KR101847364B1 - 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 preferably a photosensitive polymer containing a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, It is preferable that it is made of a resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive conductive film, a method of forming a conductive film, and a method of forming a 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. More particularly, the present invention relates to a method of forming a conductive film, such as a flat panel display such as a liquid crystal display element or an electrode wiring provided in an apparatus such as a touch screen, To a method of forming a conductive pattern.

In a display device such as a large electronic device such as a PC or a television, a small electronic device such as a car navigation device, a mobile phone, or an electronic dictionary, or an OA / FA device, a device equipped with a liquid crystal display device or a touch screen is popular . In a liquid crystal display element or a touch screen, a transparent conductive film such as a transparent electrode is used where transparency is required. The same is true for solar cells.

As a material capable of forming a transparent conductive film, indium-tin-oxide (ITO), indium oxide, tin oxide and the like are known. These materials exhibit a high transmittance with respect to visible light and serve as a mainstream material for forming a transparent electrode such as a substrate for a liquid crystal display element.

In a liquid crystal display device, a part of a wiring, a pixel electrode, a terminal, and the like may be formed of a transparent conductive film. In this case, it is necessary to set the transparent conductive film to a predetermined shape. As a method of patterning the transparent conductive film, a method is available in which a transparent conductive film is formed, a resist pattern is formed thereon by photolithography, and the conductive film is patterned by wet etching. As the etching solution, a mixture of two solutions of hydrochloric acid and ferric chloride is well used for the ITO film and the indium oxide film.

On the other hand, it has been studied to form a transparent conductive film using a material other than ITO. For example, the following Patent Document 1 discloses a method of forming a transparent cured coating having conductivity by applying a radiation curable conductive composition containing an organic conductive polymer such as polythiophene, polyaniline, . Patent Document 2 discloses a method in which a resist material such as a diazosulfonium-based material is coated on a support, a thiophene organic conductive material is further coated thereon, and a conductive pattern is formed by exposure and development .

Patent Document 1: JP-A-2005-170996 Patent Document 2: Japanese Patent Publication No. 2004-504693

Although the ITO film and the tin oxide film are generally formed by the sputtering method, the properties of the film are likely to change depending on the sputtering method, the sputtering power, the gas pressure, the substrate temperature, and the kind of atmosphere gas. The difference in the film quality of the transparent conductive film due to the fluctuation of the spatter condition is caused by the unevenness of the etching rate when the film is wet-etched and the patterning of the transparent conductive film is defective and the product yield tends to be lowered. For this reason, the method using ITO or the like is long in sputtering and resist formation, etching and processing, and is also a great burden on cost. In addition, in this method, it is difficult to obtain the uniformity of the patterning degree.

On the other hand, the formation of the conductive pattern by the organic conductive material has the following problems. Patent Document 1 does not disclose the formation of a conductive pattern. It is considered that patterning is performed by etching using a mask, but since there is no suitable etching solution, it is necessary to perform processing using plasma etching or a laser.

Patent Document 2 discloses a method of applying a liquid obtained by mixing a photosensitive material of an organic conductive material and a diazo compound to a support and patterning the same, or a method of arranging a photosensitive material between a support, a layer formed of an organic conductive material and a photosensitive material A method has been proposed. However, in these methods, the adhesion between the conductive pattern and the substrate when the conductive pattern is intended to be provided on a desired substrate is not considered, and the surface treatment of the substrate is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art described above, and it is an object of the present invention to provide a method for manufacturing a semiconductor device, which is capable of easily forming a conductive pattern including an organic conductive material, And 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 attached to the substrate so that the photosensitive resin layer is in close contact with the photosensitive conductive film, and the exposed conductive film is exposed and developed. A desired conductive pattern having sufficient transparency can be easily formed.

Further, according to the photosensitive conductive film of the present invention, a conductive film having satisfactory transparency and good adhesiveness to a substrate can be formed by attaching the photosensitive conductive film to a substrate so that the photosensitive resin layer is in close contact with the substrate, have.

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

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

It is preferable that the photosensitive conductive film of the present invention further has a protective film laminated on the side opposite to the conductive layer side of the photosensitive resin layer in terms of prevention of adherence or damage during the period from preparation to use. This protective film can be removed when using the photosensitive conductive film.

The present invention is also characterized in that the above photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a base material, at least a photosensitive resin layer and a conductive layer are laminated on the base material in this order and the photosensitive resin layer thus laminated is exposed Thereby forming a conductive film.

According to the method of forming a conductive film of the present invention, a photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a base material, and a photosensitive resin layer and a conductive layer are provided in this order on the base material. , A conductive film made of the conductive layer can be easily formed on a substrate. The conductive film is sufficiently adhered to the substrate by curing the photosensitive resin layer by exposure.

The present invention is also characterized in that the photosensitive resin layer of the photosensitive conductive film of the present invention is attached to a base material, at least a photosensitive resin layer and a conductive layer are laminated on the base material in this order, and the laminated photosensitive resin layer is exposed and developed And a conductive pattern formed on the conductive pattern.

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 applied to a substrate to form a photosensitive resin layer and a conductive layer on the substrate in this order, A conductive pattern in which the conductive layer is patterned on a substrate can be easily formed by a simple process. This conductive pattern is sufficiently adhered to the substrate by curing the photosensitive resin layer by exposure.

