JP6717439B1 - Laminated material - Google Patents

Abstract

(EN) Provided are a photosensitive conductive paste, a conductive pattern forming film, and a laminated member which can be finely processed and can suppress a decrease in conductivity of a metal fiber-containing transparent electrode under a high temperature and high humidity environment. A photosensitive conductive paste containing an organometallic compound (A), a carboxyl group-containing resin (B), a photopolymerization initiator (C), a compound (D) having an unsaturated double bond, and conductive particles (E). .. Further, a laminated member having a transparent electrode layer containing a binder resin (X) and a metal fiber on a base material, at least a part of the metal fiber being exposed, and a conductive layer, wherein the conductive layer is: It is a laminated member composed of a cured product of a composition containing an organometallic compound (A), a binder resin (Y) and conductive particles (E).

Description

The present invention relates to a photosensitive conductive paste, a conductive pattern forming film, and a laminated member.

2. Description of the Related Art In recent years, studies on capacitive touch panels have been actively conducted. The capacitive touch panel has a peripheral wiring connected to the transparent electrode around the display area. Known methods for forming the peripheral wiring include a printing method such as screen printing using a conductive paste, a photolithography method using a photoresist, and a photolithography method using a photosensitive conductive paste that can be microfabricated. .. In order to form a conductive pattern such as a peripheral wiring on a substrate having low heat resistance, conductive particles are brought into contact with each other in an insulating organic material without conducting a baking step of removing the organic material by heating at a high temperature, and a conductive path is formed. Need to be formed. As the conductive paste used in such a technique, for example, a compound having an amino group, a compound having a carboxyl group and an unsaturated double bond, a conductive filler, a conductive paste containing a photopolymerization initiator (see, for example, Patent Document 1), etc. Is proposed.

In addition, ITO (Indium-Tin-Oxide) was mainly used for the transparent electrode. However, in response to the recent demand for flexibility, ITO has a problem of low bending resistance. Therefore, transparent electrodes using metal fibers have been studied, and include, for example, a base material, a resin layer A formed on the base material, and a fibrous silver formed on the resin layer A. There has been proposed a laminated member (see, for example, Patent Document 2) including a transparent electrode layer B to be formed, and a conductive layer C formed on the resin layer A and the transparent electrode layer B.

International Publication No. 2014/156677 International Publication No. 2016/170943

In response to the recent demand for flexibility, a fibrous metal, which is superior in bending resistance to ITO, has been attracting attention as a transparent electrode.

Although the conductive paste described in Patent Document 1 can be finely processed by a photolithography method with a carboxyl group, when combined with the transparent electrode using the fibrous metal described in Patent Document 2, in a high temperature and high humidity environment, It has been clarified by the study of the present inventors that there is a problem of reducing the conductivity of the transparent electrode. Further, the laminated member described in Patent Document 2 also has a problem that the conductivity of the transparent electrode layer is reduced in a high temperature and high humidity environment.

Therefore, the present invention, even when used in combination with a metal fiber-containing transparent electrode, it is possible to suppress a decrease in conductivity of the metal fiber-containing transparent electrode under high temperature and high humidity environment, and a photosensitive conductive paste and conductive pattern forming The purpose is to provide a film.

In order to solve the above problems, the present invention mainly has the following configurations.

A photosensitive conductive paste containing an organometallic compound (A), a carboxyl group-containing resin (B), a photopolymerization initiator (C), a compound (D) having an unsaturated double bond, and conductive particles (E).

A laminated member having a transparent electrode layer and a conductive layer on a substrate I, wherein the transparent electrode layer contains a binder resin (X) and a metal fiber, and at least a part of the metal fiber is exposed. And the conductive layer comprises a cured product of a composition containing an organometallic compound (A), a binder resin (Y), and conductive particles (E).

The photosensitive conductive paste of the present invention can be finely processed, and even when used in combination with a metal fiber-containing transparent electrode, it is possible to suppress a decrease in conductivity of the transparent electrode under a high temperature and high humidity environment.

Further, the laminated member of the present invention can suppress the decrease in conductivity of the transparent electrode layer under a high temperature and high humidity environment.

It is a schematic diagram of the sample for specific resistance measurement used in the Example. It is a schematic diagram of the sample for resistance value measurement used in the Example. It is a cross-sectional schematic diagram of the sample for resistance value measurement used in the Example.

<Laminated member>
The laminated member of the present invention has a transparent electrode layer and a conductive layer on a substrate I.

<Substrate I>
Examples of the substrate I include polyester films such as polyethylene terephthalate (PET) films, polyimide films, aramid films, cycloolefin polymer (COP) films, epoxy resin substrates, polyetherimide resin substrates, polyetherketone resin substrates, and polysulfones. Examples thereof include a resin substrate, a glass substrate, a silicon wafer, an alumina substrate, an aluminum nitride substrate, a silicon carbide substrate, a decorative layer forming substrate, and an insulating layer forming substrate. Among these, a cycloolefin polymer (COP) film is preferable, which is unlikely to cause changes in optical properties and dimensions due to water absorption, has high transparency, has high heat resistance, and hardly causes oligomers. Examples of cycloolefin polymers include norbornene-based resins, monocyclic cyclic olefin-based resins, cyclic conjugated diene-based resins, vinyl alicyclic hydrocarbon-based resins, and hydrides thereof. Among these, the norbornene-based resin has good transparency and moldability, and thus can be preferably used.

The thickness of the substrate I is preferably 5 to 150 μm. When the thickness of the base material I is 5 μm or more, the base material I can be stably transported when forming the transparent electrode layer and the conductive layer, and uneven thickness of the transparent electrode layer and the conductive layer can be suppressed. .. The thickness of the substrate I is more preferably 10 μm or more. On the other hand, when the thickness of the substrate I is 150 μm or less, when forming a conductive layer made of a cured product of a photosensitive composition, the diffraction of the exposure light wrapping around the back side (non-patterned surface) of the substrate I Can be reduced, and the fine workability can be improved. In the case of the film substrate I, the thickness is more preferably 100 μm or less.

<Transparent electrode layer>
The transparent electrode layer contains a binder resin (X) and metal fibers, and has a structure in which at least a part of the metal fibers is exposed from the binder resin (X). The metal fiber has a function of imparting conductivity to the transparent electrode layer, and the binder resin (X) has a function as a binder for holding the metal fiber. In the transparent electrode layer, all of the metal fibers do not need to be covered with the binder resin (X) and have a fibrous shape, so that a part of the metal fibers is exposed from the binder resin (X). At least a part of the transparent electrode layer preferably has a laminated structure of a binder resin layer and a metal fiber layer containing metal fibers. However, the binder resin layer may have metal fibers, and the layer having the binder resin (X) and the metal fibers is classified as a binder resin layer.

The thickness of the transparent electrode layer is preferably 0.01 μm or more from the viewpoint of improving conductivity. On the other hand, the thickness of the transparent electrode layer is preferably 4.0 μm or less from the viewpoint of improving the visible light transmittance. Here, when the transparent electrode layer has a laminated structure of a binder resin layer and a metal fiber layer, the thickness of the transparent electrode layer means the total thickness thereof.

From the viewpoint of visible light transmittance of the transparent electrode layer, the light transmittance at wavelengths of 450 nm, 550 nm and 650 nm is preferably 80% or more. Here, attention was paid to the transmittance of blue light (450 nm), green light (550 nm), and red light (650 nm) as an index of visible light transmittance. The light transmittance of the transparent electrode layer can be measured by a spectrophotometer.

As a method for forming the transparent electrode layer, for example, in the case of a transparent electrode layer having a laminated portion of a binder resin layer and a metal fiber layer, after forming the metal fiber layer on the substrate I, the binder resin layer, the metal fiber of There is a method of forming the film so that at least a part of it is exposed. In this case, the binder resin layer containing the binder resin and the metal fiber and the laminated portion of the metal fiber layer are formed.

