TW201502704A - Photosensitive conductive film, fabricating method of conductive pattern using the same and conductive pattern substrate - Google Patents

Abstract

A photosensitive conductive film is provided. The photosensitive conductive film includes a supporting film, a conductive thin film disposed on the supporting film and a photosensitive resin layer disposed on the conductive thin film. The photosensitive resin layer includes (A) a binder polymer, (B) a photopolymerizable compound and (C) a photopolymerization initiator. A hydroxyl value of the solid component in the photosensitive resin layer is no more than 40 mgKOH/g.

Description

a photosensitive conductive film, and a method of forming a conductive pattern using the same And conductive pattern substrate

The present invention relates to a photosensitive conductive film, a method of forming a conductive pattern using the same, and a conductive pattern substrate. In particular, there is a photosensitive conductive film which can be used as a conductive wiring for a flat panel display such as a liquid crystal display device, a touch screen, a solar cell, or an illumination device.

From large electronic devices such as personal computers or televisions to small electronic devices such as car navigation, mobile phones, and electronic dictionaries, and display devices such as office automation-factory automation (OA.FA) devices. Use a liquid crystal display element or a touch screen. Transparent conductive electrode materials are required in these liquid crystal display elements or touch screens. The transparent conductive electrode material exhibits high transmittance, and thus Indium-Tin-Oxide (ITO), indium oxide or tin oxide was previously used.

In the touch panel, various methods have been put into practical use, but in recent years, electrostatic capacitance The use of the touch panel of the way is progressing. In the capacitive touch panel, if the fingertip (conductor) is in contact with the touch input surface, electrostatic coupling is performed between the fingertip and the conductive film to form a capacitor. Therefore, the capacitive touch panel detects its coordinates by capturing a change in the charge of the contact position of the fingertip.

Since the projection type capacitive touch panel can perform multi-point detection of the fingertip, it has good operability for performing complicated instructions, and has good operability as a mobile phone or a portable music player. The use of the input device on the display surface in the device of the small display device is advancing.

Generally, in a projection type capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes are formed in a two-layer structure in order to express two-dimensional coordinates by the X-axis and the Y-axis. A transparent conductive film containing a transparent conductive electrode material is used for the electrodes.

The patterning method of the transparent conductive film is generally as follows: after forming a transparent conductive film, a resist pattern is formed by photolithography, and a predetermined portion of the conductive film is removed by wet etching to form a conductive pattern. In the case where the transparent conductive electrode material is ITO or indium oxide, the etching liquid is a mixed liquid containing two kinds of solutions of hydrochloric acid and ferric chloride.

The ITO film or the tin oxide film is usually formed by a sputtering method, but the properties of the transparent conductive film are likely to vary depending on the sputtering method, the sputtering power or the gas pressure, the substrate temperature, the type of the ambient gas, and the like. The difference in film quality of the transparent conductive film caused by the fluctuation of the sputtering conditions is a cause of unevenness in the etching rate when the transparent conductive film is wet-etched, and it is likely to cause a good product due to poor patterning. The rate drops. Further, since the method of forming the conductive pattern passes through the sputtering step, the resist forming step, and the etching step, the steps are long and the cost is also a large burden.

Recently, in order to eliminate the above problem, attempts have been made to form a transparent conductive pattern using a material instead of ITO, indium oxide, tin oxide or the like. For example, Patent Document 1 listed below proposes a method of forming a conductive pattern using a photosensitive conductive film having a conductive film containing conductive fibers. If this technique is used, the conductive pattern can be easily formed directly on various substrates by the photolithography step.

However, a wiring circuit for transmitting an electrical change generated by the transparent electrode portion to an integrated circuit (IC) is formed in an edge region of the touch panel. Such a wiring circuit may be a vapor-deposited metal wiring circuit formed by using a vapor-deposited metal thin film, or a silver paste printed wiring circuit using a thermosetting type or an evaporative drying type silver paste, by screen printing. The printing is performed by printing a very thin wiring circuit pattern and performing heat treatment; in terms of cost, the latter silver paste printed wiring circuit is more widely used.

That is, the projection type capacitive touch panel is generally a structure in which a transparent electrode and a control IC are physically and electrically connected by a silver paste printed wiring circuit, but if the silver paste printed wiring is broken. A short circuit, or the disconnection of the silver paste and the transparent electrode, or the connection between the silver paste and the control IC, causes the problem that the touch panel is no longer functioning properly.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Patent Publication No. 2010/021224

By using the photosensitive conductive film disclosed in Patent Document 1, the sensor-electrode (conductive pattern) of the touch panel can be easily formed on various substrates by the photolithography step. However, in the case where the sensor-electrode is connected to the control IC by the silver paste printed wiring, the resistance value between the conductive pattern and the silver paste rises under high temperature and high humidity conditions, and there is a problem of disconnection. The increase in the resistance value affects the composition of the silver paste, so that an increase in the resistance value can be prevented by selecting an appropriate silver paste. However, the silver paste is also required to have printability for forming fine wiring, and it is currently the case that the silver paste which can achieve both the printability and the suppression of the resistance value is small.

Therefore, the inventors of the present invention conducted active research to solve the above problems, and as a result, invented the photosensitive conductive film which does not depend on the composition of the silver paste, and is also subjected to high temperature and high humidity conditions. It is difficult to cause a disconnection between the conductive pattern and the silver paste.

In the present invention, there is provided a photosensitive conductive film comprising a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film, and the photosensitive resin layer contains: (A The binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerizable initiator, wherein the photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less.

Further, the present invention provides a photosensitive conductive film in which the (A) component has a hydroxyl value of 60 mgKOH/g or less.

Further, the present invention provides a photosensitive conductive film in which the (B) component has a hydroxyl value of 90 mgKOH/g or less.

Further, the present invention provides a photosensitive conductive film in which the conductive film contains at least one conductive fiber in addition to the photosensitive resin layer.

Further, the present invention provides a photosensitive conductive film in which the conductive fiber is a silver fiber.

In addition, the present invention provides a method of forming a conductive pattern, comprising: a laminating step of laminating the photosensitive conductive film on a substrate in such a manner that the photosensitive resin layer is adhered; and an exposing step to the substrate a predetermined portion of the photosensitive resin layer is irradiated with actinic rays; and a developing step of developing the unexposed portion of the exposed photosensitive resin layer and the conductive film after peeling off the support film A conductive pattern is formed.

In addition, the present invention provides a method of forming a conductive pattern, comprising: a laminating step of laminating the photosensitive conductive film on a substrate in such a manner that the photosensitive resin layer is closely adhered; a predetermined portion of the photosensitive resin layer on the substrate irradiates the actinic ray; and a second exposure step of peeling the support film and then, in the presence of oxygen, a portion of the unexposed portion in the first exposure step Or irradiating all of the actinic rays; and developing a step, after the second exposing step, by using the photosensitive resin The layer and the conductive film are developed to form a conductive pattern.

Further, the present invention provides a method of producing a conductive pattern, comprising: an exposure step of irradiating a photosensitive resin layer provided on a substrate with a predetermined portion of the conductive film with actinic rays, the conductive film being disposed on the photosensitive a surface of the resin layer opposite to the substrate and comprising conductive fibers; and a developing step of forming a conductive pattern by removing the photosensitive resin layer and the unexposed portion of the conductive film; and the photosensitive The resin layer contains (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerizable initiator, and the photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less.

Further, the present invention provides a method of producing a conductive pattern, comprising: an exposure step of irradiating a photosensitive resin layer provided on a substrate with a predetermined portion of the conductive film with actinic rays, the conductive film being disposed on the photosensitive a surface of the resin layer opposite to the substrate and comprising a conductive fiber; and a second exposure step of irradiating a part or all of the unexposed portion in the first exposure step with actinic rays in the presence of oxygen And a developing step of forming a conductive pattern by developing the photosensitive resin layer and the conductive film after the second exposure step; and the photosensitive resin layer comprises (A) a binder polymer, ( B) A photopolymerizable compound and (C) a photopolymerizable initiator, wherein the photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less.

In addition, the present invention can provide a conductive pattern substrate including A conductive pattern obtained by the method of forming the conductive pattern.

Furthermore, the present invention can provide a touch panel sensor including the conductive pattern substrate.

