JP6205925B2 - Photosensitive conductive film, conductive pattern forming method using the same, and conductive pattern substrate - Google Patents

Description

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

  Liquid crystal display elements and 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 can detect multiple fingertips, so it has a good operability to give complex instructions. 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 for the electrode.

  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.

  ITO films and tin oxide films 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 Patent Publication No. 2010/021224 International Patent Publication No. 2013/051516

  By using the method for forming a photosensitive conductive film disclosed in Patent Document 2, sensor electrodes (conductive patterns) of touch panels can be easily formed on various substrates by a photolithography process. However, when the conductive pattern is passed through the slightly adhesive roll for removing foreign matter on the conductive pattern, there is a problem that the conductive pattern is disconnected.

  As a result of diligent studies to solve the above problems, the present inventors have found that static electricity generated in the photosensitive resin layer portion flows in the conductive pattern, and that the conductive pattern is damaged, and the photosensitive pattern in which disconnection failure due to static electricity does not occur. Invented a conductive film.

The present invention is a photosensitive conductive film having 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,
(A) a binder polymer,
(B) a photopolymerizable compound having an ethylenically unsaturated bond,
(C) contains a photopolymerization initiator,
Provided is a photosensitive conductive film, wherein a volume resistivity of a cured film obtained by curing the photosensitive resin layer is less than 1 × 10 ¹³ Ω · cm.

  Moreover, this invention provides the photosensitive conductive film characterized by containing (D) antistatic agent.

  The present invention also provides a photosensitive conductive film, wherein the conductive film contains at least one conductive fiber.

  Moreover, this invention provides the photosensitive conductive film whose said conductive fiber is silver fiber.

  In addition, the present invention includes a step of laminating the photosensitive conductive film so that the photosensitive resin layer is in contact with the substrate, and an actinic ray in a pattern on the photosensitive layer formed by the photosensitive resin layer and the conductive film. There is provided a method for producing a conductive pattern comprising an exposure step of irradiating and a step of developing an unexposed portion of the photosensitive layer.

In addition, the present invention includes a step of laminating the photosensitive conductive film so that the photosensitive resin layer is in contact with the substrate, and an actinic ray in a pattern on the photosensitive layer formed by the photosensitive resin layer and the conductive film. A first exposure step of irradiating
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;
And a step of developing the photosensitive layer after the second exposure step.

  Furthermore, this invention provides a conductive pattern board | substrate provided with a board | substrate and the conductive pattern formed on the said board | substrate by the manufacturing method of the said conductive pattern.

The present invention is a conductive pattern substrate having a substrate and a cured film of a patterned conductive film and a photosensitive resin layer provided on the substrate, and the volume resistivity of the cured film is 1 × 10 ¹³ Ω. A conductive pattern substrate that is less than cm.

  Moreover, this invention provides a touchscreen sensor provided with the said conductive pattern board | substrate.

  According to the photosensitive conductive film of the present invention, it is possible to form a conductive pattern that does not cause disconnection failure due to static electricity.

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” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl”, and “(meth) acryloyl” means “acryloyl” and “methacryloyl”.

<Photosensitive conductive film>
The photosensitive conductive film according to the present invention is a photosensitive conductive film having a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film. The resin layer contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, and the volume resistance of a cured film obtained by curing the photosensitive resin layer. The rate is less than 1 × 10 ¹³ Ω · cm.

  In this specification, the boundary between the conductive film and the photosensitive resin layer is not necessarily clear. Any conductive film may be used as long as conductivity is obtained in the surface direction of the photosensitive layer, and the conductive resin may be mixed with the photosensitive resin layer. 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 a photosensitive conductive film used in the present invention. 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 a conductive film 2 and a photosensitive resin provided on the conductive film 2. It consists of layer 3.

  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 viewpoint of transparency and heat resistance. In addition, since these polymer films must be removable from the photosensitive resin layer later, they may have been subjected to a surface treatment or a material that makes removal impossible. Don't be.