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

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

Carrying out the invention  Form for

Hereinafter, a preferred embodiment of the present invention will be described in detail. In the present specification, "(meth) acrylate" means "acrylate" or "methacrylate" corresponding thereto. Similarly, the term "(meth) acrylic" means "acrylic" or "methacrylic" corresponding thereto, and "(meth) acryloyl" means "acryloyl" or "methacryloyl" it means.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a suitable embodiment of the photosensitive conductive film of the present invention. Fig. The photosensitive conductive film 10 shown in Fig. 1 is obtained by laminating a film-like support 1, a conductive layer 2 containing an organic conductive material, a photosensitive resin layer 3 and a protective film 4 in this order .

Hereinafter, the film-like support constituting the photosensitive conductive film 10 according to the present embodiment (hereinafter also referred to as "film support" in some cases), the conductive layer, the photosensitive resin layer and the protective film are described in detail do.

The film support 1 is preferably a transparent support film. The term "transparent" as used herein means that the substrate has transparency to the exposure light in the exposure step after transfer, and in the present embodiment, it is preferable that it has transparency in the ultraviolet (300 to 400 nm) region.

Examples of the transparent support film include a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, and a polycarbonate film. Of these, it is preferable to use a polyethylene terephthalate film from the viewpoints of transparency and heat resistance. Further, these polymer films are not subjected to surface treatment or made of a material which can not be removed because the polymer film is removed later when developing the photosensitive resin layer 3 or exposing the conductive film formed.

The thickness of the support film is preferably 5 to 300 占 퐉, more preferably 20 to 300 占 퐉. When the thickness of the support film is less than 5 占 퐉, the mechanical strength is lowered. When the support film is peeled off when the conductive layer is formed or when the photosensitive resin layer is formed or before development of the photosensitive resin layer, On the other hand, when the thickness exceeds 300 mu m, the resolution tends to decrease and the cost tends to become higher when the photosensitive resin layer is irradiated with the active rays through the support film.

Examples of the organic conductive material contained in the conductive layer 2 include polymers of thiophene or thiophene derivatives, and polymers of aniline or aniline derivatives. Specifically, polyethylene dioxythiophene, polyhexylthiophene, polyaniline and the like can be used. Commercially available products such as " CLEVIOS P " (trade name, manufactured by H-C. Starck) and Cefurozida OC-U1 (manufactured by Shin-Etsu Polymer Co., Ltd.) can be used.

It is preferable that the organic conductive material contained in the conductive layer 2 is a material capable of forming a pattern by light irradiation. The organic conductive material may be contained in the conductive layer 2 in combination with a material capable of forming a pattern by light irradiation as long as the effect of the present invention can be obtained.

Examples of the polymer of thiophene or thiophene derivative include polymers having repeating units represented by the following formula (1).

However,

In 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, an alkoxy group having 1 to 20 carbon atoms, Or a substituted or unsubstituted aryloxy group having 6 to 40 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 2 to 40 ring carbon atoms and the neighboring substituents are bonded to each other to form a ring do. Each of the terminal groups of the polymer may be a hydrogen atom or a substituted or unsubstituted monovalent group.

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

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, N-heptyl group, n-heptyl group, n-heptyl group, n-heptyl group, n-octyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, Methylpentyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 3,5-tetramethylcyclohexyl group, and the like. Of these, preferable are a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t- n-pentyl group, n-hexadecyl group, n-hexadecyl group, n-hexadecyl group, n-hexadecyl group, pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, and 3-methylpentyl group. , And 5-tetramethylcyclohexyl group.

The haloalkyl group having 1 to 20 carbon atoms includes, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group. Of these, fluoromethyl, difluoromethyl and trifluoromethyl groups are preferred.

