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WO2013168773A1 - Stratifié de film conducteur, panneau tactile, tableau de connexions, appareil électronique, feuille transparente adhésive double face sensible à la pression et feuille transparente adhésive sensible à la pression - Google Patents

Stratifié de film conducteur, panneau tactile, tableau de connexions, appareil électronique, feuille transparente adhésive double face sensible à la pression et feuille transparente adhésive sensible à la pression Download PDF

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Publication number
WO2013168773A1
WO2013168773A1 PCT/JP2013/063064 JP2013063064W WO2013168773A1 WO 2013168773 A1 WO2013168773 A1 WO 2013168773A1 JP 2013063064 W JP2013063064 W JP 2013063064W WO 2013168773 A1 WO2013168773 A1 WO 2013168773A1
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WIPO (PCT)
Prior art keywords
group
hydrocarbon group
transparent
compound
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/063064
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English (en)
Japanese (ja)
Inventor
三田村　康弘
真也 荻窪
柴田　路宏
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
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Publication of WO2013168773A1 publication Critical patent/WO2013168773A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0108—Transparent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/07—Electric details
    • H05K2201/0753—Insulation
    • H05K2201/0769—Anti metal-migration, e.g. avoiding tin whisker growth
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol

Definitions

  • the present invention relates to a conductive film laminate, a touch panel, a wiring board, an electronic device, a transparent double-sided adhesive sheet, and a transparent adhesive sheet.
  • Patent Document 1 a method of introducing a metal ion adsorbing compound into a polymer layer has been proposed.
  • a capacitive type touch panel has a structure in which many members are laminated, and an adhesive sheet is used for the purpose of bonding the members.
  • a capacitive touch panel having a laminated structure of cover glass / adhesive sheet / conductive film / glass substrate can be mentioned.
  • Patent Document 2 discloses a transparent pressure-sensitive adhesive sheet containing a copolymer of a predetermined monomer component, and (meth) acrylic acid hydroxyalkyl ester ((E)) as a monomer component of the copolymer. It is described that whitening can be prevented when it contains (component) (paragraph 0040).
  • the present inventor provided a polymer layer in which a compound that forms an organic metal salt with a metal ion such as a thiol-containing compound disclosed in Patent Document 1 is provided on a silver-containing metal wiring, and examined its insulation reliability went.
  • the width and interval of the metal wiring in the wiring board are becoming narrower (specifically, the minimum value of the distance (interval) between the metal wirings is less than 50 ⁇ m). Is more likely to occur.
  • silver and copper having high conductivity are often used as the metal constituting the metal wiring, but these metals have a problem that ion migration is likely to occur, and this problem is particularly noticeable with silver. Under such circumstances, further improvement in insulation reliability between metal wirings containing silver in the wiring board is required.
  • the present inventor stuck a transparent adhesive sheet of a copolymer containing the component (E) disclosed in Patent Document 1 onto a substrate with metal wiring having a minimum distance between metal wirings of less than 50 ⁇ m, and the metal wiring
  • the insulation reliability was investigated.
  • a remarkable decrease in inter-wire resistance was confirmed between metal wirings, and the ion migration suppression effect did not satisfy the level required recently, and further improvement was necessary.
  • the copolymer contains a hydrophilic component such as the component (E). Therefore, when such a copolymer containing no component (E) is used, whitening proceeds and the transparency of the adhesive layer is lost. That is, in the prior art, the ion migration suppressing function and whitening prevention are often in a trade-off relationship.
  • the first aspect of the present invention is to provide a wiring board capable of suppressing the ion migration of silver from a metal wiring containing silver and improving the insulation reliability between the metal wirings.
  • a conductive film laminate including a transparent double-sided pressure-sensitive adhesive sheet, in which ion migration of silver from a conductive film containing silver can be suppressed and insulation reliability between the conductive films can be improved. It is also intended to provide.
  • the second aspect of the present invention in view of the above circumstances, the ion migration of silver between metal wirings containing silver is suppressed, and the insulation reliability between the metal wirings is excellent, and the whitening resistance of the transparent adhesive layer
  • An object of the present invention is to provide an excellent wiring board.
  • the 2nd aspect of this invention also aims at providing the transparent adhesive sheet used for the said wiring board.
  • the present inventors have found that the dispersibility in the polymer layer of a metal ion-adsorbing compound such as a thiol-containing compound disclosed in Patent Document 1 has an influence. . More specifically, the metal ion adsorbing compound such as the thiol-containing compound disclosed in Patent Document 1 has low dispersibility due to its structure. Therefore, even if the metal ion adsorbing compound is introduced into the polymer layer (resin layer), it is difficult to uniformly disperse the compound in the polymer layer, and migration of metal ions (particularly silver ions) is suppressed. The effect is not obtained.
  • the metal ion adsorbing compound when a large amount of the metal ion adsorbing compound is introduced into the polymer layer, the metal ion adsorbing compound is precipitated in the polymer layer, causing deterioration of the polymer and deterioration of electrical reliability. Furthermore, there is a possibility that problems such as promoting the diffusion of metal ions and causing wiring breakdown may occur. Based on the above knowledge, the present inventors use a compound having a specific functional group and having a reducing ability for metal ions, and using a conductive film (or metal wiring) containing a predetermined amount of silver. Thus, it has been found that the problem of the first aspect can be solved. That is, the present inventors have found that the problem of the first aspect can be solved by the following configuration.
  • a conductive film laminate comprising a transparent substrate, a conductive film containing silver disposed on the transparent substrate, and a transparent double-sided pressure-sensitive adhesive sheet bonded to the conductive film, The amount of silver contained per unit area of the conductive film is 50 ⁇ g / mm 2 or less, A conductive film laminate, wherein the transparent double-sided pressure-sensitive adhesive sheet contains at least one compound selected from the group consisting of a transparent resin and compounds represented by formulas (1) to (3) described later.
  • the conductive film laminate according to (1), wherein the compound is selected from the group consisting of compounds represented by formulas (4) to (6) described later.
  • a wiring board comprising an insulating substrate, a metal wiring containing silver disposed on the insulating substrate, and a silver ion diffusion suppressing layer disposed on the metal wiring, The amount of silver contained per unit area of the metal wiring is 50 ⁇ g / mm 2 or less, A wiring board, wherein the silver ion diffusion suppressing layer contains an insulating resin and at least one compound selected from the group consisting of compounds represented by formulas (1) to (3) described later. (9) The wiring board according to (8), wherein the compound is selected from the group consisting of compounds represented by formulas (4) to (6) described later. (10) The wiring board according to (8) or (9), wherein the compound is selected from the group consisting of compounds represented by formulas (5) to (6) described later.
  • the present inventors conducted extensive studies on the problems of the prior art. As a result, the transparent adhesive containing a compound exhibiting a predetermined oxidation-reduction potential and having a time-dependent change in haze in a predetermined environmental test. It has been found that the problem of the second aspect can be solved by using a sheet. That is, the present inventors have found that the problem of the second aspect can be solved by the following configuration.
  • the wiring board (14) an insulating substrate; A plurality of metal wirings including silver disposed on an insulating substrate; A wiring board comprising a transparent adhesive layer disposed on the metal wiring in direct contact with the metal wiring, The minimum distance between adjacent metal wires is less than 50 ⁇ m, The transparent adhesive layer contains a compound having a redox potential of 0.40 to 1.30 V, and an adhesive, The wiring substrate, wherein the transparent adhesive layer is a transparent adhesive layer having a time X of 12 hours or less in an environmental test described later. (15) The wiring board according to (14), wherein the compound includes a phenol compound. (16) The wiring board according to (14) or (15), wherein the compound contains a phenol compound having an oxidation-reduction potential of 0.50 to 1.20 V.
  • the transparent adhesive sheet according to (20), wherein the compound comprises a phenol compound.
  • the transparent adhesive according to any one of (20) to (22), wherein the compound comprises at least one selected from the group consisting of compounds represented by formulas (1) to (3) to be described later Sheet.
  • the conductive film stack including the transparent double-sided pressure-sensitive adhesive sheet can suppress the ion migration of silver from the conductive film containing silver and can improve the insulation reliability between the conductive films.
  • the body can be provided.
  • the silver ion migration between the metal wirings containing silver is suppressed, the wirings exhibit excellent insulation reliability between the metal wirings and are excellent in whitening resistance of the transparent adhesive layer.
  • a substrate can be provided.
  • the transparent adhesive sheet used for the said wiring board can also be provided.
  • the dispersibility of the reducing compound in the resin can be improved and deterioration of the resin can be suppressed, and the amount of silver in the conductive film (or metal wiring)
  • the reduction property of a predetermined reducing compound is further improved by setting the value to be a predetermined value or less.
  • the compound since the compound is well dispersed in the resin, the reduced silver is less likely to be localized, and as a result, it is difficult to have absorption in the visible region, and deterioration of coloring and haze can be suppressed.
  • the specific surface area of the silver component in the conductive film is increased by controlling the amount of silver, and the improvement effect by the reducing compound is increased. Improve more.
  • FIG. 1 is a schematic cross-sectional view of an embodiment of a wiring board.
  • the wiring board 10 includes an insulating substrate 12 and an insulating substrate 16 with a metal wiring provided on the insulating substrate 12, and a metal wiring. 14 and a silver ion diffusion suppression layer 18 covering 14. Below, each member (the insulating substrate 12, the metal wiring 14, and the silver ion diffusion suppression layer 18) is explained in full detail.
  • the type of the insulating substrate is not particularly limited as long as it is insulative and can support metal wiring.
  • an organic substrate, a ceramic substrate, a glass substrate, or the like can be used.
  • the insulating substrate may have a structure in which at least two substrates selected from the group consisting of an organic substrate, a ceramic substrate, and a glass substrate are stacked.
  • Resin is mentioned as a material of an organic substrate,
  • a thermosetting resin a thermoplastic resin, or resin which mixed them.
  • the thermosetting resin include phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicone resin, furan resin, ketone resin, xylene resin, benzocyclo Examples include butene resin.
  • the thermoplastic resin include polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, aramid resin, and liquid crystal polymer.
  • a glass woven fabric, a glass nonwoven fabric, an aramid woven fabric, an aramid nonwoven fabric, an aromatic polyamide woven fabric, a material impregnated with the above resin, or the like can be used as a material of the organic substrate.
  • the metal wiring mainly contains silver.
  • Silver may be contained in the form of a silver alloy.
  • examples of the metal contained other than silver include tin, palladium, gold, nickel, and chromium.
  • the metal wiring may contain a resin component such as a binder or a photosensitive compound as long as the effects of the present invention are not impaired, and may further contain other components as necessary. .
  • a metal wiring contains the metal nanowire which consists of silver or a silver alloy. The metal nanowire will be described in detail later.
  • the amount of silver contained per unit area of the metal wiring is 50 ⁇ g / mm 2 or less.
  • silver amount is preferably at 30 [mu] g / mm 2 or less, more preferably 15 [mu] g / mm 2 or less.
  • the conductive properties of the metal wire is more excellent, it is preferably 0.001 [mu] g / mm 2 or more, more preferably 0.005 / mm 2 or more.
  • the measuring method in particular of silver amount is not restrict
  • the amount of silver can be measured by observing a cross-sectional SEM photograph of a metal wiring and conducting elemental analysis.
  • the metal wiring is brought into contact with a strong acid such as nitric acid to dissolve silver in the metal wiring, and the amount of silver can be measured from the dissolved amount.
  • a strong acid such as nitric acid
  • the amount of silver in the metal wiring is obtained by calculation from the amount of the dispersion used to produce the metal wiring. You can also.
  • per unit area of the metal wiring means per unit area of the contact portion of the metal wiring with the insulating substrate.
  • the amount of silver is calculated based only on the area of the contact portion between the metal wiring and the insulating substrate.
  • the area of the insulating substrate surface that is not in contact with the metal wiring (for example, the surface of the insulating substrate that is not in contact with the metal wiring that is located between the metal wirings) is considered in the calculation per unit area of the metal wiring.
  • I ca n’t enter. Therefore, the amount of silver contained per unit area of the metal wiring means the amount of silver contained per unit area (mm 2 ) at the contact portion between the metal wiring and the insulating substrate.
  • the width of the metal wiring is not particularly limited, but is preferably 0.1 to 10,000 ⁇ m, and preferably 0.1 to 300 ⁇ m, from the viewpoint of ensuring electrical reliability in the highly integrated portion and the lead wiring portion (lead wiring portion) of the wiring board. More preferably, 0.1 to 100 ⁇ m is more preferable, and 0.2 to 50 ⁇ m is particularly preferable.
  • the distance between the metal wirings is not particularly limited, but is preferably 0.1 to 1000 ⁇ m, more preferably 0.1 to 300 ⁇ m, still more preferably 0.1 to 100 ⁇ m, from the viewpoint of high integration of the wiring board. Particularly preferred is ⁇ 50 ⁇ m.
  • the shape of the metal wiring is not particularly limited, and may be an arbitrary shape. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, and the like can be given. Further, a plurality of metal wirings may be arranged in a desired pattern (for example, a stripe shape).
  • the thickness of the metal wiring is not particularly limited, but is preferably 0.001 to 100 ⁇ m, more preferably 0.01 to 30 ⁇ m, and still more preferably 0.01 to 20 ⁇ m from the viewpoint of high integration of the wiring board.
  • the metal wiring 14 is provided on only one side of the insulating substrate 12, but may be provided on both sides. That is, the insulating substrate 16 with metal wiring may be a single-sided substrate or a double-sided substrate. When the metal wiring 14 is on both surfaces of the insulating substrate 12, the silver ion diffusion touching layer 18 may also be provided on both surfaces.
  • the metal wiring 14 has a single-layer wiring structure as an example, but the present invention is not limited to this. For example, as shown in FIG.
  • an insulating substrate 16a multilayer wiring substrate
  • metal wiring in which a plurality of metal wirings 14a and 14b and insulating substrates 12a and 12b are alternately stacked wiring of a multilayer wiring structure
  • the substrate 100 may be used.
  • a through hole may be formed in the insulating substrate.
  • the metal wiring on both surfaces may be made conductive by filling the through hole with a metal (for example, silver or silver alloy).
  • the silver ion diffusion suppressing layer is a layer that is disposed on the surface of the insulating substrate with metal wiring on the metal wiring side, covers the surface of the metal wiring, and suppresses silver ion migration between the metal wirings. In addition, it is preferable that a silver ion or metal silver is not substantially contained in a silver ion diffusion suppression layer. If the silver ion diffusion suppressing layer contains excessive silver ions or metallic silver, the silver ion migration suppressing effect may be lowered.
