KR102096831B1 - Lamination 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 conductive layer B formed on a substrate, and the conductive layer B is a conductive particle (a), an organic binder having a polar group A laminated member containing a resin (b) and a compound (c) having a hydroxypyridine skeleton in one molecule. Provided is a laminated member excellent in connectivity and environmental load resistance of a transparent electrode formed on a substrate and surrounding wiring.

Description

Lamination member and touch panel

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 substrate in the display area, and peripheral wiring is formed on the substrate in the non-display area around it. Is connected to a transparent electrode. The peripheral wiring is intended to transmit a change in capacitance generated by a touch operation to the display area as an electrical signal to the IC driver, and a method of applying a conductive paste by a screen printing method or the like (for example, Patent Document 1 and 2) Alternatively, as a method of thinning the line 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) or using a photosensitive conductive paste Methods (for example, Patent Documents 5 and 6) have been proposed.

Japanese Patent Publication 2009-230952 Japanese Patent Publication No. 2007-207567 Japanese Patent Publication 2011-197754 Japanese Patent Publication 2015-122046 Japanese Patent Publication No. 2013-136727 Japanese Patent Publication 2013-229284

However, when the peripheral wiring is formed using a conductive paste made of a general resin and metal powder, there is a problem that the electrical connection between the transparent electrode and the peripheral wiring deteriorates after environmental load such as high temperature and high humidity.

Therefore, it is an object of the present invention to provide a laminated member excellent in connectivity and environmental load resistance of a transparent electrode formed on a substrate and surrounding wiring.

As a result of careful review, the present inventors have found that the direct cause of deterioration in electrical connectivity after a high temperature and high humidity environment is a fine crack formed in the transparent electrode, and the factor is unreacted of the organic binder remaining in the conductive paste as the peripheral wiring. Found something on the site. It was expected that the unreacted site was gradually affected by heat or humidity under a high temperature and high humidity environment, and the curing shrinkage force generated therefrom was the cause of micro-cracks on the transparent electrode. Then, 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 was suppressed to find that it was very effective in solving the problem, and the present invention was completed.

The present invention comprises a transparent electrode layer A formed on a substrate, a part of the transparent electrode layer A and a conductive layer B formed on a substrate, and the conductive layer B has an organic binder resin having conductive particles (a) and polar groups It is a laminated member containing (b) 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 resistance can be provided.

1 is a schematic view of a laminated member used for evaluation of connectivity between a transparent electrode layer and a conductive layer.

The laminated member of the present invention includes a transparent electrode layer A formed on a substrate, a portion of the transparent electrode layer A and a conductive layer B formed on a substrate, and the conductive layer B has conductive particles (a) and polar groups It is a laminated member containing an organic binder resin (b) and a compound (c) having a hydroxypyridine skeleton in one molecule.

The substrate provided by the laminated member of the present invention refers to a support for forming a transparent electrode layer or a conductive layer on the surface. Examples of the substrate include rigid substrates such as glass and glass epoxy substrates and ceramic substrates, and flexible substrates using films 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. Further, for the purpose of improving heat resistance and optical properties, 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 provided on the entire surface, but a pattern of arbitrary shape patterned using a printing resist or a photoresist. That is, the transparent electrode layer A does not completely cover the substrate, but the substrate is exposed in a region where the pattern of the transparent electrode layer A is not formed.

The transparent electrode layer A is made of only a conductive component or contains a conductive component. As a 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 oxides of these metals or carbon nano A tube is mentioned. More specifically, for example, ITO is indium tin oxide, indium zinc oxide, indium-zinc oxide composite oxide, aluminum zinc oxide, gallium zinc oxide, fluorine zinc oxide, fluorine indium oxide, antimony tin oxide (hereinafter referred to as ATO) Fluorine tin oxide). Among them, ITO or ATO, which has high conductivity and visible light transmittance and is also advantageous in terms of price, is preferred.

As a method of forming a transparent electrode layer before pattern processing, for example, a vacuum vapor deposition method, sputtering method, ion plating method or coating method can be mentioned.

