WO2014168178A1 - Laminate - Google Patents

Laminate Download PDF

Info

Publication number
WO2014168178A1
WO2014168178A1 PCT/JP2014/060290 JP2014060290W WO2014168178A1 WO 2014168178 A1 WO2014168178 A1 WO 2014168178A1 JP 2014060290 W JP2014060290 W JP 2014060290W WO 2014168178 A1 WO2014168178 A1 WO 2014168178A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer
mass
less
component
sensitive adhesive
Prior art date
Application number
PCT/JP2014/060290
Other languages
French (fr)
Japanese (ja)
Inventor
恵子 喜多
雄也 米川
Original Assignee
綜研化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 綜研化学株式会社 filed Critical 綜研化学株式会社
Priority to JP2015511282A priority Critical patent/JP6283355B2/en
Priority to KR1020157032057A priority patent/KR102071103B1/en
Priority to CN201480020669.5A priority patent/CN105121157B/en
Publication of WO2014168178A1 publication Critical patent/WO2014168178A1/en

Links

Images

Classifications

    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • B32B2323/00—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the present invention relates to a laminate.
  • image display devices have been used under various applications and conditions. For example, they are often used not only under room temperature conditions but also under severe conditions such as high temperature and high temperature and humidity. .
  • high temperature or high temperature and humidity condition examples include use in a tropical region, use inside a vehicle, and inside an outdoor measuring instrument.
  • an optical film such as a polarizing film constituting the image display device is produced by adsorbing a dichroic dye to a polymer film such as polyvinyl alcohol, and stretching and orienting the film.
  • a protective film is usually provided on the surface of the polyvinyl alcohol film.
  • a triacetyl cellulose (TAC) film has been often used as a protective film for polyvinyl alcohol.
  • TAC triacetyl cellulose
  • COP polycycloolefin-based film
  • the pressure-sensitive adhesive used for bonding the TAC film and the adherend is used for bonding the polycycloolefin film and the adherend. There is a problem of poor adhesion.
  • Patent Document 1 discloses an acrylic pressure-sensitive adhesive composition containing a nuclear hydrogenated terpene phenol resin for the purpose of improving the fixability to polyolefin and cyclic polyolefin in a high temperature atmosphere.
  • Patent Document 2 discloses a low-polarity film pressure-sensitive adhesive containing an alicyclic monomer or an aromatic ring-containing monomer.
  • the pressure-sensitive adhesive having these alicyclic compounds or aromatic ring-containing compounds may not have sufficient durability and adhesion to a polycycloolefin-based film.
  • Patent Document 1 JP 2007-225458 A
  • Patent Document 2 JP 2005-53976 A
  • the present invention provides a laminate that exhibits excellent durability under high temperature and high humidity conditions, can reduce light leakage, and has excellent adhesion to a polycycloolefin film.
  • the present inventors have added (a1) an alkylene oxide chain-containing monomer, (a2) a hydroxyl group-containing monomer, and (a3) an amide group-containing monomer to a predetermined ratio.
  • the laminate according to one embodiment of the present invention is provided.
  • the pressure-sensitive adhesive layer comprises (A) a monomer comprising the following monomer (a1), monomer (a2), monomer (a3), monomer (a4) component and monomer (a5)
  • the copolymer is formed from a pressure-sensitive adhesive composition containing a copolymer of the composition and (B) an isocyanate-based crosslinking agent, and the copolymer has a weight average molecular weight of 400,000 or more and 2 million or less, and an acid value of 1 or less. It is.
  • the glass substrate and the polycycloolefin-based film may be bonded via the pressure-sensitive adhesive layer.
  • the laminate according to 1 or 2 may further include a polarizing film, and the polarizing film may include the polycycloolefin-based film.
  • the laminate according to 1 or 2 may further include a retardation film, and the retardation film may include the polycycloolefin film.
  • the glass substrate may be a glass substrate used for an image display device.
  • the laminate according to another embodiment of the present invention is A first polycycloolefin-based film; A second polycycloolefin-based film; An adhesive layer provided between the first polycycloolefin-based film and the second polycycloolefin-based film,
  • the pressure-sensitive adhesive layer comprises (A) a monomer (a1), a monomer (a2), a monomer (a3), a monomer (a4) component, and a monomer (a5).
  • a pressure-sensitive adhesive composition comprising a copolymer of a monomer composition and (B) an isocyanate-based crosslinking agent; (A1) Alkylene oxide chain-containing monomer 30% by mass or more and 98.8% by mass or less: (A2) Hydroxyl group-containing monomer 0.1 mass% or more and 10 mass% or less: (A3) Amide group or amino group-containing monomer 0.1% by mass or more and 10% by mass or less: (A4) (Meth) acrylic acid alkyl ester monomer 1 mass% or more and 69.8 mass% or less: (A5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less: However, the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5) are added together. 100% by mass.
  • the copolymer has
  • the loss tangent of the pressure-sensitive adhesive layer may be 0.2 or more.
  • the gel fraction of the pressure-sensitive adhesive composition may be 50% or more and 90% or less.
  • the content of the (B) isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition may be 0.1% by mass or more and 5% by mass or less.
  • the content of the (C) silane coupling agent in the pressure-sensitive adhesive composition may be 0.1% by mass or more and 5% by mass or less.
  • the content of the antistatic agent (D) in the pressure-sensitive adhesive composition may be 0% by mass or more and 10% by mass or less.
  • the copolymer has a content of a monomer having an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group of 30% by mass or less. Can be.
  • the laminate exhibits excellent durability under high-temperature conditions or high-temperature and high-humidity conditions. Adhesion between the glass substrate and the polycycloolefin film via the pressure-sensitive adhesive layer or the polycycloolefin film It is excellent in adhesion between each other and light leakage can be reduced.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminate according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an example of a laminate according to an embodiment of the present invention.
  • part means “mass%” and “%” means “mass%” unless otherwise specified.
  • the laminate according to an embodiment of the present invention includes a glass substrate, a polycycloolefin film, and an adhesive layer provided between the glass substrate and the polycycloolefin film,
  • the pressure-sensitive adhesive layer comprises (A) a monomer comprising the following monomer (a1), monomer (a2), monomer (a3), monomer (a4) component and monomer (a5)
  • the copolymer is formed from a pressure-sensitive adhesive composition containing a copolymer of the composition and (B) an isocyanate-based crosslinking agent, and the copolymer has a weight average molecular weight of 400,000 or more and 2 million or less, and an acid value of 1 or less. It is.
  • FIG. 1 is a cross-sectional view schematically showing an example (laminated body 100) of a laminated body according to an embodiment of the present invention.
  • the laminate 100 includes a glass substrate 10, a polycycloolefin-based film 32, and an adhesive layer 20 provided between the glass substrate 10 and the polycycloolefin-based (COP) film 32. And including.
  • the laminate 100 further includes a polarizing film 30, and the polarizing film 30 can include a polycycloolefin-based film 32.
  • the laminate 100 includes a glass substrate 10, a pressure-sensitive adhesive layer 20 provided on the glass substrate 10, and a polarizing film 30 provided on the glass substrate 10 via the pressure-sensitive adhesive layer 20.
  • the polarizing film 30 includes a polycycloolefin film 32, a polyvinyl alcohol film 34 provided on the polycycloolefin film 32, and a TAC film 36 provided on the polyvinyl alcohol film 34.
  • the glass substrate 10 and the polycycloolefin film 32 are bonded via the pressure-sensitive adhesive layer 20.
  • FIG. 2 is a cross-sectional view schematically showing another example (laminate 200) of the laminate according to one embodiment of the present invention.
  • the laminate 200 includes a glass substrate 10, a polycycloolefin film (retardation film) 32, and a polarizing film 130, and includes the glass substrate 10, the polycycloolefin film 32, and The polarizing film 130 is laminated in this order.
  • the polycycloolefin-based film 32 can be a retardation film.
  • the polycycloolefin film 32 and the polarizing film 130 are bonded via the pressure-sensitive adhesive layer 20. Further, the glass substrate 10 and the polycycloolefin-based film 32 are bonded via the pressure-sensitive adhesive layer 22.
  • the polarizing film 130 includes a layer (second polycycloolefin film) 38 that is a polycycloolefin film or TAC film, a polyvinyl alcohol film 34 provided on the layer 38, and a polyvinyl alcohol film 34. And a TAC film 36 provided.
  • the polycycloolefin-based film (first polycycloolefin-based film) 32 and the layer (second polycycloolefin-based film) 38 are bonded via the pressure-sensitive adhesive layer 20.
  • the adhesive layers 20 and 22 in FIGS. 1 and 2 are coated with an adhesive composition (described later) according to the present embodiment (the adhesive layer 20 in FIG. 1 and the adhesive layer 22 in FIG. 2).
  • the adherend is the glass substrate 10 or the polycycloolefin-based film 32, and the adherend is formed on the surface of the polycycloolefin-based film 32 or the layer 38) in the pressure-sensitive adhesive layer 20 in FIG.
  • the pressure-sensitive adhesive composition is applied to the surface of a release film (separator) having good smoothness, and the coating film is dried. And a transfer method for transferring the coating film onto the surface of a specific resin film.
  • the loss tangent of the pressure-sensitive adhesive layer is 0.2 or more (usually 0.20 or more and 0.40 or less) from the viewpoint of improving the adhesion between the adherend and the polycycloolefin-based film. It is preferable that it is 0.28 or more and 0.40 or less.
  • the loss tangent of an adhesive layer is the value measured by the method described in the Example mentioned later.
  • the laminate according to the present embodiment is included in, for example, an image display device (particularly a liquid crystal display device). More specifically, the laminate according to the present embodiment can be used for an image display device for a touch panel, for example.
  • the glass substrate included in the laminate according to the present embodiment is a glass substrate for a liquid crystal display device.
  • the glass substrate which comprises the laminated body which concerns on this embodiment can be a glass substrate used for image display apparatuses.
  • the image display device can be, for example, a TFT (thin film transistor) liquid crystal display device used for a liquid crystal television, a computer monitor, a mobile phone, a tablet, and the like.
  • the “polycycloolefin film” includes at least 50% of a skeleton derived from polycycloolefin in a structural unit.
  • the polycycloolefin-based film may be a polycycloolefin copolymer.
  • the polycycloolefin copolymer may be formed by, for example, ethylene and polycycloolefin (for example, tetracyclododecene) under a Ziegler catalyst. It can be obtained by copolymerization.
  • a commercially available polycycloolefin film can be used as the polycycloolefin film.
  • Examples of commercially available polycycloolefin-based films include ZEONOR films (manufactured by ZEON CORPORATION) and ARTON films (manufactured by JSR).
  • the pressure-sensitive adhesive layer constituting the laminate according to the present embodiment comprises: (A) the following monomer (a1), monomer (a2), monomer (a3), monomer (a4) component And a monomer composition copolymer comprising monomer (a5) (hereinafter sometimes simply referred to as “component (A)”) and (B) an isocyanate-based crosslinking agent (hereinafter simply referred to as “( B) component ”(sometimes referred to as“ component ”)) (hereinafter also referred to simply as“ pressure-sensitive adhesive composition ”).
  • component (a1) 30% by mass or more and 98.8% by mass or less of an alkylene oxide chain-containing monomer (hereinafter sometimes simply referred to as “component (a1)”)
  • component (a2) 0.1% by mass or more and 10% by mass or less of the hydroxyl group-containing monomer (hereinafter sometimes referred to simply as “component (a2)”)
  • component (a3) Amide group-containing monomer 0.1% by mass or more and 10% by mass or less (hereinafter sometimes simply referred to as “component (a3)”)
  • component (a4) (Meth) acrylic acid alkyl ester monomer 1% by mass to 69.8% by mass (hereinafter sometimes simply referred to as “component (a4)”)
  • component (a5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less (hereinafter sometimes referred to simply as “component (a5)”)
  • the component (A) includes the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5). It is a copolymer of the monomer composition consisting of and is preferably an acrylic polymer.
  • the “acrylic polymer” means at least one selected from acrylic acid, acrylic acid salt, acrylic acid ester, methacrylic acid, methacrylic acid salt, and methacrylic acid ester in a constituent unit of 50 mass%. The polymer containing above is said.
  • (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid
  • (meth) acrylate is a concept including both acrylate and methacrylate.
  • the alkylene oxide chain-containing monomer as component (a1) is a monomer containing an alkylene oxide chain.
  • the “alkylene oxide chain” means R 2 — (O—R 1 —) n (wherein R 1 represents an alkylene group, R 2 represents an alkyl group, and n represents an integer of 1 or more) Represents a group represented by:
  • the alkylene group represented by R 1 may be linear, branched or cyclic, and is, for example, an alkylene group having 1 to 5 carbon atoms (preferably 2 to 4 carbon atoms).