  • substantially free of silver ions or metallic silver means that the silver ion or metallic silver content in the silver ion diffusion suppressing layer is 1 ⁇ mol / l or less, and 0.1 ⁇ mol / l or less. More preferably, it is 0 mol / l.
  • the thickness of the silver ion diffusion suppression layer is not particularly limited, but is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, from the viewpoint that the ion migration suppression ability of the silver ion diffusion suppression layer is more excellent.
  • the silver ion diffusion suppressing layer contains an insulating resin and at least one compound selected from the group of compounds represented by formula (1), formula (2), and formula (3).
  • the insulating resin and the compound will be described in detail.
  • the insulating resin By including an insulating resin in the silver ion diffusion suppressing layer, the insulating resin covers the metal wiring and is disposed between the metal wirings, thereby ensuring insulation between the metal wirings.
  • a known insulating resin can be used, and a curable insulating resin (for example, thermosetting insulating resin and It is preferable to use a resin obtained by curing a photocurable insulating resin.
  • thermosetting insulating resin examples include epoxy resin, bismaleimide triazine resin, polyimide resin, acrylic resin, phenol resin, melamine resin, silicon resin, unsaturated polyester resin, cyanate ester resin, isocyanate resin, and modified products thereof.
  • examples thereof include resins.
  • examples of the photocurable insulating resin include unsaturated polyester resins, polyester acrylate resins, urethane acrylate resins, silicone acrylate resins, epoxy acrylate resins, and modified resins thereof.
  • insulating resins include, for example, polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), polylactic acid, fluorine-containing resin, poly Thermoplastic resins such as ether sulfone resin, polyphenylene sulfide resin, and polyether ether ketone resin are also included. Especially, an epoxy resin and an acrylic resin are preferable at the point which is more excellent in compatibility with the compound mentioned later.
  • an insulating resin may be impregnated into a core material such as a glass woven fabric, a glass nonwoven fabric, or an aramid nonwoven fabric.
  • a core material such as a glass woven fabric, a glass nonwoven fabric, or an aramid nonwoven fabric.
  • glass cloth epoxy resin, glass cloth bismaleimide triazine resin, glass cloth polyphenylene ether resin, aramid nonwoven fabric-epoxy resin, aramid nonwoven fabric-polyimide resin, or the like may be used.
  • the insulating resin is a curable resin, a curing agent, a curing accelerator, or the like may be used in combination as necessary. Note that two or more insulating resins may be mixed and used as the insulating resin.
  • the silver ion diffusion suppressing layer By containing at least one compound selected from the group of compounds represented by formula (1), formula (2) and formula (3) (hereinafter also simply referred to as a reducing compound) in the silver ion diffusion suppressing layer Silver ion migration is further suppressed.
  • This reducing compound plays a role of reducing silver ions. That is, even if silver ions are eluted from the metal wiring, silver ions are reduced to silver by the reducing compound, and ion migration is suppressed.
  • this reducing compound is excellent in dispersibility in the silver ion diffusion suppressing layer, and the localization of the reduced silver is suppressed. As a result, the silver ion diffusion suppressing layer is yellowed (in the visible light region). Absorption).
  • the silver ion diffusion suppressing layer may contain two or more compounds represented by the formulas (1) to (3).
  • R 1 to R 5 each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group that may have a hetero atom.
  • a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a group obtained by combining these is preferable in that the ion migration suppressing ability is more excellent.
  • the kind of the hetero atom contained in the hydrocarbon group is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom.
  • Y 1 to Y 4 are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Of these, an oxygen atom and a sulfur atom are preferred because they are easier to handle.
  • t represents an integer of 1 to 3.
  • an aliphatic hydrocarbon group which may have an oxygen atom or an aromatic which may have an oxygen atom from the viewpoint that the effect of the present invention is more excellent.
  • a group hydrocarbon group or a combination thereof is preferred.
  • the number of carbon atoms in the hydrocarbon group is not particularly limited, but is preferably 1 to 40 and more preferably 4 to 20 in terms of more excellent ion migration suppressing ability.
  • the range of the number of carbon atoms contained in the aliphatic hydrocarbon group which may have an oxygen atom, the aromatic hydrocarbon group which may have an oxygen atom or a group in which these are combined is also in the above range. It is preferable that
  • Z represents a hydrogen atom, an acyl group, or an RzOC ( ⁇ O) group.
  • Rz represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • Z is preferably a hydrogen atom in that the ion migration suppressing ability is more excellent.
  • the number of carbon atoms contained in the acyl group or RzOC ( ⁇ O) group is not particularly limited, but is preferably 2 to 12 and more preferably 2 to 8 in terms of more excellent ion migration suppressing ability.
  • the total number of carbon atoms contained in each of R 1 to R 5 is 4 or more. That is, at least one of R 1 to R 5 is a group containing a carbon atom (such as the aliphatic hydrocarbon group, the aromatic hydrocarbon group, or a combination of these). When the total number of carbon atoms is within this range, silver ion migration is suppressed, and the insulation reliability between metal wirings is improved. In addition, 8 or more are preferable and 10 or more are more preferable in the point which this effect is more excellent.
  • the upper limit is not particularly limited, but the total number is preferably 50 or less, more preferably 40 or less, from the viewpoint that synthesis is easier and dispersibility into the insulating resin is more excellent.
  • R 1 to R 5 when only one of R 1 to R 5 is a group containing a carbon atom (for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc.), the number of carbon atoms in the group is It may be 4 or more. In the compound, when a plurality of groups among R 1 to R 5 are groups containing carbon atoms (for example, alkyl groups, alkoxy groups, etc.), the total number of carbon atoms contained in each group is 4 That is all you need.
  • R 1 and R 2 are alkyl groups and R 3 to R 5 are hydrogen atoms
  • the number of carbon atoms contained in the alkyl group of R 1 and the number of carbon atoms contained in the alkyl group of R 2 As long as the total number of is 4 or more.
  • R 1 to R 5 may be bonded to each other to form a ring.
  • the type of ring formed is not particularly limited, and examples thereof include a 5- to 6-membered ring structure.
  • R 1 to R 5 may further contain a known substituent, if necessary.
  • substituents include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, and a carbamoyl group.
  • R 6 to R 8 each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
  • the number of carbon atoms contained in the aliphatic hydrocarbon group, aromatic hydrocarbon group or a combination thereof is not particularly limited, but is preferably 1 to 40 and more preferably 2 to 20 in terms of more excellent ion migration suppression ability. More preferred.
  • the total number of carbon atoms contained in each group of R 6 to R 8 is 6 or more.
  • the total number of carbon atoms is within this range, silver ion migration is suppressed, and the insulation reliability between metal wirings is improved.
  • 8 or more are preferable and 10 or more are more preferable in the point which this effect is more excellent.
  • the upper limit is not particularly limited, but the total number is preferably 50 or less, more preferably 40 or less, from the viewpoint that synthesis is easier and dispersibility into the insulating resin is more excellent.
  • R 6 to R 8 are alkyl groups, the number of carbon atoms contained in the alkyl group of R 6 and the number of carbon atoms contained in the alkyl group of R 7
  • the total number of carbon atoms contained in the alkyl group represented by R 8 may be 6 or more.
  • R 6 to R 8 may further contain a known substituent, if necessary. Examples of the substituent are the same as the substituents substituted with R 1 to R 5 described above.
  • R 6 to R 8 may be bonded to each other to form a ring.
  • R 9 to R 12 each independently represents an alkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, or a combination thereof.
  • the number of carbon atoms contained in the alkyl group or aryl group is not particularly limited, but is preferably 1 to 40 and more preferably 2 to 20 in terms of more excellent ion migration suppressing ability.
  • the alkyl group or aryl group may contain a hetero atom.
  • the type of hetero atom contained is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom.
  • X 1 to X 4 are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Of these, an oxygen atom and a sulfur atom are preferred because they are easier to handle.
  • R a , R b and R c are each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. n represents an integer of 1 to 3.
  • the total number of carbon atoms contained in each group of R 9 to R 12 is 6 or more.
  • the total number of carbon atoms is within this range, silver ion migration is suppressed, and the insulation reliability between metal wirings is improved.
  • 8 or more are preferable and 10 or more are more preferable in the point which this effect is more excellent.
  • the upper limit is not particularly limited, but the total number is preferably 50 or less, more preferably 40 or less, from the viewpoint that synthesis is easier and dispersibility into the insulating resin is more excellent.
  • R 9 to R 12 are all alkyl groups
  • the total number of carbon atoms contained in the alkyl group of R 11 and the number of carbon atoms contained in the alkyl group of R 12 may be 6 or more.
  • R 9 to R 12 may be bonded to each other to form a ring.
  • the compound represented by the formula (4) is preferably mentioned in that the ion migration suppressing ability is more excellent.
  • R 14 and R 15 are each independently a hydrogen atom, a hydroxyl group, or a hydrocarbon group optionally having a hetero atom.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group that may contain an oxygen atom, an aromatic hydrocarbon group that may contain an oxygen atom, or a group obtained by combining these in terms of more excellent effects of the present invention.
  • a tertiary carbon atom or an alkyl group containing a quaternary carbon atom is preferable from the viewpoint of more excellent ion migration suppressing ability.
  • the number of carbon atoms in the hydrocarbon group which may have a hetero atom is not particularly limited as long as it satisfies the requirements described later, but is preferably 1 to 40, and more preferably 2 to 20.
  • the range of the number of carbon atoms contained in the aliphatic hydrocarbon group which may have an oxygen atom, the aromatic hydrocarbon group which may have an oxygen atom, or a combination of these is also in the above range. It is preferable that In particular, R 14 is preferably an alkyl group having 1 to 5 carbon atoms and R 15 is an alkyl group having 10 to 20 carbon atoms.
  • the number of carbon atoms contained in at least one of R 1 , R 2 , R 14 and R 15 is 1-40.
  • the solubility in the insulating resin is improved, the dispersibility of the compound in the silver ion diffusion suppressing layer is improved, and as a result, the silver ion migration suppressing ability is improved.
  • the number of carbon atoms is preferably 8 to 40, more preferably 10 to 30.
  • the total number of carbon atoms contained in each group of R 1 , R 2 , R 14 and R 15 is 4 or more. When the total number of carbon atoms is within this range, silver ion migration is suppressed, and the insulation reliability between metal wirings is improved. In addition, 8 or more are preferable and 10 or more are more preferable in the point which this effect is more excellent.
  • the upper limit is not particularly limited, but the total number is preferably 50 or less, more preferably 40 or less, from the viewpoint that synthesis is easier and dispersibility into the insulating resin is more excellent.
  • the compound represented by the formula (5) or the formula (6) is preferable in that the ion migration suppressing ability is more excellent. Most preferred is a compound.
  • R 31 to R 38 each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
  • the hydrocarbon group include —O—R a .
  • R a represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
  • the number of carbon atoms of the hydrocarbon group is preferably 1 to 12 and more preferably 1 to 10 in terms of excellent compatibility with the insulating resin. More specifically, examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the total molecular weight of each group of R 31 to R 38 is 24 or more. Especially, 35 or more are preferable.
  • the upper limit is not particularly limited, but is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less, from the viewpoint that the effects of the present invention are more excellent.
  • the sum of the molecular weights of the respective groups is intended to be a value obtained by calculating the molecular weights of the respective groups R 31 to R 38 and summing them. Further, any two of R 31 to R 38 may be bonded to each other to form a ring.
  • the definition of the hetero atom is the same as the definition of the hetero atom in the hydrocarbon group which may have the hetero atom represented by R 1 to R 5 described above.
  • the hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom represented by R 31 to R 36 is an aliphatic hydrocarbon which may have an oxygen atom in that the effect of the present invention is more excellent. Selected from the group consisting of a group (for example, an alkyl group, an alkenyl group, an alkynyl group), an aromatic hydrocarbon group which may have an oxygen atom (for example, a phenyl group), and a combination thereof. Groups having 1 to 20 carbon atoms are preferred.
  • R 37 and R 38 each independently preferably represents a —CH 2 —R 40 group, a hydroxyl group, or an aliphatic hydrocarbon group which may have an oxygen atom.
  • the aliphatic hydrocarbon group which may have an oxygen atom is preferably a linear alkyl group from the viewpoint of more excellent ion migration suppressing ability.
  • R 40 represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • R 39 represents a C 1-20 divalent aliphatic hydrocarbon group which may contain a hetero atom.
  • the number of carbon atoms contained in the divalent aliphatic hydrocarbon group is preferably 1-10. Examples include a methylene group, an ethylidene group, an isopropylidene group, a butylidene group, an isononylidene group, and a cyclohexylidene group, but the present invention is not limited to these.
  • the definition of the hetero atom is the same as the definition of the hetero atom in the hydrocarbon group which may have the hetero atom represented by R 1 to R 5 described above.
  • R 41 to R 44 each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
  • the preferred range of the hydrocarbon group represented by R 41 to R 44 is synonymous with the preferred range of the hydrocarbon group represented by R 31 to R 38 described above.
  • the total molecular weight of each group of R 41 to R 44 is 40 or more. Especially, 50 or more are preferable.
  • the upper limit is not particularly limited, but is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less, from the viewpoint that the effects of the present invention are more excellent. Further, any two of R 41 to R 44 may be bonded to each other to form a ring.
  • the definition of the hetero atom is the same as the definition of the hetero atom in the hydrocarbon group which may have the hetero atom represented by R 1 to R 5 described above.
  • the hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom represented by R 41 to R 44 is an aliphatic hydrocarbon which may have an oxygen atom from the viewpoint of more excellent effects of the present invention.
  • a group of 1 to 20 is preferable.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • L represents a divalent or trivalent hydrocarbon group which may have a hetero atom, —S—, or a group obtained by combining these.
  • the hydrocarbon group represented by L has a divalent or trivalent aliphatic hydrocarbon group which may have an oxygen atom, or an oxygen atom, in that the effect of the present invention is more excellent. Examples thereof may include a divalent or trivalent aromatic hydrocarbon group.
  • the number of carbon atoms contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group is not particularly limited, but the aliphatic hydrocarbon group is preferably 1 to 40, more preferably 2 to 20, and the aromatic hydrocarbon group is 6 to 40 are preferable, and 6 to 20 are more preferable.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic. n represents an integer of 2 or 3.
  • Examples of the compound represented by the formula (1) include the following compounds.
  • Examples of the compound represented by the formula (4) include the following compounds.
  • Examples of the compound represented by the formula (5) include the following compounds.
  • Examples of the compound represented by the formula (2) include the following compounds.
  • Examples of the compound represented by the formula (3) include the following compounds.
