TW201804259A - Method for producing multilayer pattern formed base and method for producing touch panel - Google Patents

Abstract

A method for producing a multilayer pattern formed base, which comprises a first light exposure step wherein a laminate that is obtained by sequentially laminating a base A, a photosensitive layer B and a transparent electrode layer C is exposed to light, a coating step wherein the surface of the laminate is coated with a photosensitive conductive paste D so as to obtain a photosensitive conductive film D, a second light exposure step wherein the photosensitive conductive film D is exposed to light, and a development step wherein the laminate and the photosensitive conductive film D are collectively developed at the same time, thereby obtaining a multilayer pattern that is composed of a transparent electrode pattern C and a conductive pattern D, and wherein the photosensitive layer B contains a photosensitive resin and a photopolymerization initiator, while the photosensitive conductive paste D contains conductive particles, a photosensitive resin and a photopolymerization initiator. Consequently, the present invention provides a method for producing a multilayer pattern formed base, which is able to suppress the generation of a residue during removal of an unexposed part by dissolution, while maintaining adhesion between a conductive pattern and a photosensitive resin layer formed on a base, and which has excellent ion migration resistance between the conductive pattern and the photosensitive resin layer.

Description

Laminated pattern forming substrate and manufacturing method of touch panel

Formed in the present invention relates to a method for manufacturing a conductive (laminated) pattern forming member (base material) and a touch panel.

The display electrodes formed on the display area of the capacitive touch panel are transparent electrodes including ITO (indium tin oxide) and the like. In the process of pattern processing, generally, a metal film such as ITO is attached to a substrate by sputtering or the like, and the surface is further coated with a photoresist having a photosensitive resin, and exposed through a photomask. After the photoresist pattern is formed by development, etching and photoresist removal are performed.

On the other hand, the following technology is also designed: by preparing to laminate the photosensitive resin layer and the transparent electrode on the substrate in advance, each time a pattern of the transparent electrode is formed, a photoresist is applied at the same time, which can be eliminated. Kung Fu (Patent Documents 1 and 2).

In the capacitive touch panel, a peripheral wiring connected to a transparent electrode is formed around the display area. As a method of forming the peripheral wiring, a method of finely processing a photosensitive conductive paste by a photolithography method is known (Patent Documents 3 to 7). In the case where a conductive paste is used to form a peripheral wiring connected to a transparent electrode pattern, the transparent electrode pattern is formed from a substrate on which the above-mentioned photosensitive resin layer and the transparent electrode layer are laminated, and must be formed on the substrate formed on the substrate. This process is performed after a conductive paste is applied to the surfaces of the photosensitive resin layer and the transparent electrode layer.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 2015-18157

Patent Document 2 Japanese Patent Application Publication No. 2014-199814

Patent Document 3 Japanese Patent No. 5276632

Patent Document 4 International Publication No. 2013/108696

Patent Document 5 Japanese Patent No. 5360285

Patent Document 6 Japanese Patent No. 5403187

Patent Document 7 International Publication No. 2013/146107

However, where a coating film of conductive paste is formed on the surface of the photosensitive resin layer on the substrate, the solvent in the conductive paste causes the photosensitive resin layer to swell, and the conductive particles contained in the conductive paste are buried in it. In the development step after the conductive paste is exposed through the photomask, not only residues are generated in the unexposed portion, but poor adhesion between the formed conductive pattern and the photosensitive resin layer also occurs, and the conductive pattern and the photosensitive resin layer also appear. The problem of ion migration.

Therefore, an object of the present invention is to provide a method for manufacturing a laminated pattern-forming substrate, which can suppress the occurrence of residues of unexposed portions during dissolution and removal, and keep the conductive pattern formed on the substrate and the photosensitive resin layer dense It is important that the conductive pattern and the photosensitive resin layer have excellent ion migration resistance.

In order to solve the above-mentioned problems, the present invention provides a laminated pattern forming substrate and a method for manufacturing a touch panel according to (1) to (7).

(1) A method for manufacturing a laminated pattern forming substrate, comprising: a first exposure step of exposing a laminated body formed by laminating the substrate A, the photosensitive layer B, and the transparent electrode layer C in this order; A coating step of coating the photosensitive conductive paste D on the surface to obtain the photosensitive conductive film D; a second exposure step of exposing the photosensitive conductive film D; developing the laminated body and the photosensitive conductive film D together to obtain a transparent electrode The step of developing a laminated pattern of the pattern C and the conductive pattern D; wherein the photosensitive layer B contains a photosensitive resin and a photopolymerization initiator, and the photosensitive conductive paste D contains conductive particles, a photosensitive resin, and a photopolymerization initiator.

(2) The method for producing a laminated pattern-forming substrate according to the above (1), wherein the first exposure step includes a step of exposing through a photomask and a step of exposing in a presence of oxygen without passing through a photomask.

(3) The method for producing a laminated pattern-forming substrate according to the above (1) or (2), further comprising a hardening step of heating the laminated pattern at 100 to 300 ° C.

(4) The manufacturing method of the laminated pattern formation base material as described in said (1)-(3) whose said transparent electrode layer contains a metal nanowire.

(5) The manufacturing method of the laminated pattern formation base material as described in said (4) containing silver nanowire as said metal nanowire.

(6) The method for producing a laminated pattern-forming substrate according to any one of (1) to (5) above, which contains silver particles as the conductive particles.

(7) A method for manufacturing a touch panel, comprising steps based on the manufacturing method described in any one of (1) to (6) above.

According to the manufacturing method of the present invention, it is possible to produce a residue that can prevent the unexposed part from being dissolved and removed, and maintain the adhesion between the conductive pattern and the photosensitive resin layer formed on the substrate, and furthermore, the conductive pattern and the photosensitive A laminated pattern forming base material having excellent ion migration resistance in a flexible resin layer.

1‧‧‧ conductive pattern D

2‧‧‧ transparent electrode layer C

3‧‧‧ Photosensitive layer B

4‧‧‧ Substrate A

5‧‧‧Printing area of photosensitive conductive paste D

6‧‧‧ Unexposed area of photosensitive conductive film D

7‧‧‧ exposed area of photosensitive conductive film D

8‧‧‧Terminal

FIG. 1 is a schematic diagram of a laminated pattern forming substrate.

FIG. 2 is a schematic diagram of a conductive pattern used for residue evaluation and adhesion evaluation.

FIG. 3 is a schematic diagram of a conductive pattern used for evaluation of ion migration resistance.