<Binder resin (X)>
As the binder resin (X), a carboxyl group-containing resin is preferable, which enhances alkali developability and can act as a photoresist for forming a pattern of the transparent electrode layer. Examples of the carboxyl group-containing resin include acrylic copolymers, carboxylic acid-modified epoxy resins, carboxylic acid-modified phenol resins, polyamic acids, and carboxylic acid-modified siloxane polymers. You may contain 2 or more types of these. Among these, an acrylic copolymer or a carboxylic acid-modified epoxy resin having a high ultraviolet light transmittance is preferable, and a carboxylic acid-modified epoxy resin is more preferable.

The acrylic copolymer is preferably a copolymer of an acrylic monomer and an unsaturated acid or its acid anhydride.

Examples of acrylic monomers include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, iso-butyl acrylate, iso-propane acrylate, glycidyl acrylate, butoxytriethylene glycol acrylate, dicyclopentanyl acrylate, and dicyclopentanyl acrylate. Cyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoro Pentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, 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, triglycerol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, acrylamide, N-methoxymethylacrylamide, N -Ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, methacrylphenol, methacrylamidephenol, γ-acryloxypropyltrimethoxysilane, N-(2-hydroxyphenyl)acrylamide, N-(3 -Hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)acrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl Acrylate, p-hydroxyphenyl acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-(2-hydroxyphenyl)ethyl acrylate, 2-(3-hydroxyphenyl)ethyl acrylate, 2-(4- Examples thereof include phenolic hydroxyl group-containing monomers such as hydroxyphenyl)ethyl acrylate, and compounds in which those acrylate groups are substituted with methacryl groups. You may use 2 or more types of these. Among these, ethyl acrylate, 2-hydroxyethyl acrylate, and isobornyl acrylate are preferable.

Examples of unsaturated acids or acid anhydrides thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and acid anhydrides thereof. You may use 2 or more types of these. The acid value of the acrylic copolymer can be adjusted by the copolymerization ratio of the unsaturated acid.

The carboxylic acid-modified epoxy resin is preferably a reaction product of an epoxy compound and an unsaturated acid or an unsaturated acid anhydride. Here, the carboxylic acid-modified epoxy resin is a compound obtained by modifying an epoxy group of an epoxy compound with a carboxylic acid or a carboxylic anhydride, and does not contain an epoxy group.

Examples of the epoxy compound include glycidyl ethers, glycidyl amines, and epoxy resins. More specifically, as the glycidyl ethers, for example, 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, biphenol diglycidyl ether, tetramethyl biphenol glycidyl ether, Trimethylolpropane triglycidyl ether, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and the like can be mentioned. Examples of the glycidyl amines include tert-butyl glycidyl amine. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, and hydrogenated bisphenol A type epoxy resin. You may use 2 or more types of these.

An unsaturated double bond can be introduced by reacting the above acrylic copolymer or carboxylic acid-modified epoxy resin with a compound having an unsaturated double bond such as glycidyl (meth)acrylate. By introducing an unsaturated double bond into the carboxyl group-containing resin, it is possible to improve the crosslink density of the exposed portion during exposure, widen the development margin, and improve the fine workability.

The acid value of the carboxyl group-containing resin is preferably 50 to 250 mgKOH/g. When the acid value is 50 mgKOH/g or more, the solubility in the developing solution is high, and the development residue can be suppressed. The acid value is more preferably 60 mgKOH/g or more. On the other hand, when the acid value is 250 mgKOH/g or less, excessive dissolution in the developing solution can be suppressed, and film loss in the pattern forming portion can be suppressed. The acid value is more preferably 200 mgKOH/g or less. The acid value of the carboxyl group-containing resin can be measured according to JIS K 0070 (1992).

For example, in the case of an acrylic copolymer, the acid value of the carboxyl group-containing resin can be adjusted to a desired range by the ratio of unsaturated acid in the constituent components. In the case of a carboxylic acid-modified epoxy resin, it can be adjusted to a desired range by reacting a polybasic acid anhydride. In the case of a carboxylic acid-modified phenol resin, it can be adjusted to a desired range by the ratio of polybasic acid anhydride in the constituent components.

<Metal fiber>
Examples of the metal fiber include fibers made of indium, tin, zinc, gallium, antimony, titanium, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten, or oxides or complex oxides of these metals. And so on. You may contain 2 or more types of these. Examples of the metal oxides and metal composite oxides include ITO, indium zinc oxide, indium oxide-zinc oxide composite oxide, aluminum zinc oxide, gallium zinc oxide, fluorine zinc oxide, fluorine indium oxide, antimony. Examples thereof include tin oxide and fluorine tin oxide. Among these, metal fibers selected from silver, gold and copper are preferable from the viewpoint of conductivity, and silver fibers are more preferable from the viewpoint of cost and stability.

The metal fiber has a high probability of contact between metals due to its shape, and thus has excellent conductivity. Further, it has an effect of making the transparent electrode layer less visible.

The fiber diameter of the metal fiber is preferably 1 nm or more, more preferably 3 nm or more. On the other hand, the fiber diameter of the metal fiber is preferably 50 nm or less, more preferably 10 nm or less. The fiber length of the metal fiber is preferably 1 μm or more, more preferably 3 μm or more. On the other hand, the fiber length of the metal fiber is preferably 500 μm or less, more preferably 100 μm or less, still more preferably 10 μm or less. The fiber diameter and the fiber length of the metal fibers are 100 randomly selected by observing the metal fibers at a magnification of 200 to 5000 times using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). With respect to the metal fiber, the respective fiber diameters and fiber lengths can be measured and calculated from the respective number average values.

Examples of the method for forming the metal fiber layer include a sputtering method, an ion plating method, and a coating method.

Examples of the method for forming the binder resin layer include a method in which a binder resin solution is applied to a desired film thickness and then dried. Examples of the coating method of the binder resin solution include spin coating using a spinner, spray coating, roll coating, screen printing, coating using a blade coater, die coater, calendar coater, meniscus coater, and bar coater. Examples of the method for drying the coating film include heating and drying with an oven, a hot plate, infrared rays, and the like, and vacuum drying. The drying temperature is preferably 50 to 180° C., and the drying time is preferably 1 minute to several hours.

<Conductive layer>
The conductive layer is preferably composed of a cured product of a composition containing the organometallic compound (A), the binder resin (Y) and the conductive particles (E). The conductive layer is a composite of an organic component and an inorganic component, and the conductive particles (E) are brought into contact with each other by an atom diffusion phenomenon during thermal curing, thereby exhibiting conductivity. The binder resin (Y) has a function as a binder that holds the conductive particles (E). The present inventors corrode the metal fibers in the transparent electrode layer under a high temperature and high humidity environment at the contact portion with the conductive layer, thereby increasing the resistance value of the transparent electrode layer, that is, decreasing the conductivity. Found. Therefore, by containing the organometallic compound (A) in the conductive layer, the film formation at the interface between the transparent electrode layer and the conductive layer is promoted, and the metal fiber of the transparent electrode layer is corroded even in a high temperature and high humidity environment. It was found that it is possible to suppress the decrease in conductivity and the decrease in conductivity. In addition, when the conductive layer is used for the peripheral wiring, the requirement for being less visible (non-visibility) is lower than that for the transparent electrode layer formed in the display area. The influence of coloring of the organometallic compound (A) can be reduced as compared with the case of containing (A).

Further, the photosensitive conductive paste of the present invention comprises an organometallic compound (A), a carboxyl group-containing resin (B), a photopolymerization initiator (C), a compound (D) having an unsaturated double bond and conductive particles ( It is preferable to contain E).

Since the photosensitive conductive paste contains a photopolymerization initiator (C) and a reactive monomer (D) having an unsaturated double bond, the photosensitive conductive paste is insolubilized in alkali by photopolymerization by exposure in the photolithography method. However, it can be finely processed. The carboxyl group-containing resin (B) enhances alkali developability and enables fine processing by photolithography.

The conductive layer in the present invention preferably comprises a cured product of the photosensitive conductive paste of the present invention. The contents of the organometallic compound (A) and the conductive particles (E) in the conductive layer are the same as the contents in the paste described below.

