KR20120120372A - Photosensitive conductive film, method for forming conductive membrane, and method for forming conductive pattern - Google Patents

Abstract

The photosensitive conductive film 10 has a structure in which a film support 1, a conductive layer 2 containing an organic conductive material, and a photosensitive resin layer 3 are laminated in this order. In the photosensitive conductive film 10, the organic conductive material is preferably a polymer of a thiophene derivative, and the photosensitive resin layer 3 is a photosensitive compound containing a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. It is preferable if it consists of a resin composition.

Description

Photosensitive conductive film, forming method of conductive film and forming method of conductive pattern {PHOTOSENSITIVE CONDUCTIVE FILM, METHOD FOR FORMING CONDUCTIVE MEMBRANE, AND METHOD FOR FORMING CONDUCTIVE PATTERN}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a photosensitive conductive film, a conductive film, and a method for forming a conductive pattern, and in particular, electrode wirings provided in flat panel displays such as liquid crystal display elements, touch screens, solar cells, organic EL, and the like. It relates to a method of forming a conductive pattern.

Large electronic devices such as PCs and televisions, car navigation devices, small electronic devices such as mobile phones and electronic dictionaries, and display devices such as OA and FA devices are widely used with liquid crystal display elements and touch screens. . In liquid crystal display elements and touch screens, transparent conductive films are used where transparency such as transparent electrodes is required. The same applies to solar cells.

As a material which can form a transparent conductive film, ITO (Indium-Tin-Oxide), indium oxide, tin oxide, etc. are known. These materials show high transmittance | permeability with respect to visible light, and are mainstream as a material which forms transparent electrodes, such as a board | substrate for liquid crystal display elements.

In a liquid crystal display device, a part of wirings, pixel electrodes, terminals and the like may be formed of a transparent conductive film. In this case, it is necessary to make a transparent conductive film into a predetermined shape. As a method of patterning a transparent conductive film, after forming a transparent conductive film, the method of forming a resist pattern by the photolithographic method on this and patterning a conductive film by wet etching is used. As the etching solution, a mixed solution composed of two liquids of hydrochloric acid and ferric chloride is preferably used for the ITO film and the indium oxide film.

On the other hand, forming a transparent conductive film using materials other than ITO is examined. For example, Patent Literature 1 below discloses a method of forming a transparent cured film having conductivity by applying a radiation curable conductive composition containing an organic conductive polymer such as polythiophene and polyaniline to a substrate surface and curing the same. It is. In addition, in Patent Document 2 below, a resist material such as a diazosulfonium-based is coated on a support, a thiophene-based organic conductive material is further applied thereon, and then a method of forming a conductive pattern by exposure and development. Is disclosed.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Publication No. 2005-170996

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

By the way, although an ITO film and a tin oxide film are generally formed by the spatter method, the property of a film | membrane tends to change with the difference of a spatter system, spatter power, gas pressure, substrate temperature, the kind of atmospheric gas, etc. The difference in the film quality of the transparent conductive film due to the variation in the spatter conditions causes the imbalance in the etching rate when the film is wet etched, and the patterning failure of the transparent conductive film is likely to occur, leading to a decrease in the yield of the product. Therefore, the method using ITO etc. has long spatter and resist formation, etching, and a process, and it is a big burden also in cost. In addition, such a method is difficult to obtain uniformity of patterning degree.

On the other hand, there exists the following problem regarding formation of the conductive pattern by an organic conductive material. Patent Document 1 does not disclose the formation of a conductive pattern. Although patterning by etching with a mask is considered, since there is no appropriate etching liquid, it is necessary to process using plasma etching or a laser.

Patent Document 2 discloses a method of applying and patterning a liquid mixed with an organic conductive material and a photosensitive material of a diazo compound to a support, or further disposing a photosensitive material between a support and a layer made of an organic conductive material and a photosensitive material. A method is proposed. However, in these methods, the adhesiveness between the conductive pattern and the substrate when the conductive pattern is to be provided on the desired substrate is not considered, and the surface treatment of the substrate is required.

This invention is made | formed in view of the problem which the said prior art has, and the photosensitive property which makes it easy to form on the board | substrate the adhesive pattern with a board | substrate sufficient, and the conductive pattern which consists of an organic conductive material with sufficient resolution easily. An object of the present invention is to provide a method for forming a conductive film and a method for forming a conductive pattern using the conductive film and the photosensitive conductive film.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this invention provides the photosensitive conductive film which has a structure which the support body, the conductive layer containing an organic conductive material, and the photosensitive resin layer were laminated | stacked in this order.

According to the photosensitive conductive film of this invention, by having a said structure, the photosensitive conductive film is affixed so that a photosensitive resin layer may adhere on a board | substrate, and it exposes and develops this, and adhesiveness with a board | substrate is enough, A desired conductive pattern having sufficient transparency can be easily formed.

Moreover, according to the photosensitive conductive film of this invention, a photosensitive conductive film is affixed on a board | substrate so that a photosensitive resin layer may adhere to a board | substrate, and it exposes this, and can form the electrically conductive film which has sufficient transparency and favorable adhesiveness to a base material. have.

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

In addition, from the viewpoint of further improving the patterning property of the conductive film and the adhesiveness to the substrate, the photosensitive resin layer is composed of a photosensitive resin composition containing a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. It is preferable.

It is preferable that the photosensitive conductive film of this invention is further laminated | stacked on the opposite side to the conductive layer side of the said photosensitive resin layer from the point of prevention of foreign material adhesion and damage in the period from manufacture to use. This protective film can be removed when using the photosensitive conductive film.

The present invention further provides that the photosensitive resin layer of the photosensitive conductive film of the present invention is affixed to a substrate, and at least a photosensitive resin layer and a conductive layer are laminated on the substrate in this order to expose the laminated photosensitive resin layer. A method for forming a conductive film is provided.