Aspects of the invention

Specific examples are given below to explain the present invention in detail.

The manufacturing method of the laminated pattern forming substrate of the present invention is the following manufacturing method of the laminated pattern forming substrate, which includes: exposing a laminated body laminated in the order of the substrate A, the photosensitive layer B, and the transparent electrode layer C. First exposure step; coating photosensitivity on the surface of the laminated body A conductive paste D, a coating step of obtaining a photosensitive conductive film D; a second exposure step of exposing the photosensitive conductive film D; and developing the laminated body and the photosensitive conductive film D together to obtain transparent electrode patterns C and The step of developing a laminated pattern of the conductive pattern D. The photosensitive layer B contains a photosensitive resin and a photopolymerization initiator, and the photosensitive conductive paste D contains conductive particles, a photosensitive resin, and a photopolymerization initiator.

In the present invention, the substrate A includes polyethylene terephthalate film (PET film), polyimide film, polyester film, aramid film, epoxy substrate, Polyetherimide resin substrates, polyetherketone resin substrates, polyfluorene-based resin substrates, glass substrates, silicon wafers, alumina substrates, aluminum nitride substrates, silicon carbide substrates, but not limited thereto.

In the present invention, as for the photosensitive resin constituting the photosensitive layer B, as long as it has a carboxyl group in the molecular chain, alkali-soluble acrylic copolymers, epoxy carboxylic acid ester compounds, polyamino acids, and alkalis may be mentioned. Among the soluble silicone polymers, alkali-soluble acrylic copolymers and epoxy carboxylic acid ester compounds are preferred from the viewpoint of visible light transmittance.

The acrylic copolymer can be obtained by copolymerizing an acrylic monomer having an unsaturated double bond, and the alkali-soluble acrylic copolymer can be obtained by using an unsaturated acid such as an unsaturated carboxylic acid for the acrylic monomer. Examples of the unsaturated acid include acrylic acid (hereinafter referred to as "AA"), methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid or vinyl acetate, or anhydrides thereof. Depending on the amount of unsaturated acid used, the acid value of the acrylic copolymer obtained can be adjusted.

Examples of the acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate (hereinafter, referred to as "EA"), 2-ethylhexyl acrylate, and n-butyl acrylate (hereinafter, referred to as "BA"). ), Isobutyl acrylate, isopropyl acrylate, glycidyl acrylate, butoxy triethylene glycol acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate Ester, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate , Octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, acrylic 2 -Naphthyl ester, thiophenol acrylate or benzyl thiol acrylate, allyl cyclohexyl diacrylate, methoxylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1, 3 -Butanediol diacrylate, ethylene glycol diacrylate, diethyl Glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate or triglycerol diacrylate, trimethylol Propane triacrylate, di-trimethylolpropane tetraacrylate, diisopentaerythritol monohydroxypentaacrylate or diisopentaerythritol hexaacrylate, acrylamide, N-methoxymethacryl Amine, N-ethoxymethacrylamide, N-n-butoxymethacrylamine, or N-isobutoxymethacrylamine, ring opening of an epoxy group with an unsaturated acid, and having a hydroxyl group Acrylic acid adduct of ethylene glycol diglycidyl ether, acrylic acid adduct of diethylene glycol diglycidyl ether, acrylic acid adduct of neopentyl glycol diglycidyl ether, glycerol diglycidyl Acrylic acid adduct of ether, Acrylic adducts of bisphenol A diglycidyl ether, acrylic adducts of bisphenol F or acrylic adducts of cresol-type phenolic resin, etc. A trimethoxysilane or a compound in which the acrylfluorenyl group is substituted with a methacrylfluorenyl group. However, from the viewpoint of visible light transmittance, those having an aliphatic chain or alicyclic structure are preferred.

Examples of the photopolymerization initiator contained in the photosensitive layer B in the present invention include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzylfluorenyl) Oxime)], 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine oxide, ethyl ketone- 1- [9-ethyl-6-2 (2-methylbenzylfluorenyl) -9H-carbazol-3-yl] -1- (O-ethylfluorenyl oxime), diphenyl ketone, O-benzyl Methyl ethyl benzoate, 4,4'-bis (dimethylamino) diphenyl ketone, 4,4'-bis (diethylamino) diphenyl ketone, 4,4'-dichloro Diphenyl ketone, 4-benzylfluorenyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2'-diethoxyethenylbenzene, 2,2-dimethoxy 2-Phenylacetophenone, 2-Hydroxy-2-methylpropantole, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone , 2-isopropylthioxanthone, diethylthioxanthone, benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl ketal Aldehyde (benzyl-β-methoxyethyl acltal), benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-pentylanthraquinone, β- Anthraquinone, anthrone, benzoanthrone, dibenzocycloheptanone, methylene anthrone, 4-azidobenzaldehyde acetophenone, 2,6-bis (p-azidobenzylidene) ring Hexanone, 6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl ) Oxime, 1-phenyl-propanedione-2- (O-benzylfluorenyl) oxime, 1,3-diphenyl-propanetrione-2- (O-ethoxycarbonyl) oxime, 1- Phenyl-3-ethoxy-glycerone-2- (O-benzylfluorenyl) oxime, Michler ketone, 2-methyl- [4- (methylthio) phenyl] -2 -Morpholinyl-1-acetone, naphthalenesulfonyl chloride, quinolinsulfonyl chloride, N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyldisulfide, benzene Benzothiazole disulfide, triphenylphosphine, camphorquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, carbon tetrabromide, tribromophenylphosphonium, benzoin peroxide, eosin or A combination of a photoreducible pigment such as methylene blue and a reducing agent such as ascorbic acid or triethanolamine.

The addition amount of the photopolymerization initiator contained in the photosensitive layer B is preferably 0.01 to 5 parts by mass, and more preferably 2.0 to 4 parts by mass relative to 100 parts by mass of the photosensitive resin. When the amount of the photosensitive resin added to 100 parts by mass is 0.01 parts by mass or more, and more preferably 2.0 parts by mass or more, the hardened density of the exposed portion increases, and the residual film rate after development can be increased. On the other hand, if the addition amount of the photosensitive resin to 100 parts by mass is 5 parts by mass or less, and more preferably 4 parts by mass or less, excessive light absorption by the photopolymerization initiator on the photosensitive layer B can be suppressed. . As a result, by making the transparent electrode pattern manufactured into an inverted cone shape, it is possible to suppress a decrease in adhesion to the substrate.