<Organometallic compound (A)>
Examples of the organometallic compound (A) include organoaluminum compounds, organotitanium compounds and organozirconium compounds. Examples of the organic aluminum compound include metal alkoxide compounds such as aluminum secondary butoxide; metal chelate compounds such as aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate and aluminum trisethylacetoacetate. Examples of the organic titanium compound include metal alkoxide compounds such as tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, and tetraoctyl titanate; titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, dodecylbenzenesulfonic acid. Titanium compound, titanium phosphate compound, titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate ammonium salt, titanium lactate, titanium triethanolaminate, tetraisopropyl titanate, tetratertiary butyl titanate, tetrastearyl titanate, titanium acetylacetate And a metal chelate compound such as titanium octylene glycolate compound, titanium octylene glycolate, titanium isostearate, titanium lactate, titanium lactate ammonium salt, titanium diethanolaminate, and titanium aminoethylamino ethanolate. Examples of the organic zirconium compound include metal alkoxide compounds such as normal propyl zirconate and normal butyl zirconate; zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethyl acetoacetate, zirconium octylate compound, zirconium stearate, and chloride. Examples thereof include metal chelate compounds such as zirconyl compounds and zirconium lactate ammonium salts. You may contain 2 or more types of these. Among these, a metal chelate compound is preferable from the viewpoint of further suppressing the decrease in conductivity of the transparent electrode layer under a high temperature and high humidity environment.

The content of the organometallic compound (A) in the photosensitive conductive paste of the present invention is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (B). When the content of the organometallic compound (A) is 0.1 part by weight or more, it is easy to promote the formation of a film on the conductive pattern interface, and it is possible to further suppress the decrease in conductivity of the transparent electrode layer. The content of the organometallic compound (A) is more preferably 0.5 part by weight or more, still more preferably 1 part by weight or more. On the other hand, when the content of the organometallic compound (A) is 10 parts by weight or less, the crosslink density in the exposed area is improved, the development margin can be widened, and the fine workability can be further improved. The content of the organometallic compound (A) is more preferably 7 parts by weight or less.

<Binder resin (Y)>
<Carboxyl group-containing resin (B)>
The binder resin (Y) is preferably a carboxyl group-containing resin (B), and examples of the carboxyl group-containing resin (B) include those exemplified as the binder resin (X) constituting the transparent electrode layer described above.

As the binder resin (Y), those having a urethane bond can also be preferably used. When the binder resin (Y) has a urethane bond, it is possible to improve the bending resistance of the obtained conductive pattern. As a method of introducing a urethane bond into the binder resin (Y), for example, in the case of a hydroxyl group-containing acrylic copolymer or a hydroxyl group-containing carboxylic acid-modified epoxy resin, a method of reacting these hydroxyl groups with a diisocyanate compound can be mentioned. .. Examples of the diisocyanate compound include hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tridene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allyl cyan diisocyanate and norbornane diisocyanate. You may use 2 or more types of these.

As the binder resin (Y), those having a phenolic hydroxyl group can also be preferably used. When the binder resin (Y) has a phenolic hydroxyl group, it can form a hydrogen bond with a polar group such as a hydroxyl group or an amino group on the surface of the base material, and can improve the adhesion between the obtained conductive pattern and the base material. ..

Among these, a carboxylic acid-modified epoxy resin having a urethane bond is more preferable.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C), benzophenone derivative, acetophenone derivative, thioxanthone derivative, benzyl derivative, benzoin derivative, oxime compound, α-hydroxyketone compound, α-aminoalkylphenone compound, phosphine oxide compound, anthrone Examples thereof include compounds and anthraquinone compounds. Examples of the benzophenone derivative include benzophenone, methyl O-benzoylbenzoate, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4,4′-dichlorobenzophenone, fluorenone, 4 -Benzoyl-4'-methyldiphenyl ketone and the like. Examples of the acetophenone derivative include p-t-butyldichloroacetophenone, 4-azidobenzalacetophenone, and 2,2′-diethoxyacetophenone. Examples of the thioxanthone derivative include thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and the like. Examples of the benzyl derivative include benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal and the like. Examples of the benzoin derivative include benzoin, benzoin methyl ether, and benzoin butyl ether. Examples of the oxime compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] and ethanone-1-[9-ethyl-6-(2-methylbenzoyl). )-9H-carbazol-3-yl]-1-(O-acetyloxime), 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- Examples include propanetrione-2-(O-benzoyl)oxime. Examples of the α-hydroxyketone compound include 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-. Methyl-1-propan-1-one and the like can be mentioned. Examples of the α-aminoalkylphenone compound include 2-methyl-(4-methylthiophenyl)-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl). )-Butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one and the like. Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of the anthrone compound include anthrone, benzanthrone, dibenzosuberone, methyleneanthrone and the like. Examples of the anthraquinone compound include anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone and β-chloroanthraquinone. You may contain 2 or more types of these. Among these, oxime compounds having high photosensitivity are preferable.

The content of the photopolymerization initiator (C) in the photosensitive conductive paste of the present invention is preferably 0.05 to 30 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (B). When the content of the photopolymerization initiator (C) is 0.05 parts by weight or more, the curing density of the exposed area increases, and the residual film rate after development can be increased. The content of the photopolymerization initiator (C) is more preferably 1 part by weight or more. On the other hand, when the content of the photopolymerization initiator (C) is 30 parts by weight or less, excessive light absorption by the photopolymerization initiator (C) in the upper portion of the coating film obtained by coating the conductive paste is suppressed. As a result, the conductive pattern can be easily formed into a tapered shape, and the adhesion with the substrate can be improved.

<Compound (D) having an unsaturated double bond>
Examples of the compound (D) having an unsaturated double bond include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, glycerin dimethacrylate, 2-Hydroxy-3-acryloyloxypropyl methacrylate, dimethylol-tricyclodecane dimethacrylate, tripropylene glycol diacrylate, dioxane glycol diacrylate, cyclohexane dimethanol dimethacrylate, tricyclodecane dimethanol diacrylate, ethoxylation (4) Bifunctional monomers such as bisphenol A diacrylate, ethoxylated (10) bisphenol A diacrylate, acrylic acid adduct of ethylene glycol diglycidyl ether, acrylic acid adduct of neopentyl glycol diglycidyl ether; pentaerythritol triacrylate, pentaerythritol Trifunctional monomers such as triacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxytriacrylate, glycerine propoxytriacrylate; dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxytetraacrylate, ditrimethylolpropane tetraacrylate, etc. Tetrafunctional monomers; reactive monomers such as EBECRYL204, EBECRYL210, EBECRYL220, EBECRYL264, EBECRYL265, EBECRYL284 manufactured by Daicel Cytec and urethane bond-containing monomers such as CN972, CN975 and CN978 manufactured by Sartomer. You may contain 2 or more types of these. Among these, the urethane bond-containing monomer is preferable because it can improve the flex resistance of the conductive layer.

The content of the compound (D) having an unsaturated double bond in the photosensitive conductive paste of the present invention is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (B). When the content of the compound (D) having an unsaturated double bond is 1 part by weight or more, the crosslink density of the exposed area is increased, and the difference in solubility between the unexposed area and the exposed area in the developing solution can be increased. Therefore, the fine workability can be further improved. On the other hand, when the content of the compound (D) having an unsaturated double bond is 100 parts by weight or less, the Tg of the obtained conductive pattern can be suppressed and the bending resistance can be improved.

<Conductive particles (E)>
Examples of the conductive particles (E) include silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, indium, magnesium, cobalt, zinc, potassium, lithium, iron and mercury. , Beryllium, cadmium, rhodium, ruthenium, iridium and alloys thereof. You may contain 2 or more types of these. Among these, particles of a metal selected from silver, gold and copper are preferable from the viewpoint of conductivity, and silver particles are more preferable from the viewpoint of cost and stability. The surface of the conductive particles (E) may be covered with a resin, an inorganic oxide or the like.

