WO2017208842A1

WO2017208842A1 - Method for producing multilayer pattern formed base and method for producing touch panel

Info

Publication number: WO2017208842A1
Application number: PCT/JP2017/018670
Authority: WO
Inventors: 創水口; 友孝河野
Original assignee: 東レ株式会社
Priority date: 2016-06-02
Filing date: 2017-05-18
Publication date: 2017-12-07
Also published as: JPWO2017208842A1; TW201804259A

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

Laminate pattern forming substrate and touch panel manufacturing method

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

The display electrode formed in the display area of the capacitive touch panel is a transparent electrode made of ITO (indium tin oxide) or the like. As the pattern processing process, a metal thin film such as ITO is formed on the base material by sputtering or the like, and a photoresist, which is a photosensitive resin, is further applied to the surface and exposed through a photomask. In general, after forming a resist pattern by development, etching and resist removal are performed.

On the other hand, by preparing a laminate of a photosensitive resin layer and a transparent electrode layer on a substrate in advance, it is possible to omit applying or removing a photoresist each time a transparent electrode pattern is formed. Technology has also been devised (Patent Documents 1 and 2).

In the capacitive touch panel, peripheral wiring connected to the transparent electrode is formed around the display area. As a method of forming this peripheral wiring, a method of finely processing a conductive paste having photosensitivity by a photolithography method is known (Patent Documents 3 to 7). When this conductive paste is used to form a peripheral wiring connected to a transparent electrode pattern formed from a base material on which the photosensitive resin layer and the transparent electrode layer are laminated, the photosensitivity formed on the base material It is necessary to apply the conductive paste to the surface of the resin layer and the transparent electrode layer before processing.

Japanese Patent Laying-Open No. 2015-18157 JP 2014-199814 A Japanese Patent No. 5278632 International Publication No. 2013/108696 Japanese Patent No. 5360285 Japanese Patent No. 5403187 International Publication No. 2013/146107

However, in the part where the conductive paste coating film is formed on the surface of the photosensitive resin layer on the substrate, the photosensitive resin layer swells due to the solvent in the conductive paste, and the conductive particles contained in the conductive paste there. In the development process after the conductive paste is exposed through the photomask, not only residue is generated in the unexposed area, but also the poor adhesion between the formed conductive pattern and the photosensitive resin layer. Further, ion migration between the conductive pattern and the photosensitive resin layer has been regarded as a problem.

Therefore, the present invention can suppress the generation of residues in the dissolution and removal of unexposed portions, and maintains the adhesion between the conductive pattern formed on the substrate and the photosensitive resin layer, and further the conductive pattern and the photosensitive resin. It aims at providing the manufacturing method of a lamination pattern formation base material which is excellent in ion migration tolerance with a layer.

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

(1) The first and second exposure steps of exposing a laminate in which the substrate A, the photosensitive layer B, and the transparent electrode layer C are laminated in this order, and applying the photosensitive conductive paste D to the surface of the laminate. The photosensitive conductive film D is obtained, the coating process, the photosensitive conductive film D is exposed, the second exposure process, the laminate and the photosensitive conductive film D are collectively developed, and the transparent electrode A development step for obtaining a laminated pattern of a pattern C and a conductive pattern D, wherein the photosensitive layer B contains a photosensitive resin and a photopolymerization initiator, and the photosensitive conductive paste D includes conductive particles, photosensitive layers The manufacturing method of a lamination pattern formation base material containing a functional resin and a photoinitiator.

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

(3) The method for producing a laminated pattern forming substrate according to (1) or (2), further comprising a curing step in which the laminated pattern is heated at 100 to 300 ° C.

(4) The method for producing a laminated pattern forming substrate according to (1) to (3), wherein the transparent electrode layer contains metal nanowires.

(5) The manufacturing method of the lamination pattern formation base material given in the above (4) containing silver nanowire as the metal nanowire.

(6) The method for producing a laminated pattern forming substrate according to any one of (1) to (5), wherein the conductive particles contain silver particles.

(7) A method for manufacturing a touch panel, comprising a step based on the manufacturing method according to any one of (1) to (6).

According to the production method of the present invention, it is possible to suppress the generation of residues in the dissolution and removal of unexposed portions, and to maintain the adhesion between the conductive pattern formed on the substrate and the photosensitive resin layer. A laminated pattern forming substrate having excellent ion migration resistance between the photosensitive resin layer and the photosensitive resin layer can be produced.

It is a schematic diagram of a lamination pattern formation base material. It is a schematic diagram of the conductive pattern used for residue evaluation and adhesive evaluation. It is a schematic diagram of the conductive pattern used for evaluation of ion migration tolerance.

Hereinafter, the present invention will be described in detail with specific examples.

The manufacturing method of the lamination pattern formation base material of the present invention is the 1st exposure process which exposes the layered product laminated in order of substrate A, photosensitive layer B, and transparent electrode layer C, and the surface of the layered product A photosensitive conductive paste D is applied to obtain a photosensitive conductive film D, a coating process, the photosensitive conductive film D is exposed, a second exposure process, the laminate and the photosensitive conductive film Development step of developing D in a lump to obtain a laminated pattern of the transparent electrode pattern C and the conductive pattern D, the photosensitive layer B containing a photosensitive resin and a photopolymerization initiator, The conductive conductive paste D is a method for producing a laminated pattern forming substrate containing conductive particles, a photosensitive resin, and a photopolymerization initiator.