According to the photosensitive conductive film of the present invention, it is possible to form a conductive pattern which does not depend on the composition of the silver paste, and which is difficult to cause a disconnection between the silver paste and the silver paste under high temperature and high humidity conditions.

1‧‧‧Support film

2‧‧‧Electrical film

2a‧‧‧Conductive film (conductive pattern)

3‧‧‧Photosensitive resin layer

3b‧‧‧ resin hardened layer

4‧‧‧Photosensitive layer

5‧‧‧ mask

10‧‧‧Photosensitive conductive film

20‧‧‧Substrate

101‧‧‧Transparent substrate

102‧‧‧ touch screen

103, 104‧‧‧ transparent electrode

105‧‧‧ lead wiring (lead wire)

106‧‧‧Connecting electrode

107‧‧‧Connecting terminal

L‧‧‧ actinic ray

Hb‧‧ ̄ step

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

Fig. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film.

3(a) to 3(c) are schematic cross-sectional views for explaining an embodiment of a method of forming a conductive pattern using a photosensitive conductive film.

4(a) to 4(d) are schematic cross-sectional views for explaining another embodiment of a method of forming a conductive pattern using a photosensitive conductive film.

FIG. 5 is a schematic plan view showing an example of a capacitive touch panel sensor.

6(a) to 6(d) are schematic views for explaining an example of a method of manufacturing the touch panel sensor shown in Fig. 5.

Fig. 7 is a partial cross-sectional view taken along line a-a' shown in Fig. 5.

Fig. 8 is a partial cross-sectional view taken along line bb' of Fig. 5;

Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, In the present specification, the term "(meth)acrylate" means "acrylate" or "methacrylate" corresponding thereto, and "alkyl (meth)acrylate" means "alkyl acrylate". Or the corresponding "alkyl methacrylate". Similarly, "(meth)acrylic group" means "acrylic group" or "methacrylic acid group", and "(meth)acrylylene group" means "acrylic fluorenyl group" or its corresponding "A" Acryl fluorenyl."

<Photosensitive Conductive Film>

The photosensitive conductive film of the present invention comprises a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film, and the photosensitive resin layer contains (A) a binder polymer, (B) A photopolymerizable compound and (C) a photopolymerizable initiator, wherein the photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less.

In the present specification, the boundary between the conductive film and the photosensitive resin layer is not necessarily required to be clear. The conductive film may have conductivity in the surface direction of the photosensitive layer, and may be a state in which a photosensitive resin layer is mixed with the conductive film. For example, a composition constituting the photosensitive resin layer may be impregnated into the conductive film, or a composition constituting the photosensitive resin layer may be present on the surface of the conductive film.

Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive conductive film used in the present invention. The photosensitive conductive film 10 shown in FIG. 1 includes a support film 1 and a photosensitive layer 4 provided on the support film 1. The photosensitive layer 4 includes a conductive film 2 and a photosensitive resin layer 3 provided on the conductive film 2.

Hereinafter, the support film 1, the conductive film 2, and the photosensitive resin layer 3 constituting the photosensitive conductive film 10 will be described in detail.

The support film 1 is, for example, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polyethylene film, a polypropylene film, or a polycarbonate film. Among these films, a polyethylene terephthalate film is preferred from the viewpoint of transparency or heat resistance. Further, these polymer films must be removed from the photosensitive layer 4 at a later time, so that it is not possible to perform a surface treatment which cannot be removed, or a material which cannot be removed.

Further, the thickness of the support film 1 is preferably from 5 μm to 300 μm, more preferably from 10 μm to 200 μm, still more preferably from 15 μm to 100 μm, particularly preferably from 15 μm to 50 μm.

The step of applying a conductive dispersion liquid to form the conductive film 2, or the step of applying the photosensitive resin composition to form the photosensitive resin layer 3, or before developing the exposed photosensitive resin layer 3 In the step of supporting the film peeling, from the viewpoint of preventing cracking of the support film, it is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more.

In addition, it is preferably 300 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, and particularly preferably 50 μm or less, from the viewpoint of excellent resolution of the pattern after irradiating the actinic radiation through the support film.

The haze value of the support film 1 is preferably from 0.01% to 5.0%, more preferably from 0.01% to 3.0%, particularly preferably from 0.01% to 2.0%, and preferably from 0.01%, in terms of good sensitivity and resolution. ~1.0%. In addition, the haze value can be measured in accordance with JIS K 7105, and can be measured, for example, by a commercially available turbidity meter or the like using NDH-1001DP (manufactured by Nippon Denshoku Industries Co., Ltd., trade name).

The conductive film 2 can be used without any particular limitation, but It is preferred to contain at least one electrically conductive fiber.

Fig. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film. The conductive film 2 is preferably a mesh structure in which conductive fibers are in contact with each other as shown in FIG. 2 . The conductive film 2 having such a mesh structure can be formed on the surface of the photosensitive resin layer 3 on the support film 1 side, but the surface of the photosensitive layer 4 exposed when the support film 1 is peeled off is obtained in the surface direction thereof. The conductivity may be formed by a part of the photosensitive resin layer 3 entering the conductive film 2, or may be formed by including the conductive film 2 in the surface layer of the photosensitive resin layer 3 on the side of the support film 1.

Examples of the conductive fiber include metal fibers such as gold, silver, copper, and platinum, and carbon fibers such as carbon nanotubes. These fibers may be used singly or in combination of two or more. From the viewpoint of electrical conductivity, it is preferred to use gold fibers or silver fibers. Further, from the viewpoint of easily adjusting the conductivity of the formed conductive film, silver fibers are more preferable.

The metal fiber can be produced by a method of reducing a metal ion with a reducing agent such as NaBH ₄ or a polyol method. Further, as the carbon nanotube, a commercially available product such as a Hipco single-layer carbon nanotube of Unidym Co., Ltd. can be used.

The fiber diameter of the conductive fiber is preferably from 1 nm to 50 nm, more preferably from 2 nm to 20 nm, still more preferably from 3 nm to 10 nm. Further, the fiber length of the conductive fiber is preferably from 1 μm to 100 μm, more preferably from 2 μm to 50 μm, still more preferably from 3 μm to 10 μm. The fiber diameter and fiber length can be measured by a scanning electron microscope.

In addition, the conductive film 2 can be combined with conductive fibers to be used. Machine electrical conductor. The organic conductor can be used without particular limitation, but an organic conductor such as a polymer of a thiophene derivative or an aniline derivative is preferably used. Specifically, polyethylene dioxythiophene, polyhexylthiophene, polyaniline or the like can be used.

The thickness of the conductive film 2 is also different depending on the use of the conductive pattern formed by using the photosensitive conductive film of the present invention or the required conductivity, but is preferably 1 μm or less, more preferably 1 nm to 0.5 μm, and particularly preferably 5 nm. ~0.1μm. When the thickness of the electroconductive thin film 2 is 1 μm or less, the light transmittance in the wavelength region of 450 nm to 650 nm is high, and the pattern formation property is also excellent, and it is particularly suitable for producing a transparent electrode. Further, the thickness of the electroconductive thin film 2 means a value measured by a scanning electron micrograph.

The conductive film 2 can be formed, for example, by applying a conductive dispersion liquid to the support film 1 and then drying the conductive film or the organic conductive material to the water and/or the organic solvent. It is formed by dispersing stabilizers such as surfactants as needed. After drying, the electroconductive thin film 2 formed on the support film 1 may be laminated as needed. For example, coating can be carried out by a known method such as a roll coating method, a notch wheel coating method, a gravure coating method, an air knife coating method, a pattern coating method, a bar coating method, or a spray coating method. . Further, it can be dried at 30 ° C to 150 ° C for 1 minute to 30 minutes by using a hot air convection dryer or the like. In the electroconductive thin film 2, a conductive fiber or an organic electric conductor may coexist with a surfactant or a dispersion stabilizer.

The conductive film 2 may be a combination of a conductive fiber or an organic conductor. In this case, the film may be formed by coating the mixture, or they may be formed by sequentially coating them. For example, after the conductive fiber is formed and formed, a solution of the organic conductor can be applied and dried.

The photosensitive resin layer 3 is a layer formed of a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator.

(A) The binder polymer may, for example, be an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, a phenol resin, an ester resin, a urethane resin, An epoxy acrylate resin obtained by a reaction of an epoxy resin with (meth)acrylic acid, an acid-modified epoxy acrylate resin obtained by a reaction of an epoxy acrylate resin and an acid anhydride, or the like. These resins may be used singly or in combination of two or more.

