JP2020196212A - Laminate member and film for conductive patten formation - Google Patents

Abstract

To provide a laminate member which can suppress reduction in conductivity under high temperature and high humidity environment of a conductive fiber-containing transparent electrode layer, and can also improve conductivity of a conductive layer.SOLUTION: A laminate member has a transparent electrode layer and a conductive layer on a base material, in which the transparent electrode layer contains a binder resin and a conductive fiber, at least a part of the conductive fiber comes in contact with the conductive layer, and the conductive layer is formed of a cured product of a composition containing an organic salt (A), an organic acid (B), a carboxyl group-containing resin (C), a photopolymerization initiator (D), a compound having an unsaturated double bond (E) and conductive particles (F).SELECTED DRAWING: None

Description

The present invention relates to a laminated member and a film for forming a conductive pattern.

In recent years, studies on capacitive touch panels have been actively promoted. The capacitive touch panel has peripheral wiring that connects to a transparent electrode around the display area. Known methods for forming 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 peripheral wiring on a substrate with low heat resistance, conductive particles are brought into contact with each other in an insulating organic substance without going through a firing step of removing the organic substance by high-temperature heating to make a conductive path. Need to be formed. Examples of the conductive paste used in such a technique include a compound having an amino group, a compound having an unsaturated double bond with a carboxyl group, a conductive filler, and a conductive paste containing a photopolymerization initiator (see, for example, Patent Document 1). 4, Quadruple ammonium salt compounds, carboxyl group-containing resins, photopolymerization initiators, reactive monomers having unsaturated double bonds, conductive pastes containing conductive particles (see, for example, Patent Document 2) and the like have been proposed. ..

On the other hand, ITO (Indium-Tin-Oxide) was the mainstream for transparent electrodes. However, in response to the recent demand for flexibility, ITO has a problem of low bending resistance. Therefore, a transparent electrode using a metal fiber has been studied, and contains, for example, a base material, a resin layer A formed on the base material, and fibrous silver formed on the resin layer A. A laminated member (see, for example, Patent Document 3) including a transparent electrode layer B to be formed, a conductive layer C formed on the resin layer A and the transparent electrode layer B, and the like has been proposed.

International Publication No. 2014/156677 International Publication No. 2019/0793926 International Publication No. 2016/170943

Although the conductive paste described in Patent Document 1 or 2 can be microfabricated by a photolithography method due to a carboxyl group, when combined with a transparent electrode using a fibrous metal described in Patent Document 3, it is subjected to a high temperature and high humidity environment. In the present invention, it has been clarified by the studies by the present inventors that there is a problem of lowering the conductivity of the transparent electrode layer. Further, the laminated member described in Patent Document 3 also has a problem that the conductivity of the transparent electrode layer is lowered in a high temperature and high humidity environment.

Therefore, an object of the present invention is to provide a laminated member capable of suppressing a decrease in conductivity of a conductive fiber-containing transparent electrode layer in a high-temperature and high-humidity environment and also improving the conductivity of the conductive layer. And.

The present invention mainly has the following configurations in order to solve the above problems.
A laminated member having a transparent electrode layer and a conductive layer on a base material, the transparent electrode layer containing a binder resin and a conductive fiber, and at least a part of the conductive fiber is in contact with the conductive layer. , The conductive layer is an organic acid salt (A), an organic acid (B), a carboxyl group-containing resin (C), a photopolymerization initiator (D), a compound (E) having an unsaturated double bond, and conductive particles. A laminated member made of a cured product of a composition containing (F).

The laminated member of the present invention can suppress a decrease in conductivity of the transparent electrode layer in a high temperature and high humidity environment, and can also improve the conductivity of the conductive layer.

It is a schematic diagram of the sample for resistivity measurement used in an Example. It is a top view of the sample for resistance value measurement used in an Example. It is sectional drawing of the sample for measuring the resistance value used in an Example.

The laminated member of the present invention is a laminated member having a transparent electrode layer and a conductive layer on a base material.
The transparent electrode layer contains a binder resin and conductive fibers, and at least a part of the conductive fibers is in contact with the conductive layer, and the conductive layer is formed of an organic acid salt (A), an organic acid (B), and the like. It comprises a cured product of a composition containing a carboxyl group-containing resin (C), a photopolymerization initiator (D), a compound (E) having an unsaturated double bond, and conductive particles (F). The conductive layer is a composite of an organic component and an inorganic component, and the conductive particles (F) are sintered by contacting each other due to an atomic diffusion phenomenon during thermal curing to exhibit conductivity. Yes, hydrogen ions that dissociate from the organic acid (B) during alkaline development promote its sintering. On the other hand, the present inventors dissociate the conductive fibers in the transparent electrode layer from the organic acid (B) and the carboxyl group-containing resin (C) at the contact site with the conductive layer in a high temperature and high humidity environment. It has been found that the transparent electrode layer is corroded by the above and increases the resistance value of the transparent electrode layer, that is, decreases the conductivity. Therefore, by containing the organic acid salt (A) in the conductive layer, the dissociated hydrogen ions are uniformly distributed in the conductive layer and selectively contribute to the sintering of the conductive particles (F) to be conductive. It has been found that while improving the conductivity of the layer, it is possible to suppress a decrease in the conductivity of the transparent electrode layer by suppressing the corrosion of the conductive fibers of the transparent electrode layer.

The base material has an action of supporting the transparent electrode layer and the conductive layer to be formed. Examples of the base material include polyester films such as polyethylene terephthalate (PET) film, polyimide films, aramid films, cycloolefin polymer (COP) films, epoxy resin substrates, polyetherimide resin substrates, polyetherketone resin substrates, and polysulfon-based substrates. 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.

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

The transparent electrode layer contains a binder resin and conductive fibers, and at least a part of the conductive fibers is in contact with the conductive layer. In the transparent electrode layer, all the conductive fibers do not have to be covered with the binder resin, and since they have a fibrous shape, a part of them has a structure protruding from the binder resin. It is preferable that the transparent electrode layer has at least a part where the binder resin layer and the conductive fiber layer are laminated, and the conductive layer is in contact with the binder resin layer and the conductive fiber layer. However, the binder resin layer may have conductive fibers, and the layer having the binder resin and the conductive fibers shall be classified into the binder resin layer.