According to the formation method of the electrically conductive film of this invention, by attaching the photosensitive resin layer of the photosensitive conductive film of this invention to a base material, a photosensitive resin layer and a conductive layer are provided in this order on a base material, and it is a simple process of exposing this. The conductive film which consists of the said conductive layer can be easily formed on a base material. The conductive film is sufficiently adhered onto the substrate by curing the photosensitive resin layer by exposure.

The present invention further includes attaching the photosensitive resin layer of the photosensitive conductive film of the present invention to a substrate, laminating at least a photosensitive resin layer and a conductive layer on the substrate in this order, and exposing and developing the laminated photosensitive resin layer. A conductive pattern forming method is provided.

According to the formation method of the conductive pattern of this invention, a photosensitive resin layer and a conductive layer are provided in this order on a base material by affixing the photosensitive resin layer of the photosensitive conductive film of this invention to a base material, and exposing and developing this. By a simple process, the conductive pattern in which the said conductive layer is patterned can be easily formed on a base material. This conductive pattern is sufficiently adhered on the substrate by curing the photosensitive resin layer by exposure.

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

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

Carrying out the invention  Form for

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail. In addition, "(meth) acrylate" in this specification means "acrylate" and "methacrylate" corresponding to it. Similarly, "(meth) acryl" means "acryl" and "methacryl" corresponding thereto, and "(meth) acryloyl" means "acryloyl" and "methacryloyl" corresponding thereto. it means.

1: is a schematic cross section which shows suitable one Embodiment of the photosensitive conductive film of this invention. As for the photosensitive conductive film 10 shown in FIG. 1, the film-form support body 1, the conductive layer 2 containing an organic conductive material, the photosensitive resin layer 3, and the protective film 4 are laminated | stacked in this order, and Is done.

Hereinafter, each of the film-shaped support body (henceforth a "film support body") which comprises the photosensitive conductive film 10 which concerns on this embodiment, a conductive layer, the photosensitive resin layer, and a protective film is demonstrated in detail. do.

As the film support body 1, it is preferable that it is a transparent support film. Here, transparent means having transparency to the exposure light ray in the exposure process after the transfer to a base material, In this embodiment, it is preferable to have transparency in an ultraviolet (300-400 nm) area | region.

As a transparent support film, the polymer film which has heat resistance and solvent resistance, such as a polyethylene terephthalate film, a polypropylene film, and a polycarbonate film, is mentioned, for example. Among them, it is preferable to use a polyethylene terephthalate film from the viewpoint of transparency and heat resistance. Moreover, since these polymer films are removed in order to develop the photosensitive resin layer 3 later and to expose the formed electrically conductive film, surface treatment which becomes impossible to remove can not be performed, nor should it be a material.

It is preferable that it is 5-300 micrometers, and, as for the thickness of the said support film, it is more preferable that it is 20-300 micrometers. When the thickness of a support film is less than 5 micrometers, mechanical strength will fall, and when a support film is peeled off when forming a conductive layer, when forming a photosensitive resin layer, or before image development of a photosensitive resin layer, a support film is torn When it exceeds 300 micrometers, on the other hand, when it exceeds 300 micrometers, when the active light is irradiated to the photosensitive resin layer through a support film, the resolution tends to fall and it exists in a tendency for price to become expensive.

As an organic conductive material contained in the conductive layer 2, the polymer of a thiophene or a thiophene derivative, the polymer of aniline, or an aniline derivative is mentioned, for example. Specifically, polyethylenedioxythiophene, polyhexylthiophene, polyaniline, or the like can be used. Moreover, commercial items, such as "Creviose P" (made by H. Stark, Inc., brand name), and "Serujida OC-U1" (made by Shin-Etsu Polymer Co., Ltd., brand name), can be used.

It is preferable that the organic conductive material contained in the conductive layer 2 is a material which can form a pattern by light irradiation. In addition, as long as the effect of this invention is a range with which the effect of this invention is acquired, you may make it contain in the conductive layer 2 in combination with the material which can form a pattern by light irradiation.

As a polymer of a thiophene or a thiophene derivative, the polymer which has a repeating unit which can be represented by following formula (1) is mentioned.

However,

In formula (1), R <_1> and R <_2> is respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C20 alkyl group, a C1-C20 haloalkyl group, a C1-C20 alkoxy group, and C6 Or an arylamino group of -40, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heterocarbon group having 2 to 40 carbon atoms, and substituents adjacent to each other may be bonded to each other to form a ring; do. Moreover, 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 said Formula (1), as a halogen atom, fluorine, chlorine, bromine, iodine, etc. are mentioned, for example.

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 and n-hex. Real group, n-heptyl group, 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, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyl octa A methyl group, 3-methylpentyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a 3, 5- tetramethyl cyclohexyl group, etc. are mentioned. Among these, Preferably, 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 , 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 And a 5-tetramethylcyclohexyl group.

As a C1-C20 haloalkyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example. Among these, Preferably, they are a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.

As a C1-C20 alkoxy group, it is represented by -OY, for example, and the same thing as Y demonstrated by said alkyl group is mentioned, A preferable example is also the same.

Examples of the arylamino group having 6 to 40 carbon atoms include a phenyl group, naphthyl group, anthracenyl group, triphenylenyl group, fluoranthenyl group, and biphenyl group having, for example, a diphenylamino group or a diphenylamino group or an amino group as a substituent. Etc. can be mentioned. Among these, Preferably, they are a phenyl group and a naphthyl group which have a polyphenylamino group and an amino group as a substituent.

As an aryl group of 6-40 carbon atoms, a phenyl group, a naphthyl group, a biphenyl group, anthracenyl group, and a triphenylenyl group are mentioned, for example. As a substituent, a methyl group, an ethyl group, a cyclohexyl group, isopropyl group, a butyl group, a phenyl group, etc. are mentioned. Among these, Preferably, they are a substituted or unsubstituted phenyl group, a naphthyl group, and a biphenyl group.