The thickness of the transparent electrode layer A is preferably 0.01 to 0.5 µm, more preferably 0.05 to 0.3 µm in order to achieve 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 the imbalance of the resistance value and to suppress the influence of micro-cracks generated under high temperature and high humidity environmental load. On the other hand, when 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) and 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 provided on the entire surface, but may be an arbitrary shape pattern. In this case, the conductive layer B does not completely cover the base material and the transparent electrode layer A, but the base material and / or the transparent electrode layer A are exposed in a region where the pattern of the conductive layer B is not formed.

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, or alloys of these metals. Silver, gold or copper is preferred, and silver having high stability and advantageous in terms of price is more preferable.

As the shape of the conductive particles (a), the aspect ratio, which is the value obtained by dividing the long axis length by the short axis length, is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. When the aspect ratio of the electroconductive particle (a) is 1.0 or more, the probability of contact between electroconductive particles becomes higher. On the other hand, when the aspect ratio of the conductive particles (a) is 2.0 or less, 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) is observed by using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) at a magnification of 15000 times, and observe the conductive particles (a) at random magnification of 100 primary particles. Select and measure each long axis length and short axis length, and calculate the aspect ratio from the average value of both.

The particle size of the conductive particles (a) is preferably 0.05 to 2.0 μm, and more preferably 0.1 to 1.5 μm. When the particle diameter of the conductive particles (a) is 0.05 µm or more, the interaction between the particles is weak and it is easy to maintain the dispersion state of the conductive particles. On the other hand, if the particle diameter 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 diameter of the conductive particles (a) contained in the conductive layer B is obtained by physically collecting the conductive layer B with tweezers or adhesive tape, and dissolving the resin component with an organic solvent such as tetrahydrofuran (hereinafter referred to as THF), The precipitated conductive particles were collected, and dried at 70 ° C for 10 minutes using a box oven, observed at a magnification of 15000 times using an electron microscope, and randomly selected primary particles of 20 conductive particles. , It can be calculated by measuring the maximum width of each and obtaining their average value. At this time, the organic solvent used may be any one that can dissolve the resin component of the conductive layer B, and is not particularly limited.

The proportion of the conductive particles (a) contained in the conductive layer B is preferably 60 to 95% by mass. When the proportion of the conductive particles (a) is 60% by mass or more, the probability of contact between the conductive particles and the transparent electrode layer A increases, and the wiring resistance value of the laminated member of the present invention can be stabilized. On the other hand, if 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 more stabilized. The proportion of the conductive particles (a) contained in the conductive layer B can be determined by measuring the calcined 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 indicates a carboxyl group, hydroxyl group, and amino group, and as the organic binder resin (b), a thermosetting resin and a thermoplastic resin used in the conductive paste are preferable, and specifically Examples include acrylic resin, polyester resin, phenol resin, epoxy resin, acrylic urethane resin, polyether urethane resin, phenoxy resin, polycarbonate, polyimide, polyamide imide, polyamide, etc. It can be used in combination. When the laminated member of the present invention is used 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 viewpoint of adhesion to a substrate and flexibility. . Further, if 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) can form a strong interaction with a compound having a hydroxypyridine skeleton by having a polar group, thereby suppressing the action of the organic binder resin (b) under high temperature and high humidity and unreacted sites The probability of contact with one another or the curing agent can be reduced, and as a result, the progress of the reaction can be suppressed. In particular, the polar group is preferable because of its high effect in the carboxyl group.

When forming the conductive layer B using a photosensitive conductive paste, the organic binder resin (b) having a polar group is preferably an acrylic copolymer having a carboxyl group or an epoxy carboxylate resin, and from the viewpoint of adhesion to the substrate and the transparent electrode layer A Epoxy carboxylate resins are more preferred.

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

As the acrylic monomer, for example, 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, isobor Neil acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octa Fluoropentyl 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, methox Cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate Acrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol monohydroxy Pentaacrylate, dipentaerythritol hexa Acrylate, acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, Nn-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, ethylene glycol having a hydroxyl group obtained by opening an epoxy group with an unsaturated acid Acrylic acid adduct of diglycidyl ether, acrylic acid adduct of diethylene glycol diglycidyl ether, acrylic acid adduct of neopentyl glycol diglycidyl ether, acrylic acid adduct of glycerin diglycidyl ether, bisphenol A di Epoxy acrylate monomers such as acrylic acid adducts of glycidyl ether, acrylic acid adducts of bisphenol F, and acrylic acid adducts of cresol novolac, or γ-acryloxypropyl trimethoxysilane, or their acrylic groups substituted with methacryl groups Although a compound is mentioned, in order to increase the visible light transmittance of the organic binder resin (b) having a polar group, Acrylic monomers having a chain or alicyclic structure are preferred.

