TWI547756B - A photosensitive conductive thin film, a method for forming a conductive film, and a method for forming a conductive pattern - Google Patents

Description

Photosensitive conductive film, method of forming conductive film, and method of forming conductive pattern

The present invention relates to a photosensitive conductive film, a method of forming a conductive film, and a method of forming a conductive pattern, and more particularly to a device for forming a flat panel display or a touch screen, a solar cell, an organic EL, or the like provided on a liquid crystal display element or the like. A method of conducting patterns of electrode wiring or the like.

In a display device such as a small electronic device such as a large electronic device such as a personal computer or a television, a navigation device, a mobile phone, or an electronic dictionary, or a display device such as an OA/FA device, a liquid crystal display device or a touch screen is widely used. A liquid crystal display element or a touch screen system is used for transparency such as a transparent electrode, and a transparent conductive film can be used. The same applies to solar cells.

A material which can form a transparent conductive film is known as ITO (Indium-Tin-Oxide), indium oxide or tin oxide. These materials are high in transmittance to visible light, and a material for forming a transparent electrode such as a substrate for a liquid crystal display device has become mainstream.

In the liquid crystal display device, a portion such as a wiring, a pixel electrode, a terminal, or the like is sometimes formed with a transparent conductive film. At this time, it is necessary to form the transparent conductive film into a specific shape. The patterning method of the transparent conductive film may be a method in which a transparent conductive film is formed, a photoresist pattern is formed by photolithography, and a conductive film is patterned by wet etching. In the etching liquid, a mixed liquid composed of two liquids of hydrochloric acid and second iron chloride can be sufficiently used for the ITO film or the indium oxide film.

In addition, studies have been conducted to form a transparent conductive film using a material other than ITO. For example, in the following Patent Document 1, it is disclosed that a radiation curable conductive composition containing an organic conductive polymer such as polythiophene or polyaniline is applied to a surface of a substrate to be cured to form a conductive property. And a transparent method of hardening the film. Further, in Patent Document 2 listed below, a photoresist material such as a diazo sulfonium-based material is applied onto a support, and a thiophene-based organic conductive material is further coated thereon, followed by exposure and development. A method of forming a conductive pattern.

Prior technical literature Patent literature

Patent Document 1: JP-A-2005-170996

Patent Document 2: Japanese Patent Publication No. 2004-504693

The ITO film or the tin oxide film is generally formed by a sputtering method, but the properties of the film are easily changed depending on the difference in sputtering method, sputtering power or gas pressure, substrate temperature, and type of environmental gas. The difference in film quality of the transparent conductive film caused by the fluctuation of the sputtering conditions is a cause of unevenness in the etching rate when the film is wet-etched, resulting in poor patterning of the transparent conductive film, which tends to cause a decrease in the yield of the product. . Therefore, the method of using ITO or the like is such that sputtering and photoresist formation and etching and steps are long, which is a great burden even on the cost side. Moreover, such a method is difficult to obtain the uniformity of the patterning accuracy.

In addition, the formation of a conductive pattern obtained from an organic conductive material has the following problems. The formation of the conductive pattern is not disclosed in the above Patent Document 1. Patterning is performed by etching using a mask. However, since there is no suitable etching liquid, it is necessary to use plasma etching or laser processing.

Patent Document 2 proposes a method of applying a liquid in which a photosensitive material of an organic conductive material and a diazo compound is mixed onto a support, and performing patterning; or in a support, an organic conductive material, and a photosensitive material. A method of further arranging a photosensitive material between the constituent layers. However, these methods do not consider the adhesion between the conductive pattern and the substrate when a conductive pattern is desired to be provided on a desired substrate, and it is necessary to have a surface treatment of the substrate.

The present invention has been made in view of the problems of the above-described conventional techniques, and an object of the invention is to provide a photosensitive pattern capable of forming a conductive pattern containing an organic conductive material with sufficient resolution on a substrate and having sufficient adhesion to a substrate. a conductive film; a method of forming a conductive film using the photosensitive conductive film; and a method of 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, the photosensitive conductive film is adhered to the substrate to adhere the photosensitive resin layer, and the substrate is followed by a simple step of exposure and development. Sufficient in nature, a desired conductive pattern with sufficient transparency can be easily formed.

Further, according to the photosensitive conductive film of the present invention, the photosensitive conductive film is adhered to the substrate so that the photosensitive resin layer is adhered to the substrate, and then exposed, and the film can be formed to have sufficient transparency and good adhesion to the substrate. Conductive film.

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

Moreover, from the viewpoint of further improving the patterning property of the conductive film and the adhesion to the substrate, the photosensitive resin layer is preferably a photopolymerizable compound containing a binder polymer and having an ethylenic unsaturated bond, and A composition of a photosensitive resin composition of a photopolymerization initiator.

The photosensitive conductive film of the present invention prevents a foreign matter from adhering or scratching during the period from the production to the use, and a protective film is further laminated on the side opposite to the conductive layer side of the photosensitive resin layer. This protective film can be removed when a photosensitive conductive film is used.

The present invention provides a method of forming a conductive film, characterized in that the photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a substrate, and at least the layer is photosensitive on the substrate. The resin layer and the conductive layer are exposed, and the laminated photosensitive resin layer is exposed.

Further, according to the method for forming a conductive film of the present invention, the photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a substrate, and a photosensitive resin layer and a conductive layer are sequentially provided on the substrate. Further, a conductive film composed of the above-mentioned conductive layer can be easily formed on the substrate by a simple step of exposing this. In the conductive film, the photosensitive resin layer is cured by exposure and can be sufficiently adhered to the substrate.

The present invention provides a method of forming a conductive pattern, wherein the photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a substrate, and a photosensitive resin layer is laminated on the substrate at least sequentially. The conductive layer is exposed and developed by laminating the photosensitive resin layer.

According to the method for forming a conductive pattern of the present invention, the photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a substrate, and the photosensitive resin layer and the conductive layer are sequentially laminated on the substrate, and so-called A simple method of exposure and development can easily form a conductive pattern in which the above-mentioned conductive layer is patterned on a substrate. In the conductive pattern, the photosensitive resin layer is cured by exposure and can be sufficiently adhered to the substrate.

