preferable that the thickness of the photosensitive resin layer 3 is 1 micrometer or more from the point which is excellent in adhesiveness and patterning.

  Next, the protective film will be described. In the photosensitive conductive film of this invention, as shown in FIG. 1, a protective film can be laminated | stacked on the surface on the opposite side to the film support body 1 side of the photosensitive resin layer 3. As shown in FIG.

  As the protective film, for example, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, and a polyethylene film can be used. You may use the polymer film similar to the above-mentioned film support body as a protective film.

  The adhesive force between the protective film and the photosensitive resin layer is such that the conductive film 2 and the photosensitive resin layer 3 are adhered to the film support 1 in order to facilitate the peeling of the protective film from the photosensitive resin layer. Is preferably smaller.

The protective film is preferably a low fish eye film. Specifically, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 / m ² or less. "Fish eye" means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

  The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. When the thickness of the protective film is less than 1 μm, the protective film tends to be broken during lamination, and when it exceeds 100 μm, the price tends to increase.

  The photosensitive conductive film may further have layers such as an adhesive layer and a gas barrier layer on the film support.

  The photosensitive conductive film can be stored, for example, in the form of a flat plate as it is or in the form of a roll wound around a cylindrical core. In addition, it is preferable to wind up in this case so that a film support body may become the outermost side.

  Moreover, when the photosensitive conductive film does not have a protective film, this photosensitive conductive film can be stored as it is in the form of a flat plate.

  The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Is mentioned. Moreover, it is preferable to install an end face separator on the end face of the photosensitive conductive film wound up in a roll shape from the viewpoint of end face protection, and in addition, it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Moreover, when packing a photosensitive conductive film, it is preferable to wrap and wrap in a black sheet with small moisture permeability.

  In the photosensitive conductive film of this embodiment, a conductive layer forming dispersion is applied on a film support to form a conductive layer, and then a photosensitive resin composition is applied to form a photosensitive resin layer. It is preferable that By applying the dispersion for forming a conductive layer on the film support, it is easy to form a uniform conductive layer.

  According to the photosensitive conductive film of the present embodiment, a photosensitive resin layer and a conductive layer are transferred onto a substrate on which a conductive pattern is required, and exposure and development are performed, thereby forming a transparent and good pattern. The conductive film can be easily formed.

  Moreover, since the electrically conductive film or electrically conductive pattern formed from the photosensitive electrically conductive film of this embodiment is rich in flexibility, it is suitable as an electrode of a flexible display. Furthermore, since the conductive film or conductive pattern to be formed can be made of an organic material, migration can be sufficiently suppressed when used as an electrode of an electronic device to which a bias voltage is applied.

  As one embodiment of the method for forming a conductive film of the present invention, a laminate step of laminating the photosensitive conductive film of the present embodiment as described above so that the photosensitive resin layer is in close contact with the substrate, And an exposure step of irradiating the photosensitive resin layer with actinic rays. When the photosensitive conductive film has a protective film, the photosensitive conductive film from which the protective film has been peeled is laminated on the substrate from the photosensitive resin layer side. By the laminating step, the photosensitive resin layer, the conductive layer, and the support are laminated in this order on the base material.

  Examples of the base material include a glass substrate and a plastic substrate such as polycarbonate.

The laminating step is performed, for example, by a method of laminating the photosensitive conductive film by removing the protective film, if any, and then pressing the photosensitive resin layer side against the substrate while heating. In addition, it is preferable to laminate | stack this operation under pressure reduction from the viewpoint of adhesiveness and followable | trackability. In the lamination of the photosensitive conductive film, the photosensitive resin layer and / or the substrate is preferably heated to 70 to 130 ° C., and the pressure is about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). However, these conditions are not particularly limited. In addition, if the photosensitive resin layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the base material in advance, but the base material is pre-heated in order to further improve the lamination property. You can also.

  In the exposure step, the portion of the photosensitive resin layer irradiated by irradiation with actinic rays is cured, and the conductive layer is fixed by the cured product, whereby a conductive film is formed on the substrate. As the active light source, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used. Also, an Ar ion laser, a semiconductor laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, those that effectively radiate visible light, such as photographic flood bulbs and solar lamps, are also used.