  Moreover, it is preferable that the thickness of the support film 1 is 5-300 micrometers, It is more preferable that it is 10-200 micrometers, It is especially preferable that it is 15-100 micrometers. 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.). .

  The conductive film 2 can be used without any particular limitation, but preferably contains at least one kind of conductive 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.

  Moreover, an organic conductor can be used for the conductive film 2 together with conductive fibers. The organic conductor can be used without any particular limitation, but an organic conductor such as a polymer of a thiophene derivative or an aniline derivative is preferably used. Specifically, polyethylenedioxythiophene, polyhexylthiophene, or polyaniline 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 of the present invention and the required conductivity, but is preferably 1 μm or less, and preferably 1 nm to 0.5 μm. Is more preferable, and it is especially preferable that it is 5 nm-0.1 micrometer.
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.

  The conductive film 2 is, for example, a conductive dispersion obtained by adding the above-described conductive fiber or organic conductor to the support film 1 with water and / or an organic solvent and, if necessary, a dispersion stabilizer such as a surfactant. After coating, it can be formed by drying. 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 or the organic conductor may coexist with a surfactant or a 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 or formed, or each may be formed by sequentially applying each of them. For example, it can be formed by applying conductive fibers and then applying and drying an organic conductor solution.

  The photosensitive resin layer 3 is formed from a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. Can be mentioned.

  (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 monomer units derived from a polymerizable monomer having a (meth) acrylic group.

  The said acrylic resin can use what is manufactured by radically polymerizing the polymerizable monomer which has a (meth) acryl group. These acrylic resins can be used alone or in combination of two or more.

  Examples of the polymerizable monomer having a (meth) acryl 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.

  The acrylic resin is substituted at the α-position or aromatic ring such as styrene, vinyltoluene, α-methylstyrene, etc., in addition to the polymerizable monomer having the (meth) acrylic group as described above. 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.

  These (A) binder polymers can be used alone or in combination of two or more. 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.

The binder polymer (A) in the present invention is preferably selected from those having a low volume resistivity. For example, since the volume resistivity of polystyrene resin is as high as 10 ¹⁶ to 10 ¹⁹ Ω · cm, an acrylic resin having no cyclic structure such as styrene is preferable. Furthermore, although the volume resistivity decreases as the acid value increases, the acid value of the (A) binder polymer is preferably 75 to 200 mgKOH / g, preferably 75 to 190 mgKOH / g in consideration of resolution and other characteristics. g is more preferable, and 75 to 185 mgKOH / g is particularly preferable. When it exceeds 250 mgKOH / g, the developing solution resistance of the photocured photosensitive resin layer tends to be lowered.
The volume resistivity of the cured photosensitive resin layer can be adjusted by components (A) and (B) and further by component (D).

Next, (B) the photopolymerizable compound having an ethylenically unsaturated bond will be described.
Examples of the photopolymerizable compound having an ethylenically unsaturated bond include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid. Compound obtained by reaction, urethane monomer such as (meth) acrylate compound having urethane bond, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β Examples thereof include phthalic acid compounds such as '-(meth) acryloyloxyethyl-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) A photopolymerizable compound having an ethylenically unsaturated bond is preferably selected from those having a low volume resistivity.

  (B) It is preferable that the content rate of the photopolymerizable compound which has an ethylenically unsaturated bond is 30-80 mass parts with respect to 100 mass parts of total amounts of a binder polymer and a photopolymerizable compound, and 40-70 masses. More preferably, it is a part. In terms of excellent photocurability and coating properties of the transferred conductive film (conductive film and photosensitive resin layer), it is preferably 30 parts by mass or more, and in terms of excellent storage stability when wound as a film. 80 parts by mass or less is 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, oxime ester compounds are preferable from the viewpoint of transparency and pattern forming ability at 10 μm or less. Examples of the oxime ester compound include compounds represented by the following general formula (C-1) and general formula (C-2). From the viewpoint of fast curability and transparency, a compound represented by the following general formula (C-1) is preferred.