  • the mass relationship between the insulating resin and the reducing compound in the silver ion diffusion suppressing layer is not particularly limited, but the total mass A of the reducing compound and the total mass B of the insulating resin are more excellent in terms of ion migration suppressing ability.
  • the mass ratio (A / B) is preferably 0.20 or less, and more preferably 0.10 or less. Although a minimum in particular is not restrict
  • total mass A represents those total mass, when two or more types of reducing compounds are contained.
  • the total mass B represents the total mass when two or more kinds of insulating resins are included.
  • the insulating substrate, the metal wiring, and the wiring substrate having the silver ion diffusion suppression layer can be used for various applications and structures. Examples include a panel substrate for a plasma display panel, a substrate for a solar cell electrode, a membrane wiring board, a substrate for a touch panel electrode, and the like.
  • the wiring board according to the first aspect of the present invention is preferably included in an electronic device.
  • Electronic devices include touch panels or membrane switches, televisions equipped with them, mobile communication devices, personal computers, game devices, in-vehicle display devices, network communication devices, lighting / display LEDs, electronic wiring devices for solar cell control, RFID, etc.
  • the method for forming the metal wiring on the insulating substrate is not particularly limited, and a known method can be adopted.
  • a subtractive method using an etching process a semi-additive method using electrolytic plating, a method for producing metal wiring using a silver paste (for example, a silver nanoparticle or silver nanowire-containing paste)
  • a method for producing metal wiring using a silver paste for example, a silver nanoparticle or silver nanowire-containing paste
  • a method using a photosensitive material disclosed in Japanese Unexamined Patent Application Publication No. 2009-188360, a vacuum deposition method, a sputter film formation method, an ion plating method, and the like.
  • the silver paste is a conductive paste-like substance (paste) obtained by dispersing silver particles having a predetermined particle size in an appropriate solvent such as a resin binder, and is used for attaching a sample or conducting a conductive treatment. Yes.
  • a conductive paste-like substance obtained by dispersing silver particles having a predetermined particle size in an appropriate solvent such as a resin binder, and is used for attaching a sample or conducting a conductive treatment.
  • an appropriate solvent such as a resin binder
  • the method for producing the wiring board is not particularly limited.
  • the composition for forming a silver ion diffusion suppressing layer containing the insulating resin, the reducing compound and the solvent is applied onto the insulating board with metal wiring, and the solvent is removed.
  • stacking the film for silver ion diffusion suppression layers containing the said insulating resin and the said compound directly on an insulated substrate with metal wiring is also mentioned. From the viewpoint of easy adjustment of the thickness of the silver ion diffusion suppressing layer, the method by the above application is preferable.
  • the method for applying the silver ion diffusion suppression layer forming composition onto the insulating substrate with metal wiring is not particularly limited, and is a dispensing method, a screen printing method, a curtain coating method, a barcode method, a spin coater method, an inkjet method, A known method such as a dip dipping method can be employed.
  • the dispense method, the screen printing method, the spin coater method, and the ink jet method are preferable because the amount of adhesion of the silver ion diffusion suppression layer can be more easily controlled.
  • a heat treatment or an exposure treatment may be performed as necessary.
  • the optimum heating temperature is appropriately selected according to the thermosetting resin to be used, but it is usually preferably 100 to 300 ° C, more preferably 100 to 250 ° C.
  • the heating time is preferably 0.2 to 10 hours and more preferably 0.5 to 5 hours from the viewpoint of productivity.
  • the light used for exposure is appropriately selected according to the photocurable resin used. For example, ultraviolet rays and visible light can be used.
  • the exposure time is preferably 0.2 to 10 hours and more preferably 0.5 to 5 hours from the viewpoint of productivity.
  • the insulating layer 20 is disposed on the silver ion diffusion suppressing layer 18 as shown in FIG. Below, the material (insulating layer) used is demonstrated, and the procedure of a manufacturing method is demonstrated after that.
  • Insulating layer As a material for the insulating layer, a known insulating material can be used. For example, epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene, perfluorinated polyimide, perfluorinated amorphous resin, etc.), polyimide resin, polyether sulfone resin, polyphenylene Examples thereof include sulfide resin, polyether ether ketone resin, and acrylate resin. Moreover, you may use what is called a transparent adhesive sheet (OCA) for optics as an insulating layer.
  • OCA transparent adhesive sheet
  • OCA a commercially available product may be used, and examples thereof include 8171CL series and 8146 series manufactured by 3M Corporation. Moreover, you may use what is called a soldering resist layer as an insulating layer.
  • a commercially available solder resist may be used, for example, PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.
  • an insulating layer contains resin which has an epoxy group or a (meth) acrylate group.
  • the resin is easily bonded to the above-described silver ion diffusion suppressing layer, and as a result, the adhesion of the insulating layer is improved, and as a result, the silver ion magnation suppressing effect is further improved.
  • the resin is preferably the main component of the insulating layer.
  • the main component means that the total amount of the resin is 50% by mass or more with respect to the total amount of the insulating layer, and is preferably 60% by mass or more. In addition, as an upper limit, it is 100 mass%.
  • a known epoxy resin can be used.
  • a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, or the like can be used.
  • the resin having a (meth) acrylate group a known resin can be used.
  • an acrylate resin or a methacrylate resin can be used.
  • the method for forming the insulating layer on the wiring board is not particularly limited, and a known method can be employed. For example, a method of laminating a film of an insulating layer directly on a wiring substrate, a method of applying a composition for forming an insulating layer containing a component constituting the insulating layer on the wiring substrate, a composition of the wiring substrate for forming the insulating layer The method of immersing in a thing is mentioned.
  • the said composition for insulating layer formation may contain the solvent as needed.
  • positioning this composition on a wiring board you may heat-process in order to remove a solvent as needed.
  • the thickness of the insulating layer to be formed is not particularly limited, and is preferably 5 to 50 ⁇ m and more preferably 10 to 40 ⁇ m from the viewpoint of the insulation reliability between the metal wirings.
  • the insulating layer in the obtained wiring board with an insulating layer may be partially removed by drilling or laser processing, and a semiconductor chip may be mounted and used as a circuit board.
  • a semiconductor chip may be mounted and used as a circuit board.
  • place a mask with a predetermined pattern on the insulating layer apply energy to cure, remove the insulating layer in the non-energy-applied region, and expose the metal wiring
  • the semiconductor chip is mounted on the surface of the metal wiring.
  • metal wiring may be further provided on the obtained insulating layer.
  • the method for forming the metal wiring is not particularly limited, and a known method (plating treatment, sputtering treatment, etc.) can be used.
  • a substrate in which metal wiring is further provided on the insulating layer arranged in the outermost layer in the obtained wiring substrate with insulating layer is used as a new insulating substrate with metal wiring (inner layer substrate).
  • a number of new insulating layers and metal wirings can be stacked.
  • FIG. 4 shows a schematic cross-sectional view of one embodiment of the conductive film stack
  • the conductive film stack 300 includes a transparent substrate 302 and a conductive film 304 containing silver or a silver alloy disposed on the transparent substrate 302. And a transparent double-sided pressure-sensitive adhesive sheet 306 bonded onto the conductive film 304.
  • each member (The transparent substrate 302, the electrically conductive film 304, the transparent double-sided adhesive sheet 306) is explained in full detail.
  • the type of the transparent substrate is not particularly limited as long as it supports a conductive film and a transparent double-sided pressure-sensitive adhesive sheet described later and is a substrate transparent to visible light.
  • a polymer resin is used in addition to glass.
  • the polymer resin include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyether sulfone, polysulfone, polyarylate, cyclic polyolefin, polyimide, and the like.
  • the shape of the transparent substrate is not particularly limited, and examples thereof include a plate shape and a film shape.
  • the thickness of the transparent substrate is not particularly limited, and when the conductive film laminate is applied to a touch panel, the thickness is preferably 0.01 to 3.0 mm, and more preferably 0.05 to 1.5 mm.
  • the transparent substrate preferably has high transparency in the visible light region, and preferably has a total light transmittance of 80% or more.
  • the transparent substrate may have other functional layers such as an undercoat layer.
  • Other functional layers include, for example, matting agent layers, protective layers, solvent resistant layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers. , Antifouling layers, printed layers, and easy-adhesion layers. These may be a single layer or a plurality of layers.
  • the conductive film is disposed on the transparent substrate and mainly contains silver.
  • the conductive film can be used as a transparent electrode or peripheral wiring (lead wiring) of a touch panel when applied to a touch panel.
  • the conductive film may contain a resin component such as a binder or a photosensitive compound as long as the effects of the present invention are not impaired, and may further contain other components as necessary.
  • Silver may be contained in the form of a silver alloy, and when the conductive film contains a silver alloy, examples of the metal contained other than silver include tin, palladium, gold, nickel, and chromium.
  • the pattern shape of the conductive film is not particularly limited, and as shown in FIG.
  • a wiring shape (patterned conductive film) (in other words, provided as a conductive thin wire). Or may be provided over the entire surface.
  • the pattern shape may be an arbitrary pattern such as a stripe shape.
  • the amount of silver contained per unit area of the conductive film is 50 ⁇ g / mm 2 or less.
  • amount of silver is preferably at 30 [mu] g / mm 2 or less, more preferably 15 [mu] g / mm 2 or less.
  • 0.001 microgram / mm ⁇ 2 > or more is preferable and 0.005 microgram / mm ⁇ 2 > or more is more preferable at the point which the electroconductivity of a electrically conductive film is more excellent.
  • 0.001 microgram / mm ⁇ 2 > or more is preferable and 0.005 microgram / mm ⁇ 2 > or more is more preferable at the point which the electroconductivity of a electrically conductive film is more excellent.
  • the measuring method in particular of silver amount is not restrict
  • the amount of silver can be measured by observing a cross-sectional SEM photograph of the conductive film and conducting elemental analysis.
  • the amount of silver can be measured from the dissolved amount by bringing the conductive film into contact with a strong acid such as nitric acid to dissolve the silver in the conductive film.
  • the amount of silver in the conductive film is obtained by calculation from the amount of the dispersion used to produce the conductive film. You can also.
  • per unit area of the conductive film means per unit area of the contact portion of the conductive film with the transparent substrate. That is, the amount of silver is calculated based only on the area of the contact portion between the conductive film and the transparent substrate.
  • the area of the transparent substrate surface that is not in contact with the conductive film is the area of the conductive film. It is not taken into consideration in the calculation per unit area. Therefore, the amount of silver contained per unit area of the conductive film means the amount of silver contained per unit area (mm 2 ) at the contact portion between the conductive film and the transparent substrate.
  • the thickness of the conductive film is not particularly limited, but is preferably 0.05 to 100 ⁇ m, more preferably 0.1 to 20 ⁇ m, and still more preferably 0.1 to 10 ⁇ m from the viewpoint of application of the conductive film laminate to a touch panel.
  • the conductive film is applied as a transparent electrode of a touch panel, it is preferable to have high transparency in the visible light region, and it is preferable that the total light transmittance is 80% or more.
  • the width of the conductive film is not particularly limited. However, from the viewpoint of application of the conductive film laminate to the touch panel, 0.1 to 100,000 ⁇ m is preferable, and 1 to 20000 ⁇ m is more preferable. It is preferably 1 to 10,000 ⁇ m, more preferably 10 to 300 ⁇ m.
  • the distance between the conductive films is not particularly limited, but from the viewpoint of application of the conductive film laminate to the touch panel, 0.1 to 500 ⁇ m is preferable in the narrowest part. .1 to 100 ⁇ m is more preferable, and 0.1 to 20 ⁇ m is particularly preferable from the viewpoint of visibility.
  • the method for forming the conductive film is not particularly limited, and a physical film formation method such as a vapor deposition method or a sputtering method, or a chemical vapor phase method such as a CVD method, or a silver paste containing silver nanoparticles or silver nanowires is applied. And a method using a silver salt disclosed in JP2009-188360A.
  • the conductive film When the conductive film is applied as a transparent electrode such as a touch panel, the conductive film preferably contains a metal nanowire made of silver or a silver alloy (hereinafter also simply referred to as a metal nanowire). By using this metal nanowire, a conductive film can be formed at a low temperature, and a transparent electrode having high transmittance and low resistance can be provided.
  • a metal nanowire made of silver or a silver alloy
  • the metal nanowire is composed of silver or a silver alloy.
  • the kind of silver alloy is as above-mentioned.
  • the metal nanowire has conductivity and has a shape in which the length in the major axis direction is sufficiently longer than the diameter (length in the minor axis direction). It may be a solid fiber or a hollow fiber.
  • the material of the metal nanowire is particularly preferably silver or an alloy of silver and another metal in terms of excellent conductivity.
  • Other metals used in the alloy with silver include platinum, osmium, palladium, iridium, tin, bismuth, nickel and the like. These may be used alone or in combination of two or more.
  • the average minor axis length (sometimes referred to as “average minor axis diameter” or “average diameter”) of the metal nanowire is preferably 5 to 50 nm, more preferably 5 to 25 nm, and particularly preferably 5 to 20 nm.
  • the average minor axis length is less than 5 nm, the oxidation resistance may deteriorate and the durability may deteriorate.
  • the average minor axis length exceeds 50 nm, the scattering of the metal nanowires increases, and the haze value of the conductive film may increase.
  • the average minor axis length by setting the average minor axis length to 25 nm or less, the scattering of the metal nanowires can be reduced, and the haze value of the conductive film is greatly improved (reduced).
  • a touch panel using a conductive film having a small haze can eliminate the pattern appearance (bone appearance) of the conductive film and improve the visibility of the touch panel.
  • the average minor axis length of the metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX) and calculating the average minor axis length of the metal nanowires from the average value. I ask for it.
  • the short axis length when the short axis of the metal nanowire is not circular is the shortest axis.
  • the average major axis length of the metal nanowire (sometimes referred to as “average length”) is preferably 5 ⁇ m or more, more preferably 5 ⁇ m to 40 ⁇ m, and even more preferably 5 ⁇ m to 30 ⁇ m. If the average major axis length is less than 5 ⁇ m, it is difficult to form a dense network, and sufficient conductivity may not be obtained. If it exceeds 40 ⁇ m, metal nanowires are too long and become entangled during production. In the manufacturing process, agglomerates may occur.
  • the average major axis length of the metal nanowire is, for example, observed with 300 transmission nanoscopes using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX), and the average length of the metal nanowires from the average value. Find the shaft length.
  • TEM transmission electron microscope
  • JEM-2000FX transmission electron microscope
  • the method for producing the metal nanowire is not particularly limited and may be produced by any method, but it is preferably produced by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved.