In the resin, from the viewpoint of excellent alkali developability and film formability, an acrylic resin is preferably used, and it is more preferred that the acrylic resin has a (meth)acrylic acid and an alkyl (meth)acrylate. The monomer unit serves as a constituent unit. Here, the "acrylic resin" means a polymer mainly having a monomer unit derived from a polymerizable monomer having a (meth)acryl group.

As the acrylic resin, a resin produced by radical polymerization of a polymerizable monomer having a (meth)acryl group can be used. The acrylic resin may be used singly or in combination of two or more.

Examples of the polymerizable monomer having a (meth)acrylic group include acrylamide such as diacetone acrylamide, alkyl (meth)acrylate, benzyl (meth)acrylate, and (meth)acrylic acid. 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ( 4-hydroxybutyl methacrylate, propylene methoxyethyl 2-hydroxypropyl phthalate (Osaka Organic Chemistry, Viscoat #2311HP), tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate Ester, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid And α-bromo (meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, or the like.

Further, in addition to the polymerizable monomer having a (meth)acryl group as described above, the acrylic resin may be in the α-position or the aromatic ring such as styrene, vinyl toluene or α-methylstyrene. Intermediate-substituted polymerizable styrene derivatives, esters of vinyl alcohols such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, Maleic acid monoester such as maleic acid monoethyl ester or maleic acid monoisopropyl ester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid One or two or more kinds of polymerizable monomers are copolymerized.

The alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate or (meth)acrylic acid. Amyl ester, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (methyl) ) decyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like. These alkyl (meth)acrylates may be used singly or in combination of two or more.

The polymerizable monomer preferably contains an alkyl (meth)acrylate, a benzyl (meth)acrylate, or a glycidyl (meth)acrylate.

Further, from the viewpoint of improving alkali developability, the (A) binder polymer preferably has a carboxyl group. The polymerizable monomer having a carboxyl group may, for example, be (meth)acrylic acid as described above.

The ratio of the carboxyl group of the (A) binder polymer is preferably from 10% by mass to 50% by mass, more preferably 12%, based on the ratio of the polymerizable monomer having a carboxyl group to the total of the polymerizable monomers to be used. The mass % to 40% by mass, particularly preferably 15% by mass to 30% by mass, particularly preferably 15% by mass to 25% by mass. In terms of excellent alkali developability, it is preferably 10% by mass or more, and is preferably 50% by mass or less from the viewpoint of excellent alkali resistance.

The weight average molecular weight of the (A) binder polymer is preferably from 5,000 to 300,000, more preferably from 20,000 to 150,000, particularly preferably from 30,000 to 100,000, from the viewpoint of achieving a balance between mechanical strength and alkali developability. The weight average molecular weight is preferably 5,000 or more in terms of excellent developer resistance. Further, from the viewpoint of development time, it is preferably 300,000 or less. Further, the weight average molecular weight in the present invention is a value obtained by conversion using a standard curve prepared using standard polystyrene, which is measured by gel permeation chromatography (GPC).

These (A) binder polymers may be used singly or in combination of two or more. When the binder polymer is used in combination of two or more kinds, for example, two or more kinds of binder polymers containing different copolymerization components, two or more kinds of binder polymers having different weight average molecular weights, and different Two or more kinds of binder polymers with a degree of dispersion.

The (A) binder polymer preferably has a hydroxyl value of 60 mgKOH/g or less. In addition, when two or more types are used in combination, it is preferred to select the hydroxyl value so that the total of the values obtained by multiplying the hydroxyl value of each of the binder polymers by the mass fraction is 60 mgKOH/g or less. The hydroxyl value is more preferably 50 mgKOH/g or less, still more preferably 30 mgKOH/g or less, and particularly preferably 10 mgKOH/g or less.

In order to reduce the hydroxyl value, for example, in the case where an acrylic resin is used in the binder polymer, by reducing the amount of the polymerizable monomer having a hydroxyl group in the polymerizable monomer for producing the acrylic resin, the acrylic resin can be reduced. The ratio of hydroxyl groups reduces the hydroxyl value of the binder polymer.

For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3 (meth)acrylate can be adjusted. -phenoxypropyl ester, 4-hydroxybutyl (meth)acrylate, propylene oxiranyl ethyl-2-hydroxypropyl phthalate (Osaka Organic Chemistry, Viscoat #2311HP ) the amount.

Next, the (B) photopolymerizable compound will be described. The photopolymerizable compound preferably has an ethylenically unsaturated bond.

Examples of the photopolymerizable compound having an ethylenically unsaturated bond include a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, and an α,β-unsaturated carboxylic acid and a glycidyl group-containing compound. a urethane monomer such as a compound obtained by carrying out a reaction, a (meth) acrylate compound having a urethane bond, or γ-chloro-β-hydroxypropyl-β'-(meth) propylene oxime Oxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloxyethyl-o-phthalate, β-hydroxypropyl-β '-(methyl) A phthalic acid-based compound such as acryloxyethyl-o-phthalic acid ester or an alkyl (meth)acrylate. These compounds may be used singly or in combination of two or more.

A compound obtained by reacting an α,β-unsaturated carboxylic acid with the polyol may, for example, be 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane. , 2,2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)polyethoxypolypropoxy Bisphenol A (meth) acrylate compound such as phenyl)propane, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene polypropylene glycol di(methyl) Acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane Diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylol Propane pentaethoxy tri(meth) acrylate, tetramethylol methane tri(meth) acrylate, tetramethylol methane tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, two Pentaerythritol hexa(meth) acrylate or the like. These compounds vary in hydroxyl value depending on the esterification rate of the manufacturing process.

Examples of the urethane monomer include a (meth)acrylic monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, and 2,4-toluene diisocyanate. Addition reaction of diisocyanate compound such as 1,6-hexamethylene diisocyanate; tris[(methyl)acryloxytetraethyleneethylene glycol isocyanate] hexamethylene isocyanurate, epoxy B Ethylene oxide (EO) modified urethane di(meth) acrylate, EO and propylene oxide (PO) modified urethane Ester di(meth)acrylate and the like.

Further, "EO" means ethylene oxide, and the EO-modified compound has a block structure of an oxirane group. Further, "PO" represents propylene oxide, and the PO-modified compound has a propylene oxide group block structure. The EO modified urethane di(meth) acrylate is exemplified by "UA-11" (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). In addition, EO and PO modified urethane di(meth)acrylate are mentioned, for example, "UA-13" (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name).

(B) The photopolymerizable compound is preferably selected from compounds having a hydroxyl value of 90 mgKOH/g or less. In addition, when two or more types are used in combination, it is preferable to select the sum of the value obtained by multiplying the hydroxyl value of each photopolymerizable compound by the mass fraction to 90 mgKOH/g or less. More preferably, it is 80 mgKOH/g or less, more preferably 50 mgKOH/g or less, and particularly preferably 10 mgKOH/g or less.

In order to reduce the hydroxyl value, the hydroxyl value can be reduced by selecting a photopolymerizable compound having no OH group (hydroxyl group) in the structural formula or reducing the amount of the photopolymerizable compound containing an OH group.

Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid and a polyhydric alcohol as a photopolymerizable compound containing no OH group include trimethylolpropane triacrylate and ethylene oxide (EO). Trimethylolpropane triacrylate, propylene oxide (PO)-containing trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, and the like.

On the other hand, examples of the photopolymerizable compound containing an OH group include a compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, and γ-chloro-β-hydroxypropyl-β'. -(Methyl)acryloxyethyl-o-phthalate, β-hydroxyl Ethyl-β'-(meth)propenyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(methyl)propenyloxyethyl-o-o-benzene a phthalic acid compound such as diformate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, ( 2-hydroxy-3-phenoxypropyl methacrylate, 4-hydroxybutyl (meth) acrylate, propylene methoxyethyl 2-hydroxypropyl phthalate (Osaka Organic Chemistry, Viscoat #2311HP) and so on.

