JP6226105B1 - Laminated member and touch panel - Google Patents

Abstract

The present invention includes a transparent electrode layer A formed on the substrate, a part of the transparent electrode layer A, and a part of the conductive layer B formed on the substrate. Are laminated members containing conductive particles (a), an organic binder resin (b) having a polar group, and a compound (c) having a hydroxypyridine skeleton in one molecule. Provided is a laminated member having excellent connectivity between a transparent electrode formed on a substrate and surrounding wiring, and excellent environmental load resistance.

Description

  The present invention relates to a laminated member and a touch panel.

  In the capacitive touch panel, a transparent electrode made of indium tin oxide (hereinafter referred to as ITO) or the like is formed on the base material in the display area, and the surrounding wiring is formed on the base material in the non-display area around it. It is formed and a part is connected with the transparent electrode. The peripheral wiring is intended to transmit the capacitance change caused by the touch operation to the display area to the IC driver as an electric signal, and a method of applying a conductive paste by a screen printing method or the like (for example, Patent Document 1). And 2), and as a method of reducing the width of the surrounding wiring for the purpose of reducing the ratio of the non-display area, a method of photolithography using a photoresist (for example, Patent Documents 3 and 4), photosensitive conductive A method using a paste (for example, Patent Documents 5 and 6) has been proposed.

JP 2009-230952 A JP 2007-207567 A JP 2011-197754 A JP 2015-122046 JP 2013-136727 A JP 2013-229284 A

  However, when the surrounding wiring is formed using a conductive paste made of general resin and metal powder, the electrical connectivity between the transparent electrode and the surrounding wiring deteriorates after environmental load such as high temperature and high humidity. It had been.

  Then, an object of this invention is to provide the laminated member which is excellent in the connectivity of the transparent electrode formed on the base material and surrounding wiring, and environmental load tolerance.

  As a result of intensive studies, the present inventors have determined that the direct cause of the deterioration of electrical connectivity after a high-temperature and high-humidity environment is a fine crack generated in the transparent electrode, and the cause is a conductive paste whose surrounding wiring is It was found that the organic binder remained in the unreacted portion of the organic binder. The unreacted site was affected by heat and humidity in a high-temperature and high-humidity environment, and the reaction gradually progressed, and it was predicted that the resulting curing shrinkage force caused fine cracks in the transparent electrode. Therefore, it has been found that by containing a compound having a hydroxypyridine skeleton in the conductive paste and suppressing the progress of the reaction under high temperature and high humidity, the above phenomenon is suppressed and the present invention is extremely effective in solving the problems. completed.

  The present invention comprises a transparent electrode layer A formed on a substrate, and a conductive layer B partially formed on the transparent electrode layer A and partially on the substrate, the conductive layer B being And a laminated member containing conductive particles (a), an organic binder resin (b) having a polar group, and a compound (c) having a hydroxypyridine skeleton in one molecule.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated member excellent in the connectivity of the transparent electrode formed on the base material and surrounding wiring, and environmental load tolerance can be provided.

It is the schematic of the laminated member used for the connectivity evaluation of a transparent electrode layer and a conductive layer.

  The laminated member of the present invention includes a transparent electrode layer A formed on a base material, and a conductive layer B formed partly on the transparent electrode layer A and partly on the base material. Layer B is a laminated member containing conductive particles (a), an organic binder resin (b) having a polar group, and a compound (c) having a hydroxypyridine skeleton in one molecule.

  The base material provided in the laminated member of the present invention refers to a support for forming a transparent electrode layer, a conductive layer, etc. on the surface thereof. Examples of the substrate include a rigid substrate such as glass, a glass epoxy substrate, or a ceramic substrate, and a flexible substrate using a film such as polyester, polyimide, or cycloolefin. When using a laminated member as a touch panel, glass, a polyethylene terephthalate film, or a cycloolefin film is preferable from the viewpoint of transparency. For the purpose of improving heat resistance and optical characteristics, a modification treatment and a protective film may be formed on the surface of the substrate.

  The transparent electrode layer A formed on the substrate is not a flat layer applied to the entire surface, but is a pattern having an arbitrary shape that is patterned using a printing resist or a photoresist. That is, the transparent electrode layer A does not completely cover the base material, and the base material is exposed at a portion where the pattern of the transparent electrode layer A is not formed.