  When the film support on the conductive layer is transparent to actinic light, it can be irradiated with actinic light through the film support, and when the support is light-shielding, the film support is removed. Later, the photosensitive resin layer is irradiated with actinic rays.

  In addition, when the substrate is transparent to actinic rays, actinic rays can be irradiated from the substrate side through the substrate, but in terms of resolution, the conductive layer and the photosensitive resin layer from the conductive layer side. It is preferable to irradiate actinic rays.

By passing through said process, a base material with an electrically conductive film provided with an electrically conductive film on a base material is obtained. In the method for forming a conductive film of the present embodiment, the formed conductive film is heated to about 60 to 250 ° C. or exposed to about 0.2 to 10 J / cm ^{2 as} necessary after the film support is peeled off. Further curing may be performed by performing the above. Further curing may be performed by both heating and exposure.

  Thus, according to the method for forming a conductive film of the present invention, it is possible to easily form a transparent conductive film on a substrate such as glass or plastic.

  Next, the method for forming a conductive pattern of the present invention will be described with reference to the drawings.

  The conductive pattern forming method according to the present embodiment includes a step of laminating the above-described photosensitive conductive film 10 so that the photosensitive resin layer 3 is in close contact with the substrate 20 (FIG. 2A), and the substrate 20. The exposure process ((b) of FIG. 2) which irradiates a predetermined part of the upper photosensitive resin layer 3 with actinic rays, and the image development process which forms a conductive pattern by developing the exposed photosensitive resin layer 3 are provided. . Through these steps, a conductive film-containing substrate 40 including the conductive film (conductive pattern) 2a patterned on the substrate 20 is obtained ((c) in FIG. 2).

The laminating step is performed, for example, by a laminating method in which the photosensitive conductive film 10 is removed, if present, and then the photosensitive resin layer 3 side is pressure-bonded to the substrate while being heated. In addition, it is preferable to laminate | stack this operation under pressure reduction from the viewpoint of adhesiveness and followable | trackability. The lamination of the photosensitive conductive film 10 is preferably performed by heating the photosensitive resin layer 3 and / or the substrate 20 to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (1 to 10 kgf / cm ^2). However, these conditions are not particularly limited. Further, if the photosensitive resin layer 3 is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the substrate in advance, but the substrate may be pre-heated in order to further improve the lamination property. it can.

  Examples of the exposure method in the exposure step include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). As the active light source, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used. Also, an Ar ion laser, a semiconductor laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, those that effectively radiate visible light, such as photographic flood bulbs and solar lamps, are also used. Alternatively, a method of irradiating actinic rays in an image form by a direct drawing method using a laser exposure method or the like may be employed.

  When the film support 1 on the conductive layer 2 is transparent to actinic rays, it can be irradiated with actinic rays through the film support 1, and when the film support 1 is light-shielding, the film After removing the support 1, the photosensitive resin layer 3 is irradiated with actinic rays.

  Further, when the substrate (adherent) 20 is transparent to actinic rays, actinic rays can be irradiated from the substrate 20 side through the substrate 20, but from the viewpoint of resolution, the conductive layer 2 side can irradiate the conductive layer. 2 and the photosensitive resin layer 3 are preferably irradiated with actinic rays.

  In the development process of the present embodiment, portions other than the exposed portion of the photosensitive resin layer 3 are removed. Specifically, when the film support 1 is present on the conductive layer 2, the film support 1 is first removed, and then portions other than the exposed portion of the photosensitive resin layer 3 are removed by wet development. To do. Thereby, the conductive layer 2a containing the organic conductive material remains on the cured resin layer 3a having a predetermined pattern, and a conductive pattern is formed.

  The wet development is performed by a known method such as spraying, rocking immersion, brushing, or scraping, using a developer corresponding to a photosensitive resin such as an alkaline aqueous solution, an aqueous developer, or an organic solvent developer. .