The present invention provides a conductive film substrate comprising a substrate and a conductive film formed on the substrate by the above-described method of forming a conductive film of the present invention.

The present invention further provides a conductive film substrate comprising a substrate and a conductive pattern formed on the substrate by the above-described method of forming a conductive pattern of the present invention.

According to the present invention, it is possible to provide a photosensitive conductive film which is excellent in adhesion to a substrate on a substrate and which can easily form a conductive pattern containing an organic conductive material with sufficient resolution; and use of the photosensitivity A method of forming a conductive film of a conductive film and a method of forming a conductive pattern.

Form for implementing the invention

Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, "(meth)acrylate" in this specification means "acrylate" and the "methacrylate" corresponding to it. Similarly, the term "(meth)acrylic" means "acrylic acid" and the corresponding "methacrylic acid", and the term "(meth)acryloxy" means "acryloxy" and its corresponding "Methyl propylene oxime".

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

Hereinafter, a film-shaped support (hereinafter sometimes referred to as "thin film support") constituting the photosensitive conductive film 10 of the present embodiment, a conductive layer, a photosensitive resin layer, and a protective film will be described in detail.

The film support 1 is preferably a transparent support film. Here, the term "transparent" means that the exposure light in the exposure step after transfer to the substrate is transparent, and in the present embodiment, it is preferable to have permeability in an ultraviolet (300 to 400 nm) region.

The transparent support film may, for example, be a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film or a polycarbonate film. Among these, a polyethylene terephthalate film is preferably used from the viewpoint of transparency or heat resistance. Further, when the polymer film is used to develop the photosensitive resin layer 3, or the formed conductive film is removed by exposure, it is not a surface treatment or material which is impossible to remove.

The thickness of the above supporting film is preferably 5 to 300 μm, more preferably 20 to 300 μm. If the thickness of the supporting film is less than 5 μm, the mechanical strength is lowered, when the conductive layer is formed or when the photosensitive resin layer is formed, or when the supporting film is peeled off before the development of the photosensitive resin layer, there is a tendency that the supporting film is easily broken, and When it exceeds 300 μm, when the active light is applied to the photosensitive resin layer via the support film, the resolution tends to decrease, and the price tends to be high.

The organic conductive material contained in the conductive layer 2 may, for example, be a polymer of a thiophene or a thiophene derivative or a polymer of an aniline or an aniline derivative. Specifically, polyethylene dioxythiophene, polyhexyl thiophene, polyaniline, etc., and "CREBIOS" (HCStarck), "SEPLEGYDA OC-U1" ("Shin-Etsu Polymer Co., Ltd.", trade name ) and other commercial products.

The organic conductive material contained in the conductive layer 2 is preferably a material which can be patterned by light irradiation. Further, the organic conductive material may be used in the conductive layer 2 in combination with a material which forms a pattern by light irradiation, in the range in which the effect of the present invention can be obtained.

The polymer of the thiophene or the thiophene derivative may, for example, be a polymer having a repeating unit represented by the following formula (1).

[Chemical 1]

In the formula (1), R ₁ and R ₂ each independently represent 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, and an alkoxy group having 1 to 20 carbon atoms. a aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 40 carbon atoms, and an adjacent substituent. The inter-systems can also be bonded to each other to form a ring. Further, the terminal group of the polymer may, for example, be a hydrogen atom or a substituted or unsubstituted one.

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

The alkyl group having 1 to 20 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group or a n-hexyl group. Heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadeca , heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl , 3-methylpentyl, cyclopentyl, cyclohexyl, cyclooctyl, 3,5-tetramethylcyclohexyl, and the like. Among these, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, N-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadeca, n-ten Heptacarbyl, n-octadecyl, neopentyl, 1-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, cyclohexyl, cyclooctyl, and , 5-tetramethylcyclohexyl and the like.

The haloalkyl group having 1 to 20 carbon atoms may, for example, be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group or a pentafluoroethyl group. Among these, fluoromethyl, difluoromethyl and trifluoromethyl groups are preferred.

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

The arylamine group having 6 to 40 carbon atoms may, for example, be a phenyl group, a naphthyl group, a decyl group, a triphenylene group or a propyl group having a diphenylamino group or the like or a diphenylamino group or an amine group as a substituent. ) olefinic fluorenyl (Fluoranthenyl), biphenyl or the like. Among these, a phenyl group or a naphthyl group having a diphenylamino group or an amine group as a substituent is preferred.

Examples of the aryl group having 6 to 40 carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and a triphenylene group. The substituent may, for example, be a methyl group, an ethyl group, a cyclohexyl group, an isopropyl group, a butyl group or a phenyl group. Among these, a substituted or unsubstituted phenyl group, a naphthyl group, or a biphenyl group is preferable.