  • R 2 represents an alkyl group, and n represents an integer of 1 or more.
  • the alkyl group represented by R 2 may be linear, branched or cyclic, and is, for example, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms).
  • n is preferably an integer of 1 or more and 3 or less.
  • Examples of the (a1) component alkylene oxide chain-containing monomer include alkylene oxide chain such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2-propoxyethyl (meth) acrylate.
  • the content of the component (a1) in the monomer composition is 30% by mass or more and 98.8% by mass. Or less, more preferably 50% by mass or more and 98.8% by mass or less.
  • Component (a2) The hydroxyl group-containing monomer that is component (a2) is a component that crosslinks with the isocyanate-based crosslinking agent that is component (B). From the viewpoint of constructing an appropriate crosslinked structure, the content of the component (a2) in the monomer composition is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 2% by mass. The following is more preferable.
  • hydroxyl group-containing monomer as component (a2) examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl.
  • the component (a2) is preferably a hydroxyalkyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms.
  • Component (a3) The amide group or amino group-containing monomer as the component (a3) is a component that imparts cohesive force to the pressure-sensitive adhesive composition.
  • a hydrogen atom bonded to a nitrogen atom constituting an amide group or an amino group participates in the formation of a hydrogen bond in the pressure-sensitive adhesive composition, whereby a high cohesive force can be expressed.
  • the content of the component (a3) in the monomer composition is preferably 0.1% by mass or more and 10% by mass or less, and 0.1% by mass or more and 2% by mass or less. It is more preferable that
  • Examples of the amide group or amino group-containing monomer as the component (a3) include N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N— Dimethylaminopropylacrylamide N, N′-dimethylacrylamide, N, N′-diethylacrylamide, N, N′-dimethylaminoethylacrylamide, N, N′-dimethylaminopropylacrylamide, N-isopropylacrylamide, tert-octyl (meta ) Amide group-containing (meth) acrylic acid esters such as acrylamide and diacetone acrylamide, acryloylmorpholine, or acrylamide.
  • the (meth) acrylic acid alkyl ester monomer as the component (a4) does not contain any alkylene oxide chain, hydroxyl group, amide group, or amino group.
  • Examples of the (meth) acrylic acid alkyl ester monomer as component (a4) include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n- Butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-lauryl methacrylate, n-lauryl acrylate, n- Linear alkyl groups such as tetradecyl methacrylate, n-hexadecyl acrylate, n-hexadecyl methacrylate, stearyl
  • (Meth) acrylic acid alkyl ester having a branched alkyl group alkyl (meth) acrylate having an alicyclic alkyl group such as cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentanyl acrylate, etc. Esters are included, and one of these is used alone or in combination of two or more Rukoto can.
  • the component (a4) preferably has a linear or branched alkyl group. It is more preferable to have an alkyl group having a shape. In this case, the number of carbon atoms of the alkyl group is 1 or more and 20 or less (preferably, because the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment can further reduce the light leakage of the image display device. More preferably, it is 1 or more and 10 or less.
  • the content of the component (a4) in the monomer composition is 0.1% by mass or more and 69.8% by mass. Or less, more preferably 0.1% by mass or more and 50% by mass or less.
  • Component (a5) The monomer mixture contains a copolymerizable monomer other than the component (a1), the component (a2), the component (a3) and the component (a4) which are the component (a5). May be.
  • Component (a5) is, for example, (meth) acrylic acid ester having an aromatic ring group such as carboxyethyl acrylate, acrylonitrile, pentamethylpiperidine methacrylate, benzyl methacrylate, benzyl acrylate, 2-naphthyl acrylate, phenoxyethyl acrylate, etc .; (Meth) acrylates having an ether group such as pentenyloxyethyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, styrene monomers such as styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyren
  • the component (a1) in the monomer mixture for obtaining the copolymer as the component (A), can be 70% by mass or more and 100% by mass or less, and preferably 80% by mass or more and 100% by mass or less.
  • the alicyclic ring in the monomer mixture is preferably 30% by mass or less, and more preferably 20% by mass or less.
  • the component (A) has a weight average molecular weight (Mw) of 400,000 or more and 2 million or less.
  • Mw weight average molecular weight
  • durability may be inferior.
  • light leakage may not be sufficiently reduced.
  • the weight average molecular weight of the component (A) Is preferably 400,000 or more and 2 million or less, and more preferably 750,000 or more and 1.5 million or less.
  • the weight average molecular weight and number average molecular weight of the component (A) are GPC (gel permeation chromatography), and the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene are as follows. It is what I have sought.
  • Measuring device HLC-8120GPC (manufactured by Tosoh Corporation)
  • GPC column configuration The following five columns (all manufactured by Tosoh Corporation) (I) TSK-GEL HXL-H (guard column) (Ii) TSK-GEL G7000HXL (Iii) TSK-GEL GMHXL (Iv) TSK-GEL GMHXL (V) TSK-GEL G2500HXL Sample concentration: diluted with tetrahydrofuran to 1.0 mg / cm 3 Mobile phase solvent: tetrahydrofuran Flow rate: 1.0 cm 3 / min Column temperature: 40 ° C.
  • the dispersion index (Mw / Mn) of the component (A) is preferably 1 or more and 20 or less.
  • the component (A) has an acid value of 1 or less.
  • the acid value of component (A) refers to the number of mg of potassium hydroxide required to neutralize free fatty acids and / or resin acids present in 1 g of component (A).
  • the acid value of the component (A) is 1 or less, corrosion of the adherend can be prevented.
  • the measuring method of an acid value it describes in the Example mentioned later.
  • the acid value of the component (A) is 1 or less, a monomer having a carboxyl group (for example, an acrylic that can be used as the component (a5) in the monomer mixture for producing the component (A) It is preferable that the copolymerizable monomer having a carboxyl group such as acid and methacrylic acid is not substantially contained.
  • the fact that the monomer mixture for producing the component (A) does not substantially contain the carboxyl group-containing monomer means that the monomer mixture for producing the component (A) contains a carboxyl group. It means that the monomer content is 0.2% by mass or less, and more specifically, it is more preferable that the carboxyl group-containing monomer is not blended in the monomer mixture for producing the component (A).
  • metal oxides such as an ITO layer used for transparent electrodes are often used in image display devices.
  • the adherend contains a metal oxide
  • the metal oxide is corroded by an acid component, causing a problem that the resistance value is increased.
  • the acid value of the component (A) contained in the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive layer is 1 or less, so that the metal including the ITO layer can be used. Oxide corrosion can be prevented, and an increase in resistance can be suppressed.
  • the content of the component (A) in the pressure-sensitive adhesive composition according to this embodiment is 90 masses of the pressure-sensitive adhesive composition (when the pressure-sensitive adhesive composition is 100 mass%). % To 99.8% by mass, preferably 95% to 99.8% by mass.
  • the gel fraction of the pressure-sensitive adhesive composition according to this embodiment is preferably 50% or more and 90% or less, and more preferably 60% or more and 80% or less.
  • the gel fraction is, for example, the types and amounts of the components (a2) and (a3) in the monomer mixture used when preparing the pressure-sensitive adhesive composition, (B ) Can be adjusted according to the type and amount of the crosslinking agent.
  • the gel fraction 0.1 g (dry weight (1)) of the crosslinked adhesive was collected in a sample bottle, and 30 cc of ethyl acetate was further added to the sample bottle and shaken for 24 hours. After that, the contents of the sample bottle were filtered with a 200 mesh stainless steel wire mesh, the residue on the wire mesh was dried at 100 ° C. for 2 hours, and the dry weight (dry weight (2)) was measured. 1).
  • Gel fraction (%) (dry weight (2) / dry weight (1)) ⁇ 100 (1)
  • Tg of the component (A) is ⁇ from the viewpoint of preventing light leakage and enhancing durability and adhesion between the adherend and the polycycloolefin film. It is preferably 70 ° C. or higher and 0 ° C. or lower, and more preferably ⁇ 60 ° C. or higher and ⁇ 10 ° C. or lower.
  • the Tg of the component (A) is a value calculated by the following formula (2) (FOX formula).
  • Tg A W a1 / Tg a1 + W a2 / Tg a2 + W a3 / Tg a3 + W a4 / Tg a4 + W a5 / Tg a5 (2)
  • Tg A represents the glass transition temperature (K) of the component (A)
  • Tg a1 , Tg a2 , Tg a3 , Tg a4 , and Tg a5 are the constituent monomers (a1) and (a2), respectively.
  • Tg A glass transition temperatures (K)) of homopolymers
  • W a1 , W a2 , W a3 , W a4 , and W a5 are (A The weight fractions of the constituent monomers (a1), (a2), (a3), (a4) and (a5) contained in the component are shown.
  • Tg A is calculated as an absolute temperature (K) by the above formula (2), it is converted to a Celsius temperature (° C.) as necessary.
  • the glass transition temperatures of homopolymers prepared from typical monomers are shown in Table 1 below. More specifically, for example, Polymer Handbook 4th Edition (Polymer Handbook Third Edition, Wiley-Interscience, 2003) It is described in.
  • the viscosity of the component (A) is preferably 1 Pa ⁇ s or more and 10 Pa ⁇ s or less, and preferably 3 Pa ⁇ s or more and 7 Pa ⁇ s or less. It is more preferable.
  • the viscosity of the component (A) is a value measured with a B-type viscometer.
  • the heating residue of component (A) is preferably 15% or more and 50% or less, and 20% or more and 30% or less. It is more preferable.
  • the heating residue of the component (A) means a ratio remaining after the component (A) is heated.
  • the isocyanate-based cross-linking agent that is the (B) component is not particularly limited as long as it is a cross-linking agent that can cross-link with the (A) component at room temperature or under heating.
  • isocyanate monomers such as xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and divalent or higher divalents such as trimethylolpropane
  • isocyanate compound or an isocyanurate obtained by addition reaction with an alcohol compound or the like is exemplified.
  • urethane prepolymer type isocyanates obtained by addition reaction of isocyanate compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like can be mentioned. Of these, xylylene diisocyanate and its derivatives are preferably used.
  • the content of the component (B) in the pressure-sensitive adhesive composition according to this embodiment is a pressure-sensitive adhesive composition (pressure-sensitive adhesive) according to this embodiment from the viewpoint of achieving a predetermined gel fraction (for example, 50% to 90%).
  • a predetermined gel fraction for example, 50% to 90%.
  • the agent composition 100% by mass
  • it can be 0.1% by mass or more and 5% by mass or less, and preferably 0.2% by mass or more and 1% by mass or less.
  • the pressure-sensitive adhesive composition according to this embodiment can further contain components other than the component (A) and the component (B) as necessary.
  • the pressure-sensitive adhesive composition according to the present embodiment includes (C) a silane coupling agent (hereinafter sometimes simply referred to as “component (C)”), as long as the effects of the present invention are not impaired.
  • component (D) An ionic compound (hereinafter sometimes simply referred to as “component (D)”), an antioxidant, an ultraviolet absorber, a tackifier, a plasticizer, and the like may be blended.
  • Component (C) is, for example, a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Silicon compounds having an epoxy structure such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane And amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents, etc. (Meth) acrylic Silane coupling agents having a functional
  • the content of the component (C) in the pressure-sensitive adhesive composition according to this embodiment is the pressure-sensitive adhesive composition (pressure-sensitive adhesive composition) according to this embodiment from the viewpoint of maintaining good adhesion with the adherend. 0.1 mass% or more and 5 mass% or less, and preferably 0.2 mass% or more and 1 mass% or less with respect to 100 mass%).
  • the adhesive composition which concerns on this embodiment may contain the ionic compound (D).
  • the component (D) include an ionic compound that is composed of an anion and a cation and is liquid or solid at 25 ° C., specifically, an alkali metal salt, an ionic liquid (liquid at 25 ° C. Shape), surfactants and the like.
  • the pressure-sensitive adhesive composition according to this embodiment contains the component (D)
  • the oxygen atom of the alkylene oxide chain derived from the component (a1) constituting the component (A) is distributed to the cation constituting the component (D). Therefore, high antistatic performance can be realized.
  • alkali metal salt examples include compounds comprising an alkali metal cation such as lithium, sodium and potassium and an anion.
  • cation constituting the ionic liquid piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyra Zolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation and the like.
  • anions constituting the ionic liquid include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4.
  • ionic compound it is comprised from these cations and anions, and a liquid ionic compound is mentioned at 25 degreeC.
  • ionic compounds include 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, and 1-ethyl.
  • Carbazole tetrafluoroborate 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazole Lithium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1 Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulf
  • any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used.
  • nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyls such as polyoxyethylene octylphenyl ether and polyoxyethylene nonielphenyl ether.