  The transparent electrode layer A consists of only a conductive component or contains a conductive component. As the conductive component constituting the transparent electrode layer A, for example, indium, tin, zinc, gallium, antimony, titanium, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten, or an oxide of these metals, A carbon nanotube is mentioned. More specifically, for example, indium tin oxide that is ITO, indium zinc oxide, indium oxide-zinc oxide composite oxide, aluminum zinc oxide, gallium zinc oxide, fluorine zinc oxide, fluorine indium oxide, Examples thereof include antimony tin oxide (hereinafter referred to as ATO) or fluorine tin oxide. Among these, ITO or ATO, which has high conductivity and visible light transmittance and is advantageous in terms of price, is preferable.

  Examples of the method for forming the transparent electrode layer before pattern processing include a vacuum deposition method, a sputtering method, an ion plating method, and a coating method.

  The thickness of the transparent electrode layer A is preferably 0.01 to 0.5 μm and more preferably 0.05 to 0.3 μm in order to achieve both good conductivity and visible light transmittance. When the thickness of the transparent electrode layer A is 0.05 μm or more, it is possible to suppress variations in resistance value and to suppress the influence of fine cracks that occur under a high temperature and high humidity environment load. On the other hand, if the thickness of the transparent electrode layer A is 0.3 μm or less, the visible light transmittance can be increased.

  The conductive layer B contains conductive particles (a), an organic binder resin (b) having a polar group, and a compound (c) having a hydroxypyridine skeleton in one molecule. The conductive layer B is not a flat layer applied to the entire surface, and may be a pattern having an arbitrary shape. In this case, the conductive layer B does not completely cover and hide the base material and the transparent electrode layer A, but the base material and / or the transparent electrode layer A is exposed at a portion where the pattern of the conductive layer B is not formed. It has become a state.

  Examples of the conductive particles (a) contained in the conductive layer B include silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, indium, and alloys of these metals. Silver, gold or copper having high conductivity is preferable, and silver which is highly stable and advantageous in terms of price is more preferable.

  As the shape of the conductive particles (a), the aspect ratio, which is a value obtained by dividing the major axis length by the minor axis length, is preferably 1.0 to 3.0, and is 1.0 to 2.0. It is more preferable. When the aspect ratio of the conductive particles (a) is 1.0 or more, the contact probability between the conductive particles is further increased. On the other hand, when the aspect ratio of the conductive particles (a) is 2.0 or less, the exposure light is hardly shielded when the pattern of the conductive layer B is formed by a photolithography method, and the development margin is widened. The aspect ratio of the conductive particles (a) was determined by observing the conductive particles (a) at a magnification of 15000 times using a scanning electron microscope (SEM) or transmission electron microscope (TEM), and randomly conducting 100 conductive particles. The primary particles of the active particles are selected, the major axis length and the minor axis length of each are measured, and the aspect ratio is obtained from the average value of both.

  0.05-2.0 micrometers is preferable and, as for the particle size of electroconductive particle (a), 0.1-1.5 micrometers is more preferable. When the particle size of the conductive particles (a) is 0.05 μm or more, the interaction between the particles is weak, and the dispersed state of the conductive particles is easily maintained. On the other hand, when the particle size of the conductive particles (a) is 2.0 μm or less, the edge of the pattern of the formed conductive layer B can be sharpened. The particle size of the conductive particles (a) contained in the conductive layer B is determined by adding a resin component to an organic solvent such as tetrahydrofuran (hereinafter referred to as THF) obtained by physically collecting the conductive layer B with tweezers or an adhesive tape. Dissolved and settled conductive particles were collected and dried at 70 ° C. for 10 minutes using a box oven, and observed with an electron microscope at a magnification of 15000 times, and randomly 20 conductive particles. The primary particles can be selected, the maximum width of each can be measured, and the average value thereof can be obtained. The organic solvent used at this time is not particularly limited as long as it can dissolve the resin component of the conductive layer B.

  As for the ratio of the electroconductive particle (a) which the conductive layer B contains, 60-95 mass% is preferable. When the proportion of the conductive particles (a) is 60% by mass or more, the contact probability between the conductive particles and the transparent electrode layer A is increased, and the wiring resistance value of the laminated member of the present invention can be stabilized. On the other hand, when the proportion of the conductive particles (a) is 95% by mass or less, the conductivity of the conductive layer B when the laminated member of the present invention is bent can be further stabilized. The ratio of the conductive particles (a) contained in the conductive layer B can be determined by measuring the firing residue of the collected conductive layer B using a thermogravimetric analyzer.