In the present invention, the total light transmittance of the photosensitive layer B is preferably 80% or more, and more preferably 90% or more. The total light transmittance of the photosensitive layer B can be measured in accordance with JIS K7361-1 (1997). If the total light transmittance is 80% or more, it can be used for display products such as touch panels, and if it is 90% or more, it can improve the luminous efficiency of the display and suppress power consumption.

The transparent electrode layer C in the present invention contains a conductive component. As for the conductive component, a member selected from the group consisting of indium, tin, zinc, potassium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, and palladium can be used. And metal oxides of at least one metal in the group of tungsten. The metal oxide may optionally include metal atoms shown in the above group. For example, indium tin oxide (ITO), indium zinc oxide, indium oxide-zinc oxide composite oxide, aluminum zinc oxide, potassium zinc oxide, fluorine zinc oxide, fluorine indium oxide, antimony tin oxide can be used , Fluorine tin oxide, etc. For other conductive components, carbon nanotubes, metal fibers such as gold, silver, and platinum (nanowires) can be used. From the viewpoints of conductivity, visible light transmittance, price, etc., ITO and silver metal fibers (nanowires) are preferred. From the viewpoint of connection reliability with the conductive pattern D, silver metal fibers ( Nanometers) is even better.

The method for forming the transparent electrode layer C is not particularly limited, and a conventionally known method can be adopted. Specifically, a method for forming the transparent electrode layer C by a vacuum deposition method, a sputtering method, an ion plating method, or a coating method can be exemplified. In addition, a suitable method may be adopted according to the required film thickness.

The thickness of the transparent electrode layer C is not particularly limited, but in order to form a continuous film having good conductivity, it is preferably 0.01 μm or more, and from the viewpoint of scratch resistance, it is more preferably 0.2 μm or more. From the viewpoint of visible light transmittance, it is preferably 1.5 μm or less, and more preferably 1.0 μm or less.

In the transparent electrode layer C in the present invention, the total light transmittance is preferably 80% or more, and more preferably 90% or more. If the visible light transmittance is 80% or more, it can be used for display products such as touch panels. If it is 90% or more, the luminous efficiency of the display can be improved and the power consumption can be suppressed.

Examples of the conductive particles contained in the photosensitive conductive paste D in the present invention include silver (hereinafter referred to as "Ag"), gold (hereinafter referred to as "Au"), copper, platinum, lead, tin, and nickel. , Aluminum, tungsten, molybdenum, chromium, titanium, or an alloy of these metals, however, from the viewpoint of conductivity, Ag, Au, or copper is preferred, and from the viewpoint of cost and stability, Ag For the better. In terms of shape, a value obtained by dividing the length of the long axis by the length of the short axis, that is, the aspect ratio, is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. When the aspect ratio of the conductive particles is 1.0 or more, the accuracy of contact between the conductive particles becomes higher. On the other hand, if the aspect ratio of the conductive particles is 2.0 or less, in the exposure step described later, it may not be easily shielded by the exposed light, and the developing edge may be widened. The aspect ratio of conductive particles can be observed with a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The primary particles of 100 conductive particles are randomly selected, and the major axis length and short length are measured respectively. The shaft length is determined by obtaining the aspect ratio from the average of the two.

The particle diameter of the conductive particles is preferably 3.0 μm or less, and more preferably 2.0 μm or less.

When the particle diameter is 3.0 μm or less, the straightness of the conductive pattern can be improved, and when it is 2.0 μm or less, the straightness can be further improved. The particle diameter of the conductive particles can be measured by observing the conductive particles using an electron microscope (SEM or TEM), randomly selecting primary particles of 20 conductive particles, measuring their maximum widths, and calculating the average of these. In addition, the ratio of particles having a diameter of 3.0 μm or less among the conductive particles contained in the photosensitive conductive paste D can be observed with an electron microscope (SEM or TEM), and the primary particles of 100 conductive particles are randomly selected. , Test separately The maximum width is determined from the ratio of primary particles having a maximum width of 3.0 μm or less.

Moreover, the particle size of the conductive particles contained in the photosensitive conductive paste D can be obtained by dissolving the collected photosensitive conductive paste D in tetrahydrofuran (hereinafter, referred to as "THF") and recovering the deposited conductive particles using a box type. The oven was dried at 70 ° C for 10 minutes, and calculated in the same manner as described above.

The proportion of the conductive particles in the solid content of the photosensitive conductive paste D is preferably 60 to 95% by mass, and more preferably 70 to 85% by mass. If the ratio of the conductive particles is 60% by mass or more, the accuracy of contact between the conductive particles becomes high, and the resistance value of the obtained photosensitive conductive pattern D can be stabilized. If it is 70% by mass or more, the effect is achieved. higher. On the other hand, if the ratio of the conductive particles is 95% by mass or less, it is difficult to be shielded by the exposed light in the exposure step described later, and the developing edge is widened. If it is 85% by mass or less, the effect is higher. The solid content means all components of the photosensitive conductive paste D after excluding the solvent.

Examples of the photosensitive resin contained in the photosensitive conductive paste D of the present invention include an acrylic copolymer having an double bond and a carboxyl group, an epoxy carboxylic acid ester compound, and the like. From the viewpoint of adhesion, an epoxy carboxylic acid ester compound is preferred.

The acrylic copolymer having a double bond and a carboxyl group can be obtained by copolymerizing an unsaturated acid having a carboxyl group and an unsaturated double bond with an acrylic monomer. Examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, or vinyl acetate or anhydrides thereof. The acid value of the obtained acrylic copolymer can be adjusted according to the amount of unsaturated acid used.

Examples of the acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, isopropyl acrylate, glycidyl acrylate, and butyl Oxytriethylene glycol acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate , Lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate , Trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate or benzyl thiol acrylate, diacrylic acid Allyl cyclohexyl ester, methoxylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol Alcohol diacrylate, triethylene glycol diacrylate , Polyethylene glycol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate or triglyceride diacrylate, trimethylolpropane triacrylate, di-trimethylolpropane Tetraacrylate, diisopentaerythritol monohydroxypentaacrylate or diisopentaerythritol hexaacrylate, acrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, Acrylic addition of N-n-butoxymethacrylamide or N-isobutoxymethacrylamine, ethylene glycol diglycidyl ether having a hydroxyl group opened by an unsaturated acid and having a hydroxyl group Product, acrylic acid adduct of diethylene glycol diglycidyl ether, acrylic acid adduct of neopentyl glycol diglycidyl ether, acrylic acid adduct of glycerol diglycidyl ether, bisphenol A diglycidyl Glyceryl ether acrylic acid adduct, Epoxy adducts such as acrylic adducts of bisphenol F or acrylic adducts of cresol-type phenolic resins or γ-acrylic acid oxypropyltrimethoxysilane, or substituted with such acrylic acid groups as A methacryl group.