The aspect ratio, which is a value obtained by dividing the major axis length of the conductive particles (E) by the minor axis length, is preferably 1.1 to 2.0. Here, the aspect ratio of the conductive particles (E) is randomly selected by observing the conductive particles (E) at a magnification of 15,000 using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The major axis length and the minor axis length of each of the 100 primary particles of the conductive particles (E) are measured, and the average value of the two can be calculated.

The particle diameter of the conductive particles (E) is preferably 0.05 to 5.0 μm. By setting the particle diameter of the conductive particles (E) to 0.05 μm or more, it is possible to appropriately suppress the interaction between the particles and improve the dispersibility of the conductive particles (E) in the photosensitive conductive paste. it can. The particle diameter of the conductive particles (E) is more preferably 0.1 μm or more. On the other hand, when the particle diameter of the conductive particles (E) is 5.0 μm or less, the surface smoothness, pattern accuracy and dimensional accuracy of the obtained conductive pattern can be improved. The particle diameter of the conductive particles (E) is more preferably 2.0 μm or less. Here, the particle diameter of the conductive particles (E) can be measured by using a laser irradiation type particle size distribution meter. The value of D50 of the particle size distribution obtained by the measurement is defined as the particle diameter (D50) of the conductive particles (E).

The content of the conductive particles (E) in the photosensitive conductive paste of the present invention is preferably 65 to 90% by weight based on the total solid content. When the content of the conductive particles (E) is 65% by weight or more, the contact probability between the conductive particles (E) during curing is improved, the conductivity is further improved, and the disconnection probability can be reduced. .. The content of the conductive particles (E) is more preferably 70% by weight or more. On the other hand, when the content of the conductive particles (E) is 90% by weight or less, the translucency of the coating film in the exposure step is improved, and the fine workability and bending resistance can be further improved. Here, the total solid content refers to all the constituent components of the photosensitive conductive paste excluding the solvent.

<Other ingredients>
The composition forming the conductive layer may contain a sensitizer together with the photopolymerization initiator (C). Examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-dimethylaminobenzal)cyclohexanone, and 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-dimethylaminobenzal)acetone, 1,3-carbonylbis(4-diethylaminobenzal)acetone, 3,3-carbonylbis(7-diethylaminocoumarin), N-phenyl-N-ethyl Ethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like can be mentioned. You may contain 2 or more types of these.

The content of the sensitizer in the photosensitive conductive paste of the present invention is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (B). When the content of the sensitizer is 0.05 parts by weight or more, photosensitivity is improved. On the other hand, when the content of the sensitizer is 10 parts by weight or less, excessive light absorption in the upper portion of the coating film obtained by coating the photosensitive conductive paste is suppressed. As a result, the conductive pattern can be easily formed into a tapered shape, and the adhesion with the substrate can be further improved.

The photosensitive conductive paste of the present invention may contain a solvent. Examples of the solvent include N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, ethyl lactate, 1-methoxy-2-propanol. , 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Examples include monobutyl ether, diethylene glycol, 2,2,4,-trimethyl-1,3-pentanediol monoisobutyrate. You may contain 2 or more types of these. The boiling point of the solvent is preferably 150°C or higher. When the boiling point is 150° C. or higher, the volatilization of the solvent is suppressed, and the thickening of the photosensitive conductive paste can be suppressed.

The photosensitive conductive paste of the present invention is a non-photosensitive polymer having no unsaturated double bond in the molecule, a plasticizer, a leveling agent, a surfactant, a silane coupling agent, as long as the desired properties are not impaired. Additives such as agents, defoamers and pigments can be contained.

Examples of the non-photosensitive polymer include polyethylene terephthalate, a polyimide precursor, and a ring-closed polyimide.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.

Examples of the leveling agent include a special vinyl polymer and a special acrylic polymer.

Examples of the silane coupling agent include methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and vinyltrimethoxysilane. Examples thereof include methoxysilane.

The photosensitive conductive paste of the present invention comprises an organometallic compound (A), a carboxyl group-containing resin (B), a photopolymerization initiator (C), a compound having an unsaturated double bond (D), and conductive particles (E). And it can manufacture by mixing a solvent and an additive as needed. Examples of the mixing device include a disperser such as a three-roller mill, a ball mill, and a planetary ball mill, and a kneader.

The thickness of the conductive layer is preferably 0.5 to 10.0 μm. When the thickness of the conductive layer is 0.5 μm or more, it is possible to suppress variation in resistance value for each wiring and easily form a pattern on a substrate having irregularities. The thickness of the conductive layer is more preferably 1.0 μm or more. On the other hand, when the thickness of the conductive layer is 10.0 μm or less, in the case of forming the conductive layer from a photosensitive composition, light easily reaches the deep portion of the film during exposure, and the development margin can be widened. The thickness of the conductive layer is more preferably 5.0 μm or less. The thickness of the conductive layer can be measured using, for example, a stylus profilometer such as "Surfcom" (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thickness at three random positions is measured by a stylus type step meter (length measurement: 1 mm, scanning speed: 0.3 mm/sec), and the average value is taken as the film thickness.

<Method of forming conductive layer>
Examples of the method of forming the conductive layer include a method of curing the composition containing the organometallic compound (A), the binder resin (Y), the conductive particles (E) and, if necessary, other components. ..

The method of forming the conductive layer will be described by taking the case of using a photosensitive conductive paste as an example.

The photosensitive conductive paste is applied to the laminated member in which the transparent electrode layer is laminated on the substrate I by the method described above, and dried. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, screen printing, coating using a blade coater, die coater, calendar coater, meniscus coater or bar coater. Examples of the drying method include heat drying using an oven, a hot plate, infrared rays, and the like, and vacuum drying. The drying temperature is preferably 50 to 180° C., and the drying time is preferably 1 minute to several hours.

The coating film thickness can be appropriately determined according to the coating method, the solid content concentration and the viscosity of the photosensitive conductive paste, and the dry film thickness of the photosensitive conductive paste is described as the preferable thickness of the conductive layer. It is preferable to adjust to the above range. The film thickness of the dry film of the photosensitive conductive paste can be measured, for example, similarly to the film thickness of the conductive layer.

When the conductive pattern is formed by the photolithography method, it is preferable to expose the dry film of the photosensitive conductive paste through an arbitrary pattern forming mask. As a light source for exposure, i-line (365 nm), h-line (405 nm) or g-line (436 nm) of a mercury lamp is preferably used.

After the exposure, the unexposed portion is dissolved and removed by developing with a developing solution to obtain a desired pattern.

Examples of the developer for alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethyl acetate. Examples thereof include aqueous solutions of aminoethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like. You may use 2 or more types of these. Depending on the case, polar solutions such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and γ-butyrolactone may be added to these aqueous solutions; methanol, ethanol, isopropanol, etc. Alcohols; ethyl lactate, propylene glycol monomethyl ether acetate, etc. esters; cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. ketones; one or more surfactants may be added.

As the developing method, for example, a method of spraying a developing solution on a dry film surface while leaving or rotating a substrate having a dry film of exposed photosensitive conductive paste, a substrate having a dry film of exposed photosensitive conductive paste Examples thereof include a method of immersing in a developing solution and a method of applying ultrasonic waves while immersing a substrate having a dried film of exposed photosensitive conductive paste in a developing solution.

After development, a rinsing treatment with a rinsing solution may be performed. Examples of the rinse liquid include water or an aqueous solution in which alcohols such as ethanol and isopropyl alcohol or esters such as ethyl lactate and propylene glycol monomethyl ether acetate are added to water.

A conductive pattern can be obtained by heating and curing the pattern obtained by development. The curing temperature is preferably 100 to 200°C. When the curing temperature is 100° C. or higher, atomic diffusion can be sufficiently induced and the conductivity can be further improved. The curing temperature is more preferably 120° C. or higher. On the other hand, when the curing temperature is 200° C. or lower, the degree of freedom in selecting the base material can be increased. The curing temperature is more preferably 150°C or lower.