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

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

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

Examples of the substituted or unsubstituted heterocyclic group having 2 to 40 carbon atoms include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl, 2-pyridinyl, An indolizinyl group, a 5-indolyl group, a 6-indolyl group, a 7-indolyl group, a 8-indolyl group, a 2-indolyl group, Imidazopyridinyl, 3-imidazopyridinyl, 5-imidazopyridinyl, 6-imidazopyridinyl, 7-imidazopyridinyl, 8-imidazopyridinyl, Indolyl group, 3-pyridinyl group, 4-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2- Isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, An isobenzofuranyl group, a 5-isobenzofuranyl group, a 6-isobenzofuranyl group, a 6-isobenzofuranyl group, a 4-isobenzofuranyl group, Quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-quinolyl group, 3-quinolyl group, 4-quinolyl group, An isoquinolyl group, a 5-isoquinolyl group, a 6-isoquinolyl group, a 7-isoquinolyl group, an 8-isoquinolyl group, Quinoxalinyl group, a 1-carbazolyl group, a 2-carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group, a 9-carbazolyl group, Carbolin-5-yl, beta -carboline-6-yl, beta -carboline-7-yl ,? -carboline-8-yl,? -carboline-9-yl, 1-phenanthridinyl, 2-phenanthridinyl, A tridinyl group, a 7-phenanthridinyl group, a 8-phenanthryl group Acryidinyl group, a 4-acridinyl group, a 9-acridinyl group, a 1,7-naphthyridinyl group, a 1-adamantyl group, A phenanthroline-2-yl group, a 1,7-phenanthroline-3-yl group, a 1,7-phenanthroline-4-yl group, 6-yl group, a 1,7-phenanthroline-8-yl group, a 1,7-phenanthroline-9-yl group, a 1,7-phenanthroline- A 1,8-phenanthroline-4-yl group, a 1,8-phenanthroline-5-yl group, a 1,8-phenanthroline- Dienes, 1,8-phenanthroline-7-yl groups, 1,8-phenanthroline-9-yl groups, 1,8-phenanthroline- A 1,9-phenanthroline-6-yl group, a 1,9-phenanthroline-4-yl group, A 1,9-phenanthroline-10-yl group, a 1,10-phenanthroline-2-yl group, a 1,10-phenanthroline- Phenanthroline-3-yl group, 1,10-phenanthroline-4-yl group, 1,10-phenan Yl group, a 2,9-phenanthroline-4-yl group, a 2,9-phenanthroline-1-yl group, 6-yl group, 2,9-phenanthroline-7-yl group, 2,9-phenanthroline-8-yl group, 2,9-phenanthroline- A 2,8-phenanthroline-1-yl group, a 2,8-phenanthroline-3-yl group, a 2,8-phenanthroline- A 2,8-phenanthroline-10-yl group, a 2, 8-phenanthroline-6-yl group, A 2,7-phenanthroline-4-yl group, a 2,7-phenanthroline-5-yl group, a 2,7-phenanthroline- 6-yl group, 2,7-phenanthroline-8-yl group, 2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group, 1-phenanediyl group, 2 Phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, Oxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10- Oxazyl group, 2-oxazoyl group, 5-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-1-yl group, Methylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2- Indolyl group, 4-methyl-1-indolyl group, 4-methyl-1- 4-t-butyl-3-indolyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-t- A dibenzothiophenyl group, a 3-dibenzothiophenyl group, a 4-dibenzothiophenyl group, a 1-silafluorenyl group, a 2-silafluorenyl group, a 3- A silafluorenyl group, a 4-silafluorenyl group, a 1-germafluorenyl group, 2-germafluorenyl group, 3-germafluorenyl group, and 4-germafluorenyl group.

Of these, preferred are a 2-pyridinyl group, a 1-indolyldiyl group, a 2-indolyldiyl group, a 3-indolyldiyl group, a 5-indolyldiyl group, a 6-indolyldiyl group, Imidazopyridinyl, 2-imidazopyridinyl, 3-imidazopyridinyl, 5-imidazopyridinyl, 6-imidazopyridinyl, 7-imidazopyridinyl, Indolyl group, 1-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-indolyl group, Isoindolyl group, 3-isoindolinyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, Carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3- Benzopyranyl group, 4-dibenzofuranyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 4- There may be mentioned 1 to 3 substituents selected from the group consisting of a benzothiophenyl group, a 1-silafluorenyl group, a 2-silafluorenyl group, a 3-silafluorenyl group, a 4-silafluorenyl group, a 1-germafluorenyl group, a 2-germafluorenyl group, An o-aryl group, and a 4-germafluorenyl group.

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

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

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

The polythiophene or polythiophene derivative represented by the formula (1) may be a commercially available product or a product synthesized by a known method. The molecular weight of the polythiophene or polythiophene derivative is generally in the range of 1,000 to 100,000 as the number average molecular weight. When the molecular weight is smaller than this range, sufficient conductivity based on the? -Electro-conjugated system is not exhibited. On the other hand, if the molecular weight is excessively large, it becomes difficult to form a thin film. The repeating unit forms a polymer by bonding with adjacent repeating units in the form of head tail, head-head, or tail-tail. When the alkyl or alkoxy group substituted at the 3-position of the thiophene ring is too long, there is a possibility that the conformation of the three-dimensional structure of the molecule may be confused and the mobility may be impaired, so that the number of carbon atoms is preferably 20 or less.

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

The thickness of the conductive layer 2 is preferably 1 占 퐉 or less, more preferably 0.01 占 퐉 to 0.5 占 퐉, though it depends on the use of the conductive film or the conductive pattern formed using the photosensitive conductive film of the present invention or the conductivity to be obtained More preferably 0.01 탆 to 0.3 탆. When the thickness of the conductive layer 2 is 1 占 퐉 or less, light transmittance can be easily ensured.

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

Examples of the binder polymer include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. From the viewpoint of excellent alkali developability, it is preferable to use an acrylic resin. These may be used singly or in combination of two or more.

The above-mentioned binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted in an? -Position or aromatic ring such as styrene, vinyltoluene and? -Methylstyrene, acrylamides such as diacetone acrylamide, acrylonitrile, (Meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, diethylaminoethyl ester of (meth) acrylic acid, (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (Meth) acrylic acid, maleic acid, maleic anhydride, maleic acid monomethyl, maleic acid monoethyl, maleic acid, maleic acid, San Monoiso Maleic acid monoester, fumaric acid, cinnamic acid, α- cyano-cinnamic acid, itaconic acid, crotonic acid and propionic olsan such as ropil.