In addition, by reacting a carboxyl group of the acrylic copolymer with a compound having an unsaturated double bond such as glycidyl (meth) acrylate, an unsaturated double bond having a reactive side chain can be imparted, and the instability can be adjusted. Amount of saturated double bonds.

The epoxy carboxylic acid ester compound means a compound that can be synthesized using an epoxy compound and a carboxyl compound having an unsaturated double bond as starting materials. Examples of the epoxy compound that can be used as a starting material include glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidylamines, and epoxy resins, but more specifically Examples include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S Diglycidyl ether, bisphenol diglycidyl ether, bisphenol diglycidyl ether, tetramethyl bisphenol glycidyl ether, trimethylolpropane triglycidyl ether, 3 ', 4'- Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate or tertiary butyl glycidylamine. Examples of the carboxyl compound having an unsaturated double bond include (meth) acrylic acid, crotonic acid, cinnamic acid, and α-cyanocinnamic acid.

By reacting the epoxy carboxylic acid ester compound with a polybasic acid anhydride, the acid value of the epoxy carboxylic acid ester compound can be adjusted. In the case of polybasic anhydrides, Examples include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride, or maleic anhydride.

The reaction of the epoxy carboxylic acid ester compound can be adjusted by reacting the carboxyl group of the epoxy carboxylic acid ester compound with the above-mentioned polybasic acid anhydride with a compound having an unsaturated double bond such as glycidyl (meth) acrylate. The amount of sexually unsaturated double bonds.

By reacting a hydroxyl group possessed by the epoxy carboxylic acid ester compound with a diisocyanate compound, the urethane can be formed. Examples of the diisocyanate compound include hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, toluene diisocyanate, trimethylhexamethylene diisocyanate, isophor Ketone diisocyanate, allylcyan diisocyanate or norbornane diisocyanate.

Examples of the photopolymerization initiator contained in the photosensitive conductive paste D in the present invention include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzyl) Fluorenyl oxime)], 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine oxide, ethyl Ketone-1- [9-ethyl-6-2 (2-methylbenzylfluorenyl) -9H-carbazol-3-yl] -1- (O-ethylfluorenyl oxime), diphenyl ketone, O -Methyl benzyl benzoate, 4,4'-bis (dimethylamino) diphenyl ketone, 4,4'-bis (diethylamino) diphenyl ketone, 4,4'- Dichlorodiphenyl ketone, 4-benzylfluorenyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2'-diethoxyacetanilide, 2,2-dimethyl Oxy-2-phenylacetophenone, 2-hydroxy-2-methylpropantole, p-tertiary-butyl dichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chloro Thioxanthone, 2-isopropylthioxanthone, diethyl Thiothioxanthone, biphenyl hydrazone, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthracene Quinone, 2-tert-butylanthraquinone, 2-pentylanthraquinone, β-chloroanthraquinone, anthrone, benzoanthrone, dibenzocycloheptanone, methylene anthrone, 4-azidobenzyl Aldehyde, 2,6-bis (p-azidobenzylidene) cyclohexanone, 6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 1-phenyl -1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-propanedione 2- (O-benzylfluorenyl) oxime, 1,3-diphenyl-propanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione 2- (O-benzylfluorenyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholinyl-1-acetone, naphthalenesulfonyl chloride, quinone Porphyrinsulfonyl chloride, N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyldisulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, 2 , 4-diethylthioxanthone, isopropylthioxanthone, carbon tetrabromide, tribromophenylhydrazone, benzoin peroxide, eosin or methylene Other light reducing dye, a combination of a reducing agent, ascorbic acid or triethanolamine and the like, however, oxime ester compounds having high light perception is preferred.

The addition amount of the photopolymerization initiator contained in the photosensitive conductive paste D is preferably 0.05 to 30 parts by mass, and more preferably 2 to 10 parts by mass relative to 100 parts by mass of the photosensitive resin. When the amount of the photosensitive resin added to 100 parts by mass is 0.05 parts by mass or more, the hardened density of the exposed portion increases, and the residual film rate after development can be increased. If it is 2 parts by mass or more, the exposure time can be shortened. On the other hand, if the amount of the photosensitive resin added to 100 parts by mass is 30 parts by mass or less, the upper portion of the coating film obtained by applying the photosensitive conductive paste D can be prevented from being photopolymerized. Excessive light absorption due to initiator. As a result, it is possible to suppress a decrease in adhesion to the substrate by forming the conductive pattern into an inverse cone shape, and the effect is higher if it is 10 parts by mass or less.

The photosensitive conductive paste D in the present invention may contain a photopolymerization initiator together with a sensitizer.

Examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzylidene) cyclopentanone, 2,6-bis (4-dimethylaminobenzylidene) cyclohexanone, 2,6-bis (4-dimethylaminobenzylidene) -4-methylcyclohexanone, Michler's ketone , 4,4-bis (diethylamino) diphenyl ketone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, P-Dimethylaminoglycineindenone, p-dimethylaminobenzylideneindone, 2- (p-dimethylaminophenylphenylethenyl) isonaphthothiazole, 1,3- Bis (4-dimethylaminophenylphenylethenyl) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzylidene) acetone, 1,3-carbonylbis (4-diethyl Aminobenzylidene) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine , Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzylfluorenylthiotetrazole or 1-phenyl-5-ethoxycarbonylsulfide Tetrazolium and the like.

The addition amount of the sensitizer is preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the photosensitive resin. When the addition amount of the photosensitive resin to 100 parts by mass is 0.05 parts by mass or more, the light sensitivity is improved. On the other hand, if the addition amount of the photosensitive resin to 100 parts by mass is 10 parts by mass or less, excessive light absorption in the upper part of the coating film obtained by applying the photosensitive conductive paste D can be suppressed. As a result, by The produced conductive pattern has a reverse pyramid shape, and tends to suppress a decrease in adhesion to the substrate.