The substituted or unsubstituted heterocyclic group having 2 to 40 carbon atoms may, for example, be a 1-pyrrolyl group, a 2-pyrrolyl group, a 3-pyrrolyl group, a pyrazinyl group, a 2-pyridyl group, a 1-imidazolyl group or a 2-imidazolyl group. , 1-pyrazolyl, 1-pyridazinyl, 2-pyridazinyl, 3-pyridazinyl, 5-pyridazinyl, 6-pyridazinyl, 7-pyridazinyl, 8 -pyridazinyl, 2-imidazolidinyl, 3-imidazolidinyl, 5-imidazolidinyl, 6-imidazolidinyl, 7-imidazolidinyl, 8-imidazolidinyl, 3-pyridyl, 4-pyridine Base, 1-indenyl, 2-indenyl, 3-indenyl, 4-indenyl, 5-indenyl, 6-fluorenyl, 7-fluorenyl, 1-isodecyl , 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindenyl, 7-isoindolyl, 2-furanyl, 3- Furanyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzo Furanyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolinyl, 3 -quinolinyl, 4-quinolyl, 5-quinolinyl, 6-quinoline , 7-quinolyl, 8-quinolyl, 1-isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinolinyl, 6-isoquinolinyl, 7- Isoquinolyl, 8-isoquinolinyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 1-oxazolyl, 2-oxazolyl, 3-oxazolyl , 4-oxazolyl, 9-carbazolyl, β-carboline-1-yl, β-carbolin-3-yl, β-carbolin-4-yl, β-carboline-5-yl, β -porphyrin-6-yl, β-carboline-7-yl, β-carboline-8-yl, β-carboline-9-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 6-phenanthryl, 7-phenanthryl, 8-phenanthryl, 9-phenanthryl, 10-phenanthryl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4- Acridinyl, 9-acridinyl, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7- Phenanthroline-5-yl, 1,7-phenanthroline-6-yl, 1,7-phenanthroline-8-yl, 1,7-phenanthroline-9-yl, 1,7-phenanthrene Benzin-10-yl, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl, 1,8-phenanthroline- 5-yl, 1,8-phenanthroline-6-yl, 1,8-phenanthroline-7-yl, 1,8-phenanthroline-9-yl, 1,8-phenanthroline-10- 1,1,phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline- 4-yl, 1,9-phenanthroline-5-yl, 1,9-phenanthroline-6-yl, 1,9-phenanthroline-7-yl, 1,9-phenanthroline-8- 1,1,phenanthroline-10-yl, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1,10-phenanthroline-5-yl, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2 ,9-phenanthroline-5-yl, 2,9-phenanthroline-6-yl, 2,9-phenanthroline-7-yl, 2,9-phenanthroline-8-yl, 2,9 -phenanthroline-10-yl, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8-phenanthrene Rotunolin-5-yl, 2,8-phenanthroline-6-yl, 2,8-phenanthroline-7-yl, 2,8-phenanthroline-9-yl, 2,8-phenanthroline -10-yl, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7-phenanthroline-5 -yl, 2,7-phenanthroline-6-yl, 2,7-phenanthroline-8-yl, 2,7-phenanthroline-9-yl, 2,7-phenanthroline-10-yl , 1-phenazinyl, 2-phenazine, 1-phenothiazine, 2-phenothiazine, 3-phenothiazine, 4-phenothiazine, 10-phenothiazine, 1- Phenoazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl 2-oxadiazolyl 5-oxadiazolyl, 3-furazyl, 2-thienyl, 3-thienyl, 2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl, 2-methylpyrrole-4 -yl, 2-methylpyrrole-5-yl, 3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl, 3-methylpyrrole-5 -yl, 2-t-butylpyrrol-4-yl, 3-(2-phenylpropyl)pyrrol-1-yl, 2-methyl-1-indolyl, 4-methyl-1-indole Mercapto, 2-methyl-3-indolyl, 4-methyl-3-indolyl, 2-tert-butyl-1-indenyl, 4-tert-butyl-1-indenyl , 2-tert-butyl-3-indenyl, 4-tert-butyl-3-indenyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl , 4-dibenzofuranyl, 1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl, 4-dibenzothiophenyl, 1-fluorenyl , 2-indenyl, 3-indenyl, 4-indenyl, 1-indenyl, 2-indenyl, 3-indenyl, 4-indenyl, and the like.

Preferred among these are 2-pyridyl, 1-pyridazinyl, 2-pyridazinyl, 3-pyridazinyl, 5-pyridazinyl, 6-pyridazinyl, 7-fluorene. Pyridazinyl, 8-pyridazinyl, 2-imidazolidinyl, 3-imidazolidinyl, 5-imidazolidinyl, 6-imidazolidinyl, 7-imidazolidinyl, 8-imidazolidinyl, 3-pyridine Base, 4-pyridyl, 1-indenyl, 2-indenyl, 3-indenyl, 4-indenyl, 5-indenyl, 6-fluorenyl, 7-fluorenyl, 1 -isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isodecyl, 6-isoindenyl, 7-isoindenyl, 1- Carbazolyl, 2-carbazolyl, 3-oxazolyl, 4-oxazolyl, 9-oxazolyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuran , 4-dibenzofuranyl, 1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl, 4-dibenzothiophenyl, 1-oxime Base, 2-indenyl, 3-indenyl, 4-indenyl, 1-indenyl, 2-indenyl, 3-indenyl, 4-indenyl.

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

The R ₁ and R ₂ systems may also be bonded to each other to form a ring. The ring is preferably, for example, a dioxane ring, a benzene ring, a cyclohexane ring or a naphthyl ring.

Y ₁ and Y _{2 of the} formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having a core carbon number of 6 to 40, or a substituted or unsubstituted nucleocarbon number. a heterocyclic group of 2 to 40. The alkyl group, the aryl group or the heterocyclic group may, for example, be the same as R ₁ and R ₂ .

The polythiophene or polythiophene derivative represented by the formula (1) can be synthesized by a commercially available product or a known method. The molecular weight of the polythiophene or polythiophene derivative is generally in the range of from 1,000 to 100,000 in terms of the number average molecular weight. When the molecular weight is smaller than this, sufficient conductivity by the π-electron conjugated system cannot be exhibited, and if the molecular weight is too large, it becomes viscous, and it is difficult to form a film. The repeating unit is contiguous with the repeating unit and combines with the head-to-tail, head-to-head, tail-tail pattern to form a polymer. When the alkyl group or the alkoxy group at the 3-position of the thiophene ring is used, if the chain is too long, it is feared that the three-dimensional structure of the molecule is disordered and the degree of mobility is impaired. Therefore, it is preferably a carbon number of 20 or less.

The conductive layer 2 is applied, for example, to the film support 1 by applying a dispersion for forming a conductive layer such as a dispersion stabilizer such as water and/or an organic solvent or a surfactant as needed. Drying is carried out to form. The coating system can be carried out 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 rod coating method, or a spray coating method. Further, the drying is carried out at 30 to 150 ° C for about 1 to 30 minutes, 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 the conductive pattern formed by the photosensitive conductive film of the present invention or the conductivity sought, but is preferably 1 μm or less, more preferably 0.01 μm to 0.5 μm. It is particularly preferably from 0.01 μm to 0.3 μm. When the thickness of the conductive layer 2 is 1 μm or less, it is easy to ensure light transmittance.