  The polar group of the organic binder resin (b) having a polar group contained in the conductive layer B refers to a carboxyl group, a hydroxyl group, and an amino group, and the organic binder resin (b) is a thermosetting resin used in a conductive paste. Thermoplastic resins are preferred, and specific examples include acrylic resins, polyester resins, phenol resins, epoxy resins, acrylic urethane resins, polyether urethane resins, phenoxy resins, polycarbonates, polyimides, polyamideimides, polyamides, etc. Or it can use in combination of 2 or more types. When using the laminated member of the present invention as a touch panel, the organic binder resin (b) is preferably an acrylic resin, an epoxy resin, a polyester resin, an acrylic urethane resin, or a polyether urethane resin from the viewpoints of adhesion to a substrate and flexibility. . In addition, when the organic binder resin (b) having a polar group has a urethane skeleton, the curing shrinkage force can be relaxed, and damage to the transparent conductive layer can be reduced.

  Further, the organic binder resin (b) has a polar group, so that it can form a strong interaction with the compound having a hydroxypyridine skeleton, and suppresses the movement of the organic binder resin (b) under high temperature and high humidity. In addition, the probability of contact with unreacted sites or with the curing agent can be reduced, and as a result, the progress of the reaction can be suppressed. In particular, when the polar group is a carboxyl group, the effect is high, which is preferable.

  When the conductive layer B is formed using a photosensitive conductive paste, the organic binder resin (b) having a polar group is preferably an acrylic copolymer or epoxycarboxylate resin having a carboxyl group, and the substrate, the transparent electrode layer A An epoxy carboxylate resin is more preferable from the viewpoint of adhesiveness.

  The acrylic copolymer having a carboxyl group can be obtained by copolymerizing an acrylic monomer and an unsaturated acid such as an unsaturated carboxylic acid as a copolymerization component.

  Examples of acrylic monomers include acrylic acid (hereinafter referred to as AA), methyl acrylate, ethyl acrylate (hereinafter referred to as EA), 2-ethylhexyl acrylate, n-butyl acrylate (hereinafter referred to as BA), iso- Butyl acrylate, iso-propane acrylate, glycidyl acrylate, butoxytriethylene glycol acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, Isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate Relate, octafluoropentyl 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, Pyrene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, acrylamide, N-methoxymethylacrylamide, N -Ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, acrylic acid adduct of ethylene glycol diglycidyl ether having a hydroxyl group in which an epoxy group is opened with an unsaturated acid, diethylene glycol diglycidyl ether Acrylic acid adduct, neopentyl glycol diglycidyl ether with acrylic acid Additives, acrylic acid adducts of glycerin diglycidyl ether, acrylic acid adducts of bisphenol A diglycidyl ether, acrylic acid adducts of bisphenol F, acrylic acid adducts of cresol novolac, or γ-acryloxy Examples include propyltrimethoxysilane or a compound obtained by substituting an acrylic group thereof with a methacryl group. In order to increase the visible light transmittance of the organic binder resin (b) having a polar group, an aliphatic chain or an alicyclic structure is used. An acrylic monomer having

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

  The epoxy carboxylate compound refers to a compound that can be synthesized using an epoxy compound and a carboxyl compound having an unsaturated double bond as starting materials.

  Examples of the epoxy compound that can be a starting material include glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidyl amines, and epoxy resins. More specifically, 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 fluorenediglycidyl ether, biphenol diglycidyl ether, tetramethylbiphenol glycidyl ether, trimethylolpropane triglycidyl ether 3 ', 4'-epoxy Hexyl-3,4-epoxycyclohexane carboxylate or tert- butyl glycidyl amines.

  Examples of the carboxyl compound having an unsaturated double bond that can be used as a starting material include (meth) acrylic acid, crotonic acid, cinnamic acid, and α-cyanocinnamic acid.

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

  By reacting the carboxyl group of the epoxy carboxylate compound whose acid value has been adjusted with the above polybasic acid anhydride with a compound having an unsaturated double bond such as glycidyl (meth) acrylate, the epoxy carboxylate compound becomes You may adjust the quantity of the reactive unsaturated double bond which has.

  The urethanization may be carried out by reacting the hydroxy group of the epoxycarboxylate compound with the diisocyanate compound. Examples of the diisocyanate compound include hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tridenic diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allyl cyanide diisocyanate, and norbornane diisocyanate.