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

[Figure 2]

In the 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, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Isomers.

Examples of the compound represented by the general formula (2) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylate, octyl (meth) acrylate, octyl (meth) acrylate, heptyl (meth) acrylate, heptyl Acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester. These may be used singly or in combination of two or more.

Further, the binder polymer used in the present invention preferably has a carboxyl group from the viewpoint of improving the alkali developing property. Such a binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid as described above is preferable.

The proportion of the carboxyl group possessed by the binder polymer is preferably from 12 to 50% by weight from the viewpoint of balance of the alkali developability and the alkali resistance, as the ratio of the polymerizable monomer having a carboxyl group to the entire polymerizable monomer to be used, More preferably 12 to 40% by weight, particularly preferably 15 to 30% by weight, particularly preferably 15 to 25% by weight. When the proportion of the polymerizable monomer having a carboxyl group is less than 12% by weight, the alkali developability tends to be poor, while when it exceeds 50% by weight, the alkali resistance tends to be poor.

The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, and more preferably 40,000 to 150,000 from the viewpoint of balance between mechanical strength and alkali developability. When the weight average molecular weight is less than 20,000, the resistance to developing is liable to decrease. When the weight average molecular weight is more than 300,000, the developing time tends to be prolonged. The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene.

These binder polymers may be used singly or in combination of two or more. As the binder polymer when two or more kinds are used in combination, for example, two or more kinds of binder polymers composed of other copolymerization components, two or more kinds of binder polymers having different weight average molecular weights and two or more kinds of binder polymers having different degrees of dispersion .

Next, a photopolymerizable compound having an ethylenic unsaturated bond will be described. Examples of the photopolymerizable compound having an ethylenically unsaturated bond include a compound obtained by reacting a polyhydric alcohol with an?,? - unsaturated carboxylic acid, a compound obtained by reacting a 2,2-bis (4 - ((meth) acryloxypolyethoxy) Bis (4 - ((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, 2,2-bis A urethane monomer such as a urethane monomer-containing (meth) acrylate compound having a urethane bond, a urea monomer such as 慣 -chloro (meth) acrylate, (meth) acryloyloxyethyl-o-phthalate,? -hydroxyethyl-? '- (meth) acryloyloxyethyl-o-phthalate,? -hydroxypropyl -β '- (meth) acryloyloxyethyl-o-phthalate, alkyl (meth) acrylate, and the like The. These may be used alone or in combination of two or more.

Examples of the compound obtained by reacting the polyhydric alcohol with an alpha, beta -unsaturated carboxylic acid include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol having 2 to 14 propylene groups Di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane Acrylate, trimethylol propane triethoxy tri (meth) acrylate, trimethylol propane triethoxy tri (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane triethoxy tri (meth) Trimethylol propane (meth) acrylate such as propane tetraethoxy tri (meth) acrylate and trimethylol propane pentaethoxy tri (meth) acrylate, tetramethylol methane (Meth) acrylate such as tetramethylolmethane (meth) acrylate and tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy (Meth) acrylate such as pentaerythritol (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate and dipentaerythritol alkoxypenta (Meth) acrylate.

Of these, from the viewpoint of transparency and adhesiveness, it is preferable to use a copolymer of trimethylol propane (meth) acrylate, tetramethylol methane (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol It is preferable to include at least one species selected.

Examples of the urethane monomer include a (meth) acrylic monomer having a hydroxyl group at the? -Position and an isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene (Meth) acryloxy tetraethylene glycol isocyanate] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and diisocyanate compounds such as diisocyanate and tris Acrylate, and the like. Further, " EO " represents ethylene oxide, and the EO-modified compound has a block structure of ethylene oxide group. Further, "PO" represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide group. As the EO-modified urethane di (meth) acrylate, for example, "UA-11" (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned. As the EO, PO-modified urethane di (meth) acrylate, for example, "UA-13" (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.

The content of the photopolymerizable compound is preferably 30 to 80 parts by weight, more preferably 40 to 70 parts by weight, based on 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. If the content is less than 30 parts by weight, the photocuring tends to be insufficient, and the cured property of the transferred conductive film tends to become insufficient. When the content exceeds 80 parts by weight, storage tends to be difficult when the film is wound as a film.

Next, the photopolymerization initiator will be described. Examples of the photopolymerization initiator include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzo Phenanone, 4-methoxy-4'-dimethylaminobenzophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methylthio) phenyl] -2-morpholino-propanone-1, aromatic ketones such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butyl anthraquinone, octamethylanthraquinone, Quinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methyl anthraquinone, 1,4-naphthoquinone, Quinones such as tetraquinone, 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 compounds such as methyl benzoin and ethyl benzoin, 1,2-octanedione, 1- [4- (phenyl ) -, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- ), Benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) Triarylimidazole dimer such as a dimer dimer and a 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 the two 2,4,5-triarylimidazole are the same and may be given as the compound of interest, and asymmetric compounds may be given. In addition, a thioxanthone compound and a tertiary amine compound may be used in combination, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. Among them, from the viewpoint of transparency, aromatic ketone compounds such as 1-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Phenylthio) -, and 2- (o-benzoyloxime)] are more preferable. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight based on 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. When the content is less than 0.1 parts by weight, the photosensitivity tends to be insufficient. When the content is more than 30 parts by weight, absorption on the surface of the composition increases upon exposure, and the inside of the photopolymerization tends to become insufficient.