  • a method for producing metal nanowires JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, JP2010-86714A, The method described in JP-T-2009-505358 can be used.
  • the aspect ratio of the metal nanowire can be appropriately selected according to the purpose, but is not particularly limited as long as it is 10 or more, more preferably 50 or more, further preferably 100 or more, further preferably 5000 or more, and from 10,000 100,000 is particularly preferred.
  • the aspect ratio generally means the ratio between the long side and the short side of the fibrous material (ratio of average major axis length / average minor axis length).
  • a measuring method of an aspect ratio According to the objective, it can select suitably, For example, the method etc. which measure with an electron microscope etc. are mentioned.
  • the aspect ratio of the whole metal nanowire can be estimated by separately measuring the average major axis length and the average minor axis length of the metal nanowire.
  • the outer diameter of the tube is used as the diameter for calculating the aspect ratio.
  • a method for forming a conductive film containing metal nanowires made of silver or a silver alloy is not particularly limited, and together with the metal nanowires, as a matrix component, (1) a photosensitive composition containing at least a binder and a photopolymerizable composition, It is preferable to use a composition containing at least (2) a sol-gel cured product or (3) a composition containing at least a polymer.
  • the mass ratio of the mass of the matrix component (all components excluding the metal nanowire and the solvent contained in the conductive film) to the mass of the metal nanowire is 0.5 to 15 (more preferably 1.0 to 12, Particularly preferred is 2.0 to 10).
  • the mass ratio is less than 0.5, the binder component is small, the adhesion of the metal nanowires to the substrate surface is weak, and the film strength may be weak.
  • the mass ratio exceeds 15, the surface resistance value of the conductive film May rise.
  • the binder is a linear organic high molecular polymer, and at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) (for example, it can be appropriately selected from alkali-soluble resins having a carboxyl group, a phosphoric acid group, a sulfonic acid group, and the like. Among these, those that are soluble in an organic solvent and soluble in an aqueous alkali solution are preferable, and those that have an acid-dissociable group and become alkali-soluble when the acid-dissociable group is dissociated by the action of an acid are particularly preferable. preferable.
  • the acid dissociable group represents a functional group that can dissociate in the presence of an acid.
  • a known radical polymerization method can be applied for the production of the binder.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent and the like when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. be able to.
  • a polymer having a carboxylic acid in the side chain is preferable.
  • the polymer having a carboxylic acid in the side chain include, for example, As described in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial ester Maleic acid copolymers, acidic cellulose derivatives having a carboxylic acid in the side chain, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and a polymer having a (meth) acryloyl group in the side chain Are also preferred.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly preferable.
  • a high molecular polymer having a (meth) acryloyl group in the side chain and a multi-component copolymer composed of (meth) acrylic acid / glycidyl (meth) acrylate / other monomers are also useful.
  • the polymer can be used by mixing in an arbitrary amount.
  • linear organic polymer 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2- Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macro And monomer / benzyl methacrylate / methacrylic acid copolymer.
  • (meth) acrylic acid and other monomers copolymerizable with the (meth) acrylic acid are suitable.
  • Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds, and the like. In these, the hydrogen atom of the alkyl group and aryl group may be substituted with a substituent.
  • Examples of the alkyl (meth) acrylate or aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth).
  • the weight average molecular weight of the binder is preferably from 1,000 to 500,000, more preferably from 3,000 to 300,000, and even more preferably from 5,000 to 200,000, from the viewpoints of alkali dissolution rate, film physical properties and the like.
  • the weight average molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.
  • the content of the binder is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, and 20 to 80% by mass based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowires. Further preferred. Within the above range, both developability and conductivity of the metal nanowire can be achieved.
  • the photopolymerizable composition means a composition that imparts a function of forming an image by exposure to the conductive film or gives the trigger for the function.
  • the basic component includes (a) an addition-polymerizable unsaturated compound and (b) a photopolymerization initiator that generates radicals when irradiated with light.
  • the addition polymerizable unsaturated compound of component (a) (hereinafter also referred to as “polymerizable compound”) is polymerized by causing an addition polymerization reaction in the presence of a radical.
  • a compound having at least one, more preferably two or more, more preferably four or more, and still more preferably six or more ethylenically unsaturated double bonds at the molecular terminals is used.
  • the These have chemical forms such as monomers, prepolymers, ie dimers, trimers or oligomers, or mixtures thereof.
  • Various kinds of such polymerizable compounds are known, and they can be used as the component (a).
  • particularly preferred polymerizable compounds are trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) from the viewpoint of film strength.
  • Acrylate is particularly preferred.
  • the content of the component (a) is preferably 2.6 to 37.5% by mass based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowire, and is preferably 5.0 to 20%. More preferably, it is 0.0 mass%.
  • the photopolymerization initiator of component (b) is a compound that generates radicals when irradiated with light.
  • the photopolymerization initiator include a compound that generates an acid radical that finally becomes an acid upon irradiation with light, or a compound that generates another radical.
  • the former is referred to as “photoacid generator”, and the latter is referred to as “photoradical generator”.
  • Photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, irradiation with actinic rays or radiation used in microresists, etc.
  • photoinitiators for photocationic polymerization photoinitiators for photoradical polymerization
  • photodecolorants for dyes photochromic agents, irradiation with actinic rays or radiation used in microresists, etc.
  • known compounds that generate acid radicals and mixtures thereof can be appropriately selected and used.
  • Such a photoacid generator is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a triazine having at least one di- or tri-halomethyl group 1,3,4-oxadiazole Naphthoquinone-1,2-diazido-4-sulfonyl halide, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, o-nitrobenzyl sulfonate, and the like.
  • imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate which are compounds that generate sulfonic acid
  • imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate which are compounds that generate sulfonic acid
  • a compound in which a group or a compound that generates an acid radical upon irradiation with actinic rays or radiation is introduced into the main chain or side chain of the resin for example, US Pat. No. 3,849,137, German Patent No. 3914407.
  • JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 The compounds described in JP-A-63-146029, etc. can be used. Furthermore, compounds described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used as an acid radical generator.
  • triazine compound for example, compounds described in JP2011-018636A and JP2011-254046A can be used.
  • the photoacid generators compounds that generate sulfonic acid are preferable, and the following oxime sulfonate compounds are particularly preferable from the viewpoint of high sensitivity.
  • the photoacid generator When a compound having a 1,2-naphthoquinonediazide group is used as the photoacid generator, high sensitivity and good developability are obtained.
  • the photoacid generators the following compounds in which D is independently a hydrogen atom or a 1,2-naphthoquinonediazide group are preferred from the viewpoint of high sensitivity.
  • the photoradical generator is a compound having a function of generating radicals by directly absorbing or photosensitizing light to cause a decomposition reaction or a hydrogen abstraction reaction.
  • the photo radical generator is preferably one having absorption in a wavelength region of 300 nm to 500 nm.
  • a large number of compounds are known as such photo radical generators. For example, triazine compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds as described in JP-A-2008-268884 are known.
  • Organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, and acylphosphine (oxide) compounds can be appropriately selected according to the purpose.
  • a benzophenone compound, an acetophenone compound, a hexaarylbiimidazole compound, an oxime ester compound, or an acylphosphine (oxide) compound is particularly preferable from the viewpoint of exposure sensitivity.
  • photoradical generator for example, photoradical generators described in JP2011-018636A and JP2011-254046A can be used.
  • a photoinitiator may be used individually by 1 type and may use 2 or more types together,
  • the content is 0 on the basis of the total mass of solid content of the photopolymerizable composition containing metal nanowire. 1 to 50% by mass is preferable, 0.5 to 30% by mass is more preferable, and 1 to 20% by mass is still more preferable. In such a numerical range, when a pattern including a conductive region and a non-conductive region described later is formed on the conductive film, good sensitivity and pattern formability can be obtained.
  • additives other than the above components include, for example, chain transfer agents, crosslinking agents, dispersants, solvents, surfactants, antioxidants, sulfurization inhibitors, metal corrosion inhibitors, viscosity modifiers, preservatives, and the like. Various additives are mentioned.
  • Chain transfer agent The chain transfer agent is used for improving the exposure sensitivity of the photopolymerizable composition.
  • chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoic acid.
  • the content of the chain transfer agent is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowires described above. More preferably, it is 0.5 to 5% by mass.
  • the crosslinking agent is a compound that forms a chemical bond by free radical, acid, or heat, and cures the conductive film, and is substituted with at least one group selected from, for example, a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
  • an epoxy compound, an oxetane compound, and a compound having an ethylenically unsaturated group are particularly preferable in terms of film properties, heat resistance, and solvent resistance.
  • oxetane resin can be used individually by 1 type or in mixture with an epoxy resin.
  • the crosslinking agent when used in combination with an epoxy resin, the reactivity is high, which is preferable from the viewpoint of improving film properties.
  • the crosslinking agent is also included in the polymerizable compound, and the content thereof is included in the content of the polymerizable compound in the present invention. Should be considered.
  • the content of the cross-linking agent is preferably 1 to 250 parts by mass, and more preferably 3 to 200 parts by mass when the total mass of the solid content of the photopolymerizable composition containing the metal nanowire is 100 parts by mass.
  • Dispersing agent is used in order to disperse
  • the dispersant is not particularly limited as long as the metal nanowires can be dispersed, and can be appropriately selected depending on the purpose.
  • a commercially available dispersant can be used as a pigment dispersant, and a polymer dispersant having a property of adsorbing to metal nanowires is particularly preferable.
  • polymer dispersant examples include polyvinyl pyrrolidone, BYK series (manufactured by Big Chemie), Solsperse series (manufactured by Nippon Lubrizol Co., Ltd.), and Ajisper series (manufactured by Ajinomoto Co., Inc.).
  • the polymer dispersant is also included in the binder, and the content thereof is It should be considered that it is included in the content.
  • the content of the dispersant is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, and particularly preferably 1 to 30 parts by mass with respect to 100 parts by mass of the binder.
  • the solvent is a component used to form a coating liquid for forming a composition containing the metal nanowire and the photopolymerizable composition on the surface of the substrate in the form of a film, and is appropriately selected depending on the purpose. can do.
  • the solvent is a component used to form a coating liquid for forming a composition containing the metal nanowire and the photopolymerizable composition on the surface of the substrate in the form of a film, and is appropriately selected depending on the purpose. can do.
  • propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol
  • water 1-methoxy-2-propanol
  • isopropyl acetate methyl lactate N-methylpyrrolidone (NMP), ⁇ -butyrolactone (GBL), propylene carbonate, and the like.
  • This solvent may also serve as at least a part of the solvent of the metal nanowire dispersion described above. These may be used individually by 1 type and may use 2 or more types together.
  • the solid content concentration of the coating solution containing such a solvent is preferably contained in the range of 0.1 to 20% by mass.
  • Metal corrosion inhibitor It is preferable to contain a metal corrosion inhibitor for metal nanowires.
  • a metal corrosion inhibitor for metal nanowires There is no restriction
  • the metal corrosion inhibitor should be added to the composition for forming the photosensitive layer by dissolving it in a suitable solvent, or by adding powder, or by immersing it in a metal corrosion inhibitor bath after preparing the conductive film. Can do.
  • a metal corrosion inhibitor is added, it is preferably contained in an amount of 0.5 to 10% by mass with respect to the metal nanowires.
  • the other matrix it is possible to use, as at least a part of the components constituting the matrix, a polymer compound as a dispersant used in the production of the metal nanowire described above.
  • a composition containing at least a sol-gel cured product as a matrix component can be used together with the metal nanowires.
  • cured material is explained in full detail.
  • sol-gel cured product (Sol-gel cured product)
  • the sol-gel cured product is obtained by hydrolyzing and polycondensing an alkoxide compound of an element selected from the group consisting of Si, Ti, Zr and Al (hereinafter also referred to as “specific alkoxide compound”), and further heating and drying as desired. Is obtained.
  • the specific alkoxide compound is preferably a compound represented by the following general formula (X) because it is easily available.
  • M 1 (OR 20 ) a R 21 4-a (X)
  • M 1 represents an element selected from Si, Ti and Zr
  • R 20 and R 21 each independently represents a hydrogen atom or a hydrocarbon group, and a represents an integer of 2 to 4) Show.
  • Each hydrocarbon group of R 20 and R 21 in the general formula (X) is preferably an alkyl group or an aryl group.
  • the carbon number in the case of showing an alkyl group is preferably 1 to 18, more preferably 1 to 8, and still more preferably 1 to 4.
  • a phenyl group is preferable.
  • the alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, an alkylamino group, and a mercapto group.
  • the compound represented by the general formula (X) is a low molecular compound, and preferably has a molecular weight of 1000 or less.
  • the ratio of the specific alkoxide compound to the metal nanowire is in the range of 0.25 / 1 to 30/1. It is preferably used.
  • the mass ratio is smaller than 0.25 / 1, the transparency is inferior, and at the same time, at least one of the wear resistance, heat resistance, moist heat resistance and flex resistance becomes a conductive film,
  • the mass ratio is larger than 30/1, a conductive film having poor conductivity and bending resistance is obtained.
  • the mass ratio is more preferably in the range of 0.5 / 1 to 20/1, more preferably in the range of 1/1 to 15/1, and most preferably in the range of 2/1 to 8/1.
  • High conductivity and high transparency It is preferable because it can stably obtain a conductive material having high properties (total light transmittance and haze), excellent wear resistance, heat resistance and moist heat resistance, and excellent flex resistance.
  • the conductive film can be formed using a composition containing at least a polymer as a matrix component together with the metal nanowires.
  • a composition containing at least a polymer as a matrix component together with the metal nanowires will be described in detail.
  • Synthetic polymers and natural polymers are included as polymers, and synthetic polymers include polyester, polyimide, polyacryl, polyvinylon, polyethylene, polypropylene, polystyrene, polyvinyl chloride, methacrylic acid resin, fluorine resin, and phenol resin. , Melamine resin, silicone resin, synthetic rubber, and latex of these.
  • natural polymers include cellulosic resins and natural rubber.
  • a protective layer made of a protective coating material may be provided on the conductive film.
  • a protective coating material for forming the protective layer for example, those described in JP2011-167848A can be applied.
  • Protective coating materials include crosslinkers, polymerization initiators, stabilizers (eg, antioxidants and UV stabilizers for prolonging product life, and polymerization inhibitors for improving shelf life), surfactants, and the like You may include what has a special effect.
  • the protective coating material may further include a corrosion inhibitor that prevents corrosion of the metal nanowires.
