JP2017201350A - Photosensitive conductive film, method for forming conductive pattern, and method for producing conductive pattern substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive conductive film that enables the formation of a conductive pattern having a curable resin film resistant to water absorption; a method of forming a conductive pattern and a method for producing a conductive pattern substrate using the same; and a conductive pattern substrate and a touch panel sensor.SOLUTION: A photosensitive conductive film contains a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film. The photosensitive resin layer contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton, and (C) a photopolymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive conductive film, a method for forming a conductive pattern using the same, a method for manufacturing a conductive pattern substrate, and a conductive pattern substrate and a touch panel sensor, and in particular, a flat panel display such as a liquid crystal display element, a touch screen, and a solar cell. The present invention relates to a photosensitive conductive film for forming a conductive pattern used as an electrode wiring of a device such as an illumination.

  Liquid crystal display elements or touch screens are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones and electronic dictionaries, and display devices such as OA / FA devices.

  Various types of touch panels have already been put into practical use, but in recent years, the use of capacitive touch panels has progressed. In a capacitive touch panel, when a fingertip (conductor) contacts the touch input surface, the fingertip and the conductive film are capacitively coupled to form a capacitor. For this reason, the capacitive touch panel detects the coordinates by capturing the change in charge at the contact position of the fingertip.

  In particular, the projected capacitive touch panel is capable of multipoint detection of fingertips, and thus has a good operability that allows complicated instructions to be given. Use as an input device on a display surface in a device having a small display device such as a music player is advancing.

  In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. A transparent conductive film material is used to form these X and Y electrodes.

  Conventionally, ITO (Indium-Tin-Oxide), indium oxide, tin oxide, and the like have been used as transparent conductive film materials because they exhibit high transmittance with respect to visible light.

  As a method for patterning a transparent conductive film, a method is generally used in which 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 of an ITO and indium oxide film, a mixed liquid composed of two liquids of hydrochloric acid and ferric chloride is often used as the etching liquid.

  The ITO film and the tin oxide film are generally formed by sputtering, but the properties of the transparent conductive film are likely to change depending on the sputtering method, sputtering power, gas pressure, substrate temperature, type of atmospheric gas, and the like. Differences in the film quality of the transparent conductive film due to fluctuations in sputtering conditions cause variations in the etching rate when the transparent conductive film is wet-etched, and are liable to reduce product yield due to patterning defects. In addition, since the conductive pattern forming method described above has undergone a sputtering process, a resist forming process, and an etching process, the process is long and a great burden is imposed on the cost.

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

  Furthermore, Patent Document 2 described below describes a method of forming a conductive pattern having a small step with sufficient resolution by performing an exposure process on a photosensitive conductive film twice and then developing.

International Publication No. 2010/021224 Pamphlet International Publication No. 2013/051516 Pamphlet

  By using the method for forming a photosensitive conductive film disclosed in Patent Documents 1 and 2, sensor electrodes (conductive patterns) of touch panels can be easily formed on various substrates by a photolithography process.

  By the way, the conductive pattern formed using said photosensitive conductive film contains the cured film and electrically conductive film of a photosensitive resin composition. When the cured film absorbs water in the conductive pattern having such a structure, the dielectric constant increases and the sensitivity of the sensor may change.

  The present invention relates to a photosensitive conductive film capable of forming a conductive pattern having a cured resin film that hardly absorbs water, a method for forming a conductive pattern using the same, a method for manufacturing a conductive pattern substrate, and a conductive pattern substrate and a touch panel sensor. For the purpose of provision.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cured film obtained by curing a photosensitive resin composition containing a specific component has a sufficiently low water absorption rate in a specific water absorption test using high-temperature water. Based on this finding, the present invention has been completed.

  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, wherein the photosensitive resin layer is (A) a binder polymer, ( A photosensitive conductive film containing B) a photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton, and (C) a photopolymerization initiator is provided.

  According to the photosensitive conductive film of the present invention, a conductive pattern can be easily and directly formed on various substrates by a photolithography process, and the photosensitive resin layer is cured by curing the photosensitive resin layer by having the above configuration. The membrane can be difficult to absorb water. Therefore, when the conductive pattern formed from the photosensitive conductive film of the present invention is applied as, for example, a sensor electrode of a touch panel, the sensitivity of the sensor changes due to an increase in dielectric constant under high temperature and high humidity. It can be sufficiently suppressed.

  In the photosensitive conductive film of the present invention, when the cured film obtained by curing the photosensitive resin layer is brought into contact with distilled water at 60 ° C. for 1 hour, the water absorption rate of the cured film may be 1.8% or less. it can.

  In the photosensitive conductive film of the present invention, the conductive film may contain conductive fibers.

  The conductive fiber may be a silver fiber.

  The present invention also provides a process for laminating the photosensitive conductive film according to the present invention so that the photosensitive resin layer is in contact with the substrate, and a pattern formed on the photosensitive layer formed by the photosensitive resin layer and the conductive film. Provided is a first method for forming a conductive pattern comprising an exposure step of irradiating actinic rays and a step of developing a photosensitive layer after the exposure step.

  The present invention also provides a process for laminating the photosensitive conductive film according to the present invention so that the photosensitive resin layer is in contact with the substrate, and a pattern formed on the photosensitive layer formed by the photosensitive resin layer and the conductive film. A first exposure step of irradiating actinic rays; a second exposure step of irradiating a part or all of the unexposed portion in the first exposure step of the photosensitive layer in the presence of oxygen; a second exposure step; And a step of developing the photosensitive layer after the exposure step. A second method for forming a conductive pattern is provided.