上記一般式（Ｃ−１）中、Ｒ^１は、炭素数１〜１２のアルキル基、又は炭素数３〜２０のシクロアルキル基を示す。尚、本発明の効果を阻害しない限り、上記一般式（Ｃ−１）中の芳香環上に置換基を有していてもよい。

In the general formula (C-1), R ¹ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. In addition, unless the effect of this invention is inhibited, you may have a substituent on the aromatic ring in the said general formula (C-1).

上記一般式（Ｃ−２）中、Ｒ^２は、水素原子又は炭素数１〜１２のアルキル基、を示し、Ｒ^３は、炭素数１〜１２のアルキル基、又は炭素数３〜２０のシクロアルキル基を示し、Ｒ^４は、炭素数１〜１２のアルキル基を示し、Ｒ^５は、炭素１〜２０のアルキル基又はアリール基を示す。ｐ１は０〜３の整数を示す。尚、ｐ１が２以上である場合、複数存在するＲ^４はそれぞれ同一でも異なっていてもよい。尚、カルバゾール上には本発明の効果を阻害しない範囲で置換基を有していてもよい。

In the general 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 or a cyclohexane having 3 to 20 carbon atoms. R ⁴ represents an alkyl group having 1 to 12 carbon atoms, and R ⁵ represents an alkyl group or aryl group having 1 to 20 carbon atoms. p1 represents an integer of 0 to 3. In the case p1 is 2 or more, or different R ⁴ existing in plural each identical. In addition, you may have a substituent on the carbazole in the range which does not inhibit the effect of this invention.

In the general formula (C-2), R ² is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferably.

In the general 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, and an alkyl group having 1 to 4 carbon atoms or a carbon number. 4 to 10 cycloalkyl groups are more preferable, and an ethyl group is particularly preferable.

Examples of the compound represented by the general formula (C-1) include (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like. Examples of the compound represented by the formula (C-2) include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime). 1,2-octanedione, 1- [4- (phenylthio) -phenyl, 2- (O-benzoyloxime)] is IRGACURE.
It is available as OXE 01 (BASF Corp., trade name). Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is IRGACURE.
It is commercially available as OXE 02 (trade name, manufactured by BASF Corporation). These are used alone or in combination of two or more.

  Of the general formula (1), 1,2-octanedione, 1- [4- (phenylthio) -phenyl, 2- (O-benzoyloxime)] is particularly preferable.

  (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 a binder polymer and a photopolymerizable compound, and it is 1-10 mass parts. More preferred is 1 to 5 parts by mass. 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.

  (D) It does not specifically limit as an antistatic agent, A well-known antistatic agent can be used. Specific examples include surfactants, tin oxide, antimony tin composite oxide (ATO), and metal oxides such as ITO. These may be used alone or in combination of two or more.

  Among the above, it is preferable to select a material having good compatibility with the photosensitive resin layer 3. In particular, a surfactant is preferable, a cationic or nonionic surfactant is more preferable, and it is more preferable to select a nonionic surfactant.

  Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyalkylene alkenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, poly Examples thereof include oxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, polyoxyethylenealkylalkanolamide, alkylamine oxide and the like.

  (D) The content ratio of the antistatic agent is preferably 20 parts by mass or less, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. 1 to 5 parts by mass is particularly preferable. In terms of excellent antistatic properties, the amount is preferably 0.1 parts by mass or more, and in terms of excellent light transmission, adhesiveness, and film strength, it is preferably 20 parts by mass or less.

  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 filler, an antifoaming agent, a flame retardant, a stabilizer, a leveling agent, Additives such as 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, as required, methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl. It can form by apply | coating and drying the solution of the photosensitive resin composition about 10-60 mass% of solid content melt | dissolved in solvents, such as ether, or these mixed solvents. 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 used in the present invention, 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 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 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 outermost.

