JP2018049946A - Conductive material laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive material laminate excellent in reliability whose corrosion due to chloride ions is suppressed.SOLUTION: The conductive material laminate includes: an undercoat layer containing a compound having an amino group on a support; a conductive material having at least a conductive layer having a conductive metal fine wire line on the undercoat layer; an adhesive layer containing a compound having an epoxy group on the conductive layer of the conductive material; and a functional layer on the adhesive layer, at least in this order. The shortest distance between a side surface portion of the adhesive layer and an outermost peripheral portion of the conductive layer is 200 μm or more.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a conductive material laminate in which corrosion due to chloride ions is suppressed and excellent in reliability.

  In electronic devices such as smartphones, personal digital assistants (PDAs), notebook PCs, tablet PCs, OA devices, medical devices, and car navigation systems, touch panel sensors are widely used as input means for these displays.

  Touch panel sensors include optical methods, ultrasonic methods, resistive film methods, surface capacitive methods, projection capacitive methods, etc., depending on the position detection method. A capacitance method is preferably used. The resistive film type touch panel sensor has a structure in which two conductive materials having a light-transmitting conductive layer on a support are used and these conductive materials are arranged to face each other via a dot spacer. By applying a force to the point, the light-transmitting conductive layers come into contact with each other, and the voltage applied to each light-transmitting conductive layer is measured through the other light-transmitting conductive layer, so that the position where the force is applied is measured. The detection is performed. On the other hand, a projected capacitive touch panel sensor uses one conductive material having two light-transmitting conductive layers or two conductive materials having one light-transmitting conductive layer, such as a finger. The capacitance change between the light-transmitting conductive layers when the two are brought close to each other is detected, and the position where the finger is brought close is detected. The latter has excellent durability because it has no moving parts, and can detect multiple points at the same time. Therefore, the latter is widely used particularly in smartphones and tablet PCs.

  In a projected capacitive touch panel sensor, a sensor unit consisting of a plurality of sensors obtained by patterning a light-transmitting conductive layer on a support can be used for simultaneous detection of multiple points and movement points. Detection is possible. In order to extract the change in capacitance detected by the sensor unit to the outside as an electric signal, between all the sensors of the conductive material and a terminal unit composed of a plurality of terminals provided to extract the electric signal to the outside. Is provided with a peripheral wiring portion comprising a plurality of peripheral wirings for electrically connecting them. Usually, the light transmissive conductive layer described above is located on the display, and the peripheral wiring portion and the terminal portion are located outside the display, that is, in a so-called frame portion. In the prior art, the light transmissive conductive layer is generally formed of an ITO (indium-tin oxide) conductive film, and the peripheral wiring portion and the terminal portion are made of gold, silver, copper, nickel, aluminum, or the like. In general, the metal is formed of a metal. For example, JP-A-2015-32183 (Patent Document 1) uses a transparent conductor such as ITO, IZO (indium-zinc oxide), ZnO (zinc oxide) as a material for the light-transmitting conductive layer, and takes it out. A touch panel sensor member using a metal such as copper as a material for wiring (peripheral wiring portion) is disclosed.

  In recent years, a conductive material having a mesh-like fine metal wire pattern as a light-transmitting conductive layer has also been disclosed. For example, Japanese Unexamined Patent Application Publication No. 2015-133239 (Patent Document 2) discloses a method of forming a mesh-like metal fine line pattern and a peripheral wiring portion by printing ink containing silver fine particles, or a resin containing an electroless plating catalyst. Various methods such as a method of applying electroless plating after printing a paint, a subtractive method in which a photoresist layer is formed on a metal layer, a resist pattern is formed, and then the metal layer is etched away, a method using a silver salt photosensitive material, etc. It is described that it can be formed by a method.

  In the above-described conductive material, a pressure-sensitive adhesive is applied on a layer (conductive layer) having a conductive metal fine wire such as a metal fine wire constituting a mesh-like metal fine wire pattern, a peripheral wiring constituting a peripheral wiring portion, and a terminal constituting a terminal portion. A conductive material laminate having a layer and a functional material on the pressure-sensitive adhesive layer is also known. For example, JP-A-2014-198811 (Patent Document 3) discloses a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive sheet on a touch panel sensor. And the laminated body for touchscreens which has a protective substrate on this adhesive layer is disclosed. The pressure-sensitive adhesive layer is generally used in order to bring the members such as a display device and a touch panel sensor into close contact with each other.

  The conductive thin metal wires of the conductive layer described above may be corroded by chloride ions contained in human sweat, for example, and the resistance value may fluctuate. When the resistance value of the conductive thin metal wire fluctuates, the reliability of the touch panel sensor is significantly lowered due to a decrease in detection sensitivity of the touch panel sensor or erroneous recognition. In recent years, the frame of touch panels has been narrowed from the viewpoint of design, and it constitutes peripheral wiring in which chloride ions permeated from the side part of the adhesive layer are present in the frame part, and also a mesh-like metal fine wire pattern existing inside It has become particularly easy to act on thin metal wires, and improvement has been demanded.

  International Publication No. 2014/007333 pamphlet (Patent Document 4) is a capacitive touch panel that suppresses the occurrence of malfunction even before and after the salt water test and has excellent yield. Further, a capacitive touch panel is disclosed in which a transparent resin layer and a substrate are provided, and a sealing layer having a low water vapor transmission rate is provided on the surface of the peripheral portion of the transparent resin layer exposed from between the insulating layer and the substrate. JP-A-2006-51470 (Patent Document 5) discloses a composition for forming a touch panel electrode protective film containing a di (meth) acrylate compound, a binder polymer, and a photopolymerization initiator. It is described that a protective film for a touch panel electrode excellent in wet heat resistance can be obtained. However, none of these methods is sufficient to suppress the corrosion caused by chloride ions.

  On the other hand, JP-A-2006-45315 (Patent Document 6) discloses an adhesive composition containing an acrylic copolymer obtained by polymerizing a specific monomer and benzotriazole and / or a derivative thereof as an epoxy crosslinking agent. A touch panel member in which a pressure-sensitive adhesive layer obtained by cross-linking is attached on a metal circuit is disclosed, and it is described that metal corrosion can be prevented even when used for a long time in a high temperature and high humidity environment. Japanese Patent Application Laid-Open No. 2015-75950 (Patent Document 7) includes a touch panel laminate in which a wiring and a low moisture-permeable adhesive layer are provided on a substrate, and the side surface of the adhesive layer and the wiring are separated by a certain distance or more. It is described that migration of wiring due to contamination can be prevented. Japanese Patent Laying-Open No. 2014-29671 (Patent Document 8) discloses a conductive film for a touch panel comprising an electrode pattern obtained by exposing, developing and hardening a silver halide emulsion layer containing gelatin and an adhesive insulating layer. It is described that the use of an adhesive obtained by curing an adhesive insulating material having a specific acid value with a curing agent such as an epoxy compound in the adhesive insulating layer suppresses the occurrence of malfunction of the touch panel. Japanese Patent Laying-Open No. 2014-75115 (Patent Document 9) includes silver on an insulating substrate for the purpose of suppressing ion migration between metal wirings containing silver and improving insulation reliability between metal wirings. It is described that a resin layer containing a compound selected from a phenol compound, a phosphite compound, and a hydrazine compound having a specific structure and an insulating resin such as an epoxy resin is provided on a metal wiring.

JP-A-2015-32183 Japanese Patent Laying-Open No. 2015-133239 JP 2014-198811 A International Publication No. 2014/007333 Pamphlet JP, 2006-51470, A JP 2006-45315 A JP-A-2015-75950 JP 2014-29671 A JP 2014-75115 A

  An object of the present invention is to provide a conductive material laminate in which corrosion due to chloride ions is suppressed and excellent in reliability.