In the present invention, as the base material A, a polyethylene terephthalate film (PET film), a polyimide film, a polyester film, an aramid film, an epoxy resin substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, a glass substrate, Examples include, but are not limited to, silicon wafers, alumina substrates, aluminum nitride substrates, and silicon carbide substrates.

In the present invention, the photosensitive resin constituting the photosensitive layer B may be any resin having a carboxyl group in the molecular chain, such as an alkali-soluble acrylic copolymer, an epoxycarboxylate compound, a polyamic acid, and an alkali-soluble siloxane. Examples thereof include an alkali-soluble acrylic copolymer and an epoxy carboxylate compound from the viewpoint of visible light permeability.

An acrylic copolymer is obtained by copolymerizing an acrylic monomer having an unsaturated double bond, and an alkali-soluble acrylic copolymer is obtained by using an unsaturated acid such as an unsaturated carboxylic acid as the acrylic monomer. It is done. As an unsaturated acid, acrylic acid (henceforth "AA"), methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, or these acid anhydrides are mentioned, for example. The acid value of the obtained acrylic copolymer can be adjusted by the amount of the unsaturated acid used.

Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate (hereinafter “EA”), 2-ethylhexyl acrylate, n-butyl acrylate (hereinafter “BA”), iso-butyl acrylate, and iso-propane acrylate. Glycidyl acrylate, butoxytriethylene glycol acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octaflo Pentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate or benzyl mercaptan acrylate, allylated cyclohexyl diacrylate, Methoxylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, Propylene glycol Diacrylate, polypropylene glycol diacrylate or triglycerol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol monohydroxypentaacrylate or dipentaerythritol hexaacrylate, acrylamide, N-methoxymethylacrylamide, N-ethoxy Methyl acrylamide, Nn-butoxymethyl acrylamide or N-isobutoxymethyl acrylamide, acrylic acid adduct of ethylene glycol diglycidyl ether having a hydroxyl group in which an epoxy group is opened with an unsaturated acid, acrylic acid of diethylene glycol diglycidyl ether Adduct, neopentyl glycol diglycidyl ether acrylic acid Epoxy acrylate monomer or γ-acryloxypropyl such as an adduct, an acrylic acid adduct of glycerin diglycidyl ether, an acrylic acid adduct of bisphenol A diglycidyl ether, an acrylic acid adduct of bisphenol F, or an acrylic acid adduct of cresol novolac Examples include trimethoxysilane or a compound obtained by substituting an acrylic group thereof with a methacryl group, but those having an aliphatic chain or an alicyclic structure are preferable from the viewpoint of visible light transmittance.

Examples of the photopolymerization initiator contained in the photosensitive layer B in the present invention include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 2,4,6- Trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethanone-1- [9-ethyl-6-2 (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), benzophenone, methyl O-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, , 2′-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, Anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) Clohexanone, 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-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione -2- (O-benzoyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4, 4'-azobisisobutyronitrile Photoreducing dyes such as diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin or methylene blue, and ascorbine A combination with a reducing agent such as acid or triethanolamine can be mentioned.

The addition amount of the photopolymerization initiator contained in the photosensitive layer B is preferably 0.01 to 5 parts by mass, more preferably 2.0 to 4 parts by mass with respect to 100 parts by mass of the photosensitive resin. When the addition amount with respect to 100 parts by mass of the photosensitive resin is 0.01 parts by mass or more, more preferably 2.0 parts by mass or more, the cured density of the exposed part increases and the remaining film ratio after development can be increased. it can. On the other hand, when the addition amount with respect to 100 parts by mass of the photosensitive resin is 5 parts by mass or more, more preferably 4 parts by mass or less, excessive light absorption by the photopolymerization initiator on the photosensitive layer B is suppressed. As a result, a decrease in adhesion with the substrate due to the manufactured transparent electrode pattern having an inversely tapered shape is suppressed.

In the present invention, the photosensitive layer B preferably has a total light transmittance of 80% or more, more preferably 90% or more. The total light transmittance of the photosensitive layer B can be measured according to JIS K7361-1 (1997). If the total light transmittance is 80% or more, it can be used for a display product such as a touch panel, and if it is 90% or more, the light emission efficiency of the display can be increased and the power consumption can be suppressed.

The transparent electrode layer C in the present invention contains a conductive component, and the conductive component is made of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten. A metal oxide of at least one metal selected from the group is used. The metal oxide may further contain a metal atom shown in the above group, if necessary. For example, indium tin oxide (ITO), indium zinc oxide, indium oxide-zinc oxide composite oxide, aluminum zinc oxide, gallium zinc oxide, fluorine zinc oxide, fluorine indium oxide, antimony tin oxide, fluorine Tin oxide or the like can be used. As other conductive components, metal fibers (nanowires) such as carbon nanotubes, gold, silver, and platinum can be used. ITO and silver metal fibers (nanowires) are preferable from the viewpoint of conductivity, visible light transmittance, price, and the like, and silver metal fibers (nanowires) are more preferable from the viewpoint of connection reliability with the conductive pattern D.