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

Examples of the binder polymer include an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, and a phenol resin. From the viewpoint of excellent alkali developability, an acrylic resin is preferably used. These may be used alone or in combination of two or more.

The above binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. The polymerizable monomer may, for example, be a styrene derivative polymerizable in an α-position or an aromatic ring such as styrene, vinyltoluene or α-methylstyrene, or a diacetone acrylamide or the like. Ethers of vinyl alcohol such as acrylamide, acrylonitrile, vinyl-n-butyl ether, alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate , diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Tetrafluoropropyl (meth) acrylate, (meth) acrylate, α-bromo (meth) acrylate, α-chloro (meth) acrylate, β-furyl (meth) acrylate, β-styryl Maleic acid monoester, fumaric acid, cinnamic acid, etc. of (meth)acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, --cyano cinnamic acid, itaconic acid, crotonic acid and propionic acid.

The alkyl (meth)acrylate may, for example, be a compound represented by the following formula (2), a compound having a hydroxyl group on the alkyl group of the compound, an epoxy group, a halogen group or the like.

[Chemical 2]

In the 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. The above alkyl group having 1 to 12 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group or a dodecyl group. And such structural heterosexuals.

Examples of the compound represented by the formula (2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (methyl). Amyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (A) Ethyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate. These may be used alone or in combination of two or more.

Moreover, it is preferable that the binder polymer used in the present invention has a carboxyl group from the viewpoint of further improving the alkali developability. Such a binder polymer can be produced by radically polymerizing a polymerizable monomer having a carboxyl group with another polymerizable monomer. The above polymerizable monomer having a carboxyl group is preferably (meth)acrylic acid as described above.

The ratio of the carboxyl group of the binder polymer to the ratio of the polymerizable monomer of the carboxyl group to the total polymerizable monomer to be used is preferably from 12 to 50 from the viewpoint of balance between alkali developability and alkali resistance. The mass% is more preferably 12 to 40% by mass, particularly preferably 15 to 30% by mass, and most preferably 15 to 25% by mass. When the ratio of the carboxyl group-containing polymerizable monomer is less than 12% by mass, the alkali developability tends to be inferior, and if it exceeds 50% by mass, the alkali resistance tends to be poor.

The weight average molecular weight of the binder polymer is preferably from 20,000 to 300,000, more preferably from 40,000 to 150,000, from the viewpoint of achieving a balance between mechanical strength and alkali developability. When the weight average molecular weight is less than 20,000, the liquid crystal resistance tends to be lowered, and if it exceeds 300,000, the development time tends to be long. Further, the weight average molecular weight of the present invention can be measured by gel permeation chromatography (GPC) using a value converted from a standard amount of polystyrene.

These binder polymers may be used singly or in combination of two or more types. When the binder polymer is used in combination of two or more types, for example, two or more types of binder polymers composed of different copolymerized components, and two or more types of binder polymers having different weight average molecular weights may be used. Two or more kinds of binder polymers having different dispersities.

Next, a photopolymerizable compound having an ethylenically unsaturated bond will be described. The photopolymerizable compound having an ethylenically unsaturated bond may, for example, be a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, 2,2-bis(4-((meth)acrylofluorene). Oxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((methyl)propene) a bisphenol A-based (meth) acrylate compound such as ethoxypolypropoxy)phenyl)propane or a compound obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, having an amine group A urethane monomer such as a (meth) acrylate compound of a formate bond, γ-chloro-β-hydroxypropyl-β'-(meth) propylene methoxyethyl-phthalate , β-hydroxyethyl-β'-(meth)acrylomethoxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloxyethyl-phthalate , (meth)acrylic acid alkyl ester and the like. These may be used alone or in combination of two or more types.

The compound obtained by reacting the above polyol with an α,β-unsaturated carboxylic acid may, for example, be a polyethylene glycol di(meth)acrylate having a vinyl group number of 2 to 14, and the number of the propylene groups being 2 to 14 Polypropylene glycol di(meth) acrylate, polyethylene propylene glycol di(meth) acrylate, trimethylolpropane di(methyl) having a number of vinyl groups of 2 to 14 and a number of propylene groups of 2 to 14. Acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tris(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, three Hydroxymethylpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, etc. Tetramethylol methane (meth) acrylate such as trimethylolpropane (meth) acrylate, tetramethylol methane tri(meth) acrylate or tetramethylol methane tetra(meth) acrylate Pentaerythritol (methyl) such as ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol alkoxy tri(meth)acrylate Dipentaerythritol (meth) acrylate such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol alkoxy penta (meth) acrylate.

Among the above, in terms of transparency and adhesion, it is preferable to contain trimethylpropane (meth) acrylate, tetramethylol methane (meth) acrylate, pentaerythritol (meth) acrylate, and At least one selected from pentaerythritol (meth) acrylate.

The urethane monomer may, for example, be a (meth)acrylic monomer having a hydroxyl group at the β position, and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1, An addition reaction product of a diisocyanate compound such as 6-hexamethylene diisocyanate, tris[(meth)acryloyloxytetraethylene glycol isocyanate]hexamethylene tripolyisocyanate, EO-modified urethane Di(meth)acrylate, EO, PO modified urethane di(meth)acrylate, and the like. Further, "EO" means a structure in which ethylene oxide and a compound modified with EO have an ethylene oxide group. Moreover, "PO" means a block structure in which propylene oxide and a compound modified with PO have an oxypropylene group. The EO-modified urethane di(meth)acrylate may, for example, be "UA-11" (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). In addition, EO and PO-modified urethane di(meth)acrylate are, for example, "UA-13" (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name).

The content ratio of the photopolymerizable compound is preferably from 30 to 80 parts by mass, more preferably from 40 to 70 parts by mass, per 100 parts by mass of the total of the binder polymer and the photopolymerizable compound. When the content ratio is less than 30 parts by mass, the photocurability is insufficient, and the curable property of the transferred conductive film tends to be insufficient. When the content exceeds 80 parts by mass, it tends to be difficult to store when it is wound into a film. .