  • Sorbitan higher fatty acid esters such as ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monostearate; for example, oleic acid monoglyceride, stearic acid monoglyceride Glycerine higher fatty acid esters such as id, polyoxyethylene, polyoxypropylene, polyoxyalkylenes and their block copolymers of polyoxybutylene and the like.
  • cationic surfactant examples include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, alkyldimethylammonium ethosulphate and the like.
  • anionic surfactant examples include sodium laurate, sodium oleate, N-acyl-N-methylglycine sodium salt, sodium carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium dodecylbenzenesulfonate, dialkylsulfosuccinate.
  • amphoteric surfactant examples include carboxybetaine surfactants, aminocarboxylates, imidazolinium petines, lecithins, and alkylamine oxides.
  • conductive polymers, conductive carbon, ammonium chloride, aluminum chloride, copper chloride, iron chloride, ammonium sulfate, and the like can be used.
  • alkali metal salts are preferred.
  • content of the (D) component in the adhesive composition which concerns on this embodiment is the adhesive composition (adhesive composition) which concerns on this embodiment.
  • adhesive composition adhesive composition
  • the polymerization method of component (A) is not particularly limited and can be polymerized by known methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc. In producing the pressure-sensitive adhesive composition of the present invention using a mixture of coalesces, it is preferable to perform polymerization by solution polymerization from the viewpoint that the treatment process is relatively simple and can be performed in a short time.
  • solution polymerization generally, a predetermined organic solvent, each monomer, a polymerization initiator, a chain transfer agent used as necessary, and the like are charged in a polymerization tank, under a nitrogen stream or a reflux temperature of the organic solvent, The reaction is carried out by heating for several hours with stirring.
  • the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha;
  • aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha
  • aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil;
  • Esters such
  • organic solvents for polymerization in the polymerization of the component (A), it is preferable to use an organic solvent that hardly causes chain transfer during the polymerization reaction, for example, esters and ketones.
  • an organic solvent that hardly causes chain transfer during the polymerization reaction for example, esters and ketones.
  • use of ethyl acetate, methyl ethyl ketone, acetone or the like is preferable.
  • organic peroxides and azo compounds that can be used in ordinary solution polymerization.
  • organic peroxides include tert-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, diisopropyl peroxydicarbonate, and di-2.
  • Examples of the azo compound include 2,2′-azobis-isobuty Examples include rhonitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like.
  • polymerization initiators that do not cause a graft reaction during the polymerization reaction of component (A) are preferable, and azo-based compounds are particularly preferable.
  • the amount used is usually 0.01 parts by mass or more and 2 parts by mass or less, preferably 0.1 parts by mass or more and 1.0 parts by mass or less, with respect to 100 parts by mass of the total amount of monomers.
  • the component (A) contained in the pressure-sensitive adhesive composition of the present invention it is normal not to use a chain transfer agent, but as long as it does not impair the purpose and effect of the present invention. It is possible to use.
  • chain transfer agents examples include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene and phenanthrene.
  • Aromatic compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene; benzoquinone, 2, Benzoquinone derivatives such as 3,5,6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, Trichlorethylene, bromotrichloromethane, tribromometa Halogenated hydrocarbons such as 3-chloro-1-propene; aldehydes such as chloral and furaldehyde; alkyl mercaptans having 1 to 18 carbon atoms; aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid And alkyl esters of mercaptoacetic acid having
  • the polymerization temperature of the component (A) is generally about 30 ° C. or higher and 180 ° C. or lower, preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 90 ° C. or lower.
  • an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, it can be purified by a reprecipitation method using methanol or the like in order to remove the monomer.
  • the adhesive composition which concerns on this embodiment is normally prepared by mixing the said (A) and (B) component and arbitrary components as needed simultaneously or in arbitrary orders. Moreover, when mixing (A) component and (B) component, when preparing (A) component by solution polymerization, (B) component is added to the solution containing (A) component after the completion of polymerization. In addition, when the component (A) is prepared by bulk polymerization, uniform mixing becomes difficult after the completion of the polymerization. Therefore, it is preferable to add and mix the component (B) during the polymerization.
  • the said adhesive layer is generally formed by providing an adhesive layer on a peeling film and transferring this to the said adherend. It is.
  • the thickness of the pressure-sensitive adhesive layer is usually 1 ⁇ m or more and 50 ⁇ m or less, preferably about 5 ⁇ m or more and 30 ⁇ m or less.
  • a polymer constituting a polycycloolefin-based film is mainly composed of a low-polar group, and therefore has a low polarity. Therefore, an acrylic pressure-sensitive adhesive is difficult to adhere to the polycycloolefin-based film. For this reason, attempts have been made to improve the adhesion between the polycycloolefin film and the pressure-sensitive adhesive layer by matching the polarities of the polycycloolefin film and the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive layer containing a polymer having a low polarity group for example, an aromatic hydrocarbon group or an alicyclic hydrocarbon group
  • a polycycloolefin film for example, a polycycloolefin film
  • Patent Documents 1 and 2). reference for example, the pressure-sensitive adhesive layer obtained from a pressure-sensitive adhesive composition containing a polymer having these low polar groups has durability and adhesion to a polycycloolefin film. May not be enough.
  • the component (a1) provides an appropriate elastic modulus and light leakage prevention effect to the pressure-sensitive adhesive layer. That is, in the present invention, an adhesive layer having an elastic modulus corresponding to a polycycloolefin film can be obtained from the alkylene oxide chain-containing monomer as the component (a1). This is based on a novel and original idea that the adhesion can be improved and the light leakage prevention effect can be obtained.
  • the laminate according to this embodiment includes a glass substrate, a polycycloolefin film, and an adhesive layer provided between the glass substrate and the polycycloolefin film.
  • the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises a component (A): a single component comprising the component (a1), component (a2), component (a3), component (a4), and component (a5).
  • the component (a1) brings an appropriate elastic modulus and light leakage prevention effect to the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer is easily adapted to the surface of the polycycloolefin-based film, and the glass substrate and the polycycloolefin-based film It is possible to improve the adhesion.
  • the pressure-sensitive adhesive layer can exhibit excellent durability under high temperature and high humidity conditions, and can reduce light leakage.
  • the laminate according to this embodiment includes a first polycycloolefin film, a second polycycloolefin film, the first polycycloolefin film, and the second polycycloolefin film.
  • a pressure-sensitive adhesive layer provided between the film and the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises: (A) component: (a1) component, (a2) component, (a3) A copolymer of a monomer composition comprising the component (a), the component (a4), and the component (a5) and the component (B): an isocyanate-based crosslinking agent, and the component (a1), the component (a2), By including the (a3) component, the (a4) component, and the (a5) component at a predetermined ratio, the (a1) component brings an appropriate elastic modulus and light leakage prevention effect to the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer since the loss tangent of the pressure-sensitive adhesive layer is high and the pressure-sensitive adhesive layer has an appropriate elasticity, the pressure-sensitive adhesive layer is easily adapted to the surface of the polycycloolefin-based film, and the adhesion between the polycycloolefin-based films is Can be increased. In addition, the pressure-sensitive adhesive layer can exhibit excellent durability under high temperature and high humidity conditions, and can reduce light leakage.
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 1 was 25.0%.
  • the weight average molecular weight measured by gel permeation chromatography (GPC) about the obtained acrylic polymer 1 is 89,990,000, the dispersion index of the acrylic polymer 1 is 11, and it can stand at 23 degreeC.
  • the viscosity was 5.1 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 2 was 24.9%.
  • the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 2 is 903,000, the dispersion index of the acrylic polymer 2 is 11, and it can stand at 23 degreeC.
  • the viscosity was 5.4 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 3 was 25.2%. Moreover, the weight average molecular weight measured by gel permeation chromatography (GPC) about the obtained acrylic polymer 3 is 902,000, the dispersion index of the acrylic polymer 2 is 12, and it can stand at 23 degreeC. The viscosity was 5.2 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 4 was 25.1%.
  • the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 4 is 903,000, the dispersion index of the acrylic polymer 4 is 11, and it can stand at 23 degreeC.
  • the viscosity was 5.1 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 5 was 25.2%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 5 is 902,000, the dispersion index of the acrylic polymer 5 is 11, and it can stand at 23 degreeC. The viscosity was 4.8 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 6 was 25.0%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 6 is 915,000, the dispersion index of the acrylic polymer 6 is 11, and it can stand at 23 degreeC. The viscosity was 5.8 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 7 was 24.9%.
  • the weight average molecular weight measured by gel permeation chromatography (GPC) about the obtained acrylic polymer 7 is 931,000, the dispersion index of the acrylic polymer 7 is 11, and it can stand at 23 degreeC.
  • the viscosity was 4.9 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 8 was 35.5%.
  • the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 8 is 36.0 million, the dispersion index of the acrylic polymer 8 is 10, and it is 23 degreeC.
  • the viscosity was 3.5 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 9 was 25.0%.
  • the acrylic polymer 9 obtained had a weight average molecular weight of 891,000 measured by gel permeation chromatography (GPC), and the acrylic polymer 9 had a dispersion index of 11 at 23 ° C.
  • the viscosity was 5.3 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 10 was 24.8%.
  • the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 10 is 908,000, the dispersion index of the acrylic polymer 10 is 13, and it can stand at 23 degreeC.
  • the viscosity was 5.4 (Pa ⁇ s).
  • the heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 1 was 25.1%.
  • the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 1 is 931,000, the dispersion index of the acrylic polymer 1 is 12, and it can stand at 23 degreeC.
  • the viscosity was 5.1 (Pa ⁇ s).
  • this polarizing plate was cut into an appropriate size and bonded to a glass plate to produce laminates (glass plate and polarizing plate with an adhesive layer) of Examples 1 to 6 and Comparative Examples 1 to 5. .
  • a glass plate, an adhesive layer, and a polarizing plate are laminated in this order, and the glass plate and the polarizing plate are bonded via the adhesive layer.
  • the laminate was subjected to a 500 hour durability test, a light leakage measurement test, and a surface resistance value measurement under two conditions of 85 ° C./95 RH% and 60 ° C./95 RH%.
  • Test method 2.2.1 Gel fraction 1 g of a sample was placed in 50 ml of ethyl acetate and applied to a shaker (type name: Shaker SA-300, manufactured by Yamato Scientific Co., Ltd.). The gel content was filtered through a 200 mesh stainless steel net and dried. Then, the value which remove
  • the laminate glass plate and polarizing plate with pressure-sensitive adhesive layer
  • the laminate was cut into a size of 150 mm ⁇ 250 mm, attached to one side of the glass plate using a laminator roll, and then adjusted to 5 atm at 50 ° C.
  • a test plate was prepared by holding in an autoclave for 20 minutes. Two similar test plates were prepared and left for 500 hours under the conditions of 60 ° C. and 95% humidity, respectively, and left for 500 hours under the conditions of 80 ° C. The peeling of the interface of the layer, the occurrence of foaming, etc. were confirmed visually.
  • Two laminated bodies (glass plate and polarizing plate with adhesive layer) are cut to a size of 80 mm ⁇ 140 mm in a state where they are perpendicular to each other, so that they are perpendicular to each other on both sides of the glass plate.
  • a test plate was prepared by sticking using a laminator roll and then holding it in an autoclave adjusted to 50 ° C. and 5 atm for 20 minutes. This test plate was allowed to stand for 500 hours at 80 ° C., and light leakage was observed according to the following criteria.
  • the laminated body (glass plate and polarizing plate with adhesive layer) obtained in Examples 1 to 6 and Comparative Examples 1 to 5 was cut to 10 mm ⁇ 60 mm on an ITO vapor-deposited PET film cut to 10 mm ⁇ 100 mm. And then autoclaved at 50 ° C. ⁇ 5 atm for 20 minutes. Next, after standing at room temperature for 1 hour, placing it in an environment of 60 ° C. and 90% RH for 500 hours, standing at 23 ° C. and humidity of 65% RH for 1 hour, then the resistance of the ITO deposited film The value was measured and compared with the resistance value before the test measured in advance, and the rate of change of the resistance value with respect to the resistance value before the test was obtained.
  • -Titration solution 0.1 mol / l, ethanolic potassium hydroxide solution-Electrode: glass electrode, comparative electrode; calomel electrode
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing the component (A) and the component (B), and the weight of the component (A).
  • the average molecular weight is 400,000 or more and 2 million or less, and the acid value is 1 or less
  • the adhesiveness between the glass substrate and the polycycloolefin-based film and the polycycloolefin-based film between the pressure-sensitive adhesive layers It can be understood that the adhesiveness is excellent, high durability is realized, and light leakage can be reduced.
  • the laminate of Comparative Example 1 was corroded to ITO because the acid value of the component (A) exceeded 1.
  • the laminate of Comparative Example 2 does not contain the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A), so that the durability and light leakage prevention performance are inferior, and the adhesion to the COP It can be understood that the property is also low.