The binder resin acts as a binder for holding metal fibers. As the binder resin, a carboxyl group-containing resin is preferable, which enhances alkali developability and can act as a photoresist for pattern formation of a transparent electrode layer. Further, since the binder resin contains a photopolymerization initiator and a compound having an unsaturated double bond, the exposed portion is insolubilized in an alkaline aqueous solution by photopolymerization using exposure in a photography method, and a transparent electrode layer is formed. It becomes possible to perform fine processing.

Examples of the carboxyl group-containing resin include acrylic copolymers, carboxylic acid-modified epoxy resins, carboxylic acid-modified phenolic resins, polyamic acids, and carboxylic acid-modified siloxane polymers. Two or more of these may be contained. Among these, an acrylic copolymer having a high ultraviolet light transmittance or a carboxylic acid-modified epoxy resin is preferable.

As the acrylic copolymer, a copolymer of an acrylic monomer and an unsaturated acid or an acid anhydride thereof is preferable.

Examples of the acrylic monomer include ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, and isobornyl acrylate. Two or more of these may be used.

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. Two or more of these may be used. The acid value of the acrylic copolymer can be adjusted by the copolymerization ratio of the unsaturated acid.

As the carboxylic acid-modified epoxy resin, a reaction product of an epoxy compound and an unsaturated acid or an unsaturated acid anhydride is preferable. Here, the carboxylic acid-modified epoxy resin is one in which the epoxy group of the epoxy compound is modified with a carboxylic acid or a carboxylic acid anhydride, and does not contain an epoxy group.

Examples of the epoxy compound include glycidyl ethers, glycidyl amines, and epoxy resins. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin and the like. Two or more of these may be used.

Examples of the photopolymerization initiator include benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzyl derivatives, benzoin derivatives, oxime compounds, α-hydroxyketone compounds, α-aminoalkylphenone compounds, phosphine oxide compounds, and antron compounds. Anthraquinone compounds and the like can be mentioned. Two or more of these may be used.

Examples of the compound containing an unsaturated double bond include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated (4) bisphenol A diacrylate, ethoxylated (10) bisphenol A diacrylate, and ethylene. Bifunctional monomers such as acrylic acid adducts of glycol diglycidyl ethers and acrylic acid adducts of neopentyl glycol diglycidyl ethers; trifunctional monomers such as pentaerythritol triacrylates, trimethylolpropantriacrylates and glycerin propoxytriacrylates; dipenta Tetrafunctional monomers such as erythritol hexaacrylate, pentaerythritol tetraacrylate, and ditrimethylolpropane tetraacrylate; EBECRYL204, EBECRYL210, EBECRYL220, EBECRYL264, EBECRYL265, EBECRYL245, EBECRYL245, EBECRYL284, EBECRYL284, Sartmer CN972, CN972 Examples include monomers. Two or more of these may be contained.

The conductive fiber has an action of imparting conductivity to the transparent electrode layer. Examples of conductive fibers include indium, tin, zinc, gallium, antimony, titanium, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten, and fibers made of oxides or composite oxides of these metals. Can be mentioned. Two or more of these may be contained. Examples of the metal oxide and the metal composite oxide include ITO, indium zinc oxide, indium oxide-zinc oxide composite oxide, aluminum zinc oxide, gallium zinc oxide, fluorine zinc oxide, fluorine indium oxide, and antimony. Examples 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 conductive fibers are excellent in conductivity because the contact probability between the conductive fibers is high due to their shape. In addition, it has the effect of making the transparent electrode layer less visible.

The fiber diameter of the conductive fiber is preferably 3 to 30 nm. The fiber length of the conductive fiber is preferably 1 to 500 μm. As for the fiber diameter and fiber length of the conductive fibers, 100 fibers were randomly selected by observing the conductive fibers at a magnification of 5000 times using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The wire diameter and wire length of each of the conductive fibers can be measured and calculated from the average value of each number.

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 visible light transmission. Here, the thickness of the transparent electrode layer refers to the total thickness of the transparent electrode layer when it has a laminated structure of a binder resin layer and a conductive fiber layer.

From the viewpoint of visible light transmittance of the transparent electrode layer, the light transmittance in the wavelength range of 450 to 650 nm is preferably 80% or more. The light transmittance is a value (total light rays) measured by the method specified by JIS K7105.

From the viewpoint of improving conductivity, the sheet resistance of the transparent electrode layer is preferably 500 Ω / □ or less, more preferably 200 Ω / □ or less, and further preferably 100 Ω / □ or less. The sheet resistance can be measured by a contact type or non-contact type resistance measuring device.

The conductive layer includes an organic acid salt (A), an organic acid (B), a carboxyl group-containing resin (C), a photopolymerization initiator (D), a compound (E) having an unsaturated double bond, and conductive particles (F). ) Containing a cured product of the composition. The conductive layer can be microfabricated by a photolithography method. As described above, the conductive layer is a composite of an organic component and an inorganic component, and the conductive particles (F) are sintered by contacting each other due to the atomic diffusion phenomenon during thermal curing to obtain conductivity. Hydrogen ions that are expressed and dissociate from the organic acid (B) during alkaline development promote their sintering. On the other hand, the present inventors dissociate the conductive fibers in the transparent electrode layer from the organic acid (B) and the carboxyl group-containing resin (C) at the contact site with the conductive layer in a high temperature and high humidity environment. It has been found that the transparent electrode layer is corroded by the above and increases the resistance value of the transparent electrode layer, that is, decreases the conductivity. Therefore, by containing the organic acid salt (A) in the conductive layer, the dissociated hydrogen ions are uniformly distributed in the conductive layer and selectively contribute to the sintering of the conductive particles (F) to be conductive. It has been found that while improving the conductivity of the layer, it is possible to suppress a decrease in the conductivity of the transparent electrode layer by suppressing the corrosion of the conductive fibers of the transparent electrode layer. Further, when the composition contains a photopolymerization initiator (D) and a compound (E) having an unsaturated double bond, the photosensitive conductive paste is insolubilized in alkali by photopolymerization by exposure in a photolithography method. Can be finely processed. The carboxyl group-containing resin (C) enhances alkali developability and enables microfabrication by a photolithography method.

The organic acid salt (A) preferably contains a salt of an organic acid and an alkali metal and / or alkaline earth metal. Examples of salts of organic acids and alkali metals include sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium stearoyl lactate, and sodium isostearoyl lactate. , Sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate and the like. Examples of the salt of the organic acid and the alkaline earth metal include magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium stearoyl lactate, calcium benzoate and the like. Two or more of these may be used.