Then, the photopolymerization initiator is explained. The photopolymerization initiator may, for example, be benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (michlerone), N,N'-tetraethyl- 4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4) Aromatic ketone of 2-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1, 2-B Base, phenanthrene, 2-tert-butyl fluorene, octamethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenyl fluorene, 2,3 -diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3- a benzoin ether compound such as dimethyl hydrazine, benzoin methyl ether, benzoin ethyl ether or benzoin phenyl ether, benzoin, methyl benzoine, ethylbenzene A benzoin compound such as an occasional factor, 1,2-octanedione, 1-[4-(phenylsulfanyl)-,2-(o-benzylidenehydrazide)], ethyl ketone, 1-[9-B An oxime ester compound such as -6-(2-methylbenzhydryl)-9H-carbazol-3-yl]-, 1-(o-ethenylhydrazine), benzyl dimethyl ketal, etc. Benzyl derivative, 2-(o-chlorophenyl)-4,5- Diphenylimidazole coupler, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole, 2-(o-fluorophenyl)-4,5-diphenyl Imidazole couple, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium, 2-(p-methoxyphenyl)-4,5-diphenylimidazolium, etc. 2 , 4,5-triaryl imidazolium, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc. acridine derivatives, N-phenylglycine, N- A phenylglycine derivative, a coumarin compound, or an oxazole compound. Further, the substituent of the aryl group of the two 2,4,5-triarylimidazoles can also give a compound of the same object, and a compound which is different from the symmetry can also be obtained. Further, a combination of diethyl thioxanthone and dimethylamino benzoic acid may also be combined with a thioxanthone compound and a tertiary amine compound. Among these, from the viewpoint of transparency, an aromatic ketone compound such as 2-benzylmethyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 is more preferable. Or an oxime ester compound such as 1,2-octanedione, 1-[4-(phenylsulfanyl)-, 2-(o-benzylidenehydrazide) or the like. These may be used alone or in combination of two or more types.

The content ratio of the photopolymerization initiator is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the total of the binder polymer and the photopolymerizable compound. When the content ratio is less than 0.1 part by mass, the light sensitivity tends to be insufficient. When it exceeds 30 parts by mass, the absorption on the surface of the composition increases during exposure, and the internal photohardening tends to be insufficient.

The photosensitive resin layer 3 may be 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. Additives such as a fragrance, an imaging agent, and a thermal crosslinking agent are contained singly or in combination of two or more types. The amount of the additive to be added is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the total of the binder polymer and the photopolymerizable compound.

The photosensitive resin layer 3 is applied to the transparent film support 1 on which the conductive layer 2 is formed, and is dissolved in methanol, ethanol, propanol, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, if necessary. A solvent such as N,N-dimethylformamide or propylene glycol monomethyl ether or a solution of a photosensitive resin composition having a solid content of 10 to 60% by mass of such a mixed solvent. However, in this case, the amount of the residual organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less in order to prevent the diffusion of the organic solvent in the subsequent step.

The coating of the photosensitive resin composition can be carried out 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 rod coating method, or a spray coating method. Further, the drying is carried out at 70 to 150 ° C for about 5 to 30 minutes.

The thickness of the photosensitive resin layer 3 varies depending on the application, but the thickness after drying is preferably 1 to 50 μm, more preferably 1 to 20 μm, and particularly preferably 1 to 10 μm. When the thickness is less than 1 μm, it tends to be difficult to apply industrially. When the thickness exceeds 50 μm, the sensitivity is insufficient due to a decrease in light transmission, and the photocurability of the photosensitive resin layer tends to be lowered. Further, the adhesiveness and patterning are excellent, and the thickness of the photosensitive resin layer 3 is preferably 1 μm or more.

Next, the description relates to the protective film. In the photosensitive conductive film of the present invention, as shown in FIG. 1, the protective film can be laminated on the surface opposite to the film support 1 side of the photosensitive resin layer 3.

As the protective film, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, or a polyethylene film can be used. As the protective film, a polymer film similar to the above film support can also be used.

The adhesive force between the protective film and the photosensitive resin layer is such that the protective film is easily peeled off from the photosensitive resin layer, and is preferably smaller than the adhesion between the conductive layer 2 and the photosensitive resin layer 3 and the film support 1.

Further, the protective film is preferably a film of low fish eyes. Specifically, it is preferable that the number of fish eyes having a diameter of 80 μm or more contained in the protective film is 5/m ² or less. In addition, the "fisheye" is a method in which a material is thermally melted, kneaded, extruded, biaxially stretched, or casted, and a foreign material, an undissolved product, or an oxidized degradation product of the material is taken into the film.

The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, particularly preferably from 5 to 30 μm, and most preferably from 15 to 30 μm. When the thickness of the protective film is less than 1 μm, the protective film tends to be easily broken when laminated, and if it exceeds 100 μm, the price tends to be high.

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

The photosensitive conductive film can be stored in a roll shape, for example, in a state in which it is directly in a flat shape, or wound around a core such as a cylindrical shape. Further, at this time, it is preferable that the film support is wound as the outermost side.

Further, when the photosensitive conductive film does not have a protective film, such a photosensitive conductive film can be directly stored in the form of a flat plate.

The core of the core is not particularly limited as long as it is a conventional user, and examples thereof include a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and an ABS resin (acrylonitrile-butadiene-styrene). Copolymer) and other plastics. Further, it is preferable to provide an end face separator from the viewpoint of protecting the end face of the photosensitive conductive film wound into a roll shape from the end face, and it is preferable to provide a moisture-proof end face separator from the viewpoint of edge-fusing resistance. Further, when the photosensitive conductive film is bundled, it is preferable to wrap the package with a blank sheet having a small moisture permeability.

In the photosensitive conductive film of the present embodiment, a conductive layer is formed by applying a dispersion for forming a conductive layer on a film support, and then applying a photosensitive resin composition to form a photosensitive resin layer. It is preferable to form a uniform conductive layer by coating a conductive layer-forming dispersion on the film support.

According to the photosensitive conductive film of the present embodiment, the photosensitive resin layer and the conductive layer are transferred onto a substrate having a conductive pattern, and exposure and development are performed, whereby a transparent and excellent pattern can be easily formed. Conductive film.