  • the laminated body of the said comparative example 3 has low molecular weight, it can be understood that it is inferior to durability.
  • the laminate of Comparative Example 4 is an example in which 30% by mass of benzyl acrylate is used as the component (a4) instead of the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A). It can be understood that the durability and adhesion to the COP are not good and the light leakage prevention performance is poor.
  • the laminate of Comparative Example 5 is an example in which 30% by mass of cyclohexyl acrylate is used as the component (a5) instead of the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A). It can be understood that the durability is not good and the adhesion to the COP is inferior.
  • the laminate of Comparative Example 6 is an example in which the content of the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A) is less than 30% by mass. It can be understood that the adhesion is not good.

Abstract

Provided is a laminate that contains a glass substrate, a polycycloolefin film, and an adhesive layer provided between the glass substrate and the polycycloolefin film. The adhesive layer is formed from an adhesive composition containing (A) a copolymer of a monomer composition comprising the belowmentioned monomer (a1) to monomer (a5), and (B) an isocyanate cross-linking agent, and the copolymer has a weight average molecular weight of 400,000-2,000,000 inclusive and an acid number of no greater than 1. (a1) 30-98.8 mass% inclusive of an alkylene oxide chain-containing monomer (a2) 0.1-10 mass% inclusive of a hydroxyl group-containing monomer (a3) 0.1-10 mass% inclusive of an amide group- or amino group-containing monomer (a4) 1-69.8 mass% inclusive of a (meth)acrylate alkyl ester monomer (a5) 0-30 mass% inslusive of a copolymerizable monomer other than monomer (a1) to monomer (a4)

Description

積層体Laminated body
　本発明は、積層体に関する。 The present invention relates to a laminate.
　画像表示装置は、近年、様々な用途や条件下において使用されており、例えば、室温条件下のみならず、高温、さらには高温多湿といった過酷な条件下においても使用されることも多くなっている。高温または高温多湿条件での使用としては、例えば、熱帯地域における使用、車両内部や野外計測機器の内部での使用が挙げられる。 In recent years, image display devices have been used under various applications and conditions. For example, they are often used not only under room temperature conditions but also under severe conditions such as high temperature and high temperature and humidity. . Examples of the use under a high temperature or high temperature and humidity condition include use in a tropical region, use inside a vehicle, and inside an outdoor measuring instrument.
　また、画像表示装置を構成する偏光フィルム等の光学フィルムは、二色性を有する色素をポリビニルアルコール等の高分子フィルムに吸着させ、延伸および配向させることにより作製される。ポリビニルアルコールフィルムの表面には通常、保護フィルムが設けられる。ポリビニルアルコールの保護フィルムとして、トリアセチルセルロース（ＴＡＣ）フィルムが多く用いられてきた。しかしながら、近年、ポリビニルアルコールの保護フィルムとして、ＴＡＣフィルムに代わってポリシクロオレフィン系フィルム（ＣＯＰ）が用いられるようになっている。その理由は、ＴＡＣフィルムは反りが激しい材料であるため、偏光フィルムの反りを生じさせ、ひいては画像表示装置の反りまたは破損を招くことがあるからである。しかしながら、ポリシクロオレフィン系フィルムはＴＡＣフィルムとは異なる物性を有するため、ＴＡＣフィルムと被着体との接着に使用される粘着剤をポリシクロオレフィン系フィルムと被着体との接着に用いた場合、密着性が悪いという問題がある。 Also, an optical film such as a polarizing film constituting the image display device is produced by adsorbing a dichroic dye to a polymer film such as polyvinyl alcohol, and stretching and orienting the film. A protective film is usually provided on the surface of the polyvinyl alcohol film. A triacetyl cellulose (TAC) film has been often used as a protective film for polyvinyl alcohol. However, in recent years, a polycycloolefin-based film (COP) has been used instead of a TAC film as a protective film for polyvinyl alcohol. The reason is that since the TAC film is a material having a large warp, the polarizing film may be warped, which may result in warping or breakage of the image display device. However, since the polycycloolefin film has different physical properties from the TAC film, the pressure-sensitive adhesive used for bonding the TAC film and the adherend is used for bonding the polycycloolefin film and the adherend. There is a problem of poor adhesion.
　上記問題を解決するために、特許文献１には、高温雰囲気下におけるポリオレフィンや環状ポリオレフィンに対する固定性の向上を目的とする、核水添テルペンフェノール樹脂を含むアクリル系粘着剤組成物が開示されている。また、特許文献２には、脂環式モノマーまたは芳香環含有モノマーを含む低極性フィルム用粘着剤が開示されている。しかしながら、これらの脂環式化合物または芳香環含有化合物を有する粘着剤では、耐久性やポリシクロオレフィン系フィルムへの接着性が十分ではない場合がある。 In order to solve the above problem, Patent Document 1 discloses an acrylic pressure-sensitive adhesive composition containing a nuclear hydrogenated terpene phenol resin for the purpose of improving the fixability to polyolefin and cyclic polyolefin in a high temperature atmosphere. Yes. Patent Document 2 discloses a low-polarity film pressure-sensitive adhesive containing an alicyclic monomer or an aromatic ring-containing monomer. However, the pressure-sensitive adhesive having these alicyclic compounds or aromatic ring-containing compounds may not have sufficient durability and adhesion to a polycycloolefin-based film.
　　［特許文献１］特開２００７－２２５４５８号公報
　　［特許文献２］特開２００５－５３９７６号公報 [Patent Document 1] JP 2007-225458 A [Patent Document 2] JP 2005-53976 A
　本発明は、高温および多湿条件下で優れた耐久性を発揮し、光漏れを低減でき、かつ、ポリシクロオレフィン系フィルムとの密着性に優れた積層体を提供する。 DETAILED DESCRIPTION OF THE INVENTION The present invention provides a laminate that exhibits excellent durability under high temperature and high humidity conditions, can reduce light leakage, and has excellent adhesion to a polycycloolefin film.
　本発明者らは、このような課題を解決すべく、（ａ１）アルキレンオキシド鎖含有単量体、（ａ２）水酸基含有単量体、および（ａ３）アミド基含有単量体をそれぞれ所定の割合で含む粘着剤組成物から形成される粘着剤層を介してガラス基板とポリシクロオレフィン系フィルムとを接着した場合、または、該粘着剤層を介してポリシクロオレフィン系フィルム同士を接着した場合、高温および多湿条件下で優れた耐久性を発揮し、光漏れを低減でき、かつ、優れた密着性を有する積層体を得ることができることを見出した。 In order to solve such a problem, the present inventors have added (a1) an alkylene oxide chain-containing monomer, (a2) a hydroxyl group-containing monomer, and (a3) an amide group-containing monomer to a predetermined ratio. When the glass substrate and the polycycloolefin-based film are bonded via the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition comprising, or when the polycycloolefin-based films are bonded via the pressure-sensitive adhesive layer, It has been found that a laminate having excellent durability under high temperature and high humidity conditions, light leakage can be reduced, and excellent adhesion can be obtained.
　１．本発明の一態様に係る積層体は、
　ガラス基板と、
　ポリシクロオレフィン系フィルムと、
　前記ガラス基板と前記ポリシクロオレフィン系フィルムとの間に設けられた粘着剤層と、
を含み、
　前記粘着剤層は、（Ａ）下記単量体（ａ１）、単量体（ａ２）、単量体（ａ３）、単量体（ａ４）成分および単量体（ａ５）からなる単量体組成物の共重合体および（Ｂ）イソシアネート系架橋剤を含む粘着剤組成物から形成され、前記共重合体は、重量平均分子量が４０万以上２００万以下であり、かつ、酸価が１以下である。
　（ａ１）アルキレンオキシド鎖含有単量体３０質量％以上９８．８質量％以下：
　（ａ２）水酸基含有単量体０．１質量％以上１０質量％以下：
　（ａ３）アミド基またはアミノ基含有単量体０．１質量％以上１０質量％以下：
　（ａ４）（メタ）アクリル酸アルキルエステル単量体１質量％以上６９．８質量％以下：
　（ａ５）前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分以外の共重合性単量体０質量％以上３０質量％以下：ただし、前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分、および前記単量体（ａ５）を足し合わせて１００質量％である。 1. The laminate according to one embodiment of the present invention is provided.
A glass substrate;
A polycycloolefin-based film;
An adhesive layer provided between the glass substrate and the polycycloolefin-based film;
Including
The pressure-sensitive adhesive layer comprises (A) a monomer comprising the following monomer (a1), monomer (a2), monomer (a3), monomer (a4) component and monomer (a5) The copolymer is formed from a pressure-sensitive adhesive composition containing a copolymer of the composition and (B) an isocyanate-based crosslinking agent, and the copolymer has a weight average molecular weight of 400,000 or more and 2 million or less, and an acid value of 1 or less. It is.
(A1) Alkylene oxide chain-containing monomer 30% by mass or more and 98.8% by mass or less:
(A2) Hydroxyl group-containing monomer 0.1 mass% or more and 10 mass% or less:
(A3) Amide group or amino group-containing monomer 0.1% by mass or more and 10% by mass or less:
(A4) (Meth) acrylic acid alkyl ester monomer 1 mass% or more and 69.8 mass% or less:
(A5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less: However, the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5) are added together. 100% by mass.
　２．上記１に記載の積層体では、前記ガラス基板および前記ポリシクロオレフィン系フィルムは、前記粘着剤層を介して接着されていてもよい。 2. In the laminate according to 1 above, the glass substrate and the polycycloolefin-based film may be bonded via the pressure-sensitive adhesive layer.
　３．上記１または２に記載の積層体では、偏光フィルムをさらに含み、前記偏光フィルムは、前記ポリシクロオレフィン系フィルムを含むことができる。 3. The laminate according to 1 or 2 may further include a polarizing film, and the polarizing film may include the polycycloolefin-based film.
　４．上記１または２に記載の積層体では、位相差フィルムをさらに含み、前記位相差フィルムは、前記ポリシクロオレフィン系フィルムを含むことができる。 4. The laminate according to 1 or 2 may further include a retardation film, and the retardation film may include the polycycloolefin film.
　５．上記１ないし４のいずれか１項に記載の積層体では、前記ガラス基板は、画像表示装置に用いられるガラス基板であることができる。 5. In the laminated body according to any one of 1 to 4, the glass substrate may be a glass substrate used for an image display device.
　６．本発明の他の一態様に係る積層体は、
　第１のポリシクロオレフィン系フィルムと、
　第２のポリシクロオレフィン系フィルムと、
　前記第１のポリシクロオレフィン系フィルムと前記第２のポリシクロオレフィン系フィルムとの間に設けられた粘着剤層と、を含み、
　前記粘着剤層は、（Ａ）下記単量体（ａ１）、単量体（ａ２）、単量体（ａ３）、および単量体（ａ４）成分、および単量体（ａ５）からなる単量体組成物の共重合体および（Ｂ）イソシアネート系架橋剤を含む粘着剤組成物から形成され、
　（ａ１）アルキレンオキシド鎖含有単量体３０質量％以上９８．８質量％以下：
　（ａ２）水酸基含有単量体０．１質量％以上１０質量％以下：
　（ａ３）アミド基またはアミノ基含有単量体０．１質量％以上１０質量％以下：
　（ａ４）（メタ）アクリル酸アルキルエステル単量体１質量％以上６９．８質量％以下：
　（ａ５）前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分以外の共重合性単量体０質量％以上３０質量％以下：ただし、前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分、および前記単量体（ａ５）を足し合わせて１００質量％である。
　前記共重合体は、重量平均分子量が４０万以上２００万以下であり、かつ、酸価が１以下である。 6). The laminate according to another embodiment of the present invention is
A first polycycloolefin-based film;
A second polycycloolefin-based film;
An adhesive layer provided between the first polycycloolefin-based film and the second polycycloolefin-based film,
The pressure-sensitive adhesive layer comprises (A) a monomer (a1), a monomer (a2), a monomer (a3), a monomer (a4) component, and a monomer (a5). A pressure-sensitive adhesive composition comprising a copolymer of a monomer composition and (B) an isocyanate-based crosslinking agent;
(A1) Alkylene oxide chain-containing monomer 30% by mass or more and 98.8% by mass or less:
(A2) Hydroxyl group-containing monomer 0.1 mass% or more and 10 mass% or less:
(A3) Amide group or amino group-containing monomer 0.1% by mass or more and 10% by mass or less:
(A4) (Meth) acrylic acid alkyl ester monomer 1 mass% or more and 69.8 mass% or less:
(A5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less: However, the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5) are added together. 100% by mass.
The copolymer has a weight average molecular weight of 400,000 or more and 2 million or less, and an acid value of 1 or less.