The content of the organic acid salt (A) in the composition forming the conductive layer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the organic acid (B). When the content of the organic acid salt (A) is 0.1 parts by weight or more, it is easy to promote the dissociation of hydrogen ions from the organic acid (B), further improve the conductivity of the conductive layer, and the transparent electrode layer. It is possible to further suppress the decrease in conductivity of. The content of the organic acid salt (A) is more preferably 0.5 parts by weight or more, and further preferably 2 parts by weight or more. On the other hand, when the content of the organic acid salt (A) is 50 parts by weight or less, excessive dissolution of the conductive layer in the developing solution is suppressed, film loss of the pattern forming portion is suppressed, and microfabrication is improved. Can be done. The content of the organic acid salt (A) is more preferably 30 parts by weight or less.

Examples of the organic acid (B) include organic carboxylic acids. The organic acid preferably contains an organic dicarboxylic acid having two or more carboxyl groups, and is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, and phthalic acid. , Isophthalic acid, terephthalic acid, dodecanedioic acid, methylmalonic acid, dimethylmalonic acid, ethylmalonic acid, propylmalonic acid, isopropylmalonic acid, dipropylmalonic acid, butylmalonic acid, isobutylmalonic acid, methylsuccinic acid, 2,2 -Didimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3 -Ethyl-3-methylglutaric acid, 2,4-diethylglutaric acid, 2-oxoglutaric acid, 3-methyladiponic acid, 2,2,6,6-tetramethylpimelic acid, 1,1-cyclopropanedicarboxylic acid , 1,2-Cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid Acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid , Citric acid, malic acid, tartaric acid, phthalic acid, tricarbaryl acid, trimellitic acid, aconitic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, glutamate, ethylenediamine tetraacetic acid, 2,3-pyrazindicarboxylic acid, 2 , 3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid, 2- Methylmalonic acid, 2-ethylmalonic acid, 2-propylmalonic acid, 2-butylmalonic acid, 2- (3-methoxypropyl) malonic acid, 2- (3-propoxypropyl) malonic acid, 2- (3-propoxy) Butyl) malonic acid, (E) -2- (hexa-4-ethyl) malonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-propylsuccinic acid, 2-butylsuccinic acid, 2- (3-) Methoxypropyl) succinic acid, 2- (3-propoxypropyl) succinic acid, 2- (3-propoxybutyl) Cucinic acid, (E) -2- (hex-4-ethyl) succinic acid, 2-methyldioic acid, 2-ethyldioic acid, 2-propyldioic acid, 2-butyldioic acid, 2-( 3-Methoxypropyl) dioic acid, 2- (3-propoxypropyl) dioic acid, 2- (3-propoxybutyl) dioic acid, (E) -2- (hex-4-ethyl) dioic acid, 2-hexylpentane Geoic acid, 3-hexylpentane dioic acid, 2-methylmaleic acid, 2-ethylmaleic acid, 2-propylmaleic acid, 2-butylmaleic acid, 2- (3-methoxypropyl) maleic acid, 2-( 3-Propoxypropyl) maleic acid, 2- (3-propoxybutyl) maleic acid, (E) -2- (hexa-4-ethyl) maleic acid, 2-hexylmalonic acid, 2- (3-ethoxypropyl) succin Acid, 2- (3-ethoxybutyl) succinic acid, (E) -2 (hexa-1-enyl) succinic acid, 3-hexylpentanedioic acid, (E) -2- (hex-4-ethyl) succin Examples include acid. Among these, (E) -2- (hex-4-ethyl) succinic acid, 2-propyl succinic acid, 3-hexylpentanedioic acid, 2-hexyl malonic acid, 2- (3-ethoxypropyl) succinic acid, 2- (3-ethoxybutyl) succinic acid and (E) -2 (hexa-1-enyl) succinic acid are particularly preferable. Two or more of these may be used.

The content of the organic acid (B) in the composition forming the conductive layer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (C). When the content of the organic acid (B) is 0.1 parts by weight or more, the conductive development of the conductive layer can be further promoted by the dissociation of hydrogen ions from the organic acid (B). The content of the organic acid (B) is more preferably 0.5 parts by weight or more, and further preferably 1 part by weight or more. On the other hand, when the content of the organic acid (B) is 50 parts by weight or less, the decrease in conductivity of the transparent electrode layer can be further suppressed.

Examples of the carboxyl group-containing resin (C) include acrylic copolymers, carboxylic acid-modified epoxy resins, carboxylic acid-modified phenolic resins, polyamic acids, and carboxylic acid-modified siloxane polymers. Two or more of these may be contained. Among these, an acrylic copolymer having a high ultraviolet light transmittance or a carboxylic acid-modified epoxy resin is preferable.

As the acrylic copolymer, a copolymer of an acrylic monomer and an unsaturated acid or an acid anhydride thereof is preferable.

Examples of the acrylic monomer include ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, and isobornyl acrylate. Two or more of these may be used.

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. Two or more of these may be used. The acid value of the acrylic copolymer can be adjusted by the copolymerization ratio of the unsaturated acid.

As the carboxylic acid-modified epoxy resin, a reaction product of an epoxy compound and an unsaturated acid or an unsaturated acid anhydride is preferable. Here, the carboxylic acid-modified epoxy resin is one in which the epoxy group of the epoxy compound is modified with a carboxylic acid or a carboxylic acid anhydride, and does not contain an epoxy group.

Examples of the epoxy compound include glycidyl ethers, glycidyl amines, and epoxy resins. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin and the like. Two or more of these may be used.

An unsaturated double bond can be introduced by reacting the above-mentioned 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 (C), the crosslink density of the exposed portion can be improved at the time of exposure, the development margin can be widened, and the fine processability can be further improved.

As the carboxyl group-containing resin (C), a resin having a urethane bond can also be preferably used. When the carboxyl group-containing resin (C) has a urethane bond, the bending resistance of the obtained conductive pattern can be improved. As a method of introducing a urethane bond into the carboxyl group-containing resin (C), for example, in the case of an acrylic copolymer having a hydroxyl group or a carboxylic acid-modified epoxy resin having a hydroxyl group, a method of reacting a diisocyanate compound with these hydroxyl groups is a method. Can be mentioned. Examples of the diisocyanate compound include hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tridendiisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allylcyandiisocyanate, and norbornane diisocyanate. Two or more of these may be used.