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

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

The transparent electrode layer C in the present invention preferably has a total light transmittance of 80% or more, more preferably 90% or more. If the visible light transmittance is 80% or more, it can be used for a display product such as a touch panel, and if it is 90% or more, the light emission efficiency of the display can be increased and the power consumption can be suppressed.

As the conductive particles contained in the photosensitive conductive paste D in the present invention, silver (hereinafter “Ag”), gold (hereinafter “Au”), copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum , Chromium, titanium, or indium, or an alloy of these metals, Ag, Au, or copper is preferable from the viewpoint of conductivity, and Ag is more preferable from the viewpoint of cost and stability. As for the shape, the aspect ratio, which is a value obtained by dividing the major axis length by the minor axis length, 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 contact probability between the conductive particles is further increased. On the other hand, when the aspect ratio of the conductive particles is 2.0 or less, the exposure light is difficult to be shielded in the exposure process described later, and the development margin may be widened. The aspect ratio of the conductive particles is determined by observing the conductive particles with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and randomly selecting primary particles of 100 conductive particles. It can be determined by measuring the major axis length and minor axis length and determining the aspect ratio from the average value of both.

The particle size of the conductive particles is preferably 3.0 μm or less, and more preferably 2.0 μm or less.
If the particle size is 3.0 μm or less, the straightness of the conductive pattern can be increased, and if it is 2.0 μm or less, the straightness can be further increased. The particle size of the conductive particles is determined by observing the conductive particles with an electron microscope (SEM or TEM), randomly selecting the primary particles of 20 conductive particles, measuring the maximum width of each, It can be calculated by obtaining an average value. Further, the proportion of particles having a particle size of 3.0 μm or less in the conductive particles contained in the photosensitive conductive paste D is determined by observing the conductive particles with an electron microscope (SEM or TEM) and randomly 100 conductive particles. The primary particles of the particles can be selected, their respective maximum widths can be measured, and the maximum width can be determined from the proportion of primary particles that were 3.0 μm or less.

In addition, the particle size of the conductive particles contained in the photosensitive conductive paste D is determined by dissolving the collected photosensitive conductive paste D in tetrahydrofuran (hereinafter “THF”), collecting the precipitated conductive particles, It can calculate similarly to the above about what used and dried for 10 minutes at 70 degreeC.

The proportion of the conductive particles in the solid content of the photosensitive conductive paste D is preferably 60 to 95% by mass, more preferably 70 to 85% by mass. When the proportion of the conductive particles is 60% by mass or more, the contact probability between the conductive particles is increased, the resistance value of the resulting photosensitive conductive pattern D is stabilized, and the effect is further increased when the proportion is 70% by mass or more. . On the other hand, when the proportion of the conductive particles is 95% by mass or less, exposure light is not easily shielded in an exposure process described later, and the development margin is widened. Here, the solid content means all components of the photosensitive conductive paste D excluding the solvent.

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

An 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 as an acrylic monomer. Examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and acid anhydrides thereof. The acid value of the obtained acrylic copolymer can be adjusted by the amount of the unsaturated acid used.

Examples of acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, iso-butyl acrylate, iso-propane acrylate, glycidyl acrylate, butoxytriethylene glycol acrylate, and dicyclopentanyl. Acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate , Octafluoropentyl acrylate, phenoxye Acrylate, stearyl acrylate, trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate or benzyl mercaptan acrylate, allylated cyclohexyl diacrylate, methoxylated cyclohexyl di Acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate , Polypropylene grease Diacrylate or triglycerol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol monohydroxypentaacrylate or dipentaerythritol hexaacrylate, acrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N -N-butoxymethylacrylamide or N-isobutoxymethylacrylamide, acrylic acid adduct of ethylene glycol diglycidyl ether having a hydroxyl group whose epoxy group is opened with an unsaturated acid, acrylic acid adduct of diethylene glycol diglycidyl ether, neo Acrylic acid adduct of pentyl glycol diglycidyl ether, glycerin diglycidyl ether Epoxy acrylate monomer or γ-acryloxypropyltrimethoxysilane such as acrylic acid adduct of bisphenol A, diglycidyl ether of bisphenol A, acrylic acid adduct of bisphenol F or acrylic acid adduct of cresol novolac, or The compound which substituted those acrylic groups by the methacryl group is mentioned.

In addition, a reactive unsaturated double bond is given to the side chain by reacting the carboxyl group of the acrylic copolymer with a compound having an unsaturated double bond such as glycidyl (meth) acrylate. And the amount of unsaturated double bonds can be adjusted.

The epoxycarboxylate compound refers to 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 a starting material include glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidyl amines, or epoxy resins. More specifically, 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 full orange glycidyl ether Ether, biphenol diglycidyl ether, tetramethyl biphenol glycidyl ether, trimethylolpropane triglycidyl ether, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate or tert- butyl glycidyl amines. Examples of the carboxyl compound having an unsaturated double bond include (meth) acrylic acid, crotonic acid, cinnamic acid, and α-cyanocinnamic acid.