  When the conductive layer B is formed using a photosensitive conductive paste, the acid value of the organic binder resin (b) having a polar group is preferably 50 to 250 mgKOH / g. -150 mgKOH / g is more preferable. When the acid value is 50 mgKOH / g or more, the solubility in the developer is increased, and the generation of development residues can be suppressed. If the acid value is 250 mgKOH / g or less, excessive dissolution in the developer can be suppressed, and film loss at the pattern forming portion can be suppressed. The acid value of the organic binder resin (b) can be measured according to JIS K 0070 (1992).

  The compound (c) having a hydroxypyridine skeleton in one molecule contained in the conductive layer B only needs to have a hydroxypyridine skeleton in one molecule, and is introduced in the form of a single compound or a salt thereof. Also good. Specifically, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,4-dihydroxypyridine, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,8-dihydroxyquinoline, 5-hydroxy 2-methylpyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxy-6-methylpyridine, 2,4-dihydroxy-6-methylpyridine, 2-ethyl-3- Hydroxy-6-methylpyridine, pyridoxine-3,4-dibalmitate, 4-deoxypyridoxine, pyridoxamine, pyridoxine dicaprylate, 4-bromo-2-hydroxypyridine, 4-chloro-2-hydroxypyridine, 2-hydroxy-5 Iodopyridine, 3-hydroxyi Quinoline, 2-quinolinol, 3-quinolinol, 2-methyl-4-quinolinol, pyridoxal-5-phosphate, citrazinic acid, 6-hydroxy nicotinic acid and salts thereof. Among them, pyridoxine having a methylol group, 4-deoxypyridoxine, pyridoxal, pyridoxamine, pyridoxal-5-phosphate, 4-pyridoxy acid, isopyridoxal, 2-hydroxymethyl-3-pyridinol, 2-hydroxymethyl-6-methyl-3- Pyridinol, 2,6-bis (hydroxymethyl) -3-pyridinol, ginkotoxin, pyridoxine dicaprylate, pyridoxal oxime, 6- (hydroxymethyl) -3,4-pyridinediol, 2-bromo-6- (hydroxymethyl) -3-pyridinol, 2,5-dichloro-6- (hydroxymethyl) -3-pyridinol, 2-chloro-6- (hydroxymethyl) -4-iodo-3-pyridinol, 3- (hydroxymethyl) -6- Methyl-4-quinori Lumpur, pyridoxine 3,4 dipalmitate, and these salts are preferred because they can be more robust interaction with the organic binder resin (b) having a polar group.

The amount of the compound (c) having a hydroxypyridine skeleton in one molecule contained in the conductive layer B is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the organic binder resin (b) having a polar group. It is added in a range, more preferably 0.5 to 10 parts by mass. The amount of the compound (c) having a hydroxypyridine skeleton in one molecule is 0.1 parts by mass or more, more preferably 0.5 parts by mass with respect to 100 parts by mass of the organic binder resin (b) having a polar group. If it is as described above, the effect of stabilizing electrical connectivity after high temperature and high humidity is enhanced. The amount of the compound (c) having a hydroxypyridine skeleton in one molecule is 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the organic binder resin (b) having a polar group. If it exists, the adhesiveness of the transparent electrode layer A and the conductive layer B can be made high. Regarding the identification and content of the compound (c) having a hydroxypyridine skeleton in one molecule contained in the conductive layer B, the collected conductive layer B is subjected to solvent extraction or the like, and the obtained sample is subjected to IR, ¹ H- It can obtain | require by implementing NMR, MS measurement, etc.

  The thickness of the conductive layer B is preferably 1.0 to 10.0 μm. If the thickness of the conductive layer B is 1.0 μm or more, variation in resistance can be suppressed. If the thickness of the conductive layer B is 10.0 μm or less, the amount of curing shrinkage that occurs under high temperature and high humidity becomes small, and the effect of stabilizing electrical connectivity becomes high.

  The touch panel of the present invention includes the laminated member of the present invention. More specifically, the laminated member of the present invention is suitably used as a member for a touch panel. Examples of the touch panel method include a resistive film type, an optical type, an electromagnetic induction type, and a capacitance type. In particular, a capacitance type touch panel requires particularly fine wiring. The laminated member which formed the pattern of the conductive layer B using the photosensitive electrically conductive paste which is an aspect is used more suitably. In a touch panel provided with such a pattern of the conductive layer B as the peripheral wiring of the touch panel and the peripheral wiring is 50 μm pitch (wiring width + inter-wiring width) or less, the non-display area can be narrowed and the display area is widened. be able to.