As the carboxyl group-containing resin (C), a resin having a phenolic hydroxyl group can also be preferably used. When the carboxyl group-containing resin (C) has a phenolic hydroxyl group, it forms a hydrogen bond with a polar group such as a hydroxyl group or an amino group on the surface of the base material, and improves the adhesion between the obtained conductive pattern and the base material. Can be done.

The acid value of the carboxyl group-containing resin (C) is preferably 50 to 250 mgKOH / g. When the acid value is 50 mgKOH / g or more, the solubility in a developing solution is high, and the generation of 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 of 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 (C) can be measured in accordance with JIS K 0070 (1992).

In the case of an acrylic copolymer, for example, the acid value of the carboxyl group-containing resin (C) can be adjusted to a desired range by the ratio of the 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 with a polybasic acid anhydride. In the case of a carboxylic acid-modified phenolic resin, it can be adjusted to a desired range by the ratio of the polybasic acid anhydride in the constituents.

Examples of the photopolymerization initiator (D) include benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzyl derivatives, benzoin derivatives, oxime compounds, α-hydroxyketone compounds, α-aminoalkylphenone compounds, and phosphine oxide compounds. Examples thereof include anthrone compounds and anthraquinone compounds. Examples of the oxime compound include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- (2-methylbenzoyl)]. ) -9H-Carbazole-3-yl] -1- (O-acetyloxime), 1-phenyl-1,2-butandion-2- (O-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( O-ethoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-benzoyl) oxime, 1,3-diphenyl-propanthrion-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy- Examples thereof include propanetrion-2- (O-benzoyl) oxime. Two or more of these may be contained. Among these, oxime compounds having high photosensitivity are preferable.

The content of the photopolymerization initiator (D) in the composition forming the conductive layer is preferably 0.05 to 30 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (C). When the content of the photopolymerization initiator (D) is 0.05 parts by weight or more, the curing density of the exposed part is increased, and the residual film ratio after development can be increased. The content of the photopolymerization initiator (D) is more preferably 1 part by weight or more. On the other hand, when the content of the photopolymerization initiator is 30 parts by weight or less, excessive light absorption by the photopolymerization initiator (D) on the upper portion of the coating film obtained by applying the composition is suppressed. As a result, the conductive layer can be easily tapered, and the adhesion to the substrate can be improved.

Examples of the compound (E) having an unsaturated double bond include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated (4) bisphenol A diacrylate, and ethoxylated (10) bisphenol A diacrylate. Bifunctional monomers such as the acrylic acid adduct of ethylene glycol diglycidyl ether and the acrylic acid adduct of neopentyl glycol diglycidyl ether; pentaerythritol triacrylate, pentaerythritol triacrylate, trimethylolpropantriacrylate, trimethylolpropaneethoxytri. Trifunctional monomers such as acrylates and glycerin propoxytriacrylates; Tetrafunctional monomers such as dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxytetraacrylate and ditrimethylolpropanetetraacrylate; EBECRYL204, EBECRYL210, EBECRYL220 manufactured by Daicel Cytec. , EBECRYL264, EBECRYL265, EBECRYL284, and urethane bond-containing monomers such as CN972, CN975, and CN978 manufactured by Sartmer. Two or more of these may be contained. Among these, the urethane bond-containing monomer is preferable because it can further improve the bending resistance of the conductive layer.

The content of the compound (E) having an unsaturated double bond in the composition forming the conductive layer is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (C). When the content of the compound (E) having an unsaturated double bond is 1 part by weight or more, the crosslink density of the exposed portion is increased, and the difference in solubility of the unexposed portion and the exposed portion in the developing solution can be increased. , Fine workability can be further improved. On the other hand, when the content of the compound (E) having an unsaturated double bond is 100 parts by weight or less, the Tg of the conductive layer can be suppressed and the bending resistance can be improved.

Examples of the conductive particles (F) include silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, indium, magnesium, cobalt, zinc, potassium, lithium, iron and mercury. , Berylium, cadmium, rhodium, ruthenium, iridium and alloys thereof. Two or more of these may be contained. Among these, metal particles 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. Further, the surface of the conductive particles (F) may be coated with a resin, an inorganic oxide, or the like.

The aspect ratio, which is the value obtained by dividing the major axis length of the conductive particles (F) by the minor axis length, is preferably 1.1 to 2.0. Here, the aspect ratio of the conductive particles is 100 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). It is possible to measure the major axis length and the minor axis length of each of the primary particles of the conductive particles (F) of No. 1 and calculate from the average value of both.

The particle size of the conductive particles (F) is preferably 0.05 to 5.0 μm. By setting the particle size of the conductive particles (F) to 0.05 μm or more, the interaction between the particles can be appropriately suppressed, and the dispersibility of the conductive particles (F) in the conductive layer can be improved. The particle size of the conductive particles (F) is more preferably 0.1 μm or more. On the other hand, by setting the particle diameter of the conductive particles (F) to 5.0 μm or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the conductive layer can be improved. The particle size of the conductive particles (F) is more preferably 2.0 μm or less. Here, the particle size of the conductive particles (F) can be measured 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 (F).

The content of the conductive particles (F) in the conductive layer and the content of the conductive particles (F) in the solid content of the composition forming the conductive layer are preferably 65 to 95% by weight. When the content of the conductive particles (F) is 65% by weight or more, the contact probability between the conductive particles (F) at the time of curing is improved, the conductivity is further improved, and the disconnection probability can be reduced. .. The content of the conductive particles (F) is more preferably 70% by weight or more. On the other hand, when the content of the conductive particles (F) is 95% by weight or less, the translucency of the coating film in the exposure step is improved, and the fine processability and the bending resistance can be further improved. Here, the total solid content refers to all the constituents of the composition excluding the solvent.

The thickness of the conductive layer is preferably 0.5 to 10.0 μm. When the film thickness of the conductive layer is 0.5 μm or more, variation in resistance value for each wiring can be suppressed, and a pattern can be easily formed even on a base material 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, when the conductive layer is formed from the photosensitive composition, the light easily reaches the deep part 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 type step meter such as "Surfcom" (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thicknesses at three random positions are measured with a stylus type step meter (measurement length: 1 mm, scanning speed: 0.3 mm / sec), and the average value is taken as the film thickness.