The acid value of the epoxycarboxylate compound may be adjusted by reacting the epoxycarboxylate compound with the polybasic acid anhydride. Examples of the polybasic acid anhydride include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Examples include trimellitic anhydride or maleic anhydride.

Reaction which an epoxy carboxylate compound has by reacting the carboxyl group which the epoxy carboxylate compound made to react with the above-mentioned polybasic acid anhydride has, and the compound which has unsaturated double bonds, such as glycidyl (meth) acrylate, The amount of the unsaturated double bond may be adjusted.

The urethanization may be carried out by reacting the hydroxy group of the epoxycarboxylate compound with a diisocyanate compound. Examples of the diisocyanate compound include hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tridenic diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allyl cyanide diisocyanate, and 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-benzoyloxime)], 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethanone-1- [9-ethyl-6-2 (2-methylbenzoyl) -9H-carbazole-3 -Yl] -1- (O-acetyloxime), benzophenone, methyl O-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'- Dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, Olenone, 2,2′-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2- Chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β- Chloranthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobe) Dilidene) 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-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propane Trione-2- (O-benzoyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4 , 4'-Azobisisobu Photoreductive dyes such as nitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin or methylene blue A combination with a reducing agent such as ascorbic acid or triethanolamine can be mentioned, and an oxime ester compound having high photosensitivity is preferable.

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 with respect to 100 parts by mass of the photosensitive resin. When the addition amount with respect to 100 parts by mass of the photosensitive resin is 0.05 parts by mass or more, the cured density of the exposed part increases, and the residual film ratio after development can be increased. Time can be shortened. On the other hand, when the addition amount with respect to 100 parts by mass of the photosensitive resin is 30 parts by mass or less, excessive light absorption by the photopolymerization initiator at the upper part of the coating film obtained by applying the photosensitive conductive paste D is suppressed. Is done. As a result, a decrease in adhesion with the substrate due to the manufactured conductive pattern having an inversely tapered shape is suppressed, and the effect is further enhanced if it is 10 parts by mass or less.

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

Examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole 1,3-bis (4-dimethyl) Ruaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N- Examples include tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole or 1-phenyl-5-ethoxycarbonylthiotetrazole.

The addition amount of the sensitizer is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the photosensitive resin. Photosensitivity improves that the addition amount with respect to 100 mass parts of photosensitive resins is 0.05 mass part or more. On the other hand, when the addition amount with respect to 100 parts by mass of the photosensitive resin is 10 parts by mass or less, excessive light absorption at the upper part of the coating film obtained by applying the photosensitive conductive paste D is suppressed. As a result, the produced conductive pattern tends to have a reverse taper shape, thereby suppressing a decrease in adhesion to the substrate.

The photosensitive conductive paste D of the present invention contains an epoxy resin. Epoxy resins include ethylene glycol-modified epoxy resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy Resin, glycidyl ether type epoxy resin, heterocyclic epoxy resin, and the like. From the viewpoint of adhesion to the substrate, bisphenol A type epoxy resin and hydrogenated bisphenol A type epoxy resin are preferable, and from the viewpoint of transparency to exposure light To hydrogenated bisphenol A type epoxy resin.

The addition amount of the epoxy resin is preferably 0.05 to 50 parts by mass with respect to 100 parts by mass of the photosensitive resin. Adhesiveness with the transparent electrode layer C can be improved as the addition amount with respect to 100 parts by mass of the photosensitive resin is 0.05 parts by mass or more. On the other hand, the solubility with respect to the developing solution of the photosensitive electrically conductive paste D can be kept favorable as the addition amount with respect to 100 mass parts of photosensitive resins is 50 mass parts or less.

In the present invention, the first exposure step of exposing the laminate in which the substrate A, the photosensitive layer B, and the transparent electrode layer C are laminated in this order is a step of exposing via a photomask, and without passing through a photomask. This is divided into a process of exposing the entire surface in the presence of oxygen. When exposed in the presence of oxygen, the outermost surface layer of the exposed portion does not proceed with curing due to oxygen inhibition, and tends to be highly soluble in the developer. In the first exposure process, a light source that emits i-line (365 nm), h-line (405 nm) or g-line (436 nm) such as high-pressure mercury lamp, ultra-high pressure mercury lamp, LED, etc. is used, vacuum adsorption exposure, proxy exposure, projection Various exposure methods such as exposure and direct drawing exposure are performed. The exposure dose for exposure in the presence of oxygen is preferably 100 to 1000 mJ / cm ² . Exposure dose can increase the adhesion to the photosensitive layer B and the conductive pattern C by the 100 mJ / cm ² or more, more preferably 1000 mJ / cm ² or less in the photosensitive layer B by below 800 mJ / cm ² Because the curing reaction does not proceed on the outermost surface and the solubility in the developer is maintained high, the curing reaction proceeds in the deep part of the film and the solubility in the developing solution decreases, so the difference in solubility between the outermost surface and the deep part of the film must be increased. Can do. In this state, only the outermost surface is dissolved in the developing solution during development, and the photosensitive conductive film D laminated thereon is also flowed into the developing solution, so that the generation of residues of the photosensitive conductive paste D described later is suppressed. can do.