  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 resin layer 3 is irradiated with an actinic ray L in a pattern form through a mask 5 (FIG. 3B), and an uncured portion (unexposed portion) is removed by development to remove a conductive pattern ( A conductive film 2a) is formed (FIG. 3C). The conductive pattern thus obtained has the thickness of the cured resin layer 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.

  As shown in FIG. 4, after the first exposure step (FIG. 3 (b)) in which a predetermined portion of the photosensitive layer 4 having the support film 1 is irradiated with actinic rays, the support film 1 is peeled off, and then the oxygen In the presence, it is preferable to include a second exposure step (FIG. 3C) in which a part or all of the exposed portion and the unexposed portion in the first exposure step are irradiated with actinic rays. Thereby, the step of the conductive pattern can be reduced as compared to the case where only the conductive pattern is provided on the substrate by providing the cured resin layer not having the conductive film together with the conductive pattern on the substrate.

  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 active light source, 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 or a photosensitive resin composition to be used, preferably from ^{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, the thing which radiates | emits visible light effectively, such as a flood bulb for photography, a solar lamp, is also used

The exposure amount in the second exposure step may vary depending on the composition of the device or a photosensitive resin composition to be used, preferably from ^{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, 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 photosensitive resin layer 3 is patterned. 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 scraping, 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 battle method, a spray method, brushing, and slapping. 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 heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary after development. Good.

The volume resistivity of the resin cured layer 3a of the present invention formed as described above is set so that the volume resistivity is less than 10 ¹³ Ω · cm.

  Volume resistivity is a measure of the ease of conducting electricity, and is a value indicating resistance per unit volume (1 cm × 1 cm × 1 cm). The volume resistivity may be measured by a known method, but a method of forming an electrode by metal vapor deposition on a cured film formed on a conductive metal substrate and measuring with a microammeter is preferable. In addition, since volume resistivity has temperature dependence, the volume resistivity of this invention shall be measured at 25 degreeC. Moreover, in order to avoid the influence of the conductive pattern 2a, the volume resistivity is measured in the state of the resin cured layer 3a alone.

After the formation of the conductive pattern, various processes such as production of wiring and adhesion treatment to another substrate may be performed. For example, in the step of passing the conductive pattern through the slightly adhesive roll for removing foreign matter, the conductive pattern is disconnected when the volume resistivity of the resin cured layer 3a is 1 × 10 ¹³ Ω · cm or more. This is not exposed in the first exposure step, and static electricity generated in the portion where only the resin cured layer 3a is left exposed in the second exposure step flows to the conductive pattern, and discharge occurs from the conductive film 2a. This is because the conductive film 2a is damaged. This phenomenon does not occur when the volume resistivity of the cured resin layer 3a is less than 1 × 10 ¹³ Ω · cm. The volume resistivity of the cured film of the cured resin layer 3 after curing according to the present invention is less than 10 ¹³ Ω · cm, preferably 10 ⁷ Ω · cm or more and less than 10 ¹² Ω · cm, particularly 10 ⁸ Ω · cm or more. It is preferably less than 10 ¹² Ω · cm. When the volume resistivity is less than 10 ⁸ Ω · cm, the conductivity of the cured resin layer 3a is increased, and there is a possibility that it may not function when used for a touch panel or the like.

<Conductive pattern substrate>
The conductive pattern substrate of the present invention has a substrate, a patterned conductive film provided on the substrate, and a cured film of a photosensitive resin layer, and the volume resistivity of the cured film is less than 1 × 10 ¹³ Ω · cm. is there.
This conductive pattern substrate can be obtained by the conductive pattern forming method described above.
From the viewpoint that it can be effectively used as a transparent electrode, the surface resistivity of the conductive film or conductive pattern is preferably 2000Ω / □ or less, more preferably 1000Ω / □ or less, and particularly preferably 500Ω / □ or less. preferable. The surface resistivity can be adjusted by, for example, the concentration of the conductive fiber or organic conductor dispersion or the coating amount.