Examples of the unsaturated acid include AA, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid or vinyl acetate or these acid anhydrides. The acid value of the acrylic copolymer obtained by some of the unsaturated acids used as the copolymerization component can be adjusted.

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

As an epoxy compound which can be used as a starting material, glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidylamines, or epoxy resins are exemplified. 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, bisphenolfluorene diglycidyl ether, biphenol diglycidyl ether, tetramethylbiphenol glycidyl ether, trimethylolpropane triglycidyl ether, 3 ', 4'-epoxycyclohexylmethyl-3,4 -Epoxycyclohexane carboxylate or tert-butylglycidylamine.

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

The acid value of the epoxy carboxylate compound may be adjusted by reacting the epoxy carboxylate compound with a polybasic acid anhydride. Examples of the polybasic anhydride include succinic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, itaconic anhydride, 3-methyltetrahydro phthalic anhydride, 4-methyl-hexahydro phthalic anhydride, trimellitic anhydride or anhydride. And maleic acid.

By reacting the carboxyl group of the epoxy carboxylate compound whose acid value is adjusted by the polybasic anhydride and a compound having an unsaturated double bond such as glycidyl (meth) acrylate, the reactive unsaturated double of the epoxy carboxylate compound You may adjust the amount of binding.

Urethanization may be performed by reacting the hydroxyl group of the epoxy carboxylate compound with the diisocyanate compound. As the diisocyanate compound, for example, hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tolidene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allyl cyanic diisocyanate or nord And Bornan 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, and more preferably 60 to 150 mgKOH / g in order to further improve pattern workability. Do. When the acid value is 50 mgKOH / g or more, the solubility in the developing solution becomes high, and the development residue can be suppressed. When the acid value is 250 mgKOH / g or less, excessive dissolution in the developer can be suppressed, and the film reduction of the pattern forming portion can be suppressed. In addition, 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 may have a hydroxypyridine skeleton in one molecule, and may be introduced in the form of a single compound or a salt thereof. 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-dipalmitate, 4-deoxypyridoxine, pyridoxamine, dicaprylic acid pyridoxine, 4-bromo-2-hydroxypyridine, 4-chloro-2-hydroxypyridine, 2-hydroxy-5-iodopyridine, 3-hydroxyisoquinoline, 2-quinolinol, 3-quinolinol, 2 -Methyl-4-quinolinol, pyridoxal-5-phosphate, citrazinic acid, 6-hydroxynicotinic acid and salts thereof. Among them, pyridoxine having a methylol group, 4-deoxypyridoxine, pyridoxal, pyridoxamine, pyridoxal-5-phosphate, 4-pyridoxylic acid, isopyridoxal, 2-hydroxymethyl-3-pyridinol, 2-Hydroxymethyl-6-methyl-3-pyridinol, 2,6-bis (hydroxymethyl) -3-pyridinol, zincotoxin, dicaprylic acid pyridoxine, pyridoxaloxime, 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-quinolinol, pyridoxine-3,4-dipalmitate, and salts thereof are polar groups It is preferable because it can make the interaction with the organic binder resin (b) possessed stronger.

The amount of the compound (c) having a hydroxypyridine skeleton in one molecule contained in the conductive layer B is preferably added in a range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the organic binder resin (b) having a polar group, more It is preferably 0.5 to 10 parts by mass. If the amount of the compound (c) having a hydroxypyridine skeleton in one molecule is 0.1 parts by mass or more and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the organic binder resin (b) having a polar group, electrical connection after high temperature and high humidity The stabilizing effect is increased. Further, if 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, the transparent electrode layer A and The adhesiveness of the conductive layer B can be increased. About the specificity 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, etc., and IR, ¹ H-NMR, and MS measurements are performed on the obtained sample. It can obtain by performing etc.

The thickness of the conductive layer B is preferably 1.0 to 10.0 μm. When the thickness of the conductive layer B is 1.0 µm or more, unevenness in resistance can be suppressed. When the thickness of the conductive layer B is 10.0 µm or less, the amount of shrinkage of cure generated under high temperature and high humidity becomes small, and the effect of stabilizing electrical connection is enhanced.