The above object of the present invention is achieved by the following invention.
(1) A subbing layer containing a compound having an amino group on a support, a conductive material having at least a conductive layer having a conductive metal wire on the subbing layer, and a conductive layer of the conductive material A pressure-sensitive adhesive layer containing a compound having an epoxy group, and a functional material on the pressure-sensitive adhesive layer at least in this order, and the shortest distance between the side surface portion of the pressure-sensitive adhesive layer and the outermost edge portion of the conductive layer Is 200 μm or more, and a conductive material laminate.

  According to the present invention, it is possible to provide a conductive material laminate in which corrosion due to chloride ions is suppressed and excellent in reliability.

Schematic sectional view showing an example of the conductive material laminate of the present invention Schematic plan view showing an example of the conductive material laminate of the present invention

  The present invention will be described below with reference to the drawings. The conductive material laminate of the present invention comprises a subbing layer containing a compound having an amino group on a support, a conductive material having at least a conductive layer having a conductive metal wire on the subbing layer, and the conductive material. A pressure-sensitive adhesive layer containing a compound having an epoxy group on the conductive layer of the material and a functional material on the pressure-sensitive adhesive layer in at least this order.

  FIG. 1 is a schematic cross-sectional view showing an example of the conductive material laminate of the present invention. In FIG. 1, a conductive material laminate 50 is a conductive material having at least an undercoat layer 12 containing a compound having an amino group on a support 11 and a conductive layer 14 having a conductive fine metal wire 13 on the undercoat layer 12. 10, a pressure-sensitive adhesive layer 20 containing a compound having an epoxy group on the conductive layer 14 of the conductive material, and a functional material 30 on the pressure-sensitive adhesive layer 20. In the conductive material laminate of the present invention, the pressure-sensitive adhesive layer 20 and the subbing layer 12 are reacted by the reaction between the compound having an epoxy group in the pressure-sensitive adhesive layer 20 and the compound having an amino group included in the subbing layer 12 of the conductive material 10. Is firmly bonded, the permeation of chloride ions is suppressed, and the conductivity in the conductive layer 14 is coupled with maintaining the distance between the outermost edge of the conductive layer 14 and the side surface of the pressure-sensitive adhesive layer 20 at a certain level or more. It is estimated that the corrosion of the fine metal wires 13 is suppressed.

  The conductive material 10 included in the conductive material laminate of the present invention will be described. The material of the support 11 included in the conductive material 10 is not particularly limited. However, when the conductive material laminate of the present invention is used for applications that require light transmission, such as a touch panel sensor, from the viewpoint of transparency of the conductive material laminate. The support 11 is particularly preferably light transmissive. As a light-transmitting support, polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, polyarylate, polysulfone, polyethersulfone, polyimide, Fluorine resin, phenoxy resin, triacetyl cellulose, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, acrylic resin, cellophane, nylon, polystyrene resin, ABS resin and other various resin films, quartz glass, alkali-free glass Examples thereof include glass. From the viewpoint of transparency of the conductive material laminate, the total light transmittance of the support is preferably 60% or more, particularly preferably 70% or more, and from the same viewpoint, the haze of the support is preferably 0 to 3%. Especially preferably, it is 0 to 2%. An easily adhesive layer, a hard coat layer, an antireflection layer, an antiglare layer, etc. are known between the support 11 and the undercoat layer 12 or on the surface opposite to the surface having the undercoat layer of the support 11. You may have a layer of.

  The compound having an amino group contained in the undercoat layer 12 is not particularly limited, and a known compound having an amino group can be used. Specifically, aminated cellulose, polyethyleneimine, polyallylamine, polydiallylamine, a copolymer of allylamine and diallylamine described in “Chemical Reaction of Polymer” (Nobu Okawara 1972, Chemical Dojinsha) 2.6.4, Polymers such as copolymers of diallylamine and maleic anhydride, copolymers of diallylamine and sulfur dioxide, proteins such as gelatin, albumin, casein, polyzine, polysaccharides such as chitosan, chitin, chondroitin sulfate, arginine, Silane coupling having amino groups such as asparagine, aspartic acid, cysteine, glutamine, glutamic acid and the like, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane and the like Agent, - amino benzotriazole, 2-amino-4-mercapto-6-benzyl-1,3,5-amino group-containing nitrogen-containing heterocyclic compounds such as triazine and the like. Among them, polymer compounds and proteins are preferable, and polyethyleneimine and polyallylamine are particularly preferable.

  The undercoat layer may contain a known polymer compound having no amino group in addition to the compound having an amino group. Examples of the polymer compound having no amino group include water-soluble polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid, vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, Isoprene homopolymer, ethylene / butadiene copolymer, styrene / butadiene copolymer, styrene / p-methoxystyrene copolymer, styrene / vinyl acetate copolymer, vinyl acetate / vinyl chloride copolymer, vinyl acetate・ Diethyl maleate copolymer, methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / vinyl acetate copolymer, methyl methacrylate / vinylidene chloride Polymer, methyl acrylate / acrylonitrile copolymer, methyl acrylate / butadiene copolymer, methyl acrylate / styrene copolymer, methyl acrylate / vinyl acetate copolymer, acrylic acid / butyl acrylate copolymer, methyl acrylate / vinyl chloride Examples thereof include water-insoluble polymer compounds such as copolymers, butyl acrylate / styrene copolymers, polyether urethanes, polyester urethanes, and polycarbonate urethanes.

Preferably the amount of the compound containing amino groups in the undercoat layer is 1mg~3g / ^{m 2,} more preferably from 2mg~2g / ^{m 2.} The ratio of the compound having an amino group in the undercoat layer is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total mass of the undercoat layer.

  The undercoat layer preferably further contains a crosslinking agent in addition to the components described above. A crosslinking agent is not specifically limited, A well-known crosslinking agent can be used. Specifically, tetraisopropyl titanate, titanium acetylacetonate, titanium lactate, normal butyl zirconate, zirconium monoacetylacetonate, aluminum trisacetylacetonate and other organometallic compounds, such as formaldehyde, glyoxal, malealdehyde, glutaraldehyde Aldehydes, N-methylol compounds such as urea and ethylene urea, mucochloric acid, aldehyde equivalents such as 2,3-dihydroxy-1,4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salts, , Compounds having active halogen such as 2,4-dihydroxy-6-chloro-triazine salt, divinyl sulfone, divinyl ketone, N, N, N-triacryloyl hexahydrotriazine, active three-membered ring Among compounds having two or more renimino groups, compounds having epoxy groups contained in the adhesive layer, compounds having two or more epoxy groups, potassium aluminum sulfate (alum), and other “chemical reactions of polymers” (Okawara Examples of the crosslinking agents described in Chapter 2.6.7, Chapter 5.2, Chapter 9.3, etc.

  The content of the crosslinking agent contained in the undercoat layer is particularly preferably from the viewpoint of suppressing corrosion due to chloride ions, so that the unreacted amino group remains in the undercoat layer. The unreacted amino group in the undercoat layer preferably remains in an amount of 20 mol% or more before the reaction, and particularly preferably 40 mol% or more.

In accordance with a method disclosed in Japanese Patent Application Laid-Open No. 2003-77350, a so-called silver salt diffusion transfer method in which a silver salt photosensitive material is used as a conductive material precursor and a soluble silver salt forming agent and a reducing agent are allowed to act in an alkaline solution. When the conductive layer is used to form the conductive layer, it is particularly preferable that the undercoat layer contains physical development nuclei from the viewpoint of the conductivity of the conductive layer and the adhesiveness between the conductive layer and the undercoat layer. As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include metal colloids such as gold and silver, metal sulfides obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. The content of physical development nuclei in the undercoat layer is preferably 0.01 to 10 mg / m ² in terms of solid content.