  As the developing solution, a safe and stable solution having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Alkali metal phosphates such as sodium and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  Moreover, as alkaline aqueous solution used for image development, 0.1-5 mass% sodium carbonate aqueous solution, 0.1-5 mass% potassium carbonate aqueous solution, 0.1-5 mass% sodium hydroxide aqueous solution, 0.1-5 mass % Sodium tetraborate aqueous solution and the like are preferable. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  Further, an aqueous developer composed of water or an aqueous alkali solution and one or more organic solvents can be used. Here, as the base contained in the alkaline aqueous solution, in addition to the above-mentioned bases, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 , 3-propanediol, 1,3-diaminopropanol-2, morpholine.

  Examples of the organic solvent include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether is mentioned. These are used individually by 1 type or in combination of 2 or more types.

  The aqueous developer preferably has an organic solvent concentration of 2 to 90% by mass, and the temperature can be adjusted according to the developability. Furthermore, the pH of the aqueous developer is preferably as low as possible within the range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10. In addition, a small amount of a surfactant, an antifoaming agent, or the like can be added to the aqueous developer.

  Examples of the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by mass in order to prevent ignition.

  Two or more of the above-described developing solutions may be used in combination as necessary.

  Examples of the development method include a dip method, a battle method, a spray method, brushing, and slapping. Among these, it is preferable to use a high-pressure spray system from the viewpoint of improving the resolution.

  In this embodiment, by developing the photosensitive resin layer 3 after exposure with a predetermined pattern and removing the unexposed part, the conductive layer on the photosensitive resin layer of the unexposed part is removed together, The conductive layer on the photosensitive resin layer in the exposed portion remains, and a conductive pattern is formed. At the time of development, the developer soaks into the conductive layer 2 to swell the unexposed photosensitive resin layer, or the developer soaks from the end of the photosensitive resin layer to swell the photosensitive resin layer. The pattern is formed by dissolving and dispersing the conductive resin layer. When the thickness of the conductive layer 2 is as thin as 0.5 μm, the developer easily reaches the photosensitive resin layer 3 through the conductive layer 2 and the developability is improved.

In the method for forming a conductive pattern of the present embodiment, the conductive pattern may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary after development. Good. Further curing may be performed by both heating and exposure.

  Thus, according to the method for forming a conductive pattern of the present invention, a transparent conductive pattern can be easily formed on a substrate such as glass or plastic without forming an etching resist like an inorganic film such as ITO. Is possible.

  The conductive film-attached substrate according to the present invention can be obtained by the conductive film formation method and the conductive pattern formation method described above. From the viewpoint of being able to be effectively used as a transparent electrode, the surface resistivity of the conductive film or the conductive pattern is 10,000 Ω / □ or less is preferable, 5000 Ω / □ or less is more preferable, and 2000 Ω / □ or less is particularly preferable. The surface resistivity can be adjusted by, for example, the concentration of the dispersion liquid containing the organic conductive material or the coating amount. The surface resistivity tends to decrease as the concentration of the dispersion is increased and as the coating amount is increased and the thickness is increased. It can also be adjusted by doping treatment.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  Hereinafter, the present invention will be described more specifically with reference to examples.

<Preparation of conductive layer forming coating solution>

(Coating layer forming coating solution 1 (organic conductive material solution))
“Sepulzida OC-U1” (manufactured by Shin-Etsu Polymer Co., Ltd., photo-patterning paint, trade name), which is an alcohol solution of polyethylene dioxythiophene, was diluted 10 times with methanol, and this was used as a coating solution 1 for forming a conductive layer.

(Coating layer forming coating liquid 2 (organic conductive material solution))
“Clevios P” (trade name, manufactured by HC Starck Co., Ltd.), which is an aqueous solution of polyethylene dioxythiophene, is diluted 5 times with water. did.

