WO2017110937A1 - Adhesive sheet for conductive member, conductive member laminate, and image display device - Google Patents

Adhesive sheet for conductive member, conductive member laminate, and image display device Download PDF

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Publication number
WO2017110937A1
WO2017110937A1 PCT/JP2016/088229 JP2016088229W WO2017110937A1 WO 2017110937 A1 WO2017110937 A1 WO 2017110937A1 JP 2016088229 W JP2016088229 W JP 2016088229W WO 2017110937 A1 WO2017110937 A1 WO 2017110937A1
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WO
WIPO (PCT)
Prior art keywords
meth
adhesive sheet
pressure
sensitive adhesive
conductive member
Prior art date
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PCT/JP2016/088229
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French (fr)
Japanese (ja)
Inventor
亮太 山本
かほる 新美
秀次郎 吉川
誠 稲永
内田　貴久
Original Assignee
三菱樹脂株式会社
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Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to KR1020187021416A priority Critical patent/KR102598110B1/en
Priority to CN201680076202.1A priority patent/CN108431158B/en
Publication of WO2017110937A1 publication Critical patent/WO2017110937A1/en

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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • 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
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet for a conductive member and a conductive member laminate using the pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive sheet for a conductive member and a conductive member laminate using the pressure-sensitive adhesive sheet In particular, in an image display device using an image display panel such as a plasma display (PDP), a liquid crystal display (LCD), an organic EL display (OLED), an inorganic EL display, an electrophoretic display (EPD), an interference modulation display (IMOD), etc.
  • PDP plasma display
  • LCD liquid crystal display
  • OLED organic EL display
  • EPD electrophoretic display
  • IMOD interference modulation display
  • the present invention relates to a pressure-sensitive adhesive sheet for a conductive member suitable for bonding conductive members such as a transparent conductive layer.
  • Image display devices such as personal computers, mobile terminals (PDAs), game machines, televisions (TVs), car navigation systems, touch panels, pen tablets, for example, plasma displays (PDPs), liquid crystal displays (LCDs), organic EL displays (OLEDs) ),
  • PDAs mobile terminals
  • LCDs liquid crystal displays
  • OLEDs organic EL displays
  • An image display device using a flat or curved image display panel such as an inorganic EL display, an electrophoretic display (EPD), an interferometric modulation display (IMOD), etc.
  • a gap is not provided between the constituent members, and the constituent materials are bonded and integrated with an adhesive sheet or a liquid adhesive.
  • an adhesive sheet or liquid adhesive is provided between the surface protection panel and the viewing side of the liquid crystal module.
  • the touch panel and other constituent members, for example, the touch panel and the liquid crystal module, and the touch panel and the surface protection panel are bonded and integrated.
  • Touch panels are usually made of metal oxides such as tin-doped indium oxide (ITO), indium-gallium-zinc composite oxide (IGZO), and Ga-doped zinc oxide (GZO), and metal materials such as silver, copper, and molybdenum.
  • ITO tin-doped indium oxide
  • IGZO indium-gallium-zinc composite oxide
  • GZO Ga-doped zinc oxide
  • metal materials such as silver, copper, and molybdenum.
  • an upper electrode plate and a lower electrode plate having a transparent conductive layer formed of fine wiring, silver nanowires, carbon nanotubes, or the like.
  • a conductor pattern formed of a metal material is interposed between the transparent conductive layer and a control means such as an IC. It is formed.
  • the transparent conductive layer and conductor pattern formed from these various materials are usually fixed so that the surface is in contact with the adhesive.
  • the transparent conductive layer and the conductive pattern are vulnerable to corrosion, and may corrode due to the outgas of the adhesive material or the acid component derived from the elution component in a high temperature or wet heat environment, possibly resulting in disconnection.
  • Patent Document 1 discloses a pressure-sensitive adhesive sheet for metal sticking containing benzotriazole and / or a derivative thereof as a metal corrosion inhibitor.
  • Patent Document 2 discloses a pressure-sensitive adhesive composition
  • a pressure-sensitive adhesive composition comprising an acrylic polymer and a crosslinking agent, each of which includes an alkoxyalkyl acrylate and an acrylic monomer having a crosslinkable functional group as essential components.
  • a pressure-sensitive adhesive composition substantially free of a carboxyl group-containing monomer. According to this pressure-sensitive adhesive composition, yellowing is suppressed by using a specific amount of an aliphatic isocyanate crosslinking agent and an amine compound containing a plurality of hydroxyl groups, and the acrylic polymer has a crosslinked structure. Accordingly, it is disclosed that even when a carboxyl group-containing monomer component is not included, the anti-foaming / peeling property under high temperature can be satisfied.
  • the constituent members used in the image display device include members that generate gas (also referred to as “outgas”) over time in a high-temperature or high-humidity environment.
  • gas also referred to as “outgas”
  • the pressure-sensitive adhesive sheet also needs to have foaming reliability that can sufficiently resist the gas pressure of outgas.
  • the double-sided pressure-sensitive adhesive sheet containing the metal corrosion inhibitor of Patent Document 1 has a problem that the metal corrosion inhibitor is foamed in a durability test that is irradiated with ultraviolet rays, and optical properties are deteriorated.
  • the problem to be solved by the present invention is to provide a pressure-sensitive adhesive sheet for a conductive member that does not corrode the conductive member and has foaming reliability and good curing characteristics. More specifically, even if directly bonded to the conductive layer surface of the transparent conductive layer or a conductor pattern (wiring pattern) formed of a metal material, these are not corroded and insulated from the conductive layer surface of the transparent conductive layer. It is to provide a pressure-sensitive adhesive sheet for a conductive member that does not corrode a transparent conductive layer even when bonded through a protective film (passivation film).
  • the main feature of the present invention is that it has a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer and 1,2,3-triazole.
  • the pressure-sensitive adhesive sheet for a conductive member of the present invention has corrosion resistance reliability with respect to a conductive member and can also have foaming reliability reliability and good curing characteristics as a pressure-sensitive adhesive sheet. Therefore, the pressure-sensitive adhesive sheet for a conductive member of the present invention is a pressure-sensitive adhesive sheet suitable for bonding various conductive members such as a conductive member having a conductive pattern formed of a transparent conductive layer and / or a metal material containing copper or silver. Can be used. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.
  • (A) is the top view of the ITO pattern of the ITO glass substrate for oxidation deterioration prevention evaluation, or copper for corrosion resistance reliability evaluation
  • (B) is a top view showing a state where an adhesive sheet is coated on an ITO glass substrate for evaluating oxidation resistance, or an adhesive sheet on a copper glass substrate for evaluating corrosion resistance The top view which showed the coat
  • (C) is sectional drawing of the sample for oxidation deterioration prevention evaluation
  • (D) is sectional drawing of the sample for corrosion resistance reliability evaluation.
  • An adhesive sheet for a conductive member according to an example of an embodiment of the present invention (hereinafter also referred to as “the present adhesive sheet”) includes a (meth) acrylic (co) polymer and 1,2,3-triazole. It has the adhesive layer which consists of an adhesive composition to contain.
  • the pressure-sensitive adhesive layer may be a single layer or a multilayer, and in the case of a multilayer, other layers such as a so-called base material layer may be interposed.
  • the surface layer of the pressure-sensitive adhesive sheet is preferably a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition.
  • the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is not limited, but is preferably 10% or more, more preferably 30% or more with respect to the total thickness of the pressure-sensitive adhesive sheet. More preferably, it is 50% or more.
  • the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is in the above range, it is preferable because corrosion resistance, foaming reliability, and curing characteristics with respect to the conductive member are improved.
  • “(co) polymer” includes a homopolymer and a copolymer
  • “(meth) acrylate” includes an acrylate and a methacrylate.
  • the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive sheet contains a (meth) acrylic (co) polymer and 1,2,3-triazole.
  • the present composition may further contain a phosphite compound, a crosslinking agent, a photopolymerization initiator, an antioxidant, and other components.
  • the composition is preferably a photocurable composition.
  • (meth) acrylic (co) polymer examples include, for example, copolymers obtained by polymerizing alkyl (meth) acrylate homopolymers and copolymerizable monomer components. More preferably, among alkyl (meth) acrylates and carboxyl group-containing monomers, hydroxyl group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, amide group-containing monomers, and other vinyl monomers copolymerizable therewith. Examples thereof include a copolymer containing any one or more selected monomers as a structural unit.
  • the (meth) acrylic (co) polymer can be produced by a conventional method using the following monomers or the like, if necessary, using a polymerization initiator.
  • the (meth) acrylic (co) polymer is a copolymer containing a carboxyl group-containing monomer as a constituent unit
  • the (meth) acrylic (co) polymer contains a carboxyl group from the viewpoint of obtaining excellent adhesive properties.
  • the monomer content is preferably 1.2 to 15% by mass, more preferably 1.5% by mass or more and 10% by mass or less, and most preferably 2.0% by mass or more or 8% by mass or less.
  • a more specific (meth) acrylic (co) polymer a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain (hereinafter also referred to as “copolymerizable monomer A”). And a copolymer composed of any one or more monomer components selected from the following group copolymerizable therewith.
  • Carboxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer B”) Macromonomer (hereinafter also referred to as “copolymerizable monomer C”) (Meth) acrylate having 1 to 3 carbon atoms in the side chain (hereinafter also referred to as “copolymerizable monomer D”) Hydroxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer E”)
  • copolymerizable monomer F Other vinyl monomers
  • a (meth) acrylic (co) polymer (a) a copolymer composed of a monomer component containing a copolymerizable monomer A and a copolymerizable monomer B and / or copolymerizable monomer C And a monomer component including (b) a copolymerizable monomer A, a copolymerizable monomer B and / or a copolymerizable monomer C, and a copolymerizable monomer D and / or a copolymerizable monomer E.
  • a copolymer can also be mentioned as a particularly preferred example.
  • Examples of the straight chain or branched alkyl (meth) acrylate (copolymerizable monomer A) having 4 to 18 carbon atoms in the side chain include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acryl
  • the copolymerizable monomer A is preferably contained in the total monomer components of the copolymer in an amount of 30% by mass or more and 90% by mass or less, particularly 35% by mass or more and 88% by mass or less, and especially 40% by mass. More preferably, it is contained in the range of 85% by mass or less.
  • Examples of the carboxyl group-containing monomer (copolymerizable monomer B) include (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2 -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxy Mention may be made of ethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid and itaconic acid. These may be used alone or in combination of two or more. “(Meth) acryl” means to include acrylic and methacrylic.
  • the copolymerizable monomer B is 1.2% by mass or more and 15% by mass or less in all monomer components of the copolymer, and from the viewpoint of obtaining excellent adhesive physical properties, 1.5% by mass or more or 10% by mass or less, In particular, it is preferably contained in the range of 2% by mass or more or 8% by mass or less.
  • the macromonomer (copolymerizable monomer C) is a monomer having 20 or more carbon atoms in the side chain when it becomes a (meth) acrylic (co) polymer by polymerization.
  • a (meth) acrylic (co) polymer can be used as a graft copolymer. Therefore, the characteristics of the main chain and side chain of the graft copolymer can be changed depending on the selection and blending ratio of the copolymerizable monomer C and other monomers.
  • the skeleton component is preferably composed of an acrylic polymer or a vinyl polymer.
  • the skeleton component of the macromonomer include those exemplified by the copolymerizable monomer A, the copolymerizable monomer B, the copolymerizable monomer D described below, and the copolymerizable monomer E described below. Can be used alone or in combination of two or more.
  • the macromonomer has a radical polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, or a thiol group.
  • a radical polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, or a thiol group.
  • those having a radical polymerizable group copolymerizable with other monomers are preferable.
  • One or two or more radically polymerizable groups may be contained, and one of them is particularly preferred.
  • the macromonomer has a functional group, one or two or more functional groups may be contained, and one of them is particularly preferable. Further, either one of the radical polymerizable group and the functional group may be contained.
  • the number average molecular weight of the copolymerizable monomer C is preferably 500 to 20,000, more preferably 800 or more and 8000 or less, and particularly preferably 1000 or more and 7000 or less.
  • the macromonomer a generally produced one (for example, a macromonomer manufactured by Toa Gosei Co., Ltd.) can be appropriately used.
  • the copolymerizable monomer C is 5% by mass or more and 30% by mass or less, more preferably 6% by mass or more and 25% by mass or less, and particularly preferably 8% by mass or more or 20% by mass or less in the total monomer components of the copolymer. It is preferable to contain in the range.
  • Examples of the (meth) acrylate (copolymerizable monomer D) having 1 to 3 carbon atoms in the side chain include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) ) Acrylate and the like. These may be used alone or in combination of two or more.
  • the copolymerizable monomer D is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 70% by mass, more preferably 3% by mass or 65% by mass, and particularly preferably 5% by mass or more. Or it is further more preferable to contain in the range of 60 mass% or less.
  • hydroxyl group-containing monomer (copolymerizable monomer E) examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc. And hydroxyalkyl (meth) acrylates. These may be used alone or in combination of two or more.
  • the copolymerizable monomer E is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and more preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
  • Examples of the other vinyl monomer (copolymerizable monomer F) include compounds having a vinyl group in the molecule, excluding the copolymerizable monomers A to E.
  • Such compounds include functional monomers having functional groups such as amide groups and alkoxylalkyl groups in the molecule, and polyalkylene glycol di (meth) acrylates, and vinyls such as vinyl acetate, vinyl propionate and vinyl laurate.
  • Examples include ester monomers and aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene and other substituted styrenes. These may be used alone or in combination of two or more.
  • the copolymerizable monomer F is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 30% by mass, more preferably 0% by mass or more or 25% by mass or less, and particularly preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
  • acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth) acrylate, glycidyl ⁇ -ethyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, etc.
  • Epoxy group-containing monomers amino group-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, Nt-butyl (meth) acrylamide, N- Monomers containing amide groups or imide groups such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, maleimide; vinyl pyrrolidone , Vinyl Jin, can be appropriately used depending or the like need heterocyclic basic monomers such as vinyl carbazole.
  • amino group-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate
  • (meth) acrylic (co) polymers include, for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isostearyl (meth) acrylate, butyl ( Monomer component (a) such as (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate and the like, (meth) acrylic acid having a carboxyl group, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( (Meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxy Propyl
  • the mass average molecular weight of the (meth) acrylic (co) polymer is preferably 100,000 or more and 1.5 million or less, more preferably 150,000 or more and 1.3 million or less, and particularly preferably 200,000 or more or 1,200,000 or less.
  • the mass average molecular weight of the (meth) acrylic (co) polymer is 700,000 to 1,500,000 from the viewpoint of obtaining cohesive force due to entanglement of molecular chains as the molecular weight increases. In particular, it is particularly preferably 800,000 or more or 1.3 million or less.
  • the mass average molecular weight is preferably 100,000 or more and 700,000 or less, particularly 150,000 or more or 600,000 or less.
  • the (meth) acrylic (co) polymer has a mass average molecular weight of 100,000 or more and 700,000. In particular, 150,000 or more or 600,000 or less is preferable, and 200,000 or more or 500,000 or less is particularly preferable.
  • the composition contains 1,2,3-triazole.
  • 1,2,3-triazole has a function as a metal corrosion inhibitor for the conductive layer of the conductive member. Since 1,2,3-triazole is excellent in copper corrosion resistance against copper and foaming reliability as a pressure-sensitive adhesive sheet, the present composition containing 1,2,3-triazole contains a transparent conductive layer and copper. It can be suitably used as a conductive member having a conductor pattern (wiring pattern) formed of a metal material containing. The reason is to prevent corrosion by forming a protective film in which copper atoms and 1,2,3-triazole molecules are chemically bonded to the surface of the conductor pattern made of a metal material containing copper. It is because it is guessed. In addition, the effect of the protective film by 1,2,3-triazole can be similarly achieved in a conductive member having a conductor pattern formed of a metal material containing silver.
  • 1,2,4-triazole exists as an isomer of 1,2,3-triazole.
  • the 1,2,4-triazole is a solid having a melting point of about 120 ° C.
  • 1,2,3-triazole has a melting point of about 20 ° C. and is almost in a liquid state at room temperature. Therefore, 1,2,3-triazole has excellent advantages such as excellent dispersibility when mixed into the pressure-sensitive adhesive composition, uniform mixing, and easy masterbatch formation.
  • 1,2,3-triazole is added in an amount of 0.1 to 100 parts by mass of the (meth) acrylic (co) polymer. It is preferably contained in a proportion of 01 parts by mass or more and 5 parts by mass or less, especially 0.1 parts by mass or more or 1 part by mass or less, and among them, it is contained in a proportion of 0.2 parts by mass or more or 0.5 parts by mass or less Even more preferably.
  • 1,2,4-triazole may be used in combination with 1,2,3-triazole.
  • the present composition can further contain a phosphite compound.
  • the phosphite compound is not itself corrosive and can stabilize acid components such as carboxyl groups. Therefore, by blending a phosphite compound with this composition containing a predetermined (meth) acrylic (co) polymer, the conductive member which is an adherend even if this composition contains an acid component Oxidative degradation of the conductive member as an adherend can be prevented as well as the present composition of course when the composition does not contain an acid component.
  • an adhesive sheet is formed from the present composition containing a phosphite compound, a conductive member (typically a conductive pattern formed of a transparent conductive layer containing ITO and / or a metal material containing copper or silver)
  • a conductive member typically a conductive pattern formed of a transparent conductive layer containing ITO and / or a metal material containing copper or silver
  • the conductive member can be prevented from being oxidized and deteriorated. Therefore, for example, it can be suitably used as an adhesive sheet for an image display device having a touch panel.
  • the phosphite compound that can be contained in the composition is not limited. Among these, a phosphite compound represented by the following formula (1) is preferable.
  • R is a hydrocarbon, and specific examples include a substituted or unsubstituted aromatic group, an alicyclic ring, and an alkyl group.
  • the plurality of R may be the same or different from each other, and are adjacent to each other.
  • a plurality of R may be bonded to each other to form a saturated or unsaturated ring structure.
  • it may be a compound containing two or more structural units represented by the above formula (1).
  • Examples of the phosphite compound contained in the composition include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, tristearyl phosphite, triethyl phosphite, tris phosphite ( 2-ethylhexyl), tridecyl phosphite, trilauryl phosphite, tris phosphite (tridecyl), trioleyl phosphite, diphenyl phosphite (2-ethylhexyl), diphenyl monodecyl phosphite, diphenyl phosphite Mono (tridecyl), tetraphenyldipropylene dipropylene glycol diphosphite, tetraphenyl (tetratridecyl) pentaerythritol tetraphos
  • an aliphatic phosphite ester for example, a phosphite compound of Example 2-2 as a phosphite compound
  • Tridecyl phosphate and 3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane of Example 2-3) are preferred.
  • aromatic phosphite esters for example, tris (2,4-di-t-butylphenyl) phosphite as the phosphite compound of Example 2-1
  • a phosphite having both an aliphatic ester group such as diphenyl phosphite mono (tridecyl) and an aromatic ester group is preferable.
  • the content ratio of the phosphite compound does not impair the adhesive performance, and from the viewpoint of more effectively suppressing the oxidative deterioration of the conductive member such as ITO, (meth) acrylic (co)
  • the phosphite compound is preferably contained in an amount of 0.0001 (1 ⁇ 10 ⁇ 4 ) parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the polymer, and more preferably 0.0005 parts by mass or more. Or 0.8 parts by mass or less, more preferably 0.001 parts by mass or more or 0.7 parts by mass or less, particularly preferably 0.01 parts by mass or more or 0.6 parts by mass or less. .
  • composition may contain other metal corrosion inhibitors such as 1,2,4-triazole, benzotriazole and derivatives thereof.
  • This composition may contain a crosslinking agent as needed.
  • a crosslinking agent for example, as a method of crosslinking the above-mentioned (meth) acrylic (co) polymer, crosslinking capable of chemically bonding with a reactive group such as a hydroxyl group or a carboxyl group introduced into the (meth) acrylic (co) polymer.
  • reaction agent react by heating or curing, add reaction initiator such as polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups as crosslinking agent and photopolymerization initiator, UV irradiation
  • crosslinking by etc. can be mentioned.
  • a crosslinking method by irradiation with light such as ultraviolet rays is preferred from the viewpoint that polar functional groups such as carboxyl groups in the present composition are not consumed by the reaction and high cohesive force derived from polar components and adhesive properties can be maintained.
  • crosslinking agent examples include (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, amide group, and N-substituted.
  • the crosslinking agent which has at least 1 sort (s) of crosslinkable functional group chosen from a (meth) acrylamide group and an alkoxy silyl group can be mentioned, You may use 1 type or in combination of 2 or more types.
  • the crosslinkable functional group may be protected with a deprotectable protecting group.
  • polyfunctional (meth) acrylate is preferable from the viewpoint of easy control of the crosslinking reaction.
  • examples of such polyfunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, poly Alkylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri
  • UV-curable polyfunctional monomers such as pentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth)
  • cross-linking agent having two or more cross-linkable functional groups examples include glycidyl (meth) acrylate, glycidyl ⁇ -ethyl acrylate, 3,4-epoxybutyl (meth) acrylate, 4-hydroxybutyl ( Epoxy group-containing monomers such as (meth) acrylate glycidyl ether; 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, (meth) acrylic acid 2- (0- [ Monomers containing isocyanate groups or blocked isocyanate groups such as 1′-methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate; vinyltrimethoxysilane, Vinyltriethoxysilane, 3-glycidoxypro
  • the crosslinking agent having two or more kinds of crosslinkable functional groups has a structure in which one functional group is reacted with a (meth) acrylic (co) polymer and bonded to the (meth) acrylic (co) polymer. Good.
  • a double bondable crosslinkable functional group such as a (meth) acryloyl group or a vinyl group to the (meth) acrylic (co) polymer.
  • a crosslinking agent is couple
  • the reaction efficiency of the photocrosslinking reaction is promoted by bonding the crosslinking agent to the (meth) acrylic (co) polymer, a cured product having a higher cohesive force tends to be obtained. .
  • the present composition may further contain a monofunctional monomer that reacts with the crosslinkable functional group of the crosslinking agent.
  • monofunctional monomers include alkyl (meth) acrylates such as methyl acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyalkylene glycol (meth) acrylate, and the like.
  • Ether group-containing (meth) acrylate (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, phenyl (meth)
  • examples include (meth) acrylamide monomers such as acrylamide, N-methoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
  • a hydroxyl group-containing (meth) acrylate or a (meth) acrylamide monomer it is preferable to use a hydroxyl group-containing (meth) acrylate or a (meth) acrylamide monomer.
  • the content of the crosslinking agent is a ratio of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer, from the viewpoint of balancing the flexibility and cohesion of the composition.
  • it is preferably 0.05 parts by mass or more and 8 parts by mass or less, and particularly preferably 0.1 parts by mass or more or 5 parts by mass or less.
  • this adhesive sheet is a multilayer, about the layer used as an intermediate
  • the content of the crosslinking agent in the intermediate layer or the layer serving as the base material is preferably blended at a ratio of 0.01 to 40 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer. Especially, it is particularly preferably 1 part by mass or more and 30 parts by mass or less, and particularly preferably 2 parts by mass or more or 25 parts by mass or less.
  • Photopolymerization initiator When performing crosslinking by light irradiation, it is preferable to contain a photopolymerization initiator. Radical generation mechanisms by photopolymerization initiators are broadly classified into two types: ⁇ -cleavage type that cleaves and decomposes its own single bond to generate radicals, and hydrogen abstraction that excites hydrogen from compounds in the system to generate radicals. There is a type. Among these, it is preferable to use a hydrogen abstraction type photocrosslinking initiator.