In addition, examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol include diol methacrylate acrylate and pentaerythritol triacrylate (PET-30 manufactured by Nippon Kayaku Co., Ltd.). Etc., pentaerythritol diacrylate, pentaerythritol monoacrylate, pentaerythritol diacrylate monocarboxylate, ethylene oxide (EO)-containing pentaerythritol triacrylate, ethylene oxide (EO) pentaerythritol diacrylate Ethylene oxide (EO)-containing pentaerythritol monoacrylate, propylene oxide (PO)-containing pentaerythritol triacrylate, propylene oxide (PO)-containing pentaerythritol diacrylate, propylene oxide (PO) pentaerythritol monoacrylic acid Ester, propylene isopropane cyanide ethyl ester (M-215 manufactured by East Asia Synthetic, etc.), trimethylolpropane diacrylate, trimethylolpropane monoacrylate, ethylene oxide (EO) Trimethylolpropane diacrylate, trimethylolpropane monoacrylate containing ethylene oxide (EO), trimethylolpropane diacrylate containing propylene oxide (PO), propylene oxide ( PO) trimethylolpropane monoacrylate, dipentaerythritol Pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol monoacrylate, glycerin dimethacrylate, and the like.

Among the photopolymerizable compounds, dipentaerythritol hexaacrylate is preferred, or Trimethylolpropane triacrylate.

The content ratio of the (B) photopolymerizable compound is preferably from 30% by mass to 80% by mass, and more preferably from 40% by mass to 70% by mass, based on 100% by mass of the total of the binder polymer and the photopolymerizable compound. In the case where the photocurability and the coating film of the conductive film (the conductive film and the photosensitive resin layer) to be transferred are excellent, the storage stability in the case where the film is wound into a film is preferably 30 parts by mass or more. In an excellent aspect, it is preferably 80% by mass or less.

Next, the (C) photopolymerizable initiator will be described. The photopolymerizable initiator is not particularly limited as long as it selects a compound having a wavelength of light to be used in the exposure machine and a wavelength necessary for functional expression, and examples thereof include benzophenone and N, N'- Tetramethyl-4,4'-diaminobenzophenone (Mitchlerone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy -4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1 An aromatic ketone such as [4-(methylthio)phenyl]-2-morpholinyl-acetone-1; 2-ethyl hydrazine, phenanthrenequinone, 2-tert-butyl fluorene, eight Methyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenylindole, 2,3-diphenylfluorene, 1-chloroindole, 2-methyl Anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylhydrazine, etc.; benzoin methyl ether, benzoin a benzoin ether compound such as diethyl ether or benzoin phenyl ether; a benzoin compound such as benzoin, methylbenzoin or ethyl benzoin; 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O- Benzopyridinium), 1-[9-ethyl-6-(2-methylbenzhydryl) An oxime ester compound such as -9H-carbazol-3-yl]ethanone 1-(O-ethenyl hydrazine); a benzyl derivative such as benzyl dimethyl ketal; 2-(o-chlorophenyl)- 4,5- Diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl Imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer 2,4,5-triaryl imidazole dimer; acridine derivative such as 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine An acid, an N-phenylglycine derivative, a coumarin compound, an oxazole compound, or the like.

Among these compounds, an oxime ester compound is preferred in terms of transparency and patterning ability of 10 μm or less. Examples of the oxime ester compound include compounds represented by the following formula (C-1) and formula (C-2). From the viewpoint of rapid hardenability and transparency, a compound represented by the following formula (C-1) is more preferable.

In the formula (C-1), R ^{1 is} each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group. It is preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, more preferably an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 6 carbon atoms. Phenyl or tolyl, more preferably methyl, hexyl, cyclopentyl, phenyl or tolyl.

R is -H, -OH, -COOH, -O(CH ₂ )OH, -O(CH ₂ ) ₂ OH, -COO(CH ₂ )OH or -COO(CH ₂ ) ₂ OH. Preferred is -H, -O(CH ₂ )OH, -O(CH ₂ ) ₂ OH, -COO(CH ₂ )OH or -COO(CH ₂ ) ₂ OH, more preferably -H, -O(CH) ₂ ) ₂ OH or -COO(CH ₂ ) ₂ OH.

In the above formula (C-2), R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group. Or a tolyl group, R ⁴ represents an alkyl group having 1 to 12 carbon atoms, and R ⁵ represents an alkyl group or an aryl group having 1 to 20 carbon atoms. P1 represents an integer from 0 to 3. Further, when p1 is 2 or more, a plurality of R ⁴ may be the same or different.

In the above formula (C-2), R ² or R ^{4 is} preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. base.

In the above formula (C-2), R ^{3 is} preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 4 to 15 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, or carbon. A number of 4 to 10 cycloalkyl groups, particularly preferably an ethyl group.

In the above formula (C-2), R ^{5 is} preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 16 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 to 6. The aryl group of 14 is particularly preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

Examples of the compound represented by the above formula (C-1) include 1,2-octanedione, 1-[4-(phenylthio)-phenyl, 2-(O-benzoguanidinopurine), and the like. .

The compound represented by the above formula (C-2) may, for example, be ethyl ketone, 1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]- , 1-(O-ethinyl), and the like. These compounds are commercially available as IRGACURE OXE 01 and IRGACURE OXE 02, both manufactured by BASF (trade name). These compounds may be used singly or in combination of two or more.

Among the oxime ester compounds, preferred is 1,2-octanedione, 1-[4-(phenylthio)-phenyl, 2-(O-benzylidenehydrazine)].

The content ratio of the photopolymerizable initiator is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, based on 100 parts by mass of the total of the binder polymer and the photopolymerizable compound. Preferably, it is 1 part by mass to 5 parts by mass. In terms of excellent photosensitivity, it is preferably 0.1 part by mass or more, and is preferably 20 parts by mass or less from the viewpoint of excellent photocurability.

In the photosensitive resin layer 3, if necessary, one type of additive may be contained or two or more types of additives may be contained in combination, and the additive may be an adhesion imparting agent such as a decane coupling agent or a plasticizer such as p-toluenesulfonamide or a filler. , defoamer, flame retardant, Stabilizers, leveling agents, stripping accelerators, antioxidants, perfumes, imaging agents, thermal crosslinkers, and the like. The amount of the additives added is preferably from 0.01 part by mass to 20 parts by mass per 100 parts by mass of the total of the binder polymer and the photopolymerizable compound.

The photosensitive resin layer 3 can be formed by applying a solution of a photosensitive resin composition on the support film 1 on which the conductive film 2 is formed, if necessary, and drying, and the solution of the photosensitive resin composition is dissolved in methanol. , ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or the like or a mixed solvent thereof The solid content is about 10% by mass to 60% by mass. In this case, in order to prevent the diffusion of the organic solvent in the step described later, the amount of the residual organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less.

The application of the photosensitive resin layer 3 can be performed by a roll coating method, a slanting wheel coating method, a gravure coating method, an air knife coating method, a pattern coating method, a bar coating method, a spray coating method, or the like. A well-known method is carried out. After the application, the drying for removing the organic solvent or the like can be carried out at 70 ° C to 150 ° C for 5 minutes to 30 minutes using a hot air convection dryer or the like.

The thickness of the photosensitive resin layer 3 varies depending on the application, and is preferably 1 μm to 50 μm, more preferably 1 μm to 15 μm, and particularly preferably 1 μm to 10 μm, in terms of thickness after drying. When the thickness is less than 1 μm, the coating tends to be difficult. When the thickness is more than 50 μm, the sensitivity due to the decrease in light transmission is insufficient, and the photocurability of the transferred photosensitive resin layer is lowered. tendency.

In the photosensitive conductive film used in the present invention, when the total thickness of the two layers is 1 μm to 10 μm, the laminated body of the conductive film 2 and the photosensitive resin layer 3 is preferably a wavelength of 450 nm to 650 nm. The minimum light transmittance of the region is 80% or more, and more preferably 85% or more. When the conductive film and the photosensitive resin layer satisfy such conditions, visibility of a display panel or the like is improved.

The photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less, preferably 30 mgKOH/g or less, more preferably 20 mgKOH/g or less, even more preferably 10 mgKOH/g or less, and particularly preferably 5 mgKOH/g or less. The hydroxyl value of the photosensitive resin layer can be adjusted by adjusting the hydroxyl value of the component (A) and the component (B).

By reducing the hydroxyl value of the (A) binder polymer, (B) photopolymerizable compound or photosensitive resin layer, it is difficult to produce a conductive pattern obtained by using a photosensitive conductive film under high temperature and high humidity conditions. Poor disconnection.