<Preparation of solution of photosensitive resin composition>
[Synthesis of acrylic resin]
In a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, a mixture of methyl cellosolve and toluene (methyl cellosolve / toluene = 3/2 (mass ratio), hereinafter “solution s 400 g) was added, stirred while blowing nitrogen gas, and heated to 80 ° C. On the other hand, a solution (hereinafter referred to as “solution a”) prepared by mixing 100 g of methacrylic acid, 250 g of methyl methacrylate, 100 g of ethyl acrylate and 50 g of styrene as a monomer and 0.8 g of azobisisobutyronitrile was prepared. . Next, the solution a was added dropwise to the solution s heated to 80 ° C. over 4 hours, and then kept at 80 ° C. with stirring for 2 hours. Further, a solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of the solution s was dropped into the flask over 10 minutes. And the solution after dripping was heat-retained at 80 degreeC for 3 hours, stirring, Then, it heated at 90 degreeC over 30 minutes. The mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer solution. Acetone was added to the binder polymer solution to prepare a non-volatile component (solid content) of 50% by mass to obtain a binder polymer solution. The obtained binder polymer had a weight average molecular weight of 80,000. This was designated as acrylic polymer A.

  The material shown in Table 1 was mix | blended with the compounding quantity (unit: mass part) shown in the same table, and the solution of the photosensitive resin composition was prepared.

１）メタクリル酸：メタクリル酸メチル：アクリル酸エチル：及びスチレン＝２０：５０：２０：１０の質量比率のアクリルポリマー。

1) An acrylic polymer having a mass ratio of methacrylic acid: methyl methacrylate: ethyl acrylate: and styrene = 20: 50: 20: 10.

<Preparation of photosensitive conductive film>
Example 1
Conductive layer forming coating solution 1 is uniformly applied at 25 g / m ² on a 50 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”) which is a support film (film support). It was applied and dried for 3 minutes with a hot air convection dryer at 100 ° C. to form a conductive layer. The thickness of the conductive layer after drying was about 0.1 μm.

  Next, the photosensitive resin composition solution is uniformly applied to the side of the support film where the conductive layer is provided, and dried for 10 minutes in a 100 ° C. hot air convection dryer to form a photosensitive resin layer. did. The film thickness after drying of the photosensitive resin layer was 5 μm. Furthermore, the photosensitive resin layer was covered with a protective film made of polyethylene (manufactured by Tamapoly Co., Ltd., trade name “NF-13”) to obtain a photosensitive conductive film.

(Example 2)
The coating solution 2 for forming a conductive layer is uniformly applied at 25 g / m ² on a 50 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”) as a support film, and 100 ° C. Were dried with a hot air convection dryer for 3 hours to form a conductive layer. In addition, the film thickness of the conductive layer after drying was about 0.1 μm.

  Next, the photosensitive resin composition solution is uniformly applied to the side of the support film where the conductive layer is provided, and dried for 10 minutes in a 100 ° C. hot air convection dryer to form a photosensitive resin layer. did. The film thickness after drying of the photosensitive resin layer was 5 μm. Furthermore, the photosensitive resin layer was covered with a protective film made of polyethylene (manufactured by Tamapoly Co., Ltd., trade name “NF-13”) to obtain a photosensitive conductive film.

<Formation of conductive film>
A 0.7 mm thick soda glass plate is heated to 80 ° C., and the photosensitive conductive film obtained in Examples 1 and 2 is placed on the surface of the soda glass plate with the photosensitive resin layer facing the substrate while peeling off the protective film. And laminated under the conditions of 120 ° C. and 0.4 MPa. After lamination, when the substrate is cooled and the temperature of the substrate reaches 23 ° C., using an exposure machine (trade name “HMW-201B” manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp on the PET film surface, 1000 mJ / The conductive layer and the photosensitive resin layer were exposed with an exposure amount of cm ² . After the exposure, the film was left at room temperature (25 ° C.) for 15 minutes, and then the PET film as the support was peeled off to form the conductive film produced in the example on the soda glass plate. The surface resistances of the films formed using the films of Examples 1 and 2 were 2000Ω / □ and 2800Ω / □, respectively, and the transmittance for light at 650 nm was 90% and 85%. The results are shown in Table 2 .

In addition, said surface resistance is the surface resistivity measured based on JISK7194 by the 4-probe method using the low resistivity meter (the Mitsubishi Chemical Corporation make, Loresta GP). Moreover, said transmittance | permeability is the minimum light transmittance in the 450-650 nm wavelength range measured using the spectrophotometer (The Hitachi High-Technologies Corporation make, brand name "U-3310"). The results are shown in Table 2 .