The photosensitive conductive paste D of the present invention contains an epoxy resin. Examples of the epoxy resin include ethylene glycol modified epoxy resin, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated epoxy resin, bisphenol F epoxy resin, and phenolic resin. Resin-type epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, glycidyl ether-type epoxy resin, heterocyclic epoxy resin, etc. In other words, a bisphenol A type epoxy resin and a hydrogenated bisphenol A type epoxy resin are more preferable, and a hydrogenated bisphenol A type epoxy resin is more preferable from the viewpoint of light transmittance to light.

The addition amount of the epoxy resin is preferably 0.05 to 50 parts by mass relative to 100 parts by mass of the photosensitive resin. When the amount of the photosensitive resin added to 100 parts by mass is 0.05 parts by mass or more, the adhesiveness of the transparent electrode layer C can be improved. On the other hand, if the amount of the photosensitive resin added to 100 parts by mass is 50 parts by mass or less, the solubility to the developing solution of the photosensitive conductive paste D can be maintained well.

In the present invention, the first exposure step of exposing the laminated body laminated in the order of the substrate A, the photosensitive layer B, and the transparent electrode layer C can be divided into a step of exposing through a photomask, and a step without passing through a photomask. The step of full exposure in the presence of oxygen. When exposed in the presence of oxygen, the outermost layer of the exposed portion is blocked by oxygen without being hardened, and tends to have high solubility in the developing solution. In the first exposure step, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an LED and the like can be used to emit i-rays (365nm), h-rays (405nm) or g-rays (436nm), and perform vacuum adsorption exposure, proximity exposure, and projection exposure. , Direct exposure and other exposure methods. The exposure amount in the presence of oxygen is preferably 100 to 1000 mJ / cm ² . Adjusting the exposure to 100mJ / cm ² or more can improve the adhesion between the photosensitive layer B and the conductive pattern C. If it is 1000mJ / cm ² or less, and more preferably 800mJ / cm ² or less, the outermost surface of the photosensitive layer B The hardening reaction is not performed, and high solubility in the developing solution is maintained. The hardening reaction in the deep portion of the film reduces the solubility in the developing solution, which can increase the difference in solubility between the outermost surface and the deep portion of the film. In this state, only the outermost surface is dissolved in the developing solution during development, and the photosensitive conductive film D laminated thereon also flows with the developing solution, which can suppress the generation of the residue of the photosensitive conductive paste D described later.

The coating step of applying the photosensitive conductive paste D of the present invention to obtain the photosensitive conductive film D may include spin coating using a spinner, spray coating, roll coating, screen printing, or using a blade coater or a die. Coating method of head coater, calendar coater, meniscus coater or bar coater. The film thickness can be measured using, for example, a stylus-type step gauge of Surfcom (registered trademark) 1400 (manufactured by Tokyo Precision Co., Ltd.). More specifically, the film thickness can be measured by a stylus-type step meter (length measurement: 1 mm, scanning speed: 0.3 mm / sec) at any three positions, and the average value can be used as the film thickness.

As for the second exposure step of exposing the photosensitive conductive film D in the present invention, high-pressure mercury lamps, ultra-high-pressure mercury lamps, LEDs, etc. can be used to emit i-rays (365nm), h-rays (405nm), or g-rays (436nm). The light source performs various exposure methods such as vacuum adsorption exposure, proximity exposure, projection exposure, and direct exposure.

In the present invention, the laminated body and the photosensitive conductive film D are developed together to obtain the laminated electrode pattern of the transparent electrode pattern C and the conductive pattern D. In order to develop using an alkaline developer, the unexposed portion is dissolved and removed to obtain the desired pattern. A step of. Examples of the developer in the case of performing alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and triethylamine. , Diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine Aqueous solution of amine or hexamethylene diamine, and in these aqueous solutions, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylethyl Polar solvents such as amines, dimethyl sulfene, or γ-butyrolactone; alcohols such as methanol, ethanol, or isopropanol; esters such as ethyl lactate or propylene glycol monomethyl ether acetate; cyclopentanone, cyclic Ketones or surfactants such as hexanone, isobutyl ketone or methyl isobutyl ketone.

Examples of the developer in the case of organic development include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamidamine, N , N-dimethylformamide, dimethylmethylene or hexamethylphosphonium triamine and other polar solvents or these polar solvents and methanol, ethanol, isopropyl alcohol, xylene, water, methylcarbidine A mixed solution of alcohol or ethylcarbitol.

Examples of the development method include a method in which the substrate is allowed to stand or rotate while spraying a developing solution on the coating film surface; a method in which a conveyor belt is passed through a developing tank provided with a plurality of nozzles that eject the developing solution; immersion A method in a developing solution; or a method in which a substrate is immersed in a developing solution while irradiating with ultrasound. From "showing a large area evenly From the viewpoint of "shadow", it is better to develop through a developing tank through a conveyor belt, and the developing pressure when the developer is ejected is preferably 0.02 to 0.2 MPa. If the developing pressure is 0.02 MPa or more, it is easy to remove the laminated body and the unexposed portion of the coating film D together with the striking force, and the generation of residue can be suppressed. When the pressure of the developing solution is 0.2 MPa or less, the adhesion to the transparent electrode pattern C of the conductive pattern D does not deteriorate.

By developing the layered pattern obtained by the simultaneous development, the unexposed portion of the photosensitive layer B does not exist because the unexposed portions are removed together, and there is no residue of conductive particles in the unexposed portion of the photosensitive layer B.

In addition, since the above-mentioned laminated pattern is fully connected to the transparent electrode pattern C, the conductive pattern D can obtain high connection stability and can reduce the contact resistance between the patterns.

The laminated pattern obtained by the simultaneous development can be subjected to a rinsing treatment with a rinsing liquid. Examples of the rinse solution include water or an aqueous solution containing alcohols such as ethanol or isopropanol, or esters such as ethyl lactate or propylene glycol monomethyl ether acetate.

In the present invention, the temperature of the hardening step of hardening the laminated pattern is 100 to 300 ° C. The hardening temperature is preferably 120 ~ 180 ° C. If the curing temperature is lower than 100 ° C, the volume shrinkage of the resin component may not be increased, and the specific resistance may not be sufficiently lowered. On the other hand, if the curing temperature exceeds 300 ° C., a conductive pattern may not be produced on a material such as a substrate having low heat resistance.