  The metal type of the conductive thin metal wire 13 included in the conductive layer 14 is not limited, and examples thereof include known metals such as gold, silver, copper, aluminum, nickel, and alloys made of known metals. From the viewpoint of conductivity, silver Or it is preferable to contain copper, and it is especially preferable to contain silver. The conductive metal fine wire 13 is preferably 50% by mass or more of metal with respect to the total solid mass of the conductive metal fine wire, and the proportion of such metal is more preferably 70% by mass or more, and particularly preferably 80% by mass or more. preferable. The line width of the conductive metal thin wire is not particularly limited, but is preferably 1 to 500 μm from the viewpoint of the reliability of the conductive material laminate.

The metal amount of the conductive layer is preferably 0.5 to 20 g / m ² from the viewpoint of the reliability of the conductive material laminate. The amount of metal in the conductive layer is measured by cutting off part of the conductive material 10 together with the support and the undercoat layer to obtain a measurement sample, and measuring the amount (g) of metal in the measurement sample by fluorescent X-rays. It can calculate by converting into the area (m < ² >) of only the part in which a conductive metal fine wire exists among the surfaces which have.

  When the conductive material laminate of the present invention is used for a touch panel sensor, the conductive layer 14 of the conductive material 10 preferably has a mesh-like metal fine line pattern made of conductive metal fine lines. The mesh-like metal fine line pattern preferably has a geometric shape in which a plurality of unit lattices are arranged in a mesh shape from the viewpoint of sensor sensitivity, visibility (the sensor shape is difficult to see), and the like. Examples of unit cell shapes include triangles such as regular triangles, isosceles triangles, right triangles, squares, rectangles, rhombuses, parallelograms, trapezoids, etc., hexagons, octagons, dodecagons, decagons, etc. The shape which combined n square, star shape, etc. of these is mentioned, The repetition of these shapes independently, or the combination of two or more types of multiple shapes is mentioned. Among them, the shape of the unit cell is preferably a square or a rhombus. Further, irregular geometric shapes represented by Voronoi graphics, Delaunay graphics, Penrose tile graphics, and the like are also one of the preferred mesh-like metal fine line pattern shapes.

  The method for forming the conductive layer 14 on the undercoat layer 12 is not particularly limited. For example, according to the method disclosed in JP-A-2015-69877, a conductive metal ink or conductive paste containing a metal and a binder is used. In accordance with a method of forming a conductive layer by printing or the like on a subbing layer on a support, or a method disclosed in Japanese Patent Application Laid-Open No. 2007-59270, the subbing layer and silver halide are formed on the support. A method of forming a conductive layer by using a silver halide photosensitive material having an emulsion layer as a conductive material precursor and using a curing development method, a method disclosed in JP-A-2004-221564, JP-A-2007-12314, and the like A method for forming a conductive layer using a direct development method using a silver salt photosensitive material having an undercoat layer and a silver halide emulsion layer on a support as a conductive material precursor according to JP, In accordance with the methods disclosed in JP-A-03-77350, JP-A-2005-250169, JP-A-2007-188655, JP-A-2004-207001, etc., an undercoat layer having physical development nuclei on a support; A conductive layer using a so-called silver salt diffusion transfer method in which a silver salt photosensitive material having at least silver halide emulsion layers in this order is used as a conductive material precursor and a soluble silver salt forming agent and a reducing agent are allowed to act in an alkaline solution. In accordance with a method disclosed in JP-A-2014-197531, a photosensitive resist material obtained by laminating an undercoat layer and a photosensitive resist layer on a support is used as a conductive material precursor. After exposing to an arbitrary pattern, developing, forming a resist image, and then applying electroless plating to undercoat that is not covered with the resist image A method of localizing a metal on the surface and then removing a resist image to form a conductive layer, a method disclosed in JP-A-2015-82178, an undercoat layer, a metal film, a resist film on a support The resist film is exposed and developed to form an opening, and the metal film in the opening is removed by etching to form a conductive layer.

  Among the above methods, a method of printing conductive metal ink or conductive paste, a method of using silver salt diffusion transfer method using a silver salt photosensitive material as a conductive material precursor, a photosensitive resist material as a conductive material precursor The method to be used is preferable because the above-described method can easily form a conductive layer made of a conductive thin metal wire formed of silver having excellent conductivity, and in particular, the conductive layer made of a fine conductive metal fine wire can be easily formed. A method using a silver salt diffusion transfer method using a silver salt photosensitive material as a conductive material precursor is preferable.

  A known metal surface treatment may be applied to the surface of the conductive fine metal wires 13 of the conductive layer 14. For example, a reducing substance, a water-soluble phosphorus oxo acid compound, or a water-soluble halogen compound as described in JP 2008-34366 A may be allowed to act, as described in JP 2013-19679 A A triazine having two or more mercapto groups in the molecule or a derivative thereof may be allowed to act, and as described in JP 2011-209626 A, blackening treatment by a sulfurization reaction may be performed. Further, when forming a conductive layer using a silver salt photosensitive material as a conductive material precursor, it is processed with a processing solution containing an enzyme such as a proteolytic enzyme as described in JP-A-2007-12404. Also good.

  The pressure-sensitive adhesive layer 20 included in the conductive material laminate of the present invention will be described. The pressure-sensitive adhesive layer contains at least a compound having an epoxy group. Examples of the compound having an epoxy group include an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, and an epoxy silane compound, but are not limited thereto, and a known compound having an epoxy group can be used. . Two or more kinds of compounds having an epoxy group may be used in combination.

  An aromatic epoxy compound means an aromatic compound having one or more epoxy groups. Specifically, polyhydric compounds having at least one aromatic ring such as monovalent phenols such as phenol and cresol or glycidyl ethers of adducts thereof with alkylene oxide, bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, naphthalene diol and the like. Polyglycidyl ethers of polyhydric phenols or alkylene oxide adducts thereof, phenol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolak type epoxy compounds, etc. A compound etc. can be illustrated.

  The said aromatic epoxy compound is marketed, and all can be used preferably. Specifically, Denasel EX-141, EX-142, EX-145, EX-146, EX-147, EX-201, EX-721, etc., manufactured by Nagase ChemteX Corporation, Rikaresin BPO manufactured by Shin Nippon Rika Co., Ltd. -20E, BEO-60E, etc., jER 152, 154, 630, 802, 806, 807, 825, 827, 828, 871, 872, 1001, 1010, 1003F, 1256, 4250, YL980, YL983U, manufactured by Mitsubishi Chemical Corporation Adeka Resin EP-4000S, EP-4010S, EP-4100, Adekaglycilol ED-509E, ED-529, etc. manufactured by ADEKA Corporation, EPICLON 830, 840, 850 manufactured by DIC Corporation, EXA- 830CRP, N-660, N-690 etc. Mitsubishi Gas Chemical Co., Ltd. TETRAD-X and the like.

  An alicyclic epoxy compound means a compound having one or more epoxy groups and one or more aliphatic rings. Examples of alicyclic epoxy compounds include glycidyl ethers of monohydric alcohols having one or more alicyclic rings, polyglycidyl ethers of polyhydric alcohols having one or more alicyclic rings, cyclohexene and cyclopentene ring-containing compounds. Examples include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidation with an oxidizing agent, and compounds obtained by selectively hydrogenating aromatic rings in the presence of a catalyst. Are hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, epoxy compounds obtained by hydrogenating novolac-type epoxy compounds, 3,4-epoxycyclohexylmethyl-3,4-epoxy Chlohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxy Cyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methyl Cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6 -Methylcyclohexyl Carboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, etc. Can be illustrated. Examples of the catalyst used for hydrogenation of the aromatic ring include those in which rhodium or ruthenium is supported on activated carbon or graphite.