As a substituted or unsubstituted C2-C40 heterocyclic group, For example, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 1-imidazolyl group, 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-imidazopi Ridinyl 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-benzofur Nilyl 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-quinoquinalyl group, 5- Quinoquisalinyl group, 6-quinoquinalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, β-carr Bolin-1-yl, β-carboline-3-yl, β-carboline-4-yl, β-carboline-5-yl, β-carboline-6-yl, β-carboline-7-yl , β-carboline-8-yl, β-carboline-9-yl, 1-phenantridinyl group, 2-phenantridinyl group, 3-phenantridinyl group, 4-phenantridinyl group, 6-phenan Tridinyl group, 7-phenantridinyl group, 8-phenantri Neyl group, 9-phenantridinyl group, 10-phenantridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7- Phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenanthroline-5-diary, 1,7-phenanthrole Lin-6-diary, 1,7-phenanthroline-8-diary, 1,7-phenanthroline-9-diary, 1,7-phenanthroline-10-diary, 1,8-phenanthroline- 2-diary, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl, 1,8-phenanthroline-5-diary, 1,8-phenanthroline-6- Diary, 1,8-phenanthroline-7-diary, 1,8-phenanthroline-9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline-2-diary, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1, 9-phenanthroline-7-diary, 1,9-phenanthroline-8-diary, 1,9-phenanthroline-10-diary, 1,10-phenanthroline-2-yl, 1,10- Phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1,10-phenan Rollin-5-Diary, 2,9-Phenanthroline-1-yl, 2,9-Phenanthroline-3-yl, 2,9-Phenanthroline-4-yl, 2,9-Phenanthroline- 5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline-8-diary, 2,9-phenanthroline-10- Diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8-phenanthroline-5-diary, 2,8-phenanthroline-6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8-phenanthroline-10-diary, 2, 7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline 4-diary, 2,7-phenanthroline-5-diary, 2,7-phenan Trollin-6-diary, 2,7-phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthroline-10-diary, 1-phenadidinyl group, 2 -Phenadinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phene Noxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10- Noxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-tier Neyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1yl group, 3-methylpyrrole -2-yl group, 3-methylpyrrole-4-yl group, 3-methylpyrrole-5-yl group, 2-t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrole-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-dibenzothiophenyl group, 1-silafluorenyl group, 2-silafluorenyl group, 3- Silafluorenyl group, 4-silafluorenyl group, 1-gelmafluorenyl group, 2-gelmafluorenyl group, 3-gelmafluorenyl group, 4-gelmafluorenyl group, etc. are mentioned.

Among them, 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-imidazopyridinyl group, 3-imidazopyridinyl group, 5-imidazopyridinyl group, 6-imidazopyridinyl group, 7-imidazopyridinyl group, 8-imidazopyrididi Neyl 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-di Benzofuranyl group, 4-dibenzofuranyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 4- Benzothiophenyl group, 1-silafluorenyl group, 2-silafluorenyl group, 3-silafluorenyl group, 4-silafluorenyl group, 1-gelmafluorenyl group, 2-gelmafluorenyl group, 3-gelmaflu Orenyl group and 4-gelmafluorenyl group.

Moreover, as a substituent, a methyl group, an ethyl group, a cyclohexyl group, an isopropyl group, a butyl group, a phenyl group, etc. are mentioned, for example.

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

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 carbon atoms, or a substituted or unsubstituted nucleus. It is a C2-C40 heterocyclic group. As for an alkyl group, an aryl group, or a heterocyclic group, the same thing as R <_1> , R <_2> can be mentioned.

As the polythiophene or polythiophene derivative represented by the formula (1), a commercially available product or one synthesized by a known method can be used. The molecular weight of a polythiophene or a polythiophene derivative generally uses the thing of the range of 1,000-100,000 as a number average molecular weight. If the molecular weight is smaller than this, sufficient conductivity based on the π-electron conjugated system is not exhibited. On the other hand, if the molecular weight is excessively large, it becomes viscous and difficult to form a thin film. The repeating units combine with adjacent repeating units in the form of headtails, head-heads or tail-tails to form a polymer. If the alkyl group or alkoxy group that is substituted at the 3-position of the thiophene ring is too long, it may cause confusion in the rule of the three-dimensional structure of the molecule and possibly damage the mobility, and therefore preferably 20 or less carbon atoms.

The conductive layer 2 is formed on the film support 1 by, for example, a dispersion liquid for forming a conductive layer obtained by adding the aforementioned organic conductive material to water and / or an organic solvent and, if necessary, a dispersion stabilizer such as a surfactant. After coating, it can form by drying. Coating can be performed by well-known methods, such as the roll coating method, the comma coating method, the gravure coating method, the air knife coating method, the die coating method, the bar coating method, the spray coating method, for example. In addition, drying can be performed with a hot air convection type dryer etc. at 30-150 degreeC for about 1 to 30 minutes.

Although the thickness of the conductive layer 2 changes with the use of the electrically conductive film or electrically conductive pattern formed using the photosensitive conductive film of this invention, and the electroconductivity calculated | required, it is preferable that it is 1 micrometer or less, and it is 0.01 micrometer-0.5 micrometer More preferably, it is especially preferable that they are 0.01 micrometer-0.3 micrometer. If the thickness of the conductive layer 2 is 1 micrometer or less, it will become easy to ensure the light transmittance.

As the photosensitive resin layer 3, it is preferable to consist of the photosensitive resin composition containing a binder polymer, the photopolymerizable compound which has an ethylenically unsaturated bond, and a photoinitiator.

As a binder polymer, an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, a phenol resin, etc. are mentioned, for example. It is preferable to use an acrylic resin from a viewpoint of alkali developability. These can be used individually by 1 type or in combination of 2 or more type.

Said binder polymer can be manufactured by radically polymerizing a polymerizable monomer, for example. As said polymerizable monomer, For example, acrylamide, such as styrene derivative which can be substituted in the alpha-position or aromatic ring, such as styrene, vinyltoluene, and (alpha) -methylstyrene, diacetone acrylamide, acrylonitrile, Ethers of vinyl alcohols such as vinyl-n-butyl ether, (meth) acrylic acid alkyl esters, (meth) acrylic acid tetrahydrofurfuryl esters, (meth) acrylic acid dimethylaminoethyl esters, (meth) acrylic acid diethylaminoethyl esters, (Meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, (alpha)- Bromo (meth) acrylic acid, α-chlor (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, male San Monoiso Maleic acid monoester, fumaric acid, cinnamic acid, α- cyano-cinnamic acid, itaconic acid, crotonic acid and propionic olsan such as ropil.