  • an organic crosslinking agent having a (meth) acryloyl group is used as the crosslinking agent, it is particularly preferable to further add a photopolymerization initiator. This is because radicals are generated by light irradiation and become the starting point of the polymerization reaction in the system.
  • the photopolymerization initiator those currently known can be used as appropriate.
  • a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
  • a photopolymerization initiator sensitive to light having a wavelength longer than 380 nm is preferable in that high photoreactivity can be obtained and sensitive light can easily reach the deep part of the pressure-sensitive adhesive sheet.
  • Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage-type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself to generate a radical, and a photoexcited initiator. It is roughly classified into a hydrogen abstraction type photopolymerization initiator which can form an exciplex with a hydrogen donor in the system and transfer hydrogen of the hydrogen donor.
  • the cleavage type photopolymerization initiator decomposes to generate another compound when generating radicals by light irradiation, and once excited, it does not function as a crosslinking initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
  • a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product like a cleavage type photopolymerization initiator during radical generation reaction by irradiation with active energy rays such as ultraviolet rays, so it is difficult to become a volatile component after the reaction is completed. This is useful in that damage to the body can be reduced.
  • bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,4 is high in sensitivity to light and dissociates as a decomposition product after the reaction.
  • Acylphosphine oxides such as 6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide Photoinitiators are preferred.
  • Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meta ) Acryloyloxybenzophenone, 4- [2-((meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2- Phenyl-2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2 , 4-Dimethylthioxanthone And anthraquinone,
  • benzophenone 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, 4- [ 2-((Meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate and methyl benzoylformate are preferred.
  • the photoinitiator mentioned above may use any 1 type or its derivative (s), and may use them in combination of 2 or more type.
  • a sensitizer in addition to the photopolymerization initiator.
  • the sensitizer is not particularly limited, and any sensitizer that can be used as a photopolymerization initiator can be used without any problem. Examples include aromatic amines, anthracene derivatives, anthraquinone derivatives, coumarin derivatives, thioxanthone derivatives, phthalocyanine derivatives, aromatic ketones such as benzophenone, xanthone, thioxanthone, Michler ketone, 9,10-phenanthraquinone, and derivatives thereof.
  • the photoinitiator and the sensitizer may be contained in a state of being bonded to the (meth) acrylic (co) polymer.
  • a method for bonding a photopolymerization initiator or a sensitizer to a (meth) acrylic (co) polymer the same method as that for bonding the crosslinking agent to a (meth) acrylic (co) polymer is adopted. can do.
  • the content of the photopolymerization initiator is not particularly limited, and is typically 0.1 to 10 parts by mass, and particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer. It is particularly preferable to adjust at a ratio of 2 parts by mass or more or 5 parts by mass or less, and among them, 0.5 parts by mass or more or 3 parts by mass or less. However, this range may be exceeded in balance with other elements.
  • the present composition may contain an antioxidant as necessary.
  • the antioxidant include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), hexamethylene glycol-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene, n-octadecyl-3- (4′-hydroxy-3 ′, 5 '-Di-t-butylphenol) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidene-bis- (6
  • the present composition may appropriately contain known components blended in a normal pressure-sensitive adhesive composition.
  • light stabilizers such as light stabilizers, UV absorbers, metal deactivators, rust inhibitors (excluding metal corrosion inhibitors described above), anti-aging agents, antistatic agents, hygroscopic agents, foaming agents, antifoaming agents, inorganic
  • additives such as particles, viscosity modifiers, tackifier resins, photosensitizers, fluorescent agents, and reaction catalysts (tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.) are appropriately added. It is possible.
  • the pressure-sensitive adhesive composition used in the pressure-sensitive adhesive sheet comprises a (meth) acrylic (co) polymer, 1,2,3-triazole and other components as necessary, such as a phosphite compound, It can be obtained by mixing a predetermined amount of a crosslinking agent or the like. These mixing methods are not particularly limited, and the order of mixing the components is not particularly limited.
  • a heat treatment step may be performed at the time of producing the present composition. In this case, it is desirable to perform heat treatment after previously mixing the components of the present composition. You may use what concentrated various mixing components into the masterbatch.
  • the apparatus for mixing is not particularly limited, and for example, a universal kneader, a planetary mixer, a Banbury mixer, a kneader, a gate mixer, a pressure kneader, three rolls, and two rolls can be used. You may mix using a solvent as needed.
  • this composition can be used as a solvent-free system which does not contain a solvent. By using it as a solvent-free system, the solvent does not remain, and there can be provided the advantages that the heat resistance and light resistance are enhanced.
  • the present composition is a composition containing a monomer component constituting the (meth) acrylic (co) polymer, 1,2,3-triazole, a photopolymerization initiator, and other optional components, which is electrically conductive.
  • a monomer component constituting the (meth) acrylic (co) polymer 1,2,3-triazole, a photopolymerization initiator, and other optional components, which is electrically conductive.
  • this pressure-sensitive adhesive sheet can be used as a single-layer or multi-layer sheet on a release film. It can also be.
  • the material of the release film include a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a triacetyl cellulose film, and a fluororesin film. Among these, a polyester film and a polyolefin film are particularly preferable.
  • the thickness of the release film is not particularly limited. Among them, for example, from the viewpoint of processability and handling properties, it is preferably 25 ⁇ m to 500 ⁇ m, more preferably 38 ⁇ m or more and 250 ⁇ m or less, and particularly preferably 50 ⁇ m or more or 200 ⁇ m or less.
  • the pressure-sensitive adhesive sheet may employ a method of directly extruding the composition or a method of molding by pouring into a mold without using an adherend or a release film as described above. I can do it. Furthermore, it can also be set as the aspect of an adhesive sheet by directly filling this composition between members, such as an electrically-conductive member.
  • the resistance value ( ⁇ 0) at room temperature of the ITO wiring in the ITO wiring with the adhesive sheet is measured in advance, and the ITO wiring with the adhesive sheet is stored in an environment of 65 ° C. and 90% RH for 500 hours.
  • the resistance value ( ⁇ ) after the storage of the ITO wiring in the ITO wiring with the adhesive sheet is measured.
  • the adhesive composition for conductive member (this composition) is formed into a sheet having a thickness of 150 ⁇ m to form an adhesive sheet, and the copper wiring substrate for evaluation formed by forming a copper wiring on the glass substrate is A pressure sensitive adhesive sheet is bonded to produce a copper wiring with a pressure sensitive adhesive sheet.
  • the resistance value ( ⁇ 0) at room temperature of the copper wiring in the copper wiring with the adhesive sheet is measured in advance, and the copper wiring with the adhesive sheet is stored in an environment of 65 ° C. and 90% RH for 500 hours.
  • the resistance value ( ⁇ ) after the storage of the copper wiring in the copper wiring with the adhesive sheet is measured.
  • the pressure-sensitive adhesive sheet is preferably optically transparent. That is, it is preferably a transparent adhesive sheet.
  • optically transparent means that the total light transmittance is 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the thickness of the pressure-sensitive adhesive sheet is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 15 ⁇ m or more or 400 ⁇ m or less, and particularly preferably 20 ⁇ m or more or 350 ⁇ m or less.
  • This adhesive sheet is, for example, an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, such as a plasma display (PDP), a liquid crystal display (LCD).
  • an image display device using an image display panel such as an organic EL display (OLED), an inorganic EL display, an electrophoretic display (EPD), and an interferometric modulation display (IMOD)
  • each component member particularly a conductive member, particularly a transparent conductive member
  • OLED organic EL display
  • EPD electrophoretic display
  • MIMOD interferometric modulation display
  • each component member particularly a conductive member, particularly a transparent conductive member
  • laminating a conductive member having a conductor pattern formed of a metal material including a layer and / or copper It is also suitable for bonding a conductive member including a transparent conductive layer containing ITO or IGZO and / or
  • the conductive member laminate of the present invention (hereinafter abbreviated as “the present laminate”) can be obtained by laminating the pressure-sensitive adhesive sheet and a conductive member, for example, a conductive layer surface of a transparent conductive layer. .
  • This laminated body should just have the structure which the adhesive layer surface of any one of this adhesive sheet and the conductive layer surface of a transparent conductive layer bonded together.
  • the laminate may have a structure in which both the pressure-sensitive adhesive layer surfaces of the pressure-sensitive adhesive sheet and the conductive layer surface of the transparent conductive layer are bonded together.
  • the transparent conductive layer has an insulating protective film (passivation film) made of olefin polymer, urethane polymer, epoxy polymer, acrylic polymer, silicone polymer, or inorganic glass so as to cover the conductive layer surface of the conductive film. May be.
  • the pressure-sensitive adhesive sheet is not directly bonded to the transparent conductive layer surface (not directly in contact with the transparent conductive layer surface).
  • the adhesive sheet corrodes the transparent conductive layer by the action of 1,2,3-triazole even if the component derived from the composition (particularly the acid component) penetrates and reaches the transparent conductive layer from the insulating film. This can be prevented.
  • 1,2,3-triazole is highly water-soluble and can easily move to the transparent conductive layer when the pressure-sensitive adhesive sheet absorbs moisture in a moist heat environment, so that an excellent metal corrosion prevention effect can be achieved.
  • an excellent metal corrosion prevention effect on the adherend is exhibited as well as discoloration and alteration of the pressure-sensitive adhesive layer due to metal ions on the adherend. Can do.
  • the laminate obtained by bonding to the conductive layer surface can be suitably used for a touch panel.
  • the touch panel include a resistance film method, a capacitance method, and an electromagnetic induction method, and a capacitance method is preferable.
  • the transparent conductive layer only needs to have a conductive layer on at least one surface, and examples thereof include a transparent conductive layer in which a conductive material is provided on the surface of a transparent substrate by vapor deposition, sputtering, coating, or the like.
  • the conductive material used for the conductive layer of the transparent conductive layer is not particularly limited. Specifically, indium oxide, indium / gallium / zinc composite oxide, tin-doped indium oxide (ITO), zinc oxide, gallium oxide, titanium oxide
  • ITO tin-doped indium oxide
  • metal oxides such as, metal materials such as silver, copper, molybdenum, and aluminum can be given.
  • the transparent conductive layer the substrate on which the conductive substance is patterned is not particularly limited, and examples thereof include glass and a resin film.
  • the transparent conductive layer typically has a conductive layer on at least one surface.
  • a conductive pattern (wiring pattern) mainly composed of copper or silver is formed on the transparent conductive layer so as to route the peripheral portion. Since 1,2,3-triazole has particularly high resistance to corrosion resistance to copper, this pressure-sensitive adhesive sheet including this is particularly suitable for conductive members having a conductor pattern formed of a metal material containing copper. It can be preferably used.
  • the laminate include, for example, a release film / this adhesive sheet / touch panel, a release film / this adhesive sheet / protective panel, a release film / this adhesive sheet / image display panel, and an image display panel / book.
  • the composition of the present adhesive sheet / protective panel can be mentioned.
  • the touch panel includes a structure in which a touch panel function is included in the protective panel and a structure in which the touch panel function is included in the image display panel.
  • the image display device of the present invention includes at least the present laminate, the image display panel, and the surface protection panel as constituent members.
  • an image display device having a configuration in which the laminate obtained by bonding the adhesive sheet to the conductive layer surface of the transparent conductive layer is interposed between the image display panel and the surface protection panel is mentioned. Can do. At this time, the pressure-sensitive adhesive sheet can also be used on the image display panel side.
  • acryl-based polyolefin resin such as acrylic resin, polycarbonate resin, cycloolefin polymer, styrene resin, polyvinyl chloride resin, phenol resin, melamine resin, Plastics such as epoxy resins may be used.
  • the image display panel is composed of another optical film such as a polarizing film or other retardation film, a liquid crystal material, and a backlight system (usually, the adherend surface of the composition or the adhesive article to the image display panel is an optical film.
  • a polarizing film or other retardation film such as a liquid crystal material
  • a backlight system usually, the adherend surface of the composition or the adhesive article to the image display panel is an optical film.
  • STN method, VA method, IPS method, etc. depending on the control method of the liquid crystal material, but any method may be used.
  • an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display can be configured.
  • a liquid crystal display an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display
  • MEMS microelectromechanical system
  • “Sheet” generally refers to a product that is thin by definition in JIS and has a thickness that is small and flat for the length and width.
  • “film” is thicker than the length and width.
  • JISK6900 Japanese Industrial Standard
  • the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
  • A-1 A copolymer comprising 76 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 4 parts by mass of acrylic acid (mass average molecular weight 400,000)
  • A-2 A copolymer comprising 81 parts by mass of butyl acrylate, 15 parts by mass of methyl methacrylate and 4 parts by mass of acrylic acid (mass average molecular weight 200,000)
  • Example 1-1 1 kg of (meth) acrylic (co) polymer (A-1), 3 g of 1,2,3-triazole (manufactured by Otsuka Chemical Co., Ltd.) as a metal corrosion inhibitor, and 4-methylbenzophenone as a photopolymerization initiator 15 g of a mixture of 2,4,6-trimethylbenzophenone (manufactured by Lamberti, trade name “Ezacure TZT”) was added and mixed uniformly to obtain a resin composition for an adhesive layer.
  • 1,2,3-triazole manufactured by Otsuka Chemical Co., Ltd.
  • 4-methylbenzophenone as a photopolymerization initiator
  • 15 g of a mixture of 2,4,6-trimethylbenzophenone manufactured by Lamberti, trade name “Ezacure TZT”
  • the pressure-sensitive adhesive sheet was shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet was 150 ⁇ m, and a pressure-sensitive adhesive sheet laminate was produced.
  • the adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
  • Example 1-2 1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor, and UV curable resin propoxylated pentaerythritol triacrylate as a crosslinking agent (Shin Nakamura Kogyo Co., Ltd.) 20 g of company, trade name “ATM-4PL”), and 15 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name “Ezacure TZT”, manufactured by Lamberti) as a photopolymerization initiator were added uniformly. By mixing, a resin composition for an adhesive layer was obtained.
  • the resin composition for the pressure-sensitive adhesive layer was molded into a sheet shape so as to have a thickness of 150 ⁇ m on a polyethylene terephthalate film (trade name “Diafoil MRV”, manufactured by Mitsubishi Plastics Co., Ltd., thickness: 100 ⁇ m) subjected to release treatment. Thereafter, a peeled polyethylene terephthalate film (manufactured by Mitsubishi Plastics, trade name “Diafoil MRQ”, thickness 75 ⁇ m) was coated to prepare an adhesive sheet laminate. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
  • Example 1-3 A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 1-2 except that 5 g of 1,2,3-triazole was used as the metal corrosion inhibitor. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
  • Example 1-1 A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 1-1 except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
  • Example 1-2 A pressure-sensitive adhesive sheet laminate was prepared in the same manner as in Example 1-1, except that 5 g of benzotriazole (trade name “BT120” manufactured by Johoku Chemical Co., Ltd.) was used instead of 1,2,3-triazole as a metal corrosion inhibitor. did.
  • the adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
  • Example 1-3 5 g of tolyltriazole (mixture of 4-methylbenzotriazole and 5-methylbenzotriazole) (trade name “SEETEC TT-R” manufactured by Cypro Kasei Co., Ltd.) is used as a metal corrosion inhibitor instead of 1,2,3-triazole.
  • a pressure-sensitive adhesive sheet laminate was produced in the same manner as Example 1-1 except for the above. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
  • Example 1-1 Example 1-1 except that 5 g of 2,5-dimercapto-1,3,4-thiadiazole (trade name “MTD”, manufactured by Toyobo Co., Ltd.) was used in place of 1,2,3-triazole as a metal corrosion inhibitor. In the same manner, a pressure-sensitive adhesive sheet laminate was produced. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
  • the release film on one side of the pressure-sensitive adhesive sheet laminate (pressure-sensitive adhesive sheet thickness 150 ⁇ m) prepared in the above Examples and Comparative Examples was peeled off, and a polyethylene terephthalate (PET) film (trade name “COSMO SHINE A4100, manufactured by Toyobo Co., Ltd.” was applied to the exposed surface. ”, 125 ⁇ m) was attached with a hand roller.
  • PET polyethylene terephthalate
  • the pressure-sensitive adhesive sheet was adhered to a copper glass substrate for evaluation with a hand roller, and the cumulative amount of light with a wavelength of 365 nm was 3000 mJ / in Example 1-1 and Comparative Examples 1-1 to 1-4 via a PET film.
  • cm 2 examples 1-2 and 1-3 irradiated with ultraviolet rays using a high-pressure mercury lamp so as to be 2000 mJ / cm 2, by UV cross, corrosion reliability evaluation samples (copper wire with the pressure-sensitive adhesive sheet) It produced (refer FIG.1 (D)).
  • the resistance value ( ⁇ 0) at room temperature of the copper wiring in this corrosion resistance reliability evaluation sample was measured in advance.
  • the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) The resistance value ( ⁇ ) of the copper wiring was measured.
  • the bonded product was autoclaved at 60 ° C. in a 0.2 MPa environment for 20 minutes.
  • a metal halide lamp irradiation device Ushio Electric Co., Ltd., model UVC-0516S1, lamp UVL-8001M3-N
  • a belt conveyor so that the irradiation dose at a wavelength of 365 nm is 3000 mJ / cm 2 per irradiation.
  • UV curing characteristics (storage modulus G ′ before UV curing)
  • the storage elastic modulus before UV curing was measured using a rheometer (Eihiro Seiki Co., Ltd.) as a measurement sample obtained by punching the adhesive sheets prepared in Examples and Comparative Examples to a thickness of 1 to 2 mm and punching them into a circle with a diameter of 20 mm.
  • a “MARS” manufactured by the company adhesive jig: ⁇ 25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: ⁇ 50 to 200 ° C., heating rate: 3 ° C./min, ⁇ 50 ° C.
  • the dynamic storage elastic modulus G ′ up to 200 ° C. was measured, and the storage elastic modulus value at 125 ° C. was read. The results are shown in Table 1.
  • the storage elastic modulus after UV curing was measured as follows.
  • the pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were UV-crosslinked by irradiating UV light with a high-pressure mercury lamp through a PET film.
  • Example 1-1 and Comparative Examples 1-1 to 1-4 were irradiated so that the integrated light quantity with a wavelength of 365 nm was 3000 mJ / cm 2, and Examples 1-2 and 1-3 were the laminates. Irradiation was performed so that the amount of light was 2000 mJ / cm 2 .
  • the pressure-sensitive adhesive sheet thus UV-crosslinked was laminated to a thickness of 1 to 2 mm, and punched into a circle having a diameter of 20 mm was used as a measurement sample.
  • a rheometer (trade name “MARS”, manufactured by Eiko Seiki Co., Ltd.), adhesive jig: ⁇ 25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: ⁇ 50 to 200 ° C., heating rate: 3
  • the storage elastic modulus after ultraviolet curing was determined by measuring the dynamic storage elastic modulus G ′ of the measurement sample from ⁇ 50 ° C. to 200 ° C. at a rate of °C / min and reading the storage elastic modulus value at 125 ° C. . The results are shown in Table 1.
  • the adhesive sheets of Examples 1-1 to 1-3 contain 1,2,3-triazole as a metal corrosion inhibitor, so that there is little change in the resistance value of the copper wiring and excellent corrosion resistance reliability. there were. In addition, the foaming resistance reliability and ultraviolet curing characteristics were also good.
  • Comparative Example 1-1 did not contain a metal corrosion inhibitor and was inferior in corrosion resistance reliability.
  • Comparative Example 1-2 contained benzotriazole as a metal corrosion inhibitor, but was poor in foaming reliability due to the characteristics of benzotriazole.
  • Comparative Example 1-3 contained tolyltriazole as a metal corrosion inhibitor, but was poor in foaming reliability due to the characteristics of tolyltriazole.
  • Comparative Example 1-4 contains dimercaptothiadiazole as a metal corrosion inhibitor. However, since dimercaptothiadiazole absorbs ultraviolet rays, the pressure-sensitive adhesive sheet was inferior in ultraviolet curing properties.
  • 1,2,3-triazole has a melting point of about 20 ° C. and is almost liquid at room temperature. Therefore, it can be easily added to the main adhesive in the actual production process of the adhesive sheet. It was found to be excellent in dispersibility in the main agent.
  • 1,2,3-triazole is highly water-soluble and, when the pressure-sensitive adhesive sheet absorbs moisture in a moist heat environment, it easily moves to the surface of the metal layer (copper wiring), so it has an excellent metal corrosion prevention effect. It became clear that we could do it. It has also been clarified that 1,2,3-triazole does not inhibit the UV curing property because it does not absorb at a spectrophotometer with a wavelength of 300 to 400 nm. As described above, it has been found that 1,2,3-triazole has excellent characteristics as compared with conventional metal corrosion inhibitors and is particularly effective when used for an adhesive sheet for conductive members.
  • Example 2 200 kg of propoxylated pentaerythritol polyacrylate (trade name “ATM-4PL”, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent for 1 kg of (meth) acrylic (co) polymer (A-1), photopolymerization started As an agent, 10 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (Lamberti, trade name “Ezacure TZT”) was added and mixed uniformly to obtain an intermediate layer resin composition.
  • ATM-4PL propoxylated pentaerythritol polyacrylate
  • Two polyethylene terephthalate films (trade name “Diafoil MRV”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 100 ⁇ m, and product name “Diafoil MRT” manufactured by Mitsubishi Plastics Co., Ltd.) were prepared by removing the oil composition for the adhesive layer. , 38 ⁇ m thick) and shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet is 35 ⁇ m, to produce a resin sheet ( ⁇ ) for the pressure-sensitive adhesive layer.
  • the PET films on both sides of the intermediate layer sheet ( ⁇ ) are sequentially peeled and removed, and the PET films on one side of the adhesive layer resin sheets ( ⁇ ) and ( ⁇ ′) are peeled off to place the exposed adhesive surface in the middle.
  • Laminate bodies made of ( ⁇ ) / ( ⁇ ) / ( ⁇ ′) were prepared by sequentially laminating on both surfaces of the layer sheet ( ⁇ ).
  • Example 2-2 1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor, tridecyl phosphite as a phosphite compound (trade name, manufactured by Adeka) 3 g of “ADK STAB 3010”), 20 g of pentaerythritol tri and tetraacrylate (manufactured by Toagosei Co., Ltd., “Aronix M-306”) as a crosslinking agent, and 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF, Irgacure as a photopolymerization initiator) 184) 10 g was added and mixed uniformly to obtain a resin composition for an adhesive layer.
  • A-2 1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor, tridecyl phosphite
  • the pressure-sensitive adhesive layer resin composition was formed into a sheet shape having a thickness of 150 ⁇ m on a peeled polyethylene terephthalate film (Mitsubishi Resin, Diafoil MRV, thickness 100 ⁇ m), and then peeled.
  • a polyethylene terephthalate film (trade name “Diafoil MRQ”, thickness 75 ⁇ m, manufactured by Mitsubishi Plastics, Inc.) was coated.
  • a pressure-sensitive adhesive sheet laminate is obtained by irradiating ultraviolet rays with a high-pressure mercury lamp through an exfoliated polyethylene terephthalate film so that the integrated light quantity at a wavelength of 365 nm is 1000 mJ / cm 2 to cross-link the adhesive layer resin composition with ultraviolet rays.