To the photosensitive resin layer 3, a plasticizer, filler, defoamer, flame retardant, stabilizer, adhesion imparting agent, leveling agent, peeling promoter, antioxidant, fragrance, emulsion, thermal crosslinking agent May be used alone or in combination of two or more. The amount of these additives to be added is preferably 0.01 to 20 parts by weight per 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound.

The photosensitive resin layer 3 is formed on the transparent film support 1 on which the conductive layer 2 is formed by using methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, , N, N-dimethylformamide, and propylene glycol monomethyl ether, or a mixed solvent thereof, preferably in the range of 10 to 60% by weight of the solid content of the photosensitive resin composition. In this case, the amount of the residual organic solvent in the photosensitive resin layer after drying is preferably 2% by weight or less in order to prevent the diffusion of the organic solvent in the subsequent step.

The application of the photosensitive resin composition can be carried out by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, spray coating and the like. The drying can be carried out at 70 to 150 DEG C for about 5 to 30 minutes.

The thickness of the photosensitive resin layer 3 varies depending on the application, but is preferably 1 to 50 占 퐉, more preferably 1 to 20 占 퐉, and particularly preferably 1 to 10 占 퐉 in thickness after drying. When the thickness is less than 1 mu m, the coating tends to become difficult industrially. When the thickness exceeds 50 mu m, the sensitivity due to the decrease in light transmission tends to be insufficient and the photocurability of the photosensitive resin layer tends to decrease. From the viewpoint of excellent adhesion and patterning, the thickness of the photosensitive resin layer 3 is preferably 1 占 퐉 or more.

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

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

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

The protective film is preferably a film of low fish eye. Specifically, it is preferable that the number of fish eyes having a diameter of 80 mu m or more contained in the protective film is 5 pieces / m < 2 > In addition, the "fish eye" is a film in which a foreign matter, an undissolved product, and an oxidized heat storage material are received in the film when the film is produced by heat melting the material, and kneading, extruding, biaxially stretching or casting.

The thickness of the protective film is preferably 1 to 100 占 퐉, more preferably 5 to 50 占 퐉, still more preferably 5 to 30 占 퐉, and particularly preferably 15 to 30 占 퐉. If the thickness of the protective film is less than 1 탆, the protective film tends to be torn when laminated. If the thickness exceeds 100 탆, the protective film tends to be expensive.

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 wound, for example, in the form of a flat plate as it is, or around a core such as a cylindrical shape, and stored in the form of a roll. At this time, it is preferable that the film support is rolled so as to be the outermost side.

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.

The core is not particularly limited as long as it is conventionally used. For example, plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, an ABS resin (acrylonitrile-butadiene-styrene copolymer) . In addition, it is preferable that a cross-section separator is provided on the end face of the photosensitive conductive film wound in the form of a roll in view of protection of the cross section, and furthermore, a moisture-proof cross- When the photosensitive conductive film is wrapped, it is preferable to wrap the photosensitive conductive film wrapped in a black sheet having low moisture permeability.

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

According to the photosensitive conductive film of the present embodiment, a photosensitive resin layer and a conductive layer are transferred onto a substrate on which a conductive pattern is required, and exposure and development are carried out to easily form a conductive film having a transparent and good pattern can do.

In addition, the conductive film or conductive pattern formed from the photosensitive conductive film of this embodiment is suitable as an electrode of a flexible display or the like because of its flexibility. Furthermore, since the conductive film or conductive pattern to be formed can be composed of an organic material, when the conductive film or the conductive pattern is used as an electrode of an electronic device to which a bias voltage is applied, migration can be sufficiently suppressed.

As one embodiment of the method for forming a conductive film of the present invention, there is a laminate process in which the photosensitive conductive film of the present embodiment is laminated so that the photosensitive resin layer is in contact with the base material, and a laminate process in which the photosensitive resin layer on the substrate is irradiated with an actinic ray And a method comprising an exposure process. When the photosensitive conductive film has a protective film, the photosensitive conductive film from which the protective film is peeled is laminated from the side of the photosensitive resin layer on the substrate. The photosensitive resin layer, the conductive layer, and the support are laminated in this order on the substrate by the lamination process.

Examples of the substrate include a glass substrate, a plastic substrate such as polycarbonate, and the like.

The lamination step is performed, for example, by laminating a photosensitive conductive film by removing the protective film, if there is a protective film, and pressing the photosensitive resin layer side against the substrate while heating. In addition, this work is preferably laminated under reduced pressure in view of adhesion and followability. It is preferable to heat the photosensitive resin layer and / or the substrate to 70 to 130 占 폚 for the lamination of the photosensitive conductive film, and the pressing pressure is preferably about 0.1 to 1.OMPa (about 1 to 10 kgf / c m2) , These conditions are not particularly limited. When the photosensitive resin layer is heated to 70 to 130 DEG C as described above, it is not necessary to preheat the substrate in advance, but the substrate may be preheated to further improve the lamination property.