The composition forming the conductive layer preferably contains a solvent. Examples of the solvent include dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, ethyl lactate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, and the like. Examples thereof include tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol. Two or more of these may be contained. The boiling point of the solvent is preferably 150 ° C. or higher. When the boiling point is 150 ° C. or higher, volatilization of the solvent is suppressed, and thickening of the composition can be suppressed.

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

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

The method for forming the laminated member of the present invention will be described below with an example.

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 conductive fiber layer, after forming the conductive fiber layer on the base material, the binder resin layer is made conductive. Examples thereof include a method of forming the fiber so that at least a part of the fiber protrudes. In this case, a binder resin layer containing the binder resin and the conductive fiber and a laminated portion of the conductive fiber layer are formed.

Examples of the method for forming the conductive 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 so as to have a desired film thickness and dried. Examples of the method for applying the binder resin solution include rotary coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, and coating using a bar coater. Examples of the method for drying the coating film include heat drying using an oven, a hot plate, infrared rays, and vacuum drying. The drying temperature is preferably 50 to 180 ° C., and the drying time is preferably 1 minute to several hours.

Next, an example of a method for forming the conductive layer will be described. First, an organic acid salt (A), an organic acid (B), a carboxyl group-containing resin (C), a photopolymerization initiator (D), a compound (E) having an unsaturated double bond, and conductive particles (F). A photosensitive composition is produced by mixing a solvent or 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 photosensitive composition is applied to a member in which a transparent electrode layer is laminated on a base material by the method described above, and dried. Examples of the coating method include rotary coating using a spinner, spray coating, roll coating, screen printing, 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 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 depending on the coating method, the solid content concentration and viscosity of the photosensitive composition, etc., but the film thickness of the dry film of the photosensitive composition is described as a preferable thickness of the conductive layer. It is preferable to adjust to the specified range. The film thickness of the dry film of the photosensitive composition can be measured in the same manner as the film thickness of the conductive layer, for example.

When forming a conductive pattern by a photolithography method, it is preferable to expose the dry film of the photosensitive composition 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 alkaline development include aqueous solutions such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and dimethylaminoethanol. Two or more of these may be used. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and γ-butyrolactone are added to these aqueous solutions; methanol, ethanol, isopropanol, etc. Alcohols; Esters such as ethyl lactate and propylene glycol monomethyl ether acetate; Ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone; One or more surfactants may be added.

Examples of the developing method include a method of spraying a developer onto the surface of the dried film while allowing the substrate having the dried film of the exposed photosensitive composition to stand still or rotating, and a substrate having the dried film of the exposed photosensitive composition. Examples thereof include a method of immersing in a developing solution and a method of applying ultrasonic waves while immersing a substrate having a dry film of an exposed photosensitive composition in a developing solution.

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

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

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

The film for forming a conductive pattern of the present invention has an organic acid salt (A), an organic acid (B), a carboxyl group-containing resin (C), a photopolymerization initiator (D), and an unsaturated double bond on a releasable film. It has a dry film of a composition containing the compound (E) having a bond and the conductive particles (F).

The dried film of the photosensitive composition in the film for forming a conductive pattern of the present invention is exposed and developed to form a pattern on the releasable film, and then the pattern is formed on a curved surface or an end face of a substrate on which wiring is desired to be formed. A film for forming a conductive pattern is laminated on the substrate so as to be in contact with each other. By heating and pressurizing the laminate, the pattern is thermally transferred onto the substrate, and then the pattern is heated and cured, so that wiring can be formed on a curved surface or an end face of the substrate. Further, a substrate with double-sided wiring is formed in which wiring is formed on both sides of the substrate via the end faces of the substrate by thermally transferring the pattern to both sides and end faces of the substrate using this method and then heating and curing the pattern. Can be manufactured.

The releasable film preferably has a releasable layer on the film surface. Examples of the release agent constituting the release layer include a long-chain alkyl type release agent, a silicone type release agent, and a fluorine type release agent. Two or more of these may be used. Among these, even when the release agent is transferred during transfer, phenomena such as repelling of the developing solution are less likely to occur in the post-process, especially in the developing process, and in-plane unevenness is suppressed to improve fine workability. A long-chain alkyl 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 during transfer can be suppressed, and when the thickness is 500 nm or less, transfer of the release agent during transfer can be reduced.

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

Examples of the film base material used for the releasable film include films 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. A substrate having high optical properties can be exposed through a releasable 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 film substrate is preferably 5 to 150 μm. When the thickness of the film base material is 5 μm or more, the film base material can be stably conveyed when the dry film of the photosensitive composition is formed, and uneven thickness of the dry film can be suppressed. The thickness of the film substrate is more preferably 10 μm or more. On the other hand, when the thickness of the film base material is 150 μm or less, the influence of diffraction of the exposure light can be reduced during exposure through the releasable film, and the fine patterning property can be improved. The thickness of the film substrate is more preferably 30 μm or less.

The film thickness of the dry film of the photosensitive composition is preferably 0.5 to 10.0 μm. When the film thickness of the dry film is 0.5 μm or more, it is possible to suppress variations in the resistance value for each wiring, and it is possible to easily form a pattern even on an uneven base material. The thickness of the dry 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, the light easily reaches the deep part of the dry film during exposure, and the development margin can be widened. The film thickness of the dry film is more preferably 5.0 μm or less. The film thickness of the dry film of the photosensitive composition can be measured using, for example, a stylus type step meter such as "Surfcom" (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thicknesses at three random positions are measured with a stylus type step meter (measurement length: 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 composition on a releasable film and drying it. Examples of the coating method include the methods exemplified as the coating method of the binder resin layer described above. Examples of the drying method include the methods exemplified as the above-mentioned method for drying the binder resin layer. The drying temperature is preferably 50 to 180 ° C., and the drying time is preferably 1 minute to several hours.

A method of forming a conductive layer having a conductive pattern on a member in which a transparent electrode layer is laminated on a base material by the above-mentioned method will be described using the above-mentioned film for forming a conductive pattern.

As a method of transferring the film for forming a conductive pattern of the present invention onto a member in which a transparent electrode layer is laminated on a base material, for example, a dry film of a photosensitive composition is formed on a member in which a transparent electrode layer is laminated on a base material. Examples thereof include a method in which the film for forming a conductive pattern of the present invention is laminated on a substrate so as to be in contact with each other, and then transferred by heating and pressurizing using a nip roller or the like. Hereinafter, this method is referred to as thermal transfer. In order to improve the transferability, it is preferable to heat the nip roller to 50 to 120 ° C. for transfer.