Examples of the coating process for obtaining the photosensitive conductive film D by applying the photosensitive conductive paste D in the present invention include spin coating using a spinner, spray coating, roll coating, screen printing or blade coater, die coater, and calendar. Examples thereof include a coating method using a coater, a meniscus coater or a bar coater. The film thickness can be measured by using a stylus step meter such as Surfcom (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thickness at three random positions may be measured with a stylus-type step gauge (length measurement: 1 mm, scanning speed: 0.3 mm / sec), and the average value may be defined as the film thickness. it can.

In the present invention, as the second exposure step for exposing the photosensitive conductive film D, i-line (365 nm), h-line (405 nm), or g-line (436 nm) is emitted from a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an LED or the like. Various exposure methods such as vacuum suction exposure, proxy exposure, projection exposure, and direct drawing exposure are performed using a light source.

In the present invention, the laminate and the photosensitive conductive film D are collectively developed to obtain a laminated pattern of the transparent electrode pattern C and the conductive pattern D. The development process is performed using an alkaline developer, and the unexposed portion is dissolved. It is a process of removing and obtaining a desired pattern. Examples of the developer used for alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, and dimethyl acetate. Aminoethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine aqueous solutions may be mentioned. These aqueous solutions include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N -Polar solvents such as dimethylacetamide, dimethylsulfoxide or γ-butyrolactone; alcohols such as methanol, ethanol or isopropanol; Esters such as Le or propylene glycol monomethyl ether acetate, may be added to ketones or surfactants such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone.

Examples of the developer for organic development include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoryl Examples thereof include polar solvents such as amides or mixed solutions of these polar solvents and methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol, or ethyl carbitol.

As a developing method, for example, a method of spraying a developing solution onto the surface of a coating film while leaving or rotating a substrate, a method of passing a developing tank provided with a number of nozzles for discharging the developing solution with a conveyor, And a method of applying ultrasonic waves while immersing the substrate in a developer. From the viewpoint of uniformly developing a large area, development through a developing tank by a conveyor is preferable, and the development pressure when discharging the developer is preferably 0.02 to 0.2 MPa. When the development pressure is 0.02 MPa or more, it becomes easy to remove unexposed portions of the laminate and the coating film D all at once by striking force, and the generation of residues can be suppressed. If the pressure of the developer is 0.2 MPa or less, the adhesion of the conductive pattern D to the transparent electrode pattern C is not deteriorated.

In the laminated pattern obtained by the batch development, since the unexposed portions are removed all at once, the unexposed portions of the photosensitive layer B do not exist, and the conductive particle residues in the unexposed portions of the photosensitive layer B are removed. Can be eliminated.

Further, since the laminated pattern is connected to the transparent electrode pattern C over the entire surface of the conductive pattern D, high connection stability can be obtained and the contact resistance between the patterns can be kept low.

The laminated pattern obtained by batch development may be subjected to a rinsing treatment with a rinsing liquid. Examples of the rinsing liquid include water or an aqueous solution in which an alcohol such as ethanol or isopropyl alcohol or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate is added to water.

In the present invention, the temperature of the curing process for curing the laminated pattern is 100 to 300 ° C. The curing temperature is more preferably 120 to 180 ° C. When the curing temperature is less than 100 ° C., the volume shrinkage of the resin component does not increase, and the specific resistance may not be sufficiently low. On the other hand, when the curing temperature exceeds 300 ° C., the conductive pattern may not be manufactured on a material such as a substrate having low heat resistance.

As a method for curing the obtained laminated pattern, for example, heat drying with an oven, an inert oven or a hot plate, an electromagnetic wave such as an ultraviolet lamp, an infrared heater, a halogen heater or a xenon flash lamp, or heat drying with microwaves, or And vacuum drying. Heating increases the hardness of the manufactured laminated pattern, can suppress chipping or peeling due to contact with other members, and further improve the adhesion between the transparent electrode pattern C and the conductive pattern D. it can.

The laminate pattern forming substrate produced by the method for producing a laminate pattern forming substrate of the present invention is suitably used as a peripheral wiring for a touch panel. Examples of the touch panel system include a resistive film type, an optical type, an electromagnetic induction type, and a capacitance type. Since the capacitance type touch panel requires particularly fine wiring, the laminated pattern formation of the present invention is performed. A laminate pattern forming substrate manufactured by the substrate manufacturing method is more preferably used.

A laminate pattern manufactured by a touch panel manufacturing method, comprising a step based on the method for manufacturing a laminate pattern forming substrate of the present invention, is provided as a peripheral wiring, and the peripheral wiring is 50 μm pitch (wiring width + wiring) In the touch panel which is equal to or smaller than (width), the frame width can be narrowed and the view area can be widened.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The materials used in each example and comparative example are as follows.