As for the method for hardening the obtained laminated pattern, for example, heating and drying by an oven, an inert gas oven, or a hot plate; by means of an ultraviolet lamp, an infrared heater, a halogen heater, or a xenon flash lamp Either electromagnetic waves or microwave heating and drying; or vacuum drying. The hardness of the laminated pattern produced by heating can be increased, and defects or peeling caused by contact with other members can be suppressed. Furthermore, the adhesion between the transparent electrode pattern C and the conductive pattern D can be improved.

The multilayer pattern forming substrate manufactured by the method for manufacturing a multilayer pattern forming substrate of the present invention is suitable for use as a peripheral wiring for a touch panel. As for the method of the touch panel, examples include resistive film type, optical type, electromagnetic induction type or electrostatic capacitance type; since the electrostatic capacitance type touch panel particularly requires fine wiring, the substrates formed by the laminated pattern of the present invention The laminated pattern-forming substrate produced by the production method is more suitable for use.

A method for manufacturing a touch panel, comprising the steps of a method for manufacturing a laminated pattern forming substrate based on the present invention, wherein a laminated pattern manufactured by the method for manufacturing a laminated pattern forming substrate is used as a peripheral wiring of the touch panel. Moreover, in the touch panel with a peripheral wiring of 50 μm pitch (wiring width + wiring space width) or less, the width of the edges can be made thinner, and the viewing area can be enlarged.

[Example]

Hereinafter, the present invention will be described in more detail with examples and comparative examples, but the present invention is not limited to these.

The materials used in the examples and comparative examples will be described below.

[Photosensitive layer resin (b) forming photosensitive layer B] (Synthesis example 1)

Copolymerization ratio (mass basis): EA / 2-ethylhexyl methacrylate (hereinafter, referred to as "2-EHMA") / BA / N-hydroxymethacrylamide (hereinafter, referred to as "MAA") / AA = 20/40/20/5/15.

In a reaction container under a nitrogen atmosphere, 150 g of diethylene glycol monoethyl ether acetate (hereinafter, referred to as "DMEA") was added, and the temperature was raised to 80 ° C using an oil bath. Among them, a mixture containing 20 g of EA, 40 g of 2-EHMA, 20 g of BA, 5 g of MAA, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DMEA was divided into 1 Hours drip. After the dropwise addition was completed, a polymerization reaction was further performed for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a photosensitive resin (b-1).

(Synthesis example 2)

Copolymerization ratio (quality basis): EA / 2-EHMA / BA / MAA / AA = 20/20/20/15/25.

In a reaction vessel under a nitrogen atmosphere, 150 g of DMEA was added, and the temperature was raised to 80 ° C. using an oil bath. In it, a mixture containing 20 g of EA, 20 g of 2-EHMA, 20 g of BA, 5 g of MAA, 25 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DMEA for 1 hour. Drip into. After the dropwise addition was completed, a polymerization reaction was further performed for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a photosensitive resin (b-2).

(Synthesis example 3)

Copolymerization ratio (quality basis): EA / 2-EHMA / BA / MAA / AA = 30/20/10/25/15.

In a reaction vessel under a nitrogen atmosphere, 150 g of DMEA was added, and the temperature was raised to 80 ° C. using an oil bath. Among them, a mixture containing 30 g of EA, 20 g of 2-EHMA, 10 g of BA, 25 g of MAA, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DMEA was used as Hours drip. After the dropwise addition was completed, a polymerization reaction was further performed for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a photosensitive resin (b-3).

[Photosensitive resin (d) contained in the photosensitive conductive paste D] (Synthesis example 4)

Copolymerization ratio (mass basis): EA / 2-EHMA / styrene (hereinafter, referred to as "St") / glycidyl methacrylate (hereinafter, referred to as "GMA") / AA = 20/40/25 / 5/10.

In a reaction vessel under a nitrogen atmosphere, 150 g of DMEA was added, and the temperature was raised to 80 ° C. using an oil bath. Here, a mixture containing 20 g of EA, 40 g of 2-EHMA, 25 g of St, 10 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DMEA was added dropwise over 1 hour. After the dropwise addition was completed, a polymerization reaction was further performed for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Next, a mixture containing 5 g of GMA, 1 g of triethylbenzyl ammonium chloride, and 10 g of DMEA was added dropwise over 0.5 hours. After the end of dripping, proceed for 2 more hours Addition reaction. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a photosensitive resin (d-1).

(Synthesis example 5)

Copolymerization ratio (quality basis): Bisphenol A diacrylate modified by ethylene oxide (FA-324A; manufactured by Hitachi Chemical Industries, Ltd.) / EA / GMA / AA = 60/20/5/15.

In a reaction vessel under a nitrogen atmosphere, 150 g of DMEA was added, and the temperature was raised to 80 ° C. using an oil bath. Among them, a mixture containing 60 g of ethylene oxide modified bisphenol A diacrylate, 20 g of EA, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DMEA was added as 1 Hours drip. After the dropwise addition was completed, a polymerization reaction was further performed for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Next, a mixture containing 5 g of GMA, 1 g of triethylbenzyl ammonium chloride, and 10 g of DMEA was added dropwise over 0.5 hours. After the dropwise addition was completed, an addition reaction was further performed for 2 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a photosensitive resin (d-2).

(Synthesis example 6)

In a reaction solution in a nitrogen atmosphere, 492.1 g of carbitol acetate and 860.0 g of EOCN-103S (manufactured by Nippon Kayaku Co., Ltd .; cresol-type phenol resin epoxy resin; epoxy equivalent weight: 215.0 g / Equivalent), 288.3 g of AA, 4.92 g of 2,6-di-tertiary-butyl-p-cresol and 4.92 g of triphenylphosphine, react at a temperature of 98 ° C until the acid value of the reaction solution becomes 0.5 mg‧KOH / g or less to obtain an epoxy carboxylic acid ester compound. Then, 169.8 g of carbitol acetate and 201.6 g of tetrahydrophthalic anhydride were added to the reaction solution, and the mixture was reacted at 95 ° C for 4 hours to obtain a photosensitive resin (d-3).