  According to the first and second methods for forming a conductive pattern according to the present invention, a conductive pattern having a cured resin film that hardly absorbs water can be formed. Thereby, for example, when a conductive pattern is applied as a sensor electrode of a touch panel, it is possible to sufficiently suppress a change in sensitivity of the sensor due to an increase in dielectric constant under high temperature and high humidity.

  The present invention is also a method for manufacturing a conductive pattern substrate comprising a substrate and a conductive pattern provided on the substrate, wherein the conductive pattern substrate is formed by the method for forming a conductive pattern according to the present invention. A manufacturing method is provided.

  According to the method for manufacturing a conductive pattern substrate according to the present invention, a conductive pattern substrate including a conductive pattern having a cured resin film that hardly absorbs water can be manufactured. Thereby, for example, when a conductive pattern substrate is applied to a touch panel, it is possible to sufficiently suppress a change in sensitivity of the sensor due to an increase in dielectric constant under high temperature and high humidity.

  This invention is also a conductive pattern board | substrate provided with the board | substrate and the conductive pattern which provided the cured film and photosensitive film of the photosensitive resin composition provided on the board | substrate in this order from the board | substrate side, Comprising: Provided is a conductive pattern substrate having a water absorption of 1.8% or less when contacted with distilled water at 0 ° C. for 1 hour.

  In the conductive pattern substrate of the present invention, the cured film may include a portion having no conductive film on the side opposite to the substrate.

  The present invention also provides a touch panel sensor including the conductive pattern substrate according to the present invention.

  To provide a photosensitive conductive film capable of forming a conductive pattern having a cured resin film that hardly absorbs water, a method for forming a conductive pattern using the same, a method for manufacturing a conductive pattern substrate, and a conductive pattern substrate and a touch panel sensor. it can.

  The touch panel sensor according to the present invention can sufficiently suppress a change in sensitivity of the sensor due to an increase in dielectric constant under high temperature and high humidity.

It is a schematic cross section showing one embodiment of a photosensitive conductive film. It is a partially cutaway perspective view showing one embodiment of a photosensitive conductive film. It is a schematic cross section for demonstrating one Embodiment of the conductive pattern formation method using the photosensitive conductive film. It is a schematic cross section for demonstrating another embodiment of the formation method of the conductive pattern of this invention. It is a model top view which shows an example of an electrostatic capacitance type touch panel sensor. It is a schematic diagram for demonstrating an example of the manufacturing method of the touchscreen sensor shown by FIG. FIG. 6 is a partial cross-sectional view taken along line a-a ′ shown in FIG. 5. FIG. 6 is a partial cross-sectional view taken along line b-b ′ shown in FIG. 5.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” or “methacryl”, and “(meth) acryloyl” means “acryloyl” or “methacryloyl”. “A or B” only needs to include either A or B, and may include both. In addition, the exemplary materials may be used alone or in combination of two or more unless otherwise specified. Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.

<Photosensitive conductive film>
The photosensitive conductive film of this embodiment includes 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 is (A) a binder. It contains a polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton, and (C) a photopolymerization initiator.

  In the photosensitive conductive film of this embodiment, when the cured film obtained by curing the photosensitive resin layer is brought into contact with distilled water at 60 ° C. for 1 hour, the water absorption rate of the cured film is 1.8% or less. Can do.

  In this specification, the boundary between the conductive film and the photosensitive resin layer is not necessarily clear. The conductive film only needs to have conductivity in the surface direction of the photosensitive layer composed of the conductive film and the photosensitive resin layer, and may be an aspect in which the photosensitive resin layer is mixed with the conductive film. . For example, the composition constituting the photosensitive resin layer may be impregnated in the conductive film, or the 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 the photosensitive conductive film of the present embodiment. A photosensitive conductive film 10 shown in FIG. 1 includes a support film 1 and a photosensitive layer 4 provided on the support film 1, and the photosensitive layer 4 includes the conductive film 2 and the photosensitive resin layer 3 from the support film 1 side. Have in order.

  Hereinafter, each of 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.

  Examples of the support film 1 include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate film, polyethylene film, polypropylene film, and polycarbonate film. Among these, a polyethylene terephthalate film is preferable from the viewpoints of transparency and heat resistance. These polymer films may be surface-treated so as to be easily peeled off from the photosensitive layer 4, and are preferably materials that can be easily peeled off from the photosensitive layer 4.

  The thickness of the support film 1 is preferably 5 to 300 μm, more preferably 10 to 200 μm, and particularly preferably 15 to 100 μm. The step of applying a photosensitive resin composition to form a conductive dispersion or a photosensitive resin layer 3 in order to form a conductive film 2 due to a decrease in mechanical strength, or an exposed photosensitive resin layer 3 From the viewpoint of preventing the support film from being broken in the step of peeling the support film before development, the thickness is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. Moreover, in the point which is excellent in the resolution of the pattern after irradiating an active ray to a photosensitive resin layer through a support film, it is preferable that it is 300 micrometers or less, It is more preferable that it is 200 micrometers or less, It is further that it is 100 micrometers or less. preferable.

  The haze value of the support film 1 is preferably 0.01 to 5.0%, more preferably 0.01 to 3.0%, from the viewpoint of improving sensitivity and resolution. -2.0% is particularly preferred, and 0.01-1.0% is very particularly preferred. The haze value can be measured according to JIS K 7105. For example, it can be measured with a commercially available turbidimeter such as NDH-1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.). .

  Although it can use without a restriction | limiting especially as a material which comprises the electrically conductive film 2, It is preferable to contain at least 1 type of electroconductive fiber.