<Formation of conductive pattern>
A 1 mm thick polycarbonate substrate was heated to 80 ° C., and the photosensitive conductive film obtained in Examples 1 and 2 was placed on the surface of the polycarbonate substrate with the photosensitive resin layer facing the substrate while peeling off the protective film. Lamination was performed at 120 ° C. and 0.4 MPa. After lamination, when the substrate is cooled and the temperature of the substrate reaches 23 ° C., a photomask having a wiring pattern with a line width / space width of 100/100 μm and a length of 100 mm is adhered to the PET film surface as a support I let you. And the conductive layer and the photosensitive resin layer were exposed with the exposure amount of 200 mJ / cm < ² > using the exposure machine (Oak Seisakusho make, brand name "HMW-201B") which has a high pressure mercury lamp lamp.

  After the exposure, the film was allowed to stand at room temperature (25 ° C.) for 15 minutes. Subsequently, the PET film as a support was peeled off, and developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. After development, a conductive pattern having a line width / space width of about 100/100 μm was formed on the polycarbonate substrate. It was confirmed that each conductive pattern was well formed.

  DESCRIPTION OF SYMBOLS 1 ... Film support body, 2 ... Conductive layer, 2a ... Conductive pattern, 3 ... Photosensitive resin layer, 3a ... Hardened | cured material layer, 4 ... Protective film, 10 ... Photosensitive conductive film, 20 ... Substrate, 30 ... Artwork, 40 ... Substrate with conductive film.

Claims (14)

The photosensitive resin layer of the photosensitive conductive film having a structure in which a support, a conductive layer containing an organic conductive material, and a photosensitive resin layer are laminated in this order is attached to a base material and at least on the base material. A method for forming a conductive film, comprising: laminating the photosensitive resin layer and the conductive layer in this order, and exposing the laminated photosensitive resin layer. The organic conductive material is a polymer of thiophene or a thiophene derivative or aniline
Alternatively, the method for forming a conductive film according to claim 1, wherein the conductive film is a polymer of an aniline derivative. The method for forming a conductive film according to claim 1, wherein the organic conductive material is a polymer of a thiophene derivative . The formation method of the electrically conductive film as described in any one of Claims 1-3 in which the said photosensitive resin layer contains the binder polymer, the photopolymerizable compound which has an ethylenically unsaturated bond, and a photoinitiator. . The method for forming a conductive film according to claim 4, wherein the binder polymer has a carboxyl group. The photopolymerizable compound having an ethylenically unsaturated bond is selected from the group consisting of trimethylolpropane (meth) acrylate, tetramethylolmethane (meth) acrylate, pentaerythritol (meth) acrylate and dipentaerythritol (meth) acrylate. The method for forming a conductive film according to claim 4, comprising at least one of the above. The formation method of the electrically conductive film as described in any one of Claims 4-6 with which the said photoinitiator contains an aromatic ketone compound or an oxime ester compound. The photosensitive resin layer of the photosensitive conductive film having a structure in which a support, a conductive layer containing an organic conductive material, and a photosensitive resin layer are laminated in this order is attached to a base material and at least on the base material. A method for forming a conductive pattern, comprising: laminating the photosensitive resin layer and the conductive layer in this order, and exposing and developing the laminated photosensitive resin layer. The organic conductive material is a polymer of thiophene or a thiophene derivative or aniline
Alternatively, the conductive pattern forming method according to claim 8, which is a polymer of an aniline derivative. The method for forming a conductive pattern according to claim 8 or 9, wherein the organic conductive material is a polymer of a thiophene derivative. The method of forming a conductive pattern according to any one of claims 8 to 10, wherein the photosensitive resin layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. . The method for forming a conductive pattern according to claim 11, wherein the binder polymer has a carboxyl group. The photopolymerizable compound having an ethylenically unsaturated bond is selected from the group consisting of trimethylolpropane (meth) acrylate, tetramethylolmethane (meth) acrylate, pentaerythritol (meth) acrylate and dipentaerythritol (meth) acrylate. The method for forming a conductive pattern according to claim 11, comprising at least one of the above. The method for forming a conductive pattern according to any one of claims 11 to 13, wherein the photopolymerization initiator includes an aromatic ketone compound or an oxime ester compound.

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