  The said alicyclic epoxy compound is marketed, and all can be used preferably. Specifically, Nagase ChemteX Co., Ltd. Denacol EX-252 etc., Daicel Co., Ltd. Celoxide 2000, 2021P, 2081, Cyclomer M100, EHPE3150, Epolide GT-401, etc., ADEKA Adeka Resin EP-4080E , EP-4082HT, etc., Union Carbide UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, etc., Shin Nippon Rika Co., Ltd. Rikaresin HBE-100, DME-100, etc., Mitsubishi Chemical Examples thereof include jER YX8000 and YX8034 manufactured by Mitsubishi Electric Corporation, and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd.

  An aliphatic epoxy compound means the compound except the said alicyclic epoxy compound among the aliphatic compounds which have one or more epoxy groups. Aliphatic epoxy compounds include polyglycidyl ether of aliphatic polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, glycidyl acrylate Or a copolymer synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers, specifically 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of glycerin Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexag One or more alkylenes in glycidyl ethers of polyhydric alcohols such as sidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Examples thereof include polyglycidyl ethers of polyether polyols obtained by adding oxide and diglycidyl esters of aliphatic long-chain dibasic acids. In addition, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy Examples include octyl stearate, butyl epoxy stearate, and epoxidized polybutadiene.

  The said aliphatic epoxy compound is marketed, and all can be used preferably. Specifically, Denasel EX-111, EX-121, EX-171, EX-211, EX-212, EX-810, EX-811, EX-830, EX-850, EX-manufactured by Nagase ChemteX Corporation 861, EX-911, EX-941, EX-313, EX-314, EX-321, EX-411, EX-421, EX-521, EX-612, EX-614, etc., manufactured by ADEKA Corporation Rolls ED-503, ED-505, ED-506, etc., Kyoeisha Chemical Co., Ltd. Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 10 Examples thereof include 0MF, Epolite 4000, Epolite 3002 (N), and the like.

  An epoxy silane compound means a silane compound having one or more epoxy groups. Among these, a compound represented by the following general formula 1 is preferable from the viewpoint of suppressing corrosion caused by chloride ions.

R ^{a in} General Formula 1 represents a 3-glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) ethyl group, R ^b represents an alkyl group having 1 to 3 carbon atoms, and R ^c represents a carbon number. 1 to 3 alkyl groups are represented. N in the general formula 1 represents 0 or 1.

  Specific examples of the epoxysilane compound represented by the general formula 1 include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane. Sidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltripropoxysilane and the like are exemplified, but not limited thereto.

  The said epoxy silane compound is marketed, and all can be used preferably. Specifically, Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, etc., Toray Dow Corning Co., Ltd. Z-6040, Z-6043, Z- 6044 etc. can be illustrated.

  As epoxy silane compounds other than the epoxy silane compound represented by the general formula 1, KR-516, KR-517, X-41-1059A, X-24 manufactured by Shin-Etsu Chemical Co., Ltd., which are silicone oligomers having an epoxy group. -9590 and X-12-981S and X-12-984S manufactured by Shin-Etsu Chemical Co., Ltd., which are polymer type polyfunctional epoxy silanes.

  Among the compounds having an epoxy group, it is preferable to use an aromatic epoxy compound or an epoxysilane compound from the viewpoint of suppressing corrosion caused by chloride ions.

  The content of the compound having an epoxy group in the pressure-sensitive adhesive layer is not particularly limited, and if the epoxy group is present, the effect of the present invention can be obtained. It is preferable to contain 0.01-2.5 mass% from a viewpoint of suppressing corrosion, More preferably, it is 0.05-1.5 mass%.

  The pressure-sensitive adhesive layer of the conductive material laminate of the present invention preferably contains a resin in addition to the compound having an epoxy group. The resin is not particularly limited, and examples thereof include known resins such as acrylic resins, urethane resins, and silicone resins. The resin is obtained by polymerizing a resin precursor with a polymerization initiator.

  The resin precursor is not particularly limited, and monomers and oligomers of various resins can be used. Among these, acrylic monomers are particularly preferable because the resin obtained by polymerization is excellent in transparency and it is easy to control the polymerization of the monomer to impart tackiness to the resin. Accordingly, a preferred resin contained in the pressure-sensitive adhesive layer of the conductive material laminate of the present invention is an acrylic resin. A single acrylic monomer may be used as the resin precursor, two or more acrylic monomers may be used, and monomers and oligomers other than the acrylic monomer and the acrylic monomer may be used. Examples of acrylic monomers include (meth) acrylic acid alkyl esters having a linear or branched alkyl group and (meth) acrylic acid alkoxyalkyl esters. “(Meth) acryl” means “acryl” and / or “methacryl”, and the same applies to others.

  The (meth) acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meta ) Isopentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, Isononyl (meth) acrylate, decyl (meth) acrylate, iso (meth) acrylate Sil, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate , Having a linear or branched alkyl group having 1 to 20 carbon atoms, such as octadecyl (meth) acrylate, isostearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate ( Examples include (meth) acrylic acid alkyl esters. Two or more kinds of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group may be used.

  Although it does not specifically limit as said (meth) acrylic-acid alkoxyalkylester, For example, (meth) acrylic-acid-2-methoxyethyl, (meth) acrylic-acid-2-ethoxyethyl, (meth) acrylic-acid methoxytriethylene glycol , (Meth) acrylic acid-3-methoxypropyl, (meth) acrylic acid-3-ethoxypropyl, (meth) acrylic acid-4-methoxybutyl, (meth) acrylic acid-4-ethoxybutyl, and the like. Two or more kinds of the (meth) acrylic acid alkoxyalkyl esters may be used in combination.

  Among the acrylic monomers, it is preferable to use (meth) acrylic acid alkoxyalkyl ester as an acrylic monomer from the viewpoint of suppressing corrosion caused by chloride ions. Specifically, the total amount of the resin precursor used for polymerization is 100 mass. Among the parts, the mass of the (meth) acrylic acid alkoxyalkyl ester is preferably 30 to 90 parts by mass, more preferably 35 to 90 parts by mass, and particularly preferably 40 to 85 parts by mass.

  Examples of monomers other than the acrylic monomers described above include polar group-containing monomers and polyfunctional monomers.

  Although it does not specifically limit as said polar group containing monomer, For example, carboxy group containing monomers, such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, or its anhydride (maleic anhydride etc.) ), (Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid-6-hydroxyhexyl, etc. Hydroxyl group-containing monomers such as hydroxyalkyl acrylate, vinyl alcohol and allyl alcohol, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N -Butoxymethyl (meth) acrylamide Amide group-containing monomers such as N- (2-hydroxyethyl) acrylamide, amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and (t-butylaminoethyl) (meth) acrylate In addition to glycidyl group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, cyano group-containing monomers such as acrylonitrile and methacrylonitrile, N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, Heterocyclic-containing vinyl monomers such as N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole and N-vinyloxazole, and sulfonic acids such as sodium vinylsulfonate Group-containing monomer , 2-hydroxyethyl acryloyl phosphate, etc. of the phosphate group-containing monomer, cyclohexyl maleimide, imide group-containing monomers such as isopropyl maleimide, 2-methacryloyl isocyanate group-containing monomers oxyethyl isocyanate, and the like. Two or more kinds of the polar group-containing monomers may be mixed and used.

  Although it does not specifically limit as said polyfunctional monomer, For example, di (meth) acrylic-acid hexanediol, di (meth) acrylic-acid butanediol, di (meth) acrylic-acid (poly) ethylene glycol, di (meth) acrylic Acid (poly) propylene glycol, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryl Examples include trimethylolpropane acid, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, and vinyl (meth) acrylate. Two or more of the above polyfunctional monomers may be used in combination.