  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 materials used in each example and comparative example are as follows.
[Material of transparent electrode layer A]
・ ITO (97% by mass of indium oxide, 3% by mass of tin oxide)
・ ATO
[Organic binder resin having polar group (b)]
・ JER (registered trademark) 828 (Mitsubishi Chemical Corporation)
ARUFON (registered trademark) UC-3000 (manufactured by Toagosei Co., Ltd.) (hereinafter referred to as UC-3000)
-Resins (b-1) to (b-4).

[Synthesis Example 1]
Copolymerization ratio (mass basis): EA / 2-ethylhexyl methacrylate (hereinafter referred to as 2-EHMA) / BA / N-methylolacrylamide (hereinafter referred to as MAA) / AA = 20/40/20/5/15
150 g of diethylene glycol monoethyl ether acetate (hereinafter referred to as 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 consisting of 20 g EA, 40 g 2-EHMA, 20 g BA, 5 g MAA, 15 g AA, 0.8 g 2,2′-azobisisobutyronitrile and 10 g DMEA was added 1 It was added dropwise over time. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. The reaction solution obtained was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a resin (b-1). The acid value of the obtained resin (b-1) was 103 mgKOH / g.

[Synthesis Example 2]
Copolymerization ratio (mass basis): EA / 2-EHMA / styrene (hereinafter referred to as St) / glycidyl methacrylate (hereinafter referred to as GMA) / AA = 30/30/25/5/10
In a nitrogen atmosphere reaction vessel, 150 g of DMEA was charged and heated to 80 ° C. using an oil bath. To this was added dropwise a mixture of 30 g EA, 30 g 2-EHMA, 25 g St, 10 g AA, 0.8 g 2,2′-azobisisobutyronitrile and 10 g DMEA over 1 hour. did. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Subsequently, a mixture consisting of 5 g GMA, 1 g triethylbenzylammonium chloride and 10 g DMEA was added dropwise over 0.5 hours. After completion of the dropwise addition, an additional reaction was performed for 2 hours. The reaction solution obtained was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a resin (b-2). The acid value of the obtained resin (b-2) was 83 mgKOH / g.

[Synthesis Example 3]
492.1 g carbitol acetate, 860.0 g EOCN-103S (manufactured by Nippon Kayaku Co., Ltd .; cresol novolac type epoxy resin; epoxy equivalent: 215.0 g / equivalent), 288. 3 g of AA, 4.92 g of 2,6-di-tert-butyl-p-cresol and 4.92 g of triphenylphosphine were charged, and the acid value of the reaction solution was reduced to 0.5 mgKOH / g or less at a temperature of 98 ° C. The reaction was continued until an epoxycarboxylate compound was obtained. Subsequently, 169.8 g of carbitol acetate and 201.6 g of tetrahydrophthalic anhydride were added to this reaction solution and reacted at 95 ° C. for 4 hours to obtain a resin (b-3). The acid value of the obtained resin (b-3) was 104 mgKOH / g.

[Synthesis Example 4]
In a nitrogen atmosphere reaction vessel, 368.0 g of RE-310S (manufactured by Nippon Kayaku Co., Ltd .; bisphenol A type epoxy resin; epoxy equivalent: 184.0 g / equivalent), 141.2 g of AA, 1.02 g of Hydroquinone monomethyl ether and 1.53 g of triphenylphosphine were charged and reacted at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mgKOH / g or less to obtain an epoxycarboxylate compound. Thereafter, 755.5 g carbitol acetate, 268.3 g 2,2-bis (dimethylol) -propionic acid, 1.08 g 2-methylhydroquinone and 140.3 g spiroglycol were added to the reaction solution, The temperature was raised to. To this solution, 485.2 g of trimethylhexamethylene diisocyanate was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropwise addition, the reaction temperature was raised to 80 ° C., and the mixture was reacted for 6 hours until absorption near 2250 cm ⁻¹ disappeared by an infrared absorption spectrum measurement method to obtain a resin (b-4). The acid value of the obtained resin (b-4) was 80.0 mgKOH / g.

[Photopolymerization initiator]
IRGACURE (registered trademark) OXE-01 (manufactured by Ciba Japan Co., Ltd.) (hereinafter referred to as OXE-01)
[Thermal polymerization initiator]
・ Permenta (registered trademark) H (manufactured by NOF Corporation)
[Curing agent]
Cureazole (registered trademark) 1B2MZ
[monomer]
Light acrylate MPD-A (manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter referred to as MPD-A).