As said (meth) acrylic-acid alkylester, the compound in which the hydroxyl group, the epoxy group, the halogen group etc. substituted the alkyl group of the compound represented by following General formula (2), and these compounds is mentioned, for example.

[Figure 2]

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 structures thereof. Isomers are mentioned.

As a compound represented by the said General formula (2), (meth) acrylic-acid methyl ester, (meth) acrylic-acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic-acid butyl ester, (meth) acrylate pentyl, for example 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 and (meth) acrylic acid dodecyl ester are mentioned. These may be used singly or in combination of two or more.

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 manufactured by radically polymerizing the polymerizable monomer which has a carboxyl group, and another polymerizable monomer, for example. As a polymerizable monomer which has the said carboxyl group, the above-mentioned (meth) acrylic acid is preferable.

As for the ratio of the carboxyl group which a binder polymer has, as a ratio of the polymerizable monomer which has a carboxyl group with respect to all the polymerizable monomers used, it is preferable that it is 12-50 weight% from a viewpoint of balance of alkali developability and alkali tolerance, It is more preferable that it is 12-40 weight%, It is especially preferable that it is 15-30 weight%, It is extremely preferable that it is 15-25 weight%. When the ratio of the polymerizable monomer having a carboxyl group is less than 12% by weight, alkali developability tends to be inferior, and when it exceeds 50% by weight, alkali resistance tends to be inferior.

From the viewpoint of achieving a balance between mechanical strength and alkali developability, the weight average molecular weight of the binder polymer is preferably 20000 to 300000, and more preferably 40000 to 150000. When the weight average molecular weight is less than 20000, the developer resistance tends to decrease, and when the weight average molecular weight exceeds 300000, 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 into the analytical curve created using the standard polystyrene.

These binder polymers are used individually by 1 type or in combination of 2 or more types. As a binder polymer at the time of using in combination of 2 or more types, For example, two or more types of binder polymers which consist of another copolymerization component, two or more types of binder polymers of different weight average molecular weight, and two or more types of binder polymers of different dispersion degree are used, for example. Can be mentioned.

Next, the photopolymerizable compound which has an ethylenically unsaturated bond is demonstrated. As a photopolymerizable compound which has an ethylenically unsaturated bond, For example, the compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with a polyhydric alcohol, 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 Urethane monomers, such as the compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with the bisphenol-A (meth) acrylate compound, glycidyl group containing compound, such as these, and the (meth) acrylate compound which have a urethane bond, (gamma) -chloro -β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl -(beta)-(meth) acryloyloxyethyl-o-phthalate, the (meth) acrylic-acid alkylester, etc. are mentioned. The. These may be used alone or in combination of two or more.

As a compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with the said polyhydric alcohol, the polyethyleneglycol di (meth) acrylate whose number of ethylene groups is 2-14, for example, the polypropylene glycol whose number of propylene groups is 2-14 Di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate, trimetholpropanedi (meth) acrylate, trimetholpropane having 2 to 14 ethylene groups and 2 to 14 propylene groups Tri (meth) acrylate, trimetholpropane ethoxytri (meth) acrylate, trimetholpropane diethoxy tri (meth) acrylate, trimetholpropane triethoxy tri (meth) acrylate, trimethol Trimetholpropane (meth) acrylates, such as propane tetraethoxy tri (meth) acrylate and trimetholpropane pentaethoxy tri (meth) acrylate, and tetramethol methane Tetrametholmethane (meth) acrylate, such as (meth) acrylate and tetrametholmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy tree Pentaerythritol (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol, such as dipentaerythritol alkoxypenta (meth) acrylate (Meth) acrylate is mentioned.

Among the above, from the point which is excellent in transparency and adhesiveness, from a trimetholpropane (meth) acrylate, tetrametholmethane (meth) acrylate, pentaerythritol (meth) acrylate, and dipentaerythritol (meth) acrylate It is preferable to include at least 1 sort (s) selected.

As said urethane monomer, the (meth) acryl monomer which has a hydroxyl group in a (beta) position, isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4- toluene diisocyanate, 1, 6- hexamethylene, for example Addition reactant with diisocyanate compounds, such as diisocyanate, Tris [(meth) acryloxy tetraethylene glycol isocyanate] hexamethylene isocyanurate, EO modified urethane di (meth) acrylate, EO, PO modified urethane di (meth) Acrylates and the like. "EO" represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. In addition, "PO" represents a propylene oxide and the PO modified compound has a block structure of a propylene oxide group. As EO modified urethane di (meth) acrylate, "UA-11" (made by Shin-Nakamura Chemical Co., Ltd., brand name) is mentioned, for example. Moreover, as EO and PO modified urethane di (meth) acrylate, "UA-13" (made by Shin-Nakamura Chemical Industry Co., Ltd., brand name) is mentioned, for example.

It is preferable that it is 30-80 weight part with respect to 100 weight part of total amounts of a binder polymer and a photopolymerizable compound, and, as for the content rate of a photopolymerizable compound, it is more preferable that it is 40-70 weight part. When this content rate is less than 30 weight part, photocuring will become inadequate, and there exists a tendency for the sclerosis | hardenability of the transferred electrically conductive film to become inadequate, and when it exceeds 80 weight part, when winding up as a film, it will become difficult to store.