  Examples of the conductive fibers include metal fibers such as gold, silver, and platinum, and carbon fibers such as carbon nanotubes. These can be used alone or in combination of two or more. From the viewpoint of conductivity, it is preferable to use gold fiber or silver fiber. Furthermore, silver fiber is more preferable from the viewpoint of easily adjusting the conductivity of the conductive film to be formed. A conductive fiber can be used individually or in combination of 2 or more types.

The metal fiber can be prepared by, for example, a method of reducing metal ions with a reducing agent such as NaBH ₄ or a polyol method. The carbon nanotubes may be commercial products such as Hipym single-walled carbon nanotubes from Unidim.

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

  FIG. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film. As shown in FIG. 2, the conductive film 2 preferably has a network structure in which conductive fibers are in contact with each other. The conductive film 2 having such a network structure may be formed on the surface of the photosensitive resin layer 3 on the support film 1 side, but on the surface of the photosensitive layer 4 exposed when the support film 1 is peeled off. As long as conductivity is obtained in the surface direction, the conductive film 2 may be formed so that a part of the photosensitive resin layer 3 enters the conductive film 2, and the conductive film is formed on the surface layer of the photosensitive resin layer 3 on the support film 1 side. 2 may be included.

  An organic conductor can be used for the conductive film 2 together with the conductive fiber. The organic conductor can be used without particular limitation, but it is preferable to use an organic conductor such as a polymer of a thiophene derivative and a polymer of an aniline derivative. Specifically, polyethylenedioxythiophene, polyhexylthiophene, polyaniline, or the like can be used.

  The thickness of the conductive film 2 varies depending on the use of the conductive pattern formed using the photosensitive conductive film or the required conductivity, but is preferably 1 μm or less, more preferably 1 nm to 0.5 μm. A thickness of 5 nm to 0.1 μm is particularly preferable. When the thickness of the conductive film 2 is 1 μm or less, the light transmittance in the wavelength region of 450 to 650 nm is high, the pattern forming property is excellent, and it is particularly suitable for the production of a transparent electrode. In addition, the thickness of the electrically conductive film 2 points out the value measured by a scanning electron micrograph.

  For example, the conductive film 2 is coated on the support film 1 with a conductive dispersion liquid in which the above-described conductive fiber or organic conductor is added with water or an organic solvent and, if necessary, a dispersion stabilizer such as a surfactant. After processing, it can be formed by drying. After drying, the conductive film 2 formed on the support film 1 may be laminated as necessary. The coating can be performed by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. The drying can be performed at 30 to 150 ° C. for about 1 to 30 minutes using a hot air convection dryer or the like. In the conductive film 2, the conductive fiber and the organic conductor may coexist with the surfactant and the dispersion stabilizer.

  The conductive film 2 may be a combination of conductive fibers and organic conductors. In that case, a mixture of them may be applied and formed, or each may be formed by sequentially applying each of them. For example, the conductive fiber dispersion can be applied and dried, and then the organic conductor solution can be applied and dried.

  As the photosensitive resin layer 3, a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton, and (C) a photopolymerization initiator. Are formed.

  (A) As a binder polymer, for example, obtained by reaction of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meth) acrylic acid Examples thereof include epoxy acrylate resins and acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins and acid anhydrides. These resins can be used alone or in combination of two or more.

  Among these, from the viewpoint of excellent alkali developability and film formability, it is preferable to use an acrylic resin, and the acrylic resin is derived from (meth) acrylic acid and a (meth) acrylic acid alkyl ester as a constituent unit. More preferably. Here, “acrylic resin” means a polymer mainly having a monomer unit derived from a polymerizable monomer having a (meth) acryloyl group.

  As the acrylic resin, those produced by radical polymerization of a polymerizable monomer having a (meth) acryloyl group can be used. These acrylic resins can be used alone or in combination of two or more.

  Examples of the polymerizable monomer having a (meth) acryloyl group include acrylamide such as diacetone acrylamide, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, and (meth) acrylic acid dimethylamino. Ethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (Meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid and the like.

  In addition to the polymerizable monomer having the (meth) acryloyl group as described above, the acrylic resin is substituted at the α-position or aromatic ring such as styrene, vinyltoluene, α-methylstyrene and the like. Polymerizable styrene derivatives, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoester such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid One or two or more polymerizable monomers such as cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and the like may be copolymerized.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid. Pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid Examples include decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester. These can be used alone or in combination of two or more.

  Moreover, it is preferable that (A) binder polymer has a carboxyl group from a viewpoint of making alkali developability more favorable. Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid as described above.

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

  (A) The weight average molecular weight of the binder polymer is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, and more preferably 30,000 to 100,000 from the viewpoint of balancing the mechanical strength and alkali developability. Particularly preferred. In terms of excellent developer resistance, the weight average molecular weight is preferably 5000 or more. Further, from the viewpoint of development time, it is preferably 300000 or less. The weight average molecular weight in the present invention is a value measured by a gel permeation chromatography method (GPC) and converted by a calibration curve prepared using standard polystyrene.

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

  From the balance between resolution and other characteristics, the acid value of the (A) binder polymer is preferably 75 to 250 mgKOH / g, more preferably 75 to 200 mgKOH / g, and 75 to 190 mgKOH / g. Is more preferable, and it is especially preferable that it is 75-185 mgKOH / g. When it exceeds 250 mgKOH / g, the developing solution resistance of the photocured photosensitive resin layer tends to be lowered.