When forming a conductive pattern by a photolithography method, it is preferable to expose the dry film of the photosensitive composition through an arbitrary pattern forming mask. When the method of providing the dry film by transferring the conductive pattern forming film of the present invention is used, the film may be exposed through the releasable film of the conductive pattern forming film, or the releasable film may be peeled off. After that, it may be exposed. 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 off the releasable film. As another aspect, a method of exposing and developing a dry film on the conductive pattern forming film of the present invention in the same manner as described above and then transferring the obtained pattern to a substrate can also be adopted.

Examples of the developing method and the curing method include the same methods as those exemplified above.

The conductive pattern obtained by using the laminated member of the present invention or the film for forming a conductive pattern is suitably used for a substrate with wiring used for a touch panel, a laminated ceramic capacitor, a laminated inductor, a solar cell, or the like. Among them, it is more preferably used as a peripheral wiring which is suitable for a touch panel application and has a relatively low demand for difficulty in being visually recognized, particularly as a peripheral wiring to be combined with a transparent electrode using a conductive fiber in a flexible type touch panel.

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.

<Micro workability (formation of fine wiring)>
For Examples 1 to 17 and Comparative Examples 1 to 2, the PET films "Lumirror" (registered trademark) T60 (manufactured by Toray Industries, Inc.) having a film thickness of 50 μm were subjected to Examples 1 to 17 and Comparative Examples 1 to 2. The obtained photosensitive composition was applied so that the film thickness after drying was 3 μm, and dried in a drying oven at 100 ° C. for 5 minutes.

In Example 18, the photosensitive composition obtained in Example 18 was applied onto the release layer surface of the release film AL-5 (manufactured by Lintec Corporation, peeling force 1480 mN / 20 mm, film thickness 16 μm). The film was applied so that the film thickness after drying was 3 μm, and dried in a drying oven at 100 ° C. for 5 minutes to obtain a film for forming a conductive pattern. Subsequently, for forming a conductive pattern with the PET film at a speed of 1.0 m / min at 60 ° C. using a laminator so that the dry film is in contact with the PET film "Lumirror" (registered trademark) T60 (manufactured by Toray Industries, Inc.). The film was thermocompression bonded.

An exposure apparatus having an ultra-high pressure mercury lamp (hereinafter referred to as L / S) via 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 thickness of the exposed portion. Using PEM-6M; manufactured by Union Optical Co., Ltd., full-line exposure was performed at an exposure amount of 500 mJ / cm ² (wavelength 365 nm conversion). In Example 18, a photomask was brought into close contact with the releasable film surface, and the entire line was similarly exposed at an exposure amount of 300 mJ / cm ² (wavelength 365 nm conversion).

After the exposure, the mixture was spray-developed for 20 seconds using a 0.1 wt% Na ₂ CO ₃ aqueous solution, and rinsed with ultrapure water. Then, using a hot air oven, heat treatment (cure) 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 of each unit are 30/30, 20/20, 15/15 and 10/10. The obtained conductive pattern was observed with an optical microscope. Among the conductive patterns having no residue between patterns and no pattern peeling, the smallest L / S value was set as the developable L / S value, and the microfabrication was evaluated. The smaller the L / S value, the better the microfabrication.

<Conductivity (specific resistance)>
For Examples 1 to 17 and Comparative Examples 1 and 2, the photosensitive compositions obtained in Examples 1 to 17 and Comparative Examples 1 and 2 were obtained on a PET film "Lumirror" (registered trademark) T60 having a film thickness of 50 μm. Was applied so that the film thickness after drying was 3 μm, and the coating film was dried in a drying oven at a temperature of 100 ° C. for 5 minutes.

In Example 18, the photosensitive composition obtained in Example 18 was applied onto the release layer surface of the release film AL-5 so that the film thickness after drying was 3 μm, and the temperature was 100 ° C. It was dried in a drying oven for 5 minutes to obtain a film for forming a conductive pattern. Subsequently, the PET film and the conductive pattern forming film were thermocompression bonded using a laminator at a speed of 1.0 m / min at 60 ° C. so that the dry film was in contact with the PET film “Lumilar” (registered trademark) T60.

A wiring pattern was obtained by exposure and development under the conditions described in the above <fine processability> via a photomask. The obtained wiring pattern sample was heat-treated (cured) for 30 minutes in a hot air oven at 140 ° C. to obtain a sample for resistivity measurement 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. Is shown. Connect the ends of each conductive pattern 1 of the obtained resistivity measurement sample with a tester (CDM-2000D; manufactured by Custom Co., Ltd.), measure the resistance value, and determine the resistivity based on the following formula (1). It was calculated and the conductivity was evaluated.
Specific resistance (Ω · cm) = {resistance value (Ω) x film thickness (m) x line width (m)} / {line length (m) x 100} ... (1).

<Bending resistance>
The sample for specific resistance measurement shown in FIG. 1 obtained by the method described in the above <Conductivity (specific resistance)> was applied to a surface state no-load U-shaped expansion / contraction tester DLDMLH-FS (Yuasa System Co., Ltd.). The bending operation was repeated 10,000 times in which the conductive pattern was set so as to form a mountain fold, and the short side A and the short side B shown in FIG. 1 were brought close to each other until the distance was 10 mm and then restored. The wiring resistance values before and after the test were measured, and the bending resistance was evaluated from the rate of change shown in the following equation (2). The smaller the value of the rate of change, the better the bending resistance.
Rate of change (%) = {Wiring resistance value after test (Ω) / Wiring resistance value before test (Ω)} × 100 ... (2).

<Conductivity in high temperature and high humidity environment (resistance value ratio)>
FIG. 2 shows a schematic top view of the resistance value measurement sample obtained in each Example and Comparative Example, and FIG. 3 shows a schematic cross-sectional view thereof. In FIGS. 2 and 3, reference numeral 2 is a PET film, reference numeral 3 is a conductive pattern, reference numeral 4 is a transparent electrode pattern, and reference numeral 5 is 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 the initial resistance value R1 between the two points was measured. After that, the sample for resistance value measurement was put into a constant temperature and humidity chamber SH-661 (manufactured by ESPEC CORPORATION) 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 ratio of R2 to R1 (R2 / R1) was defined as the resistance value ratio (Rr) and evaluated according to the following criteria.
A: 1 <Rr ≦ 5
B: 5 <Rr
C: No continuity.