  • the adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
  • Example 2-3 3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (trade name “JPE-10” manufactured by Johoku Chemical Co., Ltd.) as a phosphite compound
  • JPE-10 Japanese Patent Application Laid-Pak Company
  • a pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-2 except that 3 g was used. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
  • Example 2-1 1,2,3-triazole as a metal corrosion inhibitor and tris (2,4-di-t-butylphenyl) phosphite as a phosphite compound (trade name “Irgaphos 168” manufactured by BASF) Except not being added, in the same manner as in Example 2-1, the pressure-sensitive adhesive sheet laminate in which the pressure-sensitive adhesive sheet laminate was produced was subjected to various evaluations described below. The results are shown in Table 2.
  • Example 2-2 A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1, except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
  • Example 2-3 As a metal corrosion inhibitor, except that 1.5 g of benzotriazole (manufactured by Johoku Chemical Co., Ltd., trade name “BT120”) is added in place of 1,2,3-triazole, and the phosphite compound is not added.
  • a pressure-sensitive adhesive sheet laminate was produced in the same manner as Example 2-1. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
  • ITO Indium oxide
  • the resistance value ( ⁇ 0) at room temperature of the ITO wiring in this oxidation deterioration prevention evaluation sample (ITO wiring with adhesive sheet) was measured in advance.
  • the oxidation degradation prevention evaluation sample (ITO wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the oxidation degradation resistance evaluation sample (ITO wiring with adhesive sheet) is stored. ) was measured for the resistance value ( ⁇ ) of the ITO wiring.
  • the resistance value ( ⁇ 0) at room temperature of the copper wiring in this corrosion resistance reliability evaluation sample was measured in advance.
  • the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) The resistance value ( ⁇ ) of the copper wiring was measured.
  • the adhesive sheets of Examples 2-1 to 2-3 contain 1,2,3-triazole as a metal corrosion inhibitor, and further contain a phosphite, so that the resistance value of both ITO wiring and copper wiring changes. There were few, and it was excellent in corrosion resistance reliability and oxidation deterioration prevention property.
  • Comparative Example 2-1 contained neither a phosphite compound nor a metal corrosion inhibitor, and was inferior in corrosion resistance reliability and oxidation deterioration prevention properties. Since Comparative Example 2-2 did not contain a metal corrosion inhibitor, corrosion of copper wiring was particularly remarkable. Comparative Example 2-3 did not contain a phosphite compound and was inferior in the ability to prevent oxidative deterioration of the ITO wiring.
  • the pressure-sensitive adhesive sheet for a conductive member of the present invention has corrosion resistance and reliability against a conductive member (typically a conductive member having a conductive pattern formed of a transparent conductive layer and / or a metal material containing copper or silver). Since it can have foaming reliability, it can be used as an adhesive sheet suitable for bonding various conductive members. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.
  • a conductive member typically a conductive member having a conductive pattern formed of a transparent conductive layer and / or a metal material containing copper or silver. Since it can have foaming reliability, it can be used as an adhesive sheet suitable for bonding various conductive members. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

Abstract

Provided are: an adhesive sheet for conductive members, which will not corrode a conductive member such as, for example, a transparent conductive layer, and which has forming resistance reliability and fine curing properties; a conductive member laminate; and an image display device. Particularly , the present invention provides an adhesive sheet for conductive members, which is preferable for bonding a conductive member such as a transparent conductive layer in an image display device using an image display panel such as a plasma display (PDP), a liquid crystal display (LCD), an organic EL display (OLED), or the like. The adhesive sheet for conductive members has an adhesive agent layer comprising an adhesive agent composition containing a (meth)acryl-based copolymer and 1,2,3-triazole.

Description

導電部材用粘着シート、導電部材積層体及び画像表示装置Adhesive sheet for conductive member, conductive member laminate, and image display device
　本発明は、導電部材用粘着シート及び当該粘着シートを用いた導電部材積層体等に関する。特に、プラズマディスプレイ（ＰＤＰ）、液晶ディスプレイ（ＬＣＤ）、有機ＥＬディスプレイ（ＯＬＥＤ）、無機ＥＬディスプレイ、電気泳動ディスプレイ（ＥＰＤ）、干渉変調ディスプレイ（ＩＭＯＤ）等の画像表示パネルを用いた画像表示装置において、透明導電層等の導電部材を貼り合わせるのに好適な導電部材用粘着シート等に関する。 The present invention relates to a pressure-sensitive adhesive sheet for a conductive member and a conductive member laminate using the pressure-sensitive adhesive sheet. In particular, in an image display device using an image display panel such as a plasma display (PDP), a liquid crystal display (LCD), an organic EL display (OLED), an inorganic EL display, an electrophoretic display (EPD), an interference modulation display (IMOD), etc. The present invention relates to a pressure-sensitive adhesive sheet for a conductive member suitable for bonding conductive members such as a transparent conductive layer.
　パーソナルコンピューター、モバイル端末（ＰＤＡ）、ゲーム機、テレビ（ＴＶ）、カーナビゲーションシステム、タッチパネル、ペンタブレット等の画像表示装置、例えば、プラズマディスプレイ（ＰＤＰ）、液晶ディスプレイ（ＬＣＤ）、有機ＥＬディスプレイ（ＯＬＥＤ）、無機ＥＬディスプレイ、電気泳動ディスプレイ（ＥＰＤ）、干渉変調ディスプレイ（ＩＭＯＤ）等の平面型又は曲面を有する画像表示パネルを用いた画像表示装置においては、視認性確保や破損防止等のため、各構成部材間に空隙を設けず、各構成物材間を粘着シートや液状粘着剤で貼り合わせて一体化することが行われている。 Image display devices such as personal computers, mobile terminals (PDAs), game machines, televisions (TVs), car navigation systems, touch panels, pen tablets, for example, plasma displays (PDPs), liquid crystal displays (LCDs), organic EL displays (OLEDs) ), In an image display device using a flat or curved image display panel such as an inorganic EL display, an electrophoretic display (EPD), an interferometric modulation display (IMOD), etc. A gap is not provided between the constituent members, and the constituent materials are bonded and integrated with an adhesive sheet or a liquid adhesive.
　例えば、液晶モジュールの視認側と表面保護パネルとの間にタッチパネルが介挿されてなる構成を備えた画像表示装置では、表面保護パネルと液晶モジュールの視認側との間に粘着シートや液状粘着剤を配置し、タッチパネルと他の構成部材、例えば、タッチパネルと液晶モジュール、タッチパネルと表面保護パネルとを貼り合わせて一体化することが行われている。 For example, in an image display device having a configuration in which a touch panel is interposed between the viewing side of the liquid crystal module and the surface protection panel, an adhesive sheet or liquid adhesive is provided between the surface protection panel and the viewing side of the liquid crystal module. The touch panel and other constituent members, for example, the touch panel and the liquid crystal module, and the touch panel and the surface protection panel are bonded and integrated.
　タッチパネルは通常、錫ドープ酸化インジウム（ＩＴＯ）、インジウム・ガリウム・亜鉛複合酸化物（ＩＧＺＯ）、Ｇａドープ酸化亜鉛（ＧＺＯ）等の金属酸化物や、銀、銅、モリブデン等の金属材料で形成された微細配線や、銀ナノワイヤー、カーボンナノチューブ等から形成された透明導電層を有する上部電極板及び下部電極板を備えている。また、透明導電層により検知した指やタッチペンなどの位置情報を集約して通信するために、金属材料で形成された導体パターン（配線パターン）が透明導電層とＩＣ等の制御手段との間に形成される。これらの各種材料から形成された透明導電層や導体パターンは、通常、表面が粘着剤と接するように固定される。この透明導電層や導体パターンは、腐食に対して脆弱であり、高温や湿熱環境下において粘着材のアウトガスや溶出成分由来の酸成分などにより腐食し、場合によっては断線するなどのおそれがある。 Touch panels are usually made of metal oxides such as tin-doped indium oxide (ITO), indium-gallium-zinc composite oxide (IGZO), and Ga-doped zinc oxide (GZO), and metal materials such as silver, copper, and molybdenum. And an upper electrode plate and a lower electrode plate having a transparent conductive layer formed of fine wiring, silver nanowires, carbon nanotubes, or the like. In addition, in order to collect and communicate positional information such as a finger and a touch pen detected by the transparent conductive layer, a conductor pattern (wiring pattern) formed of a metal material is interposed between the transparent conductive layer and a control means such as an IC. It is formed. The transparent conductive layer and conductor pattern formed from these various materials are usually fixed so that the surface is in contact with the adhesive. The transparent conductive layer and the conductive pattern are vulnerable to corrosion, and may corrode due to the outgas of the adhesive material or the acid component derived from the elution component in a high temperature or wet heat environment, possibly resulting in disconnection.
　そこで、例えば特許文献１には、金属腐食防止剤としてベンゾトリアゾール及び／又はその誘導体を含有する金属貼付用粘着シートが開示されている。 Thus, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet for metal sticking containing benzotriazole and / or a derivative thereof as a metal corrosion inhibitor.
　また、例えば特許文献２には、アルコキシアルキルアクリレート及び架橋可能な官能基を有するアクリル系モノマーを必須成分として構成されるアクリル系ポリマー及び架橋剤を含む粘着剤組成物であって、アクリル系ポリマー中にカルボキシル基含有モノマーを実質的に含まない粘着剤組成物が開示されている。かかる粘着剤組成物によれば、特定量の脂肪族系イソシアネート架橋剤及び複数のヒドロキシル基を含有するアミン系化合物を使用することによって黄変を抑制し、また、アクリル系ポリマーが架橋構造をとることによって、カルボキシル基含有モノマー成分を含まなくても、高温下の耐発泡・剥がれ性を満足することができることが開示されている。 Further, for example, Patent Document 2 discloses a pressure-sensitive adhesive composition comprising an acrylic polymer and a crosslinking agent, each of which includes an alkoxyalkyl acrylate and an acrylic monomer having a crosslinkable functional group as essential components. Discloses a pressure-sensitive adhesive composition substantially free of a carboxyl group-containing monomer. According to this pressure-sensitive adhesive composition, yellowing is suppressed by using a specific amount of an aliphatic isocyanate crosslinking agent and an amine compound containing a plurality of hydroxyl groups, and the acrylic polymer has a crosslinked structure. Accordingly, it is disclosed that even when a carboxyl group-containing monomer component is not included, the anti-foaming / peeling property under high temperature can be satisfied.
特開２００６－４５３１５号公報JP 2006-45315 A 特開２００９－０７９２０３号公報JP 2009-079203 A1
　画像表示装置に用いられる構成部材には、高温や高湿環境下において経時的にガス（「アウトガス」とも称する。）を発生する部材が含まれているため、これら画像表示装置の構成部材を粘着シートで貼り合せる場合には、該粘着シートは、アウトガスのガス圧に対して十分に対抗できる耐発泡信頼性を有する必要もある。 The constituent members used in the image display device include members that generate gas (also referred to as “outgas”) over time in a high-temperature or high-humidity environment. In the case of bonding with a sheet, the pressure-sensitive adhesive sheet also needs to have foaming reliability that can sufficiently resist the gas pressure of outgas.
　上記特許文献１の金属腐食防止剤を含有する両面粘着シートでは、金属腐食防止剤が紫外線を照射する耐久性試験で発泡し、光学特性を低下させるなどの問題点があった。 The double-sided pressure-sensitive adhesive sheet containing the metal corrosion inhibitor of Patent Document 1 has a problem that the metal corrosion inhibitor is foamed in a durability test that is irradiated with ultraviolet rays, and optical properties are deteriorated.
　上記特許文献２の粘着剤組成物によれば、アクリル酸等のカルボキシル基含有モノマーを含まないアクリル系ポリマーであっても、高温下の耐発泡・剥がれ性を満足することができるとされているが、腐食の要因である水分の粘着剤中への浸入は防ぐことができないため、金属腐食防止性の観点から必ずしも満足できるものではなかった。 According to the pressure-sensitive adhesive composition of Patent Document 2, it is said that even an acrylic polymer that does not contain a carboxyl group-containing monomer such as acrylic acid can satisfy the resistance to foaming and peeling at high temperatures. However, since it is impossible to prevent moisture from entering the pressure-sensitive adhesive, which is a cause of corrosion, it is not always satisfactory from the viewpoint of metal corrosion prevention.
　そこで、本発明が解決しようとする課題は、導電部材を腐食させることなく、また、耐発泡信頼性及び良好な硬化特性を有する導電部材用粘着シートを提供することにある。より具体的には、透明導電層の導電層面や金属材料で形成された導体パターン（配線パターン）と直接貼り合わせても、これらを腐食させることがなく、また、透明導電層の導電層面と絶縁保護膜（パシベーション膜）を介して貼り合わせても透明導電層を腐食させることのない導電部材用粘着シートを提供することである。 Therefore, the problem to be solved by the present invention is to provide a pressure-sensitive adhesive sheet for a conductive member that does not corrode the conductive member and has foaming reliability and good curing characteristics. More specifically, even if directly bonded to the conductive layer surface of the transparent conductive layer or a conductor pattern (wiring pattern) formed of a metal material, these are not corroded and insulated from the conductive layer surface of the transparent conductive layer. It is to provide a pressure-sensitive adhesive sheet for a conductive member that does not corrode a transparent conductive layer even when bonded through a protective film (passivation film).
　本発明は、（メタ）アクリル系共重合体及び１，２，３－トリアゾールを含有する粘着剤組成物からなる粘着剤層を有することを主要な特徴とする。 The main feature of the present invention is that it has a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer and 1,2,3-triazole.
　本発明の導電部材用粘着シートは、導電部材に対する耐腐食信頼性を有すると共に粘着シートとしての耐発泡信頼性及び良好な硬化特性をも有することができる。そのため、本発明の導電部材用粘着シートは、透明導電層及び／又は銅若しくは銀を含む金属材料で形成された導体パターンを有する導電部材等の各種導電部材を貼り合わせるのに好適な粘着シートとして用いることができる。とりわけ、タッチパネルを有する画像表示装置用の粘着シートとして好適に用いることができる。 The pressure-sensitive adhesive sheet for a conductive member of the present invention has corrosion resistance reliability with respect to a conductive member and can also have foaming reliability reliability and good curing characteristics as a pressure-sensitive adhesive sheet. Therefore, the pressure-sensitive adhesive sheet for a conductive member of the present invention is a pressure-sensitive adhesive sheet suitable for bonding various conductive members such as a conductive member having a conductive pattern formed of a transparent conductive layer and / or a metal material containing copper or silver. Can be used. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.
後述する実施例において、耐腐食信頼性の評価試験方法を説明するための図であり、（Ａ）は酸化劣化防止性評価用ＩＴＯガラス基板のＩＴＯパターンの上面図又は耐腐食信頼性評価用銅ガラス基板の銅パターンの上面図、（Ｂ）は酸化劣化防止性評価用ＩＴＯガラス基板上に粘着シートを被覆した状態を示した上面図又は耐腐食信頼性評価用銅ガラス基板上に粘着シートを被覆した状態を示した上面図、（Ｃ）は酸化劣化防止性評価用サンプルの断面図、（Ｄ）は耐腐食信頼性評価用サンプルの断面図である。BRIEF DESCRIPTION OF THE DRAWINGS In the Example mentioned later, it is a figure for demonstrating the evaluation test method of corrosion resistance reliability, (A) is the top view of the ITO pattern of the ITO glass substrate for oxidation deterioration prevention evaluation, or copper for corrosion resistance reliability evaluation The top view of the copper pattern of a glass substrate, (B) is a top view showing a state where an adhesive sheet is coated on an ITO glass substrate for evaluating oxidation resistance, or an adhesive sheet on a copper glass substrate for evaluating corrosion resistance The top view which showed the coat | covered state, (C) is sectional drawing of the sample for oxidation deterioration prevention evaluation, (D) is sectional drawing of the sample for corrosion resistance reliability evaluation.
　以下、本発明の実施形態の一例について詳細に説明する。但し、本発明は下記実施形態に限定されるものではない。 Hereinafter, an example of an embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiment.
＜導電部材用粘着シート＞
　本発明の実施形態の一例に係る導電部材用粘着シート（以下、省略して「本粘着シート」とも称する。）は、（メタ）アクリル系(共)重合体及び１，２，３－トリアゾールを含有する粘着剤組成物からなる粘着剤層を有する。 <Pressure sensitive adhesive sheet>
An adhesive sheet for a conductive member according to an example of an embodiment of the present invention (hereinafter also referred to as “the present adhesive sheet”) includes a (meth) acrylic (co) polymer and 1,2,3-triazole. It has the adhesive layer which consists of an adhesive composition to contain.
　かかる粘着剤層は、単層であっても多層であってもよく、また、多層の場合には、いわゆる基材層のような他の層が介在してもよい。粘着剤層が他の層を有する多層構成である場合は、本粘着シートの表面層が前記粘着剤組成物からなる粘着剤層であることが好ましい。
　本粘着シートが多層である場合、前記粘着剤組成物からなる粘着剤層の厚さは限定されないが、本粘着シート全体の厚みに対し１０％以上であるのが好ましく、より好ましくは３０％以上、更に好ましくは５０％以上である。前記粘着剤組成物からなる粘着剤層の厚さが上記範囲であれば、導電部材に対する耐腐食信頼性、耐発泡信頼性、硬化特性が良好となるため好ましい。
　なお、本発明において、「（共）重合体」とは単独重合体及び共重合体を包括する意味であり、「（メタ）アクリレート」とはアクリレート及びメタクリレートを包括する意味である。 The pressure-sensitive adhesive layer may be a single layer or a multilayer, and in the case of a multilayer, other layers such as a so-called base material layer may be interposed. When the pressure-sensitive adhesive layer has a multilayer structure having other layers, the surface layer of the pressure-sensitive adhesive sheet is preferably a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition.
When the pressure-sensitive adhesive sheet is a multilayer, the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is not limited, but is preferably 10% or more, more preferably 30% or more with respect to the total thickness of the pressure-sensitive adhesive sheet. More preferably, it is 50% or more. If the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is in the above range, it is preferable because corrosion resistance, foaming reliability, and curing characteristics with respect to the conductive member are improved.
In the present invention, “(co) polymer” includes a homopolymer and a copolymer, and “(meth) acrylate” includes an acrylate and a methacrylate.
［粘着剤組成物］
　本粘着シートに用いる粘着剤組成物（以下、省略して「本組成物」という。）は、（メタ）アクリル系(共)重合体及び１，２，３－トリアゾールを含有する。
　本組成物は、さらに亜リン酸エステル化合物、架橋剤、光重合開始剤、酸化防止剤、その他の成分を含有してもよい。
　本組成物は光硬化性の組成物であることが好ましい。 [Adhesive composition]
The pressure-sensitive adhesive composition used for the pressure-sensitive adhesive sheet (hereinafter abbreviated as “the present composition”) contains a (meth) acrylic (co) polymer and 1,2,3-triazole.
The present composition may further contain a phosphite compound, a crosslinking agent, a photopolymerization initiator, an antioxidant, and other components.
The composition is preferably a photocurable composition.
（（メタ）アクリル系(共)重合体）
　（メタ）アクリル系(共)重合体としては、例えば、アルキル（メタ）アクリレートの単独重合体の他、これと共重合性を有するモノマー成分とを重合することにより得られる共重合体を挙げることができ、より好ましくは、アルキル（メタ）アクリレートと、これと共重合可能なカルボキシル基含有モノマー、水酸基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー、アミド基含有モノマー及びその他ビニルモノマーの中から選択されるいずれか一つ以上のモノマーとを構成単位として含む共重合体を挙げることができる。
　（メタ）アクリル系（共）重合体は、以下に例示したモノマー等を、必要により重合開始剤を用いて常法により製造することができる。 ((Meth) acrylic (co) polymer)
Examples of (meth) acrylic (co) polymers include, for example, copolymers obtained by polymerizing alkyl (meth) acrylate homopolymers and copolymerizable monomer components. More preferably, among alkyl (meth) acrylates and carboxyl group-containing monomers, hydroxyl group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, amide group-containing monomers, and other vinyl monomers copolymerizable therewith. Examples thereof include a copolymer containing any one or more selected monomers as a structural unit.
The (meth) acrylic (co) polymer can be produced by a conventional method using the following monomers or the like, if necessary, using a polymerization initiator.
　（メタ）アクリル系（共）重合体がカルボキシル基含有モノマーを構成単位として含む共重合体である場合、（メタ）アクリル系（共）重合体は、優れた粘着物性を得る観点からカルボキシル基含有モノマーを１．２～１５質量％含有するのが好ましく、中でも１．５質量％以上或いは１０質量％以下、その中でも２．０質量％以上或いは８質量％以下含有するのがさらに好ましい。 When the (meth) acrylic (co) polymer is a copolymer containing a carboxyl group-containing monomer as a constituent unit, the (meth) acrylic (co) polymer contains a carboxyl group from the viewpoint of obtaining excellent adhesive properties. The monomer content is preferably 1.2 to 15% by mass, more preferably 1.5% by mass or more and 10% by mass or less, and most preferably 2.0% by mass or more or 8% by mass or less.
　より具体的な（メタ）アクリル系(共)重合体の一例として、側鎖の炭素数が４～１８の直鎖又は分岐アルキル（メタ）アクリレート（以下「共重合性モノマーＡ」とも称する。）と、これと共重合可能な以下の群から選択されるいずれか一つ以上のモノマー成分から構成される共重合体を挙げることができる。 As an example of a more specific (meth) acrylic (co) polymer, a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain (hereinafter also referred to as “copolymerizable monomer A”). And a copolymer composed of any one or more monomer components selected from the following group copolymerizable therewith.
・カルボキシル基含有モノマー（以下「共重合性モノマーＢ」とも称する。）
・マクロモノマー（以下「共重合性モノマーＣ」とも称する。）
・側鎖の炭素数が１～３の（メタ）アクリレート（以下「共重合性モノマーＤ」とも称する。）
・水酸基含有モノマー（以下「共重合性モノマーＥ」とも称する。）
・その他のビニルモノマー（以下「共重合性モノマーＦ」とも称する。） Carboxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer B”)
Macromonomer (hereinafter also referred to as “copolymerizable monomer C”)
(Meth) acrylate having 1 to 3 carbon atoms in the side chain (hereinafter also referred to as “copolymerizable monomer D”)
Hydroxyl group-containing monomer (hereinafter also referred to as “copolymerizable monomer E”)
Other vinyl monomers (hereinafter also referred to as “copolymerizable monomer F”)
　また、（メタ）アクリル系(共)重合体の一例として、（ａ）共重合性モノマーＡと、共重合性モノマーＢ及び/又は共重合性モノマーＣとを含むモノマー成分から構成される共重合体や、（ｂ）共重合性モノマーＡと、共重合性モノマーＢ及び/又は共重合性モノマーＣと、共重合性モノマーＤ及び/又は共重合性モノマーＥとを含むモノマー成分から構成される共重合体も特に好適な例示として挙げることができる。 Further, as an example of a (meth) acrylic (co) polymer, (a) a copolymer composed of a monomer component containing a copolymerizable monomer A and a copolymerizable monomer B and / or copolymerizable monomer C And a monomer component including (b) a copolymerizable monomer A, a copolymerizable monomer B and / or a copolymerizable monomer C, and a copolymerizable monomer D and / or a copolymerizable monomer E. A copolymer can also be mentioned as a particularly preferred example.
　上記側鎖の炭素数４～１８の直鎖又は分岐アルキル（メタ）アクリレート（共重合性モノマーＡ）としては、例えば、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、３，５，５－トリメチルシクロヘキサン（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート等を挙げることができる。これらは１種又は２種以上を組み合わせて使用してもよい。 Examples of the straight chain or branched alkyl (meth) acrylate (copolymerizable monomer A) having 4 to 18 carbon atoms in the side chain include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) Acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexane (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( A meth) acrylate, a benzyl (meth) acrylate, etc. can be mentioned. These may be used alone or in combination of two or more.