Examples of the curing method include heating and drying with an oven, an inert oven, and a hot plate, heating and drying with electromagnetic waves and microwaves such as an ultraviolet lamp, an infrared heater, a halogen heater, and a xenon flash lamp, and vacuum drying. Since the hardness of the conductive pattern is increased by heating, chipping or peeling due to contact with other members can be suppressed, and further, the adhesiveness between the conductive layer and the substrate can be improved.

<Conductive pattern forming film>
The conductive pattern forming film of the present invention has a dry film of the above-mentioned photosensitive conductive paste on the release film.

The release film preferably has a release layer on the film surface. Examples of the release agent constituting the release layer include long-chain alkyl release agents, silicone release agents, and fluorine release agents. You may use 2 or more types of these. Among these, even when the release agent is transferred during transfer, phenomena such as cissing of the developer are less likely to occur in the post-process, particularly in the development process, and in-plane unevenness is suppressed to improve fine workability. A long-chain alkyl-based release agent is preferable because it can be improved. The thickness of the release layer is preferably 50 to 500 nm. When the thickness of the release layer is 50 nm or more, transfer unevenness at the time of transfer can be suppressed, and when it is 500 nm or less, transfer of the release agent at the time of transfer can be reduced.

The release force of the release film is preferably 500 to 5000 mN/20 mm. When the peeling force is 500 mN/20 mm or more, it is possible to suppress the occurrence of cissing when forming a dry film of the photosensitive conductive paste. When the peeling force is 5000 mN/20 mm or less, the process margin at the time of transferring the dry film to the base material can be widened. Here, the release force of the release film in the present invention means that the acrylic adhesive tape "31B" manufactured by Nitto Denko Corporation is applied to the release layer surface of the release film using a 2 kg roller, and after 30 minutes, the acrylic film is used. It indicates the peeling force when the adhesive tape is peeled at a peeling angle of 180° and a peeling speed of 0.3 m/min.

Examples of the substrate II used for the releasable film include a film containing polyethylene terephthalate, cycloolefin, polycarbonate, polyimide, aramid, fluororesin, acrylic resin and/or polyurethane resin. From the viewpoint of optical properties, a film containing polyethylene terephthalate, cycloolefin and/or polycarbonate is preferable. If the substrate II has high optical characteristics, it can be exposed through the release film, and since the dry film and the photomask do not come into contact with each other, mask contamination can be suppressed. The thickness of the substrate II is preferably 5 to 150 μm. When the thickness of the base material II is 5 μm or more, the base material II can be stably transported when forming a dry film of the photosensitive conductive paste, and unevenness in the thickness of the dry film can be suppressed. The thickness of the substrate II is more preferably 10 μm or more. On the other hand, when the thickness of the substrate II is 150 μm or less, the influence of the diffraction of the exposure light can be reduced during the exposure through the release film, and the fine patterning property can be further improved. The thickness of the substrate II is more preferably 30 μm or less.

The film thickness of the dry film of the photosensitive conductive paste is preferably 0.5 to 10.0 μm. When the thickness of the dry film is 0.5 μm or more, it is possible to suppress the variation in resistance value for each wiring and to easily form a pattern on the base material II having irregularities. The thickness of the dried film is more preferably 1.0 μm or more. On the other hand, when the film thickness of the dry film is 10.0 μm or less, it is easy for light to reach the deep part of the dry film during exposure, and the development margin can be widened. The dry film thickness is more preferably 5.0 μm or less. The film thickness of the dry film of the photosensitive conductive paste can be measured by using a stylus profilometer, such as "Surfcom" (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thickness at three random positions is measured by a stylus type step meter (length measurement: 1 mm, scanning speed: 0.3 mm/sec), and the average value is taken as the film thickness.

The film for forming a conductive pattern of the present invention can be produced by applying the above-mentioned photosensitive conductive paste onto a release film and drying. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, screen printing, coating using a blade coater, die coater, calendar coater, meniscus coater or bar coater. Examples of the drying method include heat drying using an oven, a hot plate, infrared rays, and the like, and vacuum drying. The drying temperature is preferably 50 to 180° C., and the drying time is preferably 1 minute to several hours.

<Method of forming conductive pattern on substrate III using photosensitive conductive paste>
Next, a method for forming a conductive pattern on the substrate III using the photosensitive conductive paste of the present invention will be described. A conductive film is formed on the base material III by forming a dry film of the photosensitive conductive paste of the present invention on the base material III, patterning by exposing and developing the dry film, and curing the obtained pattern. A pattern can be formed. The dry film of the photosensitive conductive paste may be formed by applying the photosensitive conductive paste of the present invention onto the substrate III and drying it, or using the film for forming a conductive pattern described above to form a photosensitive conductive paste. It may be formed by transferring a dry film of the paste onto the substrate III.

Examples of the substrate III include polyester films such as polyethylene terephthalate (PET) films, polyimide films, aramid films, cycloolefin polymer (COP) films, epoxy resin substrates, polyetherimide resin substrates, polyetherketone resin substrates, and polysulfones. Examples thereof include a resin substrate, a glass substrate, a silicon wafer, an alumina substrate, an aluminum nitride substrate, a silicon carbide substrate, a decorative layer forming substrate, and an insulating layer forming substrate.

Examples of the method for applying the photosensitive conductive paste include the methods exemplified as the method for applying the photosensitive conductive paste in the method for producing a film for forming a conductive pattern.

The coating film thickness can be appropriately determined according to the coating method, the solid content concentration and the viscosity of the photosensitive conductive paste, and the dry film thickness of the photosensitive conductive paste is 0.1 to 50.0 μm. It is preferable to set so that When the film thickness of the dry film is 0.1 μm or more, it is possible to suppress the variation in the resistance value for each wiring. The thickness of the dry film is more preferably 0.5 μm or more, further preferably 1.0 μm or more. On the other hand, when the film thickness of the dry film is 50.0 μm or less, it is easy for light to reach the deep part of the dry film during exposure, and the development margin can be widened. The thickness of the dried film is more preferably 10.0 μm or less. The thickness of the dry film of the photosensitive conductive paste can be measured in the same manner as the thickness of the dry film of the photosensitive conductive paste in the conductive pattern forming film.

After forming the coating film, it is preferable to dry the coating film to volatilize the solvent. Examples of the drying method include the methods exemplified as the method for drying the photosensitive conductive paste in the conductive pattern forming film.

As a method of transferring the conductive pattern forming film of the present invention on the substrate, for example, so that the dry film of the photosensitive conductive paste is in contact with the substrate, after laminating the conductive pattern forming film of the present invention on the substrate, A method of transferring by heating and pressing using a nip roller or the like can be mentioned. Hereinafter, this method is called thermal transfer. In order to improve transferability, it is preferable to heat the nip roller to 50 to 120° C. for transfer.

When the conductive pattern is formed by the photolithography method, it is preferable to expose the dry film of the photosensitive conductive paste through an arbitrary pattern forming mask. When the method of providing a dry film by transferring the conductive pattern forming film of the present invention is used, it may be exposed through the release film of the conductive pattern forming film, or the release film is peeled off. You may expose after doing. As a light source for exposure, i-line (365 nm), h-line (405 nm) or g-line (436 nm) of a mercury lamp is preferably used.

After the exposure, the unexposed portion is dissolved and removed by developing with a developing solution to obtain a desired pattern. When the method of providing a dry film by transferring the conductive pattern forming film of the present invention is used, it is preferable to perform development after peeling the release film. As another embodiment, it is possible to employ a method in which the film for conductive pattern formation of the present invention is subjected to exposure and development of a dry film in the same manner as above, and then the obtained pattern is transferred to a substrate.

Examples of the developing method and the curing method include the methods exemplified as the developing method and the curing method in forming a conductive layer using a photosensitive conductive paste.