　７．上記１ないし６のいずれか１項に記載の積層体では、前記粘着剤層の損失正接が０．２以上であることができる。 7. In the laminate according to any one of 1 to 6 above, the loss tangent of the pressure-sensitive adhesive layer may be 0.2 or more.
　８．上記１ないし７のいずれか１項に記載の積層体では、前記粘着剤組成物のゲル分率が５０％以上９０％以下であることができる。 8. In the laminated body according to any one of 1 to 7, the gel fraction of the pressure-sensitive adhesive composition may be 50% or more and 90% or less.
　９．上記１ないし８のいずれか１項に記載の積層体では、前記粘着剤組成物における前記（Ｂ）イソシアネート系架橋剤の含有量が０．１質量％以上５質量％以下であることができる。 9. In the laminate according to any one of 1 to 8, the content of the (B) isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition may be 0.1% by mass or more and 5% by mass or less.
　１０．上記１ないし９のいずれか１項に記載の積層体では、前記粘着剤組成物における前記（Ｃ）シランカップリング剤の含有量が０．１質量％以上５質量％以下であることができる。 10. In the laminate according to any one of 1 to 9, the content of the (C) silane coupling agent in the pressure-sensitive adhesive composition may be 0.1% by mass or more and 5% by mass or less.
　１１．上記１ないし１０のいずれか１項に記載の積層体では、前記粘着剤組成物における前記（Ｄ）帯電防止剤の含有量が０質量％以上１０質量％以下であることができる。 11. In the laminate according to any one of 1 to 10, the content of the antistatic agent (D) in the pressure-sensitive adhesive composition may be 0% by mass or more and 10% by mass or less.
　１２．上記１ないし１１のいずれか１項に記載の積層体では、前記共重合体は、脂環式炭化水素基および／または芳香族炭化水素基を有する単量体の含有量が３０質量％以下であることができる。 12. In the laminate according to any one of 1 to 11 above, the copolymer has a content of a monomer having an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group of 30% by mass or less. Can be.
　上記積層体は、高温条件下あるいは高温多湿条件下で優れた耐久性を発揮し、前記粘着剤層を介した前記ガラス基板と前記ポリシクロオレフィン系フィルムとの密着性または前記ポリシクロオレフィン系フィルム同士の密着性に優れ、かつ、光漏れを低減することができる。 The laminate exhibits excellent durability under high-temperature conditions or high-temperature and high-humidity conditions. Adhesion between the glass substrate and the polycycloolefin film via the pressure-sensitive adhesive layer or the polycycloolefin film It is excellent in adhesion between each other and light leakage can be reduced.
図１は、本発明の一実施形態に係る積層体の一例を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing an example of a laminate according to an embodiment of the present invention. 図２は、本発明の一実施形態に係る積層体の一例を模式的に示す断面図である。FIG. 2 is a cross-sectional view schematically showing an example of a laminate according to an embodiment of the present invention.
　以下、図面を参照しつつ、本発明を詳細に説明する。なお、本発明において、格別に断らない限り、「部」は「質量％」を意味し、「％」は「質量％」を意味する。 Hereinafter, the present invention will be described in detail with reference to the drawings. In the present invention, “part” means “mass%” and “%” means “mass%” unless otherwise specified.
　１．積層体
　本発明の一実施形態に係る積層体は、ガラス基板と、ポリシクロオレフィン系フィルムと、前記ガラス基板と前記ポリシクロオレフィン系フィルムとの間に設けられた粘着剤層と、を含み、前記粘着剤層は、（Ａ）下記単量体（ａ１）、単量体（ａ２）、単量体（ａ３）、単量体（ａ４）成分および単量体（ａ５）からなる単量体組成物の共重合体および（Ｂ）イソシアネート系架橋剤を含む粘着剤組成物から形成され、前記共重合体は、重量平均分子量が４０万以上２００万以下であり、かつ、酸価が１以下である。
　（ａ１）アルキレンオキシド鎖含有単量体３０質量％以上９８．８質量％以下：
　（ａ２）水酸基含有単量体０．１質量％以上１０質量％以下：
　（ａ３）アミド基またはアミノ基含有単量体０．１質量％以上１０質量％以下：
　（ａ４）（メタ）アクリル酸アルキルエステル単量体１質量％以上６９．８質量％以下：
　（ａ５）前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分以外の共重合性単量体０質量％以上３０質量％以下：ただし、前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分、および前記単量体（ａ５）を足し合わせて１００質量％である。 1. Laminate The laminate according to an embodiment of the present invention includes a glass substrate, a polycycloolefin film, and an adhesive layer provided between the glass substrate and the polycycloolefin film, The pressure-sensitive adhesive layer comprises (A) a monomer comprising the following monomer (a1), monomer (a2), monomer (a3), monomer (a4) component and monomer (a5) The copolymer is formed from a pressure-sensitive adhesive composition containing a copolymer of the composition and (B) an isocyanate-based crosslinking agent, and the copolymer has a weight average molecular weight of 400,000 or more and 2 million or less, and an acid value of 1 or less. It is.
(A1) Alkylene oxide chain-containing monomer 30% by mass or more and 98.8% by mass or less:
(A2) Hydroxyl group-containing monomer 0.1 mass% or more and 10 mass% or less:
(A3) Amide group or amino group-containing monomer 0.1% by mass or more and 10% by mass or less:
(A4) (Meth) acrylic acid alkyl ester monomer 1 mass% or more and 69.8 mass% or less:
(A5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less: However, the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5) are added together. 100% by mass.
　１．１．積層構造
　図１は、本発明の一実施形態に係る積層体の一例（積層体１００）を模式的に示す断面図である。積層体１００は、図１に示されるように、ガラス基板１０と、ポリシクロオレフィン系フィルム３２と、ガラス基板１０とポリシクロオレフィン系（ＣＯＰ）フィルム３２との間に設けられた粘着剤層２０と、を含む。積層体１００は偏光フィルム３０をさらに含み、偏光フィルム３０は、ポリシクロオレフィン系フィルム３２を含むことができる。 1.1. Laminated Structure FIG. 1 is a cross-sectional view schematically showing an example (laminated body 100) of a laminated body according to an embodiment of the present invention. As shown in FIG. 1, the laminate 100 includes a glass substrate 10, a polycycloolefin-based film 32, and an adhesive layer 20 provided between the glass substrate 10 and the polycycloolefin-based (COP) film 32. And including. The laminate 100 further includes a polarizing film 30, and the polarizing film 30 can include a polycycloolefin-based film 32.
　より具体的には、積層体１００は、ガラス基板１０と、ガラス基板１０の上に設けられた粘着剤層２０と、ガラス基板１０の上に粘着剤層２０を介して設けられた偏光フィルム３０とを含む。偏光フィルム３０は、ポリシクロオレフィン系フィルム３２と、ポリシクロオレフィン系フィルム３２の上に設けられたポリビニルアルコールフィルム３４と、ポリビニルアルコールフィルム３４の上に設けられたＴＡＣフィルム３６とを有する。ガラス基板１０とポリシクロオレフィン系フィルム３２とは粘着剤層２０を介して接着されている。 More specifically, the laminate 100 includes a glass substrate 10, a pressure-sensitive adhesive layer 20 provided on the glass substrate 10, and a polarizing film 30 provided on the glass substrate 10 via the pressure-sensitive adhesive layer 20. Including. The polarizing film 30 includes a polycycloolefin film 32, a polyvinyl alcohol film 34 provided on the polycycloolefin film 32, and a TAC film 36 provided on the polyvinyl alcohol film 34. The glass substrate 10 and the polycycloolefin film 32 are bonded via the pressure-sensitive adhesive layer 20.
　図２は、本発明の一実施形態に係る積層体の他の一例（積層体２００）を模式的に示す断面図である。積層体２００は、図２に示されるように、ガラス基板１０と、ポリシクロオレフィン系フィルム（位相差フィルム）３２と、偏光フィルム１３０とを含み、ガラス基板１０、ポリシクロオレフィン系フィルム３２、および偏光フィルム１３０がこの順で積層している。ポリシクロオレフィン系フィルム３２は位相差フィルムであることができる。 FIG. 2 is a cross-sectional view schematically showing another example (laminate 200) of the laminate according to one embodiment of the present invention. As shown in FIG. 2, the laminate 200 includes a glass substrate 10, a polycycloolefin film (retardation film) 32, and a polarizing film 130, and includes the glass substrate 10, the polycycloolefin film 32, and The polarizing film 130 is laminated in this order. The polycycloolefin-based film 32 can be a retardation film.
　ポリシクロオレフィン系フィルム３２と偏光フィルム１３０とは、粘着剤層２０を介して接着されている。また、ガラス基板１０とポリシクロオレフィン系フィルム３２とは、粘着剤層２２を介して接着されている。偏光フィルム１３０は、ポリシクロオレフィン系フィルムまたはＴＡＣフィルムである層（第２のポリシクロオレフィン系フィルム）３８と、層３８の上に設けられたポリビニルアルコールフィルム３４と、ポリビニルアルコールフィルム３４の上に設けられたＴＡＣフィルム３６とを有する。ポリシクロオレフィン系フィルム（第１のポリシクロオレフィン系フィルム）３２と層（第２のポリシクロオレフィン系フィルム）３８とは、粘着剤層２０を介して接着されている。 The polycycloolefin film 32 and the polarizing film 130 are bonded via the pressure-sensitive adhesive layer 20. Further, the glass substrate 10 and the polycycloolefin-based film 32 are bonded via the pressure-sensitive adhesive layer 22. The polarizing film 130 includes a layer (second polycycloolefin film) 38 that is a polycycloolefin film or TAC film, a polyvinyl alcohol film 34 provided on the layer 38, and a polyvinyl alcohol film 34. And a TAC film 36 provided. The polycycloolefin-based film (first polycycloolefin-based film) 32 and the layer (second polycycloolefin-based film) 38 are bonded via the pressure-sensitive adhesive layer 20.
　図１および図２における粘着剤層２０，２２は、本実施形態に係る粘着剤組成物（後述する）を被着体（図１における粘着剤層２０および図２における粘着剤層２２では、被着体はガラス基板１０またはポリシクロオレフィン系フィルム３２であり、図２における粘着剤層２０では、被着体はポリシクロオレフィン系フィルム３２または層３８）の表面に形成されている。本発明で使用する粘着剤組成物を被着体の表面に形成する方法としては、平滑性の良好な離型フィルム（セパレーター）の表面に粘着剤組成物を塗布し、塗膜を乾燥した後、当該塗膜を特定の樹脂フィルムの表面に転写する転写法を挙げることができる。  The adhesive layers 20 and 22 in FIGS. 1 and 2 are coated with an adhesive composition (described later) according to the present embodiment (the adhesive layer 20 in FIG. 1 and the adhesive layer 22 in FIG. 2). The adherend is the glass substrate 10 or the polycycloolefin-based film 32, and the adherend is formed on the surface of the polycycloolefin-based film 32 or the layer 38) in the pressure-sensitive adhesive layer 20 in FIG. As a method for forming the pressure-sensitive adhesive composition used in the present invention on the surface of the adherend, the pressure-sensitive adhesive composition is applied to the surface of a release film (separator) having good smoothness, and the coating film is dried. And a transfer method for transferring the coating film onto the surface of a specific resin film.
　本実施形態に係る積層体では、被着体とポリシクロオレフィン系フィルムとの密着性を高める観点から、粘着剤層の損失正接が０．２以上（通常、０．２０以上０．４０以下）であることが好ましく、より好ましくは０．２８以上０．４０以下である。本発明において、粘着剤層の損失正接は、後述する実施例に記載された方法で測定された値である。 In the laminate according to this embodiment, the loss tangent of the pressure-sensitive adhesive layer is 0.2 or more (usually 0.20 or more and 0.40 or less) from the viewpoint of improving the adhesion between the adherend and the polycycloolefin-based film. It is preferable that it is 0.28 or more and 0.40 or less. In this invention, the loss tangent of an adhesive layer is the value measured by the method described in the Example mentioned later.
　本実施形態に係る積層体は例えば、画像表示装置（特に液晶表示装置）に含まれる。より具体的には、本実施形態に係る積層体は例えば、タッチパネル用の画像表示装置に用いることができる。この場合、本実施形態に係る積層体に含まれるガラス基板は、液晶表示装置用のガラス基板である。 The laminate according to the present embodiment is included in, for example, an image display device (particularly a liquid crystal display device). More specifically, the laminate according to the present embodiment can be used for an image display device for a touch panel, for example. In this case, the glass substrate included in the laminate according to the present embodiment is a glass substrate for a liquid crystal display device.