Next, a photoinitiator is demonstrated. As a photoinitiator, for example, benzophenone, N, N'- tetramethyl-4,4'- diamino benzophenone (Mihilerketone), N, N'- tetraethyl-4, 4'- diamino benzo Phenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethyl amino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- ( Aromatic ketones such as methylthio) phenyl] -2-morpholino-propane-1, 2-ethyl anthraquinone, phenanthrene quinone, 2-tert- butyl anthraquinone, octamethyl anthraquinone, 1,2-benzanthra Quinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenan Quinones, such as taraquinone, 2-methyl 1, 4- naphthoquinone, and 2, 3- dimethyl anthraquinone, benzoin ether compounds, such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, benzoin, Benzoin compounds such as methyl benzoin and ethyl benzoin, 1,2-octanedione, 1- [4- (phenylthione )-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime Oxime ester compounds such as), benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimida 2,4,5-triarylimidazole dimers, such as a sol dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1, Acridine derivatives such as 7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, and oxazole compounds. In addition, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same, and may give a target compound, and may give a compound asymmetrically different. Moreover, the combination of a thioxanthone type compound and a tertiary amine compound may be sufficient like the combination of diethyl thioxanthone and dimethylamino benzoic acid. Among them, in terms of transparency, aromatic ketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 1, 1,2-octanedione, 1- [4- ( Oxime ester compounds such as phenylthio)-and 2- (o-benzoyl oxime)] are more preferable. These may be used alone or in combination of two or more.

It is preferable that it is 0.1-30 weight part with respect to 100 weight part of total amounts of a binder polymer and a photopolymerizable compound, and, as for the content rate of a photoinitiator, it is more preferable that it is 1-10 weight part. When this content rate is less than 0.1 weight part, there exists a tendency for the photosensitivity to become inadequate, and when it exceeds 30 weight part, there exists a tendency for the absorption on the surface of a composition to increase at the time of exposure, and the internal photocuring may become inadequate.

In the photosensitive resin layer 3, if necessary, plasticizers such as p-toluenesulfonamide, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, flavoring agents, imaging agents, thermal crosslinking agents, and the like. Additives may be contained alone or in combination of two or more thereof. It is preferable that the addition amount of these additives is 0.01-20 weight part with respect to 100 weight part of total amounts of a binder polymer and a photopolymerizable compound, respectively.

On the transparent film support 1 in which the photosensitive resin layer 3 provided the conductive layer 2, as needed, methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene It is preferable to apply | coat the solution of the photosensitive resin composition about 10 to 60 weight% of solid content melt | dissolved in solvents, such as N, N- dimethylformamide, a propylene glycol monomethyl ether, or these mixed solvents. In this case, however, the amount of the remaining organic solvent in the photosensitive resin layer after drying is preferably 2% by weight or less in order to prevent diffusion of the organic solvent in the subsequent step.

Application | coating of the photosensitive resin composition can be performed by well-known methods, such as the roll coating method, the comma coating method, the gravure coating method, the air knife coating method, the die coating method, the bar coating method, the spray coating method, for example. In addition, drying can be performed at about 70 to 150 degreeC for about 5 to 30 minutes.

Although the thickness of the photosensitive resin layer 3 changes with a use, it is preferable that it is 1-50 micrometers in thickness after drying, It is more preferable that it is 1-20 micrometers, It is especially preferable that it is 1-10 micrometers. When this thickness is less than 1 micrometer, there exists a tendency for coating to become industrially difficult, and when it exceeds 50 micrometers, the sensitivity by the fall of light transmission will become inadequate, and there exists a tendency for the photocurability of the photosensitive resin layer to fall. Moreover, from the point which is excellent in adhesiveness and patterning, it is preferable that the thickness of the photosensitive resin layer 3 is 1 micrometer or more.

Next, a protective film is demonstrated. In the photosensitive conductive film of this invention, 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 a protective film, the polymer film which has heat resistance and solvent resistance, such as a polyethylene terephthalate film, a polypropylene film, a polyethylene film, can be used, for example. As a protective film, you may use the polymer film similar to the film support body mentioned above.

The adhesive force between the protective film and the photosensitive resin layer is less than the adhesive force between the conductive layer 2 and the photosensitive resin layer 3 and the film support 1 in order to facilitate peeling of the protective film from the photosensitive resin layer. Small ones are preferable.

Moreover, it is preferable that a protective film is a film of low fisheye. Specifically, it is preferable that the number of fisheye of 80 micrometers or more contained in a protective film is 5 pieces / m <2> or less. In addition, the "fish eye" heat-melts a material, and when the film is manufactured by kneading, extrusion, biaxial stretching, a casting method, etc., the foreign material, undissolved matter, oxidative deterioration, etc. of a material are taken in in a film.

It is preferable that the thickness of a protective film is 1-100 micrometers, It is more preferable that it is 5-50 micrometers, It is still more preferable that it is 5-30 micrometers, It is especially preferable that it is 15-30 micrometers. When the thickness of a protective film is less than 1 micrometer, when it laminates, a protective film will become easy to tear, and when it exceeds 100 micrometers, it will become expensive.

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

The photosensitive conductive film can be stored in the form of a flat plate as it is, or wound in a roll shape by winding in a core such as a cylindrical shape. Moreover, at this time, it is preferable to wind so that a film support body may become outermost.

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

The core is not particularly limited as long as it is conventionally used, and examples thereof include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). Can be. Moreover, it is preferable to provide a cross-sectional separator in the cross section of the photosensitive conductive film wound in roll shape from a viewpoint of end surface protection, and to provide a moisture proof cross-section separator from a viewpoint of inner diffusion. In addition, when packing the photosensitive electrically conductive film, it is preferable to wrap and package in the black sheet | seat with small moisture permeability.

It is preferable that the photosensitive conductive film of this embodiment forms the conductive layer by coating the dispersion liquid for conductive layer formation on a film support body, and then coats the photosensitive resin composition and forms the photosensitive resin layer. By coating the dispersion liquid for conductive layer formation on a film support body, it becomes easy to form a uniform conductive layer.

According to the photosensitive conductive film of this embodiment, the conductive film which has a transparent and favorable pattern is easily formed by transferring a photosensitive resin layer and a conductive layer, and exposing and developing on the base material on which a conductive pattern is needed. can do.