  Among monomers other than the above acrylic monomers, it is preferable to use a polar group-containing monomer from the viewpoint of effectively suppressing corrosion by chloride ions, and it is particularly preferable to use a hydroxy group-containing monomer.

  In addition to the above monomers, known copolymerizable monomers such as (meth) acrylic acid alkyl esters having a cyclic alkyl group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. Can be used.

  Examples of the oligomer used as the resin precursor described above include acrylic oligomers such as urethane acrylate, epoxy acrylate, polyester acrylate, isoprene acrylate, and butadiene acrylate. The acrylic oligomer in the present invention means an oligomer having at least one acrylic group.

  The above acrylic oligomers are commercially available, and any of them can be preferably used. Urethane acrylates include Aronix M-1100, Aronix M-1200, manufactured by Toagosei Co., Ltd., UA-1100H, UA-160TM, Shin-Nakamura Chemical Co., Ltd., EBECRYL210, EBECRYL230, EBECRYL270, Arakawa Examples thereof include a beam set 505A-6, a beam set 550B, and a beam set 575 manufactured by Chemical Industry Co., Ltd. Examples of the epoxy acrylate include DIC Corporation Unidic V-5500, Unidic V-5502, Kyoeisha Chemical Co., Ltd. Epoxy Ester 80MFA, and Epoxy Ester 3000MK. Examples of the polyester acrylate include Aronix M-7100 and Aronix M-8100 manufactured by Toagosei Co., Ltd., EBECRYL 436, EBECRYL 450, and EBECRYL 810 manufactured by Daicel Ornex Co., Ltd. Examples of isoprene acrylate include UC-102 and UC-203 manufactured by Kuraray Co., Ltd. Examples of butadiene acrylate include NISSO-PB TE-2000 manufactured by Nippon Soda Co., Ltd.

  The polymerization initiator used for the polymerization of the resin precursor is not particularly limited, and examples thereof include known polymerization initiators. Here, the polymerization initiator means a compound that initiates the polymerization reaction of the resin precursor by heat or ionizing radiation. Polymerization initiators that initiate the polymerization reaction by heat include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, (2-ethylhexanoyl) (tert-butyl) peroxide, tert-butyl. Organic peroxides such as benzoyl peroxide and lauroyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-2-methylbuty Examples thereof include azo compounds such as ronitrile, and examples of the polymerization initiator that initiates the polymerization reaction by ionizing radiation include 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2 , 2-Dimethoxy-2-fe Ruacetophenone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone }, 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, etc., benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether Benzoin compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethyl Benzophenone compounds such as ammonium chloride, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2- Examples thereof include thioxanthone compounds such as hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride. The ionizing radiation means electromagnetic waves or charged particles having energy capable of initiating the polymerization reaction of the resin precursor, and examples thereof include ultraviolet rays, visible rays, gamma rays, X-rays, electron beams, etc. Among them, ultraviolet rays are used. It is preferable from the viewpoint of productivity.

  The above polymerization initiators are commercially available, and any of them can be preferably used. Specifically, IRGACURE127, IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE651, IRGACURE754, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE1173, etc. made by BASF Japan Co., Ltd., N

  The amount of the polymerization initiator used for the polymerization of the resin precursor is not particularly limited, but the polymerization initiator has a polymerization rate of 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin precursor to be subjected to polymerization. From a viewpoint, 0.1-3 mass parts is especially preferable.

  Examples of the polymerization method for the resin precursor include known polymerization methods such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and an ionizing radiation irradiation polymerization method. When a polymerization initiator that starts a polymerization reaction by heat is used. What is necessary is just to select the solution polymerization method according to the characteristic of the polymerization initiator to be used, such as when using a polymerization initiator that initiates a polymerization reaction by ionizing radiation.

  The polymerization solvent used when polymerizing the resin precursor using the solution polymerization method is not particularly limited, and a known organic solvent capable of dissolving the resin precursor and the polymerization initiator can be used. Specific examples include ester solvents such as ethyl acetate and methyl acetate, ketone solvents such as acetone and 2-butanone, hydrocarbon solvents such as hexane and cyclohexane, and alcohol solvents such as ethanol and 2-propanol. A mixture of two or more organic solvents may be used as the polymerization solvent.

  The pressure-sensitive adhesive layer of the conductive material laminate of the present invention includes a crosslinking agent (isocyanate-based crosslinking agent, metal chelate-based crosslinking agent, and the above-described compound having an epoxy group, in addition to the resin and the epoxy group-containing compound, Epoxy-based crosslinking agents typified by compounds having two or more epoxy groups), silane coupling agents (silane coupling agents having mercapto groups such as 3-mercaptopropyltrimethoxysilane, 3-acryloxypropyltrimethoxy) Silane coupling agents having an acrylic group such as silane), tackifiers (rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), metal corrosion inhibitors (benzotriazole compounds, etc.), antioxidants ( Hindered phenol compounds, phosphite compounds, thioether compounds, etc.), External line absorbers (benzotriazole compounds, triazine compounds, benzophenone compounds, etc.), light stabilizers (hindered amine compounds, etc.), fillers, colorants (pigments, dyes, etc.), chain transfer agents, plasticizers, softeners, surfactants In addition, a known additive for resin such as an antistatic agent may be contained.

  As the isocyanate-based crosslinking agent, 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, lower aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, Arocyclic polyisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylene diisocyanate, aromatics such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate Well-known isocyanate type crosslinking agents, such as polyisocyanate, can be illustrated. Also, trimethylolpropane / tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), trimethylolpropane / hexamethylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL ") and the like can also be preferably used.

  Examples of the metal chelate-based crosslinking agent include acetylacetone and acetoacetyl ester coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium.

  The pressure-sensitive adhesive layer of the conductive material laminate of the present invention may be composed of two or more pressure-sensitive adhesive layers having different compositions. For example, the pressure-sensitive adhesive layer A containing the compound having an epoxy group is provided on the surface of the conductive material on the side having the thin conductive metal wires, and the pressure-sensitive adhesive layer does not contain the compound having an epoxy group on the pressure-sensitive adhesive layer A. B may be provided as one adhesive layer.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited, but if it is too thin, it may not be able to follow the irregularities on the surface of the conductive material on the side having the conductive metal fine wires, and bubbles may enter the conductive material laminate, and if it is too thick, the conductive layer will become conductive. The transparency of the material laminate may be impaired. Therefore, the thickness of the pressure-sensitive adhesive layer is preferably 5 to 300 μm, more preferably 10 to 250 μm. Further, from the viewpoint of transparency of the conductive material laminate, the total light transmittance of the pressure-sensitive adhesive layer is preferably 90% or more, and particularly preferably 95% or more. From the same viewpoint, the haze of the pressure-sensitive adhesive layer is preferably 0 to 3%, particularly preferably 0 to 2%.

  The method for forming the pressure-sensitive adhesive layer of the conductive material laminate of the present invention is not particularly limited, but the above-described resins, compounds having an epoxy group, additives that other pressure-sensitive adhesive layers may contain, and more A method of preparing a pressure-sensitive adhesive layer-forming coating solution in which is dissolved in a solvent, and applying and drying the coating liquid to form a pressure-sensitive adhesive layer is particularly preferred from the viewpoint of productivity. Therefore, in the present invention, the resin is preferably polymerized by a solution polymerization method from the viewpoint of productivity because the polymerization solvent can be used as it is as the solvent for the adhesive layer forming coating solution, and the polymerization initiator is polymerized by heat as the polymerization initiator. It is preferable to use a polymerization initiator that initiates the reaction.