  • the method for forming the protective layer is not particularly limited as long as it is a known wet coating method. Specifically, spray coating, bar coating, roll coating, die coating, ink jet coating, screen coating, dip coating and the like can be mentioned.
  • the protective layer When forming the protective layer while impregnating the transparent conductive film with the protective layer coating, if the film thickness of the protective layer after application and drying is too thin relative to the conductive film before application, scratch resistance, abrasion resistance, The function as a protective layer such as weather resistance is reduced, and if it is too thick, the contact resistance as a conductor increases.
  • the film thickness after coating and drying is preferably 30 to 150 nm.
  • the surface resistivity, haze, and the like can be adjusted to achieve predetermined values.
  • 40 to 175 nm is more preferable, and 50 to 150 nm is particularly preferable.
  • the film thickness after drying of the coating material for the protective layer depends on the film thickness of the transparent conductive film, the protective function by the protective layer tends to work better when the film thickness is 30 nm or more, and the film thickness is 150 nm or less. When it is, it exists in the tendency which can ensure more favorable electroconductive performance.
  • the conductive film may be patterned into a desired shape depending on the application.
  • the method for patterning the conductive film is not particularly limited.
  • the conductive film is exposed and developed. More specifically, it includes a pattern exposure step and a development step, and further includes other steps as necessary.
  • the matrix of the conductive film is non-photosensitive, it is preferably patterned by the following methods (1) to (2).
  • a photoresist layer is provided on the conductive film, and a desired pattern exposure and development are performed on the photoresist layer to form the patterned resist (etching mask material), and then the conductive film can be etched.
  • a patterning method in which a conductive film in a region not protected by a resist is etched to be disconnected or lost by a wet process in which an etching solution is used or a dry process such as reactive ion etching. This method is described, for example, in JP-T-2010-507199 (particularly, paragraphs 0212 to 0217).
  • a photo-curing resin is provided on a pattern in a desired region on the conductive film by an ink jet method or a screen printing method, and the photo-curing resin layer is subjected to a desired exposure to form a resist (etching)
  • etching A patterning method in which, after forming a mask material, the conductive film is immersed in an etchant that can be etched or the etchant is showered to disconnect or disappear the conductive film in a region that is not protected by the resist.
  • the coating method is not particularly limited, and examples thereof include roll coating, bar coating, dip coating, spin coating, casting, die coating, blade coating, bar coating, gravure coating, curtain coating, and spray. Examples thereof include a coating method and a doctor coating method. Examples of printing methods include letterpress (letterpress) printing, stencil (screen) printing, lithographic (offset) printing, and intaglio (gravure) printing.
  • the resist layer formed in this step may be a positive resist layer or a negative resist layer.
  • the pattern-shaped exposed region is solubilized, and a patterned resist layer is formed in the unexposed region (unsolubilized region).
  • the exposed region is A cured resist layer is formed, and by application of the solution, the unexposed portion, that is, the uncured portion of the resist layer is removed, and a patterned resist layer is formed.
  • the type of the resist layer forming material used in the method (1) is not particularly limited, and any of a negative type, a positive type and a dry film type can be used.
  • a commercially available alkali-soluble photoresist can be appropriately selected and used.
  • Fujifilm Color Mosaic Series, FILS Series, FIOS Series, FMES Series, FTENS Series, FIES Series, Positive Type for Semiconductor Processes, Negative Photoresist Series, Fuji Chemical Fujiresist Series, Above all, FR Series, FPPR Series, FMR series, FDER series, etc. can be used preferably.
  • AZ Electronic Materials photoresist series among them, RFP series, TFP series, SZP series, HKT series, SFP, series, SR series, SOP series, SZC series, CTP series, ANR series, P4000 series, TPM606, 40XT, nXT series, etc. are preferably mentioned.
  • As dry film resists Hitachi Chemical, photosensitive film for printed wiring boards, Asahi Kasei E-materials photosensitive dry film SUNFORT series, DuPont MRC dry film FXG series, FXR series, FX900 series, JSF100 series, SA100 series , LDI series, FRA series, CM series, FUJIFILM Transer series, etc., which can be used as appropriate.
  • These resist layer forming materials may be appropriately selected according to the resolution of the pattern formed in the conductive film.
  • a photosensitive resist layer of a dry film resist prepared in advance may be transferred to the surface of the formed conductive film.
  • exposure is performed at an oxygen concentration of 5% or less using an etching mask material containing a photopolymerization initiator.
  • the conductive film may be patterned on the target substrate by transfer using a transfer material. Further, as described in JP 2011-167848 A, [0147] to [0148], a conductive film can be patterned by applying a remover (etching solution) on the conductive film by screen printing. Is possible.
  • the transparent double-sided PSA sheet is a sheet that is transparent and has adhesiveness on the front and back surfaces.
  • the sheet is laminated on the conductive film so that one of the adhesive surfaces is attached to the conductive film.
  • the transparent double-sided PSA sheet is attached to the conductive film side of a transparent substrate with a conductive film having a transparent substrate and a conductive film disposed thereon.
  • the transparent double-sided pressure-sensitive adhesive sheet 306 is placed on the conductive film 304 so that the front surface 306 c and the back surface 306 d of the transparent double-sided pressure-sensitive adhesive sheet 306 exhibit adhesiveness, Be placed.
  • the transparent double-sided pressure-sensitive adhesive sheet only needs to have at least a pressure-sensitive adhesive layer, and may be a type having a base material in which the pressure-sensitive adhesive layer is disposed on both sides of the base material (transparent double-sided pressure-sensitive adhesive sheet with a base material) It may be of a type consisting only of an adhesive layer and having no substrate (baseless transparent double-sided pressure-sensitive adhesive sheet). Of these, a substrate-less transparent double-sided pressure-sensitive adhesive sheet is preferable from the viewpoint of thinning a product using the transparent double-sided pressure-sensitive adhesive sheet.
  • the transparent double-sided PSA sheet contains the reducing compound described above.
  • the preferred embodiment of the reducing compound contained is as described above.
  • the transparent double-sided pressure-sensitive adhesive sheet is a transparent double-sided pressure-sensitive adhesive sheet with a substrate
  • the reducing compound may be contained in either the substrate or the pressure-sensitive adhesive layer. It may be included.
  • the conductive film laminate was left in a high-temperature and high-humidity environment because the dispersibility of the reducing compound in the adhesive is more excellent. Even if it is a case, the fall of the adhesive force of an adhesive layer is not seen.
  • the content of the reducing compound in the transparent double-sided pressure-sensitive adhesive sheet is not particularly limited, but the mass ratio (A / C) of the total mass A of the reducing compound and the total mass C of the transparent resin is the inside of the transparent resin of the reducing compound.
  • the precipitation of the sheet is further suppressed and the transparency of the sheet is more excellent, the precipitation of the reducing compound in the vicinity of the sheet surface is further suppressed, the adhesion between the sheet and the adherend is further improved, and the electrical reliability is further improved. From the point of improvement, 0.20 or less is preferable, and 0.10 or less is more preferable.
  • total mass A represents those total mass, when two or more types of reducing compounds are contained.
  • the total mass C represents the total mass thereof.
  • the thickness of the transparent double-sided PSA sheet is not particularly limited, and is preferably 5 to 150 ⁇ m and more preferably 20 to 100 ⁇ m from the viewpoint of application of the conductive film laminate to a touch panel.
  • the thickness of the transparent double-sided pressure-sensitive adhesive sheet 20 ⁇ m or more it is possible to cover the steps and irregularities of the substrate to be attached, and by making the thickness 100 ⁇ m or less, it is possible to sufficiently secure the transmittance of the transparent double-sided pressure-sensitive adhesive sheet. can get.
  • the adhesive layer is provided on both sides of the substrate.
  • the type of substrate used is not particularly limited, but it is preferable to use a transparent substrate.
  • the transparent substrate for example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film , Fluorine resin film, nylon film, acrylic It can be exemplified a resin
  • the material of the pressure-sensitive adhesive layer of the transparent double-sided pressure-sensitive adhesive sheet is not particularly limited, and known materials can be used.
  • various transparent resin pressure sensitive adhesives such as rubber pressure sensitive adhesive, acrylic pressure sensitive adhesive, silicone pressure sensitive adhesive, urethane pressure sensitive adhesive, etc. can be used, but the transparency is more excellent and the compatibility with the reducing compound is more.
  • An acrylic pressure-sensitive adhesive is preferred from the viewpoint of superiority.
  • the acrylic adhesive is based on an acrylic polymer having a main skeleton of an alkyl (meth) acrylate monomer unit.
  • (Meth) acrylate refers to acrylate and / or methacrylate.
  • the average carbon number of the alkyl group of the alkyl (meth) acrylate constituting the main skeleton of the acrylic polymer is preferably about 1 to 12, and specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like.
  • the transparent double-sided PSA sheet has a total light transmittance of 80% or more (more preferably 85% or more, more preferably 90% or more) immediately after standing at 60 ° C. and 90% RH for 100 hours, and a haze of 1 It is preferably 0.0% or less (more preferably 0.7% or less).
  • the water absorption of the transparent double-sided PSA sheet is 2.0% or less (more preferably 1.25% or less, more preferably 1.0% or less) after 100 hours of static value at 60 ° C. and 90% RH. ) Is preferable.
  • the method for measuring the water absorption rate is in accordance with the method described in JP2012-11637A.
  • the said transparent double-sided adhesive sheet can be manufactured by a well-known method.
  • a pressure-sensitive adhesive composition containing a reducing compound on a separator (release liner) is applied so that the thickness after drying becomes a predetermined thickness.
  • the coating layer is dried and cured as necessary to form a pressure-sensitive adhesive layer, whereby a transparent double-sided PSA sheet can be produced.
  • a pressure-sensitive adhesive composition containing a reducing compound may be directly applied to the substrate surface and dried to provide a pressure-sensitive adhesive layer (direct copying method).
  • the pressure-sensitive adhesive layer may be provided on the substrate by transferring (bonding) to the substrate (transfer method).
  • the method of apply coating an adhesive composition to the base-material surface containing a reducing compound, providing an adhesive layer, and manufacturing a transparent double-sided adhesive sheet with a base material is also mentioned, for example.
  • the conductive film 304 and the transparent double-sided pressure-sensitive adhesive sheet 306 are provided on one surface of the transparent substrate 302, but the embodiment is not limited thereto.
  • conductive films 304a and 304b and transparent double-sided pressure-sensitive adhesive sheets 306a and 306b may be provided on both surfaces of the transparent substrate 302 as in a conductive film laminate 400 shown in FIG.
  • the pattern shapes of both may be different.
  • the conductive films 304a and 304b are both thin lines, and are disposed so as to be orthogonal to each other.
  • the conductive film laminate according to the first aspect of the present invention includes a transparent substrate, a conductive film containing silver disposed on the transparent substrate, and a transparent double-sided pressure-sensitive adhesive sheet bonded to the conductive film. . If necessary, another member (for example, a protective substrate described later) may be bonded to the exposed surface of the transparent double-sided PSA sheet.
  • a conductive film laminated body is a touch panel, a display electrode, an electromagnetic wave shield, an organic or inorganic EL display electrode, an electronic paper, a flexible display electrode, an integrated solar cell, for example. It is widely applied to display devices and other various devices. Among these, the lead wiring part of the touch panel is particularly preferable. Below, the aspect of the lead wiring part of a touchscreen is explained in full detail.
  • FIG. 6A is a schematic plan view of a part of the touch panel member
  • FIG. 6B is a schematic cross-sectional view taken along the line AA.
  • a touch panel member 500 illustrated in FIG. 6A includes a touch panel conductive film stack 600 and a flexible circuit 30 that is bonded to a predetermined position of the touch panel conductive film stack 600.
  • the conductive film laminate 600 for a touch panel is provided with a transparent electrode layer 34 (for example, an ITO layer or a silver-containing layer) and a transparent double-sided pressure-sensitive adhesive sheet 42 on one surface side of the transparent substrate 32.
  • the transparent electrode layer 34 is formed in a pattern in which a plurality of diamond shapes aligned on the transparent substrate 32 are linearly connected in one direction.
  • the transparent electrode layer 34 is provided with a plurality of lead wires 36 that are electrically connected.
  • a conductor (not shown) is provided at the end of the lead wiring 36 and is electrically connected to a terminal (not shown) in the flexible circuit 30.
  • the transparent substrate 32 includes an active area 38 that functions as a sensing unit (sensor unit) that can be visually recognized by a touch panel user and can detect a touch position in an area where the transparent electrode layer 34 is provided.
  • the outside is an inactive area 40.
  • the frame portion of the touch panel corresponds to the inactive area 40.
  • the lead wiring 36 and the flexible circuit 30 exist in the inactive area 40 as described above.
  • the transparent double-sided pressure-sensitive adhesive sheet 42 By disposing the transparent double-sided pressure-sensitive adhesive sheet 42 on the lead wiring 36 so as to cover the lead wiring 36, disconnection of the lead wiring 36 and short-circuiting between the lead wirings 36 can be further suppressed.
  • one of the preferred embodiments of the conductive film laminate is a transparent substrate, an electrode pattern portion that is disposed on the transparent substrate and functions as a sensor, the electrode of the electrode pattern portion is connected to one end on the transparent substrate, and the other
  • a conductive film laminate for a touch panel having a terminal wiring portion made of a lead wiring containing silver and having an end connected to a terminal connected to an external control circuit, and at least the transparent double-sided pressure-sensitive adhesive sheet disposed on the lead wiring Is mentioned.
  • the amount of silver contained per unit area of the lead wiring is 50 ⁇ g / mm 2 or less, and the transparent double-sided PSA sheet contains the above-described transparent resin and reducing compound.
  • the transparent adhesive layer which shows a predetermined characteristic by the environmental test mentioned later is easy to interact with a water
  • ion migration suppression ability and whitening resistance which have conventionally been in a trade-off relationship, at a higher level.
  • the compound is a phenol compound
  • the hydroxyl group in the compound easily interacts with the material (adhesive) constituting the transparent adhesive layer, and the dispersibility in the transparent adhesive layer is more excellent.
  • ion migration suppression ability and whitening resistance can be achieved at a higher level.
  • the transparent adhesive sheet includes at least a compound having an oxidation-reduction potential of 0.40 to 1.30 V and a transparent adhesive layer containing the adhesive.
  • a transparent adhesion layer containing the adhesive.
  • the transparent adhesive layer of the transparent adhesive sheet contains a compound having a redox potential of 0.40 to 1.30 V (hereinafter also referred to as a reducing compound as appropriate).
  • This reducing compound is a so-called migration inhibitor (migration inhibitor), and when this reducing compound is contained in the transparent adhesive layer, the silver ions in the transparent adhesive layer are reduced to metallic silver, thereby causing ion migration. Suppress.