Moreover, since the conductive film or the conductive pattern formed by the photosensitive conductive film of the present embodiment is flexible, it is suitable as an electrode of a flexible display or the like. Further, since the formed conductive film or conductive pattern can be made of an organic material, it is effective as an effect of suppressing migration when it is used as an electrode of an electronic device to which a bias voltage is applied.

In one embodiment of the method for forming a conductive film of the present invention, for example, a method of laminating a photosensitive conductive film of the present embodiment on a substrate to form a photosensitive resin layer is adhered; and an exposure step The photosensitive resin layer on the substrate is irradiated with active light. When the photosensitive conductive film has a protective film, the photosensitive conductive film having the peeled protective film is laminated on the substrate from the side of the photosensitive resin layer. The photosensitive resin layer, the conductive layer, and the support are sequentially laminated on the substrate by the above-described lamination step.

The substrate may, for example, be a plastic substrate such as a glass substrate or polycarbonate.

In the laminating step, for example, when the photosensitive conductive film is removed as a protective film, the photosensitive resin layer side is pressure-bonded to the substrate while heating to perform lamination. Moreover, this operation is preferably laminated under reduced pressure from the viewpoint of adhesion and traceability. The lamination of the photosensitive conductive film is preferably such that the photosensitive resin layer and/or the substrate are heated to 70 to 130 ° C, and the pressure of the bonding is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm ² ). The conditions are not particularly limited. Further, when the photosensitive resin layer is heated to 70 to 130 ° C as described above, it is not necessary to preheat the substrate in advance, but in order to further improve the laminate property, the substrate may be subjected to preheat treatment.

In the exposure step, the photosensitive resin layer irradiated with the active light is cured, whereby the conductive layer is fixed by the cured material, and a conductive film is formed on the substrate. As the light source of the active light, a known light source such as 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 can be used to efficiently emit ultraviolet rays, visible light or the like. It is possible to effectively emit ultraviolet rays, visible light, or the like using an Ar ion laser or a semiconductor laser. Further, it is also possible to use a photographic light-emitting bulb, a solar lamp, or the like to efficiently emit visible light or the like.

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

Further, when the substrate is transparent to the active light, the active light can be irradiated from the substrate side through the substrate. However, in terms of resolution, it is preferable to irradiate the conductive layer and the photosensitive resin layer with the active light from the conductive layer side.

By the above steps, a substrate having a conductive film attached to a conductive film on a substrate can be obtained. In the method for forming a conductive film according to the present embodiment, after the formed conductive film and the film support are peeled off, if necessary, further heating is performed by heating at about 60 to 250 ° C or exposure of 0.2 to 10 J/cm ² . . It is also possible to perform further hardening by heating or exposure.

As described above, according to the method for forming a conductive film of the present invention, a transparent conductive film can be easily formed on a substrate such as glass or plastic.

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

The method for forming a conductive pattern according to the present embodiment includes a method of laminating a step of laminating the photosensitive conductive film 10 on the substrate 20 to form a photosensitive resin layer 3 (Fig. 2(a)); In the exposure step, a specific portion of the photosensitive resin layer 3 on the substrate 20 is irradiated with active light (Fig. 2 (b)); a developing step is performed by developing the exposed photosensitive resin layer 3 to form a conductive Graphic type. By the above steps, the substrate 40 with the conductive film of the conductive film (conductive pattern) 2a patterned on the substrate 20 can be obtained ((c) of FIG. 2).

The lamination step is performed, for example, by removing the photosensitive conductive film 10 as a protective film, and then laminating the photosensitive resin layer 3 side to the substrate while heating. Moreover, this operation is preferably laminated under reduced pressure from the viewpoint of adhesion and traceability. Preferably, the photosensitive conductive film 10 is laminated to heat the photosensitive resin layer 3 and/or the substrate 20 to 70 to 130 ° C, and the pressure of the bonding is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm ² ). These conditions are not particularly limited. Further, when the photosensitive resin layer 3 is heated to 70 to 130 ° C as described above, it is not necessary to preheat the substrate in advance, but the substrate may be preheated in order to improve the lamination property.

The exposure method in the exposure step is, for example, a method of irradiating active rays in an image form by a negative or positive mask pattern called a artwork (mask exposure method). As the light source of the active light, a known light source such as 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 can be used to efficiently emit ultraviolet rays, visible light or the like. It is possible to effectively emit ultraviolet rays, visible light, or the like using an Ar ion laser or a semiconductor laser. Further, it is also possible to use a photographic light-emitting bulb, a solar lamp, or the like to efficiently emit visible light or the like. Further, a method of irradiating the active light in an image form by a direct drawing method such as a laser exposure method may be employed.

When the film support 1 on the conductive layer 2 is transparent to the active light, the active light can be irradiated through the film support 1, and when the film support 1 is light-shielding, the photosensitive resin layer 3 is irradiated after the film support 1 is removed. Active light.

Further, when the substrate (adhered matter) 20 is transparent to the active light, the active light can be irradiated from the substrate 20 side through the substrate 20, but the conductive layer 2 and the photosensitive layer are preferably from the conductive layer 2 side in terms of resolution. The resin layer 3 irradiates the active light.

In the developing step of the present embodiment, portions other than the exposed portion of the photosensitive resin layer 3 can be removed. Specifically, when the film support 1 is present on the conductive layer 2, the film support 1 is first removed, and then the portion other than the exposed portion of the photosensitive resin layer 3 is removed by wet development. Thereby, the conductive layer 2a containing the organic conductive material remains on the resin hardened layer 3a having a specific pattern, and a conductive pattern can be formed.

As the wet development system, a development liquid corresponding to a photosensitive resin such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent-based developing liquid can be used, and a known method such as spraying, shaking, brushing, rubbing or the like can be used. .

The developing liquid system can be safe and stable using an alkaline aqueous solution or the like, and has good workability. As the base of the alkaline aqueous solution, for example, an alkali hydroxide such as lithium, sodium or potassium hydroxide, or a carbonate or bicarbonate such as lithium, sodium, potassium or ammonium carbonate, potassium phosphate or phosphoric acid can be used. An alkali metal pyrophosphate such as an alkali metal phosphate such as sodium, sodium pyrophosphate or potassium pyrophosphate.