　上記共重合性モノマーＡは、共重合体の全モノマー成分中に、３０質量％以上９０質量％以下含有されることが好ましく、中でも３５質量％以上或いは８８質量％以下、その中でも特に４０質量％以上或いは８５質量％以下の範囲で含有されることがさらに好ましい。 The copolymerizable monomer A is preferably contained in the total monomer components of the copolymer in an amount of 30% by mass or more and 90% by mass or less, particularly 35% by mass or more and 88% by mass or less, and especially 40% by mass. More preferably, it is contained in the range of 85% by mass or less.
　上記カルボキシル基含有モノマー（共重合性モノマーＢ）としては、例えば、（メタ）アクリル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシプロピルフタル酸、２－（メタ）アクリロイルオキシエチルマレイン酸、２－（メタ）アクリロイルオキシプロピルマレイン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシプロピルコハク酸、クロトン酸、フマル酸、マレイン酸、イタコン酸を挙げることができる。これらは１種又は２種以上を組み合わせてもよい。なお、「（メタ）アクリル」はアクリル及びメタクリルを包括する意味である。同様に「（メタ）アクリロイル」はアクリロイル及びメタクリロイルを包括する意味である。 Examples of the carboxyl group-containing monomer (copolymerizable monomer B) include (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2 -(Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxy Mention may be made of ethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid and itaconic acid. These may be used alone or in combination of two or more. “(Meth) acryl” means to include acrylic and methacrylic. Similarly, “(meth) acryloyl” means acryloyl and methacryloyl.
　上記共重合性モノマーＢは、共重合体の全モノマー成分中に１．２質量％以上１５質量％以下、中でも優れた粘着物性を得る観点から１．５質量％以上或いは１０質量％以下、その中でも特に２質量％以上或いは８質量％以下の範囲で含有されることが好ましい。 The copolymerizable monomer B is 1.2% by mass or more and 15% by mass or less in all monomer components of the copolymer, and from the viewpoint of obtaining excellent adhesive physical properties, 1.5% by mass or more or 10% by mass or less, In particular, it is preferably contained in the range of 2% by mass or more or 8% by mass or less.
　上記マクロモノマー（共重合性モノマーＣ）は、重合により（メタ）アクリル系（共）重合体となった際に側鎖の炭素数が２０以上となるモノマーである。共重合性モノマーＣを用いることにより、（メタ）アクリル系（共）重合体をグラフト共重合体とすることができる。従って、共重合性モノマーＣと、それ以外のモノマーの選択や配合比率によって、グラフト共重合体の主鎖と側鎖の特性を変化させることが出来る。 The macromonomer (copolymerizable monomer C) is a monomer having 20 or more carbon atoms in the side chain when it becomes a (meth) acrylic (co) polymer by polymerization. By using the copolymerizable monomer C, a (meth) acrylic (co) polymer can be used as a graft copolymer. Therefore, the characteristics of the main chain and side chain of the graft copolymer can be changed depending on the selection and blending ratio of the copolymerizable monomer C and other monomers.
　上記マクロモノマー（共重合性モノマーＣ）としては、骨格成分がアクリル系重合体またはビニル系重合体から構成されるのが好ましい。マクロモノマーの骨格成分としては、例えば、上記共重合性モノマーＡ、上記共重合性モノマーＢ、後述の共重合性モノマーＤ、後述の共重合性モノマーＥ等に例示されるものが挙げられ、これらは単独で又は２種類以上を組み合わせて使用することができる。 As the macromonomer (copolymerizable monomer C), the skeleton component is preferably composed of an acrylic polymer or a vinyl polymer. Examples of the skeleton component of the macromonomer include those exemplified by the copolymerizable monomer A, the copolymerizable monomer B, the copolymerizable monomer D described below, and the copolymerizable monomer E described below. Can be used alone or in combination of two or more.
　マクロモノマーは、ラジカル重合性基、またはヒドロキシル基、イソシアネート基、エポキシ基、カルボキシル基、アミノ基、アミド基、チオール基等の官能基を有するものである。マクロモノマーとしては、他のモノマーと共重合可能なラジカル重合性基を有するものが好ましい。ラジカル重合性基は一つ或いは二つ以上含有していてもよく、中でも一つであるものが特に好ましい。マクロモノマーが官能基を有する場合も官能基は一つ或いは二つ以上含有していてもよく、中でも一つであるものが特に好ましい。また、ラジカル重合性基と官能基はどちらか一方でも、両方含有していてもよい。 The macromonomer has a radical polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, or a thiol group. As the macromonomer, those having a radical polymerizable group copolymerizable with other monomers are preferable. One or two or more radically polymerizable groups may be contained, and one of them is particularly preferred. When the macromonomer has a functional group, one or two or more functional groups may be contained, and one of them is particularly preferable. Further, either one of the radical polymerizable group and the functional group may be contained.
　共重合性モノマーＣの数平均分子量は、５００～２万であるのが好ましく、中でも８００以上或いは８０００以下、その中でも１０００以上或いは７０００以下であるのが好ましい。
　マクロモノマーは、一般に製造されているもの（例えば、東亜合成社製マクロモノマーなど）を適宜使用することができる。
　上記共重合性モノマーＣは、共重合体の全モノマー成分中に５質量％以上３０質量％以下、中でも６質量％以上或いは２５質量％以下、その中でも特に８質量％以上或いは２０質量％以下の範囲で含有されることが好ましい。 The number average molecular weight of the copolymerizable monomer C is preferably 500 to 20,000, more preferably 800 or more and 8000 or less, and particularly preferably 1000 or more and 7000 or less.
As the macromonomer, a generally produced one (for example, a macromonomer manufactured by Toa Gosei Co., Ltd.) can be appropriately used.
The copolymerizable monomer C is 5% by mass or more and 30% by mass or less, more preferably 6% by mass or more and 25% by mass or less, and particularly preferably 8% by mass or more or 20% by mass or less in the total monomer components of the copolymer. It is preferable to contain in the range.
　上記側鎖の炭素数が１～３の（メタ）アクリレート（共重合性モノマーＤ）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉ－プロピル（メタ）アクリレート等を挙げることができる。これらは１種又は２種以上を組み合わせてもよい。 Examples of the (meth) acrylate (copolymerizable monomer D) having 1 to 3 carbon atoms in the side chain include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) ) Acrylate and the like. These may be used alone or in combination of two or more.
　上記共重合性モノマーＤは、共重合体の全モノマー成分中に０質量％以上７０質量％以下含有されることが好ましく、中でも３質量％以上或いは６５質量％以下、その中でも特に５質量％以上或いは６０質量％以下の範囲で含有されることがさらに好ましい。 The copolymerizable monomer D is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 70% by mass, more preferably 3% by mass or 65% by mass, and particularly preferably 5% by mass or more. Or it is further more preferable to contain in the range of 60 mass% or less.
　上記水酸基含有モノマー（共重合性モノマーＥ）としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類を挙げることができる。これらは１種又は２種以上を組み合わせてもよい。 Examples of the hydroxyl group-containing monomer (copolymerizable monomer E) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc. And hydroxyalkyl (meth) acrylates. These may be used alone or in combination of two or more.
　上記共重合性モノマーＥは、共重合体の全モノマー成分中に０質量％以上３０質量％以下含有されることが好ましく、中でも０質量％以上或いは２５質量％以下、その中でも特に０質量％以上或いは２０質量％以下の範囲で含有されることがさらに好ましい。 The copolymerizable monomer E is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and more preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
　上記その他のビニルモノマー（共重合性モノマーＦ）としては、共重合性モノマーＡ～Ｅを除く、ビニル基を分子内に有する化合物が挙げられる。このような化合物としては、分子内にアミド基やアルコキシルアルキル基等の官能基を有する官能性モノマー類並びにポリアルキレングリコールジ（メタ）アクリレート類並びに酢酸ビニル、プロピオン酸ビニル及びラウリン酸ビニル等のビニルエステルモノマー並びにスチレン、クロロスチレン、クロロメチルスチレン、α－メチルスチレン及びその他の置換スチレン等の芳香族ビニルモノマーを例示することができる。これらは１種又は２種以上を組み合わせてもよい。 Examples of the other vinyl monomer (copolymerizable monomer F) include compounds having a vinyl group in the molecule, excluding the copolymerizable monomers A to E. Such compounds include functional monomers having functional groups such as amide groups and alkoxylalkyl groups in the molecule, and polyalkylene glycol di (meth) acrylates, and vinyls such as vinyl acetate, vinyl propionate and vinyl laurate. Examples include ester monomers and aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene and other substituted styrenes. These may be used alone or in combination of two or more.
　上記共重合性モノマーＦは、共重合体の全モノマー成分中に０質量％以上３０質量％以下含有されることが好ましく、中でも０質量％以上或いは２５質量％以下、その中でも特に０質量％以上或いは２０質量％以下の範囲で含有されることがさらに好ましい。 The copolymerizable monomer F is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass to 30% by mass, more preferably 0% by mass or more or 25% by mass or less, and particularly preferably 0% by mass or more. Or it is further more preferable to contain in 20 mass% or less.
　上記に掲げるものの他、無水マレイン酸、無水イタコン酸等の酸無水物基含有モノマー；（メタ）アクリル酸グリシジル、α－エチルアクリル酸グリシジル、（メタ）アクリル酸－３,４－エポキシブチル等のエポキシ基含有モノマー；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有（メタ）アクリル酸エステル系モノマー；（メタ）アクリルアミド、Ｎ－ｔ－ブチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド、マレイン酸アミド、マレイミド等のアミド基又はイミド基を含有するモノマー；ビニルピロリドン、ビニルピリジン、ビニルカルバゾール等の複素環系塩基性モノマー等も必要に応じて適宜用いることができる。 In addition to those listed above, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, etc. Epoxy group-containing monomers; amino group-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, Nt-butyl (meth) acrylamide, N- Monomers containing amide groups or imide groups such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, maleimide; vinyl pyrrolidone , Vinyl Jin, can be appropriately used depending or the like need heterocyclic basic monomers such as vinyl carbazole.
　（メタ）アクリル系(共)重合体の最も典型的な例としては、例えば、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリート、デシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ブチル（メタ）アクリレート、エチル（メタ）アクリレート、メチル（メタ）アクリレート等のモノマー成分（ａ）と、カルボキシル基をもつ（メタ）アクリル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシプロピルフタル酸、２－（メタ）アクリロイルオキシエチルマレイン酸、２－（メタ）アクリロイルオキシプロピルマレイン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシプロピルコハク酸、クロトン酸、フマル酸、マレイン酸、イタコン酸等のモノマー成分（ｂ）と、有機官能基等をもつヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、グリセロール（メタ）アクリレート、マレイン酸モノメチル、イタコン酸モノメチル、酢酸ビニル、グリシジル（メタ）アクリレート、（メタ）アクリルアミド、（メタ）アクリロニトリル、フッ素化（メタ）アクリレート、シリコーン（メタ）アクリレート等のモノマー成分（ｃ）と、を共重合させて得られる（メタ）アクリル酸エステル共重合体を挙げることができる。 The most typical examples of (meth) acrylic (co) polymers include, for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isostearyl (meth) acrylate, butyl ( Monomer component (a) such as (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate and the like, (meth) acrylic acid having a carboxyl group, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( (Meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxy Propyl maleic acid, 2- (meth) Monomer component (b) such as acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, and hydroxyethyl (meth) acrylate having an organic functional group , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, monomethyl maleate, monomethyl itaconate, vinyl acetate, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, fluorination Mention may be made of (meth) acrylic acid ester copolymers obtained by copolymerizing monomer components (c) such as (meth) acrylates and silicone (meth) acrylates.
　（メタ）アクリル系(共)重合体の質量平均分子量は、１０万以上１５０万以下、中でも１５万以上或いは１３０万以下、その中でも特に２０万以上或いは１２０万以下であることが好ましい。 The mass average molecular weight of the (meth) acrylic (co) polymer is preferably 100,000 or more and 1.5 million or less, more preferably 150,000 or more and 1.3 million or less, and particularly preferably 200,000 or more or 1,200,000 or less.
　凝集力の高い粘着組成物を得たい場合は、分子量が大きい程分子鎖の絡み合いにより凝集力が得られる観点から、（メタ）アクリル系(共)重合体の質量平均分子量は７０万以上１５０万以下、特に８０万以上或いは１３０万以下であることが好ましい。一方、流動性や応力緩和性の高い粘着組成物を得たい場合は、質量平均分子量は１０万以上７０万以下、特に１５万以上或いは６０万以下であることが好ましい。
　他方、粘着シート等を成形する際に溶剤を使用しない場合には、分子量が大きなポリマーを使用することが難しいため、（メタ）アクリル系(共)重合体の質量平均分子量は１０万以上７０万以下、特に１５万以上或いは６０万以下、中でも特に２０万以上或いは５０万以下であることが好ましい。 In order to obtain a pressure-sensitive adhesive composition having a high cohesive force, the mass average molecular weight of the (meth) acrylic (co) polymer is 700,000 to 1,500,000 from the viewpoint of obtaining cohesive force due to entanglement of molecular chains as the molecular weight increases. In particular, it is particularly preferably 800,000 or more or 1.3 million or less. On the other hand, when it is desired to obtain an adhesive composition having high fluidity and stress relaxation properties, the mass average molecular weight is preferably 100,000 or more and 700,000 or less, particularly 150,000 or more or 600,000 or less.
On the other hand, when a solvent is not used when forming an adhesive sheet or the like, it is difficult to use a polymer having a large molecular weight, and therefore the (meth) acrylic (co) polymer has a mass average molecular weight of 100,000 or more and 700,000. In particular, 150,000 or more or 600,000 or less is preferable, and 200,000 or more or 500,000 or less is particularly preferable.
（金属腐食防止剤）
　本組成物は１，２，３－トリアゾールを含有する。
　１，２，３－トリアゾールは、導電部材の導電層に対する金属腐食防止剤としての機能を有する。１，２，３－トリアゾールは、銅に対する耐銅腐食信頼性及び粘着シートとしての耐発泡信頼性に優れることから、１，２，３－トリアゾールを含有する本組成物は、透明導電層及び銅を含む金属材料で形成された導体パターン（配線パターン）を有する導電部材として好適に使用することができる。その理由は、銅を含む金属材料で形成された導体パターン表面に、銅原子と１，２，３－トリアゾールの分子が化学的に結合した保護皮膜が形成されることで、腐食を防止するものと推察されるからである。また、銀を含む金属材料で形成された導体パターンを有する導電部材においても、１，２，３－トリアゾールによる保護皮膜の効果は同様に奏することができる。 (Metal corrosion inhibitor)
The composition contains 1,2,3-triazole.
1,2,3-triazole has a function as a metal corrosion inhibitor for the conductive layer of the conductive member. Since 1,2,3-triazole is excellent in copper corrosion resistance against copper and foaming reliability as a pressure-sensitive adhesive sheet, the present composition containing 1,2,3-triazole contains a transparent conductive layer and copper. It can be suitably used as a conductive member having a conductor pattern (wiring pattern) formed of a metal material containing. The reason is to prevent corrosion by forming a protective film in which copper atoms and 1,2,3-triazole molecules are chemically bonded to the surface of the conductor pattern made of a metal material containing copper. It is because it is guessed. In addition, the effect of the protective film by 1,2,3-triazole can be similarly achieved in a conductive member having a conductor pattern formed of a metal material containing silver.
　なお、１，２，３－トリアゾールの異性体として１，２，４－トリアゾールが存在する。この１，２，４－トリアゾールは融点が約１２０℃の固体である一方、１，２，３－トリアゾールは融点が約２０℃と室温でほぼ液体状態である。よって、１，２，３－トリアゾールは、粘着剤組成物中に混合する際の分散性に優れ、均一に混合することができ、また、マスターバッチ化しやすい等の優れた利点がある。 In addition, 1,2,4-triazole exists as an isomer of 1,2,3-triazole. The 1,2,4-triazole is a solid having a melting point of about 120 ° C., whereas 1,2,3-triazole has a melting point of about 20 ° C. and is almost in a liquid state at room temperature. Therefore, 1,2,3-triazole has excellent advantages such as excellent dispersibility when mixed into the pressure-sensitive adhesive composition, uniform mixing, and easy masterbatch formation.
　本組成物において、金属腐食防止剤のブリードアウトや金属腐食防止効果などの観点から、１，２，３－トリアゾールは、（メタ）アクリル系(共)重合体１００質量部に対して、０．０１質量部以上５質量部以下の割合で含有されることが好ましく、中でも０．１質量部以上或いは１質量部以下、その中でも０．２質量部以上或いは０．５質量部以下の割合で含有されることがより一層好ましい。 In this composition, from the viewpoint of bleeding out of the metal corrosion inhibitor and the effect of preventing metal corrosion, 1,2,3-triazole is added in an amount of 0.1 to 100 parts by mass of the (meth) acrylic (co) polymer. It is preferably contained in a proportion of 01 parts by mass or more and 5 parts by mass or less, especially 0.1 parts by mass or more or 1 part by mass or less, and among them, it is contained in a proportion of 0.2 parts by mass or more or 0.5 parts by mass or less Even more preferably.
　なお、本組成物には、１，２，３－トリアゾールとともに１，２，４－トリアゾールを併用してもよい。 In the present composition, 1,2,4-triazole may be used in combination with 1,2,3-triazole.
（亜リン酸エステル化合物）
　本組成物は、さらに亜リン酸エステル化合物を含有することができる。
　亜リン酸エステル化合物はそれ自体が腐食性を有さないばかりか、カルボキシル基などの酸成分を安定化させることができる。そのため、所定の（メタ）アクリル系(共)重合体を含む本組成物に亜リン酸エステル化合物を配合することにより、本組成物が酸成分を含んでいても、被着体である導電部材の酸化劣化を防止することができるし、本組成物が酸成分を含んでいない場合は勿論、被着体である導電部材の酸化劣化を防止することができる。
　よって、亜リン酸エステル化合物を含有する本組成物から粘着シートを形成すれば、導電部材（典型的にはＩＴＯを含む透明導電層及び／又は銅や銀を含む金属材料で形成された導体パターンを有する導電部材）に対する耐腐食信頼性を有すると共に、導電部材の酸化劣化を防止することができる。よって、例えばタッチパネルを有する画像表示装置用の粘着シートとして好適に用いることができる。 (Phosphite compound)
The present composition can further contain a phosphite compound.
The phosphite compound is not itself corrosive and can stabilize acid components such as carboxyl groups. Therefore, by blending a phosphite compound with this composition containing a predetermined (meth) acrylic (co) polymer, the conductive member which is an adherend even if this composition contains an acid component Oxidative degradation of the conductive member as an adherend can be prevented as well as the present composition of course when the composition does not contain an acid component.
Therefore, if an adhesive sheet is formed from the present composition containing a phosphite compound, a conductive member (typically a conductive pattern formed of a transparent conductive layer containing ITO and / or a metal material containing copper or silver) In addition, the conductive member can be prevented from being oxidized and deteriorated. Therefore, for example, it can be suitably used as an adhesive sheet for an image display device having a touch panel.
　本組成物に含有することが可能な亜リン酸エステル化合物は限定されない。中でも、下記式（１）で示される亜リン酸エステル化合物であるのが好ましい。 The phosphite compound that can be contained in the composition is not limited. Among these, a phosphite compound represented by the following formula (1) is preferable.
　式（１）・・Ｐ［－ＯＲ］３
（式中のＲは炭化水素であり、具体的には、置換又は非置換芳香族、脂肪環及びアルキル基などが挙げることができる。複数のＲは互いに同一でも異なっていてもよく、隣接した複数のＲは、互いに結合して飽和又は不飽和の環構造を形成していてもよい。）
　また、上記式（１）で表される構造単位を２個以上含む化合物であってもよい。 Formula (1) ··· P [-OR] 3
(In the formula, R is a hydrocarbon, and specific examples include a substituted or unsubstituted aromatic group, an alicyclic ring, and an alkyl group. The plurality of R may be the same or different from each other, and are adjacent to each other. A plurality of R may be bonded to each other to form a saturated or unsaturated ring structure.)
Further, it may be a compound containing two or more structural units represented by the above formula (1).
　所定の（メタ）アクリル系(共)重合体及び１，２，３－トリアゾールを含む本組成物に、上記式（１）で示される様々な亜リン酸エステル化合物を配合した結果、いずれの亜リン酸エステル化合物も酸化劣化防止効果を示すことが確認され、特にＩＴＯを含む透明導電層に対する酸化劣化防止効果に優れていることが確認された。 As a result of blending various phosphite compounds represented by the above formula (1) with the present composition containing a predetermined (meth) acrylic (co) polymer and 1,2,3-triazole, It was confirmed that the phosphoric acid ester compound also showed an effect of preventing oxidative degradation, and in particular, it was confirmed that the phosphoric acid ester compound was excellent in the oxidative degradation preventive effect for the transparent conductive layer containing ITO.
　本組成物が含有する亜リン酸エステル化合物としては、例えば、亜リン酸トリフェニル、亜リン酸トリスノニルフェニル、亜リン酸トリクレジル、亜リン酸トリステアリル、亜リン酸トリエチル、亜リン酸トリス（２－エチルヘキシル）、亜リン酸トリデシル、亜リン酸トリラウリル、亜リン酸トリス（トリデシル）、亜リン酸トリオレイル、亜リン酸ジフェニル（２－エチルヘキシル）、亜リン酸ジフェニルモノデシル、亜リン酸ジフェニルモノ（トリデシル）、テトラフェニルジプロピレンジプロピレングリコールジフォスファイト、テトラフェニル（テトラトリデシル）ペンタエリスリトールテトラフォスファイト、テトラ（Ｃ１２～Ｃ１５アルキル）－４，４－イソプロピリデンジフェニルジフォスファイト、亜リン酸トリス(２,４－ジ－ｔ－ブチルフェニル)、亜リン酸トリス（４－ノニルフェニル）、３，９－ビス（ノニルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカン、３，９－ビス（４－ノニルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカン、３，９－ビス（デシルオキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカン、３，９－ビス（トリデシルオキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカン、３，９－ビス(ステアリルオキシ)－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカン、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカン、３，９－ビス（２，４－ジ－ｔｅｒｔ－ブチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカン、３，９－ビス｛２，４－ビス(１－メチル－１－フェニルエチル)フェノキシ｝－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ[５，５]ウンデカン、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチル－１－フェニルオキシ）フォスファイト、４，４’－イソプロピリデンジフェノールＣ１２－１５アルコールホスファイト、ジステアリルペンタエリスリトールジフォスファイト、２，４，８，１０－テトラキス（１，１－ジメチルエチル）－６－｛（２－エチルヘキシル）オキシ｝－１２Ｈ-ジベンゾ［ｄ,ｇ][１,３,２]ジオキサフォスフォシン、２，４，８，１０－テトラキス（１，１－ジメチルエチル）－６－（トリデシルオキシ）－１２Ｈ-ジベンゾ［ｄ,ｇ][１,３,２]ジオキサフォスフォシン、１，１’－ビフェニル－４，４’－ジイルビス[亜リン酸ビス(２,４－ジ－ｔ－ブチルフェニル)]、水添ビスフェノールＡ・ペンタエリスリトールフォスファイトポリマー、水添ビスフェノールＡフォスファイトポリマー、亜リン酸ジエチル、亜リン酸ビス（２－エチルヘキシル）、亜リン酸ジラウリル、亜リン酸ジオレイル、亜リン酸ジフェニル等を挙げることができる。 Examples of the phosphite compound contained in the composition include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, tristearyl phosphite, triethyl phosphite, tris phosphite ( 2-ethylhexyl), tridecyl phosphite, trilauryl phosphite, tris phosphite (tridecyl), trioleyl phosphite, diphenyl phosphite (2-ethylhexyl), diphenyl monodecyl phosphite, diphenyl phosphite Mono (tridecyl), tetraphenyldipropylene dipropylene glycol diphosphite, tetraphenyl (tetratridecyl) pentaerythritol tetraphosphite, tetra (C12-C15 alkyl) -4,4-isopropylidene diphenyl diphosphite, phosphorous Acid Tris (2, -Di-t-butylphenyl), tris (4-nonylphenyl) phosphite, 3,9-bis (nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] Undecane, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (decyloxy) -2,4,8 , 10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (tridecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (stearyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (2,6-di-tert-butyl- 4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (2,4-di-tert-butylphenoxy) -2,4 8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis {2,4-bis (1-methyl-1-phenylethyl) phenoxy} -2,4,8,10- Tetraoxa-3,9-diphosphaspiro [5,5] undecane, 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) phosphite, 4,4′-isopropylidenediphenol C12- 15 alcohol phosphite, distearyl pentaerythritol diphosphite, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6-{(2- Tilhexyl) oxy} -12H-dibenzo [d, g] [1,3,2] dioxaphosphine, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6- (tridecyloxy) ) -12H-dibenzo [d, g] [1,3,2] dioxaphosphine, 1,1′-biphenyl-4,4′-diylbis [bis (2,4-di-t-phosphite) Butylphenyl)], hydrogenated bisphenol A / pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, diethyl phosphite, bis (2-ethylhexyl) phosphite, dilauryl phosphite, dioleyl phosphite, And diphenyl phosphate.