Moreover, since the conductive film or conductive pattern formed from the photosensitive conductive film of this embodiment is rich in flexibility, it is suitable as an electrode etc. of a flexible display. In addition, since the conductive film or conductive pattern 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 formation method of the electrically conductive film of this invention, the lamination process of laminating the photosensitive conductive film of said this embodiment so that a photosensitive resin layer may adhere on a base material, and irradiating actinic light to the photosensitive resin layer on a base material The method of providing an exposure process is mentioned. When the photosensitive conductive film has a protective film, the photosensitive conductive film which peeled the protective film is laminated on the base material from the photosensitive resin layer side. By the said lamination process, the photosensitive resin layer, a conductive layer, and a support body are laminated | stacked in this order on a base material.

As a base material, plastic substrates, such as a glass substrate and a polycarbonate, etc. are mentioned, for example.

A lamination process is performed by the method of laminating | stacking the photosensitive resin layer side to a base material, heating, for example, after removing a photosensitive conductive film, when there exists a protective film. Moreover, it is preferable to laminate | stack this operation | work under reduced pressure from the standpoint of adhesiveness and followability. In the lamination of the photosensitive conductive film, it is preferable to heat the photosensitive resin layer and / or the substrate to 70 to 130 ° C, and the crimping pressure is preferably about 0.1 to 1.OMPa (about 1 to 10 kgf / cm 2). There is no restriction | limiting in particular in these conditions. In addition, when the photosensitive resin layer is heated to 70-130 degreeC as mentioned above, it is not necessary to preheat-process a base material beforehand, but a preheating process of a base material can also be performed in order to further improve lamination property.

In an exposure process, the photosensitive resin layer of the irradiated part is hardened by irradiating an actinic light, and a conductive film is formed on a base material by fixing a conductive layer by this hardened | cured material. As a light source of an active light beam, a well-known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, an ultraviolet ray, such as a xenon lamp, etc. which radiate effectively, is used. Moreover, what radiates ultraviolet-ray, visible light, etc. effectively, such as Ar ion laser and a semiconductor laser, are also used. Moreover, what radiates visible light, such as a photographic light bulb and a solar lamp, is also used effectively.

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

Moreover, when a base material is transparent with respect to an actinic light, it can irradiate an actinic light through the base material from the base material side, but it is preferable to irradiate an actinic light to the conductive layer and the photosensitive resin layer from the conductive layer side from the point of resolution.

By passing through the said process, the base material with an electrically conductive film provided with an electrically conductive film on a base material is obtained. In the formation method of the conductive film of this embodiment, after peeling of a film support body, you may further harden the formed conductive film by heating about 60-250 degreeC or exposing about 0.2-10 J / cm <2> as needed. . Both heating and exposure may be performed to further cure.

As described above, according to the method for forming the 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 formation method of the conductive pattern of this invention is demonstrated, referring drawings.

The formation method of the conductive pattern which concerns on this embodiment is the process of laminating the photosensitive conductive film 10 mentioned above so that the photosensitive resin layer 3 may adhere to the board | substrate 20 (FIG.2 (a)), and An electrically conductive pattern is formed by developing the exposure process (FIG. 2B) which irradiates an actinic light to the predetermined part of the photosensitive resin layer 3 on the board | substrate 20, and the exposed photosensitive resin layer 3. The developing process is provided. By passing through these processes, the board | substrate 40 with an electrically conductive film provided with the electrically conductive film (conductive pattern) 2a patterned on the board | substrate 20 is obtained (FIG.2 (c)).

A lamination process is performed by the lamination | stacking method which crimps | bonds the photosensitive resin layer 3 side to a board | substrate, heating, for example, after removing the photosensitive conductive film 10, when there exists a protective film. Moreover, it is preferable to laminate | stack this operation | work under reduced pressure from the standpoint of adhesiveness and followability. It is preferable that the laminated | stack of the photosensitive conductive film 10 heats the photosensitive resin layer 3 and / or the board | substrate 20 to 70-130 degreeC, and a crimping pressure is about 0.1-1.OMPa (1-10 kgf /). c 2 m 2), but these conditions are not particularly limited. In addition, when the photosensitive resin layer 3 is heated to 70-130 degreeC as mentioned above, it is not necessary to preheat-process a board | substrate beforehand, but a preheating process of a board | substrate can also be performed in order to further improve lamination property.

As an exposure method in an exposure process, the method (mask exposure method) which irradiates an actinic light onto an image through the negative or positive mask shell called artwork is mentioned. As a light source of an active light beam, a well-known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, an ultraviolet ray, such as a xenon lamp, etc. which radiate effectively, is used. Moreover, what radiates ultraviolet-ray, visible light, etc., such as Ar ion laser and a semiconductor laser, are also used effectively. Moreover, what radiates visible light, such as a photographic light bulb and a solar lamp, is also used effectively. Moreover, you may employ | adopt the method of irradiating an actinic light to an image by the direct drawing method using a laser exposure method.

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

In addition, when the board | substrate (adherment) 20 is transparent with respect to actinic light, actinic light can be irradiated through the board | substrate 20 from the board | substrate 20 side, but in terms of the resolution, the conductive layer 2 It is preferable to irradiate actinic light to the conductive layer 2 and the photosensitive resin layer 3 from a side.

In the developing process of this embodiment, parts other than the exposed part of the photosensitive resin layer 3 are removed. Specifically, in the case where the film support 1 is present on the conductive layer 2, the film support 1 is first removed, and then, except for the exposed portion of the photosensitive resin layer 3 by wet development. Remove the part of. Thereby, the conductive layer 2a containing an organic conductive material remains on the resin cured layer 3a which has a predetermined pattern, and a conductive pattern is formed.

Wet development is performed by well-known methods, such as spraying, shaking immersion, brushing, and scraping, for example using developing solution corresponding to photosensitive resin, such as alkaline aqueous solution, aqueous developing solution, and organic solvent developing solution.