  Next, (B) a photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton will be described. Examples of the ethylenically unsaturated bond in the photopolymerizable compound include a (meth) acryloyl group. Examples of the alicyclic skeleton in the photopolymerizable compound include a tricyclodecane skeleton and a dicyclopentanyl skeleton. The photopolymerizable compound preferably has two or more ethylenically unsaturated bonds.

  Examples of the photopolymerizable compound include tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and hydrogenated dicyclopentanyl di (meth). ) Acrylate and the like. From the viewpoint of ease of use, it is preferable to use tricyclodecane di (meth) acrylate.

  The photopolymerizable compound which has an ethylenically unsaturated bond and an alicyclic skeleton can be used individually by 1 type or in combination of 2 or more types.

  The content ratio of the photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton is based on the film forming property with respect to 100 parts by mass of the total photopolymerizable compound contained in the binder polymer and the photosensitive resin layer. From the viewpoint of achieving both high water absorption reduction and film formability of the cured film at a high level, it is more preferably 10 to 60 parts by mass, and 30 to 40 parts by mass. It is particularly preferred.

  The photosensitive resin layer 3 can contain a photopolymerizable compound other than (B) a photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton. Examples of such a photopolymerizable compound include photopolymerizable compounds having an ethylenically unsaturated bond other than (B). Examples of such compounds include compounds obtained by reacting α, β-unsaturated carboxylic acids with polyhydric alcohols, compounds obtained by reacting α, β-unsaturated carboxylic acids with glycidyl group-containing compounds, Urethane monomers such as (meth) acrylate compounds having a urethane bond, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxy Examples thereof include phthalic acid compounds such as ethyl-o-phthalate and β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2- Bisphenol A-based (meth) acrylate compounds such as bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, 2 to 14 ethylene groups, Polyethylene polypropylene glycol di (meth) acrylate and trimethylol having 2 to 14 numbers Propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane Tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol dipropylene having 2 to 14 propylene groups (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate

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

  (B) The content rate of the photopolymerizable compound which has an ethylenically unsaturated bond other than a component is 30-80 mass with respect to 100 mass parts of total amounts of all the photopolymerizable compounds contained in a binder polymer and the photosensitive resin layer. Part is preferable, and 40 to 70 parts by mass is more preferable.

  Next, (C) the photopolymerization initiator will be described. (C) The photopolymerization initiator is not particularly limited as long as it matches the light wavelength of the exposure machine to be used and the wavelength necessary for function expression. For example, benzophenone, N, N′-tetra Methyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- Aromatic ketones such as (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert -Butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzant Quinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3 -Quinones such as dimethyl anthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 1,2-octanedione-1- [4- ( Oximes such as phenylthio) phenyl] -2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) Ester compounds; Benzyl derivatives such as dimethyl dimethyl ketal; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenyl 2,4,5-triarylimidazole dimers such as imidazole dimer; acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane; N-phenylglycine, N- Examples include phenylglycine derivatives, coumarin compounds, and oxazole compounds. Moreover, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  Among these, an oxime ester compound or a phosphine oxide compound is preferable from the viewpoint of transparency and pattern forming ability at 10 μm or less.

  (C) It is preferable that the content rate of a photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of total amounts of all the photopolymerizable compounds contained in a binder polymer and the photosensitive resin layer, 2 More preferably, it is -15 mass parts, and it is especially preferable that it is 5-12 mass parts. In terms of excellent photosensitivity, it is preferably 0.1 parts by mass or more, and in terms of excellent internal photocurability, it is preferably 20 parts by mass or less.

  The photosensitive resin layer 3 can further contain an organic peroxide from the viewpoint of reducing the water absorption of the cured film. Organic peroxides include tertiary butyl oxylaurate, benzoyl peroxide, acetyl peroxide, t-butyl hydrooxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1 , 1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, p-menthane hydroperoxide, di-t-butyl peroxide , Di-isopropylbenzene hydroperoxide, t-butylcumyl peroxide, α, α-bis a (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl Peroxy) hexane, 3,3 ′, 4,4 ′,-tetra-(-t-butyl) Loperoxycarbonyl) benzophenone, di-cumyl peroxide and the like. From the viewpoint of ease of use, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 100 ° C. or higher. An organic peroxide can be used individually by 1 type or in combination of 2 or more types.

  The content ratio of the organic peroxide is preferably 0.1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. It is particularly preferably 5 to 12 parts by mass.

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

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

  The photosensitive resin layer 3 can be applied by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. After coating, drying for removing the organic solvent and the like can be performed at 70 to 150 ° C. for about 5 to 30 minutes with a hot air convection dryer or the like.

  Although the thickness of the photosensitive resin layer 3 changes with uses, it is preferable that it is 1-200 micrometers in thickness after drying, it is more preferable that it is 1-15 micrometers, and it is especially preferable that it is 1-10 micrometers. If the thickness is less than 1 μm, coating tends to be difficult, and if it exceeds 200 μm, the sensitivity due to the decrease in light transmission is insufficient, and the photocuring property of the photosensitive resin layer to be transferred tends to decrease.

  In the photosensitive conductive film of this embodiment, the laminate of the conductive film 2 and the photosensitive resin layer 3 has a minimum light transmission in a wavelength region of 450 to 650 nm when the total film thickness of both layers is 1 to 10 μm. The rate is preferably 80% or more, and more preferably 85% or more. When the conductive film and the photosensitive resin layer satisfy such conditions, it is easy to increase the brightness in a display panel or the like.

  In the photosensitive conductive film of the present embodiment, a protective film can be laminated so as to be in contact with the surface of the photosensitive resin layer 3 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, and a polyethylene film can be used. Moreover, you may use the polymer film similar to the above-mentioned support body film as a protective film.