  • the redox potential of the reducing compound is 0.40 to 1.30 V, and in particular, 0.50 to 1.20 V is preferable, and 0.55 to 1.1 V is more preferable in that the ion migration suppressing ability is more excellent. 0.55 to 1.0 V is more preferable.
  • the measuring method of the oxidation-reduction potential of the reducing compound used in the second aspect of the present invention can be measured by methods described in many literatures, in the present invention, the value measured by the following method Is defined as a redox potential.
  • a redox potential After bubbling Ar for 5 minutes in a DMF solution containing 1 mM of reducing compound and tetrabutylammonium perchlorate as a supporting electrolyte, cyclic voltammetry was performed with a potentiostat (ALS-604A). Measure.
  • Working electrode Glassy Carbon
  • counter electrode Pt
  • reference electrode redox potential when using saturated calomel electrode is measured.
  • the type of the reducing compound is not particularly limited as long as it satisfies the oxidation-reduction potential, and examples thereof include phenol compounds, amine compounds, sulfur compounds, and phosphorus compounds. Since the reducing compound in the second aspect of the present invention is oxidized instead of being oxidized if the oxidation-reduction potential is within a specified range, the intended effect can be obtained. Especially, a phenol compound is preferable at the point which is excellent in the dispersibility in a transparent adhesion layer, and is more excellent in ion migration suppression ability. More specifically, since the pressure-sensitive adhesive layer exhibits a relatively hydrophilic property, the hydroxyl group in the phenol compound tends to form an interaction with the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. Dispersibility is excellent, and as a result, ion migration suppression ability is improved.
  • the type of phenol compound is not particularly limited as long as the above redox potential is satisfied, and examples thereof include DL- ⁇ -tocopherol.
  • Preferable embodiments of the phenol compound include compounds represented by the following formulas (1A) to (3A). If it is this compound, it is excellent in compatibility with an adhesive and it is excellent in ion migration suppression ability.
  • R 11a to R 15a each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
  • the hydrocarbon group include —O—R 31a .
  • R 31a represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. When there are a plurality of —O—R 31a , they may be the same or different.
  • the number of carbon atoms of the hydrocarbon group is preferably 1 to 12 and more preferably 1 to 10 in terms of excellent compatibility with the pressure-sensitive adhesive. More specifically, examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the total molecular weight of each group of R 11a to R 15a is 21 or more. Especially, 35 or more are preferable.
  • the upper limit is not particularly limited, but is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less, from the viewpoint that the effects of the present invention are more excellent.
  • the sum of the molecular weights of the above groups is intended to be a value obtained by calculating the molecular weights of the respective groups of R 11a to R 15a and summing them. Further, any two of R 11a to R 15a may be bonded to each other to form a ring.
  • two adjacent groups such as R 11a and R 12a , R 12a and R 13a , R 13a and R 14a , or R 14a and R 15a may be bonded to form a ring.
  • the type of ring formed is not particularly limited, and examples thereof include a 5- to 6-membered ring structure.
  • the kind of the hetero atom contained in the hydrocarbon group is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom.
  • a halogen atom an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom.
  • Y 1 to Y 4 are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Of these, an oxygen atom and a sulfur atom are preferred because they are easier to handle.
  • t represents an integer of 1 to 3.
  • R 11a and R 15a each independently preferably represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom.
  • the number of carbon atoms of the hydrocarbon group is preferably 1 to 8 and more preferably 1 to 4 in terms of excellent compatibility with the pressure-sensitive adhesive.
  • the hydrocarbon group that may contain an oxygen atom includes an aliphatic hydrocarbon group that may contain an oxygen atom, an aromatic hydrocarbon group that may contain an oxygen atom, or these The group which combined these is mentioned.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the hydrocarbon group may contain an oxygen atom.
  • R 12a and R 14a each independently preferably represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom.
  • the number of carbon atoms of the hydrocarbon group is preferably 2 to 9 and more preferably 3 to 8 in view of excellent compatibility with the pressure-sensitive adhesive.
  • R 13a preferably represents a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom (for example, —O—R a ).
  • R a represents a hydrocarbon group having 1 to 20 carbon atoms.
  • the number of carbon atoms of the hydrocarbon group represented by R 13a and R a is preferably 1 to 18 and more preferably 1 to 15 in terms of excellent compatibility with the pressure-sensitive adhesive.
  • R 11a to R 15a may be bonded to each other to form a ring. That is, any two of R 11a to R 15a may be bonded to each other to form a ring.
  • two adjacent groups such as R 11a and R 12a , R 12a and R 13a , R 13a and R 14a , or R 14a and R 15a may be bonded to form a ring.
  • the type of ring formed is not particularly limited, and examples thereof include a 5- to 6-membered ring structure.
  • R 16a to R 23a each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
  • the preferred range of the hydrocarbon group represented by R 16a to R 23a is synonymous with the preferred range of the hydrocarbon group represented by R 11a to R 15a described above.
  • the total molecular weight of each group of R 16a to R 23a is 24 or more. Especially, 35 or more are preferable.
  • the upper limit is not particularly limited, but is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less, from the viewpoint that the effects of the present invention are more excellent.
  • any two of R 16a to R 23a may be bonded to each other to form a ring.
  • R 24a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
  • R 16a , R 23a and R 24a each independently preferably represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom.
  • the preferred range of the hydrocarbon group optionally containing oxygen atoms represented by R 16a , R 23a and R 24a is the hydrocarbon group optionally containing oxygen atoms represented by R 11a and R 15a described above. It is synonymous with the suitable range of.
  • R 17a , R 19a, R 20a and R 22a each independently preferably represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom.
  • the preferred range of the hydrocarbon group optionally containing the oxygen atom represented by R 17a , R 19a, R 20a and R 22a may contain the oxygen atom represented by R 12a and R 14a described above. It is synonymous with the suitable range of a hydrocarbon group.
  • R 18a and R 21a each independently represent a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom (for example, —O—R a ).
  • R a represents a hydrocarbon group having 1 to 20 carbon atoms.
  • the preferred range of the hydrocarbon group represented by R 18a and R 21a is synonymous with the preferred range of the hydrocarbon group represented by R 13a and R a described above.
  • R 25a to R 28a each independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms that may contain a hetero atom.
  • the preferred range of the hydrocarbon group represented by R 25a to R 28a is synonymous with the preferred range of the hydrocarbon group represented by R 11a to R 15a described above.
  • the total molecular weight of each group of R 25a to R 28a is 40 or more. Especially, 50 or more are preferable.
  • the upper limit is not particularly limited, but is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less, from the viewpoint that the effects of the present invention are more excellent.
  • any two of R 25a to R 28a may be bonded to each other to form a ring.
  • L represents a divalent or trivalent hydrocarbon group which may have a hetero atom, —S—, or a group obtained by combining these.
  • the number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 12 and more preferably 1 to 10 in terms of excellent compatibility with the insulating resin.
  • m represents an integer of 2 or 3.
  • R 25a to R 28a each independently preferably represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom.
  • the preferred range of the hydrocarbon group optionally containing oxygen atoms represented by R 25a to R 28a is the preferred range of the hydrocarbon group optionally containing oxygen atoms represented by R 11a and R 15a described above. It is synonymous with.
  • L preferably represents a divalent or trivalent hydrocarbon group optionally having an oxygen atom, —S—, or a group obtained by combining these.
  • the number of carbon atoms contained in the hydrocarbon group is not particularly limited, but is preferably 1 to 40, and more preferably 2 to 20.
  • the hydrocarbon group may be any of linear, branched, cyclic, or aromatic forms, and examples thereof include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • the oxygen atom may be contained in the hydrocarbon group in the form of a linking group such as —O— or —COO—.
  • R 13a in formula (1A) and R 18a and R 21a in formula (2A) includes a group represented by formula (4)
  • R 32a represents a hydrogen atom or a hydrocarbon group having 1 to 19 carbon atoms.
  • the number of carbon atoms of the hydrocarbon group represented by R 32a is preferably 1 to 15 and more preferably 1 to 12 in terms of excellent compatibility with the pressure-sensitive adhesive.
  • * represents a bonding position.
  • the compound represented by the formula (5) is preferably mentioned in that the ion migration suppressing ability is more excellent.
  • R 40a and R 41a each independently represent a hydrogen atom, a hydroxyl group, an aliphatic hydrocarbon group that may contain an oxygen atom, or an aromatic hydrocarbon group that may contain an oxygen atom.
  • a tertiary carbon atom or an alkyl group containing a quaternary carbon atom is preferable from the viewpoint of more excellent ion migration suppressing ability.
  • the number of carbon atoms contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group is not particularly limited, but 2 to 20 is more preferable.
  • R 40a is preferably an alkyl group having 1 to 5 carbon atoms
  • R 41a is preferably an alkyl group having 10 to 20 carbon atoms.
  • the number of carbon atoms contained in at least one of R 11a , R 15a , R 40a and R 41a is preferably 1-20.
  • the solubility in the pressure-sensitive adhesive is improved, the dispersibility of the compound is improved, and as a result, the ability to suppress ion migration of silver is improved.
  • the number of carbon atoms is preferably 8-20, and more preferably 10-18.
  • the total number of carbon atoms contained in each of R 11a , R 15a , R 40a and R 41a is preferably 4 or more. When the total number of carbon atoms is within this range, silver ion migration is suppressed, and the insulation reliability between metal wirings is improved. In addition, 8 or more are preferable and 10 or more are more preferable in the point which this effect is more excellent.
  • the upper limit is not particularly limited, but the total number is preferably 50 or less, more preferably 40 or less, from the viewpoint that synthesis is easier and dispersibility in the adhesive is more excellent.
  • Adhesive It does not specifically limit as an adhesive, If a material (for example, adhesive resin) which shows adhesiveness, a well-known material can be used. For example, various adhesives such as rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives can be used, but in terms of better transparency and compatibility with reducing compounds. An acrylic adhesive is preferred.
  • the acrylic adhesive is based on an acrylic polymer having a main skeleton of an alkyl (meth) acrylate monomer unit.
  • (Meth) acrylate refers to acrylate and / or methacrylate.
  • the average carbon number of the alkyl group of the alkyl (meth) acrylate constituting the main skeleton of the acrylic polymer is preferably about 1 to 12, and specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like.
  • the transparent pressure-sensitive adhesive sheet has a base material in which the transparent pressure-sensitive adhesive layer is disposed on at least one main surface of the base material, even if the transparent pressure-sensitive adhesive sheet is composed of only the transparent pressure-sensitive adhesive layer and does not have a base material Even if it is a type (transparent adhesive sheet with a substrate.
  • a transparent double-sided adhesive sheet with a substrate having an adhesive layer on both sides of the substrate a transparent single-sided adhesive sheet with a substrate having an adhesive layer only on one side of the substrate
  • a substrate-less transparent double-sided pressure-sensitive adhesive sheet is preferable from the viewpoint of thinning a product using the pressure-sensitive adhesive sheet.
  • the type of substrate used is not particularly limited, but it is preferable to use a transparent substrate.
  • the transparent substrate for example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film , Fluorine resin film, nylon film, acrylic It can be exemplified a resin film or the like.
  • the transparent adhesive layer contained in the transparent adhesive sheet is a transparent adhesive layer in which time X indicates 12 hours or less in the following environmental test. Especially, it is preferable that the said time X is less than 6 hours at the point which the ion migration suppression capability of a transparent adhesion layer is more excellent. When the said time X is over 12 hours, it is inferior to ion migration suppression ability.
  • a transparent adhesive layer (length 5 cm ⁇ width 4 cm ⁇ thickness 50 ⁇ m) containing the reducing compound and a predetermined adhesive is provided on a glass substrate, and a PET substrate (50 ⁇ m) is formed on the transparent adhesive layer. To prepare an evaluation sample. Thereafter, the evaluation sample is allowed to stand for 72 hours at 65 ° C.
  • the evaluation sample is taken out and left in an environment of 23 ° C. and 50% RH.
  • the haze of the transparent adhesive layer in the evaluation sample is measured using “HR-100 type” manufactured by Murakami Color Research Laboratory, and the time X until the haze reaches 3% or less is measured.
  • the mass ratio (A / B) of the mass (A) of the reducing compound and the mass (B) of the pressure-sensitive adhesive in the transparent pressure-sensitive adhesive layer is not particularly limited. In terms of superiority, 0.0001 to 0.20 is preferable, and 0.0005 to 0.10 is more preferable.
  • the total light transmittance of the transparent adhesive sheet is not particularly limited, but is preferably 80% or more (more preferably 85% or more, still more preferably 90% or more).
  • the total light transmittance is measured using “HR-100 type” manufactured by Murakami Color Research Laboratory.
  • the thickness of the transparent adhesive layer in the transparent adhesive sheet is not particularly limited, and is preferably 5 to 250 ⁇ m and more preferably 20 to 200 ⁇ m from the viewpoint of application of the adhesive sheet to a touch panel.
  • the thickness of the transparent adhesive layer is not particularly limited, and is preferably 5 to 250 ⁇ m and more preferably 20 to 200 ⁇ m from the viewpoint of application of the adhesive sheet to a touch panel.
  • the said transparent adhesive sheet can be manufactured by a well-known method.
  • a pressure-sensitive adhesive composition containing the reducing compound and the pressure-sensitive adhesive is applied on a separator (release liner) so that the thickness after drying becomes a predetermined thickness.
  • the coating layer is dried and cured as necessary to form a transparent pressure-sensitive adhesive layer, whereby a transparent double-sided pressure-sensitive adhesive sheet can be produced.
  • a transparent pressure-sensitive adhesive layer may be provided by directly applying and drying the pressure-sensitive adhesive composition containing the reducing compound and the pressure-sensitive adhesive on the surface of the substrate ( (Direct copying method), after forming a transparent adhesive layer containing the above-mentioned compound on the separator in the same manner as described above, a transparent adhesive layer may be provided on the substrate by transferring (bonding) to the substrate (transfer method) . Furthermore, after apply
  • FIG. 7 is a schematic cross-sectional view of an embodiment of the wiring board.
  • the wiring board 10 includes an insulating substrate 12, a metal wiring 14 disposed on the insulating substrate 12, and a transparent adhesive layer 19 that covers the metal wiring 14. With.
  • the insulating substrate 12 and the metal wiring 14 constitute an insulating substrate 16 with metal wiring.
  • each member (the insulated substrate 12, the metal wiring 14, and the transparent adhesion layer 19) is explained in full detail.
  • the type of the insulating substrate is not particularly limited as long as it is insulative and can support metal wiring.