　中でも、本組成物が含有する亜リン酸エステル化合物としては、例えば本組成物との相溶性を考慮すると、脂肪族亜リン酸エステル（例えば、実施例２－２の亜リン酸エステル化合物として亜リン酸トリデシルや実施例２－３の３，９－ビス（デシルオキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５．５］ウンデカンなど）が好ましい。また、耐加水分解性を考慮すると、芳香族亜リン酸エステル（例えば、実施例２－１の亜リン酸エステル化合物としての亜リン酸トリス(２,４－ジ－ｔ－ブチルフェニル)など）が好ましい。また、溶解性と耐加水分解性とのバランスを考慮すれば、亜リン酸ジフェニルモノ（トリデシル）等の脂肪族エステル基と芳香族エステル基とを併せ持つ亜リン酸エステルが好ましい。 Among these, as the phosphite compound contained in the composition, for example, considering compatibility with the composition, an aliphatic phosphite ester (for example, a phosphite compound of Example 2-2 as a phosphite compound) is used. Tridecyl phosphate and 3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane of Example 2-3) are preferred. In consideration of hydrolysis resistance, aromatic phosphite esters (for example, tris (2,4-di-t-butylphenyl) phosphite as the phosphite compound of Example 2-1) Is preferred. In consideration of the balance between solubility and hydrolysis resistance, a phosphite having both an aliphatic ester group such as diphenyl phosphite mono (tridecyl) and an aromatic ester group is preferable.
　本組成物において、亜リン酸エステル化合物の含有割合は、粘着性能を損なわず、ＩＴＯなどの導電部材の酸化劣化をより効果的に抑制することができる観点から、（メタ）アクリル系(共)重合体１００質量部に対し、亜リン酸エステル化合物が０．０００１（１×１０－４）質量部以上２．０質量部以下の割合で含有されることが好ましく、中でも０．０００５質量部以上或いは０．８質量部以下、その中でも０．００１質量部以上或いは０．７質量部以下、特には０．０１質量部以上或いは０．６質量部以下の割合で含有されることがより一層好ましい。 In the present composition, the content ratio of the phosphite compound does not impair the adhesive performance, and from the viewpoint of more effectively suppressing the oxidative deterioration of the conductive member such as ITO, (meth) acrylic (co) The phosphite compound is preferably contained in an amount of 0.0001 (1 × 10 −4 ) parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the polymer, and more preferably 0.0005 parts by mass or more. Or 0.8 parts by mass or less, more preferably 0.001 parts by mass or more or 0.7 parts by mass or less, particularly preferably 0.01 parts by mass or more or 0.6 parts by mass or less. .
（その他の金属腐食防止剤）
　本組成物には、１，２，３－トリアゾール及び亜リン酸エステル化合物以外に、１，２，４－トリアゾール、ベンゾトリアゾール及びその誘導体等、その他の金属腐食防止剤を併用してもよい。 (Other metal corrosion inhibitors)
In addition to 1,2,3-triazole and phosphite compounds, the composition may contain other metal corrosion inhibitors such as 1,2,4-triazole, benzotriazole and derivatives thereof.
（架橋剤）
　本組成物は必要に応じて架橋剤を含んでもよい。
　例えば、上記した（メタ）アクリル系（共）重合体を架橋する方法としては、（メタ）アクリル系（共）重合体中に導入した水酸基やカルボキシル基等の反応性基と化学結合しうる架橋剤を添加し、加熱や養生により反応させる方法や、架橋剤としての（メタ）アクリロイル基を２個以上有する多官能（メタ）アクリレート及び光重合開始剤等の反応開始剤を添加し、紫外線照射等によって架橋する方法を挙げることができる。中でも、本組成物中のカルボキシル基等の極性官能基を反応によって消費せず、極性成分由来の高い凝集力や粘着物性を維持できる観点から、紫外線等の光照射による架橋方法が好ましい。 (Crosslinking agent)
This composition may contain a crosslinking agent as needed.
For example, as a method of crosslinking the above-mentioned (meth) acrylic (co) polymer, crosslinking capable of chemically bonding with a reactive group such as a hydroxyl group or a carboxyl group introduced into the (meth) acrylic (co) polymer. Add reaction agent, react by heating or curing, add reaction initiator such as polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups as crosslinking agent and photopolymerization initiator, UV irradiation The method of bridge | crosslinking by etc. can be mentioned. Among these, a crosslinking method by irradiation with light such as ultraviolet rays is preferred from the viewpoint that polar functional groups such as carboxyl groups in the present composition are not consumed by the reaction and high cohesive force derived from polar components and adhesive properties can be maintained.
　上記架橋剤としては、例えば、（メタ）アクリロイル基、エポキシ基、イソシアネート基、カルボキシル基、ヒドロキシル基、カルボジイミド基、オキサゾリン基、アジリジン基、ビニル基、アミノ基、イミノ基、アミド基、Ｎ－置換（メタ）アクリルアミド基、アルコキシシリル基から選ばれる少なくとも１種の架橋性官能基を有する架橋剤を挙げることができ、１種又は２種以上を組み合わせて使用してもよい。なお、架橋性官能基は、脱保護可能な保護基で保護されていてもよい。 Examples of the crosslinking agent include (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, amide group, and N-substituted. The crosslinking agent which has at least 1 sort (s) of crosslinkable functional group chosen from a (meth) acrylamide group and an alkoxy silyl group can be mentioned, You may use 1 type or in combination of 2 or more types. The crosslinkable functional group may be protected with a deprotectable protecting group.
　中でも、架橋反応の制御のし易さの観点からは、多官能（メタ）アクリレートが好ましい。
　このような多官能（メタ）アクリレートとしては、例えば１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート等の紫外線硬化型の多官能モノマー類のほか、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエーテル（メタ）アクリレート等の多官能アクリルオリゴマー類や、多官能アクリルアミド等を挙げることができる。 Among these, polyfunctional (meth) acrylate is preferable from the viewpoint of easy control of the crosslinking reaction.
Examples of such polyfunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, poly Alkylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri In addition to UV-curable polyfunctional monomers such as pentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tris (acryloxyethyl) isocyanurate, polyester (meth ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or polyfunctional acrylic oligomers of the polyether (meth) acrylate, may be mentioned polyfunctional acrylamide.
　また、２種以上の架橋性官能基を有する架橋剤としては、例えば（メタ）アクリル酸グリシジル、α－エチルアクリル酸グリシジル、（メタ）アクリル酸－３，４－エポキシブチル、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等のエポキシ基含有モノマー；２－イソシアナトエチル（メタ）アクリレート、２－（２－（メタ）アクリロイルオキシエチルオキシ）エチルイソシアナート、（メタ）アクリル酸２－(０－[１'－メチルプロピリデンアミノ]カルボキシアミノ)エチル、２－[(３，５－ジメチルピラゾリル)カルボニルアミノ]エチル（メタ）アクリレート等のイソシアネート基またはブロックイソシアネート基を含有するモノマー；ビニルトリメトキシシラン、ビニルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－（メタ）アクリロキシプロピルメチルジエトキシシラン、３－（メタ）アクリロキシプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－イソシアネートプロピルトリエトキシシラン等の各種シランカップリング剤を挙げることができる。 Examples of the cross-linking agent having two or more cross-linkable functional groups include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl (meth) acrylate, 4-hydroxybutyl ( Epoxy group-containing monomers such as (meth) acrylate glycidyl ether; 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, (meth) acrylic acid 2- (0- [ Monomers containing isocyanate groups or blocked isocyanate groups such as 1′-methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate; vinyltrimethoxysilane, Vinyltriethoxysilane, 3-glycidoxypro Rutrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-isocyanatopropyl Examples include various silane coupling agents such as triethoxysilane.
　２種以上の架橋性官能基を有する架橋剤は、一方の官能基を(メタ)アクリル系（共）重合体と反応させ、（メタ）アクリル系（共）重合体に結合された構造をとってもよい。このような構造をとることにより、（メタ）アクリル系（共）重合体に、例えば（メタ）アクリロイル基やビニル基等の二重結合性の架橋性官能基を化学結合させることができる。また、架橋剤が（メタ）アクリル系（共）重合体に結合されることで、架橋剤のブリードアウトや、本粘着シートの予期せぬ可塑化を抑制することができる傾向にある。また、架橋剤が（メタ）アクリル系（共）重合体に結合されることで、光架橋反応の反応効率が促進されることから、より凝集力の高い硬化物を得ることができる傾向にある。 The crosslinking agent having two or more kinds of crosslinkable functional groups has a structure in which one functional group is reacted with a (meth) acrylic (co) polymer and bonded to the (meth) acrylic (co) polymer. Good. By taking such a structure, it is possible to chemically bond a double bondable crosslinkable functional group such as a (meth) acryloyl group or a vinyl group to the (meth) acrylic (co) polymer. Moreover, it exists in the tendency which can suppress the bleeding out of a crosslinking agent and the unexpected plasticization of this adhesive sheet because a crosslinking agent is couple | bonded with a (meth) acrylic-type (co) polymer. Moreover, since the reaction efficiency of the photocrosslinking reaction is promoted by bonding the crosslinking agent to the (meth) acrylic (co) polymer, a cured product having a higher cohesive force tends to be obtained. .
　本組成物は、架橋剤の架橋性官能基と反応する単官能モノマーをさらに含有してもよい。このような単官能モノマーとしては、例えば、メチルアクリレート等のアルキル（メタ）アクリレート；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ポリアルキレングリコール（メタ）アクリレート等の水酸基含有（メタ）アクリレート；（メタ）アクリル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシエチルマレイン酸、２－（メタ）アクリロイルオキシプロピルマレイン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシプロピルコハク酸、クロトン酸、フマル酸、マレイン酸、イタコン酸等のカルボキシル基含有モノマー；無水マレイン酸、無水イタコン酸等の酸無水物基含有モノマー；テトラヒドロフルフリル（メタ）アクリレート、メトキシポリエチレングリコール(メタ)アクリレート等のエーテル基含有（メタ）アクリレート；（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、ジエチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、イソプロピル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、フェニル（メタ）アクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド等の（メタ）アクリルアミド系モノマー等を挙げることができる。
　中でも被着体への密着性や湿熱白化抑制の効果を向上させる観点から、水酸基含有（メタ）アクリレートや、（メタ）アクリルアミド系モノマーを用いるのが好ましい。 The present composition may further contain a monofunctional monomer that reacts with the crosslinkable functional group of the crosslinking agent. Examples of such monofunctional monomers include alkyl (meth) acrylates such as methyl acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyalkylene glycol (meth) acrylate, and the like. Hydroxyl group-containing (meth) acrylate; (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, Carboxyl group-containing monomers such as rotonic acid, fumaric acid, maleic acid, and itaconic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; tetrahydrofurfuryl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, etc. Ether group-containing (meth) acrylate: (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, phenyl (meth) Examples include (meth) acrylamide monomers such as acrylamide, N-methoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
Among these, from the viewpoint of improving the adhesion to the adherend and the effect of suppressing the moist heat whitening, it is preferable to use a hydroxyl group-containing (meth) acrylate or a (meth) acrylamide monomer.
　架橋剤の含有量は、本組成物の柔軟性と凝集力をバランスさせる観点から、前記（メタ）アクリル系(共)重合体１００質量部に対して、０．０１以上１０質量部以下の割合で配合するのが好ましく、中でも０．０５質量部以上或いは８質量部以下、その中でも０．１質量部以上或いは５質量部以下であることが特に好ましい。
　なお、本粘着シートが多層である場合は、粘着シートを構成する層のうち、中間層や基材となる層については、架橋剤の含有量が上記範囲を超えていてもよい。中間層や基材となる層における架橋剤の含有量は、前記（メタ）アクリル系(共)重合体１００質量部に対して、０．０１以上４０質量部以下の割合で配合するのが好ましく、中でも１質量部以上或いは３０質量部以下、その中でも２質量部以上或いは２５質量部以下であることが特に好ましい。 The content of the crosslinking agent is a ratio of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer, from the viewpoint of balancing the flexibility and cohesion of the composition. In particular, it is preferably 0.05 parts by mass or more and 8 parts by mass or less, and particularly preferably 0.1 parts by mass or more or 5 parts by mass or less.
In addition, when this adhesive sheet is a multilayer, about the layer used as an intermediate | middle layer and a base material among the layers which comprise an adhesive sheet, content of a crosslinking agent may exceed the said range. The content of the crosslinking agent in the intermediate layer or the layer serving as the base material is preferably blended at a ratio of 0.01 to 40 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer. Especially, it is particularly preferably 1 part by mass or more and 30 parts by mass or less, and particularly preferably 2 parts by mass or more or 25 parts by mass or less.
（光重合開始剤）
　光照射による架橋を行う場合は光重合開始剤を含有するのが好ましい。
　光重合開始剤によるラジカル発生機構は大きく２つに分類され、自身の単結合を開裂し分解してラジカルを発生させるα開裂型と、系中の化合物から水素を励起させラジカルを発生させる水素引抜型とがある。これらの中でも水素引抜型光架橋開始剤を用いることが好ましい。 (Photopolymerization initiator)
When performing crosslinking by light irradiation, it is preferable to contain a photopolymerization initiator.
Radical generation mechanisms by photopolymerization initiators are broadly classified into two types: α-cleavage type that cleaves and decomposes its own single bond to generate radicals, and hydrogen abstraction that excites hydrogen from compounds in the system to generate radicals. There is a type. Among these, it is preferable to use a hydrogen abstraction type photocrosslinking initiator.
　中でも、架橋剤として（メタ）アクリロイル基を有する有機系架橋剤を用いる場合は、特に光重合開始剤をさらに添加するのが好ましい。光照射によりラジカルを発生させて系中の重合反応の起点となるためである。 Among these, when an organic crosslinking agent having a (meth) acryloyl group is used as the crosslinking agent, it is particularly preferable to further add a photopolymerization initiator. This is because radicals are generated by light irradiation and become the starting point of the polymerization reaction in the system.
　光重合開始剤は、現在公知のものを適宜使用することができる。中でも、波長３８０ｎｍ以下の紫外線に感応する光重合開始剤が、架橋反応の制御のしやすさの観点から好ましい。
　一方、波長３８０ｎｍより長波長の光に感応する光重合開始剤は、高い光反応性を得られる点及び、感応する光が、本粘着シートの深部まで到達しやすい点で好ましい。 As the photopolymerization initiator, those currently known can be used as appropriate. Among these, a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
On the other hand, a photopolymerization initiator sensitive to light having a wavelength longer than 380 nm is preferable in that high photoreactivity can be obtained and sensitive light can easily reach the deep part of the pressure-sensitive adhesive sheet.
　光重合開始剤は、ラジカル発生機構によって大きく２つに分類され、光重合開始剤自身の単結合を開裂分解してラジカルを発生させることができる開裂型光重合開始剤と、光励起した開始剤と系中の水素供与体とが励起錯体を形成し、水素供与体の水素を転移させることができる水素引抜型光重合開始剤と、に大別される。 Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage-type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself to generate a radical, and a photoexcited initiator. It is roughly classified into a hydrogen abstraction type photopolymerization initiator which can form an exciplex with a hydrogen donor in the system and transfer hydrogen of the hydrogen donor.
　これらのうちの開裂型光重合開始剤は、光照射によってラジカルを発生する際に分解して別の化合物となり、一度励起されると架橋開始剤としての機能をもたなくなる。このため、架橋反応が終了した後の粘着材中に活性種として残存することがなく、粘着材に予期せぬ光劣化等をもたらす可能性がないため、好ましい。
　他方、水素引抜型光重合開始剤は、紫外線などの活性エネルギー線照射によるラジカル発生反応時に、開裂型光重合開始剤のような分解物を生じないので、反応終了後に揮発成分となりにくく、被着体へのダメージを低減させることができる点で有用である。 Of these, the cleavage type photopolymerization initiator decomposes to generate another compound when generating radicals by light irradiation, and once excited, it does not function as a crosslinking initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
On the other hand, a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product like a cleavage type photopolymerization initiator during radical generation reaction by irradiation with active energy rays such as ultraviolet rays, so it is difficult to become a volatile component after the reaction is completed. This is useful in that damage to the body can be reduced.
　前記開裂型光重合開始剤としては、光に対する感応性が高く、かつ反応後に分解物となり消色する点で、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、（２，４，６－トリメチルベンゾイル）エトキシフェニルホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）２，４，４－トリメチルペンチルフォスフィンオキサイド等のアシルホスフィンオキサイド系光重合開始剤が好ましい。 As the cleavage type photopolymerization initiator, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,4 is high in sensitivity to light and dissociates as a decomposition product after the reaction. Acylphosphine oxides such as 6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide Photoinitiators are preferred.
　前記水素引抜型光重合開始剤としては、例えばベンゾフェノン、４－メチル－ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－フェニルベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン、４－（メタ）アクリロイルオキシベンゾフェノン、４－［２－(（メタ）アクリロイルオキシ)エトキシ］ベンゾフェノン、４－（メタ）アクリロイルオキシ－４’－メトキシベンゾフェノン、２－ベンゾイル安息香酸メチル、ベンゾイルギ酸メチル、ビス（２－フェニル－２－オキソ酢酸）オキシビスエチレン、４－（１，３－アクリロイル－１，４，７，１０，１３－ペンタオキソトリデシル）ベンゾフェノン、チオキサントン、２－クロロチオキサントン、３－メチルチオキサントン、２，４－ジメチルチオキサントン、アントラキノン、２－メチルアントラキノン、２－エチルアントラキノン、２－ｔｅｒｔ－ブチルアントラキノン、２－アミノアントラキノン、カンファーキノンやその誘導体などを挙げることができる。
　これらの中でも、ベンゾフェノン、４－メチル－ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－フェニルベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン、４－（メタ）アクリロイルオキシベンゾフェノン、４－［２－(（メタ）アクリロイルオキシ)エトキシ］ベンゾフェノン、４－（メタ）アクリロイルオキシ－４’－メトキシベンゾフェノン、２－ベンゾイル安息香酸メチル、ベンゾイルギ酸メチルが好ましい。 Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meta ) Acryloyloxybenzophenone, 4- [2-((meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2- Phenyl-2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2 , 4-Dimethylthioxanthone And anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, camphorquinone and derivatives thereof.
Among these, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, 4- [ 2-((Meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4′-methoxybenzophenone, methyl 2-benzoylbenzoate and methyl benzoylformate are preferred.
　なお、上記に挙げた光重合開始剤は、いずれか１種またはその誘導体を使用してもよいし、それらを２種以上を組み合わせて使用してもよい。
　さらに、光重合開始剤に加えて増感剤を使用することも可能である。増感剤としては、特に限定はなく、光重合開始剤に用いられる増感剤であれば問題なく使用できる。例えば芳香族アミンやアントラセン誘導体、アントラキノン誘導体、クマリン誘導体、チオキサントン誘導体、フタロシアニン誘導体等や、ベンゾフェノン、キサントン、チオキサントン、ミヒラーケトン、９，１０－フェナントラキノンなどの芳香族ケトン及びこれらの誘導体などを挙げることができる。
　なお、光重合開始剤や増感剤は、（メタ）アクリル系（共）重合体に結合された状態で含まれていてもよい。光重合開始剤や増感剤を（メタ）アクリル系（共）重合体に結合させる方法としては、前記架橋剤を（メタ）アクリル系（共）重合体に結合させる場合と同様の方法を採用することができる。 In addition, the photoinitiator mentioned above may use any 1 type or its derivative (s), and may use them in combination of 2 or more type.
Furthermore, it is also possible to use a sensitizer in addition to the photopolymerization initiator. The sensitizer is not particularly limited, and any sensitizer that can be used as a photopolymerization initiator can be used without any problem. Examples include aromatic amines, anthracene derivatives, anthraquinone derivatives, coumarin derivatives, thioxanthone derivatives, phthalocyanine derivatives, aromatic ketones such as benzophenone, xanthone, thioxanthone, Michler ketone, 9,10-phenanthraquinone, and derivatives thereof. be able to.
In addition, the photoinitiator and the sensitizer may be contained in a state of being bonded to the (meth) acrylic (co) polymer. As a method for bonding a photopolymerization initiator or a sensitizer to a (meth) acrylic (co) polymer, the same method as that for bonding the crosslinking agent to a (meth) acrylic (co) polymer is adopted. can do.
　光重合開始剤の含有量は、特に制限されるものではなく、典型的には、（メタ）アクリル系(共)重合体１００質量部に対して０．１以上１０質量部以下、中でも０．２質量部以上或いは５質量部以下、その中でも０．５質量部以上或いは３質量部以下の割合で調整することが特に好ましい。但し、他の要素とのバランスでこの範囲を超えてもよい。 The content of the photopolymerization initiator is not particularly limited, and is typically 0.1 to 10 parts by mass, and particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic (co) polymer. It is particularly preferable to adjust at a ratio of 2 parts by mass or more or 5 parts by mass or less, and among them, 0.5 parts by mass or more or 3 parts by mass or less. However, this range may be exceeded in balance with other elements.
（酸化防止剤）
　上記以外にも、本組成物は必要に応じて酸化防止剤を含有してもよい。
　酸化防止剤としては、例えば、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、ヘキサメチレングリコール－ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシヒドロシンナメート）、テトラキス〔メチレン（３，５－ジ－ｔ－ブチル－４－ヒドロキシヒドロシンナメート）〕メタン、トリエチレングリコール－ビス－３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ベンジル）ベンゼン、ｎ－オクタデシル－３－（４’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェノール）プロピオネート、４，４’－メチレンビス（２，６－ジ－ｔ－ブチルフェノール）、４，４’－ブチリデン－ビス－（６－ｔ－ブチル－３－メチル－フェノール）等のヒンダードフェノール系酸化防止剤や、硫黄系、アミン系等の各種酸化防止剤が挙げられる。 (Antioxidant)
In addition to the above, the present composition may contain an antioxidant as necessary.