　１．２．ガラス基板
　本実施形態に係る積層体を構成するガラス基板は、画像表示装置用に用いられるガラス基板であることができる。画像表示装置としては、例えば、液晶テレビ、コンピュータのモニタ、携帯電話、タブレットなどに用いられるＴＦＴ（薄膜トランジスタ）液晶表示装置であることができる。 1.2. Glass substrate The glass substrate which comprises the laminated body which concerns on this embodiment can be a glass substrate used for image display apparatuses. The image display device can be, for example, a TFT (thin film transistor) liquid crystal display device used for a liquid crystal television, a computer monitor, a mobile phone, a tablet, and the like.
　１．３．ポリシクロオレフィン系フィルム
　本発明において、「ポリシクロオレフィン系フィルム」とは、ポリシクロオレフィンに由来する骨格を構成単位中に少なくとも５０％含むものである。ポリシクロオレフィン系フィルムは、ポリシクロオレフィン共重合体であってもよく、この場合、ポリシクロオレフィン共重合体は、例えば、エチレンとポリシクロオレフィン（例えばテトラシクロドデセン）とをチーグラー触媒下で共重合して得ることができる。 1.3. Polycycloolefin film In the present invention, the “polycycloolefin film” includes at least 50% of a skeleton derived from polycycloolefin in a structural unit. The polycycloolefin-based film may be a polycycloolefin copolymer. In this case, the polycycloolefin copolymer may be formed by, for example, ethylene and polycycloolefin (for example, tetracyclododecene) under a Ziegler catalyst. It can be obtained by copolymerization.
　ポリシクロオレフィン系フィルムとして、市販のポリシクロオレフィン系フィルムを使用することができる。市販のポリシクロオレフィン系フィルムとしては、例えば、ゼオノアフィルム（日本ゼオン製）、アートンフィルム（ＪＳＲ製）などが挙げられる。 A commercially available polycycloolefin film can be used as the polycycloolefin film. Examples of commercially available polycycloolefin-based films include ZEONOR films (manufactured by ZEON CORPORATION) and ARTON films (manufactured by JSR).
　１．４．粘着剤層
　本実施形態に係る積層体を構成する粘着剤層は、（Ａ）下記単量体（ａ１）、単量体（ａ２）、単量体（ａ３）、単量体（ａ４）成分および単量体（ａ５）からなる単量体組成物の共重合体（以下、単に「（Ａ）成分」と記載する場合もある。）および（Ｂ）イソシアネート系架橋剤（以下、単に「（Ｂ）成分」と記載する場合もある。）を含む粘着剤組成物（以下、単に「粘着剤組成物」と記載する場合もある。）から形成される。
　（ａ１）アルキレンオキシド鎖含有単量体３０質量％以上９８．８質量％以下（以下、単に「（ａ１）成分」と記載する場合もある。）
　（ａ２）水酸基含有単量体０．１質量％以上１０質量％以下（以下、単に「（ａ２）成分」と記載する場合もある。）
　（ａ３）アミド基含有単量体０．１質量％以上１０質量％以下（以下、単に「（ａ３）成分」と記載する場合もある。）
　（ａ４）（メタ）アクリル酸アルキルエステル単量体１質量％以上６９．８質量％以下（以下、単に「（ａ４）成分」と記載する場合もある。）
　（ａ５）前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分以外の共重合性単量体０質量％以上３０質量％以下（以下、単に「（ａ５）成分」と記載する場合もある。）：ただし、前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分、および前記単量体（ａ５）を足し合わせて１００質量％である。 1.4. Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer constituting the laminate according to the present embodiment comprises: (A) the following monomer (a1), monomer (a2), monomer (a3), monomer (a4) component And a monomer composition copolymer comprising monomer (a5) (hereinafter sometimes simply referred to as “component (A)”) and (B) an isocyanate-based crosslinking agent (hereinafter simply referred to as “( B) component ”(sometimes referred to as“ component ”)) (hereinafter also referred to simply as“ pressure-sensitive adhesive composition ”).
(A1) 30% by mass or more and 98.8% by mass or less of an alkylene oxide chain-containing monomer (hereinafter sometimes simply referred to as “component (a1)”)
(A2) 0.1% by mass or more and 10% by mass or less of the hydroxyl group-containing monomer (hereinafter sometimes referred to simply as “component (a2)”)
(A3) Amide group-containing monomer 0.1% by mass or more and 10% by mass or less (hereinafter sometimes simply referred to as “component (a3)”)
(A4) (Meth) acrylic acid alkyl ester monomer 1% by mass to 69.8% by mass (hereinafter sometimes simply referred to as “component (a4)”)
(A5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less (hereinafter sometimes referred to simply as “component (a5)”): However, the monomer (a1), the monomer (a2), the monomer (a3), and the monomer The sum of the monomer (a4) component and the monomer (a5) is 100% by mass.
　１．４．１．粘着剤組成物
　１．４．１－１．（Ａ）成分
　（Ａ）成分は、上記単量体（ａ１）、上記単量体（ａ２）、上記単量体（ａ３）、上記単量体（ａ４）成分および上記単量体（ａ５）からなる単量体組成物の共重合体であり、アクリル系重合体であることが好ましい。本発明において、「アクリル系重合体」とは、アクリル酸、アクリル酸塩、アクリル酸エステル、メタアクリル酸、メタクリル酸塩、およびメタクリル酸エステルから選ばれる少なくとも１種を構成単位中に５０質量％以上含むポリマーをいう。 1.4.1. Adhesive composition 1.4.1.1-1. Component (A) The component (A) includes the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5). It is a copolymer of the monomer composition consisting of and is preferably an acrylic polymer. In the present invention, the “acrylic polymer” means at least one selected from acrylic acid, acrylic acid salt, acrylic acid ester, methacrylic acid, methacrylic acid salt, and methacrylic acid ester in a constituent unit of 50 mass%. The polymer containing above is said.
　また、本発明において、（メタ）アクリル酸とは、アクリル酸およびメタクリル酸の両方を含む概念であり、（メタ）アクリレートとは、アクリレートおよびメタクリレートの両方を含む概念である。 In the present invention, (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid, and (meth) acrylate is a concept including both acrylate and methacrylate.
　（１）（ａ１）成分
　（ａ１）成分であるアルキレンオキシド鎖含有単量体は、アルキレンオキシド鎖を含有する単量体である。本発明において、「アルキレンオキシド鎖」とは、Ｒ２－（Ｏ－Ｒ１－）ｎ（ここで、Ｒ１はアルキレン基を表し、Ｒ２はアルキル基を表し、ｎは１以上の整数を表す。）で表される基をいう。ここで、Ｒ１で表されるアルキレン基は直鎖状、分岐状または環状であってもよく、例えば、炭素原子数１以上５以下（好ましくは２以上４以下）のアルキレン基であり、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、メチレン基(－ＣＨ２－)、エチレン基(－ＣＨ２ＣＨ２－)、プロピレン基(－(ＣＨ２)３－)、シクロへキシレン基(－Ｃ６Ｈ１０－)が挙げられ、このうち、エチレン基（エチレンオキシド鎖）またはプロピレン基（プロピレンオキシド鎖）がより好ましく、エチレン基がさらに好ましい。また、Ｒ２はアルキル基を表し、ｎは１以上の整数を表す。）で表される基をいう。ここで、Ｒ２で表されるアルキル基は直鎖状、分岐状または環状であってもよく、例えば、炭素原子数１以上１０以下（好ましくは１以上４以下）のアルキル基であり、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基、シクロへキシル基が挙げられ、このうち、メチル基またはエチル基がより好ましく、メチル基がさらに好ましい。また、アルキレンオキシド鎖を表す上記式において、ｎは１以上３以下の整数であることが好ましい。（Ａ）成分が（ａ１）成分を含むことにより、粘着剤層が複屈折率の調整作用を奏することができるため、光漏れを防止することができる。 (1) Component (a1) The alkylene oxide chain-containing monomer as component (a1) is a monomer containing an alkylene oxide chain. In the present invention, the “alkylene oxide chain” means R 2 — (O—R 1 —) n (wherein R 1 represents an alkylene group, R 2 represents an alkyl group, and n represents an integer of 1 or more) Represents a group represented by: Here, the alkylene group represented by R 1 may be linear, branched or cyclic, and is, for example, an alkylene group having 1 to 5 carbon atoms (preferably 2 to 4 carbon atoms). , Methylene group, ethylene group, propylene group, butylene group, methylene group (—CH 2 —), ethylene group (—CH 2 CH 2 —), propylene group (— (CH 2 ) 3 —), cyclohexylene group ( -C 6 H 10- ), among which an ethylene group (ethylene oxide chain) or a propylene group (propylene oxide chain) is more preferable, and an ethylene group is more preferable. R 2 represents an alkyl group, and n represents an integer of 1 or more. ). Here, the alkyl group represented by R 2 may be linear, branched or cyclic, and is, for example, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms). , A methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a sec-butyl group, and a cyclohexyl group. Among these, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable. . In the above formula representing an alkylene oxide chain, n is preferably an integer of 1 or more and 3 or less. When the component (A) includes the component (a1), the pressure-sensitive adhesive layer can exert a birefringence adjusting function, and thus light leakage can be prevented.
　（ａ１）成分であるアルキレンオキシド鎖含有単量体としては、例えば、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－プロポキシエチル（メタ）アクリレート等のアルキレンオキシド鎖含有（メタ）アクリル酸エステル（アルコキシアルキル基含有単量体、より具体的には、アルキレンオキシド鎖を表す上記式において、ｎ＝１であるアルキレンオキシド鎖含有（メタ）アクリル酸エステル）が挙げられる。 Examples of the (a1) component alkylene oxide chain-containing monomer include alkylene oxide chain such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2-propoxyethyl (meth) acrylate. (Meth) acrylic acid ester (an alkoxyalkyl group-containing monomer, more specifically, an alkylene oxide chain-containing (meth) acrylic acid ester in which n = 1 in the above formula representing an alkylene oxide chain).
　本実施形態に係る粘着剤組成物から得られる粘着剤層に適度な弾性率を付与する観点で、単量体組成物中の（ａ１）成分の含有量は３０質量％以上９８．８質量％以下であることが好ましく、５０質量％以上９８．８質量％以下であることがより好ましい。 From the viewpoint of imparting an appropriate elastic modulus to the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to this embodiment, the content of the component (a1) in the monomer composition is 30% by mass or more and 98.8% by mass. Or less, more preferably 50% by mass or more and 98.8% by mass or less.
　（２）（ａ２）成分
　（ａ２）成分である水酸基含有単量体は、（Ｂ）成分であるイソシアネート系架橋剤と架橋する成分である。適度な架橋構造を構築できる観点で、単量体組成物中の（ａ２）成分の含有量は０．１質量％以上１０質量％以下であることが好ましく、０．１質量％以上２質量％以下であることがより好ましい。 (2) Component (a2) The hydroxyl group-containing monomer that is component (a2) is a component that crosslinks with the isocyanate-based crosslinking agent that is component (B). From the viewpoint of constructing an appropriate crosslinked structure, the content of the component (a2) in the monomer composition is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 2% by mass. The following is more preferable.
　（ａ２）成分である水酸基含有単量体としては、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルアクリレート、３－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルアクリレート、４－ヒドロキシブチルメタクリレート、２－ヒドロキシ－３－クロロプロピルアクリレート、２－ヒドロキシ－３－クロロプロピルメタクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、２－ヒドロキシ－３－フェノキシプロピルメタクリレート等や、エチレングリコールアクリレート、ポリエチレングリコールアクリレート、プロピレングリコールアクリレート、ポリプロピレングリコールアクリレート等のアルキレングリコールアクリレート、エチレングリコールメタクリレート、ポリエチレングリコールメタクリレート、プロピレングリコールメタクリレート、ポリプロピレングリコールメタクリレート等のアルキレングリコールメタクリレート等の水酸基含有（メタ）アクリル酸エステルが挙げられる。（ａ２）成分としては、炭素原子数１以上４以下のヒドロキシアルキル基含有（メタ）アクリル酸エステルであることが好ましい。 Examples of the hydroxyl group-containing monomer as component (a2) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl. Methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- Phenoxypropyl methacrylate, etc., ethylene glycol acrylate, polyethylene glycol acrylate, propylene glycol acrylate, polypropylene Alkylene glycol acrylates such as recall acrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, hydroxyl group-containing (meth) alkylene glycol methacrylate and polypropylene glycol methacrylate and acrylic acid ester. The component (a2) is preferably a hydroxyalkyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms.