In the photosensitive conductive film used in the present invention, a protective film can be laminated so as to be in contact with the surface of the photosensitive resin layer 3 on the side opposite to the support film 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, or a polyethylene film can be used. Further, a polymer film identical to the support film may be used as the protective film.

In order to facilitate the peeling of the protective film from the photosensitive resin layer, the adhesive force between the protective film and the photosensitive resin layer is preferably smaller than the adhesive force between the photosensitive layer 4 and the support film 1.

Moreover, it is preferable that the number of fisheyes having a diameter of 80 μm or more contained in the protective film is 5/m ² or less. In addition, the term "fisheye" means that when a film is produced by heat-melting a material, by kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, undissolved matter, oxidative degradation or the like of the material enters the film. In the middle.

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

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

The photosensitive conductive film can be stored in a roll form, for example, in the form of an original flat plate or by winding a core such as a cylindrical shape. Further, in this case, it is preferable to wind up the support film so as to be the outermost side.

Further, in the case where the photosensitive conductive film does not have a protective film, the photosensitive conductive film can be stored in the original flat shape.

The core is not particularly limited as long as it is a prior user, and examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and acrylonitrile butadiene styrene (ABS). Plastics such as resin (acrylonitrile-butadiene-styrene copolymer). Further, in the end face of the photosensitive conductive film wound into a roll shape, it is preferable to provide an end face separator from the viewpoint of end face protection, and in addition, from the viewpoint of edge fusion resistance, It is best to provide a moisture-proof end face separator. Further, when the photosensitive conductive film is packaged, it is preferably packaged in a black sheet having a small moisture permeability.

<Method of Forming Conductive Pattern>

Hereinafter, a method of forming the conductive pattern of the present invention will be described using a drawing.

As shown in FIGS. 3( a ) to 3 ( c ), the photosensitive resin layer 3 having the photosensitive conductive film 10 having the support film 1 , the conductive film 2 , and the photosensitive resin layer 3 is laminated on the substrate 20 ( FIG. 3(a)), then, the photosensitive resin layer 3 is irradiated with the actinic ray L in a pattern shape via the mask 5 (FIG. 3(b)), and the unhardened portion is removed by development (unexposed portion) Thereby, a conductive pattern (conductive film 2a) is formed (Fig. 3(c)). The conductive pattern obtained in the above manner has the thickness of the resin hardened layer 3b in addition to the thickness of the conductive film 2a. These thicknesses become the step difference Hb from the substrate. If the step is large, the conductive pattern is easily visible, and therefore it may be used separately from the method shown in FIGS. 4(a) to 4(d) depending on the application. Further, the method of forming the conductive pattern is preferably formed using a photosensitive conductive film, and the photosensitive resin layer of the present invention and the conductive film containing the conductive fibers are separately formed on the substrate, and then exposed and developed. .

As shown in FIGS. 4(a) to 4(d), it is preferable that the first exposure step (FIG. 4(b)) of irradiating the predetermined portion of the photosensitive layer 4 having the support film 1 with the actinic rays is as follows: Second exposure step (Fig. 4 (c)): After the support film 1 is peeled off, a part or all of the exposed portion and the unexposed portion in the first exposure step are irradiated with actinic rays in the presence of oxygen. The second exposure step is carried out in the presence of oxygen, for example preferably in air. In addition, it may be a condition for increasing the oxygen concentration.

In the developing step, the insufficiently hardened surface portion of the exposed photosensitive resin layer 3 in the second exposure step is removed. Specifically, by the wet phenomenon, The insufficiently hardened surface portion of the photosensitive resin layer 3, that is, the surface layer containing the conductive film 2 is removed. Thereby, a conductive pattern and a resin hardened layer having no conductive film are provided on the substrate, and the step of the conductive pattern can be reduced as compared with a case where only the conductive pattern is provided on the substrate.

The method for forming a conductive pattern of the present invention comprises the steps of: laminating step of laminating the photosensitive conductive film of the present invention on a substrate in a manner of closely bonding the photosensitive resin layer; and exposing step in a state with the support film a step of irradiating a predetermined portion of the photosensitive resin layer on the substrate with actinic rays; then peeling the support film; and a developing step of forming a conductive pattern by developing the unexposed portions of the photosensitive resin layer and the conductive film . By performing the steps, a conductive pattern substrate including the patterned conductive pattern on the substrate is obtained.

Examples of the substrate include a glass substrate, a plastic substrate such as polycarbonate, and the like. The substrate is preferably a substrate having a minimum light transmittance of 80% or more in a wavelength region of 450 nm to 650 nm.

The laminating step is carried out, for example, by a method in which the protective film is removed, and the photosensitive conductive film is pressed against the substrate while heating the photosensitive conductive film to form a layer. Further, in terms of the adhesion and the follow-up, the work is preferably carried out under reduced pressure. Preferably, the photosensitive conductive film is laminated to heat the photosensitive resin layer or the substrate to 70 ° C to 130 ° C, and the pressure of the pressure is preferably set to about 0.1 MPa to 1.0 MPa (about 1 kgf / cm ² to 10 kgf / cm ² ). However, there are no special restrictions on these conditions. Further, when the photosensitive resin layer is heated to 70° C. to 130° C. as described above, it is not necessary to preheat the substrate in advance, but in order to further improve the buildup property, the substrate may be subjected to preheat treatment.

The exposure method in the exposure step of irradiating the predetermined portion of the photosensitive resin layer on the substrate with the actin film in the exposure step may be exemplified by a negative or positive mask pattern called an artwork. A method of irradiating actinic rays in an image form (mask exposure method). The light source of the actinic ray uses a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like to efficiently emit a light source such as ultraviolet light or visible light. Further, a light source such as an ultraviolet laser or a visible light is efficiently emitted by using an Ar ion laser or a semiconductor laser. Further, a light source that efficiently emits visible light, such as a flood bulb for photography, a solar lamp, or the like, is also used. Further, a method of irradiating the actinic rays in an image form by direct drawing using a laser exposure method or the like may be employed.

The exposure amount in the exposure step varies depending on the composition of the device or the photosensitive resin composition to be used, and is preferably ⁵ mJ/cm ² to 1000 mJ/cm ² , more preferably 10 mJ/cm ² to 200 mJ/cm ² . In terms of excellent photocurability, it is preferably 10 mJ/cm ² or more, and in terms of analytical properties, it is preferably 200 mJ/cm ² or less.

For example, a developing solution corresponding to a photosensitive resin such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent-based developing solution can be used by a known method such as spraying, shaking, scouring, scrubbing, or scrubbing.

The developer is a solution which is safe, stable, and has good handleability, such as an aqueous alkaline solution. The base of the alkaline aqueous solution is, for example, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium, a carbonate of lithium, sodium, potassium or ammonium or a carbonate such as hydrogencarbonate, phosphoric acid. An alkali metal phosphate such as potassium or sodium phosphate, an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate, or an alkali borate such as an aqueous solution of sodium tetraborate.

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

Further, an aqueous developing solution containing water or an aqueous alkaline solution and one or more organic solvents can be used. Here, the base contained in the alkaline aqueous solution may be exemplified by borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, and diethylideneamine. 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine and the like.

Examples of the organic solvent include acetol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, diethylene glycol monobutyl ether and the like. These organic solvents may be used singly or in combination of two or more.

The aqueous developing solution preferably has a concentration of the organic solvent of 2% by mass to 90% by mass, and the temperature thereof can be adjusted according to the developability. Further, the pH of the aqueous developing solution is preferably as small as possible within a range in which development of the resist can be sufficiently performed, and is preferably pH 8 to pH 12, more preferably pH 9 ~pH value of 10. In addition, A small amount of a surfactant, an antifoaming agent, or the like may be added to the aqueous developing solution.

Examples of the organic solvent-based developing solution include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ- Butyrolactone and the like. In order to prevent ignition, it is preferred that the organic solvent be added with water in a range of from 1% by mass to 20% by mass.

The developer may be used in combination of two or more kinds as needed. Further, examples of the development method include a immersion method, a puddle method, a spray method, a brushing, and a scrubbing. Among these methods, from the viewpoint of improving the resolution, it is preferable to use a high pressure injection method.