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

<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 invention. 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 pattern 2a is formed. The transparent electrode 103 for detecting the X position coordinate is formed by the conductive pattern 2a (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, a transparent electrode (Y position coordinate) 104 is formed as shown in FIG. 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.

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

The components (B), (C), and (D) used in Examples and Comparative Examples are as follows.
<(B) component>
・ Trimethylolpropane triacrylate (TMPTA, Nippon Kayaku Co., Ltd.)

<(C) component>
1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (OXE-01, manufactured by BASF Corporation)

<(D) component>
Nonionic surfactant 1 (Unigri (registered trademark) GO-102R, manufactured by NOF Corporation)
Nonionic surfactant 2 (Elegan (registered trademark) S-100, manufactured by NOF Corporation)
Cationic surfactant 1 (Elegan (registered trademark) 264-WAX, manufactured by NOF Corporation)
Cationic surfactant 2 (New Elegan (registered trademark) AI, manufactured by NOF Corporation)
-Reactive surfactant (Blemmer (registered trademark) PE-200, manufactured by NOF Corporation)
Nonionic surfactant 3 (Electro Stripper EA, manufactured by Kao Corporation)
・ Nonionic surfactant 4 (Rheidol SP-L10, manufactured by Kao Corporation)
・ Special polycarboxylic acid type polymer surfactant (homogenol L-18, manufactured by Kao Corporation)
・ Nonionic surfactant 5 (Anstex SA-300F, manufactured by Toho Chemical Industry Co., Ltd.)

<Others>
-Octamethylcyclotetrasiloxane (SH-30, manufactured by Toray Dow Corning Co., Ltd.)
・ Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.)

Production Example 1
<Preparation of Conductive Dispersion (Conductivity Forming Coating Liquid (Silver Fiber Dispersion))>
[Preparation of silver fiber by polyol method]
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.

Production Example 2
<Preparation of component solution (A)>
[Preparation of binder polymer solution (A1)]
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.

[Preparation of binder polymer solution (A2)]
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 2, 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% by weight) (A2) having a weight average molecular weight of about 45,000. The acid value of (A2) was 78 mgKOH / g.

[Preparation of binder polymer solution (A3)]
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 2, 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 3 was uniformly added dropwise 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% by weight) (A3) having a weight average molecular weight of about 40,000. The acid value of (A3) was 176 mgKOH / g.

  In the said manufacture example, the weight average molecular weight and the acid value were measured with the following method.

(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 to obtain 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)
(In the formula, 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 proportion (mass%) of the non-volatile content in the measured resin solution. )

Example 1
<Preparation of photosensitive conductive film>
[Preparation of conductive film (conductive film of photosensitive conductive film)]
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. In addition, the film thickness after drying of the electrically conductive film was about 0.1 μm, and the sheet resistance value measured by NC-10 manufactured by Napson Co., Ltd. was 100 ± 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.

<Evaluation of sensitivity and resolution of photosensitive conductive film>
[sensitivity]
In order to investigate the sensitivity, while removing the polyethylene film of the obtained photosensitive conductive film, on the polyethylene terephthalate film (product name A4300, manufactured by Toyobo Co., Ltd., length 12 cm × width 12 cm, thickness 125 μm) Using a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000 type) so that the layers are in contact, under conditions of a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 105 Pa. Lamination was performed to produce a substrate in which a photosensitive conductive film was laminated on a polyethylene terephthalate film substrate.

Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) on the substrate on which the photosensitive conductive film is laminated, 41 steps from the support film side (above the photosensitive conductive film conductive film) A negative mask having a tablet was closely attached and irradiated with ultraviolet rays (measured value at i-line (wavelength 365 nm)) with an exposure amount of 40 mJ / cm ² . The negative mask and the support film were removed, and ultraviolet rays were irradiated from above the conductive film at an exposure amount of 50 mJ / cm ² (measured value at i-line (wavelength 365 nm)).