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

Moreover, as alkaline aqueous solution used for image development, 0.1-5 weight% sodium carbonate aqueous solution, 0.1-5 weight% potassium carbonate aqueous solution, 0.1-5 weight% sodium hydroxide aqueous solution, 0.1-5 weight% sodium tetraborate aqueous solution, etc. 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 addition, in alkaline aqueous solution, you may mix surface active agent, an antifoamer, a small amount of organic solvents for promoting image development, etc ..

Moreover, the aqueous developing solution which consists of water or alkali aqueous solution, and 1 or more types of organic solvent can be used. Here, as a base contained in aqueous alkali solution, in addition to the base mentioned above, it is borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxy, for example. Methyl-1,3-propanediol, 1,3-diaminopropanol-2, and morpholine.

As the organic solvent, for example, 3-acetone alcohol, acetone, ethyl acetate, alkoxy ethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether and diethylene glycol monobutyl ether are mentioned. These are used individually by 1 type or in combination of 2 or more types.

It is preferable that the aqueous developing solution makes the density | concentration of the organic solvent into 2 to 90 weight%, and the temperature can be adjusted according to developability. Moreover, it is preferable to make pH of an aqueous developing solution as small as possible in the range in which image development of a resist is enough, It is preferable to set it as pH8-12, and it is more preferable to set it as pH9-10. Moreover, a small amount of surfactant, an antifoamer, etc. can also be added to an aqueous developing solution.

As the organic solvent developer, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, etc. Can be mentioned. It is preferable that these organic solvents add water in 1 to 20weight% of a range for ignition prevention.

The developing solution mentioned above may use 2 or more types together as needed.

As a system of image development, a dip system, a battle system, a spray system, blushing, slapping etc. are mentioned, for example. Among these, it is preferable to use a high pressure spray system from a viewpoint of a resolution improvement.

In this embodiment, the conductive layer on the photosensitive resin layer of an unexposed part is removed together, and the photosensitive resin layer of an unexposed part is removed by developing the photosensitive resin layer 3 after exposing to a predetermined pattern, and removing an unexposed part. The conductive layer on the resin layer remains, and a conductive pattern is formed. At the time of image development, the photosensitive resin layer melt | dissolves by developing a solution soaking into the conductive layer 2 and swelling an unexposed photosensitive resin layer, or a developer soaking from the edge part of the photosensitive resin layer and swelling the photosensitive resin layer. It is dispersed and a pattern is formed. When the layer thickness of the conductive layer 2 is 0.5 micrometers thin, the developing solution easily reaches the photosensitive resin layer 3 through the conductive layer 2, and developability improves.

In the formation method of the electrically conductive pattern of this embodiment, after image development, you may further harden an electrically conductive pattern by performing about 60-250 degreeC heating or exposure of about 0.2-10 J / cm <2> as needed. Both heating and exposure may be performed to further cure.

As described above, according to the method for forming the conductive pattern of the present invention, it is possible to easily form a transparent conductive pattern on a substrate such as glass or plastic without forming an etching resist like an inorganic film such as ITO.

Although the board | substrate with a conductive film which concerns on this invention is obtained by the formation method of the conductive film mentioned above, or the formation method of a conductive pattern, the surface resistivity of a conductive film or a conductive pattern is 10000 ohm from a viewpoint which can be utilized effectively as a transparent electrode. It is preferable that it is / square or less, It is more preferable that it is 5000Ω / square or less, It is especially preferable that it is 2000Ω / square or less. Surface resistivity can be adjusted by the density | concentration or coating amount of the dispersion liquid containing an organic conductive material, for example. The surface resistivity tends to decrease as the concentration of the dispersion is increased, and as the coating amount is increased to increase the thickness. Moreover, it can also adjust by a doping process.

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

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive conductive film which makes it easy to form the conductive pattern which has sufficient adhesiveness with a board | substrate and consists of an organic conductive material with sufficient resolution on a board | substrate, and the formation method of the conductive film using the same And a method of forming a conductive pattern.

1: 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.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples.

<Preparation of coating liquid for conductive layer formation>

(Conductive Solution 1 for Forming Electroconductive Layer (Organic Conductive Material Solution))

"Sepuruzida OC-U1" (Shin-Etsu Polymer Co., Ltd., optical patterning paint, brand name) which is an alcohol solution of polyethylene dioxythiophene was diluted by 10 times methanol, and this was made into the coating liquid (1) for conductive layer formation.

(Conductive Solution 2 for Forming Electroconductive Layer (Organic Conductive Material Solution))

"Creviose P" (trade name, manufactured by H.C. Starck, Inc.), which is an aqueous solution of polyethylenedioxythiophene, was diluted five times with water, and this was used as a coating solution 2 for forming a conductive layer.

<Preparation of the solution of the photosensitive resin composition>

Synthesis of Acrylic Resin

Mixture of methyl cellosolve and toluene (methyl cellosolve / toluene = 3/2 (weight ratio)) to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping lot, and a nitrogen gas inlet tube (hereinafter, `` solution s '') 400g was added, it stirred, blowing nitrogen gas, and it heated to 80 degreeC. On the other hand, the solution (henceforth "solution a") which mixed 100 g of methacrylic acid, 250 g of methyl methacrylate, 100 g of ethyl acrylate, and 50 g of styrene, and 0.8 g of azobisisobutyronitrile was prepared as a monomer. Next, the solution a was dripped at the solution s heated at 80 degreeC over 4 hours, and it kept warm for 2 hours, stirring at 80 degreeC. Furthermore, the solution which melt | dissolved 1.2 g of azobisisobutyronitrile in 100 g of solution s was dripped in the flask over 10 minutes. And after stirring the solution after dripping for 3 hours, stirring at 80 degreeC, it heated over 90 degreeC over 30 minutes. After heat-retaining at 90 degreeC for 2 hours, it cooled and obtained the binder polymer solution. Acetone was added to this binder polymer solution, and it was prepared so that the non volatile component (solid content) may be 50 weight%, and the binder polymer solution was obtained. The weight average molecular weight of the obtained binder polymer was 80000. This was referred to as acrylic polymer A.