In the exposure step, the photosensitive resin layer of the portion irradiated with the actinic light is cured, and the conductive layer is fixed by the cured product to form a conductive film on the substrate. As the light source of the active light ray, a known light source such as a carbon arc, a mercury vapor arc, or the like, which effectively emits ultraviolet rays or visible light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp is used. It is also possible to effectively radiate ultraviolet rays or visible light such as Ar ion lasers and semiconductor lasers. In addition, it is also effective to radiate visible light such as a photographic plate lamp or a solar lamp.

When the film support on the conductive layer is transparent to the actinic ray, the actinic ray can be irradiated through the film support. When the support is shielded, the actinic ray is irradiated to the photosensitive resin layer after removing the film support.

When the base material is transparent to the active ray, it is preferable to irradiate the active layer with the conductive layer and the photosensitive resin layer from the side of the conductive layer in terms of resolution, although the active ray can be irradiated from the base side through the base.

By passing through the above-described process, a substrate with a conductive film having a conductive film on a substrate is obtained. In the method for forming a conductive film of the present embodiment, the formed conductive film may be further cured by heating at about 60 to 250 ° C or by exposure at about 0.2 to 10 J / cm 2, if necessary, after peeling off the film support . Both of heating and exposure may be performed to further cure.

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

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

The method of forming a conductive pattern according to the present embodiment includes the steps of laminating the above-described photosensitive conductive film 10 so that the photosensitive resin layer 3 is in close contact with the substrate 20 (Fig. 2 (a)) and An exposure step (FIG. 2 (b)) of irradiating a predetermined portion of the photosensitive resin layer 3 on the substrate 20 with an actinic ray and a step of developing the exposed photosensitive resin layer 3 to form a conductive pattern And a development step of Through these steps, a conductive film-attached substrate 40 having a patterned conductive film (conductive pattern) 2a on the substrate 20 is obtained (FIG. 2 (c)).

The lamination process is performed, for example, by a lamination method in which the photosensitive conductive film 10 is pressed on the substrate while removing the protective film, if there is a protective film, while heating the side. In addition, this work is preferably laminated under reduced pressure in view of adhesion and followability. It is preferable to heat the photosensitive resin layer 3 and / or the substrate 20 to 70 to 130 占 폚 and the pressing pressure to be about 0.1 to 1.OMPa (1 to 10 kgf / c m2), but the conditions are not particularly limited. When the photosensitive resin layer 3 is heated to 70 to 130 캜 as described above, it is not necessary to preheat the substrate in advance, but the substrate may be preheated to further improve the lamination property.

Examples of the exposure method in the exposure step include a method (mask exposure method) of irradiating an actinic ray on a picture image through a negative or positive mask pattern called an artwork. As the light source of the active light ray, a known light source such as a carbon arc, a mercury vapor arc, or the like, which effectively emits ultraviolet rays or visible light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp is used. It is also possible to effectively radiate ultraviolet rays or visible light such as Ar ion lasers and semiconductor lasers. In addition, it is also effective to radiate visible light such as a photographic plate lamp or a solar lamp. Further, a method of irradiating an active ray on an image plane by a direct drawing method using a laser exposure method or the like may be employed.

When the film support 1 on the conductive layer 2 is transparent to the active ray, it is possible to irradiate the active ray through the film support 1, and when the film support 1 is shielded from light, The photosensitive resin layer 3 is irradiated with an actinic ray.

When the substrate (adherend) 20 is transparent to the active ray, it is possible to irradiate the active ray through the substrate 20 from the substrate 20 side, but in view of the resolution, It is preferable to irradiate the conductive layer 2 and the photosensitive resin layer 3 with an actinic ray.

In the developing step of this embodiment, portions other than the exposed portion of the photosensitive resin layer 3 are removed. Specifically, when the film support 1 is present on the conductive layer 2, the film support 1 is first removed, and thereafter, the wet film is removed from the exposed portion of the photosensitive resin layer 3 . As a result, the conductive layer 2a containing the organic conductive material remains on the resin cured layer 3a having a predetermined pattern, and a conductive pattern is formed.

The wet phenomenon is performed by a known method such as spraying, swinging dipping, brushing, scraping, or the like using a developer corresponding to a photosensitive resin such as an alkaline aqueous solution, an aqueous developer, or an organic solvent developer.

As the developer, an alkaline aqueous solution or the like, which is safe, stable, and has good operability, is used. Examples of the base of the alkaline aqueous solution include alkaline hydroxides such as hydroxides of lithium, sodium or potassium, alkali metal carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium, alkali metal phosphates such as potassium phosphate, sodium phosphate, Alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate and the like are used.

The alkaline aqueous solution used for development is preferably an aqueous solution of 0.1 to 5 wt% of sodium carbonate, an aqueous solution of 0.1 to 5 wt% of potassium carbonate, an aqueous solution of sodium hydroxide of 0.1 to 5 wt%, and an aqueous solution of sodium tetraborate of 0.1 to 5 wt%. The pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature is adjusted in accordance with developability of the photosensitive resin layer. In the alkaline aqueous solution, a surface active agent, a defoaming agent, and a small amount of an organic solvent for promoting development may be mixed.