The method of forming a conductive pattern according to the present invention, after the development, if necessary, also by heating for about ² exposure of about 60 ℃ ~ 250 ℃ or ^{0.2J / cm 2 ~ 10J / cm} , the conductive pattern further hardening.

As described above, according to the method for forming a conductive pattern of the present invention, an etching resist is not formed as in an inorganic film such as ITO, and a transparent conductive pattern can be easily formed on a substrate such as glass or plastic.

The conductive pattern substrate of the present invention is obtained by the method of forming the conductive film or the method of forming a conductive pattern, and the surface resistivity of the conductive film or the conductive pattern is preferably from the viewpoint of effective use as a transparent electrode. 2000 Ω / □ or less, more preferably 1000 Ω / □ or less, particularly preferably 500 Ω / □ or less. The surface resistivity can be adjusted, for example, according to the concentration or the coating amount of the dispersion of the conductive fiber or the organic conductor.

In addition, the conductive pattern substrate of the present invention is preferably between 450 nm and 650 nm. The minimum light transmittance in the wavelength region is 80% or more, and more preferably 85% or more.

<Touch Panel Sensor>

The touch panel sensor of the present invention includes the conductive pattern substrate.

FIG. 5 is a schematic plan view showing an example of a capacitive touch panel sensor. The touch panel sensor shown in FIG. 5 has a touch screen 102 for detecting a touch position on one side of the transparent substrate 101, and detects a change in electrostatic capacitance in the area, including a transparent electrode 103 as an X position coordinate. And a transparent electrode 104 as a coordinate of the Y position. Arranged on each of the transparent electrodes 103 and the transparent electrodes 104 which are coordinates of the X and Y positions, the lead wires 105 are connected to the driver elements for controlling the electrical signals as the touch panel; and the connection electrodes 106, which connects the lead wiring 105 to the transparent electrode 103 and the transparent electrode 104. Further, a connection terminal 107 that is electrically connected to the driver element is disposed at an end portion of the lead wiring 105 opposite to the connection electrode 106.

6(a) to 6(d) are schematic diagrams showing an example of a method of manufacturing the touch panel sensor shown in Fig. 5. In the manufacturing method, the transparent electrode 103 and the transparent electrode 104 are formed by the method of forming the conductive pattern of the present invention.

First, as shown in FIG. 6(a), a transparent electrode (X position coordinate) 103 is formed on the transparent substrate 101. Specifically, the photosensitive conductive film 10 is laminated such that the photosensitive resin layer 3 is connected to the transparent substrate 101. The transferred photosensitive layer 4 (the conductive film 2 and the photosensitive resin layer 3) is irradiated with actinic rays in a pattern through a light-shielding mask having a desired shape (first exposure step). Then, the light-shielding mask is removed, and after the support film is peeled off, the photosensitive layer 4 is irradiated with actinic rays (second exposure step). Exposure After the photo-step, by performing development, the electroconductive thin film 2 and the photosensitive resin layer 3 which is insufficiently hardened are collectively removed, and the conductive pattern 2a is formed. The transparent electrode 103 for detecting the X position coordinate is formed by the conductive pattern 2a (Fig. 6(b)). Fig. 6 (b) is a schematic cross-sectional view of the I-I cut surface of Fig. 6 (a). By forming the transparent electrode 103 by the method of forming a conductive pattern of the present invention, a transparent electrode 103 having a small step can be provided.

Then, a transparent electrode (Y position coordinate) 104 is formed as shown in FIG. 6(c). A new photosensitive conductive film 10 is laminated on the substrate 101 including the transparent electrode 103 formed by the above steps, and the transparent electrode 104 for detecting the Y position coordinate is formed by the same operation as described above (Fig. 6(d)). Fig. 6(d) is a schematic cross-sectional view of the II-II cut surface of Fig. 6(c). By forming the transparent electrode 104 by the method for forming a conductive pattern of the present invention and forming the transparent electrode 104 on the transparent electrode 103, it is also possible to produce a decrease in aesthetics caused by the step or the entrapment of the bubble. A highly smooth touch panel sensor that is sufficiently suppressed.

Then, a lead wire 105 for connecting to an external circuit and a connection bulb 106 (not shown) for connecting the lead wire to the transparent electrode 103 and the transparent electrode 104 are formed on the surface of the transparent substrate 101. In FIGS. 6(a) to 6(d), the lead line 105 and the connection electrode 106 are formed so as to form the transparent electrode 103 and the transparent electrode 104, but they may be formed simultaneously when each transparent electrode is formed. The lead wire 105 can be formed at the same time as the formation of the connection electrode 106 by a screen printing method using, for example, a conductive paste material containing silver in the form of flakes.

7 and 8 are partial cross-sectional views along a-a' and b-b' shown in Fig. 5, respectively. These figures represent the intersection of the transparent electrodes of the XY position coordinates. Figure 7 and As shown in FIG. 8, by forming a transparent electrode by the method of forming a conductive pattern of the present invention, a touch panel sensor having a small step and high smoothness can be obtained.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

The components (B) used in the examples and comparative examples are as follows.

. DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate, hydroxyl value 40)

. TMPTA (manufactured by Nippon Kayaku Co., Ltd., trimethylolpropane triacrylate, hydroxyl value 0)

. PET-30 (manufactured by Nippon Kayaku Co., Ltd., pentaerythritol triacrylate, hydroxyl value 110)

. A-9550 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dipentaerythritol polyacrylate, hydroxyl value 40)

. A-9570 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dipentaerythritol polyacrylate, hydroxyl value 70)

. A-TMM-3 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., pentaerythritol triacrylate, hydroxyl value 110)

. A-TMM-3LMN (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., pentaerythritol triacrylate, hydroxyl value 114)

Manufacturing example 1

<Electrically conductive dispersion (coating liquid for forming a conductive film) (silver fiber dispersion) Preparation>

[Preparation of Silver Fiber by Polyol Method]

500 ml of ethylene glycol was placed in a 2000 ml three-necked flask, and the mixture was heated to 160 ° C in an oil bath while stirring under a nitrogen atmosphere using a magnetic stirrer. A solution prepared by dissolving 2 mg of PtCl ₂ in 50 ml of ethylene glycol separately was added dropwise thereto. After 4 minutes to 5 minutes, a solution obtained by dissolving 5 g of AgNO ₃ in 300 ml of ethylene glycol and a polyvinylpyrrolidine having a weight average molecular weight of 40,000 were added dropwise over 1 minute using respective dropping funnels. A solution of 5 g of a ketone (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 150 ml of ethylene glycol was stirred at 160 ° C for 60 minutes.

The reaction solution was allowed to stand at 30 ° C or lower, diluted with acetone to 10 times, centrifuged at 2000 rpm for 20 minutes by a centrifugal separator, and the supernatant was decanted. After adding acetone to the precipitate and stirring, the mixture was centrifuged under the same conditions as described above, and acetone was decanted. Then, using centrifugal water, centrifugation was carried out twice in the same manner to obtain silver fibers. The obtained silver fiber was observed by an optical microscope, and as a result, the fiber diameter (diameter) was about 5 nm, and the fiber length was about 5 μm.

[Preparation of Silver Fiber Dispersion]

The obtained silver fiber 0.2% by mass and dodecyl-pentaethylene glycol were dispersed in pure water so as to have a concentration of 0.1% by mass to obtain a silver fiber dispersion.

Manufacturing Example 2

<Preparation of (A) component solution>

[Production of Binder Polymer Solution (A1)]

In the flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, (1) shown in Table 1 was placed, and the temperature was raised to 80 ° C in a nitrogen atmosphere while maintaining the reaction temperature at 80 ° C ± 2 ° C. It took 4 hours to uniformly drop (2) shown in Table 1. After the dropwise addition of (2), stirring was continued at 80 ° C ± 2 ° C for 6 hours to obtain a binder polymer solution (solid content: 50% by mass) (A1) having a weight average molecular weight of about 45,000.

[Production of Binder Polymer Solution (A2)]

In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, (1) shown in Table 2 was placed, and the temperature was raised to 80 ° C in a nitrogen atmosphere while maintaining the reaction temperature at 80 ° C ± 2 ° C. It took 4 hours to uniformly drop (2) shown in Table 2. After the dropwise addition of (2), stirring was continued at 80 ° C ± 2 ° C for 6 hours to obtain a binder polymer solution (solid content: 50% by mass) (A2) having a weight average molecular weight of about 50,000.