The materials used in the examples and comparative examples are as follows.

[Organic acid salt (A)]
・ Sodium acetate (alkali metal compound)
・ Potassium acetate (alkali metal compound)
・ Sodium stearate (alkali metal compound)
・ Potassium stearate (alkali metal compound)
・ Calcium acetate (alkaline earth metal compound)
-Calcium stearate (alkaline earth metal compound).

[Organic acid (B)]
・ Adipic acid ・ (E) -2- (hex-4-ethyl) succinic acid ・ 2-propyl succinic acid ・ 3-hexylpentanedioic acid ・ 2-hexyl malonic acid ・ 2- (3-ethoxypropyl) succinic acid -2- (3-ethoxybutyl) succinic acid- (E) -2 (hexa-1-enyl) succinic acid.

[Carboxylic group-containing resin (C)]
(Synthesis Example 1) Carboxyl Group-Containing Acrylic Copolymer (C-1)
150 g of diethylene glycol monoethyl ether acetate (hereinafter, “DMEA”) was charged in a reaction vessel having a nitrogen atmosphere, and the temperature was raised 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"), and 15 g of N- A mixture of trimethylolacrylamide (“MAA”), 25 g acrylic acid (“AA”), 0.8 g 2,2'-azobisisobutyronitrile and 10 g DMEA over 1 hour. Dropped. After completion of the dropping, the polymerization reaction was carried out by further heating at 80 ° C. for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. The obtained reaction solution was purified with methanol to remove unreacted impurities, and vacuum dried for 24 hours to obtain a copolymerization ratio (weight basis): EA / 2-EHMA / BA / MAA / AA = 20 /. A carboxyl group-containing acrylic copolymer (C-1) of 20/20/15/25 was obtained. The acid value of the obtained carboxyl group-containing acrylic copolymer (C-1) was 153 mgKOH / g.

(Synthesis Example 2) Carboxyl group-containing acrylic copolymer having an unsaturated double bond (C-2)
150 g of DMEA was charged in a reaction vessel having a nitrogen atmosphere, and the temperature was raised to 80 ° C. using an oil bath. A mixture of 20 g of EA, 40 g of 2-EHMA, 20 g of BA, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile and 10 g of DMEA was added dropwise thereto over 1 hour. did. After completion of the dropping, the polymerization reaction was carried out by further heating at 80 ° C. for 6 hours. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. Subsequently, a mixture consisting of 5 g of glycidyl methacrylate (“GMA”), 1 g of triethylbenzylammonium chloride and 10 g of DMEA was added dropwise over 0.5 hours. After completion of the dropping, the addition reaction was carried out by heating for another 2 hours. Unreacted impurities were removed by purifying the obtained reaction solution with methanol, and the copolymer was vacuum-dried for 24 hours to achieve a copolymerization ratio (mass basis): EA / 2-EHMA / BA / GMA / AA = 20 /. A carboxyl group-containing acrylic copolymer (C-2) having an unsaturated double bond of 40/20/5/15 was obtained. The acid value of the obtained carboxyl group-containing acrylic copolymer (C-2) was 107 mgKOH / g.

(Synthesis Example 3) Carboxylic group-containing resin having urethane bond (C-3)
In a reaction vessel with 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 to react to obtain an epoxy carboxylate compound. Then, 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 were added to the reaction solution, and the temperature was raised to 45 ° C. It was warm. 485.2 g of trimethylhexamethylene diisocyanate was gradually added dropwise to this solution 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 reaction was carried out by heating for 6 hours until absorption near 2250 cm- ¹ disappeared by infrared absorption spectroscopy, and the reaction was carried out. ) Was obtained. The acid value of the obtained carboxyl group-containing resin (C-3) having a urethane bond was 80.0 mgKOH / g.

[Photopolymerization Initiator (D)]
-"IRGACURE" OXE01 (Oxime compound manufactured by BASF Japan Ltd.) (hereinafter referred to as OXE01).

[Compound (E) having an unsaturated double bond]
・ "Light Acrylate" (registered trademark) BP-4EA (manufactured by Kyoeisha Chemical Co., Ltd.)
[Conductive particles (F)]
-Ag particles having a particle diameter (D50) of 0.7 μm and an aspect ratio of 1.1.

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

[Overcoat resin]
(Synthesis Example 4)
150 g of DMEA was charged in a reaction vessel having 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 over 1 hour. .. After completion of the dropping, the mixture was further heated for 6 hours to carry out a polymerization reaction. Then, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. Unreacted impurities were removed by purifying the obtained reaction solution with methanol, and vacuum dried for 24 hours to obtain a copolymerization ratio (mass basis): EA / 2-EHMA / BA / MAA = 25/40 /. A 25/10 overcoat resin was obtained.

(Example 1)
(Formation of transparent electrode layer)
A silver fiber dispersion in which silver fibers and dodecylpentaethylene glycol were dispersed in pure water was applied onto a PET film "Lumilar" T60 having a thickness of 50 μm, and dried in a drying oven at 100 ° C. for 5 minutes. Then, on the silver fiber, the overcoat resin obtained in Synthesis Example 4, a compound having an unsaturated double bond (“light acrylate” (registered trademark) MPD-A; manufactured by Kyoeisha Chemical Co., Ltd.) and photopolymerization A 100: 50: 1 (weight ratio) mixture of initiator (“IRGACURE”® 369: manufactured by BASF Japan Ltd.) was applied, heat-treated and dried to form a transparent electrode layer with a thickness of 4 μm. .. When the sheet resistance of the transparent electrode layer was measured using a resistivity meter (MCP-T610; manufactured by Mitsubishi Chemical Corporation) by a 4-terminal 4-probe method constant current application method, the sheet resistance was 80Ω / □. It was. Further, when the transmission spectrum of the transparent electrode layer was measured using a microscopic differential light device (OSP-SP2000; manufactured by OLYMPUS Corporation) with reference to the transmittance in the visible light region of the PET film, it was found in the wavelength range of 450 to 650 nm. The light transmittance was 90%.