  In the present invention, the pressure-sensitive adhesive layer 20 may be directly formed on the conductive material 10, and the functional material 30 described later may be laminated on the pressure-sensitive adhesive layer 20. The pressure-sensitive adhesive layer 20 is directly formed on the functional material 30. The conductive material 10 may be laminated on the pressure-sensitive adhesive layer 20, and the pressure-sensitive adhesive layer 20 is formed on the release-processed support, and the pressure-sensitive adhesive layer 20 is laminated on the conductive material 10, The release-processed support may be peeled off from the adhesive layer 20 and the functional material 30 may be laminated on the pressure-sensitive adhesive layer 20. Among them, the method of forming the pressure-sensitive adhesive layer 20 on the release-processed support is particularly preferable from the viewpoint of productivity because the possibility of damaging the conductive material and the functional material during the step of forming the pressure-sensitive adhesive layer can be avoided.

  The support of the release-treated support is not particularly limited. Polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, polyarylate, polysulfone, and polyethersulfone. Von, polyimide, fluororesin, phenoxy resin, triacetyl cellulose, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, acrylic resin, cellophane, nylon, polystyrene resin, ABS resin, and various resin films, various metals Examples thereof include glass such as quartz glass and non-alkali glass. Examples of the release processing method include a method of treating the surface of the support with a known release treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.

  The method for applying the coating solution for forming the adhesive layer onto the support that has been peel-processed is not particularly limited. The bar coating method, the dip coating method, the spin coating method, the die coating method, the blade coating method, the gravure coating method, and the curtain coating method. Application methods using known methods such as spray coating and kiss coating, and known methods such as gravure printing, flexographic printing, inkjet printing, screen printing, offset printing, gravure offset printing, dispenser printing, pad printing, etc. Examples of the printing method are as follows. After applying the coating liquid for forming the pressure-sensitive adhesive layer, the solvent is dried by a known drying method such as heating or natural drying to obtain a pressure-sensitive adhesive layer. The solvent remaining in the pressure-sensitive adhesive layer after drying is preferably 4% by mass or less based on the total mass of the pressure-sensitive adhesive layer from the viewpoint of the reliability of the conductive material laminate.

  Providing a heating step after forming the pressure-sensitive adhesive layer on the conductive material by the above-described method is a reaction between the compound having an epoxy group in the pressure-sensitive adhesive layer and the compound having an amino group contained in the undercoat layer of the conductive material. This is one of the preferred embodiments from the viewpoint of promoting and suppressing corrosion by chloride ions. The heating temperature is preferably 35 ° C. or higher, and particularly preferably 45 ° C. or higher. The upper limit of the heating temperature is not particularly limited, but if the temperature is too high, the support of the conductive material may thermally expand or thermal degradation of the undercoat layer or the pressure-sensitive adhesive layer may occur. Is preferred. The heating time is preferably 10 minutes or more, particularly preferably 20 minutes or more. The upper limit of the heating time is preferably 120 minutes or less from the viewpoint of productivity.

  The functional material 30 included in the conductive material laminate of the present invention includes the conductive material 10 described above, chemically tempered glass, glass such as soda glass, quartz glass, alkali-free glass, films made of various resins such as polyethylene terephthalate, and the like. Examples include materials having a known functional layer such as a hard coating layer, an antireflection layer, an antiglare layer, a polarizing layer, a conductive non-metallic layer made of ITO or the like on at least one surface of the glass or film described above.

  Next, the distance between the side surface portion of the pressure-sensitive adhesive layer 20 and the outermost edge portion of the conductive layer 14 will be described with reference to the drawings. FIG. 2 is a schematic plan view showing an example of the conductive material laminate 50 of the present invention. In FIG. 2, the conductive material 10 has a sensor part 41 having a mesh-like metal fine line pattern, terminal parts 42 and 42 ′, and peripheral wiring parts 43 and 43 ′ that electrically connect the sensor part and the terminal part. The sensor part 41, the terminal parts 42 and 42 ', and the peripheral wiring parts 43 and 43' are all formed of conductive metal thin wires. The sensor portion 41 is formed by arranging a plurality of sensors (for example, 41a, 41b, 41c, etc.) having a mesh-like metal fine line pattern extending in the x direction in the drawing in the y direction in the drawing. In FIG. 2, the sensor unit 41 does not necessarily have a mesh-like fine metal wire pattern, and may be a patterned conductive non-metal layer made of ITO or the like. Further, in FIG. 2, when the sensor unit 41 is illustrated as a mesh metal fine line pattern, the sensor unit 41 is represented by a pattern having a square unit grid as an example. However, as described above, the shape of the unit grid of the mesh metal thin line pattern is limited to a square. In addition, the size of the unit cell is shown to be extremely larger than the actual size in the drawing. In FIG. 2, peripheral wiring parts 43 and 43 ′ are a plurality of peripheral wirings (43a, 43b, 43c, 43′a, 43′b, 43 in the figure) that electrically connect the sensor part 41 and the terminal parts 42 and 42 ′. 'c etc.). The terminal portions 42 and 42 'are portions for electrically connecting the sensor portion 41 and the outside, and a plurality of terminals (42a, 42b, 42c, 42 in the figure) are selected according to the number of sensors included in the sensor portion 41. 'a, 42'b, 42'c, etc.). The sensor 41a is electrically connected to the terminals 42a and 42'a via the peripheral wirings 43a and 43'a, and the capacitance change detected by the sensor 41a is externally transmitted as an electric signal through the terminals 42a and 42'a. It is taken out. A wiring member such as a flexible printed wiring board that is responsible for electrical connection with the outside is generally connected to the terminal portions 42 and 42 ′ of the conductive material 10 described above.

  In FIG. 2, the broken line represents the position of the side surface portion 44 of the adhesive layer 20, and the double arrow represents the outermost edge portion of the sensor portion 41 and the peripheral wiring portions 43 and 43 ′ from the side surface portion 44. Represents the shortest distance 45 between the length of the perpendicular drawn with respect to the side of the pressure-sensitive adhesive layer and the outermost edge of the sensor part 41 and the peripheral wiring parts 43, 43 ′. There is no actual conductive material laminate. The portion where the shortest distance 45 is 200 μm or more is the conductive layer of the present invention, more preferably 300 μm or more, and particularly preferably 400 μm or more. When the shortest distance 45 is less than 200 μm, the suppression of chloride ion penetration is insufficient, so that the corrosion cannot be suppressed and the reliability of the conductive material laminate is lowered. As described above, the conductive layer in the present invention includes most of the sensor portion and the peripheral wiring portion, but the periphery forming the terminal portion for taking out an electric signal to the outside and the connection portion with the terminal portion. Since a part of the wiring cannot be covered with the adhesive layer in principle, these portions are not included in the conductive layer of the present invention. Specifically, the terminal portion and the portion of the peripheral wiring that forms the connection portion with the terminal portion, the shortest distance from the side surface portion of the adhesive layer being less than 200 μm and covered with the adhesive layer, The portion not covered with the agent layer is not included in the conductive layer of the present invention. These parts are usually provided with a countermeasure against corrosion by a sealant or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.

<Preparation of conductive material 1>
A polyethylene terephthalate film having a thickness of 100 μm was used as the support. The support had a total light transmittance of 91% and a haze of 0.8%.

  Next, an undercoat layer 1 coating solution having the following composition was applied onto a support and dried to provide an undercoat layer 1 containing a compound having an amino group. It is estimated that 90.3 mol% or more of the unreacted amino group in the undercoat layer 1 remains before the reaction with the crosslinking agent.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
Hydrochloric acid 40ml
1000ml distilled water
B liquid sodium sulfide 8.6g
1000ml distilled water
Liquid A and liquid B were mixed with stirring, and 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.