Further, the alkaline aqueous solution used for development is preferably 0.1 to 5% by mass of sodium carbonate aqueous solution, 0.1 to 5% by mass of potassium carbonate aqueous solution, 0.1 to 5% by mass of sodium hydroxide aqueous solution, and 0.1 to 5% by mass of sodium tetraborate aqueous solution. Wait. Further, the pH of the aqueous alkaline solution used for development is preferably in the range of 9 to 11, and the temperature is adjusted in accordance with the developability of the photosensitive resin layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

Further, a water-based developing solution composed of water or an aqueous alkaline solution and one or more organic solvents can be used. Here, the base contained in the alkaline aqueous solution may be, for example, borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethyltriamine or 2-, in addition to the above-mentioned base. Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine.

Examples of the organic solvent include 3-acetone alcohol, propanol, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. These may be used alone or in combination of two or more.

The water-based imaging liquid should have a concentration of the organic solvent of 2 to 90% by mass, and the temperature can be adjusted in accordance with the developing property. Further, the pH of the water-based imaging liquid is preferably as small as possible in the range in which the photoresist can be sufficiently imaged, and is preferably pH 8 to 12, more preferably pH 9 to 10. Further, a small amount of a surfactant, an antifoaming agent, or the like may be added to the aqueous developing solution.

The organic solvent-based developing solution may, for example, be 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone or γ- Butyrolactone and the like. These organic solvents are intended to prevent ignition, and it is preferred to add water in the range of 1 to 20% by mass.

The above-mentioned developing liquid may be used in combination of two or more kinds as needed.

Examples of the development method include an immersion method, a paddle method, a spray method, a brush coating, and rubbing. Among these, the viewpoint of improving the resolution is preferably a high pressure spraying method.

In the present embodiment, the photosensitive resin layer 3 exposed in a specific pattern is developed to remove the unexposed portion, and the conductive layer on the photosensitive resin layer of the unexposed portion is removed together, and the exposed portion is removed. The conductive layer on the photosensitive resin layer remains, and a conductive pattern can be formed. When developing, the developing solution penetrates into the conductive layer 2, swells the unexposed photosensitive resin layer, or infiltrates the developing liquid from the end portion of the photosensitive resin layer, swells the photosensitive resin layer, and dissolves the photosensitive resin layer. Disperse to form a pattern. When the layer thickness of the conductive layer 2 is as small as 0.5 μm, the developing liquid easily reaches the photosensitive resin layer 3 via the conductive layer 2, and the developability is improved.

In the method of forming a conductive pattern of the present embodiment, the conductive pattern is further cured by heating at about 60 to 250 ° C or exposure at 0.2 to 10 J/cm ² as needed. It is also possible to perform further hardening by heating or exposure.

As described above, 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 photoresist like an inorganic film such as ITO.

The substrate with a conductive film of the present invention can be obtained by the above-described method for forming a conductive film or a method for forming a conductive pattern, but from the viewpoint of effectively utilizing as a transparent electrode, it is preferable to have a surface resistance of a conductive film or a conductive pattern. The rate is 10000 Ω/□ or less, more preferably 5,000 Ω/□ or less, and particularly preferably 2,000 Ω/□ or less. The surface resistivity can be adjusted by the concentration or coating amount of the dispersion containing the organic conductive material. As the concentration of the dispersion is increased, the coating amount is increased and the thickness is increased, and the surface resistivity tends to be lower. Moreover, it can also be adjusted by a doping process.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

Example

Hereinafter, the present invention will be more specifically described by way of examples.

<Adjustment of coating liquid for forming a conductive layer> (coating liquid 1 for forming a conductive layer (organic conductive material solution)

"SEPLEGYDA OC-U1" (manufactured by Shin-Etsu Polymer Co., Ltd., photo-patterning paint, trade name) of the alcohol solution of polyethylene dioxythiophene was diluted 10 times with methanol to prepare a coating liquid for forming a conductive layer. .

(coating liquid 2 for forming a conductive layer (organic conductive material solution)

"Crebios P" (manufactured by H. C. Starck Co., Ltd., trade name) of an aqueous solution of polyethylene dioxythiophene was diluted with water to obtain a coating liquid 2 for forming a conductive layer.

<Preparation of Solution of Photosensitive Resin Composition> [Synthesis of acrylic resin]

A mixture of methyl cellosolve and toluene (methyl cellosolve/toluene=3/2 (mass ratio), or less, is added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube. 400 g, which is called "solution s"), was stirred while blowing nitrogen gas, and heated to 80 °C. Further, a solution of 100 g of (meth)acrylic acid as a monomer, 250 g of methyl methacrylate, 100 g of ethyl acrylate, 50 g of styrene, and 0.8 g of azobisisobutyronitrile (hereinafter referred to as "solution a" is prepared. "). Then, the solution a was added dropwise to the solution s heated to 80 ° C for 4 hours, and then kept at 80 ° C for 2 hours while stirring. Further, a solution of 1.2 g of fluorobisisobutyronitrile dissolved in 100 g of the solution s was dropped for 10 minutes in the flask. Then, the solution after the dropwise addition was stirred while maintaining the temperature at 80 ° C for 3 hours, and heated to 90 ° C for 30 minutes. After holding at 90 ° C for 2 hours, it was cooled to obtain a binder polymer solution. To the binder polymer solution, acetone was added to prepare a nonvolatile component (solid content) to be 50% by mass to obtain a binder polymer solution. The resulting binder polymer had a weight average molecular weight of 80,000. This was taken as the acrylic polymer A.

The materials shown in Table 1 were prepared by mixing the amounts shown in the same table (unit: parts by mass) to prepare a solution of the photosensitive resin composition.

<Production of photosensitive conductive film> (Example 1)

A 50 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Co., Ltd., trade name) in which the coating liquid for forming a conductive layer 1 was uniformly applied to a support film (film support) at 25 g/m ² On G2-50"), it was dried by a hot air convection dryer at 100 ° C for 3 minutes to form a conductive layer. Further, the film thickness after drying of the conductive layer was about 0.1 μm.