[Production of Binder Polymer Solution (A3)]

In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, (1) shown in Table 3 was placed, and the temperature was raised to 80 ° C in a nitrogen atmosphere while maintaining the reaction temperature at 80 ° C ± 2 ° C. It took 4 hours to uniformly add (2) shown in Table 3. After the dropwise addition of (2), stirring was continued at 80 ° C ± 2 ° C for 6 hours to obtain a binder polymer solution (solid content: 50% by mass) (A3) having a weight average molecular weight of about 50,000.

[Production of Binder Polymer Solution (A4)]

In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, (1) shown in Table 4 was placed, and the temperature was raised to 80 ° C in a nitrogen atmosphere while maintaining the reaction temperature at 80 ° C ± 2 ° C. It took 4 hours to uniformly add (2) shown in Table 4. After the dropwise addition of (2), stirring was continued at 80 ° C ± 2 ° C for 6 hours to obtain a binder polymer solution (solid content: 50% by mass) (A4) having a weight average molecular weight of about 50,000.

[Evaluation of binder polymer solution]

With respect to the produced binder polymer solution A1 to binder polymer solution A4, the following characteristics were measured by the following methods. The results are shown in Table 5.

(1) Weight average molecular weight

The weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) and is converted using a standard curve of standard polystyrene. The conditions of GPC are shown below.

GPC condition

Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., product name)

Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above manufactured by Hitachi Chemical Co., Ltd., product name)

Lysate: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd., product name)

(2) Hydroxyl value

The hydroxyl value was measured in the following manner. First, the produced binder polymer solution was heated at 130 ° C for 1 hour to remove volatile components to obtain a solid component. Next, after weighing 1 g of the polymer to be measured for the hydroxyl value, the accurately weighed polymer was placed in an Erlenmeyer flask, 10 mL of a 10% by mass acetic anhydride pyridine solution was added thereto, and it was uniformly dissolved, and heated at 100 ° C. hour. After heating, 10 mL of water and 10 mL of pyridine were added, and after heating at 100 ° C for 10 minutes, an auto-titration machine ("COM-1700" manufactured by Hiranuma Satoshi Co., Ltd.) was used, and a 0.5 mol/L potassium hydroxide ethanol solution was used. Neutralize and titrate. Then, the hydroxyl value was calculated by the following formula.

Hydroxyl value = (A-B) × f × 28.05 / sample (g) + acid value

(wherein A represents the amount (mL) of a 0.5 mol/L potassium hydroxide ethanol solution used in the blank test, and B represents a 0.5 mol/L potassium hydroxide ethanol solution used in the titration. The amount (mL), f represents the factor. )

(3) Acid value

The acid value was measured in the following manner. First, the produced binder polymer solution was heated at 130 ° C for 1 hour to remove volatile components to obtain a solid component. Next, after accurately measuring the acid value of the polymer to be measured by 1 g, a precisely weighed polymer was placed in an Erlenmeyer flask, and 30 g of acetone was added to the polymer to uniformly dissolve it. Then, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was carried out using a 0.1 N aqueous KOH solution. Then, the acid value was calculated by the following formula.

Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)

(In the formula, Vf represents the titer (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I represents the ratio (% by mass) of the nonvolatile component in the measured resin solution.)

(4) Glass transition temperature (Tg)

The prepared binder polymer solution was uniformly applied to a polyethylene terephthalate film (manufactured by Teijin Dupont Film Co., Ltd., under the name "Purex A53". The film was dried by a hot air convection dryer at 90 ° C for 10 minutes to form a film containing a binder polymer having a thickness of 40 μm after drying. Then, using an exposure machine having a high-pressure mercury lamp (manufactured by ORC Manufacturing Co., Ltd., trade name "EXM-1201"), the film was exposed in such a manner that the amount of irradiation energy became 400 mJ/cm ² . . The exposed film was heated on a hot plate at 65 ° C for 2 minutes, followed by heating at 95 ° C for 8 minutes, and heated at 180 ° C for 60 minutes using a hot air convection dryer, self-polyethylene terephthalate. The diester film was peeled off, and the thermal expansion coefficient of the cured film when the temperature was raised at a temperature increase rate of 5 ° C/min was measured using a TMA/SS6000 manufactured by Seiko Instruments Co., Ltd., and the inflection point obtained from the curve was obtained. (inflection point) as the glass transition temperature Tg.

Example 1

<Production of Photosensitive Conductive Film>

[Production of Conductive Film (Electrically Conductive Film of Photosensitive Conductive Film)]

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

[Production of photosensitive resin composition solution]

The materials shown in Table 6 were mixed in an amount (parts by mass) shown in Table 6 using a stirrer for 15 minutes to prepare a photosensitive resin composition solution.

Further, the amount of the component (A) in the table is a part by mass of a solid component other than the solvent. SH-30 in the table is an anthrone homogenizer (manufactured by Toray Dow Corning Co., Ltd.).

The hydroxyl value of the photosensitive resin composition was measured in the same manner as the binder polymer solution. The results are shown in Table 6.

[Production of Photosensitive Conductive Film]

The photosensitive resin composition solution was uniformly applied onto a 50 μm-thick polyethylene terephthalate (PET) film in which a conductive film was formed of a conductive film, and dried by a hot air convection dryer at 100 ° C for 10 minutes. A photosensitive resin layer is formed. Then, the photosensitive resin layer was covered with a protective film made of polyethylene (manufactured by Tamapoly Co., Ltd., trade name "NF-13") to obtain a photosensitive conductive film. Further, the film thickness after drying of the photosensitive resin layer was 5 μm.

[Measurement of Light Transmittance of Photosensitive Conductive Film]

The peeling machine (manufactured by Hitachi Chemical Co., Ltd., trade name HLM-3000) was used in a roll temperature of 110, and the polyethylene film of the obtained photosensitive conductive film was peeled off. °C, the substrate feed rate is 1 m/min, and the crimping pressure (cylinder pressure) is 4 × 10 ⁵ Pa (due to the use of a substrate having a thickness of 1 mm, a length of 10 cm, and a width of 10 cm, the line pressure at this time is Under the conditions of 9.8×10 ³ N/m), the polyethylene film was laminated on a glass substrate having a thickness of 1 mm, and a substrate on which a photosensitive conductive film containing a support film was laminated on a glass substrate was produced.

Then, for the photosensitive conductive film on the substrate, a parallel light exposure machine (manufactured by ORC Co., Ltd., EXM1201) was used, and the exposure amount was 5 × 10 ² J/m ² (i-ray) from the support film side. After the ultraviolet ray was irradiated, the support film was removed, and a sample for transmittance measurement of the photosensitive resin layer and the conductive film (photosensitive layer) (thickness: 5.0 μm) was obtained.

Then, an ultraviolet-visible spectrophotometer (U-3310) manufactured by Hitachi Metro Service Co., Ltd. was used to measure the visible light transmittance of the obtained sample in a measurement wavelength region of 400 nm to 700 nm.

The transmittance of the obtained sample was 92% at a wavelength of 700 nm, 91% at a wavelength of 550 nm, and 87% at a wavelength of 400 nm, and a good transmittance was ensured.

[Solidity Test of Silver Paste Connection of Photosensitive Conductive Film]

In the following, it is said that "the silver paste connection reliability is good" in the case where the wire is not broken between the photosensitive conductive film and the silver paste under high temperature and high humidity conditions, and the person who is prone to disconnection is called "silver paste connection is reliable". Poor sex." In addition, a method of investigating the merits of the reliability of the silver paste connection is referred to as a silver paste connection reliability test.

The peeling machine (manufactured by Hitachi Chemical Co., Ltd., trade name HLM-3000) was used in a film temperature of 110 ° C while peeling off the polyethylene film of the obtained photosensitive conductive film while being in contact with the photosensitive resin layer. The substrate feed rate was 1 m/min, and the pressure of the pressure (rotor pressure) was 4 × 10 ⁵ Pa. The polyethylene film was laminated on a PET film (manufactured by Toyobo Co., Ltd., trade name A4300, vertical 12 cm). × 12 cm in width and 125 μm in thickness, a substrate on which a photosensitive conductive film containing a support film was laminated on a PET film substrate.