<Undercoat layer 1 coating solution / per 1 m ² >
0.4 mg of palladium sulfide sol (physical development nucleus, as solid content)
0.2% aqueous 2 mass% glyoxal solution
Surfactant (S-1) 4mg
Denacol EX-830 50mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
10 mass% SP-200 aqueous solution 0.5g
(Nippon Shokubai Polyethyleneimine; average molecular weight 10,000)

  Subsequently, an intermediate layer, a silver halide emulsion layer, and a protective layer having the following composition were coated on the undercoat layer 1 in order from the side closer to the support and dried to obtain a silver salt photosensitive material. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared with 95 mol% of silver chloride and 5 mol% of silver bromide, and an average grain size of 0.15 μm. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per gram of silver.

<Intermediate layer composition / per 1 m ² >
Gelatin 0.5g
Surfactant (S-1) 5mg
Dye 1 5mg

<Silver halide emulsion layer composition / 1m ² per>
Gelatin 0.5g
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3mg
Surfactant (S-1) 20mg

<Protective layer composition / per 1 m ² >
1g of gelatin
Amorphous silica matting agent (average particle size 3.5μm) 10mg
Surfactant (S-1) 10mg

  The silver salt photosensitive material and a positive transmission document having a mesh-like fine line pattern, a peripheral wiring pattern, and a terminal pattern are brought into close contact with each other, and exposed through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source. . Thereafter, the film was immersed in the following diffusion transfer developer at 20 ° C. for 60 seconds, and then the silver halide emulsion layer, intermediate layer, and protective layer were washed away with warm water at 40 ° C. and dried. Thus, the conductive material 1 shown in FIG. 2 was obtained.

<Diffusion transfer developer composition>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
Total volume 1000ml with water
Adjust to pH = 12.2.

The conductive material 1 has a sensor portion 41, terminal portions 42 and 42 ′, and peripheral wiring portions 43 and 43 ′ as conductive layers on the undercoat layer, all of which are formed of conductive metal fine wires. The sensor part 41 is formed by a mesh-like metal fine wire pattern composed of a rhomboid unit cell having a line width of 4.5 μm, a side length of 300 μm, and a narrower angle of 60 °. The wiring portions 43 and 43 ′ are all solid patterns (filled patterns). The peripheral wirings constituting the peripheral wiring portions 43 and 43 ′ all have a line width of 20 μm, and the shortest distance between adjacent peripheral wirings is 20 μm. As a result of measurement by fluorescent X-ray analysis, the metal amount of the conductive metal fine wire was 1.0 g / m ² .

<Preparation of conductive material 2>
A conductive material 2 was obtained in the same manner as the conductive material 1 except that the undercoat layer 2 coating solution having the following composition was applied on a support and dried to provide the undercoat layer 2 containing a compound having an amino group. . The line width and the amount of metal of the conductive metal fine wire included in the conductive layer of the conductive material 2 were the same as those of the conductive material 1. It is estimated that 80.7 mol% or more of unreacted amino groups in the undercoat layer 2 remain before the reaction with the crosslinking agent.

<Undercoat layer 2 coating liquid / per 1 m ² >
0.4 mg of palladium sulfide sol (physical development nucleus, as solid content)
0.2% aqueous 2 mass% glyoxal solution
Surfactant (S-1) 4mg
Denacol EX-830 50mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
10% gelatin aqueous solution 0.5g

<Preparation of conductive material 3>
A conductive material 3 was obtained in the same manner as the conductive material 1 except that the undercoat layer 3 coating solution having the following composition was applied on a support and dried to provide the undercoat layer 3 not containing a compound having an amino group. . The line width and the amount of metal of the conductive metal thin wire of the conductive material 3 were the same as those of the conductive material 1.

<Undercoat layer 3 coating solution / per 1 m ² >
0.4 mg of palladium sulfide sol (physical development nucleus, as solid content)
0.2% aqueous 2 mass% glyoxal solution
Surfactant (S-1) 4mg
Denacol EX-830 50mg
(Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
10% by mass PVA-117 aqueous solution 0.5g
(Polyvinyl alcohol manufactured by Kuraray Co., Ltd.)

<Preparation of adhesive layer A>
60 parts by mass of 2-methoxyethyl acrylate, 39 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of 4-hydroxybutyl acrylate, 2,2′-azobisisobutyronitrile as a polymerization initiator 0.5 parts by mass (AIBN manufactured by Otsuka Chemical Co., Ltd.), 300 parts of ethyl acetate as a polymerization solvent, and the above were put into a separable flask and stirred for 1 hour while introducing nitrogen gas. Then, it heated up at 65 degreeC, stirred for 10 hours, and polymerized the resin precursor by the solution polymerization method, and obtained the resin solution with a solid content concentration of 25 mass%.

  To 100 parts by mass of this resin solution (in terms of solid content), 0.5 parts by mass (in terms of solid content) of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) was added, and these were then mixed uniformly. A coating liquid A for forming an adhesive layer was obtained. The pressure-sensitive adhesive layer-forming coating liquid A was applied onto a release-processed surface of a 38 μm-thick release-processed polyethylene terephthalate film (MRF38 manufactured by Mitsubishi Resin Co., Ltd.), heated for 3 minutes with hot air at 100 ° C., and dried. An adhesive layer A (thickness 50 μm) was produced. Thereafter, the release-processed surface of a release-processed polyethylene terephthalate film (MRF38 manufactured by Mitsubishi Resin Co., Ltd.) was bonded onto the adhesive layer A.

<Preparation of adhesive layer B>
For the above-mentioned adhesive layer forming coating liquid A, jER 152 manufactured by Mitsubishi Chemical Corporation as a compound having an epoxy group is used as the total solid content of the adhesive layer forming coating liquid (total mass of the adhesive layer after formation). The pressure-sensitive adhesive layer B was prepared in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 0.2% by mass.

<Preparation of adhesive layer C>
For the adhesive layer forming coating liquid A described above, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer C was produced in the same manner as the pressure-sensitive adhesive layer A, except that 0.2% by mass was added and mixed with respect to the total mass).

<Preparation of adhesive layer D>
With respect to the above-mentioned adhesive layer forming coating liquid A, as a compound having an epoxy group, Daicel Corporation's Celoxide 2000 was added to the total solid content of the adhesive layer forming coating liquid (the total mass of the adhesive layer after formation). A pressure-sensitive adhesive layer D was prepared in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 0.2% by mass.

<Preparation of adhesive layer E>
Denacol EX-252 manufactured by Nagase ChemteX Corp. as a compound having an epoxy group was added to the above-mentioned pressure-sensitive adhesive layer-forming coating liquid A as a total solid content of the pressure-sensitive adhesive layer-forming coating liquid. The pressure-sensitive adhesive layer E was prepared in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 0.2% by mass relative to the total mass of

<Preparation of adhesive layer F>
With respect to the coating liquid A for forming an adhesive layer described above, Epolite M-1230 manufactured by Kyoeisha Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the coating liquid for forming the adhesive layer (of the adhesive layer after formation). A pressure-sensitive adhesive layer F was produced in the same manner as the pressure-sensitive adhesive layer A, except that 0.2% by mass was added and mixed with respect to the total weight).

<Preparation of adhesive layer G>
With respect to the coating liquid A for forming an adhesive layer described above, Epolite 80MF manufactured by Kyoeisha Chemical Co., Ltd. as a compound having an epoxy group is added to the total solid content of the coating liquid for forming an adhesive layer (total mass of the adhesive layer after formation). The pressure-sensitive adhesive layer G was prepared in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 0.2% by mass.