The conductive pattern obtained by using the photosensitive conductive paste or the film for forming a conductive pattern of the present invention is suitably used for wiring applications used in touch panels, laminated ceramic capacitors, laminated inductors, solar cells and the like. Among them, it is suitable for use in touch panels and is more preferably used as peripheral wiring having relatively low requirements for visibility, particularly as peripheral wiring to be combined with transparent electrodes made of fibrous metal in a flexible type touch panel. Silver fibers are preferred as the fibrous metal forming the transparent electrode.

Further, by using the conductive pattern forming film of the present invention, it is possible to easily form a wiring on a curved substrate or an acute-angled surface such as a substrate end surface. The dry film of the photosensitive conductive paste of the present invention in the conductive pattern forming film of the present invention is exposed and developed to form a pattern on the release film. A conductive pattern forming film is laminated on the substrate so that the pattern is in contact with a curved surface on which wiring is to be formed or an end surface of the substrate. By heating and pressing the laminate to thermally transfer the pattern onto the substrate, and then heating and curing the pattern, the wiring can be formed on the curved surface or the end surface of the substrate. A substrate with double-sided wiring, in which wiring is formed on both sides of the substrate via the substrate end face by thermally transferring the pattern to both faces and end faces of the substrate using this method, and then heating the pattern to cure. Can be manufactured. Examples of the method for thermally transferring the pattern formed on the release film include thermocompression bonding using a heat roll or a mold.

INDUSTRIAL APPLICABILITY The laminated member of the present invention is suitable for use in substrates with wiring used in touch panels, laminated ceramic capacitors, laminated inductors, solar cells and the like. Above all, it is preferably used for touch panel applications.

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

The evaluation method in each example is as follows.

<Microfabrication (formation of fine wiring)>
For Examples 1 to 16 and Comparative Example 1, the photosensitivity obtained in Examples 1 to 16 and Comparative Example 1 was applied on a PET film “Lumirror (registered trademark)” T60 (manufactured by Toray Industries, Inc.) having a film thickness of 50 μm. The conductive paste was applied so that the film thickness after drying was 2 μm, and dried in a drying oven at 100° C. for 5 minutes.

For Example 17, the photosensitive conductive paste obtained in Example 17 was applied onto the release layer surface of the release film AL-5 (manufactured by Lintec Corporation, release force 1480 mN/20 mm, film thickness 16 μm). It was applied so that the film thickness after drying would be 2 μm, and dried in a drying oven at 100° C. for 5 minutes to obtain a conductive pattern forming film. Then, using a laminator, the dry film contacts the PET film "Lumirror (registered trademark)" T60 (manufactured by Toray Industries, Inc.) at 60° C. at a speed of 1.0 m/min to form a conductive pattern with the PET film. The film was thermocompression bonded.

An exposure apparatus having an ultra-high pressure mercury lamp through a photomask adjusted so that the obtained conductive pattern has a constant line-and-space (hereinafter referred to as L/S) in consideration of the amount of line thickening in the exposed portion ( Full line exposure was performed using PEM-6M (Union Optical Co., Ltd.) at an exposure dose of 400 mJ/cm ² (wavelength 365 nm conversion).

After the exposure, spray development was performed for 20 seconds using a 0.1 wt% Na ₂ CO ₃ aqueous solution, and a rinse treatment was performed with ultrapure water. Then, using a hot air oven, heat treatment (curing) was performed at 140° C. for 30 minutes to obtain a cured product pattern (conductive pattern) of five types of photosensitive compositions having different L/S values. The L/S values for each unit are 30/30, 20/20, 15/15, 10/10 and 7/7. The obtained conductive pattern was observed with an optical microscope. Among the conductive patterns having no residue between the patterns and having no pattern peeling, the smallest L/S value was used as the developable L/S value to evaluate the fine workability.

In Example 18, the conductive paste obtained in Example 18 was pattern-coated on a PET film “Lumirror” T60 (manufactured by Toray Industries, Inc.) having a film thickness of 50 μm so that the film thickness after drying would be 2 μm. And dried in a drying oven at 100° C. for 5 minutes. Then, heat treatment (curing) was performed at 140° C. for 30 minutes to obtain a cured product pattern (conductive pattern) of three types of non-photosensitive compositions having different L/S values. The L/S values for each unit are 90/90, 75/75 and 60/60. The obtained conductive pattern was evaluated by the same method as described above.

<Conductivity (specific resistance)>
For Examples 1 to 16 and Comparative Example 1, the photosensitive conductive pastes obtained in Examples 1 to 16 and Comparative Example 1 were dried on a PET film "Lumirror (registered trademark)" T60 having a film thickness of 50 μm after drying. Was applied so as to have a film thickness of 2 μm, and the applied film was dried in a drying oven at a temperature of 100° C. for 5 minutes.

For Example 17, the photosensitive conductive paste obtained in Example 17 was applied onto the release layer surface of the release film AL-5 so that the film thickness after drying was 2 μm, and the temperature was 100° C. The film was dried in a drying oven for 5 minutes to obtain a conductive pattern forming film. Subsequently, the PET film and the conductive pattern forming film were thermocompression bonded at 60° C. at a speed of 1.0 m/min using a laminator so that the dry film was in contact with the PET film “Lumirror (registered trademark)” T60.

Through a photomask, exposure and development were performed under the conditions described in <Microfabrication> above to obtain a wiring pattern. The obtained wiring pattern sample was heat-treated (cured) in a hot air oven at 140° C. for 30 minutes to obtain a sample for measuring specific resistance shown in FIG. In FIG. 1, reference numeral 1 is a conductive pattern made of a cured product of a photosensitive composition, reference numeral 2 is a PET film, A is one short side of a resistivity measurement sample, and B is the other short side of a resistivity measurement sample. Indicates.

In Example 18, the conductive paste obtained in Example 18 was pattern-coated on a PET film “Lumirror” T60 (manufactured by Toray Industries, Inc.) having a film thickness of 50 μm so that the film thickness after drying would be 2 μm. And dried in a drying oven at 100° C. for 5 minutes. Then, heat treatment (curing) was performed at 140° C. for 30 minutes to obtain a sample for measuring specific resistance shown in FIG. 1. In FIG. 1, reference numeral 1 is a conductive pattern made of a cured product of a non-photosensitive composition, reference numeral 2 is a PET film, A is one short side of a resistivity measurement sample, and B is the other short side of a resistivity measurement sample. Indicates an edge.

The end of each conductive pattern 1 of the obtained sample for measuring specific resistance was connected with a tester (CDM-2000D; manufactured by Custom Co., Ltd.) to measure the resistance value, and the specific resistance was calculated based on the following formula (1). It calculated and evaluated conductivity.
Specific resistance (Ω·cm)={resistance value (Ω)×film thickness (m)×line width (m)}/{line length (m)×100} (1).

<Bending resistance>
The resistivity measurement sample shown in FIG. 1 obtained by the method described in <Conductivity (Resistance)> was applied to a plane state unloaded U-shaped stretch tester DLDMLH-FS (Yuasa System Equipment Co., Ltd.). The conductive pattern was set so as to have a mountain fold, and the bending operation was repeated 10,000 times until the distance between the short side A and the short side B shown in FIG. The wiring resistance value before and after the test was measured, and the bending resistance was evaluated from the change rate shown in the following formula (2).
Change rate (%)={wiring resistance value (Ω) after test/wiring resistance value (Ω) before test}×100 (2).

<Reduction of conductivity under high temperature and high humidity environment (resistance value ratio)>
A silver fiber dispersion liquid in which silver fibers and dodecylpentaethylene glycol were dispersed in pure water was applied on a PET film “Lumirror (registered trademark)” T60 having a film thickness of 50 μm, and dried in a drying oven at 100° C. for 5 minutes. .. Then, on the silver fiber, an overcoat resin obtained by Synthesis Example 5 described later, a monomer having an unsaturated double bond (“Light acrylate” (registered trademark) MPD-A; manufactured by Kyoeisha Chemical Co., Ltd.), and A 100:50:1 (weight ratio) mixture of a photopolymerization initiator (“IRGACURE” (registered trademark) 369: manufactured by BASF Japan Ltd.) is applied, heat-treated and dried to form a transparent electrode layer having a thickness of 4 μm. Formed.