Examples of the antioxidant include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), hexamethylene glycol-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene, n-octadecyl-3- (4′-hydroxy-3 ′, 5 '-Di-t-butylphenol) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidene-bis- (6-t Butyl-3-methyl - phenol) and hindered phenol antioxidants such as, sulfur-based, include various antioxidants amine and the like.
（その他の成分）
　さらに、本組成物は、通常の粘着剤組成物に配合される公知の成分を適宜含有してもよい。例えば、光安定化剤、紫外線吸収剤、金属不活性化剤、防錆剤（前記した金属腐食防止剤を除く）、老化防止剤、帯電防止剤、吸湿剤、発泡剤、消泡剤、無機粒子、粘度調整剤、粘着付与樹脂、光増感剤、蛍光剤などの各種の添加剤や、反応触媒（三級アミン系化合物、四級アンモニウム系化合物、ラウリル酸スズ化合物など）を適宜含有させることが可能である。 (Other ingredients)
Furthermore, the present composition may appropriately contain known components blended in a normal pressure-sensitive adhesive composition. For example, light stabilizers, UV absorbers, metal deactivators, rust inhibitors (excluding metal corrosion inhibitors described above), anti-aging agents, antistatic agents, hygroscopic agents, foaming agents, antifoaming agents, inorganic Various additives such as particles, viscosity modifiers, tackifier resins, photosensitizers, fluorescent agents, and reaction catalysts (tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.) are appropriately added. It is possible.
（粘着剤組成物の調整）
　本粘着シートに用いる粘着剤組成物（本組成物）は、（メタ）アクリル系（共）重合体、１，２，３－トリアゾール及び必要に応じてその他の成分、例えば亜リン酸エステル化合物、架橋剤などをそれぞれ所定量混合することにより得られる。
　これらの混合方法としては、特に制限されず、各成分の混合順序も特に限定されない。また、本組成物製造時に熱処理工程を入れてもよく、この場合は、予め、本組成物の各成分を混合してから熱処理を行うことが望ましい。各種の混合成分を濃縮してマスターバッチ化したものを使用してもよい。 (Adjustment of adhesive composition)
The pressure-sensitive adhesive composition used in the pressure-sensitive adhesive sheet (the present composition) comprises a (meth) acrylic (co) polymer, 1,2,3-triazole and other components as necessary, such as a phosphite compound, It can be obtained by mixing a predetermined amount of a crosslinking agent or the like.
These mixing methods are not particularly limited, and the order of mixing the components is not particularly limited. In addition, a heat treatment step may be performed at the time of producing the present composition. In this case, it is desirable to perform heat treatment after previously mixing the components of the present composition. You may use what concentrated various mixing components into the masterbatch.
　また、混合する際の装置も特に制限されず、例えば、万能混練機、プラネタリミキサー、バンバリーミキサー、ニーダー、ゲートミキサー、加圧ニーダー、三本ロール、二本ロールを用いることができる。必要に応じて溶剤を用いて混合してもよい。また、本組成物は、溶剤を含まない無溶剤系として使用することできる。無溶剤系として使用することで溶剤が残存せず、耐熱性及び耐光性が高まるという利点を備えることができる。 Also, the apparatus for mixing is not particularly limited, and for example, a universal kneader, a planetary mixer, a Banbury mixer, a kneader, a gate mixer, a pressure kneader, three rolls, and two rolls can be used. You may mix using a solvent as needed. Moreover, this composition can be used as a solvent-free system which does not contain a solvent. By using it as a solvent-free system, the solvent does not remain, and there can be provided the advantages that the heat resistance and light resistance are enhanced.
　さらに、本組成物は、（メタ）アクリル系(共)重合体を構成するモノマー成分、１，２，３－トリアゾール、光重合開始剤及びその他の任意成分を含む組成物としておき、これを導電部材用粘着シートとして使用する際に、光照射し重合反応を進行させて（メタ）アクリル系(共)重合体が生成されるようにして使用することもできる。 Further, the present composition is a composition containing a monomer component constituting the (meth) acrylic (co) polymer, 1,2,3-triazole, a photopolymerization initiator, and other optional components, which is electrically conductive. When used as a pressure-sensitive adhesive sheet for members, it can be used in such a way that a (meth) acrylic (co) polymer is produced by light irradiation to cause a polymerization reaction to proceed.
＜導電部材用粘着シートの形態＞
　本粘着シートは、被着体に本組成物を直接塗布し、シート状に形成して使用する以外にも、離型フィルム上に単層又は多層のシート状に成型した離型フィルム付き粘着シートとすることもできる。
　かかる離型フィルムの材質としては、例えば、ポリエステルフィルム、ポリオレフィンフィルム、ポリカーボネートフィルム、ポリスチレンフィルム、アクリルフィルム、トリアセチルセルロースフィルム、フッ素樹脂フィルム等を挙げることができる。これらの中でも、ポリエステルフィルム及びポリオレフィンフィルムが特に好ましい。 <Form of adhesive sheet for conductive member>
In addition to directly applying the composition to an adherend and forming it into a sheet, this pressure-sensitive adhesive sheet can be used as a single-layer or multi-layer sheet on a release film. It can also be.
Examples of the material of the release film include a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a triacetyl cellulose film, and a fluororesin film. Among these, a polyester film and a polyolefin film are particularly preferable.
　離型フィルムの厚みは特に制限されない。中でも、例えば加工性及びハンドリング性の観点からは、２５μｍ～５００μｍであるのが好ましく、その中でも３８μｍ以上或いは２５０μｍ以下、その中でも５０μｍ以上或いは２００μｍ以下であるのがさらに好ましい。 The thickness of the release film is not particularly limited. Among them, for example, from the viewpoint of processability and handling properties, it is preferably 25 μm to 500 μm, more preferably 38 μm or more and 250 μm or less, and particularly preferably 50 μm or more or 200 μm or less.
　なお、本粘着シートは、上記の様に被着体や離型フィルムを使用せずに、本組成物を直接に押出成形する方法や、型に注入することによって成形する方法を採用することも出来る。更には、導電部材等の部材間に本組成物を直接充填することによって、粘着シートの態様とすることも出来る。 The pressure-sensitive adhesive sheet may employ a method of directly extruding the composition or a method of molding by pouring into a mold without using an adherend or a release film as described above. I can do it. Furthermore, it can also be set as the aspect of an adhesive sheet by directly filling this composition between members, such as an electrically-conductive member.
＜導電部材用粘着シートの物性＞
（導電部材の導電層に対する腐食防止効果）
　本粘着シートは、導電部材、とりわけ透明導電層や銅を含む金属材料で形成された導体パターンに対する腐食防止性を有している。そのため、以下の（１）～（２）の方法で測定したＩＴＯ抵抗値の変化率［（（Ω／Ω０）－１）×１００］を５％未満、中でも３％未満とすることができる。また、以下の（３）～（４）の方法で測定した銅抵抗値の変化率［（（Ω／Ω０）－１）×１００］を２０％未満、中でも１０％未満、更には５％未満、特には３％未満とすることができる。 <Physical properties of adhesive sheet for conductive member>
(Corrosion prevention effect on conductive layer of conductive member)
This pressure-sensitive adhesive sheet has corrosion resistance to conductive members, particularly conductive patterns formed of metal materials including a transparent conductive layer and copper. Therefore, the change rate [((Ω / Ω0) -1) × 100] of the ITO resistance value measured by the following methods (1) to (2) can be made less than 5%, particularly less than 3%. Also, the rate of change in copper resistance [((Ω / Ω0) -1) × 100] measured by the following methods (3) to (4) is less than 20%, particularly less than 10%, and even less than 5%. In particular, it can be less than 3%.
（１）導電部材用粘着剤組成物（本組成物）を厚さ１５０μｍのシート状に製膜して粘着シートとし、酸化インジウム（ＩＴＯ）からなるＩＴＯ配線がガラス基板上に形成されてなる評価用ＩＴＯガラス基板に、前記粘着シートを貼合させて粘着シート付ＩＴＯ配線を作製する。 (1) Evaluation in which an adhesive wiring for conductive member (this composition) is formed into a 150 μm thick sheet to form an adhesive sheet, and an ITO wiring made of indium oxide (ITO) is formed on a glass substrate. The said adhesive sheet is bonded to the ITO glass substrate for manufacture, and an ITO wiring with an adhesive sheet is produced.
（２）前記粘着シート付ＩＴＯ配線におけるＩＴＯ配線の室温での抵抗値（Ω０）を予め測定しておき、６５℃・９０％ＲＨ環境下で５００時間、前記粘着シート付ＩＴＯ配線を保管し、前記粘着シート付ＩＴＯ配線におけるＩＴＯ配線の前記保管後の抵抗値（Ω）を測定する。 (2) The resistance value (Ω0) at room temperature of the ITO wiring in the ITO wiring with the adhesive sheet is measured in advance, and the ITO wiring with the adhesive sheet is stored in an environment of 65 ° C. and 90% RH for 500 hours. The resistance value (Ω) after the storage of the ITO wiring in the ITO wiring with the adhesive sheet is measured.
（３）導電部材用粘着剤組成物（本組成物）を厚さ１５０μｍのシート状に製膜して粘着シートとし、銅配線がガラス基板上に形成されてなる評価用銅ガラス基板に、前記粘着シートを貼合させて粘着シート付銅配線を作製する。 (3) The adhesive composition for conductive member (this composition) is formed into a sheet having a thickness of 150 μm to form an adhesive sheet, and the copper wiring substrate for evaluation formed by forming a copper wiring on the glass substrate is A pressure sensitive adhesive sheet is bonded to produce a copper wiring with a pressure sensitive adhesive sheet.
（４）前記粘着シート付銅配線における銅配線の室温での抵抗値（Ω０）を予め測定しておき、６５℃・９０％ＲＨ環境下で５００時間、前記粘着シート付銅配線を保管し、前記粘着シート付銅配線における銅配線の前記保管後の抵抗値（Ω）を測定する。 (4) The resistance value (Ω0) at room temperature of the copper wiring in the copper wiring with the adhesive sheet is measured in advance, and the copper wiring with the adhesive sheet is stored in an environment of 65 ° C. and 90% RH for 500 hours. The resistance value (Ω) after the storage of the copper wiring in the copper wiring with the adhesive sheet is measured.
（透明性）
　本粘着シートは、光学的に透明であることが好ましい。つまり、透明粘着シートであることが好ましい。ここで、「光学的に透明」とは、全光線透過率は８０％以上であることを意図し、８５％以上が好ましく、９０％以上がより好ましい。 (transparency)
The pressure-sensitive adhesive sheet is preferably optically transparent. That is, it is preferably a transparent adhesive sheet. Here, “optically transparent” means that the total light transmittance is 80% or more, preferably 85% or more, and more preferably 90% or more.
（厚さ）
　本粘着シートの厚さは、１０μｍ以上５００μｍ以下であるのが好ましく、中でも１５μｍ以上或いは４００μｍ以下であるのがより好ましく、その中でも特に２０μｍ以上或いは３５０μｍ以下であるのことがさらに好ましい。 (thickness)
The thickness of the pressure-sensitive adhesive sheet is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more or 400 μm or less, and particularly preferably 20 μm or more or 350 μm or less.
＜導電部材用粘着シートの用途＞
　本粘着シートは、例えば、パーソナルコンピューター、モバイル端末（ＰＤＡ）、ゲーム機、テレビ（ＴＶ）、カーナビゲーションシステム、タッチパネル、ペンタブレットなどの画像表示装置、例えばプラズマディスプレイ（ＰＤＰ）、液晶ディスプレイ（ＬＣＤ）、有機ＥＬディスプレイ（ＯＬＥＤ）、無機ＥＬディスプレイ、電気泳動ディスプレイ（ＥＰＤ）、干渉変調ディスプレイ（ＩＭＯＤ）などの画像表示パネルを用いた画像表示装置において、各構成部材、中でも導電部材、その中でも透明導電層及び／又は銅を含む金属材料で形成された導体パターンを有する導電部材を貼り合わせるのに好適である。また、ＩＴＯ若しくはＩＧＺＯを含む透明導電層及び／又は銅や銀を含む金属材料で形成された導体パターンを有する透明導電層を含む導電部材を貼り合わせるのにも好適である。 <Use of adhesive sheet for conductive members>
This adhesive sheet is, for example, an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, such as a plasma display (PDP), a liquid crystal display (LCD). In an image display device using an image display panel such as an organic EL display (OLED), an inorganic EL display, an electrophoretic display (EPD), and an interferometric modulation display (IMOD), each component member, particularly a conductive member, particularly a transparent conductive member It is suitable for laminating a conductive member having a conductor pattern formed of a metal material including a layer and / or copper. It is also suitable for bonding a conductive member including a transparent conductive layer containing ITO or IGZO and / or a transparent conductive layer having a conductor pattern formed of a metal material containing copper or silver.
＜導電部材積層体＞
　本発明の導電部材積層体（以下、省略して「本積層体」とも称する。）は、本粘着シートと、導電部材、例えば、透明導電層の導電層面とを貼り合わせることにより得ることができる。
　本積層体は、少なくとも本粘着シートの何れか一方の粘着剤層面と透明導電層の導電層面とが貼り合わせた構成を有するものであればよい。
　本粘着シートが両面粘着シートの場合には、本積層体は本粘着シートの両方の粘着剤層面と透明導電層の導電層面とが貼り合わされた構成を有するものであってもよい。 <Conductive member laminate>
The conductive member laminate of the present invention (hereinafter abbreviated as “the present laminate”) can be obtained by laminating the pressure-sensitive adhesive sheet and a conductive member, for example, a conductive layer surface of a transparent conductive layer. .
This laminated body should just have the structure which the adhesive layer surface of any one of this adhesive sheet and the conductive layer surface of a transparent conductive layer bonded together.
In the case where the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, the laminate may have a structure in which both the pressure-sensitive adhesive layer surfaces of the pressure-sensitive adhesive sheet and the conductive layer surface of the transparent conductive layer are bonded together.
　上記透明導電層は、その導電膜の導電層面を覆うようにオレフィン系ポリマー、ウレタン系ポリマー、エポキシ系ポリマー、アクリル系ポリマー、シリコーン系ポリマー、あるいは無機ガラス等による絶縁保護膜（パシベーション膜）が形成されていてもよい。
　この場合、本粘着シートは、透明導電層面と直接貼り合わされない（透明導電層面と直接接していない）。本粘着シートは、本組成物に由来する成分（特に酸成分）が浸透して該絶縁膜から透明導電層に到達したとしても、１，２，３－トリアゾールの作用により透明導電層が腐食することを防止することができる。特に１，２，３－トリアゾールは水溶性が高く、湿熱環境下において本粘着シートが吸湿した際に透明導電層に移動しやすいため、優れた金属腐食防止効果を奏することができる。
　このように、本粘着シートによると、絶縁保護膜の有無に関わらず、被着体の金属イオンによる粘着剤層の変色や変質のみならず、被着体に対する優れた金属腐食防止効果も奏することができる。 The transparent conductive layer has an insulating protective film (passivation film) made of olefin polymer, urethane polymer, epoxy polymer, acrylic polymer, silicone polymer, or inorganic glass so as to cover the conductive layer surface of the conductive film. May be.
In this case, the pressure-sensitive adhesive sheet is not directly bonded to the transparent conductive layer surface (not directly in contact with the transparent conductive layer surface). The adhesive sheet corrodes the transparent conductive layer by the action of 1,2,3-triazole even if the component derived from the composition (particularly the acid component) penetrates and reaches the transparent conductive layer from the insulating film. This can be prevented. In particular, 1,2,3-triazole is highly water-soluble and can easily move to the transparent conductive layer when the pressure-sensitive adhesive sheet absorbs moisture in a moist heat environment, so that an excellent metal corrosion prevention effect can be achieved.
Thus, according to the present pressure-sensitive adhesive sheet, not only the presence or absence of an insulating protective film, but also an excellent metal corrosion prevention effect on the adherend is exhibited as well as discoloration and alteration of the pressure-sensitive adhesive layer due to metal ions on the adherend. Can do.
　導電層面と貼り合わせて得られる本積層体は、タッチパネルに好適に用いることができる。タッチパネルとしては、抵抗膜方式、静電容量方式、電磁誘導方式等の方式のものが挙げられるが、静電容量方式であることが好ましい。 The laminate obtained by bonding to the conductive layer surface can be suitably used for a touch panel. Examples of the touch panel include a resistance film method, a capacitance method, and an electromagnetic induction method, and a capacitance method is preferable.
　上記透明導電層としては、少なくとも片面の表層に導電層を有するものであればよく、透明基材の表層に導電物質が蒸着やスパッタ、コーティング等により設けられた透明導電層を挙げられる。
　透明導電層の導電層に用いられる導電物質は特に限定されず、具体的には、酸化インジウム、インジウム・ガリウム・亜鉛複合酸化物、錫ドープ酸化インジウム（ＩＴＯ）、酸化亜鉛、酸化ガリウム、酸化チタン等の金属酸化物の他、銀、銅、モリブデン、アルミニウム等の金属材料が挙げられる。中でも、透明性に優れる、錫ドープ酸化インジウム（ＩＴＯ）及びインジウム・ガリウム・亜鉛複合酸化物（ＩＧＺＯ）が好適に用いられる。また、導電性に優れる観点から、銅や銀も好適に用いることができる。透明導電層において、導電物質がパターン形成される基材としては、特に限定されるものではないが、ガラス、樹脂フィルムなどが挙げられる。 The transparent conductive layer only needs to have a conductive layer on at least one surface, and examples thereof include a transparent conductive layer in which a conductive material is provided on the surface of a transparent substrate by vapor deposition, sputtering, coating, or the like.
The conductive material used for the conductive layer of the transparent conductive layer is not particularly limited. Specifically, indium oxide, indium / gallium / zinc composite oxide, tin-doped indium oxide (ITO), zinc oxide, gallium oxide, titanium oxide In addition to metal oxides such as, metal materials such as silver, copper, molybdenum, and aluminum can be given. Among them, tin-doped indium oxide (ITO) and indium / gallium / zinc composite oxide (IGZO), which are excellent in transparency, are preferably used. Moreover, copper and silver can also be used suitably from a viewpoint which is excellent in electroconductivity. In the transparent conductive layer, the substrate on which the conductive substance is patterned is not particularly limited, and examples thereof include glass and a resin film.
　透明導電層は、典型的には、少なくとも片面の表層に導電層を有する。また、典型的には、透明導電層には周辺部を引き回すように銅や銀を主成分とする導体パターン（配線パターン）が形成される。１，２，３－トリアゾールは、中でも銅に対する耐腐食信頼性が高いことから、これを含む本粘着シートは、特に、銅を含む金属材料で形成された導体パターンを備えた導電部材に対して好適に使用することができる。 The transparent conductive layer typically has a conductive layer on at least one surface. Typically, a conductive pattern (wiring pattern) mainly composed of copper or silver is formed on the transparent conductive layer so as to route the peripheral portion. Since 1,2,3-triazole has particularly high resistance to corrosion resistance to copper, this pressure-sensitive adhesive sheet including this is particularly suitable for conductive members having a conductor pattern formed of a metal material containing copper. It can be preferably used.
　その他の本積層体の具体例としては、例えば離型フィルム／本粘着シート／タッチパネル、離型フィルム／本粘着シート／保護パネル、離型フィルム／本粘着シート／画像表示パネル、画像表示パネル／本粘着シート／タッチパネル、画像表示パネル／本粘着シート／保護パネル、画像表示パネル／本粘着シート／タッチパネル／本粘着シート／保護パネル、偏光フィルム／本粘着シート／タッチパネル、偏光フィルム／本粘着シート／タッチパネル／本粘着シート／保護パネルなどの構成を挙げることができる。また、上記の構成において、本粘着シートと、これと隣接するタッチパネル、保護パネル、画像表示パネル、偏光フィルム等の部材との間に前記の導電層を介入する全ての構成を挙げることができる。但し、これらの積層例に限定されるものではない。
　なお、上記タッチパネルには、保護パネルにタッチパネル機能を内在させた構造体や、画像表示パネルにタッチパネル機能を内在させた構造体も含む。 Other specific examples of the laminate include, for example, a release film / this adhesive sheet / touch panel, a release film / this adhesive sheet / protective panel, a release film / this adhesive sheet / image display panel, and an image display panel / book. Adhesive sheet / touch panel, image display panel / main adhesive sheet / protection panel, image display panel / main adhesive sheet / touch panel / main adhesive sheet / protection panel, polarizing film / main adhesive sheet / touch panel, polarizing film / main adhesive sheet / touch panel / The composition of the present adhesive sheet / protective panel can be mentioned. Moreover, in said structure, all the structures which interpose the said conductive layer between members, such as this adhesive sheet and an adjacent touch panel, a protection panel, an image display panel, a polarizing film, can be mentioned. However, it is not limited to these lamination examples.
The touch panel includes a structure in which a touch panel function is included in the protective panel and a structure in which the touch panel function is included in the image display panel.
＜画像表示装置＞
　本発明の画像表示装置（以下、省略して「本装置」とも称する。）は、少なくとも本積層体、画像表示パネル及び表面保護パネルを構成部材として有するものである。 <Image display device>
The image display device of the present invention (hereinafter abbreviated as “this device”) includes at least the present laminate, the image display panel, and the surface protection panel as constituent members.
　より具体的には、本粘着シートを透明導電層の導電層面と貼り合わせて得られる本積層体が、画像表示パネルと表面保護パネルとの間に介挿された構成の画像表示装置を挙げることができる。この際、画像表示パネル側にも本粘着シートを用いることができる。 More specifically, an image display device having a configuration in which the laminate obtained by bonding the adhesive sheet to the conductive layer surface of the transparent conductive layer is interposed between the image display panel and the surface protection panel is mentioned. Can do. At this time, the pressure-sensitive adhesive sheet can also be used on the image display panel side.
　表面保護パネルの材質としては、ガラスの他、アクリル系樹脂、ポリカーボネート系樹脂、シクロオレフィンポリマー等の脂環式ポリオレフィン系樹脂、スチレン系樹脂、ポリ塩化ビニル系樹脂、フェノール系樹脂、メラミン系樹脂、エポキシ系樹脂等のプラスチックであってもよい。 As the material of the surface protection panel, in addition to glass, acryl-based polyolefin resin such as acrylic resin, polycarbonate resin, cycloolefin polymer, styrene resin, polyvinyl chloride resin, phenol resin, melamine resin, Plastics such as epoxy resins may be used.
　画像表示パネルは、偏光フィルムその他位相差フィルム等の他の光学フィルム、液晶材料及びバックライトシステムから構成される（通常、本組成物又は粘着物品の画像表示パネルに対する被着面は光学フィルムとなる。）ものであり、液晶材料の制御方式によりＳＴＮ方式やＶＡ方式やＩＰＳ方式等があるが、何れの方式であってもよい。 The image display panel is composed of another optical film such as a polarizing film or other retardation film, a liquid crystal material, and a backlight system (usually, the adherend surface of the composition or the adhesive article to the image display panel is an optical film. There are STN method, VA method, IPS method, etc. depending on the control method of the liquid crystal material, but any method may be used.