  The adhesive force between the protective film and the photosensitive resin layer 3 is such that the conductive film 2 and the photosensitive resin layer 3 and the support film 1 have an adhesive force so that the protective film is easily peeled from the photosensitive resin layer. Is preferably smaller.

Moreover, it is preferable that the number of fish eyes with a diameter of 80 micrometers or more contained in a protective film is 5 pieces / m < ² > or less. “Fish eye” means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

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

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

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

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

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

<Method for forming conductive pattern>
As shown in FIG. 3, the photosensitive resin layer 3 of 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 ((a) of FIG. 3), Next, the photosensitive layer 4 composed of the conductive film 2 and the photosensitive resin layer 3 is irradiated with an actinic ray L in a pattern through a mask 5 ((b) of FIG. 3), and an uncured portion (unexposed) is developed by a development process. The conductive pattern (conductive film 2a) is formed by removing the portion (FIG. 3C). The conductive pattern thus obtained has the thickness of the cured resin layer (cured film) 3b in addition to the thickness of the conductive film 2a. These thicknesses become a step Hb with the substrate, and if this step is large, it becomes difficult to obtain the smoothness required for a display or the like. Moreover, since a conductive pattern will be easily visually recognized if a level | step difference is large, what is necessary is just to use properly with the method shown in the following FIG.

  FIG. 4 is a schematic cross-sectional view for explaining another embodiment of a method for forming a conductive pattern using a photosensitive conductive film. In this embodiment, as shown in FIG. 4, the step of laminating the photosensitive resin layer 3 of the photosensitive conductive film 10 having the support film 1, the conductive film 2, and the photosensitive resin layer 3 on the substrate 20 (FIG. 4). (A)), a first exposure step (FIG. 4 (b)) in which a predetermined portion of the photosensitive layer 4 having the support film 1 is irradiated with actinic rays, and then the support film 1 is peeled off, In the presence of oxygen, after the second exposure step (FIG. 4 (c)) in which a part or all of the exposed and unexposed portions in the first exposure step are irradiated with actinic rays, and the second exposure step. It is preferable to include a development step of forming a conductive pattern by performing development processing on the photosensitive layer. Thereby, the resin cured layer (cured film) and the conductive film are included on the substrate in this order from the substrate side, and the portion where the resin cured layer (cured film) does not have the conductive film on the side opposite to the substrate and the conductive film A conductive pattern including a portion having a conductive pattern can be provided, and the step of the conductive pattern can be compared to the case where a conductive pattern in which the cured resin layer (cured film) and the conductive film have the same pattern is provided on the substrate. Can be reduced.

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

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

  As an exposure method in the first exposure step of irradiating a predetermined portion of the photosensitive resin layer on the substrate with the support film attached thereto, the active light is imaged through a negative or positive mask pattern called artwork. And a method of irradiating (mask exposure method). As the light source of actinic light, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, an Ar ion laser, a semiconductor laser, or the like that effectively emits ultraviolet light, visible light, or the like is also used. Furthermore, what effectively radiates | emits visible light, such as a photographic flood light bulb and a solar lamp, is also used. Alternatively, a method of irradiating actinic rays in an image shape by a direct drawing method using a laser exposure method or the like may be employed.

The exposure amount of the first exposure step may vary depending on the composition of the device and the photosensitive resin composition used, preferably ^{5mJ / cm 2 ~1000mJ / cm 2} , more preferably 10mJ ^/ cm 2 ~200mJ / Cm ² . In terms of excellent photocurability, it is preferably 10 mJ / cm ² or more, and in terms of resolution, it is preferably 200 mJ / cm ² or less.

  As a light source in the second exposure step of irradiating actinic rays after peeling off the support film, a known light source, for example, an ultraviolet ray such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, etc. Those that effectively radiate visible light or the like are used. Further, an Ar ion laser, a semiconductor laser, or the like that effectively emits ultraviolet light, visible light, or the like is also used. Furthermore, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can also be used.

The exposure amount in the second exposure step may vary depending on the composition of the device and the photosensitive resin composition used, preferably ^{5mJ / cm 2 ~1000mJ / cm 2} , more preferably 10mJ ^/ cm 2 ~200mJ / Cm ² . In terms of excellent photocurability, it is preferably 10 mJ / cm ² or more, and in terms of work efficiency, it is preferably 200 mJ / cm ² or less. The exposure amount of the second exposure step is to utilize the fact that the reactive species generated from the initiator by exposure is deactivated by oxygen from the surface by removing the support film and exposing, Excessive exposure is not preferable because it sufficiently cures.

  The atmosphere in which the exposure in the second exposure step is performed requires the presence of oxygen, and exposure in the air is preferable. It does not matter even if the oxygen concentration is increased.

  In the development process of the present embodiment, the sufficiently uncured surface portion of the photosensitive resin layer exposed in the second exposure process in which actinic rays are irradiated after peeling off the support film is removed. Specifically, as the development processing, the surface portion of the photosensitive resin layer that is not sufficiently cured, that is, the surface layer including the conductive film is removed by wet development. As a result, the conductive film having a predetermined pattern remains on the cured resin layer in the region exposed in the second exposure process, and there is no conductive film in the portion removed in the development process, and only the cured film of the photosensitive resin layer. Pattern is formed. Therefore, in the development process, the entire photosensitive resin layer is removed from the part that is not exposed in both the first and second exposure processes.