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

1) Methacrylic acid: Methyl methacrylate: Ethyl acrylate: and styrene = 20: 50: 20: 10 Acrylic polymer of the weight ratio

<Production of Photosensitive Conductive Film>

(Example 1)

The coating liquid 1 for conductive layer formation is apply | coated uniformly at 25 g / m <2> on 50-micrometer-thick polyethylene terephthalate film (PET film, Teijin Corporation make, brand name "G2-50") which is a support film (film support). Then, it dried for 3 minutes with the hot air convection type dryer of 100 degreeC, and formed the conductive layer. Moreover, the film thickness after drying of a conductive layer was about 0.1 micrometer.

Next, the solution of the said photosensitive resin composition was apply | coated uniformly to the side in which the conductive layer of a support film is provided, and it dried for 10 minutes with the hot air convection type dryer of 100 degreeC, and formed the photosensitive resin layer. The film thickness after drying of the photosensitive resin layer was 5 micrometers. Moreover, the photosensitive resin layer was covered with the protective film (made by Tama Poly, Ltd., brand name "NF-13") made from polyethylene, and the photosensitive electrically conductive film was obtained.

(Example 2)

The coating liquid 2 for conductive layer formation is apply | coated uniformly at 25 g / m <2> on the 50-micrometer-thick polyethylene terephthalate film (PET film, Teijin Corporation make, brand name "G2-50") which is a support film, and the hot air of 100 degreeC It dried with the convection dryer for 3 hours, and formed the conductive layer. Moreover, the film thickness of the conductive layer after drying was about 0.1 micrometer.

Next, the solution of the said photosensitive resin composition was apply | coated uniformly to the side in which the conductive layer of a support film is provided, and it dried for 10 minutes with the hot air convection type dryer of 100 degreeC, and formed the photosensitive resin layer. The film thickness after drying of the photosensitive resin layer was 5 micrometers. Moreover, the photosensitive resin layer was covered with the protective film (made by Tama Poly, Ltd., brand name "NF-13") made from polyethylene, and the photosensitive conductive film was obtained.

<Formation of Conductive Film>

The soda glass plate of 0.7 mm thickness was heated at 80 degreeC, and the photosensitive resin layer was made to oppose a board | substrate, peeling a protective film, and the photosensitive conductive film obtained in Examples 1 and 2 on the surface, and the conditions of 120 degreeC and 0.4 MPa Laminated from. After lamination, the substrate was cooled and the exposure amount of 1000 mJ / cm 2 was obtained by using an exposure machine (Oak Manufacturing Co., Ltd., trade name "HMW-201B") having a high-pressure mercury lamp on the PET film surface when the temperature of the substrate became 23 ° C. The conductive layer and the photosensitive resin layer were exposed. After exposure, it was left to stand at room temperature (25 ° C) for 15 minutes, and then the PET film serving as the support was peeled off to form the conductive film produced in the example on a soda glass plate. The surface resistance of what was formed using the films of Examples 1 and 2 was 2000 ohms / square and 2800 ohms / square, respectively, and the transmittance | permeability with respect to the light of 650 nm was 90% and 85%, respectively. The results are shown in Table 1.

In addition, said surface resistance is the surface resistivity measured based on JISK7194 by the four probe method using the low-resistance meter (the Mitsubishi Chemical Corporation, Lorestar GP). In addition, 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 1.

<Formation of a conductive pattern>

A polycarbonate substrate having a thickness of 1 mm was heated to 80 ° C, and the photosensitive resin layer was opposed to the substrate while the protective film was peeled off on the surface of the photosensitive conductive film obtained in Examples 1 and 2, and the 120 ° C was 0.4 MPa. Laminated under conditions. After lamination, when the substrate was cooled and the temperature of the substrate reached 23 ° C., a photomask having a wiring pattern having a line width / space width of 100/100 μm and a length of 100 mm was applied to the PET film surface as the support. It adhered closely. And the electrically conductive layer and the photosensitive resin layer were exposed by the exposure amount of 200mJ / cm <2> using the exposure machine (Oak Corporation make, brand name "HMW-201B") which has a high pressure mercury lamp.

After exposure, it was left to stand at room temperature (25 ° C) for 15 minutes, followed by peeling off the PET film serving as a support, followed by development by spraying a 1% by weight 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 탆 was formed on the polycarbonate substrate. It was confirmed that each conductive pattern was formed satisfactorily.

One… Film support, 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 (8)

The photosensitive conductive film which has a structure in which a support body, the conductive layer containing an organic conductive material, and the photosensitive resin layer were laminated | stacked in this order. The photosensitive conductive film of Claim 1 whose said organic conductive material is a polymer of a thiophene derivative. The photosensitive conductive film of Claim 1 or 2 in which the said photosensitive resin layer consists of a photosensitive resin composition containing a binder polymer, the photopolymerizable compound which has an ethylenically unsaturated bond, and a photoinitiator. The photosensitive conductive film in any one of Claims 1-3 by which the protective film is further laminated | stacked on the opposite side to the said conductive layer side of the said photosensitive resin layer. The said photosensitive resin layer of the photosensitive conductive film in any one of Claims 1-4 is affixed on a base material, and the said photosensitive resin layer and the said conductive layer are laminated | stacked in this order on the base material, and the said photosensitive laminated | stacked The resin layer is exposed, The formation method of the conductive film characterized by the above-mentioned. The said photosensitive resin layer of the photosensitive conductive film in any one of Claims 1-4 is affixed on a base material, and the said photosensitive resin layer and the said conductive layer are laminated | stacked in this order on the base material, and the said photosensitive laminated | stacked The resin layer is exposed and developed, The formation method of the conductive pattern characterized by the above-mentioned. A conductive film substrate comprising a substrate and a conductive film formed by the method for forming a conductive film according to claim 5 on the substrate. A conductive film substrate comprising a substrate and a conductive pattern formed by the method for forming a conductive pattern according to claim 6 on the substrate.

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