　本画像表示装置としては、例えば液晶ディスプレイ、有機ＥＬディスプレイ、無機ＥＬディスプレイ、電子ペーパー、プラズマディスプレイ及びマイクロエレクトロメカニカルシステム（ＭＥＭＳ）ディスプレイなどの画像表示装置を構成することができる。 As the present image display device, for example, an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display can be configured.
＜語句の説明＞ 
　本明細書において「Ｘ～Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含する。
　また、「Ｘ以上」（Ｘは任意の数字）或いは「Ｙ以下」（Ｙは任意の数字）と表現した場合、「Ｘより大きいことが好ましい」或いは「Ｙ未満であることが好ましい」旨の意図も包含する。 <Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” or “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
　一般的に「シート」とは、ＪＩＳにおける定義上、薄く、その厚さが長さと幅のわりには小さく平らな製品をいい、一般的に「フィルム」とは、長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいう（日本工業規格ＪＩＳＫ６９００）。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。 “Sheet” generally refers to a product that is thin by definition in JIS and has a thickness that is small and flat for the length and width. In general, “film” is thicker than the length and width. A thin flat product with an extremely small thickness and an arbitrarily limited maximum thickness, usually supplied in the form of a roll (Japanese Industrial Standard JISK6900). However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
　以下、実施例及び比較例によりさらに詳しく説明する。但し、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
＜（メタ）アクリル系（共）重合体＞　
　（メタ）アクリル系（共）重合体は、以下のものを用いた。
・Ａ－１：　２－エチルヘキシルアクリレート７６質量部、酢酸ビニル２０質量部及びアクリル酸４質量部からなる共重合体（質量平均分子量４０万）
・Ａ－２：　ブチルアクリレート８１質量部、メチルメタクリレート１５質量部及びアクリル酸４質量部からなる共重合体（質量平均分子量２０万） <(Meth) acrylic (co) polymer>
The (meth) acrylic (co) polymer used the following.
A-1: A copolymer comprising 76 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 4 parts by mass of acrylic acid (mass average molecular weight 400,000)
A-2: A copolymer comprising 81 parts by mass of butyl acrylate, 15 parts by mass of methyl methacrylate and 4 parts by mass of acrylic acid (mass average molecular weight 200,000)
＜実施例１＞
[実施例１－１]
　（メタ）アクリル系（共）重合体（Ａ－１）１ｋｇに対して、金属腐食防止剤として１，２，３－トリアゾール（大塚化学社製）３ｇ、光重合開始剤として４－メチルベンゾフェノンと２，４，６－トリメチルベンゾフェノンの混合物（Ｌａｍｂｅｒｔｉ社製、商品名「エザキュアＴＺＴ」）１５ｇを添加して均一混合し、粘着剤層用樹脂組成物を得た。 <Example 1>
[Example 1-1]
1 kg of (meth) acrylic (co) polymer (A-1), 3 g of 1,2,3-triazole (manufactured by Otsuka Chemical Co., Ltd.) as a metal corrosion inhibitor, and 4-methylbenzophenone as a photopolymerization initiator 15 g of a mixture of 2,4,6-trimethylbenzophenone (manufactured by Lamberti, trade name “Ezacure TZT”) was added and mixed uniformly to obtain a resin composition for an adhesive layer.
　粘着剤層用樹脂組成物を、剥離処理した２枚のポリエチレンテレフタレートフィルム（三菱樹脂社製、商品名「ダイアホイルＭＲＶ」、厚さ１００μｍ及び、三菱樹脂社製、商品名「ダイアホイルＭＲＱ」、厚さ７５μｍ）で挟み、粘着シートの厚さが１５０μｍとなるようシート状に賦形し、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表１に示す。 Two polyethylene terephthalate films (trade name “Diafoil MLV”, manufactured by Mitsubishi Plastics, Inc., 100 μm thick, and product name “Diafoil MRQ” manufactured by Mitsubishi Plastics, Inc.) The pressure-sensitive adhesive sheet was shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet was 150 μm, and a pressure-sensitive adhesive sheet laminate was produced. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
[実施例１－２]
　（メタ）アクリル系（共）重合体（Ａ－２）１ｋｇに対し、金属腐食防止剤として１，２，３－トリアゾール３ｇ、架橋剤として紫外線硬化樹脂プロポキシ化ペンタエリスリトールトリアクリレート（新中村工業株式会社、商品名「ＡＴＭ－４ＰＬ」）２０ｇ、光重合開始剤として４－メチルベンゾフェノンと２，４，６－トリメチルベンゾフェノンの混合物（Ｌａｍｂｅｒｔｉ社製、商品名「エザキュアＴＺＴ」）１５ｇを添加し、均一混合して、粘着剤層用樹脂組成物を得た。 [Example 1-2]
1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor, and UV curable resin propoxylated pentaerythritol triacrylate as a crosslinking agent (Shin Nakamura Kogyo Co., Ltd.) 20 g of company, trade name “ATM-4PL”), and 15 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name “Ezacure TZT”, manufactured by Lamberti) as a photopolymerization initiator were added uniformly. By mixing, a resin composition for an adhesive layer was obtained.
　次に、前記粘着剤層用樹脂組成物を、剥離処理したポリエチレンテレフタレートフィルム（三菱樹脂社製、商品名「ダイアホイルＭＲＶ」、厚さ１００μｍ）上に厚さ１５０μｍとなるようシート状に成形した後、剥離処理したポリエチレンテレフタレートフィルム（三菱樹脂社製、商品名「ダイアホイルＭＲＱ」、厚さ７５μｍ）を被覆して、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表１に示す。 Next, the resin composition for the pressure-sensitive adhesive layer was molded into a sheet shape so as to have a thickness of 150 μm on a polyethylene terephthalate film (trade name “Diafoil MRV”, manufactured by Mitsubishi Plastics Co., Ltd., thickness: 100 μm) subjected to release treatment. Thereafter, a peeled polyethylene terephthalate film (manufactured by Mitsubishi Plastics, trade name “Diafoil MRQ”, thickness 75 μm) was coated to prepare an adhesive sheet laminate. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
[実施例１－３]
　金属腐食防止剤として１，２，３－トリアゾール５ｇを用いる以外は、実施例１－２と同様にして粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表１に示す。 [Example 1-3]
A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 1-2 except that 5 g of 1,2,3-triazole was used as the metal corrosion inhibitor. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
[比較例１－１]
　金属腐食防止剤としての１，２，３－トリアゾールを加えない以外は、実施例１－１と同様にして、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表１に示す。 [Comparative Example 1-1]
A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 1-1 except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
[比較例１－２]
　金属腐食防止剤として１，２，３－トリアゾールの代わりにベンゾトリアゾール（城北化学社製、商品名「ＢＴ１２０」）５ｇを用いる以外は実施例１－１と同様にして、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表１に示す。 [Comparative Example 1-2]
A pressure-sensitive adhesive sheet laminate was prepared in the same manner as in Example 1-1, except that 5 g of benzotriazole (trade name “BT120” manufactured by Johoku Chemical Co., Ltd.) was used instead of 1,2,3-triazole as a metal corrosion inhibitor. did. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
[比較例１－３]
　金属腐食防止剤として１，２，３－トリアゾールの代わりにトリルトリアゾール（４－メチルベンゾトリアゾールと５－メチルベンゾトリアゾールの混合物）（シプロ化成社製、商品名「ＳＥＥＴＥＣ　ＴＴ－Ｒ」）５ｇを用いる以外は、実施例１－１と同様にして、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表１に示す。 [Comparative Example 1-3]
5 g of tolyltriazole (mixture of 4-methylbenzotriazole and 5-methylbenzotriazole) (trade name “SEETEC TT-R” manufactured by Cypro Kasei Co., Ltd.) is used as a metal corrosion inhibitor instead of 1,2,3-triazole. A pressure-sensitive adhesive sheet laminate was produced in the same manner as Example 1-1 except for the above. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
[比較例１－４]
　金属腐食防止剤として１，２，３－トリアゾールの代わりに２，５－ジメルカプト－１，３，４－チアジアゾール（東洋紡社製、商品名「ＭＴＤ」）５ｇを用いる以外は、実施例１－１と同様にして、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表１に示す。 [Comparative Example 1-4]
Example 1-1 except that 5 g of 2,5-dimercapto-1,3,4-thiadiazole (trade name “MTD”, manufactured by Toyobo Co., Ltd.) was used in place of 1,2,3-triazole as a metal corrosion inhibitor. In the same manner, a pressure-sensitive adhesive sheet laminate was produced. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 1.
＜各種評価＞
（１）耐腐食信頼性
　ガラス基板（６０ｍｍ×４５ｍｍ）上に、線巾７０μｍ、線長さ４６ｍｍ、線間隔３０μｍで、１０．５往復するように、厚さ１３００ÅのＩＴＯ、厚さ３０００Åの銅膜をこの順に積層してなる金属膜の往復線を形成すると共に、該往復線の両末端に２ｍｍ角の正方形を形成して銅パターン（長さ約９７ｃｍ）を形成し、耐腐食信頼性評価用銅ガラス基板を作製した（図１（Ａ）を参照）。 <Various evaluations>
(1) Corrosion resistance reliability On a glass substrate (60 mm x 45 mm), with a line width of 70 μm, a line length of 46 mm, and a line interval of 30 μm, 10.5 mm thick ITO and 3000 mm thick copper A metal film round-trip line is formed by laminating the films in this order, and 2 mm squares are formed at both ends of the round-trip line to form a copper pattern (about 97 cm in length) to evaluate corrosion resistance reliability. A copper glass substrate was prepared (see FIG. 1A).
　上記実施例及び比較例で作製した粘着シート積層体（粘着シート厚さ１５０μｍ）の片面の剥離フィルムを剥がし、その露出面にポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、商品名「コスモシャインＡ４１００」、１２５μｍ）をハンドローラーにて貼着した。次に、前記ＰＥＴフィルム付き粘着シートを５２ｍｍ×４５ｍｍに切り出した後、残る剥離フィルムを剥がして、図１（Ｂ）に示すように、金属膜の往復線上を被覆するように、耐腐食信頼性評価用銅ガラス基板に該粘着シートをハンドローラーにて貼着し、さらに、ＰＥＴフィルムを介して、波長３６５ｎｍの積算光量が実施例１－１及び比較例１－１～１－４は３０００ｍＪ／ｃｍ２、実施例１－２及び１－３は２０００ｍＪ／ｃｍ２となるよう高圧水銀ランプにて紫外線を照射し、紫外線架橋させて、耐腐食信頼性評価用サンプル（粘着シート付銅配線）を作製した（図１（Ｄ）参照）。 The release film on one side of the pressure-sensitive adhesive sheet laminate (pressure-sensitive adhesive sheet thickness 150 μm) prepared in the above Examples and Comparative Examples was peeled off, and a polyethylene terephthalate (PET) film (trade name “COSMO SHINE A4100, manufactured by Toyobo Co., Ltd.” was applied to the exposed surface. ”, 125 μm) was attached with a hand roller. Next, after cutting out the pressure-sensitive adhesive sheet with the PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. The pressure-sensitive adhesive sheet was adhered to a copper glass substrate for evaluation with a hand roller, and the cumulative amount of light with a wavelength of 365 nm was 3000 mJ / in Example 1-1 and Comparative Examples 1-1 to 1-4 via a PET film. cm 2, examples 1-2 and 1-3 irradiated with ultraviolet rays using a high-pressure mercury lamp so as to be 2000 mJ / cm 2, by UV cross, corrosion reliability evaluation samples (copper wire with the pressure-sensitive adhesive sheet) It produced (refer FIG.1 (D)).
　この耐腐食信頼性評価用サンプル（粘着シート付銅配線）における銅配線の室温での抵抗値（Ω０）を予め測定した。 The resistance value (Ω0) at room temperature of the copper wiring in this corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) was measured in advance.
　他方、当該耐腐食信頼性評価用サンプル（粘着シート付銅配線）を、６５℃・９０％ＲＨ環境下で５００時間保管し、保管後、耐腐食信頼性評価用サンプル（粘着シート付銅配線）における銅配線の抵抗値（Ω）を測定した。 On the other hand, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) The resistance value (Ω) of the copper wiring was measured.
　そして、銅抵抗値すなわち線末端間抵抗値の変化率（％）［（（Ω／Ω０）－１）×１００］を算出し、表１には「抵抗値変化」として示した。 Then, the change rate (%) [((Ω / Ω0) -1) × 100] of the copper resistance value, that is, the resistance value between the wire ends was calculated and shown in Table 1 as “resistance value change”.
　耐腐食信頼性について、抵抗値の変化率が２０％以上のものを「×（poor）」、２０％未満を「○（good）」と判定した。結果は表１に示す。 Regarding corrosion resistance reliability, those with a resistance change rate of 20% or more were judged as “× (poor)”, and those with less than 20% were judged as “good”. The results are shown in Table 1.
（２）耐発泡信頼性
　実施例及び比較例で作製した粘着シート積層体（厚さ１５０μｍ）の片面の剥離フィルムを剥がしソーダライムガラス板（１５０×２００ｍｍ、厚さ０．５５ｍｍ）にハンドロールにて貼合した。さらに、残った剥離フィルムを剥がし、化学強化ガラス板（１８０×２２０ｍｍ、厚さ０．６ｍｍ）をそらせながらハンドロールで貼合した。 (2) Anti-foaming reliability One side release film of the pressure-sensitive adhesive sheet laminate (thickness 150 μm) prepared in the examples and comparative examples is peeled off and hand rolls on a soda lime glass plate (150 × 200 mm, thickness 0.55 mm). And pasted. Furthermore, the remaining release film was peeled off, and bonded with a hand roll while deflecting the chemically strengthened glass plate (180 × 220 mm, thickness 0.6 mm).
　次に、貼合品を６０℃、０．２ＭＰａ環境下に２０分間おいてオートクレーブ処理した。このサンプルを、メタルハライドランプ照射装置（ウシオ電機社製、形式ＵＶＣ－０５１６Ｓ１、ランプＵＶＬ－８００１Ｍ３－Ｎ）を用いて、照射１回につき波長３６５ｎｍにおける照射量が３０００ｍＪ／ｃｍ２になるようにベルトコンベア速度・放射照度を調整し、１５回照射を行った後、外観の変化を観察した。 Next, the bonded product was autoclaved at 60 ° C. in a 0.2 MPa environment for 20 minutes. Using this metal halide lamp irradiation device (Ushio Electric Co., Ltd., model UVC-0516S1, lamp UVL-8001M3-N), a belt conveyor so that the irradiation dose at a wavelength of 365 nm is 3000 mJ / cm 2 per irradiation. After adjusting the speed and irradiance and irradiating 15 times, the appearance change was observed.
　耐発泡信頼性について、外観を観察したときに、紫外線照射前と変化がないものを「○（good）」、気泡が発生しているものを「×（poor）」として判定した。結果は表１に示す。 Regarding the anti-foaming reliability, when the appearance was observed, it was determined as “◯ (good)” when there was no change from before UV irradiation, and “× (poor)” when bubbles were generated. The results are shown in Table 1.
（３）紫外線硬化特性
（紫外線硬化前貯蔵弾性率Ｇ’）
　紫外線硬化前の貯蔵弾性率は、実施例及び比較例で作製した粘着シートを１～２ｍｍ厚みになるよう積層したものを直径２０ｍｍの円状に打ち抜いたものを測定試料とし、レオメータ（英弘精機株式会社製「ＭＡＲＳ」）を用いて、粘着治具：Φ２５ｍｍパラレルプレート、歪み：０．５％、周波数：１Ｈｚ、温度：－５０～２００℃、昇温速度：３℃／ｍｉｎで、－５０℃～２００℃までの動的貯蔵弾性率Ｇ’を測定し、１２５℃における貯蔵弾性率値を読み取ることで求めた。結果は表１に示す。 (3) UV curing characteristics (storage modulus G ′ before UV curing)
The storage elastic modulus before UV curing was measured using a rheometer (Eihiro Seiki Co., Ltd.) as a measurement sample obtained by punching the adhesive sheets prepared in Examples and Comparative Examples to a thickness of 1 to 2 mm and punching them into a circle with a diameter of 20 mm. Using a “MARS” manufactured by the company, adhesive jig: Φ25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: −50 to 200 ° C., heating rate: 3 ° C./min, −50 ° C. The dynamic storage elastic modulus G ′ up to 200 ° C. was measured, and the storage elastic modulus value at 125 ° C. was read. The results are shown in Table 1.
（紫外線硬化後貯蔵弾性率Ｇ’）
　紫外線硬化後の貯蔵弾性率は次のように測定した。
　実施例及び比較例で作製した粘着シートを、ＰＥＴフィルムを介して、高圧水銀ランプにて紫外線を照射して紫外線架橋させた。この際、実施例１－１及び比較例１－１～１－４については、波長３６５ｎｍの積算光量が３０００ｍＪ／ｃｍ２となるように照射し、実施例１－２及び１－３は当該積層光量が２０００ｍＪ／ｃｍ２となるように照射した。このように紫外線架橋させた粘着シートを１～２ｍｍ厚みになるよう積層し、直径２０ｍｍの円状に打ち抜いたものを測定試料とした。
　レオメータ（英弘精機株式会社製、商品名「ＭＡＲＳ」）を用いて、粘着治具：Φ２５ｍｍパラレルプレート、歪み：０．５％、周波数：１Ｈｚ、温度：－５０～２００℃、昇温速度：３℃／ｍｉｎで、－５０℃～２００℃までの当該測定試料の動的貯蔵弾性率Ｇ’を測定し、１２５℃における貯蔵弾性率値を読み取ることで、紫外線硬化後の貯蔵弾性率を求めた。結果は表１に示す。 (Storage modulus G ′ after UV curing)
The storage elastic modulus after UV curing was measured as follows.
The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were UV-crosslinked by irradiating UV light with a high-pressure mercury lamp through a PET film. At this time, Example 1-1 and Comparative Examples 1-1 to 1-4 were irradiated so that the integrated light quantity with a wavelength of 365 nm was 3000 mJ / cm 2, and Examples 1-2 and 1-3 were the laminates. Irradiation was performed so that the amount of light was 2000 mJ / cm 2 . The pressure-sensitive adhesive sheet thus UV-crosslinked was laminated to a thickness of 1 to 2 mm, and punched into a circle having a diameter of 20 mm was used as a measurement sample.
Using a rheometer (trade name “MARS”, manufactured by Eiko Seiki Co., Ltd.), adhesive jig: Φ25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: −50 to 200 ° C., heating rate: 3 The storage elastic modulus after ultraviolet curing was determined by measuring the dynamic storage elastic modulus G ′ of the measurement sample from −50 ° C. to 200 ° C. at a rate of ℃ / min and reading the storage elastic modulus value at 125 ° C. . The results are shown in Table 1.
　紫外線硬化特性について、紫外線硬化前貯蔵弾性率Ｇ’と紫外線硬化後貯蔵弾性率Ｇ’を比較し、硬化後の値が有意に上昇しているものを「○（good）」、値にほとんど変化がないものを「×（poor）」として判定した。結果は表１に示す。 Compare the storage modulus G 'before UV curing and the storage modulus G' after UV curing for UV curing characteristics. The value after curing is significantly increased to "Good", almost changed to the value. Those without were judged as “× (poor)”. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（評価結果）
　実施例１－１～１－３の粘着シートは、金属腐食防止剤として１，２，３－トリアゾールを含有することで、銅配線の抵抗値の変化が少なく、耐腐食信頼性に優れるものであった。また、耐発泡信頼性、紫外線硬化特性も良好であった。 (Evaluation results)
The adhesive sheets of Examples 1-1 to 1-3 contain 1,2,3-triazole as a metal corrosion inhibitor, so that there is little change in the resistance value of the copper wiring and excellent corrosion resistance reliability. there were. In addition, the foaming resistance reliability and ultraviolet curing characteristics were also good.
　一方、比較例１－１は、金属腐食防止剤を含まず、耐腐食信頼性に劣るものであった。
　比較例１－２は、金属腐食防止剤としてベンゾトリアゾールを含むが、ベンゾトリアゾールの特性により耐発泡信頼性に劣るものであった。
　比較例１－３は、金属腐食防止剤としてトリルトリアゾールを含むが、トリルトリアゾールの特性により耐発泡信頼性に劣るものであった。
　比較例１－４は、金属腐食防止剤としてジメルカプトチアジアゾールを含むが、ジメルカプトチアジアゾールは紫外線を吸収するため、粘着シートは紫外線硬化特性に劣るものであった。 On the other hand, Comparative Example 1-1 did not contain a metal corrosion inhibitor and was inferior in corrosion resistance reliability.
Comparative Example 1-2 contained benzotriazole as a metal corrosion inhibitor, but was poor in foaming reliability due to the characteristics of benzotriazole.
Comparative Example 1-3 contained tolyltriazole as a metal corrosion inhibitor, but was poor in foaming reliability due to the characteristics of tolyltriazole.
Comparative Example 1-4 contains dimercaptothiadiazole as a metal corrosion inhibitor. However, since dimercaptothiadiazole absorbs ultraviolet rays, the pressure-sensitive adhesive sheet was inferior in ultraviolet curing properties.
　以上の結果より、１，２，３－トリアゾールは融点が約２０℃であり、常温ではほぼ液体であるため、粘着シートの実製造工程において、粘着主剤への添加が容易であり、また、粘着主剤への分散性にも優れることが分かった。
　また、１，２，３－トリアゾールは、水溶性が高く、湿熱環境下において粘着シートが吸湿した際に、金属層（銅配線）の表面に移動しやすいため、優れた金属腐食防止効果を発揮することができることも明らかとなった。
　また、１，２，３－トリアゾールは、波長３００～４００ｎｍの分光光度で吸収がないため、ＵＶ硬化特性を阻害しないことも明らかとした。
　このように、１，２，３－トリアゾールは、従来の金属腐食防止剤と比べて優れた特性を持ち、特に導電部材用の粘着シートに用いると効果的であることを見出した。 From the above results, 1,2,3-triazole has a melting point of about 20 ° C. and is almost liquid at room temperature. Therefore, it can be easily added to the main adhesive in the actual production process of the adhesive sheet. It was found to be excellent in dispersibility in the main agent.
In addition, 1,2,3-triazole is highly water-soluble and, when the pressure-sensitive adhesive sheet absorbs moisture in a moist heat environment, it easily moves to the surface of the metal layer (copper wiring), so it has an excellent metal corrosion prevention effect. It became clear that we could do it.
It has also been clarified that 1,2,3-triazole does not inhibit the UV curing property because it does not absorb at a spectrophotometer with a wavelength of 300 to 400 nm.
As described above, it has been found that 1,2,3-triazole has excellent characteristics as compared with conventional metal corrosion inhibitors and is particularly effective when used for an adhesive sheet for conductive members.
＜実施例２＞
[実施例２－１]
　（メタ）アクリル系（共）重合体（Ａ－１）１ｋｇに対して、架橋剤としてプロポキシ化ペンタエリスリトールポリアクリレート（新中村化学工業社製、商品名「ＡＴＭ－４ＰＬ」）２００ｇ、光重合開始剤として４－メチルベンゾフェノンと２，４，６－トリメチルベンゾフェノンの混合物（Ｌａｍｂｅｒｔｉ社製、商品名「エザキュアＴＺＴ」）１０ｇを添加して均一混合し、中間層用樹脂組成物を得た。 <Example 2>
[Example 2-1]
200 kg of propoxylated pentaerythritol polyacrylate (trade name “ATM-4PL”, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent for 1 kg of (meth) acrylic (co) polymer (A-1), photopolymerization started As an agent, 10 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (Lamberti, trade name “Ezacure TZT”) was added and mixed uniformly to obtain an intermediate layer resin composition.