[Photosensitive layer resin for forming photosensitive layer B (b)]
(Synthesis Example 1)
Copolymerization ratio (mass basis): EA / 2-ethylhexyl methacrylate (hereinafter “2-EHMA”) / BA / N-methylolacrylamide (hereinafter “MAA”) / AA = 20/40/20/5/15 .

In a nitrogen atmosphere reaction vessel, 150 g of diethylene glycol monoethyl ether acetate (hereinafter “DMEA”) was charged, and the temperature was raised to 80 ° C. using an oil bath. To this, a mixture of 20 g EA, 40 g 2-EHMA, 20 g BA, 5 g MAA, 15 g AA, 0.8

g

2,2′-azobisisobutyronitrile and 10 g DMEA was added. It was added dropwise over time. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 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 vacuum-dried for 24 hours to obtain a photosensitive resin (b-1).

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

In a nitrogen atmosphere reaction vessel, 150 g of DMEA was charged and heated to 80 ° C. using an oil bath. To this, a mixture of 20 g EA, 20 g 2-EHMA, 20 g BA, 5 g MAA, 25 g AA, 0.8

g

2,2′-azobisisobutyronitrile and 10 g DMEA was added. It was added dropwise over time. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 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 vacuum-dried for 24 hours to obtain a photosensitive resin (b-2).

(Synthesis Example 3)
Copolymerization ratio (mass basis): EA / 2-EHMA / BA / MAA / AA = 30/20/10/25/15.

In a nitrogen atmosphere reaction vessel, 150 g of DMEA was charged and heated to 80 ° C. using an oil bath. To this, a mixture consisting of 30 g EA, 20 g 2-EHMA, 10 g BA, 25 g MAA, 15 g AA, 0.8

g

2,2′-azobisisobutyronitrile and 10 g DMEA is 1 It was added dropwise over time. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 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 vacuum-dried for 24 hours to obtain a photosensitive resin (b-3).

[Photosensitive resin (d) contained in photosensitive conductive paste D]
(Synthesis Example 4)
Copolymerization ratio (mass basis): EA / 2-EHMA / styrene (hereinafter “St”) / glycidyl methacrylate (hereinafter “GMA”) / AA = 20/40/25/5/10.

In a nitrogen atmosphere reaction vessel, 150 g of DMEA was charged and heated to 80 ° C. using an oil bath. To this was added a mixture of 20 g EA, 40 g 2-EHMA, 25 g St, 10 g AA, 0.8

g

2,2′-azobisisobutyronitrile and 10 g DMEA dropwise over 1 hour. did. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Subsequently, a mixture consisting of 5 g GMA, 1 g triethylbenzylammonium chloride and 10 g DMEA was added dropwise over 0.5 hours. After completion of the dropwise addition, an additional reaction was performed for 2 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further vacuum-dried for 24 hours to obtain a photosensitive resin (d-1).

(Synthesis Example 5)
Copolymerization ratio (mass basis): ethylene oxide modified bisphenol A diacrylate (FA-324A; manufactured by Hitachi Chemical Co., Ltd.) / EA / GMA / AA = 60/20/5/15.

In a nitrogen atmosphere reaction vessel, 150 g of DMEA was charged and heated to 80 ° C. using an oil bath. To this was added dropwise a mixture of 60 g ethylene oxide modified bisphenol A diacrylate, 20 g EA, 15 g AA, 0.8

g

2,2′-azobisisobutyronitrile and 10 g DMEA over 1 hour. did. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Subsequently, a mixture consisting of 5 g GMA, 1 g triethylbenzylammonium chloride and 10 g DMEA was added dropwise over 0.5 hours. After completion of the dropwise addition, an additional reaction was performed for 2 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further vacuum-dried for 24 hours to obtain a photosensitive resin (d-2).

(Synthesis Example 6)
492.1 g carbitol acetate, 860.0 g EOCN-103S (manufactured by Nippon Kayaku Co., Ltd .; cresol novolac type epoxy resin; epoxy equivalent: 215.0 g / equivalent), 288. 3 g of AA, 4.92 g of 2,6-di-tert-butyl-p-cresol and 4.92 g of triphenylphosphine were charged, and the acid value of the reaction solution at a temperature of 98 ° C. was 0.5 mg · KOH / g. It was made to react until it became the following, and the epoxy carboxylate compound was obtained. Subsequently, 169.8 g of carbitol acetate and 201.6 g of tetrahydrophthalic anhydride were added to this reaction solution and 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 g of triphenylphosphine was charged and 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 epoxycarboxylate compound. Thereafter, 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 spiroglycol were added to the reaction solution at 45 ° C. The temperature was raised to. To this solution, 485.2 g of trimethylhexamethylene diisocyanate was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the reaction temperature was raised to 80 ° C., and the mixture was reacted for 6 hours until absorption near 2250 cm ⁻¹ disappeared by an infrared absorption spectrum measurement method to obtain 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 “IC-369”; manufactured by Ciba Japan Co., Ltd.).

[monomer]
Light acrylate MPD-A (hereinafter “MPD-A”; manufactured by Kyoeisha Chemical Co., Ltd.)

[Alcohol solvent]
Diethylene glycol (hereinafter “DEG”).