(Synthesis example 7)

In a reaction vessel under a nitrogen atmosphere, 368.0 g of RE-310S (manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent: 184.0 g / equivalent), 141.2 g of AA, 1.02 g of hydroquinone monomethyl ether, and 1.53 were added. g of triphenylphosphine was reacted at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mgKOH / g or less to obtain an epoxy carboxylic acid ester compound. Then, 755.5 g of carbitol acetate, 268.3 g of 2,2-bis (dimethylol) -propionic acid, 1.08 g of 2-methylhydroquinone, and 140.3 g of spiroline were added to the reaction solution. Diol, heated to 45 ° C. In this solution, 485.2 g of trimethylhexamethylene diisocyanate was slowly dropped so that the reaction temperature did not exceed 65 ° C. After the dropwise addition was completed, the reaction temperature was raised to 80 ° C., and the reaction was continued for 6 hours, until it became non-absorptive around 2250 cm ^{−1 as} measured by infrared absorption spectrometry, thereby obtaining a photosensitive resin (d-4).

[Photopolymerization initiator]

‧IRGACURE (registered trademark) OXE-01 (hereinafter referred to as "OXE-01"; manufactured by Ciba Japan Co., Ltd.)

‧IRGACURE (registered trademark) 369 (hereinafter referred to as "IC-369"; manufactured by Ciba Japan Co., Ltd.).

[monomer]

‧Light Acrylate MPD-A (hereinafter referred to as "MPD-A"; manufactured by Kyoeisha Chemical Co., Ltd.).

[Alcohol solvents]

‧Diethylene glycol (hereinafter referred to as "DEG").

[Epoxy resin]

‧JER (registered trademark) 828 (hereinafter referred to as "828"; manufactured by Mitsubishi Chemical Corporation)

‧JER (registered trademark) YX-8000 (hereinafter referred to as "YX-8000"; manufactured by Mitsubishi Chemical Corporation).

[Transparent electrode material]

‧Silver fiber (wire diameter 5nm, wire length 5μm)

‧ITO (97% by mass of indium oxide, 3% by mass of tin oxide).

(Example 1) <Formation of Photosensitive Layer B>

As the substrate A, a biaxially stretched polyethylene terephthalate film having a thickness of 30 μm was prepared. A composition B1 obtained by mixing photosensitive resin (b-1), MPD-A, and IC-369 at a ratio of 100: 50: 1 was coated on one side of substrate A, and was heat-treated and dried to a thickness of 4 μm. The photosensitive layer B1.

<Formation of transparent electrode layer C>

A silver fiber aqueous dispersion (solid content: 0.2% by mass) was applied onto the photosensitive layer B1 and dried at 100 ° C. for 5 minutes to form a transparent electrode layer C1 of a silver fiber (nanowire) film having a thickness of 1.0 μm.

<1st exposure>

The transparent electrode layer C1 is closely adhered to the photomask, and the photoreceptor layer B and the transparent electrode layer C are exposed by an exposure machine with an ultra-high pressure mercury lamp at an exposure amount of 200mJ / cm ² , and further without passing through the photomask at 200mJ / The exposure amount of cm ² fully exposes the photosensitive layer B1 and the transparent electrode layer C1.

<Preparation of photosensitive conductive paste D>

In a 100mL clean bottle, add 10.0g of photosensitive resin (d-1), 2.0g of IC-369, and 5.0g of diethylene glycol, and use a rotation-revolution vacuum mixer to "remove the foaming Taro" (registered Trademark) ARE-310 (manufactured by Thinky Co., Ltd.) was mixed to obtain 17.0 g of a resin solution D1 (solid content: 70.1% by mass).

The obtained 17.0 g of the resin solution D1 and 68.0 g of silver particles were mixed and kneaded using a three-roll mill (EXAKT M-50: manufactured by EXAKT) to obtain 85.0 g of a photosensitive conductive paste D1.

<Formation of Photosensitive Conductive Film D>

On the surfaces of the photosensitive layer B1 and the exposed transparent electrode layer C1, a photosensitive conductive paste D1 was applied with a screen printing machine to a film thickness of 5 μm, and then dried at 70 ° C. for 10 minutes to obtain a photosensitive conductive film D1.

<2nd exposure>

The photosensitive conductive film D1 was brought into close contact with the photomask, and was exposed at an exposure amount of 300 mJ / cm ² by an exposure machine having an ultra-high pressure mercury lamp.

<Formation of laminated pattern>

For a laminated substrate including the transparent electrode layer C1 and the photosensitive conductive film D1, a 1% by mass sodium carbonate aqueous solution was applied at a pressure of 0.1 MPa. After performing spray development for 30 seconds, curing was performed at 140 ° C. for 60 minutes, and a laminated pattern-forming substrate including a transparent electrode pattern C1 and a conductive pattern D1 was produced.

<Evaluation method of residue>

The conductive pattern shown in FIG. 2 is formed, and the total light transmittance of the unexposed portion and the total light transmittance of only the first exposed area are measured. Compared with the total light transmittance before the conductive paste D is applied, the reduction rate is 10%. In the following, it is judged as good, and those larger than 10% are judged as bad. In addition, the total light transmittance was determined using NDH-7000SP manufactured by Nippon Denshoku Industries Co., Ltd., and the ratio of the light intensity to the incident light intensity was calculated in accordance with JIS K7361-1 (1997).

<Adhesion evaluation method>

The conductive pattern shown in FIG. 2 is formed, and for a portion where the first exposure area overlaps with the second exposure area and a portion having only the second exposure area, a cutter guide and a cutter are used, and the conductive pattern D can be squared by 1 mm. 100 pieces were cut, and an adhesive tape (CT405AP-24, manufactured by Nichiban Co., Ltd.) was affixed thereon. The adhesive tape was peeled off in one go, and the number of conductive patterns D peeled from the transparent electrode layer C was counted and evaluated. Adhesiveness.

<Evaluation of Ion Migration Resistance>

The laminated pattern-forming substrate 1 forming the conductive pattern D1 shown in FIG. 3 was put into a high-temperature and high-humidity tank at 85 ° C and 85% RH, and a voltage of 5 VDC was applied from the terminal portion. It was confirmed that the resistance value was rapidly reduced by a 3-digit short. time. The same evaluation was repeated with a total of 10 laminated pattern-forming substrates 1, and the average of them was used as the value of ion migration resistance. The results are shown in Table 2.

(Examples 2 to 18)

Except for the case where the transparent electrode layer C is ITO, it was formed by the following method, and a laminated pattern having the conditions shown in Table 1 was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Formation of transparent electrode layer C>

On the surface of the photosensitive layer B, a transparent electrode layer C2 including an ITO thin film with a thickness of 22 nm was formed using a sputtering device provided with a sintered body target of ITO.

(Comparative example 1)

In the steps following the first exposure, except that the formation of the laminated pattern is formed by the following method, a laminated pattern with the conditions shown in Table 1 is produced in the same manner as in Example 1, and is performed in the same manner as in Example 1. Evaluation. The results are shown in Table 2.