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

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

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

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

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

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

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

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

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

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

<Conductive pattern substrate>
The conductive pattern substrate of this embodiment is a conductive pattern substrate comprising a substrate, and a conductive pattern provided on the substrate, the conductive pattern including a cured film of the photosensitive resin composition and a conductive film in this order from the substrate side, and cured. The membrane has a water absorption of 1.8% or less when contacted with distilled water at 60 ° C. for 1 hour. This conductive pattern substrate can be obtained by the conductive pattern forming method described above. In addition, the said water absorption can be calculated | required similarly to the measuring method of the water absorption described in the Example mentioned later.

  From the viewpoint of effective use as a transparent electrode, the surface resistivity of the conductive film or conductive pattern is preferably 2000 Ω / □ or less, more preferably 1000 Ω / □ or less, and particularly preferably 500 Ω / □ or less. preferable. The surface resistivity can be adjusted by, for example, the concentration of the conductive fiber or the dispersion of the organic conductor or the coating amount.

  In the conductive pattern substrate of this embodiment, the minimum light transmittance in the wavelength region of 450 to 650 nm is preferably 80% or more, and more preferably 85% or more.

  From the viewpoint that the conductive pattern is hardly visible, the cured film preferably includes a portion that does not have a conductive film on the side opposite to the substrate. This conductive pattern substrate can be obtained by the conductive pattern forming method having the above-described two exposure steps.

<Touch panel sensor>
A touch panel sensor according to the present invention includes the conductive pattern substrate.

  FIG. 5 is a schematic top view illustrating 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 surface of a transparent substrate 101, and a transparent electrode 103 that detects a change in capacitance in this region and uses it as an X position coordinate; A transparent electrode 104 having Y position coordinates is provided. Each of the transparent electrodes 103 and 104 having the X and Y position coordinates includes a lead wire 105 for connecting to a driver element circuit for controlling an electric signal as a touch panel, and the lead wire 105 and the transparent electrodes 103 and 104. A connection electrode 106 for connecting the two is disposed. Further, a connection terminal 107 connected to the driver element circuit is disposed at the end of the lead-out wiring 105 opposite to the connection electrode 106.

  FIG. 6 is a schematic view showing an example of a method for manufacturing the touch panel sensor shown in FIG. In the present embodiment, the transparent electrodes 103 and 104 are formed by the conductive pattern forming method according to the present embodiment. First, as shown in FIG. 6A, a transparent electrode (X position coordinate) 103 is formed on a transparent substrate 101. Specifically, the photosensitive conductive film 10 is laminated so that the photosensitive resin layer 3 is in contact with the transparent substrate 101. The transferred photosensitive layer 4 (the conductive film 2 and the photosensitive resin layer 3) is irradiated with an actinic ray in a desired shape through a light-shielding mask (first exposure step). Thereafter, the light shielding mask is removed, the support film is further peeled off, and the photosensitive layer 4 is irradiated with actinic rays (second exposure step). By performing development after the exposure step, the conductive film 2 is removed together with the photosensitive resin layer 3 that is not sufficiently cured, and a conductive film 2a having a predetermined pattern is formed. A transparent electrode 103 (conductive pattern) for detecting the X position coordinate is formed by the conductive film 2a having the predetermined pattern (FIG. 6B). FIG. 6B is a schematic cross-sectional view taken along the line II of FIG. By forming the transparent electrode 103 by the method for forming a conductive pattern according to the present invention, the transparent electrode 103 with a small step can be provided.

  Subsequently, as shown in FIG. 6C, a transparent electrode (Y position coordinate) 104 (conductive pattern) is formed. A new photosensitive conductive film 10 is further laminated on the substrate 101 including the transparent electrode 103 formed by the above-described process, and the transparent electrode 104 for detecting the Y position coordinate is formed by the same operation as described above (see FIG. 6 (d)). FIG.6 (d) is a schematic cross section of the II-II cut surface of FIG.6 (c). By forming the transparent electrode 104 by the conductive pattern forming method according to the present invention, even when the transparent electrode 104 is formed on the transparent electrode 103, reduction in aesthetics due to stepping or entrainment of bubbles is sufficiently suppressed. A touch panel sensor with high smoothness can be created.

  Next, on the surface of the transparent substrate 101, a lead wire 105 for connecting to an external circuit and a connection electrode 106 for connecting the lead wire and the transparent electrodes 103 and 104 are formed. In FIG. 6, the lead line 105 and the connection electrode 106 are shown to be formed after the formation of the transparent electrodes 103 and 104, but they may be formed simultaneously with the formation of the transparent electrodes. The lead line 105 can be formed at the same time as the connection electrode 106 is formed by screen printing using a conductive paste material containing flaky silver, for example.

  7 and 8 are partial cross-sectional views along a-a 'and b-b' shown in FIG. 5, respectively. These indicate the intersections of the transparent electrodes at the XY position coordinates. As shown in FIGS. 7 and 8, the transparent electrode is formed by the conductive pattern forming method according to the present invention, so that a touch panel sensor with small steps and high smoothness can be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

  (B), (C) and other components used in Examples and Comparative Examples are as follows.

<(B) component>
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name).
DCP: Tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name).
FA-513M: Dicyclopentanyl methacrylate: (manufactured by Hitachi Chemical Co., Ltd., trade name)

<Photopolymerizable compound other than component (B)>
T-1420: Ditrimethylolpropane tetraacrylate (Nippon Kayaku Co., Ltd., trade name)

<(C) component>
Irgacure-TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name, manufactured by BASF Corp.)