[Example 1]
<Formation of transparent electrode layer A>
A biaxial centrifugal polyethylene terephthalate (PET) film having a thickness of 30 μm was prepared as a substrate. An ITO thin film made of ITO having a thickness of 50 nm (0.05 μm) was formed on the surface of the base material using a sputtering apparatus equipped with an ITO sintered body target.

<Pattern processing of ITO thin film>
After laminating a photoresist film on the ITO thin film, a photomask is adhered, and the photoresist is exposed at an exposure amount of 200 mJ / cm ² with an exposure machine having an ultra-high pressure mercury lamp, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. The photoresist is patterned by spray development for 30 seconds. And after etching ITO with 0.1 mass% hydrochloric acid aqueous solution, the resist was peeled off with 1 mass% sodium hydroxide aqueous solution, and the transparent electrode layer A1 patterned on the board | substrate was formed.

<Preparation of composition for forming conductive layer B>
In a 100 mL clean bottle, put 10.0 g of jER828, 1.5 g of 2-hydroxypyridine, 0.5 g of Curazole 1B2MZ and 5.0 g of diethylene glycol, and rotate and revolve vacuum mixer "Awatori Rentaro" (Registered) Trademark) ARE-310 (manufactured by Sinky Corporation) was mixed to obtain 17.0 g of a resin solution (solid content: 70.6 mass%)

  To the obtained 17.0 g resin solution, 68.0 g of silver particles having a particle size of 1.0 μm and an aspect ratio of 1.1 are mixed and kneaded using a three roller mill (EXAKT M-50; manufactured by EXAKT). 85.0 g of composition B1 was obtained.

<Formation of conductive layer B>
On the surface of the transparent electrode layer A1 patterned on the PET film, the composition B1 is applied with a screen printer so that the thickness of the conductive layer B1 is 6 μm, and is cured at 140 ° C. for 60 minutes. B1 was formed.

<Evaluation of connection stability between transparent electrode A and conductive layer B>
The laminated member shown in FIG. 1 is manufactured by the above method, put into a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 480 hours, and after taking out, the resistance value between terminals is measured. The rate of increase from the resistance value before the introduction of the high-temperature and high-humidity tank was determined from the following formula, and was used as the value of connection stability. The results are shown in Table 3.

[Examples 2 to 5]
The laminated members shown in Tables 1 and 2 were manufactured by the same method as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

[Example 6]
In the same manner as in Example 1, the ITO thin film was patterned on the substrate.
<Formation of conductive layer B>
The composition B6 was applied to the surface of the transparent electrode layer A6 patterned on the substrate with a screen printer so that the thickness of the dried film was 5 μm, dried at 70 ° C. for 10 minutes with a hot air dryer, and then predetermined. The film was exposed at an exposure amount of 300 mJ / cm ² with an exposure machine having an ultra-high pressure mercury lamp through a photomask, and 0.2 mass% sodium carbonate aqueous solution was spray-developed at a pressure of 0.1 MPa for 30 seconds, and then 140 ° C. Was cured for 60 minutes to produce a laminated member shown in FIG.

  The laminated member was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Examples 7 to 14]
The laminated members shown in Tables 1 and 2 were manufactured by the same method as in Example 6, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

[Comparative Examples 1 and 2]
The laminated members shown in Tables 1 and 2 were manufactured by the same method as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

[Comparative Example 3]
The laminated members shown in Tables 1 and 2 were manufactured by the same method as in Example 6, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

  In Examples 1-14, it turns out that the laminated member excellent in the connectivity of a transparent electrode and surrounding wiring, and environmental load tolerance is manufactured in all.

  The laminated member of this invention can be utilized suitably as a component of a touch panel.

1 Substrate 2 Transparent electrode layer A
3 Conductive layer B

Claims (5)

A transparent electrode layer A formed on the substrate;
A conductive layer B partially formed on the transparent electrode layer A and partially on the substrate;
The conductive layer B contains conductive particles (a), an organic binder resin (b) having a polar group, and a compound (c) having a hydroxypyridine skeleton in one molecule ,
Laminated member in which the compound having a hydroxy pyridine skeleton in one molecule (c) is have a methylol group. The thickness of the transparent electrode layer A is 0.5μm or less, according to claim 1 Symbol placement lamination member. The laminated member according to claim 1 or 2 , wherein the polar group of the organic binder resin (b) having the polar group contains a carboxyl group. The laminated member according to any one of claims 1 to 3 , wherein the organic binder resin (b) having the polar group has a urethane skeleton. A touch panel provided with the lamination | stacking member as described in any one of Claims 1-4 .