Then, for the photosensitive conductive film on the substrate, a parallel light exposure machine (manufactured by ORC), EXM1201, from the side of the support film (above the conductive film of the photosensitive conductive film) was used for the exposure amount. 5×10 ² J/m ² (measured value of i-ray (wavelength: 365 nm)) After the ultraviolet ray is irradiated, the support film is removed, and further, from the conductive film of the photosensitive conductive film, the exposure amount is 1×10 ⁴ J/m. ² (Measured value of i-ray (wavelength: 365 nm)) Ultraviolet rays were irradiated, and a film (photosensitive layer full-surface film) in which a photosensitive resin layer and a conductive film (photosensitive layer) (film thickness: 5.0 μm) were formed on the entire surface of the PET film was obtained. Further, the sheet resistance of the obtained photosensitive layer mask was measured by a non-contact resistance measuring device (manufactured by Napson Co., Ltd., NC-10) and found to be 270 ± 20 Ω / □.

Then, on the obtained pre-photosensitive layer mask, silver paste electrodes were formed at intervals of 3 cm. The silver paste electrode was applied in a manner of 2 mm in diameter and 1 mm in thickness. TB3351C (manufactured by ThreeBond), AF4500 (manufactured by Sun Ink Manufacturing Co., Ltd.), AF6100 (manufactured by Sun Ink Manufacturing Co., Ltd.), DW-117H-41 (manufactured by Toyobo Co., Ltd.), DW -250H-5 (manufactured by Toyobo Co., Ltd.), DW-250H-23 (manufactured by Toyobo Co., Ltd.), DW-420L-2 (manufactured by Toyobo Co., Ltd.), FA-301CA (manufactured by Fujikura Kasei Co., Ltd.), FA-401CA (manufactured by Fujikura Kasei Co., Ltd.) is a silver paste. For any silver paste, it is applied to the entire surface of the photosensitive layer, and then used in a box dryer (made by Nanben Chemical Co., Ltd., ETAC HISPEC HG220). Heat treatment was carried out at 120 ° C / 30 minutes. As described above, a silver paste electrode was formed on the entire surface of the photosensitive layer to obtain a sample for evaluating the reliability of silver paste connection of the photosensitive conductive film.

The obtained silver paste was used to connect the samples for reliability evaluation, and the reliability of silver paste connection was evaluated. First, the resistance value between the silver paste electrodes formed at intervals of 3 cm was measured using a pocket tester (manufactured by Custom Co., Ltd., CDM-03D). The resistance value is 350 Ω to 400 Ω, and this resistance value is used as an initial value (R0) before the reliability evaluation of the silver paste connection.

Then, the silver paste connection reliability evaluation sample was placed in a 90% high temperature and high humidity layer at 60 ° C for 100 hours, and then allowed to stand at room temperature for 1 hour in the atmosphere, and then the resistance between the silver paste electrodes was measured again. value. This resistance value was used as the resistance value (R1) after the reliability evaluation of the silver paste connection.

Based on the resistance value R0 and the resistance value R1 before and after the reliability evaluation, the silver paste connection reliability of the photosensitive conductive film was evaluated based on the following evaluation points. Here, the ratio (R1/R0) of R0 to R1 is set to Rr. The results are shown in Table 6.

◎: Rr≦1.1

○: 1.1<Rr≦1.25

△: 1.25 < Rr ≦ 2

×:Rr>2

××: Rr>2, R1>1×10 ⁶ Ω

Embodiment 2 to Embodiment 9

A photosensitive conductive film was produced in the same manner as in Example 1 except that the photosensitive resin composition solution shown in Table 6 was used, and a silver paste connection reliability test was performed to evaluate the silver paste connection reliability. The results are shown in Table 6.

Comparative Example 1 to Comparative Example 6

A photosensitive conductive film was produced in the same manner as in Example 1 except that the photosensitive resin composition solution shown in Table 6 was used, and a silver paste connection reliability test was performed to evaluate the silver paste connection reliability. The results are shown in Table 6.

As shown in Table 6, in Examples 1 to 9 in which the components (A) to (C) were combined, the silver paste connection reliability was good regardless of the type of the silver paste.

On the other hand, as shown in Table 6, silver paste was used in Comparative Example 2, Comparative Example 4, Comparative Example 5, and Comparative Example 6 in which the binder polymer (A3) having a high hydroxyl value and the binder polymer (A4) were used. The connection reliability is poor. In particular, in Comparative Example 4 and Comparative Example 6 in which the binder polymer (A4) was used, the silver paste connection reliability was poor regardless of which silver paste was used. Further, in Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 5 in which PET-30, A-TMM-3, and A-TMM-3LMN, which are high photo-hydroxylizable compounds, were used as the component (B), The same is true for the poor reliability of the silver paste connection.

[Industrial availability]

According to the photosensitive conductive film of the present invention, it is possible to form a conductive pattern which is less likely to cause a disconnection between the silver paste and the silver paste even under high temperature and high humidity conditions without depending on the composition of the silver paste.

The embodiments and/or the embodiments of the present invention have been described in detail hereinabove, but those skilled in the art will be able to practice the exemplary embodiments without departing from the novel teachings and / or a variety of changes to the embodiment. Accordingly, such various modifications are intended to be included within the scope of the present invention.

The contents of the Japanese application specification which is the basis of the Paris priority of the present application are all incorporated in the present specification.

1‧‧‧Support film

2‧‧‧Electrical film

3‧‧‧Photosensitive resin layer

4‧‧‧Photosensitive layer

10‧‧‧Photosensitive conductive film

Claims (11)

A photosensitive conductive film comprising a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film, and the photosensitive resin layer contains: (A) a binder The polymer, (B) photopolymerizable compound, and (C) photopolymerizable initiator, the photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less. The photosensitive conductive film according to claim 1, wherein the component (A) has a hydroxyl value of 60 mgKOH/g or less. The photosensitive conductive film according to claim 1, wherein the component (B) has a hydroxyl value of 90 mgKOH/g or less. The photosensitive conductive film according to any one of claims 1 to 3, wherein the conductive film contains at least one conductive fiber. The photosensitive conductive film according to claim 4, wherein the conductive fiber is a silver fiber. A method of forming a conductive pattern, comprising: a laminating step of laminating a photosensitive conductive film according to any one of claims 1 to 5 on a substrate in a manner that the photosensitive resin layer is in close contact with each other And an exposure step of irradiating a predetermined portion of the photosensitive resin layer on the substrate with actinic rays; and a developing step of peeling off the support film by exposing the exposed light The unexposed portions of the resin layer and the conductive film are developed to form a conductive pattern. A method of forming a conductive pattern, comprising: a laminating step of laminating a photosensitive conductive film according to any one of claims 1 to 5 on a substrate in a manner that the photosensitive resin layer is in close contact with each other a first exposure step of irradiating a predetermined portion of the photosensitive resin layer on the substrate with actinic rays; and a second exposing step of peeling the support film, in the presence of oxygen, to the first A part or all of the unexposed portion in the exposure step is irradiated with actinic rays; and a developing step is performed to develop a conductive pattern by developing the photosensitive resin layer and the conductive film after the second exposure step. A method for producing a conductive pattern, comprising: an exposure step of irradiating a photosensitive resin layer provided on a substrate with a predetermined portion of the conductive film with an actinic ray, wherein the conductive film is provided on the photosensitive resin layer The substrate is a surface on the opposite side and includes a conductive fiber; and a developing step of forming a conductive pattern by removing the unexposed portion of the photosensitive resin layer and the conductive film; and the photosensitive resin layer contains ( A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerizable initiator, wherein the photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less. A method of manufacturing a conductive pattern, comprising: a first exposure step of a photosensitive resin layer disposed on a substrate, and a thin conductive film a predetermined portion of the film is irradiated with actinic rays, the conductive film is disposed on a surface of the photosensitive resin layer opposite to the substrate, and includes conductive fibers; and a second exposure step, in the presence of oxygen, a part or all of the unexposed portion in the first exposure step is irradiated with actinic rays; and a developing step, after the second exposing step, forming the conductive layer by developing the photosensitive resin layer and the conductive film The photosensitive resin layer contains (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerizable initiator, and the photosensitive resin layer has a hydroxyl value of 40 mgKOH/g or less. . A conductive pattern substrate comprising a conductive pattern obtained by a method of forming a conductive pattern according to any one of claims 6 to 9. A touch panel sensor comprising the conductive pattern substrate according to claim 10 of the patent application.