　中間層用樹脂組成物を、剥離処理した２枚のポリエチレンテレフタレートフィルム（三菱樹脂社製、商品名「ダイアホイルＭＲＦ」、厚さ７５μｍ及び、三菱樹脂社製、商品名「ダイアホイルＭＲＴ」、厚さ３８μｍ）で挟み、粘着シートの厚さが８０μｍとなるようシート状に賦形し、中間層用樹脂シート（α）を作製した。 Two polyethylene terephthalate films (trade name “Diafoil MRF”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 μm and a product name “Diafoil MRT” manufactured by Mitsubishi Plastics, Inc. 38 μm) and shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet is 80 μm, to produce an intermediate layer resin sheet (α).
　（メタ）アクリル系（共）重合体（Ａ－１）１ｋｇに対して、金属腐食防止剤として１，２，３－トリアゾール１．５ｇ、亜リン酸エステル化合物として亜リン酸トリス（２，４－ジ－ｔ－ブチルフェニル）（ＢＡＳＦ社製、商品名「イルガフォス１６８」）５ｇ及び光重合開始剤として４－メチルベンゾフェノンと２，４，６－トリメチルベンゾフェノンの混合物（Ｌａｍｂｅｒｔｉ社製、商品名「エザキュアＴＺＴ」）１５ｇを添加して均一混合し、粘着剤層用樹脂組成物を得た。 For 1 kg of the (meth) acrylic (co) polymer (A-1), 1.5 g of 1,2,3-triazole as a metal corrosion inhibitor and Tris phosphite (2,4 as a phosphite compound) -Di-t-butylphenyl) (BASF, trade name “Irgafos 168”) and a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone as a photopolymerization initiator (Lamberti, trade name “ Ezacure TZT ”) 15 g was added and mixed uniformly to obtain a resin composition for an adhesive layer.
　前記粘着剤層用脂組成物を、剥離処理した２枚のポリエチレンテレフタレートフィルム（三菱樹脂社製、商品名「ダイアホイルＭＲＶ」、厚さ１００μｍ及び、三菱樹脂社製、商品名「ダイアホイルＭＲＴ」、厚さ３８μｍ）で挟み、粘着シートの厚さが３５μｍとなるようシート状に賦形し、粘着剤層用樹脂シート（β）を作製した。 Two polyethylene terephthalate films (trade name “Diafoil MRV”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 100 μm, and product name “Diafoil MRT” manufactured by Mitsubishi Plastics Co., Ltd.) were prepared by removing the oil composition for the adhesive layer. , 38 μm thick) and shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet is 35 μm, to produce a resin sheet (β) for the pressure-sensitive adhesive layer.
　さらに、前記粘着剤層用脂組成物を、剥離処理した２枚のポリエチレンテレフタレートフィルム（三菱樹脂社製、商品名「ダイアホイルＭＲＱ」、厚さ７５μｍ及び、三菱樹脂社製、商品名「ダイアホイルＭＲＴ」、厚さ３８μｍ）で挟み、粘着シートの厚さが３５μｍとなるようシート状に賦形し、粘着剤層用樹脂シート（β’）を作製した。 Further, two polyethylene terephthalate films (trade name “Diafoil MRQ”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 μm) and a product name “Diafoil” manufactured by Mitsubishi Plastics Co., Ltd. were peeled off from the above fat composition for the pressure-sensitive adhesive layer. MRT ”, thickness 38 μm), and shaped into a sheet shape so that the thickness of the pressure-sensitive adhesive sheet was 35 μm, to produce a resin sheet (β ′) for the pressure-sensitive adhesive layer.
　前記中間層用シート（α）の両側のＰＥＴフィルムを順次剥離除去すると共に、粘着剤層用樹脂シート（β）及び（β’）の一側のＰＥＴフィルムを剥がして、露出した粘着面を中間層用シート（β）の両表面に順次貼合し、（β）／（α）／（β’）からなる積層体を作製した。 The PET films on both sides of the intermediate layer sheet (α) are sequentially peeled and removed, and the PET films on one side of the adhesive layer resin sheets (β) and (β ′) are peeled off to place the exposed adhesive surface in the middle. Laminate bodies made of (β) / (α) / (β ′) were prepared by sequentially laminating on both surfaces of the layer sheet (β).
　前記（β）及び（β’）の表面に残るＰＥＴフィルムを介して、波長３６５ｎｍの積算光量が２０００ｍＪ／ｃｍ２となるよう高圧水銀ランプにて紫外線を照射し、（α）、（β）及び（β’）を紫外線架橋させて、粘着シート積層体（厚さ１５０μｍ）を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表２に示す。 Irradiate ultraviolet rays with a high-pressure mercury lamp through the PET film remaining on the surfaces of (β) and (β ′) so that the integrated light quantity at a wavelength of 365 nm is 2000 mJ / cm 2, and (α), (β) and (Β ′) was UV-crosslinked to prepare an adhesive sheet laminate (thickness 150 μm). The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
[実施例２－２]
　（メタ）アクリル系（共）重合体（Ａ－２）１ｋｇに対し、金属腐食防止剤として１，２，３－トリアゾール３ｇ、亜リン酸エステル化合物として亜リン酸トリデシル（アデカ社製、商品名「アデカスタブ３０１０」）３ｇ、架橋剤としてペンタエリスリトールトリ及びテトラアクリレート（東亜合成社製、「アロニックスＭ－３０６」）２０ｇ、並びに光重合開始剤として１－ヒドロキシ－シクロヘキシルフェニルケトン（ＢＡＳＦ社製、イルガキュア１８４）１０ｇを添加し、均一混合して、粘着剤層用樹脂組成物を得た。 [Example 2-2]
1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor, tridecyl phosphite as a phosphite compound (trade name, manufactured by Adeka) 3 g of “ADK STAB 3010”), 20 g of pentaerythritol tri and tetraacrylate (manufactured by Toagosei Co., Ltd., “Aronix M-306”) as a crosslinking agent, and 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF, Irgacure as a photopolymerization initiator) 184) 10 g was added and mixed uniformly to obtain a resin composition for an adhesive layer.
　次に、前記粘着剤層用樹脂組成物を、剥離処理したポリエチレンテレフタレートフィルム（三菱樹脂社製、ダイアホイルＭＲＶ、厚さ１００μｍ）上に厚さ１５０μｍとなるようシート状に成形した後、剥離処理したポリエチレンテレフタレートフィルム（三菱樹脂社製、商品名「ダイアホイルＭＲＱ」、厚さ７５μｍ）を被覆した。剥離処理したポリエチレンテレフタレートフィルムを介して、波長３６５ｎｍの積算光量が１０００ｍＪ／ｃｍ２となるよう高圧水銀ランプにて紫外線を照射して粘着剤層用樹脂組成物を紫外線架橋させて、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表２に示す。 Next, the pressure-sensitive adhesive layer resin composition was formed into a sheet shape having a thickness of 150 μm on a peeled polyethylene terephthalate film (Mitsubishi Resin, Diafoil MRV, thickness 100 μm), and then peeled. A polyethylene terephthalate film (trade name “Diafoil MRQ”, thickness 75 μm, manufactured by Mitsubishi Plastics, Inc.) was coated. A pressure-sensitive adhesive sheet laminate is obtained by irradiating ultraviolet rays with a high-pressure mercury lamp through an exfoliated polyethylene terephthalate film so that the integrated light quantity at a wavelength of 365 nm is 1000 mJ / cm 2 to cross-link the adhesive layer resin composition with ultraviolet rays. Was made. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
[実施例２－３]
　亜リン酸エステル化合物として３，９－ビス（デシルオキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５．５］ウンデカン（城北化学社製、商品名「ＪＰＥ－１０」）３ｇを用いる以外は、実施例２－２と同様にして粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表２に示す。 [Example 2-3]
3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (trade name “JPE-10” manufactured by Johoku Chemical Co., Ltd.) as a phosphite compound A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-2 except that 3 g was used. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
［比較例２－１］
　金属腐食防止剤としての１，２，３－トリアゾール及び亜リン酸エステル化合物としての亜リン酸トリス（２，４－ジ－ｔ－ブチルフェニル）（ＢＡＳＦ社製、商品名「イルガフォス１６８」）を加えない以外は、実施例２－１と同様にして、粘着シート積層体を作製したかかる粘着シート積層体について、下述する各種評価を行った。結果は表２に示す。 [Comparative Example 2-1]
1,2,3-triazole as a metal corrosion inhibitor and tris (2,4-di-t-butylphenyl) phosphite as a phosphite compound (trade name “Irgaphos 168” manufactured by BASF) Except not being added, in the same manner as in Example 2-1, the pressure-sensitive adhesive sheet laminate in which the pressure-sensitive adhesive sheet laminate was produced was subjected to various evaluations described below. The results are shown in Table 2.
［比較例２－２］
　金属腐食防止剤としての１，２，３－トリアゾールを加えない以外は実施例２－１と同様にして、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表２に示す。 [Comparative Example 2-2]
A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1, except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
［比較例２－３］
　金属腐食防止剤として、１，２，３－トリアゾールの代わりにベンゾトリアゾール（城北化学社製、商品名「ＢＴ１２０」）１．５ｇを添加し、亜リン酸エステル化合物を加えない以外は、以外は実施例２－１と同様にして、粘着シート積層体を作製した。かかる粘着シート積層体について、下述する各種評価を行った。結果は表２に示す。 [Comparative Example 2-3]
As a metal corrosion inhibitor, except that 1.5 g of benzotriazole (manufactured by Johoku Chemical Co., Ltd., trade name “BT120”) is added in place of 1,2,3-triazole, and the phosphite compound is not added. A pressure-sensitive adhesive sheet laminate was produced in the same manner as Example 2-1. The adhesive sheet laminate was subjected to various evaluations described below. The results are shown in Table 2.
＜各種評価＞
（１）酸化劣化防止性
　ガラス基板（６０ｍｍ×４５ｍｍ）上に、厚さ１５０～２００Å、線巾７０μｍ、線長さ４６ｍｍ、線間隔３０μｍで１０．５往復するように酸化インジウム（ＩＴＯ）の往復線を形成すると共に、該往復線の両末端にＩＴＯからなる２ｍｍ角の正方形を形成してＩＴＯパターン（長さ約９７ｃｍ）を形成し、酸化劣化防止性評価用ＩＴＯガラス基板を作製した（図１（Ａ）を参照）。 <Various evaluations>
(1) Oxidation degradation prevention property Indium oxide (ITO) reciprocation on a glass substrate (60 mm x 45 mm) so as to reciprocate 10.5 with a thickness of 150 to 200 mm, a line width of 70 μm, a line length of 46 mm, and a line interval of 30 μm. In addition to forming a line, 2 mm squares made of ITO were formed at both ends of the reciprocating line to form an ITO pattern (length of about 97 cm) to produce an ITO glass substrate for evaluating oxidation resistance (see FIG. 1 (A)).
　上記実施例及び比較例で作製した粘着シート積層体（厚さ１５０μｍ）の片面の剥離フィルムを剥がし、その露出面にＰＥＴフィルム（東洋紡績社製、商品名「コスモシャインＡ４１００」、１２５μｍ）をハンドローラーにて貼着した。次に、前記ＰＥＴフィルム付き粘着シートを５２ｍｍ×４５ｍｍに切り出した後、残る剥離フィルムを剥がして、図１（Ｂ）に示すように、ＩＴＯの往復線上を被覆するように、酸化劣化防止性評価用ＩＴＯガラス基板に該粘着シートをハンドローラーにて貼着し、酸化劣化防止性評価用サンプル（粘着シート付ＩＴＯ配線）を作製した（図１（Ｃ）参照）。 Peel off the release film on one side of the adhesive sheet laminate (thickness 150 μm) prepared in the above examples and comparative examples, and hand the PET film (trade name “COSMO SHINE A4100”, 125 μm, manufactured by Toyobo Co., Ltd.) on the exposed surface. Sticking with a roller. Next, after cutting out the pressure-sensitive adhesive sheet with the PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. The pressure-sensitive adhesive sheet was attached to an ITO glass substrate for use with a hand roller to produce a sample for evaluating oxidation resistance (ITO wiring with pressure-sensitive adhesive sheet) (see FIG. 1C).
　この酸化劣化防止性評価用サンプル（粘着シート付ＩＴＯ配線）におけるＩＴＯ配線の室温での抵抗値（Ω０）を予め測定した。 The resistance value (Ω0) at room temperature of the ITO wiring in this oxidation deterioration prevention evaluation sample (ITO wiring with adhesive sheet) was measured in advance.
　他方、当該酸化劣化防止性評価用サンプル（粘着シート付ＩＴＯ配線）を、６５℃・９０％ＲＨ環境下で５００時間保管し、保管後、耐酸化劣化防止性評価用サンプル（粘着シート付ＩＴＯ配線）におけるＩＴＯ配線の抵抗値（Ω）を測定した。 On the other hand, the oxidation degradation prevention evaluation sample (ITO wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the oxidation degradation resistance evaluation sample (ITO wiring with adhesive sheet) is stored. ) Was measured for the resistance value (Ω) of the ITO wiring.
　そして、ＩＴＯ抵抗値すなわち線末端間抵抗値の変化率（％）［（（Ω／Ω０）－１）×１００］を算出し、表２には「抵抗値変化」として示した。 Then, the change rate (%) [((Ω / Ω0) -1) × 100] of the ITO resistance value, that is, the resistance value between line ends was calculated, and shown in Table 2 as “resistance value change”.
　酸化劣化防止性について、抵抗値の変化率が５％以上のものを「×（poor）」、５％未満を「○（good）」と判定した。結果は表２に示す。 As for the oxidative degradation prevention property, a resistance value change rate of 5% or more was judged as “× (poor)”, and less than 5% was judged as “good”. The results are shown in Table 2.
（２）耐腐食信頼性
　ガラス基板（６０ｍｍ×４５ｍｍ）上に、線巾７０μｍ、線長さ４６ｍｍ、線間隔３０μｍで、１０．５往復するように、厚さ１３００ÅのＩＴＯ、厚さ３０００Åの銅膜をこの順に積層してなる金属膜の往復線を形成すると共に、該往復線の両末端に２ｍｍ角の正方形を形成して銅パターン（長さ約９７ｃｍ）を形成し、耐腐食信頼性評価用銅ガラス基板を作製した（図１（Ａ）を参照）。 (2) Corrosion resistance reliability On a glass substrate (60 mm x 45 mm), with a line width of 70 µm, a line length of 46 mm, and a line interval of 30 µm, 10.5 mm thick ITO and 3000 mm thick copper A metal film round-trip line is formed by laminating the films in this order, and 2 mm squares are formed at both ends of the round-trip line to form a copper pattern (about 97 cm in length) to evaluate corrosion resistance reliability. A copper glass substrate was prepared (see FIG. 1A).
　上記実施例及び比較例で作製した粘着シート積層体（厚さ１５０μｍ）の片面の剥離フィルムを剥がし、その露出面にＰＥＴフィルム（東洋紡績社製、商品名「コスモシャインＡ４１００」、１２５μｍ）をハンドローラーにて貼着した。次に、前記ＰＥＴフィルム付き粘着シートを５２ｍｍ×４５ｍｍに切り出した後、残る剥離フィルムを剥がして、図１（Ｂ）に示すように、金属膜の往復線上を被覆するように、耐腐食信頼性評価用銅ガラス基板に粘着シートをハンドローラーにて貼着し、耐腐食信頼性評価用サンプル（粘着シート付銅配線）を作製した（図１（Ｄ）参照）。 Peel off the release film on one side of the adhesive sheet laminate (thickness 150 μm) prepared in the above examples and comparative examples, and hand the PET film (trade name “COSMO SHINE A4100”, 125 μm, manufactured by Toyobo Co., Ltd.) on the exposed surface. Sticking with a roller. Next, after cutting out the pressure-sensitive adhesive sheet with the PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. A pressure-sensitive adhesive sheet was attached to a copper glass substrate for evaluation with a hand roller to prepare a corrosion resistance reliability evaluation sample (copper wiring with pressure-sensitive adhesive sheet) (see FIG. 1D).
　この耐腐食信頼性評価用サンプル（粘着シート付銅配線）における銅配線の室温での抵抗値（Ω０）を予め測定した。 The resistance value (Ω0) at room temperature of the copper wiring in this corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) was measured in advance.
　他方、当該耐腐食信頼性評価用サンプル（粘着シート付銅配線）を、６５℃・９０％ＲＨ環境下で５００時間保管し、保管後、耐腐食信頼性評価用サンプル（粘着シート付銅配線）における銅配線の抵抗値（Ω）を測定した。 On the other hand, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) is stored in an environment of 65 ° C. and 90% RH for 500 hours, and after storage, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) The resistance value (Ω) of the copper wiring was measured.
　そして、銅抵抗値すなわち線末端間抵抗値の変化率（％）［（（Ω／Ω０）－１）×１００］を算出し、表２には「抵抗値変化」として示した。 Then, the change rate (%) [((Ω / Ω0) -1) × 100] of the copper resistance value, that is, the resistance value between the wire ends was calculated and shown in Table 2 as “resistance value change”.
　耐腐食信頼性について、抵抗値の変化率が２０％以上のものを「×（poor）」、２０％未満を「○（good）」と判定した。結果は表２に示す。 Regarding corrosion resistance reliability, those with a resistance change rate of 20% or more were judged as “× (poor)”, and those with less than 20% were judged as “good”. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（評価結果）
　実施例２－１～２－３の粘着シートは、金属腐食防止剤として１，２，３－トリアゾールを含有し、更に亜リン酸エステルを含むことで、ＩＴＯ配線、銅配線ともに抵抗値の変化が少なく、耐腐食信頼性及び酸化劣化防止性に優れるものであった。 (Evaluation results)
The adhesive sheets of Examples 2-1 to 2-3 contain 1,2,3-triazole as a metal corrosion inhibitor, and further contain a phosphite, so that the resistance value of both ITO wiring and copper wiring changes. There were few, and it was excellent in corrosion resistance reliability and oxidation deterioration prevention property.
　一方、比較例２－１は、亜リン酸エステル化合物及び金属腐食防止剤をともに含まず、耐腐食信頼性及び酸化劣化防止性に劣るものであった。
　比較例２－２は、金属腐食防止剤を含まないため、特に銅配線の腐食が顕著であった。
　比較例２－３は、亜リン酸エステル化合物を含まず、ＩＴＯ配線への酸化劣化防止性に劣るものであった。 On the other hand, Comparative Example 2-1 contained neither a phosphite compound nor a metal corrosion inhibitor, and was inferior in corrosion resistance reliability and oxidation deterioration prevention properties.
Since Comparative Example 2-2 did not contain a metal corrosion inhibitor, corrosion of copper wiring was particularly remarkable.
Comparative Example 2-3 did not contain a phosphite compound and was inferior in the ability to prevent oxidative deterioration of the ITO wiring.
　本発明の導電部材用粘着シートは、導電部材（典型的には透明導電層及び／又は銅若しくは銀を含む金属材料で形成された導体パターンを有する導電部材）に対する耐腐食信頼性を有すると共に耐発泡信頼性を有することができるので、各種導電部材を貼り合わせるのに好適な粘着シートとして用いることができる。とりわけ、タッチパネルを有する画像表示装置用の粘着シートとして好適に用いることができる。 The pressure-sensitive adhesive sheet for a conductive member of the present invention has corrosion resistance and reliability against a conductive member (typically a conductive member having a conductive pattern formed of a transparent conductive layer and / or a metal material containing copper or silver). Since it can have foaming reliability, it can be used as an adhesive sheet suitable for bonding various conductive members. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

Claims (13)

  1. 　（メタ）アクリル系共重合体及び１，２，３－トリアゾールを含有する粘着剤組成物からなる粘着剤層を有する導電部材用粘着シート。 A pressure-sensitive adhesive sheet for a conductive member having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer and 1,2,3-triazole.
  2. 　前記粘着剤組成物が亜リン酸エステル化合物を含有する請求項１に記載の導電部材用粘着シート。 The pressure-sensitive adhesive sheet for conductive members according to claim 1, wherein the pressure-sensitive adhesive composition contains a phosphite compound.
  3. 　前記亜リン酸エステル化合物は、脂肪族亜リン酸エステル、芳香族亜リン酸エステル並びに脂肪族エステル基及び芳香族エステル基を有する亜リン酸エステルから選択される何れか一種以上からなるものである請求項１又は２に記載の導電部材用粘着シート。 The phosphite compound comprises at least one selected from aliphatic phosphites, aromatic phosphites, and phosphites having an aliphatic ester group and an aromatic ester group. The adhesive sheet for conductive members according to claim 1 or 2.
  4. 　前記（メタ）アクリル系共重合体は、カルボキシル基含有モノマーを構成単位として含むものであることを特徴とする請求項１～３のいずれか一項に記載の導電部材用粘着シート。 The pressure-sensitive adhesive sheet for a conductive member according to any one of claims 1 to 3, wherein the (meth) acrylic copolymer contains a carboxyl group-containing monomer as a structural unit.
  5. 　前記（メタ）アクリル系共重合体は、カルボキシル基含有モノマーを１．２～１５質量％含有するものである請求項４に記載の導電部材用粘着シート。 The pressure-sensitive adhesive sheet for conductive members according to claim 4, wherein the (meth) acrylic copolymer contains 1.2 to 15% by mass of a carboxyl group-containing monomer.
  6. 　前記粘着剤組成物は光硬化性を有する組成物である請求項１～５のいずれか一項に記載に導電部材用粘着シート。 The pressure-sensitive adhesive sheet for conductive members according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive composition is a photocurable composition.
  7. 　前記粘着剤組成物は架橋剤を含むものである請求項１～６のいずれか一項に記載の導電部材用粘着シート。 The pressure-sensitive adhesive sheet for conductive members according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive composition contains a crosslinking agent.
  8. 　前記導電部材が透明導電層を有するものである請求項１～７のいずれか一項に記載の導電部材用粘着シート。 The pressure-sensitive adhesive sheet for a conductive member according to any one of claims 1 to 7, wherein the conductive member has a transparent conductive layer.
  9. 　前記透明導電層が絶縁保護膜を有するものである請求項８に記載の導電部材用粘着シート。 The pressure-sensitive adhesive sheet for a conductive member according to claim 8, wherein the transparent conductive layer has an insulating protective film.
  10. 　前記導電部材が、錫ドープ酸化インジウムを含む透明導電層及び／又は銅を含む金属材料で形成された導体パターンを有するものである、請求項１～９のいずれか一項に記載の導電部材用粘着シート。 The conductive member according to any one of claims 1 to 9, wherein the conductive member has a conductive pattern formed of a transparent conductive layer containing tin-doped indium oxide and / or a metal material containing copper. Adhesive sheet.
  11. 　請求項１～１０のいずれか一項に記載の導電部材用粘着シートを導電部材と貼り合わせた構成を有する導電部材積層体。 A conductive member laminate having a structure in which the conductive member pressure-sensitive adhesive sheet according to any one of claims 1 to 10 is bonded to a conductive member.
  12. 　請求項１１に記載の導電部材積層体、画像表示パネル及び表面保護パネルを構成部材として有する画像表示装置。 An image display device comprising the conductive member laminate according to claim 11, an image display panel, and a surface protection panel as constituent members.
  13. 　（メタ）アクリル系共重合体及び１，２，３－トリアゾールを含有する導電部材用粘着剤組成物。 A pressure-sensitive adhesive composition for conductive members containing a (meth) acrylic copolymer and 1,2,3-triazole.
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