<Formation of transparent electrode pattern C>

The transparent electrode layer C1 is closely adhered to the photomask, and the photoreceptor layer B and the transparent electrode layer C are exposed by an exposure machine with an ultra-high pressure mercury lamp at an exposure amount of 200mJ / cm ² , and further without passing through the photomask at 200mJ / cm After an exposure amount of ² is obtained, the photosensitive layer B1 and the transparent electrode layer C1 are fully exposed, and then spray-developed in a 1% by mass sodium carbonate aqueous solution at 30 ° C. for 30 seconds to form a transparent electrode pattern C2 on the photosensitive layer B2.

<Preparation of photosensitive conductive paste D>

In a 100mL clean bottle, add 10.0g of photosensitive resin (d-2), 1.0g of OXE-01, and 5.0g of diethylene glycol, and use a rotation-revolution vacuum mixer "Defoaming Taro" (registrar) (Subject) ARE-310 (manufactured by Thinky Co., Ltd.) was mixed to obtain 17.0 g of a resin solution D2 (solid content: 70.1% by mass).

The obtained 17.0 g of the resin solution D2 and 68.0 g of silver particles were mixed and kneaded using a three-roll mill (EXAKT M-50; manufactured by EXAKT) to obtain 85.0 g of a photosensitive conductive paste D2.

<Formation of Photosensitive Conductive Film D>

On the surfaces of the photosensitive layer B2 and the transparent electrode pattern C2, a photosensitive conductive paste D2 was applied by a screen printing machine to a film thickness of 5 μm, and then dried at 70 ° C. for 10 minutes to obtain a photosensitive conductive film D2.

<Formation of laminated pattern>

Through a set mask, an exposure machine with an ultra-high pressure mercury lamp was used for exposure at an exposure of 300 mJ / cm ² , and a 1% by mass sodium carbonate aqueous solution was spray-developed at a pressure of 0.1 MPa for 30 seconds, and then carried out at 140 ° C. for 60 seconds. It hardens in a minute, and manufactures a laminated pattern forming substrate including a transparent electrode pattern C2 and a conductive pattern D2.

(Comparative example 2)

In the steps below the first exposure, except that the formation of the laminated pattern is formed by the following method, a laminated pattern with the conditions shown in Table 1 is produced in the same manner as in Example 1, and is performed in the same manner as in Example 1. Evaluation. The results are shown in Table 2.

<1st exposure>

The photosensitive layer B3 and the transparent electrode layer C3 were fully exposed at an exposure amount of 200 mJ / cm ² without passing through a photomask.

<Preparation of photosensitive conductive paste D>

In a 100mL clean bottle, add 10.0g of photosensitive resin (d-3), 2.0g of OXE-01, and 5.0g of diethylene glycol, and use a rotation-revolution vacuum mixer to "remove the foaming Taro" (registered Trademark) ARE-310 (manufactured by Thinky Co., Ltd.) was mixed to obtain 17.0 g of a resin solution D3 (solid content: 70.1% by mass).

The obtained 17.0 g of the resin solution D3 and 68.0 g of silver particles were mixed and kneaded using a three-roll mill (EXAKT M-50; manufactured by EXAKT) to obtain 85.0 g of a photosensitive conductive paste D3.

<Formation of Photosensitive Conductive Film D>

On the surfaces of the photosensitive layer B3 and the transparent electrode layer C3, a photosensitive conductive paste D3 was applied with a screen printing machine to a film thickness of 5 μm, and then dried at 70 ° C. for 10 minutes to obtain a photosensitive conductive film D3.

<2nd exposure>

The photosensitive conductive film D3 was brought into close contact with the photomask, and exposed with an exposure amount of 300 mJ / cm ² by an exposure machine having an ultra-high pressure mercury lamp.

<Formation of laminated pattern>

The laminated substrate including the transparent electrode layer C3 and the photosensitive conductive film D3 was spray-developed with a 1% by mass sodium carbonate aqueous solution at a pressure of 0.1 MPa for 30 seconds, and then cured at 140 ° C for 60 minutes to produce a transparent electrode pattern C3. And the laminated pattern of the conductive pattern D3 forms a substrate.

Based on Table 2, it was determined that in any of Examples 1 to 18, the build-up pattern forming base material was sufficiently suppressed that the residue was produced, and the adhesion and ion migration resistance were excellent.

[Industrial possibilities]

The present invention can be used for suppressing the generation of residues in unexposed parts and maintaining the adhesion between the conductive pattern and the photosensitive resin layer formed on the substrate, and furthermore, the conductive pattern and the photosensitive resin layer are excellent in ion migration resistance. Manufacturing of touch panels.

1‧‧‧ conductive pattern D

2‧‧‧ transparent electrode layer C

3‧‧‧ Photosensitive layer B

4‧‧‧ Substrate A

Claims (7)

A method for manufacturing a laminated pattern-forming substrate, comprising: a first exposure step of exposing a laminated body formed by sequentially laminating a substrate A, a photosensitive layer B, and a transparent electrode layer C; and coating a photosensitive layer on the surface of the laminated body Coating step of obtaining the conductive conductive film D; a second exposure step of exposing the photosensitive conductive film D; developing the laminated body and the photosensitive conductive film D together to obtain a transparent electrode pattern C and The step of developing a laminated pattern of the conductive pattern D. The photosensitive layer B contains a photosensitive resin and a photopolymerization initiator, and the photosensitive conductive paste D contains conductive particles, a photosensitive resin, and a photopolymerization initiator. For example, the method for manufacturing a laminated pattern-forming substrate according to claim 1, wherein the first exposure step includes a step of exposing through a photomask and a step of exposing in a presence of oxygen without passing through the photomask. For example, the method for manufacturing a laminated pattern forming substrate according to claim 1 or 2, further comprising a hardening step of heating the laminated pattern at 100 to 300 ° C. The method for manufacturing a laminated pattern forming substrate according to any one of claims 1 to 3, wherein the transparent electrode layer contains a metal nanowire. The method for manufacturing a laminated pattern-forming substrate according to claim 4, comprising silver nanowires as the metal nanowires. The method for producing a laminated pattern-forming substrate according to any one of claims 1 to 5, comprising silver particles as the conductive particles. A method for manufacturing a touch panel, comprising the steps of the method for manufacturing a touch panel according to any one of claims 1 to 6.