Further, an aqueous developer containing water or an aqueous alkali solution and at least one organic solvent may be used. Here, examples of the base contained in the aqueous alkali solution include, in addition to the above-mentioned base, borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, Methyl-1,3-propanediol, 1,3-diaminopropanol-2, and morpholine.

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

In the aqueous developing solution, the concentration of the organic solvent is preferably 2 to 90% by weight, and the temperature can be adjusted according to developability. Further, the pH of the aqueous developer is preferably as small as possible within a range where the development of the resist is sufficiently possible, and the pH is preferably 8 to 12, more preferably 9 to 10. Further, a small amount of a surfactant, defoaming agent or the like may be added to the aqueous developing solution.

Examples of the organic solvent-based developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methylisobutylketone, . In order to prevent the occurrence of flammability, water is preferably added to the organic solvent in an amount of 1 to 20% by weight.

The developer may be used in combination of two or more thereof, if necessary.

Examples of the developing method include a dip method, a battle method, a spray method, blushing, and slapping. Of these, it is preferable to use a high-pressure spraying method from the viewpoint of resolution improvement.

In the present embodiment, by removing the unexposed portion by developing the photosensitive resin layer 3 after exposure in a predetermined pattern, the conductive layer on the photosensitive resin layer of the unexposed portion is removed together, and the photosensitive portion of the exposed portion The conductive layer on the resin layer remains, and a conductive pattern is formed. At the time of development, the developer is permeated into the conductive layer 2 to swell the photosensitive resin layer of unexposed light, or the developer is allowed to swell from the end of the photosensitive resin layer to swell the photosensitive resin layer, Thereby forming a pattern. When the thickness of the conductive layer 2 is as thin as 0.5 占 퐉, the developer easily reaches the photosensitive resin layer 3 via the conductive layer 2, and the developing property is improved.

In the method for forming a conductive pattern according to the present embodiment, after the development, the conductive pattern may be further cured by heating at about 60 to 250 DEG C or by about 0.2 to 10 J / cm2. Both of heating and exposure may be performed and further cured.

As described above, according to the conductive pattern forming method 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.

The substrate with a conductive film according to the present invention can be obtained by the method for forming a conductive film or the method for forming a conductive pattern as described above. However, from the viewpoint that the conductive film or the conductive pattern can be effectively utilized as a transparent electrode, / &Amp; squ &, more preferably 5000 OMEGA / or less, and particularly preferably 2000 OMEGA / or less. The surface resistivity can be adjusted, for example, by the concentration or the coating amount of the dispersion containing the organic conductive material. The surface resistivity tends to decrease as the concentration of the dispersion increases, and as the thickness increases as the coating amount increases. It can also be adjusted by doping.

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

According to the present invention, there is provided a photosensitive conductive film which is capable of easily forming a conductive pattern having sufficient adhesiveness to a substrate and containing an organic conductive material on a substrate with sufficient resolution, and a method of forming a conductive film using the same And a method of forming a conductive pattern.

1 is a schematic sectional view showing one embodiment of the photosensitive conductive film of the present invention.
2 is a schematic cross-sectional view for explaining an embodiment of a method of forming a conductive pattern according to the present invention.

Example

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

≪ Preparation of coating liquid for forming conductive layer &

(Conductive layer forming liquid (1) (organic conductive material solution))

&Quot; Sephulizide OC-U1 " (photo patterning paint, trade name, manufactured by Shin-Etsu Polymer Co., Ltd.) as an alcohol solution of polyethylene dioxythiophene was diluted with methanol 10 times and used as a conductive layer-forming liquid (1).

(Conductive layer forming liquid 2 (organic conductive material solution))

(Trade name, product of HC Starck Co., Ltd.) as an aqueous solution of polyethylene dioxythiophene was diluted 5-fold with water to prepare a conductive layer-forming coating solution 2.

≪ Preparation of solution of photosensitive resin composition >

[Synthesis of acrylic resin]

(Methylcellosolve / toluene = 3/2 (weight ratio), hereinafter referred to as "solution s") was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube, ) Were added, and the mixture was stirred while blowing nitrogen gas, and heated to 80 占 폚. On the other hand, a solution prepared by mixing 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 as a monomer (hereinafter referred to as "solution a") was prepared. Then, the solution a heated to 80 캜 was dropped for 4 hours, and then kept at 80 캜 for 2 hours while being stirred. Further, a solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of the solution s was dropped into the flask over 10 minutes. Then, after the dropwise addition, the solution was kept at 80 DEG C for 3 hours while stirring, and then heated at 90 DEG C for 30 minutes. The mixture was kept at 90 DEG C for 2 hours and then cooled to obtain a binder polymer solution. Acetone was added to this binder polymer solution so that the non-volatile component (solid content) became 50% by weight to obtain a binder polymer solution. The weight average molecular weight of the obtained binder polymer was 80,000. This was designated as Acrylic Polymer A.

The materials shown in Table 1 were compounded in the amount (unit: parts by weight) shown in the table to prepare a solution of the photosensitive resin composition.