<Preparation of adhesive layer H>
With respect to the above-mentioned adhesive layer forming coating liquid A, Shin-Etsu Chemical Co., Ltd. KBE-402 as an epoxy group-containing compound was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer H was produced in the same manner as the pressure-sensitive adhesive layer A, except that 0.2% by mass was added and mixed with respect to the total mass).

<Preparation of adhesive layer I>
For the adhesive layer forming coating liquid A described above, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer I was prepared in the same manner as the pressure-sensitive adhesive layer A except that 0.02% by mass was added and mixed with respect to the total mass).

<Preparation of adhesive layer J>
For the adhesive layer forming coating liquid A described above, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer J was prepared in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 0.08% by mass relative to the total mass).

<Preparation of adhesive layer K>
For the adhesive layer forming coating liquid A described above, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer K was prepared in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 0.75% by mass relative to the total mass).

<Preparation of adhesive layer L>
For the adhesive layer forming coating liquid A described above, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer L was produced in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 1.25% by mass relative to the total mass).

<Preparation of adhesive layer M>
For the adhesive layer forming coating liquid A described above, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer M was produced in the same manner as the pressure-sensitive adhesive layer A, except that it was added and mixed so as to contain 1.75% by mass relative to the total mass).

<Preparation of adhesive layer N>
For the adhesive layer forming coating liquid A described above, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group was added to the total solid content of the adhesive layer forming coating liquid (of the adhesive layer after formation). A pressure-sensitive adhesive layer N was produced in the same manner as the pressure-sensitive adhesive layer A except that it was added and mixed so as to contain 2.25% by mass relative to the total mass).

<Preparation of pressure-sensitive adhesive layer O>
60 parts by mass of 2-methoxyethyl acrylate, 34 parts by mass of n-butyl acrylate, 3.5 parts by mass of N-vinyl-2-pyrrolidone, 1 part by mass of N- (2-hydroxyethyl) acrylamide, 1 part by mass of 4-hydroxybutyl-2-acrylate, 0.5 part by mass of acrylic acid, and 2,2′-azobis-2-methylbutyronitrile (AMBN manufactured by Otsuka Chemical Co., Ltd.) as a polymerization initiator 0.5 parts by mass, 300 parts of ethyl acetate as a polymerization solvent, and the above were put into a separable flask and stirred for 1 hour while introducing nitrogen gas. Then, it heated up at 65 degreeC, stirred for 10 hours, and polymerized the resin precursor by the solution polymerization method, and obtained the resin solution with a solid content concentration of 25 mass%.

  To 100 parts by mass of this resin solution (in terms of solid content), 0.5 parts by mass (in terms of solid content) of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) was added, and these were then mixed uniformly. A coating liquid O for forming an adhesive layer was obtained. The pressure-sensitive adhesive layer-forming coating solution O was applied onto a release-processed surface of a 38 μm-thick release-processed polyethylene terephthalate film (MRF38 manufactured by Mitsubishi Resin Co., Ltd.), heated at 100 ° C. for 3 minutes and dried. An adhesive layer O (thickness 50 μm) was prepared. Thereafter, the release-processed surface of a release-processed polyethylene terephthalate film (MRF38 manufactured by Mitsubishi Resin Co., Ltd.) was bonded onto the pressure-sensitive adhesive layer O.

<Preparation of adhesive layer P>
Mitsubishi Gas Chemical Co., Ltd. as a compound having an epoxy group relative to the total solid content (corresponding to the total mass of the pressure-sensitive adhesive layer after formation) of the pressure-sensitive adhesive layer-forming coating liquid for the pressure-sensitive adhesive layer-forming coating liquid O described above. Adhesive in the same manner as the adhesive layer O except that 0.1% by mass of TETRAD-X manufactured by Co., Ltd. and 0.1% by mass of KBE-402 manufactured by Shin-Etsu Chemical Co., Ltd. were added and mixed. The agent layer P was produced.

<Preparation of Samples 1-16>
One release-processed polyethylene terephthalate film of the pressure-sensitive adhesive layer A was peeled off to expose one surface of the pressure-sensitive adhesive layer A. Next, the exposed surface of the pressure-sensitive adhesive layer A was bonded to the region surrounded by the side surface portion 44 shown in FIG. 2 on the conductive material 1. Thereafter, the other peel-processed polyethylene terephthalate film of the pressure-sensitive adhesive layer A was peeled off, and non-alkali glass (Eagle 2000 manufactured by Corning Japan Co., Ltd.) was bonded onto the pressure-sensitive adhesive layer A. This procedure was repeated to prepare 30 samples 1. 30 samples 30 to 16 were produced in the same manner except that the adhesive layers B to P were used. The shortest distance 45 between the side surface portion 44 on the right side of the conductive material laminate in FIG. 2 and the peripheral wiring 43a was 450 μm for all of the samples 1 to 16.

<Preparation of Samples 17 and 18>
30 samples 17 and 18 were prepared in the same manner as sample 3 except that conductive materials 2 and 3 were used. The shortest distance 45 between the side surface 44 on the right side of the conductive material laminate in FIG. 2 and the peripheral wiring 43a was 450 μm for both the samples 17 and 18.

<Preparation of Samples 19 to 21>
2 except that the size of the adhesive layer to be bonded was changed so that the shortest distance 45 between the right side surface portion 44 of the conductive material laminate in FIG. 2 and the peripheral wiring 43a was 350 μm, 250 μm, and 150 μm. Similarly, 30 samples 19 to 21 were produced.

<Preparation of Sample 22>
30 samples 22 were prepared in the same manner as sample 3 except that a step of heating at 40 ° C. for 30 minutes after bonding the conductive material, the pressure-sensitive adhesive layer, and the alkali-free glass was provided.

<Preparation of Sample 23>
30 samples 23 were produced in the same manner as sample 3 except that a step of heating at 50 ° C. for 30 minutes after bonding the conductive material, the pressure-sensitive adhesive layer, and the alkali-free glass was provided.

<Number of samples with corrosion>
All samples were placed in a salt spray test apparatus manufactured by Suga Test Instruments Co., Ltd., and a neutral salt spray test was performed for 120 hours in accordance with JIS Z 2371. The sodium chloride concentration of the sodium chloride aqueous solution used for the test was 50 g / L, and the water temperature during the test was 35 ° C. With respect to all the samples after the test, the peripheral wiring 43a on the right side of the conductive material laminate in FIG. 2 was observed with a digital microscope VHX-5000 manufactured by Keyence Corporation, and the metallic luster was lost and discoloration to black occurred. The number of samples was counted (the number of samples in which corrosion occurred). The results are shown in Table 1.

  From the results in Table 1, it can be seen that according to the present invention, corrosion due to chloride ions is suppressed, and a conductive material laminate excellent in reliability can be obtained.

DESCRIPTION OF SYMBOLS 10 Conductive material 11 Support body 12 Undercoat layer 13 Conductive metal thin wire 14 Conductive layer 20 Adhesive layer 30 Functional material 41 Sensor part 41a, 41b, 41c Sensor 42, 42 'Terminal part 42a, 42b, 42c, 42'a, 42'b, 42'c Terminals 43, 43 'Peripheral wiring portions 43a, 43b, 43c, 43'a, 43'b, 43'c Peripheral wiring 44 Side surface portion 45 Shortest distance 50 Conductive material laminate

Claims (1)

  On the support, an undercoat layer containing a compound having an amino group, a conductive material having at least a conductive layer having a conductive metal wire on the undercoat layer, and an epoxy group on the conductive layer of the conductive material A pressure-sensitive adhesive layer containing a compound having a functional layer and a functional material on the pressure-sensitive adhesive layer at least in this order, and the shortest distance between the side surface portion of the pressure-sensitive adhesive layer and the outermost edge portion of the conductive layer is 200 μm or more A conductive material laminate characterized by the above.