For Examples 1 to 16 and 18 and Comparative Example 1, the conductive paste obtained in Examples 1 to 16 and 18 and Comparative Example 1 was applied onto the transparent electrode layer so that the film thickness after drying was 2 μm. Was pattern-coated and dried in a drying oven at 100° C. for 5 minutes. In Example 17, the film for conductive pattern formation obtained by the method described in <Microfabrication (formation of fine wiring)> was used so that the surface on which the conductive pattern was formed was in contact with the transparent electrode layer. Was used for thermocompression bonding at 60° C. and a speed of 1.0 m/min.

Using an exposure device (PEM-6M; manufactured by Union Optical Co., Ltd.) having an ultra-high pressure mercury lamp without using a photomask, Examples 1 to 16 and Comparative Example 1 have exposure amounts of 400 mJ/cm ² (wavelength 365 nm). Full-line exposure was performed. In Example 17, the releasable film surface was similarly subjected to full-line exposure with an exposure amount of 300 mJ/cm ² (wavelength 365 nm conversion).

In Examples 1 to 17 and Comparative Example 1, after exposure, spray development was performed for 20 seconds using a 0.1 wt% Na ₂ CO ₃ aqueous solution, and a rinse treatment was performed with ultrapure water. Since the conductive paste obtained in Example 18 is non-photosensitive in Example 18, the exposure and development steps are unnecessary.

Then, in Examples 1 to 18 and Comparative Example 1, heat treatment (curing) was performed at 140° C. for 30 minutes using a hot air oven to obtain resistance value measurement samples shown in FIGS. 2 and 3.

FIG. 2 is a schematic diagram of a resistance value measuring sample, and FIG. 3 is a schematic sectional view thereof. 2 and 3, reference numeral 3 indicates a conductive pattern, reference numeral 4 indicates a transparent electrode pattern, reference numeral 5 indicates a PET film, and reference numeral 6 indicates a tester. A tester (CDM-2000D; manufactured by Custom Co., Ltd.) was brought into contact with points C and D on the transparent electrode pattern, and an initial resistance value R1 between the two points was measured. After that, the resistance value measurement sample was put into a constant temperature and humidity chamber SH-661 (manufactured by ESPEC Corp.) at 85° C. and 85% RH for 72 hours, then the sample was taken out, and the initial resistance value R1 was measured at two points. The resistance value R2 between them was measured. The resistance value ratio (Rr) was defined as the ratio of R2 to R1 (R2/R1), and evaluation was made according to the following criteria.
A: 1.0<Rr≦1.5
B: 1.5<Rr≦3.0
C: 3.0<Rr
D: No continuity.

The materials used in Examples and Comparative Examples are as follows.

[Organometallic compound (A)]
・Aluminum secondary butoxide (metal alkoxide compound)
・Aluminum trisacetylacetonate (metal chelate compound)
・Tetraisopropyl titanate (metal alkoxide compound)
・Titanium acetylacetonate (metal chelate compound)
・Normal propyl zirconate (metal alkoxide compound)
-Zirconium tetraacetylacetonate (metal chelate compound).

[Carboxyl group-containing resin]
(Synthesis Example 1) Acrylic copolymer containing a carboxyl group (B-1)
In a reaction vessel under a nitrogen atmosphere, 150 g of diethylene glycol monoethyl ether acetate (hereinafter, "DMEA") was charged and heated to 80°C using an oil bath. To this, 20 g of ethyl acrylate (hereinafter, "EA"), 20 g of 2-ethylhexyl methacrylate (hereinafter, "2-EHMA"), 20 g of n-butyl acrylate (hereinafter, "BA"), 15 g of N- A mixture of methylol acrylamide (hereinafter "MAA"), 25 g of acrylic acid (hereinafter "AA"), 0.8 g of 2,2'-azobisisobutyronitrile and 10 g of DMEA was added over 1 hour. Dropped. After completion of dropping, the mixture was further heated at 80° C. for 6 hours to carry out a polymerization reaction. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Unreacted impurities were removed by purifying the obtained reaction solution with methanol, and further vacuum dried for 24 hours to give a copolymerization ratio (weight basis): EA/2-EHMA/BA/MAA/AA=20/ A 20/20/15/25 carboxyl group-containing acrylic copolymer (B-1) was obtained. The acid value of the obtained carboxyl group-containing acrylic copolymer (B-1) was 153 mgKOH/g.

(Synthesis example 2) Acrylic copolymer containing a carboxyl group having an unsaturated double bond (B-2)
150 g of DMEA was charged into a reaction vessel in a nitrogen atmosphere, 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, 15 g AA, 0.8 g 2,2'-azobisisobutyronitrile and 10 g DMEA was added dropwise over 1 hour. did. After completion of dropping, the mixture was further heated at 80° C. for 6 hours to carry out a polymerization reaction. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Subsequently, a mixture of 5 g of glycidyl methacrylate (hereinafter, "GMA"), 1 g of triethylbenzylammonium chloride and 10 g of DMEA was added dropwise over 0.5 hour. After the dropping was completed, the reaction was further heated for 2 hours to carry out the addition reaction. Unreacted impurities were removed by purifying the obtained reaction solution with methanol, and further vacuum dried for 24 hours to give a copolymerization ratio (mass basis): EA/2-EHMA/BA/GMA/AA=20/. A carboxyl group-containing acrylic copolymer (B-2) having an unsaturated double bond of 40/20/5/15 was obtained. The acid value of the obtained carboxyl group-containing acrylic copolymer (B-2) was 107 mgKOH/g.

(Synthesis Example 3) Carboxylic acid-modified epoxy resin (B-3)
In a reaction vessel under a nitrogen atmosphere, 492.1 g of DMEA, 860.0 g of EOCN-103S (manufactured by Nippon Kayaku Co., Ltd.; cresol novolac type epoxy resin; epoxy equivalent: 215.0 g/equivalent), 288.3 g AA, 4.92 g of 2,6-di-tert-butyl-p-cresol and 4.92 g of triphenylphosphine were charged, and at a temperature of 98° C., the acid value of the reaction solution was 0.5 mg·KOH/g or less. The mixture was heated until it was reacted to obtain an epoxycarboxylate compound. Subsequently, 169.8 g of DMEA and 201.6 g of tetrahydrophthalic anhydride were charged into this reaction solution, and the mixture was heated at 95° C. for 4 hours to cause a reaction to obtain a carboxylic acid-modified epoxy resin (B-3). The acid value of the obtained carboxylic acid-modified epoxy resin (B-3) was 104 mgKOH/g.

(Synthesis Example 4) Carboxyl group-containing resin having a urethane bond (B-4)
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 heated at a temperature of 98° C. until the acid value of the reaction solution became 0.5 mgKOH/g or less and reacted to obtain an epoxycarboxylate compound. Then, to this reaction solution were added 755.5 g of DMEA, 268.3 g of 2,2-bis(dimethylol)-propionic acid, 1.08 g of 2-methylhydroquinone and 140.3 g of spiroglycol, and the temperature was raised to 45°C. Warmed. 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 is raised to 80° C., and the mixture is heated and reacted for 6 hours until the absorption around 2250 cm ⁻¹ disappears by the infrared absorption spectrum measurement method, and the reaction is carried out, and the carboxyl group-containing resin having a urethane bond (B-4 ) Got. The acid value of the obtained carboxyl group-containing resin (B-4) having a urethane bond was 80.0 mgKOH/g.

[Other resins]
"JER" (registered trademark) 828 (manufactured by Mitsubishi Chemical Corporation).

[Photopolymerization initiator (C)]
-"IRGACURE" (registered trademark) 369: (manufactured by BASF Japan Ltd.)
"IRGACURE" OXE01 (BASF Japan Ltd., oxime-based compound) (hereinafter referred to as OXE01).