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. As a method of the touch panel, for example, a resistive film type, an optical type, an electromagnetic induction type, or a capacitive type may be mentioned. In particular, however, since a fine wiring is particularly required for the capacitive type touch panel, a photosensitive conductive paste, which is one embodiment of the present invention, is required. The laminated member which formed the pattern of the conductive layer B using is used more suitably. Such a pattern of the conductive layer B is provided as the peripheral wiring of the touch panel, and in the touch panel in which the peripheral wiring is 50 µm or less in pitch (wiring width + inter-wiring width), the non-display area can be narrowed to widen the display area. You can.

Example

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

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 with Polar Group (b)]

JER (registered trademark) 828 (Mitsubishi Chemical Corporation product)

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 (by mass): 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 added to a reaction vessel in a nitrogen atmosphere, and the temperature was raised to 80 ° C using an oil bath. A mixture of 20 g EA, 40 g 2-EHMA, 20 g BA, 5 g MAA, 15 g AA, 0.8 g 2,2'-azobisisobutyronitrile and 10 g DMEA was added dropwise over 1 hour. did. After completion of the dropwise addition, a polymerization reaction was further performed for 6 hours. Thereafter, 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 drying was further performed for 24 hours to obtain resin (b-1). The acid value of the obtained resin (b-1) was 103 mgKOH / g.

[Synthesis Example 2]

Copolymerization ratio (by mass): EA / 2-EHMA / styrene (hereinafter referred to as St) / glycidyl methacrylate (hereinafter referred to as GMA) / AA = 30/30/25/5/10

150 g of DMEA was charged into the reaction vessel in a nitrogen atmosphere, and the temperature was raised 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. After completion of the dropwise addition, the 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 of GMA, 1 g of triethylbenzylammonium chloride and 10 g of DMEA was added dropwise over 0.5 hour. After completion of the dropwise addition, an additional reaction was further performed for 2 hours. The unreacted impurities were removed by purifying the obtained reaction solution with methanol, and resin (b-2) was obtained by vacuum drying for 24 hours. The acid value of the obtained resin (b-2) was 83 mgKOH / g.

[Synthesis Example 3]

492.1 g of carbitol acetate, 860.0 g of EOCN-103S (manufactured by Nippon Kayaku Co., Ltd .; cresol novolac type epoxy resin; epoxy equivalent: 215.0 g / equivalent), 288.3 g of AA in a nitrogen atmosphere reaction solution, 4.92g of 2,6-di-tert-butyl-p-cresol and 4.92g of triphenylphosphine were added and reacted at a temperature of 98 ° C until the acid value of the reaction solution became 0.5 mgKOH / g or less, resulting in epoxy A carboxylate compound was obtained. Subsequently, 169.8 g of carbitol acetate and 201.6 g of tetrahydro phthalic anhydride were added to the 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 was added 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 epoxy carboxylate compound. Thereafter, 755.5 g of carbitol acetate, 268.3 g of 2,2-bis (dimethylol) -propionic acid, 1.08 g of 2-methylhydroquinone and 140.3 g of spiroglycol were added to the reaction solution, and at 45 ° C. It was heated. To this solution, 485.2 g of trimethylhexamethylene diisocyanate was slowly 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 reaction was performed for 6 hours until absorption in the vicinity of 2250 cm ⁻¹ disappeared by infrared absorption spectrum measurement, thereby obtaining 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 Specialty Chemicals Corp.) (hereinafter referred to as OXE-01)

[Thermal polymerization initiator]

PERMENTHA (registered trademark) H (NOF CORPORATION product)

[Curing agent]

CUREZOL (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>

As a substrate, a biaxially centrifugal polyethylene terephthalate (PET) film having a thickness of 30 µm was prepared. An ITO thin film having a thickness of 50 nm (0.05 µm) made of ITO was formed using a sputtering device provided with a sintered body target of ITO on the substrate surface.