  After the exposure, the film was allowed to stand at room temperature (25 ° C.) for 15 minutes, and then developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. A conductive pattern was formed on the cured resin layer by development. The sensitivity was evaluated based on the number of remaining steps after development. When the sensitivity of the photosensitive conductive film obtained in this example was evaluated, it was 15 steps. Moreover, it was confirmed that the level | step difference with the resin cured layer of a conductive pattern is 0.1 micrometer. In addition, it means that it is so highly sensitive that the number of steps of the remaining step tablet is high (a numerical value is large).

[resolution]
In the same manner as the sensitivity evaluation, a photosensitive conductive film was laminated on a polyethylene terephthalate film. Next, a negative mask having a wiring pattern having a line width / space width of 30/30 to 200/200 (unit: μm) as a resolution evaluation negative is adhered from the support film side (above the photosensitive conductive film conductive film), Exposure and development were performed in the same manner as the sensitivity evaluation. Then, the resolution was evaluated based on the smallest value of the space width between the line widths in which the conductive film in the unexposed portion could be removed cleanly by the development process. It was 40 micrometers when the resolution of the photosensitive conductive film was evaluated. In addition, the evaluation of resolution means that it is so favorable that a numerical value is small.

<Measurement of volume resistivity 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., trade name: HLM-3000 type) so that the photosensitive resin layer is in contact with the SUS304 substrate having a thickness of 0.5 mm while peeling the polyethylene film of the obtained photosensitive film. Using a roll temperature of 110 ° C., a substrate feed speed of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa (thickness of 1 mm, length of 10 cm × width of 10 cm, the linear pressure at this time was 9 (8 × 10 ³ N / m) was laminated to produce a substrate (laminated substrate) in which a photosensitive resin layer and a support film were laminated on a SUS304 substrate.

Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Seisakusho Co., Ltd.) on the obtained multilayer substrate, the exposure amount is 40 mJ / cm ² from the support film side (measured value at i-line (wavelength 365 nm)). After irradiating with ultraviolet rays, the support film is removed, and subsequently, the cured photosensitive resin layer (film thickness) is irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd. A sample for volume resistivity measurement of 5.0 μm) was obtained.

Next, an electrode having a diameter of 50 mm was produced on the obtained sample by aluminum vapor deposition, and the volume resistance value was measured at a measurement temperature of 25 ° C. and a measurement voltage of DC 5 V using 8340A ULTRA HIGH RESISTANCE METER manufactured by ADC Co., Ltd. . The volume resistivity was calculated from the obtained volume resistance value by the following formula (1). The volume resistivity of the photosensitive resin layer of the photosensitive conductive film was 9.6 × 10 ¹² Ω · cm.

<Measurement of resistance increase rate of photosensitive conductive film and presence / absence of disconnection>
While peeling the polyethylene film of the obtained photosensitive conductive film, a laminator is placed so that the photosensitive resin layer is in contact with a polyethylene terephthalate film (product name: A4300, manufactured by Toyobo Co., Ltd., length 12 cm × width 12 cm, thickness 125 μm). (Hitachi Chemical Industry Co., Ltd., trade name: HLM-3000 type) is laminated under the conditions of a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure (cylinder pressure) of 4 × 105 Pa, and then polyethylene terephthalate A substrate in which a photosensitive conductive film was laminated on a film substrate was produced.

Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.), a line from the support film side (above the photosensitive conductive film conductive film) is applied to the substrate on which the photosensitive conductive film obtained is laminated. A negative mask having 10 line patterns having a length of 10 cm and a line width of 200 (unit: μm) was brought into close contact, and irradiated with ultraviolet rays at an exposure amount of 40 mJ / cm ² (measured value at i-line (wavelength 365 nm)). The negative mask and the support film are removed, and ultraviolet rays are irradiated from above the conductive film at an exposure amount of 50 mJ / cm ² (measured value at i-line (wavelength 365 nm)), and then an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd. is used. Then, ultraviolet rays were irradiated with an energy amount of 1 J / cm ² to obtain a sample in which the photosensitive resin layer and the conductive film were patterned.