<Preparation of Conductive Dispersion (Conductivity Forming Coating Liquid (Silver Fiber Dispersion))> [Preparation of Silver Fiber by Polyol Method]
Production Example 1
In a 2000 ml three-necked flask, 500 ml of ethylene glycol was placed and heated to 160 ° C. with an oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. A solution prepared by dissolving ₂ mg of PtCl ₂ separately prepared in 50 ml of ethylene glycol was added dropwise thereto. After 4 to 5 minutes, a solution in which 5 g of AgNO ₃ was dissolved in 300 ml of ethylene glycol and a solution in which 5 g of polyvinylpyrrolidone having a weight average molecular weight of 40,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 150 ml of ethylene glycol were respectively obtained. From the dropping funnel in 1 minute, and then stirred at 160 ° C. for 60 minutes.

  The reaction solution was allowed to stand at 30 ° C. or lower, diluted 10 times with acetone, centrifuged at 2000 rpm for 20 minutes with a centrifuge, and the supernatant was decanted. Acetone was added to the precipitate, stirred, and then centrifuged under the same conditions as described above, and acetone was decanted. Then, it centrifuged twice similarly using distilled water, and obtained the silver fiber. When the obtained silver fiber was observed with an optical microscope, the fiber diameter (diameter) was about 5 nm, and the fiber length was about 5 μm.

[Preparation of silver fiber dispersion]
The silver fiber obtained above was dispersed in pure water so that the concentration was 0.2% by mass and dodecyl-pentaethylene glycol was 0.1% by mass to obtain a silver fiber dispersion.

<Preparation of component solution (A)> [Preparation of binder polymer solution (A1)]
Production Example 2
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 1, heated to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was 80 ° C. ± 2 While maintaining the temperature, (2) shown in Table 1 was added dropwise uniformly over 4 hours. After dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution (solid content 50 wt%) (A1) having a weight average molecular weight of about 42,000. The acid value of (A1) was 196 mgKOH / g.

  In Production Example 2, the weight average molecular weight and acid value were measured by the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below. GPC conditions Pump: Hitachi L-6000 type (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)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

(2) Acid value The acid value was measured as follows. First, the binder polymer solution prepared above was heated at 130 ° C. for 1 hour to remove volatile components, thereby obtaining a solid content. Then, after precisely weighing 1 g of the polymer whose acid value is to be measured, the precisely weighed polymer was put into an Erlenmeyer flask, 30 g of acetone was added to this polymer, and this was uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula. Acid value = 10 × Vf × 56.1 / (Wp × I) (where Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the weight (g) of the measured resin solution, and I represents the measurement. The ratio (% by mass) of the non-volatile content in the obtained resin solution is indicated.)

<Preparation of photosensitive conductive film> [Preparation of conductive film (conductive film of photosensitive conductive film)] (Example 1)
The silver fiber dispersion obtained above was uniformly applied at 25 g / m ² on a 50 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”) as a support film. The film was dried for 3 minutes with a hot air convection dryer at 100 ° C. to form a conductive film. The film thickness after drying of the conductive film was about 0.1 μm, and the sheet resistance value measured by EC-80P manufactured by Napson Co., Ltd. was 50 ± 10Ω / □.

[Preparation of photosensitive resin composition solution]
The materials shown in Table 4 were mixed in the blending amounts (parts by weight) shown in Table 4 for 15 minutes using a stirrer to prepare a photosensitive resin composition solution for a photosensitive conductive film. In addition, the compounding quantity of (A) component in a table | surface is the weight part of solid content except a solvent.

[Preparation of photosensitive conductive film]
The photosensitive resin composition solution obtained above was uniformly applied onto a 50 μm-thick polyethylene terephthalate film on which a conductive film was formed with the conductive film obtained above, and 10 times with a hot air convection dryer at 100 ° C. The photosensitive resin layer was formed by drying for a minute. Thereafter, 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. In addition, the film thickness after drying of the photosensitive resin layer was 5 micrometers.

<Measurement of water absorption rate of photosensitive resin layer of photosensitive conductive film>
The photosensitive resin composition solution obtained above is uniformly applied to a 50 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”), which is a support film, at 100 ° C. The photosensitive resin layer was formed by drying for 10 minutes with a hot air convection dryer. Thereafter, 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 film. In addition, the film thickness after drying of the photosensitive resin layer was 5 micrometers. Laminator (manufactured by Hitachi Chemical Co., Ltd., product) so that the photosensitive resin layer is in contact with the 0.5 mm thick SUS304 (W1) substrate measured in advance while peeling the polyethylene film of the obtained photosensitive film. Using a substrate having a roll temperature of 110 ° C., a substrate feed speed of 0.6 m / min, and a pressure (cylinder pressure) of 4 × 10 ⁵ Pa (thickness of 1 mm, length of 10 cm × width of 10 cm). Therefore, the substrate was laminated under the condition that the linear pressure was 9.8 × 10 ³ N / m), and a substrate (laminated substrate) in which the photosensitive resin layer and the support film were laminated on the SUS304 substrate was produced. .

Next, the obtained multilayer substrate was irradiated with ultraviolet rays at a dose of 1 J / cm ² (measured value at i-line (wavelength 365 nm)) using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.). Then, it was heated at 140 ° C. for 30 minutes with a hot air convection dryer. It cooled to 23 +/- 2 degreeC, and obtained the sample (W2) for the water absorption rate measurement of the photosensitive resin layer (film thickness of 5.0 micrometers).