[Compound (D) Having Unsaturated Double Bond]
-"Light acrylate" (registered trademark) MPD-A (manufactured by Kyoeisha Chemical Co., Ltd.)
・"Light acrylate" (registered trademark) BP-4EA (manufactured by Kyoeisha Chemical Co., Ltd.)
-CN972 (urethane bond-containing photopolymerizable compound manufactured by Sartomer Co., Ltd.).

[Conductive particles (E)]
-Ag particles having a particle diameter (D50) of 0.7 µm and an aspect ratio of 1.1-Ag particles having a particle diameter (D50) of 0.7 µm and an aspect ratio of 2.2

[Transparent electrode material]
-Silver fiber (wire diameter 5 nm, wire length 5 μm).

[Overcoat resin]
(Synthesis example 5)
150 g of DMEA was charged into a reaction vessel in a nitrogen atmosphere, and the temperature was raised to 80° C. using an oil bath. To this was added a mixture of 25 g EA, 40 g 2-EHMA, 25 g BA, 10 g MAA, 0.8 g 2,2-azobisisobutyronitrile and 10 g DMEA dropwise over 1 hour. .. After completion of the dropping, the mixture was further heated for 6 hours to carry out a polymerization reaction. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Unreacted impurities were removed by purifying the obtained reaction solution with methanol, and further vacuum dried for 24 hours to give a copolymerization ratio (mass basis): EA/2-EHMA/BA/MAA=25/40/. A 25/10 overcoat resin was obtained.

(Example 1)
In a 100 mL clean bottle, 10.0 g of a carboxyl group-containing acrylic copolymer (B-2) having an unsaturated double bond, 0.50 g of OXE01, 5 g of light acrylate BP-4EA, 10.0 g of DMEA and 0.30 g of aluminum secondary butoxide was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro" (registered trademark) ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 25.80 g of a resin solution (solid). 61.1 mass%) was obtained.

The obtained 25.80 g of the resin solution was mixed with 47.22 g of Ag particles having a particle diameter (D50) of 0.7 μm and an aspect ratio of 1.1, and a three-roll mill (EXAKT M-50; manufactured by EXAKT) was used. It kneaded using and obtained 73.02g of photosensitive conductive paste. Table 1 shows the composition of the photosensitive conductive paste.

The obtained photosensitive conductive paste was pattern-coated on the transparent electrode layer so that the film thickness after drying was 2 μm, and dried in a drying oven at 100° C. for 5 minutes.

Full-line exposure was performed with an exposure amount of 400 mJ/cm ² (converted to a wavelength of 365 nm) using an exposure device (PEM-6M; manufactured by Union Optical Co., Ltd.) having an ultra-high pressure mercury lamp without using a photomask.

After the exposure, spray development was performed for 20 seconds using a 0.1 wt% Na ₂ CO ₃ aqueous solution, and a rinse treatment was performed with ultrapure water. After that, heat treatment (curing) was performed at 140° C. for 30 minutes using a hot air oven to obtain a resistance value measurement sample (laminated member) shown in FIGS. 2 and 3.

By using the obtained photosensitive conductive paste and the laminated member, the fine processability, the conductivity, the bending resistance, and the decrease in the conductivity under the high temperature and high humidity environment were evaluated by the above-mentioned methods. The evaluation results are shown in Table 3.

(Examples 2 to 16, Comparative Example 1)
Photosensitive conductive pastes having the compositions shown in Tables 1 and 2 were prepared in the same manner as in Example 1, and the obtained photosensitive conductive paste was used to prepare laminated members in the same manner as in Example 1 and evaluated. .. The evaluation results are shown in Table 3.

(Example 17)
In a 100 mL clean bottle, 10.0 g of a carboxyl group-containing resin having a urethane bond (B-4), 0.5 g of OXE01, 5 g of CN972, 30.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PMAC), and 0.30 g of titanium acetylacetonate was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro" (registered trademark) ARE-310 (manufactured by Shinky Co., Ltd.) to prepare 45.80 g of a resin solution ( Solid content 34.4 mass%) was obtained.

The obtained 45.80 g of the resin solution was mixed with 47.22 g of Ag particles having a particle diameter (D50) of 0.7 μm and an aspect ratio of 1.1, and a three roller mill (EXAKT M-50; manufactured by EXAKT) was used. It kneaded using and obtained 93.02g of photosensitive conductive paste. The obtained photosensitive conductive paste was used and evaluated by the method described above. The evaluation results are shown in Table 3.

(Example 18)
In a 100 mL clean bottle, 10.0 g of "jER" 828, 0.50 g of OXE01, 5 g of CN972, 10.0 g of DMEA and 0.30 g of titanium acetylacetonate were put, and a rotation-revolution vacuum mixer "Awatori smelt" was used. Taro" (registered trademark) ARE-310 (manufactured by Shinky Co., Ltd.) was mixed to obtain 25.80 g of a resin solution (solid content: 61.1% by mass).

The obtained 25.80 g of the resin solution was mixed with 47.22 g of Ag particles having a particle diameter (D50) of 0.7 μm and an aspect ratio of 1.1, and a three-roll mill (EXAKT M-50; manufactured by EXAKT) was used. It kneaded using and obtained 73.02g of conductive paste.

The obtained conductive paste was pattern-coated on the transparent electrode layer so that the film thickness after drying was 2 μm, dried in a drying oven at 100° C. for 5 minutes, and then heat-treated at 140° C. for 30 minutes (cure). ) Was performed to obtain a resistance value measurement sample (laminated member) shown in FIGS. 2 and 3.

Table 3 shows the results of evaluations made in the same manner as in Example 1 using the obtained conductive paste and laminated member.

All of the laminated members of Examples 1 to 18 were able to suppress the decrease in conductivity of the transparent electrode layer in a high temperature and high humidity environment. On the other hand, in the laminated member of Comparative Example 1 in which the conductive layer did not contain the organometallic compound (A), the conductivity of the transparent electrode layer was reduced in a high temperature and high humidity environment.

1: Conductive pattern 2: PET film 3: Conductive pattern 4: Transparent electrode pattern 5: PET film 6: Tester A: One short side of the sample for measuring resistivity B: The other short side C of the sample for measuring resistivity: Point C of transparent electrode pattern: Point D of transparent electrode pattern

Claims (9)

On the substrate I, a laminated member having a transparent electrode layer and a conductive layer,
The transparent electrode layer contains a binder resin (X) and a metal fiber, and at least a part of the metal fiber is exposed,
A laminated member in which the conductive layer is a cured product of a composition containing an organometallic compound (A), a binder resin (Y), and conductive particles (E). The cured product is
Photosensitive conductive paste containing organometallic compound (A), carboxyl group-containing resin (B), photopolymerization initiator (C), compound (D) having unsaturated double bond and conductive particles (E)
The laminated member according to claim 1, which is a cured product of. The cured product is
0.1 to 10 parts by weight of the organometallic compound (A) is contained per 100 parts by weight of the carboxyl group-containing resin (B).
Photosensitive conductive paste containing organometallic compound (A), carboxyl group-containing resin (B), photopolymerization initiator (C), compound (D) having unsaturated double bond and conductive particles (E)
The laminated member according to claim 1, which is a cured product of. The transparent electrode layer,
It has a laminated portion of a binder resin (X) layer and a metal fiber layer containing metal fibers,
The laminated member according to claim 1, wherein the conductive layer is in contact with the binder resin (X) layer and the metal fiber layer. The transparent electrode layer is laminated member according to any one of claims 1 to 4 containing silver fiber. The organometallic compound (A), organic aluminum compounds, organic titanium compounds, and, laminated member of claims 1 to 5, wherein any one containing at least one selected from the group consisting of organic zirconium compound. The organometallic compound (A), the laminated member according to any one of claims 1 to 6 containing the metal chelate compound. Wherein the substrate I is a cycloolefin polymer (COP) film in which claims 1-7 laminate member according to any one. A touch panel comprising a laminate member according to any of claims 1-8.

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