  The chargeability was evaluated using the obtained chargeability evaluation sample. First, after removing the charge until the charge amount of the sample was within 0.05 KV, the resistance value between both ends of each conductive line pattern was measured using a pocket tester (CDM-03D manufactured by Custom Co., Ltd.). Thereafter, the TEKNEK fine adhesive roll was rolled on the conductive pattern at a constant speed, and the resistance value between both ends of each conductive line pattern was measured again. The room temperature during the experiment was 25 ° C. and the humidity was 25-30%. Based on the resistance values before and after the roller, the evaluation was made according to the following score.

◎; No change ○; Partial resistance increase (Increase rate is less than 10%)
△ ： Resistance increase in some areas (Increase rate of 10% or more)
×: Partially broken

  When the chargeability of the photosensitive conductive film was evaluated, there was no disconnection, and a partial resistance increase of less than 10% was observed.

Examples 2-12
A photosensitive conductive film was prepared and evaluated in the same manner as in Example 1 except that the photosensitive resin composition solution shown in Table 4 was used. The results are shown in Table 4.

Comparative Examples 1-3
A photosensitive conductive film was prepared and evaluated in the same manner as in Example 1 except that the photosensitive resin composition solution shown in Table 4 was used. The results are shown in Table 4.

As shown in Table 4, in Examples 1 to 12, it was found that the volume resistivity of the cured film was less than 10 ¹³ Ω · cm, and no breakage occurred even when a slightly adhesive roller was applied.

On the other hand, as shown in Table 4, in Comparative Examples 1 to 3, the volume resistivity of the cured film was 10 ¹³ Ω · cm or more, and disconnection occurred.

  According to the photosensitive conductive film of the present invention, it is possible to form a conductive pattern that does not cause disconnection failure due to static electricity.

  DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Conductive film, 2a ... Conductive pattern, 3 ... Photosensitive resin layer, 3a, 3b ... Resin hardened layer, 4 ... Photosensitive layer, 5 ... Mask pattern, 10, 12 ... Photosensitive conductive film, 20 ... Board, 40, 42 ... Conductive pattern board, 101 ... Transparent board, 102 ... Touch screen, 103 ... Transparent electrode (X position coordinate), 104 ... Transparent electrode (Y position coordinate), 105 ... Lead-out wiring, 106 ... Connection electrode 107 Connection terminals.

Claims (5)

A photosensitive conductive film having a support film, a conductive film containing conductive fibers 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,
(B) a photopolymerizable compound having an ethylenically unsaturated bond,
(C) contains a photopolymerization initiator,
The volume resistivity of the cured film obtained by curing the photosensitive resin layer is less than 1 × 10 ¹³ Ω · cm, and the cured film is a laminated substrate in which a substrate, the photosensitive resin layer, and the support film are laminated in this order. Then, the photosensitive resin layer on the substrate was irradiated with ultraviolet rays at an exposure dose of 40 mJ / cm ² at the i-line (wavelength 365 nm) from the support film side, and then the support film was removed to remove 1 J / cm ^2. A photosensitive conductive film which is cured by irradiating with an ultraviolet ray at an energy amount of, and whose volume resistivity is measured at 25 ° C.   The photosensitive conductive film according to claim 1, wherein the photosensitive resin layer contains (D) an antistatic agent. The conductive fibers, the photosensitive conductive film according to claim 1 or 2 which is silver fiber. Laminating the photosensitive conductive film according to any one of claims 1 to 3 so that the photosensitive resin layer is in contact with the substrate;
An exposure step of irradiating the photosensitive layer formed of the photosensitive resin layer and the conductive film with actinic rays in a pattern;
And a step of developing an unexposed portion of the photosensitive layer. Laminating the photosensitive conductive film according to any one of claims 1 to 3 so that the photosensitive resin layer is in contact with the substrate;
A first exposure step of irradiating the photosensitive layer formed of the photosensitive resin layer and the conductive film with actinic rays 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;
And a step of developing the photosensitive layer after the second exposure step.

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