Next, a sample for water absorption was added to distilled water at 60 ° C., and the mixture was kept warm for 1 hour to absorb water. Thereafter, it was cooled to 23 ± 2 ° C. while immersed in distilled water. After cooling, the sample was taken out, excess water was wiped off, and the weight was measured (W3). After the weight measurement, it was dried at 140 ° C. for 1 hour with a dryer and cooled to 23 ° C. in a desiccator, and then the weight (W4) was measured.
The water absorption was calculated according to the following formula (1). The results are shown in Table 2.
Water absorption rate (%) = [(W3-W4) / (W4-W1)] × 100 (1)

<Measurement of reaction rate>
While peeling the protective film of the photosensitive conductive film obtained above on the surface of a 125 μm-thick PET film (trade name “Cosmo Shine-A300” manufactured by Toyobo Co., Ltd.), the photosensitive resin layer was placed on the PET film. Was laminated under the conditions of 110 ° C., 0.6 m / min, and 0.4 MPa. After the lamination, light was irradiated from the support film side with an exposure amount of 40 mJ / cm ² using an exposure machine having a high-pressure mercury lamp (trade name “EXM-1201” manufactured by Oak Seisakusho Co., Ltd.). After light irradiation, the support film was peeled off and irradiated with light at an exposure amount of 100 mJ / cm2. The sample was further irradiated with an exposure dose of 1 J / cm ² using a UV exposure machine, and then thermally cured at 140 ° C./30 minutes using a hot air convection dryer to obtain a sample (a) for reaction rate measurement. The sample for reaction rate measurement was the unexposed film (b) as a reference.

Samples for the reaction rate measured (a) and (b) FT-IR (VERTEX 70, Bluker Co., Ltd.) Was calculated from the peak of ^{810 cm} -1, 1730 cm ^-1 was used to calculate the reaction rate. The results are shown in Table 2.

<Formation of conductive pattern>
While peeling the protective film of the photosensitive conductive film obtained above on the surface of a 125 μm-thick PET film (trade name “Cosmo Shine-A300” manufactured by Toyobo Co., Ltd.), the photosensitive resin layer was placed on the PET film. Was laminated under the conditions of 110 ° C., 0.6 m / min, and 0.4 MPa.

After lamination, when the PET film is cooled and the temperature of the substrate reaches 23 ° C., a step tablet for investigating photosensitive characteristics (S / T; L / S = x / 400, x = 6 to 47) is covered and supported. Using an exposure machine having a high-pressure mercury lamp from the film side (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.), light irradiation was performed at an exposure amount of 40 mJ / cm ² . After light irradiation, the support film was peeled off and irradiated with light at an exposure amount of 100 mJ / cm ² .

Next, development was performed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 40 seconds. Further, an exposure dose of 1 J / cm ² was irradiated with a UV exposure machine.

  By the above operation, the conductive pattern shown in FIG. 3C was formed on the PET film.

  As an evaluation of missing resolution, the line width of a line / space (L / 400 μm) pattern was measured. The narrower the line width, the higher the resolution. The results are shown in Table 2.

  As shown in Table 2, it can be seen that the photosensitive conductive films of Examples 1 to 3 have a water absorption rate of the cured film of 1.8% or less and a patterning property equivalent to that of Comparative Example 1.

  DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Conductive film, 2a ... Conductive film which has a predetermined pattern, 3 ... Photosensitive resin layer, 3a, 3b ... Resin hardened layer, 4 ... Photosensitive layer, 5 ... Mask pattern, 10, 12 ... Photosensitive Conductive film, 20 ... substrate, 40, 42 ... conductive pattern substrate, 101 ... transparent substrate, 102 ... touch screen, 103 ... transparent electrode (X position coordinate), 104 ... transparent electrode (Y position coordinate), 105 ... lead wiring , 106 ... connection electrode, 107 ... connection terminal.

Claims (10)

A support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film,
The photosensitive conductive film in which the photosensitive resin layer contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond and an alicyclic skeleton, and (C) a photopolymerization initiator.   The photosensitive conductive film of Claim 1 whose water absorption is 1.8% or less when the cured film which hardened | cured the said photosensitive resin layer was made to contact distilled water of 60 degreeC for 1 hour.   The photosensitive conductive film of Claim 1 or 2 in which the said electrically conductive film contains a conductive fiber.   The photosensitive conductive film according to claim 3, wherein the conductive fibers are silver fibers. Laminating the photosensitive conductive film according to any one of claims 1 to 4 so that the photosensitive resin layer is in contact with a substrate;
An exposure step of irradiating the photosensitive layer formed by the photosensitive resin layer and the conductive film with actinic rays in a pattern;
A step of developing the photosensitive layer after the exposure step;
A method for forming a conductive pattern. Laminating the photosensitive conductive film according to any one of claims 1 to 4 so that the photosensitive resin layer is in contact with the substrate;
A first exposure step of irradiating the photosensitive layer formed by the photosensitive resin layer and the conductive film with an actinic ray in a pattern;
A second exposure step of irradiating a part or all of the unexposed portion in the first exposure step of the photosensitive layer with actinic rays in the presence of oxygen;
A step of developing the photosensitive layer after the second exposure step;
A method for forming a conductive pattern. A method for manufacturing a conductive pattern substrate, comprising: a substrate; and a conductive pattern provided on the substrate,
The manufacturing method of the conductive pattern board | substrate which forms the said conductive pattern with the formation method of the conductive pattern of Claim 5 or 6.   A conductive pattern substrate comprising a substrate and a conductive pattern provided on the substrate and including a cured film of the photosensitive resin composition and a conductive film in this order from the substrate side, wherein the cured film is distilled water at 60 ° C. A conductive pattern substrate having a water absorption rate of 1.8% or less when contacted for 1 hour.   The conductive pattern substrate according to claim 8, wherein the cured film includes a portion that does not have a conductive film on a side opposite to the substrate.   A touch panel sensor comprising the conductive pattern substrate according to claim 8.

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