　（３）（ａ３）成分
　（ａ３）成分であるアミド基またはアミノ基含有単量体は、粘着剤組成物に凝集力を付与する成分である。アミド基またはアミノ基を構成する窒素原子に結合する水素原子が、粘着剤組成物内での水素結合の形成に関与することにより、高い凝集力を発現することができる。高い凝集力を発現できる観点で、単量体組成物中の（ａ３）成分の含有量は０．１質量％以上１０質量％以下であることが好ましく、０．１質量％以上２質量％以下であることがより好ましい。 (3) Component (a3) The amide group or amino group-containing monomer as the component (a3) is a component that imparts cohesive force to the pressure-sensitive adhesive composition. A hydrogen atom bonded to a nitrogen atom constituting an amide group or an amino group participates in the formation of a hydrogen bond in the pressure-sensitive adhesive composition, whereby a high cohesive force can be expressed. From the viewpoint of expressing a high cohesive force, the content of the component (a3) in the monomer composition is preferably 0.1% by mass or more and 10% by mass or less, and 0.1% by mass or more and 2% by mass or less. It is more preferable that
　（ａ３）成分であるアミド基またはアミノ基含有単量体としては、例えば、Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノエチルメタクリレート、Ｎ，Ｎ－ジエチルアミノエチルメタクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミドＮ，Ｎ’－ジメチルアクリルアミド、Ｎ，Ｎ’－ジエチルアクリルアミド、Ｎ，Ｎ’－ジメチルアミノエチルアクリルアミド、Ｎ，Ｎ’－ジメチルアミノプロピルアクリルアミド、Ｎ－イソプロピルアクリルアミド、ｔｅｒｔ－オクチル（メタ）アクリルアミド、ダイアセトンアクリルアミド等のアミド基含有（メタ）アクリル酸エステル、アクリロイルモルホリン、またはアクリルアミドが挙げられる。 Examples of the amide group or amino group-containing monomer as the component (a3) include N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N— Dimethylaminopropylacrylamide N, N′-dimethylacrylamide, N, N′-diethylacrylamide, N, N′-dimethylaminoethylacrylamide, N, N′-dimethylaminopropylacrylamide, N-isopropylacrylamide, tert-octyl (meta ) Amide group-containing (meth) acrylic acid esters such as acrylamide and diacetone acrylamide, acryloylmorpholine, or acrylamide.
　（４）（ａ４）成分
　（ａ４）成分である（メタ）アクリル酸アルキルエステル単量体は、アルキレンオキサイド鎖、水酸基、およびアミド基、アミノ基のいずれも含まない。 (4) Component (a4) The (meth) acrylic acid alkyl ester monomer as the component (a4) does not contain any alkylene oxide chain, hydroxyl group, amide group, or amino group.
　（ａ４）成分である（メタ）アクリル酸アルキルエステル単量体としては、例えば、メチルアクリレート、エチルアクリレート、メチルメタクリレート、エチルメタクリレート、ｎ－プロピルアクリレート、ｎ－プロピルメタクリレート、ｎ－ブチルアクリレート、ｎ－ブチルメタクリレート、ｎ－ペンチルアクリレート、ｎ－ヘキシルアクリレート、ｎ－ヘキシルメタクリレート、ｎ－ヘプチルアクリレート、ｎ－オクチルアクリレート、ｎ－オクチルメタクリレート、ｎ－ノニルアクリレート、ｎ－ラウリルメタクリレート、ｎ－ラウリルアクリレート、ｎ－テトラデシルメタクリレート、ｎ－ヘキサデシルアクリレート、ｎ－ヘキサデシルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート等の直鎖状アルキル基を有するアルキル（メタ）アクリル酸アルキルエステル；イソプロピルアクリレート、イソブチルアクリレート、ｔｅｒｔ－ブチルアクリレート、イソプロピルメタクリレート、イソブチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、イソオクチルアクリレート、イソオクチルメタクリレート、２－エチルヘキシルアクリレート、２－エチルヘキシルメタクリレート等の分岐状アルキル基を有する（メタ）アクリル酸アルキルエステル；シクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート、ジシクロペンタニルアクリレート等の脂環アルキル基を有する（メタ）アクリル酸アルキルエステルが挙げられ、このうち１種を単独でまたは２種以上を組み合わせて使用することができる。 Examples of the (meth) acrylic acid alkyl ester monomer as component (a4) include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n- Butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-lauryl methacrylate, n-lauryl acrylate, n- Linear alkyl groups such as tetradecyl methacrylate, n-hexadecyl acrylate, n-hexadecyl methacrylate, stearyl acrylate, stearyl methacrylate Alkyl (meth) acrylic acid alkyl ester: isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc. (Meth) acrylic acid alkyl ester having a branched alkyl group: alkyl (meth) acrylate having an alicyclic alkyl group such as cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentanyl acrylate, etc. Esters are included, and one of these is used alone or in combination of two or more Rukoto can.
　このうち、本実施形態に係る粘着剤組成物から得られる粘着剤層が光漏れの調整という観点で、（ａ４）成分は、直鎖状または分岐状のアルキル基を有することが好ましく、直鎖状のアルキル基を有することがより好ましい。この場合、本実施形態に係る粘着剤組成物を用いて形成された粘着剤層が画像表示装置の光漏れをさらに低減できる点で、前記アルキル基の炭素原子数は１以上２０以下（好ましくは１以上１０以下）であることがさらに好ましい。 Among these, from the viewpoint that the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to this embodiment adjusts light leakage, the component (a4) preferably has a linear or branched alkyl group. It is more preferable to have an alkyl group having a shape. In this case, the number of carbon atoms of the alkyl group is 1 or more and 20 or less (preferably, because the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment can further reduce the light leakage of the image display device. More preferably, it is 1 or more and 10 or less.
　本実施形態に係る粘着剤組成物から得られる粘着剤層が光漏れの調整という観点で、単量体組成物中の（ａ４）成分の含有量は０．１質量％以上６９．８質量％以下であることが好ましく、０．１質量％以上５０質量％以下であることがより好ましい。 From the viewpoint of adjusting the light leakage of the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to this embodiment, the content of the component (a4) in the monomer composition is 0.1% by mass or more and 69.8% by mass. Or less, more preferably 0.1% by mass or more and 50% by mass or less.
　（５）（ａ５）成分
　単量体混合物は、（ａ５）成分である前記（ａ１）成分、（ａ２）成分、（ａ３）成分および（ａ４）成分以外の共重合性単量体を含んでいてもよい。（ａ５）成分は例えば、カルボキシエチルアクリレート、アクリロニトリル、ペンタメチルピペリジンメタクリレートや、ベンジルメタクリレート、ベンジルアクリレート、２－ナフチルアクリレート、フェノキシエチルアクリレート、等の芳香環基を有する（メタ）アクリル酸エステル；ジシクロペンテニルオキシエチルアクリレート、グリシジルメタクリレート、テトラヒドロフルフリルメタクリレート等のエーテル基を有する(メタ)アクリレート、スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｐ－メチルスチレン等のスチレン系モノマー；酢酸ビニル等のカルボン酸ビニルエステル；ビニルピリジン、Ｎ－ビニルピロリドン、ビニルカプロラクタム、ビニル（メタ）アクリロイル基含有マクロモノマーなどが挙げられ、このうち１種または２種以上を組み合わせて使用することができる。単量体組成物中の（ａ５）成分の含有量は０質量％以上３０質量％以下であることが好ましく、０質量％以上２０質量％以下であることがより好ましい。 (5) Component (a5) The monomer mixture contains a copolymerizable monomer other than the component (a1), the component (a2), the component (a3) and the component (a4) which are the component (a5). May be. Component (a5) is, for example, (meth) acrylic acid ester having an aromatic ring group such as carboxyethyl acrylate, acrylonitrile, pentamethylpiperidine methacrylate, benzyl methacrylate, benzyl acrylate, 2-naphthyl acrylate, phenoxyethyl acrylate, etc .; (Meth) acrylates having an ether group such as pentenyloxyethyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, styrene monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene; carboxyl such as vinyl acetate Acid vinyl ester; vinyl pyridine, N-vinyl pyrrolidone, vinyl caprolactam, vinyl (meth) acryloyl group-containing macromonomer, etc. 1 type, or 2 or more types can be used in combination. The content of the component (a5) in the monomer composition is preferably 0% by mass or more and 30% by mass or less, and more preferably 0% by mass or more and 20% by mass or less.
　（６）（ａ１）成分、（ａ２）成分、（ａ３）成分および（ａ４）成分の合計量
　本実施形態に係る粘着剤組成物では、優れた耐久性、ならびに被着体とポリシクロオレフィン系フィルムとの高い密着性およびポリシクロオレフィン系フィルム同士の高い密着性を達成できる観点から、（Ａ）成分である共重合体を得るための前記単量体混合物中における前記（ａ１）成分、（ａ２）成分、（ａ３）成分および（ａ４）成分の合計量が７０質量％以上１００質量％以下であることができ、８０質量％以上１００質量％以下であることが好ましい。 (6) Total amount of component (a1), component (a2), component (a3) and component (a4) In the pressure-sensitive adhesive composition according to this embodiment, excellent durability, adherend and polycycloolefin type From the viewpoint of achieving high adhesion with the film and high adhesion between the polycycloolefin-based films, the component (a1) in the monomer mixture for obtaining the copolymer as the component (A), ( The total amount of the component a2), the component (a3) and the component (a4) can be 70% by mass or more and 100% by mass or less, and preferably 80% by mass or more and 100% by mass or less.
　（７）その他の成分
　耐久性、ならびにガラス基板とポリシクロオレフィン系フィルムとの間の接着性およびポリシクロオレフィン系フィルム同士の接着性を十分に確保する観点で、単量体混合物における、脂環式炭化水素基および／または芳香族炭化水素基を有する共重合性単量体の含有量が３０質量％以下であることが好ましく、２０質量％以下であることがより好ましい。 (7) Other components From the viewpoint of ensuring durability, adhesion between the glass substrate and the polycycloolefin film, and adhesion between the polycycloolefin films, the alicyclic ring in the monomer mixture The content of the copolymerizable monomer having a formula hydrocarbon group and / or an aromatic hydrocarbon group is preferably 30% by mass or less, and more preferably 20% by mass or less.
　（８）重量平均分子量および分散指数
　（Ａ）成分は、重量平均分子量（Ｍｗ）が４０万以上２００万以下である。（Ａ）成分の重量平均分子量が４０万未満であると、耐久性に劣ることがあり、一方、２００万を超えると、光漏れを十分に低減することができないことがある。ガラス基板とポリシクロオレフィン系フィルムとの接着性およびポリシクロオレフィン系フィルム同士の接着性を高め、光漏れを防止し、かつ耐久性を高めることができる観点から、（Ａ）成分の重量平均分子量は、４０万以上２００万以下であることが好ましく、７５万以上１５０万以下であることがより好ましい。ここで、（Ａ）成分の重量平均分子量および数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用い、下記の条件で標準ポリスチレン換算による重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を求めたものである。 (8) Weight average molecular weight and dispersion index The component (A) has a weight average molecular weight (Mw) of 400,000 or more and 2 million or less. When the weight average molecular weight of the component (A) is less than 400,000, durability may be inferior. On the other hand, when it exceeds 2 million, light leakage may not be sufficiently reduced. From the viewpoint of improving the adhesion between the glass substrate and the polycycloolefin-based film and the adhesion between the polycycloolefin-based films, preventing light leakage, and enhancing the durability, the weight average molecular weight of the component (A) Is preferably 400,000 or more and 2 million or less, and more preferably 750,000 or more and 1.5 million or less. Here, the weight average molecular weight and number average molecular weight of the component (A) are GPC (gel permeation chromatography), and the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene are as follows. It is what I have sought.
　＜ＧＰＣ測定条件＞
　測定装置：ＨＬＣ－８１２０ＧＰＣ（東ソー社製）
　ＧＰＣカラム構成：以下の５連カラム（すべて東ソー社製）
　（ｉ）ＴＳＫ－ＧＥＬ　ＨＸＬ－Ｈ（ガードカラム）
　（ｉｉ）ＴＳＫ－ＧＥＬ　Ｇ７０００ＨＸＬ
　（ｉｉｉ）ＴＳＫ－ＧＥＬ　ＧＭＨＸＬ
　（ｉｖ）ＴＳＫ－ＧＥＬ　ＧＭＨＸＬ
　（ｖ）ＴＳＫ－ＧＥＬ　Ｇ２５００ＨＸＬ
　サンプル濃度：１．０ｍｇ／ｃｍ３となるように、テトラヒドロフランで希釈
　移動相溶媒：テトラヒドロフラン
　流量：１．０ｃｍ３／分
　カラム温度：４０℃ <GPC measurement conditions>
Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation)
GPC column configuration: The following five columns (all manufactured by Tosoh Corporation)
(I) TSK-GEL HXL-H (guard column)
(Ii) TSK-GEL G7000HXL
(Iii) TSK-GEL GMHXL
(Iv) TSK-GEL GMHXL
(V) TSK-GEL G2500HXL
Sample concentration: diluted with tetrahydrofuran to 1.0 mg / cm 3 Mobile phase solvent: tetrahydrofuran Flow rate: 1.0 cm 3 / min Column temperature: 40 ° C.