Then, a solution of the above-mentioned photosensitive resin composition was uniformly applied to the side of the conductive layer provided with the support film, and dried by a hot air convection dryer at 100 ° C for 10 minutes to form a photosensitive resin layer. The film thickness after drying of the photosensitive resin layer was about 5 μm. Further, the photosensitive resin layer was coated with a protective film made of polyethylene (manufactured by Tamapoly Co., Ltd., trade name "NF-13") to obtain a photosensitive conductive film.

(Example 2)

A 50 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Co., Ltd., trade name "G2-50") which was uniformly applied to a support film at 25 g/m ² in a coating liquid for forming a conductive layer 2 The upper layer was dried by a hot air convection dryer at 100 ° C for 3 minutes to form a conductive layer. Further, the film thickness of the dried conductive layer was about 0.1 μm.

Then, a solution of the above-mentioned photosensitive resin composition was uniformly applied to the side of the conductive layer provided with the support film, and dried by a hot air convection dryer at 100 ° C for 10 minutes to form a photosensitive resin layer. The film thickness after drying of the photosensitive resin layer was about 5 μm. Further, the photosensitive resin layer was coated 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>

The 0.7 mm thick soda glass plate was heated to 80 ° C, and the photosensitive conductive films obtained in Examples 1 and 2 were placed on the surface thereof, and the photosensitive resin layer was faced to the substrate while peeling off the protective film at 120 ° C. , 0.4MPa conditional layering. After laminating, the substrate was cooled, and when the temperature of the substrate was 23 ° C, an exposure machine having a high-pressure mercury lamp (trade name "HMW-201B" manufactured by OAK Co., Ltd.) was used for the PET film surface, and exposed at 1000 mJ/cm ² . The conductive layer and the photosensitive resin layer were exposed in an amount. After the exposure, the film was allowed to stand at room temperature (25 ° C) for 15 minutes, and then the PET film of the support was peeled off, and the conductive film produced in the example was formed on a soda glass plate. Using the films of Examples 1 and 2, the surface resistance of the formed ones was 2000 Ω/□. 2800 Ω / □, the transmittance for light of 650 nm is 90%, 85%. The results are shown in Table 1.

In addition, the surface impedance is a surface resistivity measured by a four-probe method in accordance with JIS K 7194 using a low-impedance meter (Loresta GP, manufactured by Mitsubishi Chemical Corporation). In addition, the transmittance is measured by a spectrophotometer (manufactured by Hitachi High-Tech Co., Ltd., trade name "U-3310"), and is a minimum light transmittance in a wavelength region of 450 to 650 nm. The results are shown in Table 1.

<Formation of Conductive Pattern>

The polycarbonate substrate having a thickness of 1 mm was heated to 80 ° C, and the photosensitive conductive films obtained in Examples 1 and 2 were placed on the surface thereof, and the photosensitive resin layer was faced to the substrate while peeling off the protective film at 120 ° C. , 0.4MPa conditional layering. After lamination, the substrate was cooled, and when the temperature of the substrate was 23 ° C, the PET film surface of the support was adhered to a mask having a line width/line width of about 100/100 μm and a length of 100 mm. Then, an exposure machine having a high-pressure mercury lamp (manufactured by OAK Co., Ltd., trade name "HMW-201B") was used, and the conductive layer and the photosensitive resin layer were exposed at an exposure amount of 200 mJ/cm ² .

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

1. . . Film support

2. . . Conductive layer

2a. . . Conductive pattern

3. . . Photosensitive resin layer

3a. . . Hardened layer

4. . . Protective film

10. . . Photosensitive conductive film

20. . . Substrate

30. . . artwork

40. . . Substrate with conductive film

Fig. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive conductive film of the present invention.

Fig. 2 is a schematic cross-sectional view for explaining an embodiment of a method of forming a conductive pattern of the present invention.

1. . . Film support

2. . . Conductive layer

3. . . Photosensitive resin layer

4. . . Protective film

10. . . Photosensitive conductive film

Claims (12)

A transfer type 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. The transfer type photosensitive conductive film of claim 1, wherein the organic conductive material is a polymer of a thiophene or a thiophene derivative or a polymer of an aniline or an aniline derivative. The transfer type photosensitive conductive film of claim 1 or claim 2, wherein the organic conductive material is a polymer of a thiophene derivative. The transfer-type photosensitive conductive film of claim 1 or claim 2, wherein the photosensitive resin layer is a photopolymerizable compound containing a binder polymer, having an ethylenically unsaturated bond, and a photopolymerization initiator The composition of the photosensitive resin composition. The transfer type photosensitive conductive film of claim 4, wherein the binder polymer has a carboxyl group. The transfer type photosensitive conductive film of claim 4, wherein the photopolymerizable compound having an ethylenically unsaturated bond comprises at least one trimethylolpropane (meth) acrylate, tetrahydroxy group selected from the group consisting of Methyl methane (meth) acrylate, pentaerythritol (meth) acrylate, and dipentaerythritol (meth) acrylate. The transfer type photosensitive conductive film according to claim 4, wherein the photopolymerization initiator comprises an aromatic ketone compound or an oxime ester compound. The transfer type photosensitive conductive film of claim 1 or claim 2, wherein a side of the photosensitive resin layer opposite to the side of the conductive layer is further A protective film is laminated. A method of forming a conductive film, wherein the photosensitive resin layer of the transfer-type photosensitive conductive film according to any one of claims 1 to 8 is attached to a substrate, and at least The photosensitive resin layer and the conductive layer are laminated in this order, and the laminated photosensitive resin layer is exposed. A method of forming a conductive pattern, wherein the photosensitive resin layer of the transfer type photosensitive conductive film according to any one of claims 1 to 8 is attached to a substrate, and the substrate is at least sequentially The photosensitive resin layer and the conductive layer are laminated, and the laminated photosensitive resin layer is exposed and developed. A conductive film substrate comprising a substrate and a conductive film formed on the substrate by a method of forming a conductive film according to claim 9. A conductive film substrate comprising a substrate and a conductive pattern formed on the substrate by a method of forming a conductive pattern as claimed in claim 10.