[Epoxy resin]
JER (registered trademark) 828 (hereinafter, “828”; manufactured by Mitsubishi Chemical Corporation)
JER (registered trademark) YX-8000 (hereinafter, “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. On one side of the substrate A, the composition B1 in which the photosensitive resin (b-1), MPD-A and IC-369 are mixed in a ratio of 100: 50: 1 is applied, heat-treated and dried. A photosensitive layer B1 having a thickness of 4 μm was formed.

<Formation of transparent electrode layer C>
A transparent electrode layer, which is a silver fiber (nanowire) thin film having a thickness of 1.0 μm, coated with an aqueous dispersion of silver fiber (solid content: 0.2% by mass) on the photosensitive layer B1 and dried at 100 ° C. for 5 minutes. C1 was formed.

<First exposure>
A photomask is brought into close contact with the transparent electrode layer C1, and the photosensitive layer B and the transparent electrode layer C are exposed at an exposure amount of 200 mJ / cm ² with an exposure machine having an ultrahigh pressure mercury lamp, and further 200 mJ without passing through the photomask. The entire surface of the photosensitive layer B1 and the transparent electrode layer C1 was exposed with an exposure amount of / cm ² .

<Preparation of photosensitive conductive paste D>
Put 100 g of photosensitive resin (d-1), 2.0 g of IC-369 and 5.0 g of diethylene glycol into a 100 mL clean bottle, and rotate and revolve vacuum mixer “Awatori Rentaro” (registered trademark) ) ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 17.0 g of a resin solution D1 (solid content: 70.1% by mass).

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

<Formation of photosensitive conductive film D>
A photosensitive conductive paste D1 is applied to the surface of the photosensitive layer B1 and the exposed transparent electrode layer C1 with a screen printer so that the film thickness becomes 5 μm, and then dried at 70 ° C. for 10 minutes to form the photosensitive conductive film D1. Obtained.

<Second exposure>
A photomask was brought into close contact with the photosensitive conductive film D1, and exposure was performed at an exposure amount of 300 mJ / cm ² using an exposure machine having an ultrahigh pressure mercury lamp.

<Formation of laminated pattern>
A 1% by weight sodium carbonate aqueous solution is spray-developed at a pressure of 0.1 MPa for 30 seconds on a laminated substrate composed of the transparent electrode layer C1 and the photosensitive conductive film D1, and then cured at 140 ° C. for 60 minutes to obtain the transparent electrode pattern C1 and A laminated pattern forming substrate composed of the conductive pattern D1 was manufactured.

<Method for evaluating residue>
The conductive pattern shown in FIG. 2 is formed, the total light transmittance of the unexposed part and the total light transmittance of only the first exposed area are measured, and compared with the total light transmittance before application of the conductive paste D, If the rate of decrease was 10% or less, it was judged as good if it was greater than 10%. The total light transmittance was obtained as a ratio of the transmittance light intensity to the incident light intensity using NDH-7000SP manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7361-1 (1997).

<Adhesion evaluation method>
The conductive pattern shown in FIG. 2 is formed, and a 1 mm square is set to 100 in the conductive pattern D using a cutter guide and a cutter in a portion where the first exposure region and the second exposure region overlap and only a portion of the second exposure region. Cut the adhesive tape (CT405AP-24, manufactured by Nichiban Co., Ltd.), peel off the adhesive tape at once, and count the number of conductive patterns D peeled off from the transparent electrode layer C. Sex was evaluated.

<Evaluation of ion migration resistance>
The laminated pattern forming substrate 1 on which the conductive pattern D1 shown in FIG. 3 is formed is put into a high-temperature and high-humidity tank at 85 ° C. and 85% RH, a voltage of DC 5 V is applied from the terminal portion, and the resistance value suddenly becomes 3 The short-circuiting time with a digit drop was confirmed. The same evaluation was repeated with a total of ten laminated pattern-forming substrates 1, and the average value thereof was taken as the value of ion migration resistance. The results are shown in Table 2.

(Examples 2 to 18)
When the transparent electrode layer C was ITO, a laminated pattern having the conditions shown in Table 1 was produced by the same method as in Example 1 except that the transparent electrode layer C was formed by the following method, and the same evaluation as in Example 1 was performed. 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 which is an ITO thin film made of ITO and having a thickness of 22 nm was formed using a sputtering apparatus equipped with an ITO sintered body target.

(Comparative Example 1)
A laminated pattern having the conditions shown in Table 1 was manufactured in the same manner as in Example 1 except that the laminated pattern was formed by the following method in the steps after the first exposure, and the same evaluation as in Example 1 was performed. went. The results are shown in Table 2.

<Formation of transparent electrode pattern C>
A photomask is brought into close contact with the transparent electrode layer C1, and the photosensitive layer B and the transparent electrode layer C are exposed at an exposure amount of 200 mJ / cm ² with an exposure machine having an ultrahigh pressure mercury lamp, and further 200 mJ without passing through the photomask. / cm ² after exposure of the photosensitive layer B1 and the transparent electrode layer C1 was entirely exposed with an exposure amount, and 30 seconds spray development with a 1 mass% sodium carbonate aqueous solution 30 ° C., to form a transparent electrode pattern C2 on the photosensitive layer B2 .