<Pattern processing of ITO thin film>

After laminating the photoresist film on the ITO thin film, the photomask is adhered, the photoresist is exposed with an exposure amount of 200 mJ / cm 2 with an exposure machine having an ultra-high pressure mercury lamp, and spray development is performed for 30 seconds with an aqueous solution of 1 mass% sodium carbonate at 30 ° C. The photoresist is patterned. Then, the ITO was etched with a 0.1% by mass aqueous hydrochloric acid solution, and then the resist was peeled with a 1% by mass aqueous sodium hydroxide solution to form a patterned transparent electrode layer A1 on the substrate.

<Preparation of composition for forming conductive layer B>

In a 100 mL clean bottle, 10.0 g of jER 828, 1.5 g of 2-hydroxypyridine, 0.5 g of CUREZOL 1B2MZ and 5.0 g of diethylene glycol were added, and an auto-revolution vacuum mixer "AWATORI RENTARO" (registered trademark) ARE-310 It was mixed with (manufactured by Shinki Corporation) 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 were mixed, and kneaded using a three-roller mill (EXAKT M-50; manufactured by Exakt Technologies. Inc.) to prepare 85.0 g of composition B1 Got

<Formation of conductive layer B>

On the surface of the transparent electrode layer A1 patterned on the PET film, the composition B1 was applied with a screen printing machine so that the film thickness of the conductive layer B1 was 6 µm, followed by curing at 140 ° C for 60 minutes to form the conductive layer B1.

<Evaluation of connection stability between the transparent electrode (A) and the conductive layer B>

The laminated member shown in FIG. 1 was prepared by the above method, and was put into a high-temperature and high-humidity bath at 85 ° C and 85% RH for 480 hours, and the resistance value between terminals was measured after withdrawal. The rate of increase from the resistance value before the introduction of the high-temperature high-humidity tank was obtained from the following formula, and it was referred to as the value of connection stability. Table 3 shows the results.

[Examples 2 to 5]

The laminated members shown in Tables 1 and 2 were produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Table 3 shows the results.

[Example 6]

Pattern processing of the ITO thin film was performed on the substrate in the same manner as in Example 1.

<Formation of conductive layer B>

On the surface of the transparent electrode layer A6 patterned on the substrate, the composition B6 was coated with a screen printing machine so that the film thickness of the dried film was 5 μm, dried at 70 ° C. for 10 minutes with a hot air dryer, and then ultra-high pressure mercury through a predetermined photomask. After exposing with an exposure apparatus having a lamp at an exposure amount of 300 mJ / cm 2, and spraying the 0.2 mass% aqueous sodium carbonate solution at a pressure of 0.1 MPa for 30 seconds, curing was performed at 140 ° C. for 60 minutes to prepare a laminated member shown in FIG. 1. .

The same evaluation as in Example 1 was performed for the laminated member. Table 3 shows the results.

[Examples 7 to 14]

The laminated members shown in Tables 1 and 2 were produced in the same manner as in Example 6, and the same evaluation as in Example 1 was performed. Table 3 shows the results.

[Comparative Examples 1 and 2]

The laminated members shown in Tables 1 and 2 were produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Table 3 shows the results.

[Comparative Example 3]

The laminated members shown in Tables 1 and 2 were produced in the same manner as in Example 6, and the same evaluation as in Example 1 was performed. Table 3 shows the results.

In Examples 1-14, it turns out that the laminated member excellent in the connection property of a transparent electrode and surrounding wiring, and environmental load resistance can be manufactured.

(Industrial availability)

The laminated member of the present invention can be suitably used as a component of a touch panel.

1: description
2: transparent electrode layer A
3: Conductive layer B

Claims (6)

A transparent electrode layer A formed on the substrate,
A part of the transparent electrode layer A is provided with a conductive layer B formed on a part and a substrate,
The conductive layer B contains conductive particles (a) and an organic binder resin (b) having a polar group and a compound (c) having a hydroxypyridine skeleton in one molecule,
A layered member in which the compound (c) having a hydroxypyridine skeleton in the above molecule has a methylol group. According to claim 1,
A laminated member having a thickness of the transparent electrode layer A of 0.5 µm or less. The method of claim 1 or 2,
A laminated member in which the polar group of the organic binder resin (b) having the polar group includes a carboxyl group. The method of claim 1 or 2,
The laminated member in which the organic binder resin (b) having the polar group has a urethane skeleton. A touch panel comprising the laminated member according to claim 1 or 2. delete

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