(Formation of conductive layer)
In a 100 mL clean bottle, 10.0 g of a carboxyl group-containing acrylic copolymer (C-2) having an unsaturated double bond, 0.50 g of OXE01, 5.0 g of light acrylate BP-4EA, 10.0 g of Add DMEA, 0.075 g of sodium acetate and 0.500 g of (E) -2- (hex-4-ethyl) succinic acid, and rotate-revolve vacuum mixer "Awatori Rentaro" (registered trademark) ARE-310 (registered trademark). Mixing was performed using Shinky Co., Ltd. to obtain 26.08 g of a resin solution (solid content: 61.6% by mass).

The obtained 26.08 g of the resin solution is mixed with 48.22 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) is used. It was used and kneaded to obtain 74.30 g of a photosensitive composition. Table 1 shows the composition of the photosensitive composition.

The obtained photosensitive composition was patterned on the transparent electrode layer so that the film thickness after drying was 3 μm, and dried in a drying oven at 100 ° C. for 5 minutes.

A full-line exposure was performed with an exposure amount of 500 mJ / cm ² (wavelength 365 nm conversion) using an exposure apparatus (PEM-6M; manufactured by Union Optical Co., Ltd.) having an ultra-high pressure mercury lamp without using a photomask.

After the exposure, the mixture was spray-developed for 20 seconds using a 0.1 wt% Na ₂ CO ₃ aqueous solution, and rinsed with ultrapure water. Then, using a hot air oven, heat treatment (cure) was performed at 140 ° C. for 30 minutes to obtain samples (laminated members) for measuring resistance values shown in FIGS. 2 and 3.

Using the obtained photosensitive composition and laminated member, the microfabrication, conductivity, bending resistance, and decrease in conductivity in a high temperature and high humidity environment were evaluated by the above-mentioned methods. The evaluation results are shown in Table 3.

(Examples 2 to 17, Comparative Example 1)
Photosensitive compositions having the compositions shown in Tables 1 and 2 were prepared in the same manner as in Example 1, and laminated members were prepared in the same manner as in Example 1 using the obtained photosensitive compositions, and evaluated. .. The evaluation results are shown in Table 3.

(Example 18)
(Formation of transparent electrode layer)
A transparent electrode layer was formed on the base material in the same manner as in Example 1.

(Formation of conductive layer)
A photosensitive composition having the composition shown in Table 2 was prepared in the same manner as in Example 1, and the obtained photosensitive composition was placed on the release layer surface of the release film AL-5, and the thickness after drying was 3 μm. And dried in a drying oven at 100 ° C. for 5 minutes to obtain a film for forming a conductive pattern. The obtained conductive pattern forming film was thermocompression bonded at 60 ° C. and 1.0 m / min using a laminator so that the surface on which the conductive pattern was formed was in contact with the transparent electrode layer.
Subsequently, the PET film and the conductive pattern forming film were thermocompression bonded using a laminator at a speed of 1.0 m / min at 60 ° C. so that the dry film was in contact with the PET film “Lumilar” (registered trademark) T60.

Using an exposure device (PEM-6M; manufactured by Union Optical Co., Ltd.) equipped with an ultra-high pressure mercury lamp without using a photomask, the entire line is exposed on the releasable film surface at an exposure of 300 mJ / cm ² (wavelength 365 nm conversion). Exposed.

After the exposure, the mixture was spray-developed for 20 seconds using a 0.1 wt% Na ₂ CO ₃ aqueous solution, and rinsed with ultrapure water. Then, using a hot air oven, heat treatment (cure) was performed at 140 ° C. for 30 minutes to prepare a laminated member, which was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Comparative Example 2)
(Formation of transparent electrode layer)
A transparent electrode layer was formed on the base material in the same manner as in Example 1.

(Formation of conductive layer)
In a 100 mL clean bottle, 10.0 g of a carboxyl group-containing acrylic copolymer having an unsaturated double bond (C-2), 0.50 g of OXE01, 5 g of light acrylate BP-4EA, 10.0 g of DMEA and Add 0.24 g of tetramethylammonium chloride and mix using a rotation-copolymer vacuum mixer "Awatori Rentaro" (registered trademark) ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 25.74 g of a resin solution ( Solid content 61.1% by mass) was obtained.

The obtained 25.74 g of the resin solution is 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) is used. The mixture was kneaded using the mixture to obtain 72.96 g of a photosensitive conductive paste. Using the obtained photosensitive composition, a laminated member was prepared in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 3.

All of the laminated members of Examples 1 to 18 were able to suppress a decrease in conductivity of the transparent electrode layer in a high temperature and high humidity environment, and were able to obtain a low resistance conductive pattern. On the other hand, in the laminated members of Comparative Examples 1 and 2 in which the conductive layer does not contain an organic acid salt, the conductivity of the transparent electrode layer was lowered in a high temperature and high humidity environment.

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

Claims (10)

A laminated member having a transparent electrode layer and a conductive layer on a base material.
The transparent electrode layer contains a binder resin and conductive fibers, and at least a part of the conductive fibers is in contact with the conductive layer, and the conductive layer is composed of an organic acid salt (A), an organic acid (B), and the like. A laminated member composed of a cured product of a composition containing a carboxyl group-containing resin (C), a photopolymerization initiator (D), a compound (E) having an unsaturated double bond, and conductive particles (F). The laminated member according to claim 1, wherein the transparent electrode layer has a laminated portion of a binder resin layer and a conductive fiber layer, and the conductive layer is in contact with the binder resin layer and the conductive fiber layer. The laminated member according to claim 1 or 2, wherein the transparent electrode layer contains silver fibers. The laminated member according to any one of claims 1 to 3, wherein the transparent electrode layer has a sheet resistance of 500 Ω / □ or less. The laminated member according to any one of claims 1 to 4, wherein the transparent electrode layer has a light transmittance of 80% or more. The laminated member according to any one of claims 1 to 5, wherein the organic acid salt (A) contains a salt of an organic acid and an alkali metal and / or an alkaline earth metal. The laminated member according to any one of claims 1 to 6, wherein the organic acid (B) contains a dicarboxylic acid. On the releasable film, an organic acid salt (A), an organic acid (B), a carboxyl group-containing resin (C), a photopolymerization initiator (D), a compound (E) having an unsaturated double bond, and conductivity. A film for forming a conductive pattern having a dry film of a composition containing particles (F). The film for forming a conductive pattern according to claim 8, wherein the salt of the organic acid salt (A) contains a salt of an organic acid and an alkali metal and / or an alkaline earth metal. The film for forming a conductive pattern according to claim 8 or 9, wherein the organic acid (B) contains a dicarboxylic acid.

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