<Preparation of photosensitive conductive paste D>
Put 100 g of photosensitive resin (d-2), 1.0 g of OXE-01 and 5.0 g of diethylene glycol into a 100 mL clean bottle, and rotate and revolve vacuum mixer “Awatori Rentaro” (registered trademark) ARE-310 (manufactured by Shinky Co., Ltd.) 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 roller mill (EXAKT M-50; manufactured by EXAKT), and 85.0 g of a photosensitive conductive paste D2. Got.

<Formation of photosensitive conductive film D>
The photosensitive conductive paste D2 was applied to the surface of the photosensitive layer B2 and the transparent electrode pattern C2 with a screen printer so that the film thickness became 5 μm, and then dried at 70 ° C. for 10 minutes to obtain a photosensitive conductive film D2.

<Formation of laminated pattern>
It is exposed at an exposure amount of 300 mJ / cm ² with an exposure machine having an ultra-high pressure mercury lamp through a predetermined photomask, sprayed with a 1% by mass aqueous sodium carbonate solution at a pressure of 0.1 MPa for 30 seconds, and then at 140 ° C. Curing was performed for 60 minutes to produce a laminated pattern forming substrate composed of the transparent electrode pattern C2 and the conductive pattern D2.

(Comparative Example 2)
A laminated pattern having the conditions shown in Table 1 was manufactured in the same manner as in Example 1 except that the laminated pattern was formed by the following method in the steps after the first exposure, and the same evaluation as in Example 1 was performed. It was. The results are shown in Table 2.

<First exposure>
The entire surface of the photosensitive layer B3 and the transparent electrode layer C3 was exposed with an exposure amount of 200 mJ / cm ² without using a photomask.

<Preparation of photosensitive conductive paste D>
Into a 100 mL clean bottle, put 10.0 g of photosensitive resin (d-3), 2.0 g of OXE-01 and 5.0 g of diethylene glycol, and rotate and revolve vacuum mixer “Awatori Rentaro” (registered trademark) ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 17.0 g of a resin solution D3 (solid content: 70.1% by mass).

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

<Formation of photosensitive conductive film D>
A photosensitive conductive paste D3 was applied to the surface of the photosensitive layer B3 and the transparent electrode layer C3 with a screen printer so that the film thickness was 5 μm, and then dried at 70 ° C. for 10 minutes to obtain a photosensitive conductive film D3.
<Second exposure>
A photomask was adhered to the photosensitive conductive film D3, and exposure was performed at an exposure amount of 300 mJ / cm ² using an exposure machine having an ultrahigh pressure mercury lamp.

<Formation of laminated pattern>
A 1% by weight aqueous sodium carbonate solution is spray-developed at a pressure of 0.1 MPa for 30 seconds on a laminated substrate composed of the transparent electrode layer C3 and the photosensitive conductive film D3, and then cured at 140 ° C. for 60 minutes to obtain the transparent electrode pattern C3 and A laminated pattern forming substrate made of the conductive pattern D3 was produced.

From Table 2, it can be seen that in Examples 1 to 18, the residue was sufficiently suppressed, and a laminated pattern-forming substrate having excellent adhesion and ion migration resistance could be produced.

The present invention can suppress the generation of residues in unexposed areas, and maintains the adhesive force between the conductive pattern formed on the substrate and the photosensitive resin layer. Furthermore, the conductive pattern and the photosensitive resin layer It can be used to manufacture touch panels with excellent ion migration resistance.

1 Conductive pattern D
2 Transparent electrode layer C
3 Photosensitive layer B
4 Substrate A
5 Print area 6 of photosensitive conductive paste D Unexposed area 7 of photosensitive conductive film D Exposed area 8 of photosensitive conductive film D Terminal area

Claims

A first exposure step of exposing the laminate in which the substrate A, the photosensitive layer B, and the transparent electrode layer C are laminated in this order; and
A coating step of applying a photosensitive conductive paste D to obtain a photosensitive conductive film D on the surface of the laminate, and
A second exposure step of exposing the photosensitive conductive film D;
And developing the laminated body and the photosensitive conductive film D at a time to obtain a laminated pattern of the transparent electrode pattern C and the conductive pattern D,
The photosensitive layer B contains a photosensitive resin and a photopolymerization initiator,
The said photosensitive conductive paste D is a manufacturing method of the lamination pattern formation base material containing electroconductive particle, photosensitive resin, and a photoinitiator.
The method for producing 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 the presence of oxygen without using a photomask.
The method for producing a laminated pattern forming substrate according to claim 1 or 2, further comprising a curing step in which the laminated pattern is heated at 100 to 300 ° C.
The method for producing a laminated pattern forming substrate according to claims 1 to 3, wherein the transparent electrode layer contains metal nanowires.
The manufacturing method of the lamination pattern formation base material of Claim 4 containing silver nanowire as said metal nanowire.
The method for producing a laminated pattern forming substrate according to any one of claims 1 to 5, wherein the conductive particles contain silver particles.
A touch panel manufacturing method comprising a step based on the manufacturing method according to any one of claims 1 to 6.