  • an organic substrate, a ceramic substrate, a glass substrate, or the like can be used.
  • the insulating substrate may have a structure in which at least two substrates selected from the group consisting of an organic substrate, a ceramic substrate, and a glass substrate are stacked.
  • Resin is mentioned as a material of an organic substrate,
  • a thermosetting resin a thermoplastic resin, or resin which mixed them.
  • the thermosetting resin include phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicone resin, furan resin, ketone resin, xylene resin, benzocyclo Examples include butene resin.
  • the thermoplastic resin include polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, aramid resin, and liquid crystal polymer.
  • a glass woven fabric, a glass nonwoven fabric, an aramid woven fabric, an aramid nonwoven fabric, an aromatic polyamide woven fabric, a material impregnated with the above resin, or the like can be used as a material of the organic substrate.
  • the metal wiring mainly contains silver.
  • Silver may be contained in the form of a silver alloy.
  • examples of the metal contained other than silver include tin, palladium, gold, nickel, and chromium.
  • the metal wiring may contain a resin component such as a binder or a photosensitive compound as long as the effects of the present invention are not impaired, and may further contain other components as necessary. .
  • a metal wiring contains the metal nanowire which consists of silver or a silver alloy. The metal nanowire will be described in detail later.
  • the method of forming the metal wiring is not particularly limited, and a physical film formation method such as a vapor deposition method or a sputtering method, or a chemical vapor phase method such as a CVD method, or a silver paste containing silver nanoparticles or silver nanowires is applied. And a method using a silver salt disclosed in JP2009-188360A.
  • a plurality of metal wirings are arranged on the insulating substrate, and the minimum distance (interval) between adjacent metal wirings is less than 50 ⁇ m. In other words, at least one portion (region) where the distance between adjacent metal wirings is less than 50 ⁇ m is included.
  • the minimum value of the distance (interval) between adjacent metal wirings is preferably less than 40 ⁇ m from the viewpoint of increasing the degree of integration of the metal wirings. Further, the distance between the metal wirings only needs to satisfy the above range in the minimum value, and there may be a distance (interval) of 50 ⁇ m or more.
  • the average distance between the metal wirings is not particularly limited, but is preferably 0.1 to 60 ⁇ m and particularly preferably 0.2 to 50 ⁇ m from the viewpoint of high integration of the wiring board.
  • interval here is the value which measured the space
  • the amount of silver contained per unit area of the metal wiring is preferably 50 ⁇ g / mm 2 or less.
  • silver amount is preferably at 30 [mu] g / mm 2 or less, more preferably 15 [mu] g / mm 2 or less.
  • limit in particular regarding a minimum 0.001 microgram / mm ⁇ 2 > or more is preferable and 0.005 microgram / mm ⁇ 2 > or more is more preferable at the point which the electroconductivity of a metal wiring is more excellent.
  • the metal wiring when ion migration occurs when the amount of silver contained in the metal wiring is small, disconnection of the metal wiring is likely to occur due to elution of silver forming the metal wiring.
  • a transparent resin layer containing a predetermined reducing compound by covering the metal wiring with a transparent resin layer containing a predetermined reducing compound, silver ion migration can be suppressed and disconnection of the metal wiring can be suppressed.
  • the measuring method in particular of silver amount is not restrict
  • the amount of silver can be measured by observing a cross-sectional SEM photograph of a metal wiring and conducting elemental analysis.
  • the metal wiring is brought into contact with a strong acid such as nitric acid to dissolve silver in the metal wiring, and the amount of silver can be measured from the dissolved amount.
  • the amount of silver in the metal wiring is obtained by calculation from the amount of the dispersion used to produce the metal wiring. You can also.
  • per unit area of the metal wiring means in other words per unit area of the contact portion of the metal wiring with the insulating substrate.
  • the amount of silver is calculated based only on the area of the contact portion between the metal wiring and the insulating substrate.
  • the area of the insulating substrate surface that is not in contact with the metal wiring (for example, the surface of the insulating substrate that is not in contact with the metal wiring that is located between the metal wirings) is considered in the calculation per unit area of the metal wiring.
  • I ca n’t enter. Therefore, the amount of silver contained per unit area of the metal wiring means the amount of silver contained per unit area (mm 2 ) at the contact portion between the metal wiring and the insulating substrate.
  • the width of the metal wiring is not particularly limited, but is preferably 0.1 to 10,000 ⁇ m, and preferably 0.1 to 300 ⁇ m, from the viewpoint of ensuring electrical reliability in the highly integrated portion and the lead wiring portion (lead wiring portion) of the wiring board. More preferably, 0.1 to 100 ⁇ m is more preferable, and 0.2 to 50 ⁇ m is particularly preferable.
  • the shape of the metal wiring is not particularly limited, and may be an arbitrary shape. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, and the like can be given.
  • the arrangement (pattern) of the metal wiring is not particularly limited, and examples thereof include a stripe shape.
  • two metal wirings 14 are provided in FIG. 1, the number is not particularly limited. Usually, a plurality of metal wirings are provided.
  • the thickness of the metal wiring is not particularly limited, but is preferably 0.001 to 100 ⁇ m, more preferably 0.01 to 30 ⁇ m, and still more preferably 0.01 to 20 ⁇ m from the viewpoint of high integration of the wiring board.
  • the metal wiring 14 is provided only on one side of the insulating substrate 12, but may be provided on both sides. That is, the insulating substrate 16 with metal wiring may be a single-sided substrate or a double-sided substrate. When the metal wiring 14 is on both sides of the insulating substrate 12, the transparent adhesive layer 19 may also be provided on both sides.
  • the metal wiring 14 has a single-layer wiring structure as an example, but the present invention is not limited to this.
  • an insulating substrate with a metal wiring (multilayer wiring substrate) in which a plurality of metal wirings and insulating substrates are alternately laminated may be used to provide a wiring substrate having a multilayer wiring structure.
  • a through hole may be formed in the insulating substrate.
  • the metal wiring on both surfaces may be made conductive by filling the through hole with a metal (for example, silver or silver alloy).
  • the metal nanowire is composed of silver or a silver alloy.
  • the kind of silver alloy is as above-mentioned.
  • the metal nanowire has conductivity and has a shape in which the length in the major axis direction is sufficiently longer than the diameter (length in the minor axis direction). It may be a solid fiber or a hollow fiber.
  • the material of the metal nanowire is particularly preferably silver or an alloy of silver and another metal in terms of excellent conductivity.
  • Other metals used in the alloy with silver include platinum, osmium, palladium, iridium, tin, bismuth, nickel and the like. These may be used alone or in combination of two or more.
  • the average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter”) is 5 to 50 nm, more preferably 5 to 25 nm, and even more preferably 5 to 20 nm.
  • An average minor axis diameter of 5 nm or more is preferable because oxidation resistance can be improved, and an average minor axis diameter of 50 nm or less is preferable because scattering of metal nanowires can be reduced.
  • the scattering of metal nanowires can be greatly reduced, which is more preferable.
  • the average minor axis diameter of the metal nanowires was determined by observing the minor axis diameters of 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). Find the minor axis diameter.
  • shaft diameter be the short axis diameter when the cross section of metal nanowire is not circular.
  • the average major axis length of the metal nanowire (sometimes referred to as “average major axis diameter”) is preferably 5 ⁇ m or more, more preferably 5 ⁇ m to 40 ⁇ m, and even more preferably 5 ⁇ m to 30 ⁇ m.
  • An average major axis diameter of 5 ⁇ m or more is preferable because the metal nanowires come into contact with each other to easily form a conductive network, and an average major axis diameter of 40 ⁇ m or less is preferable because the possibility of the metal nanowires becoming entangled during manufacturing is reduced.
  • the average major axis diameter of the metal nanowires is determined by, for example, observing the major axis diameters of 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average major axis diameter is obtained.
  • TEM transmission electron microscope
  • JEM-2000FX transmission electron microscope
  • the method for producing the metal nanowire is not particularly limited and may be produced by any method, but it is preferably produced by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved.
  • a method for producing metal nanowires JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, JP2010-86714A, The method described in JP-T-2009-505358 can be used.
  • the aspect ratio of the metal nanowire can be appropriately selected according to the purpose, but is not particularly limited as long as it is 10 or more, more preferably 50 or more, further preferably 100 or more, further preferably 5000 or more, and from 10,000 100,000 is particularly preferred.
  • the aspect ratio generally means the ratio between the long side and the short side of the fibrous material (ratio of average major axis diameter / average minor axis diameter).
  • a measuring method of an aspect ratio According to the objective, it can select suitably, For example, the method etc. which measure with an electron microscope etc. are mentioned.
  • the aspect ratio of the whole metal nanowire can be estimated by measuring the average major axis diameter and the average minor axis diameter of the metal nanowire separately.
  • the outer diameter of the tube is used as the diameter for calculating the aspect ratio.
  • the transparent adhesive layer is a layer that is disposed on the surface on the metal wiring side of the insulating substrate with metal wiring, covers the metal wiring surface, and suppresses silver ion migration between the metal wirings.
  • the transparent adhesive layer corresponds to a silver ion diffusion suppression layer.
  • it is preferable that a silver ion or metallic silver is not substantially contained in the transparent adhesion layer. If the transparent adhesive layer contains excessive silver ions or metallic silver, the ion migration suppressing effect may be reduced.
  • the phrase “substantially free of silver ions or metallic silver” means that the content of silver ions or metallic silver in the transparent adhesive layer is 1 ⁇ mol / l or less, and is 0.1 ⁇ mol / l or less. Is more preferable, and most preferably 0 mol / l.
  • the transparent adhesive layer contains the reducing compound and the adhesive described above.
  • the definition of each component is as described above.
  • mass ratio of the reducing compound and adhesive in a transparent adhesive layer is synonymous with mass ratio of the reducing compound and adhesive in the transparent adhesive sheet mentioned above, and a suitable aspect is also synonymous.
  • the thickness of the transparent adhesive layer is not particularly limited, but is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, from the viewpoint of better ion migration suppression ability.
  • the total light transmittance of the transparent adhesive layer is not particularly limited, but is preferably 80% or more (more preferably 85% or more, still more preferably 90% or more).
  • the total light transmittance is measured using “HR-100 type” manufactured by Murakami Color Research Laboratory.
  • the production method of the transparent adhesive layer is not particularly limited, for example, an adhesive layer forming composition containing a reducing compound and an adhesive is applied on an insulating substrate with metal wiring, and the solvent is removed as necessary. There is a method of forming a transparent adhesive layer. Moreover, the method of laminating
  • an insulating layer may be further provided on the surface of the transparent adhesive layer of the wiring board obtained above.
  • a metal wiring can be further provided on the insulating layer to obtain a multilayer wiring board.
  • the touch panel for example, the touch panel, display electrode, electromagnetic wave shield, organic or inorganic EL display electrode, electronic paper, flexible display electrode, integrated solar cell, display It is widely applied to devices and other various devices.
  • a touch panel is particularly preferable. That is, the wiring board is preferably used for a touch panel. More specifically, an embodiment in which the metal wiring in the wiring board becomes a lead wiring connected to the touch panel electrode part is preferable.
  • the touch panel electrode unit means, for example, a sensing electrode unit that senses a change in capacitance in a capacitive touch panel.
  • An acrylic copolymer (1) having a molecular weight of 800,000 was obtained.
  • the acrylic copolymer (1) (98 parts by mass) and the tocopherol (2 parts by mass) were diluted with ethyl acetate to obtain an adhesive composition having a resin solid content of 30%.
  • the film was coated on a 50 ⁇ m thick PET film so that the thickness after drying was 25 ⁇ m, and dried at 75 ° C.
  • the obtained pressure-sensitive adhesive sheet was bonded to a PET film having a thickness of 38 ⁇ m, one side of which was peeled off with a silicone compound. Thereafter, it was aged at 23 ° C. for 5 days to obtain a transparent double-sided pressure-sensitive adhesive sheet (baseless pressure-sensitive adhesive sheet) S-1 having a thickness of 25 ⁇ m.
  • the pressure-sensitive adhesive sheet had a total light transmittance of 90.8%, a haze of 0.6%, and a water absorption of 1.24%.
  • the method for measuring the total light transmittance, haze, and water absorption is in accordance with the method described in JP 2012-11637 A. More specifically, the measurement was performed by the method described later.
  • content of the tocopherol in a transparent double-sided adhesive sheet was 2 mass% with respect to the transparent double-sided adhesive sheet total mass.
  • Total light transmittance and haze measurement of transparent double-sided PSA sheet The obtained transparent double-sided PSA sheet S-1 was allowed to stand for 100 hours at 60 ° C. and 90% RH, and then a test sample was prepared by laminating PET film and glass in this order. Using the “HR-100 Model” manufactured by Murakami Color Research Laboratory Co., Ltd., the total light transmittance and haze (%) of the adjusted sample were measured.
  • the insulating substrate A with metal wiring was produced by the following method. After the copper foil of the copper clad laminate was peeled off by etching, conductive silver paste (Fujikura Kasei FA-451) was patterned on the substrate through a metal mask using a screen printing apparatus. Thereafter, heat treatment was performed for 30 minutes at 150 ° C.
  • the cross section of the silver wiring formed using screen printing had a trapezoidal shape in which the lower side (corresponding to the side where the wiring and the substrate contact) was slightly longer than the upper side.
  • the average thickness in the vicinity of the center of the wiring portion is 16 ⁇ m, and the amount of silver component in the conductive silver paste used is 70 wt%, which is included per unit area of the silver wiring itself at the contact portion between the silver wiring and the insulating substrate.
  • the amount of silver was calculated to be about 24.2 ⁇ g / mm 2 with a specific gravity of silver of 10.5 g / cm 3 .
  • calculation is based on the area of the portion where the silver wiring and the insulating substrate are in contact, and the surface of the insulating substrate not in contact with the silver wiring (for example, The area of the insulating substrate surface between the silver wires not in contact with the silver wires is not considered.
  • the amount of silver was also calculated from the result of elemental analysis of a cross-sectional SEM photograph of the metal wiring.
  • the amount of silver calculated from the total equivalent circle-shaped area of all silver particles and the cross-sectional area ratio of the wiring observed by SEM observation is the value of the amount of silver calculated from the amount of conductive silver paste used. It was roughly the same.