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

≪ Preparation of photosensitive conductive film >

(Example 1)

The conductive layer forming coating liquid 1 was uniformly applied to a polyethylene terephthalate film (PET film, trade name: "G2-50" manufactured by Teijin Co., Ltd.) having a thickness of 50 μm as a support film (film support) at 25 g / And dried in a hot air convection type drier at 100 ° C for 3 minutes to form a conductive layer. The thickness of the conductive layer after drying was about 0.1 mu m.

Next, the solution of the photosensitive resin composition was uniformly coated on the side of the support film on which the conductive layer was provided, and dried by a hot air convection type drier at 100 캜 for 10 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer after drying was 5 占 퐉. Further, the photosensitive resin layer was covered with a protective film made of polyethylene (manufactured by Tama Poly Co., Ltd., trade name " NF-13 ") to obtain a photosensitive conductive film.

(Example 2)

The coating solution 2 for forming a conductive layer was uniformly coated on a polyethylene terephthalate film (PET film, trade name " G2-50 ", manufactured by Teijin Co., Ltd.) having a thickness of 50 mu m as a supporting film at 25 g / m & Followed by drying with a convection type drier for 3 hours to form a conductive layer. The film thickness of the conductive layer after drying was about 0.1 mu m.

Next, the solution of the photosensitive resin composition was uniformly coated on the side of the support film on which the conductive layer was provided, and dried by a hot air convection type drier at 100 캜 for 10 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer after drying was 5 占 퐉. Further, the photosensitive resin layer was covered with a protective film made of polyethylene (manufactured by Tama Poly Co., Ltd., trade name " NF-13 ") to obtain a photosensitive conductive film.

≪ Formation of conductive film &

A 0.7 mm thick soda glass plate was heated to 80 deg. C, and the photosensitive conductive film obtained in Examples 1 and 2 was placed on the surface of the glass substrate so that the photosensitive resin layer was opposed to the substrate while peeling the protective film. Laminated in. After the laminating, the substrate was cooled and exposed to light having an exposure amount of 1000 mJ / cm < 2 > using an exposure machine (trade name "HMW-201B" available from Oak Production Co., Ltd.) having a high pressure mercury lamp on the surface of the PET film at a temperature of 23 [ To expose the conductive layer and the photosensitive resin layer. After exposure, the film was allowed to stand at room temperature (25 DEG C) for 15 minutes, and then the PET film as a support was peeled off to form the conductive film produced in the examples on a soda glass plate. The surface resistances of the films formed using the films of Examples 1 and 2 were 2,000? / ?, 2800? / ?, respectively, and the transmittances to light of 650 nm were 90% and 85%, respectively. The results are shown in Table 1.

The surface resistivity is a surface resistivity measured by a 4-probe method in accordance with JIS K 7194 using a low resistivity meter (manufactured by Mitsubishi Chemical Corporation, Loresta GP). The transmittance is the minimum light transmittance in a wavelength range of 450 to 650 nm as measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, trade name " U-3310 "). The results are shown in Table 1.

<Formation of Conductive Pattern>

A 1 mm thick polycarbonate substrate was heated to 80 deg. C and the photosensitive conductive film obtained in Examples 1 and 2 was placed on the surface of the polycarbonate substrate so that the photosensitive resin layer was opposed to the substrate while the protective film was being peeled off. Laminated under the conditions. After the laminating, the substrate was cooled and a photomask having a wiring pattern with a line width / space width of 100/100 mu m and a length of 100 mm was formed on the surface of the support PET film at a temperature of 23 DEG C Respectively. Then, the conductive layer and the photosensitive resin layer were exposed with an exposure amount of 200 mJ / cm 2 using an exposure machine (trade name: "HMW-201B", manufactured by Oak Production Co., Ltd.) having a high pressure mercury lamp.

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

One… Film support, 2 ... Conductive layer, 2a ... Conductive pattern, 3 ... Photosensitive resin layer, 3a ... Cured layer, 4 ... Protective film, 10 ... Photosensitive conductive film, 20 ... Substrate, 30 ... Artwork, 40 ... A substrate with a conductive film,

Claims (6)

A support, a conductive layer containing an organic conductive material, and a photosensitive resin layer laminated in this order,
Wherein the organic conductive material is a thiophene derivative polymer having a number average molecular weight of 1000 to 100000,
The thickness of the conductive layer is 0.01 to 0.5 mu m,
For wet developing with an alkaline aqueous solution,
A transfer-type photosensitive conductive film for forming a transparent conductive pattern. The method according to claim 1,
Wherein 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. 3. The method of claim 2,
Wherein the binder polymer has a carboxyl group. 3. The method of claim 2,
Wherein the photopolymerizable compound having an ethylenically unsaturated bond is at least one selected from the group consisting of trimethylol propane (meth) acrylate, tetramethylol methane (meth) acrylate, pentaerythritol (meth) acrylate, and dipentaerythritol (meth) And at least one selected from the group consisting of the photosensitive resin composition and the photosensitive resin composition. 3. The method of claim 2,
Wherein the photopolymerization initiator comprises an aromatic ketone compound or an oxime ester compound. 6. The method according to any one of claims 1 to 5,
Wherein a protective film is further laminated on the side opposite to the conductive layer side of the photosensitive resin layer.

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