  • the release film on one side of the transparent double-sided pressure-sensitive adhesive sheet S-1 corresponding to the silver ion diffusion suppressing layer is peeled off, and one surface showing adhesiveness is used as the laminated surface. Further, the release film on the other side of the transparent double-sided pressure-sensitive adhesive sheet S-1 was peeled off, and a PET film (film thickness: 50 ⁇ m) was pasted on the other surface showing adhesiveness to obtain a wiring board. . Thereafter, the obtained wiring board was autoclaved for 20 minutes at 45 ° C. and 0.5 MPa. As a result, a wiring board T-1 was obtained. The following lifetime measurement was performed on the obtained wiring board T-1.
  • the release film on the other side of the film was peeled off, and a PET film (film thickness: 50 ⁇ m) was bonded onto the other surface exhibiting adhesiveness to obtain a comparative wiring board.
  • a PET film film thickness: 50 ⁇ m
  • the lifetime was measured under the above conditions, and the time X until the resistance value between the silver wirings fell below 1 ⁇ 10 5 ⁇ was measured.
  • the lifetime measurement was performed on the wiring board T-1 under the above conditions, and the time Y until the resistance value between the silver wirings fell below 1 ⁇ 10 5 ⁇ was measured.
  • the life improvement effect (Y / X) was calculated using the obtained time X and time Y. The results are shown in Table 1.
  • the amount of silver contained per unit area of the metal wiring was 8.7 ⁇ g / mm 2 .
  • a wiring board T-2 was prepared according to the same procedure as in Examples 1 and 2 except that the insulating board B with metal wiring was used instead of the insulating board A with metal wiring, and evaluation of the evaluation method 1 was performed. .
  • the results are shown in Table 1.
  • Example 4> Manufacture of transparent substrate with conductive film
  • a transparent substrate made of a PET substrate (thickness 125 ⁇ m) corresponding to the transparent substrate was prepared, and a conductive film containing silver having a comb-shaped electrode pattern (L / S 200 ⁇ m / 200 ⁇ m) was produced on the transparent substrate according to the following procedure.
  • the amount of silver contained per unit area of the conductive film can be calculated by measuring the concentration of the aqueous silver nitrate solution obtained by immersing the wiring board in nitric acid and measuring the concentration using ICP-MS. 0.014 ⁇ g / mm 2 .
  • the PET substrate also corresponds to an insulating substrate.
  • a silver nitrate solution 101 was prepared by dissolving 60 g of silver nitrate powder in 370 g of propylene glycol. 72.0 g of polyvinylpyrrolidone (molecular weight 55,000) was added to 4.45 kg of propylene glycol, and the temperature was raised to 90 ° C. while venting nitrogen gas through the gas phase portion of the container. This solution was designated as reaction solution 101. 2.50 g of the silver nitrate solution 101 was added to the vigorously stirred reaction solution 101 while maintaining the nitrogen gas flow, and the mixture was heated and stirred for 1 minute.
  • reaction solution 102 a solution in which 11.8 g of tetrabutylammonium chloride was dissolved in 100 g of propylene glycol was added to this solution to obtain a reaction solution 102.
  • 200 g of the silver nitrate solution 101 was added to the reaction solution 102 which was kept at 90 ° C. and stirred at a stirring speed of 500 rpm at an addition speed of 50 cc / min. The stirring speed was reduced to 100 rpm, the aeration of nitrogen gas was stopped, and heating and stirring were performed for 15 hours.
  • 220 g of the silver nitrate solution 101 was added at an addition speed of 0.5 cc / min to this liquid kept at 90 ° C.
  • silver nanowire dispersion (1) indicates the silver nanowire dispersion obtained by the above method.
  • PET substrate thickness 125 [mu] m
  • amount of silver 0.015 g / m 2 by a bar coating method on, after the total solid content in the coating solution was coated silver nanowire coating solution (1) so that 0.120 g / m 2, It dried at 120 degreeC for 1 minute, and the electrically conductive film 1 containing a silver nanowire was formed.
  • a photoresist (TMSMR-8900LB: manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the conductive film 1 by spin coating and baked at 90 ° C. for 60 seconds. Next, pattern exposure was performed using a photomask (exposure amount: 12 mW / cm 2 , 20 seconds), developed with a developer (NMD-W: Tokyo Sensitivity), washed with water and dried, then at 120 ° C. A patterned photoresist was formed on the conductive film 1 by baking for 60 seconds.
  • TMSMR-8900LB manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • a transparent double-sided pressure-sensitive adhesive sheet S-1 was bonded to the obtained transparent substrate with a conductive film in the same manner as in Example 2 to obtain a conductive film laminate (also applicable to a wiring board) T-3. It was.
  • the release film on one side of the transparent double-sided pressure-sensitive adhesive sheet S-0 is peeled off on a transparent substrate with a conductive film, and one surface showing adhesiveness is bonded as a laminated surface, and further the transparent double-sided pressure-sensitive adhesive sheet
  • the release film on the other side was peeled off, and a PET film (film thickness: 50 ⁇ m) was bonded onto the other surface showing tackiness to obtain a comparative conductive film laminate.
  • the lifetime was measured under the above conditions, and the time X until the resistance value between the conductive films increased by 10% was measured.
  • Example 5 A wiring substrate T-4 was prepared in accordance with the same procedure as in Examples 1 and 2 except that the following compound A-1 was used instead of tocopherol, and evaluation of the evaluation method 1 was performed. The results are shown in Table 1.
  • Example 6 A wiring substrate T-5 was prepared according to the same procedure as in Examples 1 and 2 except that the following compound A-2 was used instead of tocopherol, and the evaluation method 1 was evaluated. The results are shown in Table 1.
  • Example 7 A wiring board T-6 was produced in accordance with the same procedure as in Examples 1 and 2 except that the following compound A-3 was used instead of tocopherol, and the evaluation method 1 was evaluated. The results are shown in Table 1.
  • Example 8 A wiring board T-7 was produced in accordance with the same procedure as in Examples 1 and 2 except that the following compound A-4 was used instead of tocopherol, and the evaluation method 1 was evaluated. The results are shown in Table 1.
  • Example 9 A wiring board T-8 was prepared according to the same procedure as in Examples 1 and 5 except that the amount of silver was changed from 24.2 ⁇ g / mm 2 to 0.011 ⁇ g / mm 2 , and the evaluation method 1 was evaluated. did. The results are shown in Table 1.
  • Example 10 A wiring board T-9 was prepared according to the same procedure as in Examples 1 and 2 except that the following compound A-5 was used instead of tocopherol, and the evaluation method 1 was evaluated. The results are shown in Table 1.
  • Example 11 A wiring board T-9 was prepared according to the same procedure as in Examples 1 and 2 except that the following compound A-6 was used instead of tocopherol, and the evaluation method 1 was evaluated. The results are shown in Table 1.
  • Example 12 A wiring substrate T-10 was produced according to the same procedure as in Examples 1 and 2 except that the following compound A-7 was used instead of tocopherol, and the evaluation method 1 was evaluated. The results are shown in Table 1.
  • a transparent double-sided PSA sheet S-0 was produced according to the same procedure as in Example 1 except that no tocopherol was used.
  • a wiring board R-1 was prepared according to the same procedure as in Examples 1 and 2 except that the transparent double-sided pressure-sensitive adhesive sheet S-0 was used instead of the transparent double-sided pressure-sensitive adhesive sheet S-1, and the evaluation method 1 was evaluated. Carried out. The results are shown in Table 1.
  • a wiring board R-3 was prepared according to the same procedure as in Examples 1 and 2 except that ascorbic acid was used instead of tocopherol, and the evaluation method 1 was evaluated. The results are shown in Table 1.
  • Example 4 is a result evaluated by the said evaluation method 2
  • Example and a comparative example are the results evaluated by the said evaluation method 1.
  • the pressure-sensitive adhesive composition was coated on a 50 ⁇ m-thick PET film having one surface peel-treated with a silicone compound so that the thickness after drying was 50 ⁇ m, and dried at 75 ° C. for 5 minutes.
  • the obtained pressure-sensitive adhesive sheet was bonded to a PET film having a thickness of 38 ⁇ m, one side of which was peeled off with a silicone compound. Thereafter, it was aged at 23 ° C. for 5 days to obtain a transparent double-sided PSA sheet (base material-less PSA sheet) S-1 having a thickness of 50 ⁇ m.
  • Synthesis Example 12 Production of transparent double-sided pressure-sensitive adhesive sheet S-12
  • a transparent double-sided pressure-sensitive adhesive sheet S-12 was produced according to the same procedure as in Synthesis Example 10 except that DL- ⁇ -tocopherol was changed to Compound C (redox potential: 1.17 V).
  • the obtained pressure-sensitive adhesive sheet and a 38 ⁇ m-thick PET film peeled from one side with a silicone compound were bonded together, and irradiated with a low-pressure mercury lamp from both sides for 5 minutes to obtain a transparent double-sided pressure-sensitive adhesive sheet S-18.
  • Synthesis Example 19 Production of transparent double-sided pressure-sensitive adhesive sheet S-19
  • a transparent double-sided PSA sheet S-19 was produced according to the same procedure as in Synthesis Example 18 except that DL- ⁇ -tocopherol was changed to Compound B (redox potential: 1.09 V).
  • the pressure-sensitive adhesive composition was applied onto a 50 ⁇ m thick PET film so that the thickness after drying was 50 ⁇ m, and the solvent was dried.
  • the obtained pressure-sensitive adhesive sheet and a 38 ⁇ m-thick PET film peeled from one side with a silicone compound were bonded together, and irradiated with a low-pressure mercury lamp from both sides for 5 minutes to obtain a transparent double-sided pressure-sensitive adhesive sheet S-21.
  • Synthesis Example 30 Production of transparent double-sided PSA sheet S-30
  • a transparent double-sided PSA sheet S-30 was produced according to the same procedure as in Synthesis Example 5 except that DL- ⁇ -tocopherol was not used.
  • Synthesis Example 35 Production of transparent double-sided PSA sheet S-35
  • a transparent double-sided PSA sheet S-35 was produced according to the same procedure as in Synthesis Example 16 except that DL- ⁇ -tocopherol was not used.
  • LS-450-7HL manufactured by Asahi Chemical Research Laboratory
  • the release film on one side of the transparent double-sided pressure-sensitive adhesive sheet S-1 is peeled off, and one surface showing adhesiveness is bonded as a laminated surface, and further a transparent double-sided pressure-sensitive adhesive sheet
  • the release film on the other side of the film was peeled off, and a PET film (film thickness: 50 ⁇ m) was bonded onto the other surface exhibiting adhesiveness to obtain a wiring board.
  • the obtained wiring board was subjected to autoclave treatment at 45 ° C. and 0.5 MPa for 20 minutes. As a result, a wiring board T-1 was obtained. The following lifetime measurement was performed on the obtained wiring board T-1.
  • the transparent double-sided pressure-sensitive adhesive sheets S-1 to S-38 are cut into a predetermined size (length 5 cm ⁇ width 4 cm ⁇ thickness 50 ⁇ m), the release film on one side is peeled off, and one surface showing adhesiveness is removed.
  • a laminated surface was attached to a glass substrate, the release film on the other side of the transparent double-sided PSA sheet was peeled off, and a PET substrate (thickness: 50 ⁇ m) was attached to prepare a sample for evaluation.
  • the sample for evaluation was left for 72 hours at 65 ° C. and 95% RH. Then, when the sample for evaluation was allowed to stand at 23 ° C.
  • Examples 2A to 25A and Comparative Examples 1A to 15A> As shown in Table 2, using the transparent double-sided pressure-sensitive adhesive sheets S-2 to S-38 described above in place of the transparent double-sided pressure-sensitive adhesive sheet S-1, a wiring board was manufactured in the same procedure as in Example 1A, and the life was extended. Effectiveness measurements and environmental tests were performed. The results are summarized in Table 2.
  • Example 26A> A wiring board was produced in the same manner as in Example 6A, except that L / S was changed to 30 ⁇ m / 30 ⁇ m, and the same life measurement as in Example 1A was performed.

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PCT/JP2013/063064 2012-05-10 2013-05-09 Stratifié de film conducteur, panneau tactile, tableau de connexions, appareil électronique, feuille transparente adhésive double face sensible à la pression et feuille transparente adhésive sensible à la pression Ceased WO2013168773A1 (fr)

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CN103714882A (zh) * 2013-12-07 2014-04-09 深圳市金凯新瑞光电有限公司 一种应用于触摸屏感应器的镀Ag导电膜的生产方法
WO2015145634A1 (fr) * 2014-03-26 2015-10-01 リンテック株式会社 Feuille adhésive double face
WO2016148208A1 (fr) * 2015-03-17 2016-09-22 日立化成株式会社 Feuille adhésive pour dispositif d'affichage d'image, corps stratifié adhésif pour dispositif d'affichage d'image, et dispositif d'affichage d'image
JP2017501867A (ja) * 2013-12-20 2017-01-19 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード 極低温の流体を分配する可動工具用の保護筐体
CN107636105A (zh) * 2015-07-23 2018-01-26 三菱化学株式会社 导电构件用粘合剂组合物
CN113604171A (zh) * 2021-08-18 2021-11-05 深圳市高仁电子新材料有限公司 一种黑色光学胶及其制备方法

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US10091887B2 (en) * 2015-04-02 2018-10-02 Tactotek Oy Multi-material structure with embedded electronics
CN108932073A (zh) 2017-05-22 2018-12-04 祥达光学（厦门）有限公司 触控面板与其引线结构
CN111025692B (zh) * 2019-10-10 2022-06-03 信利半导体有限公司 一种高效率的lcd制作方法

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CN103714882A (zh) * 2013-12-07 2014-04-09 深圳市金凯新瑞光电有限公司 一种应用于触摸屏感应器的镀Ag导电膜的生产方法
CN103714882B (zh) * 2013-12-07 2016-08-31 深圳市金凯新瑞光电有限公司 一种应用于触摸屏感应器的镀Ag导电膜的生产方法
JP2017501867A (ja) * 2013-12-20 2017-01-19 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード 極低温の流体を分配する可動工具用の保護筐体
WO2015145634A1 (fr) * 2014-03-26 2015-10-01 リンテック株式会社 Feuille adhésive double face
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WO2016148208A1 (fr) * 2015-03-17 2016-09-22 日立化成株式会社 Feuille adhésive pour dispositif d'affichage d'image, corps stratifié adhésif pour dispositif d'affichage d'image, et dispositif d'affichage d'image
CN107636105A (zh) * 2015-07-23 2018-01-26 三菱化学株式会社 导电构件用粘合剂组合物
CN107636105B (zh) * 2015-07-23 2020-04-03 三菱化学株式会社 导电构件用粘合剂组合物
CN113604171A (zh) * 2021-08-18 2021-11-05 深圳市高仁电子新材料有限公司 一种黑色光学胶及其制备方法

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