　また、より優れた耐久性および接着性を確保である観点から、（Ａ）成分の分散指数（Ｍｗ／Ｍｎ）は１以上２０以下であることが好ましい。 Also, from the viewpoint of ensuring superior durability and adhesion, the dispersion index (Mw / Mn) of the component (A) is preferably 1 or more and 20 or less.
　（９）酸価
　（Ａ）成分は、酸価が１以下である。本発明において、（Ａ）成分の酸価は、（Ａ）成分１ｇ中に存在する遊離脂肪酸および／または樹脂酸を中和するのに必要とされる水酸化カリウムのｍｇ数をいう。（Ａ）成分の酸価が１以下であることにより、被着体の腐食を防止することができる。酸価の測定方法については、後述する実施例の中に記載する。（Ａ）成分の酸価が１以下である場合、（Ａ）成分を製造するための単量体混合物中に、カルボキシル基を有する単量体（例えば、（ａ５）成分として使用可能な、アクリル酸、メタクリル酸等のカルボキシル基を有する共重合性単量体）を実質的に含まないことが好ましい。この場合、（Ａ）成分を製造するための単量体混合物中にカルボキシル基含有モノマーを実質的に含まないとは、（Ａ）成分を製造するための単量体混合物中における、カルボキシル基含有モノマー含有量が０．２質量％以下であることをいい、より具体的には、（Ａ）成分を製造するための単量体混合物に、カルボキシル基含有モノマーが配合されないことがより好ましい。 (9) Acid value The component (A) has an acid value of 1 or less. In the present invention, the acid value of component (A) refers to the number of mg of potassium hydroxide required to neutralize free fatty acids and / or resin acids present in 1 g of component (A). When the acid value of the component (A) is 1 or less, corrosion of the adherend can be prevented. About the measuring method of an acid value, it describes in the Example mentioned later. When the acid value of the component (A) is 1 or less, a monomer having a carboxyl group (for example, an acrylic that can be used as the component (a5) in the monomer mixture for producing the component (A) It is preferable that the copolymerizable monomer having a carboxyl group such as acid and methacrylic acid is not substantially contained. In this case, the fact that the monomer mixture for producing the component (A) does not substantially contain the carboxyl group-containing monomer means that the monomer mixture for producing the component (A) contains a carboxyl group. It means that the monomer content is 0.2% by mass or less, and more specifically, it is more preferable that the carboxyl group-containing monomer is not blended in the monomer mixture for producing the component (A).
　近年、画像表示装置には、例えば透明電極に使用されるＩＴＯ層等の金属酸化物が多く用いられている。被着体が金属酸化物を含む場合、金属酸化物が酸成分により腐食され、抵抗値が高くなるという問題が生じる。これに対して、本実施形態に係る積層体では、粘着剤層に使用される粘着剤組成物に含まれる（Ａ）成分の酸価が１以下であることにより、ＩＴＯ層をはじめとする金属酸化物の腐食を防止して、抵抗値の上昇を抑えることができる。 In recent years, metal oxides such as an ITO layer used for transparent electrodes are often used in image display devices. When the adherend contains a metal oxide, the metal oxide is corroded by an acid component, causing a problem that the resistance value is increased. On the other hand, in the laminate according to this embodiment, the acid value of the component (A) contained in the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive layer is 1 or less, so that the metal including the ITO layer can be used. Oxide corrosion can be prevented, and an increase in resistance can be suppressed.
　（１０）粘着剤組成物における含有量
　本実施形態に係る粘着剤組成物における（Ａ）成分の含有量は、該粘着剤組成物（粘着剤組成物を１００質量％とした場合）の９０質量％以上９９．８質量％以下であることができ、９５質量％以上９９.８質量％以下であることが好ましい。 (10) Content in pressure-sensitive adhesive composition The content of the component (A) in the pressure-sensitive adhesive composition according to this embodiment is 90 masses of the pressure-sensitive adhesive composition (when the pressure-sensitive adhesive composition is 100 mass%). % To 99.8% by mass, preferably 95% to 99.8% by mass.
　（１１）ゲル分率
　さらに、本実施形態に係る粘着剤組成物において、光漏れを防止し、かつ耐久性および被着体とポリシクロオレフィン系フィルムとの密着性を高めることができる観点から、本実施形態に係る粘着剤組成物のゲル分率が５０％以上９０％以下であることが好ましく、６０％以上８０％以下であることがより好ましい。 (11) Gel fraction Further, in the pressure-sensitive adhesive composition according to the present embodiment, from the viewpoint of preventing light leakage and enhancing the durability and adhesion between the adherend and the polycycloolefin film, The gel fraction of the pressure-sensitive adhesive composition according to this embodiment is preferably 50% or more and 90% or less, and more preferably 60% or more and 80% or less.
　本実施形態に係る粘着剤組成物において、上記ゲル分率は例えば、粘着剤組成物を調製する際に使用するモノマー混合物中の（ａ２）成分および（ａ３）成分の種類や使用量、（Ｂ）成分である架橋剤の種類や使用量によって調整することができる。なお、上記ゲル分率は、架橋された粘着剤を乾燥重量で０．１ｇ（乾燥重量（１））をサンプル瓶に採取し、更に、サンプル瓶に、酢酸エチル３０ｃｃを加えて２４時間振とうした後、該サンプル瓶の内容物を２００メッシュのステンレス製金網でろ別し、金網上の残留物を１００℃で２時間乾燥して乾燥重量（乾燥重量（２））を測定し、下記式（１）により求められる。
ゲル分率（％）＝（乾燥重量（２）／乾燥重量（１））×１００　・・・（１） In the pressure-sensitive adhesive composition according to this embodiment, the gel fraction is, for example, the types and amounts of the components (a2) and (a3) in the monomer mixture used when preparing the pressure-sensitive adhesive composition, (B ) Can be adjusted according to the type and amount of the crosslinking agent. As for the gel fraction, 0.1 g (dry weight (1)) of the crosslinked adhesive was collected in a sample bottle, and 30 cc of ethyl acetate was further added to the sample bottle and shaken for 24 hours. After that, the contents of the sample bottle were filtered with a 200 mesh stainless steel wire mesh, the residue on the wire mesh was dried at 100 ° C. for 2 hours, and the dry weight (dry weight (2)) was measured. 1).
Gel fraction (%) = (dry weight (2) / dry weight (1)) × 100 (1)
　（１２）Ｔｇ
　本実施形態に係る粘着剤組成物では、光漏れを防止し、かつ耐久性および被着体とポリシクロオレフィン系フィルムとの密着性を高めることができる観点から、（Ａ）成分のＴｇは－７０℃以上０℃以下であることが好ましく、－６０℃以上－１０℃以下であることがより好ましい。なお、本発明において、（Ａ）成分のＴｇは、下記式（２）（ＦＯＸの式）により算出された値である。 (12) Tg
In the pressure-sensitive adhesive composition according to this embodiment, Tg of the component (A) is − from the viewpoint of preventing light leakage and enhancing durability and adhesion between the adherend and the polycycloolefin film. It is preferably 70 ° C. or higher and 0 ° C. or lower, and more preferably −60 ° C. or higher and −10 ° C. or lower. In the present invention, the Tg of the component (A) is a value calculated by the following formula (2) (FOX formula).
　１／ＴｇＡ＝Ｗａ１／Ｔｇａ１＋Ｗａ２／Ｔｇａ２＋Ｗａ３／Ｔｇａ３＋Ｗａ４／Ｔｇａ４＋Ｗａ５／Ｔｇａ５　・・・・（２）
　（式中、ＴｇＡは、（Ａ）成分のガラス転移温度（Ｋ）を示し、Ｔｇａ１，Ｔｇａ２，Ｔｇａ３，Ｔｇａ４，Ｔｇａ５はそれぞれ、構成単量体（ａ１），（ａ２），（ａ３），（ａ４），（ａ５）から調製されたホモポリマーのガラス転移温度（Ｔｇ（Ｋ））を示し、Ｗａ１，Ｗａ２，Ｗａ３，Ｗａ４，Ｗａ５はそれぞれ、（Ａ）成分中に含まれる、構成単量体（ａ１），（ａ２），（ａ３），（ａ４），（ａ５）の重量分率を示す。）
　なお、上記式（２）により、ＴｇＡは、絶対温度（Ｋ）として算出されるので、必要に応じて摂氏温度（℃）に換算される。 1 / Tg A = W a1 / Tg a1 + W a2 / Tg a2 + W a3 / Tg a3 + W a4 / Tg a4 + W a5 / Tg a5 (2)
(In the formula, Tg A represents the glass transition temperature (K) of the component (A), and Tg a1 , Tg a2 , Tg a3 , Tg a4 , and Tg a5 are the constituent monomers (a1) and (a2), respectively. , (A3), (a4), and (a5) show the glass transition temperatures (Tg (K)) of homopolymers, and W a1 , W a2 , W a3 , W a4 , and W a5 are (A The weight fractions of the constituent monomers (a1), (a2), (a3), (a4) and (a5) contained in the component are shown.
In addition, since Tg A is calculated as an absolute temperature (K) by the above formula (2), it is converted to a Celsius temperature (° C.) as necessary.
　また、代表的なモノマーから調製されたホモポリマーのガラス転移温度は、下記表１に示されるが、より具体的には、たとえば、ポリマーハンドブック４版（Polymer Handbook Third Edition, Wiley-Interscience,2003）などに記載されている。 The glass transition temperatures of homopolymers prepared from typical monomers are shown in Table 1 below. More specifically, for example, Polymer Handbook 4th Edition (Polymer Handbook Third Edition, Wiley-Interscience, 2003) It is described in.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（１３）粘度
　また、より優れた塗工適性を確保できる観点から、（Ａ）成分の粘度は、１Ｐａ・ｓ以上１０Ｐａ・ｓ以下であることが好ましく、３Ｐａ・ｓ以上７Ｐａ・ｓ以下であることがより好ましい。本発明において、（Ａ）成分の粘度は、Ｂ型粘度計にて測定した値である。 (13) Viscosity From the viewpoint of ensuring better coating suitability, the viscosity of the component (A) is preferably 1 Pa · s or more and 10 Pa · s or less, and preferably 3 Pa · s or more and 7 Pa · s or less. It is more preferable. In the present invention, the viscosity of the component (A) is a value measured with a B-type viscometer.
　（１４）加熱残分
　また、より優れた塗工適性を確保できる観点から、（Ａ）成分の加熱残分は、１５％以上５０％以下であることが好ましく、２０％以上３０％以下であることがより好ましい。本発明において、（Ａ）成分の加熱残分は、（Ａ）成分を加熱した後に残留する割合を意味する。加熱残分（％）は以下の式から算出される値である（加熱残分（％）＝加熱後の残留成分の質量／加熱前の（Ａ）成分の質量×１００）。 (14) Heating residue From the viewpoint of ensuring better coating suitability, the heating residue of component (A) is preferably 15% or more and 50% or less, and 20% or more and 30% or less. It is more preferable. In the present invention, the heating residue of the component (A) means a ratio remaining after the component (A) is heated. The heating residue (%) is a value calculated from the following formula (heating residue (%) = mass of residual component after heating / mass of component (A) before heating × 100).
　１．４．１－２．（Ｂ）成分
　本実施形態に係る粘着剤組成物において、（Ｂ）成分であるイソシアネート系架橋剤は、常温または加熱下で（Ａ）成分と架橋し得る架橋剤であれば特に限定されないが、例えば、キシリレンジイソシアネート、トリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマーや、それらをトリメチロールプロパンなどの２価以上のアルコール化合物等に付加反応させたイソシアネート化合物やイソシアヌレート化物等が例示される。 1.4.1-2. (B) Component In the pressure-sensitive adhesive composition according to the present embodiment, the isocyanate-based cross-linking agent that is the (B) component is not particularly limited as long as it is a cross-linking agent that can cross-link with the (A) component at room temperature or under heating. For example, isocyanate monomers such as xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and divalent or higher divalents such as trimethylolpropane An isocyanate compound or an isocyanurate obtained by addition reaction with an alcohol compound or the like is exemplified.
　また、公知のポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどにイソシアネート化合物を付加反応させたウレタンプレポリマー型のイソシアネート等も挙げられる。これらのうち、キシリレンジイソシアネートおよびその誘導体などが好ましく用いられる。 Also, urethane prepolymer type isocyanates obtained by addition reaction of isocyanate compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like can be mentioned. Of these, xylylene diisocyanate and its derivatives are preferably used.
　本実施形態に係る粘着剤組成物における（Ｂ）成分の含有量は、所定のゲル分率（例えば５０％以上９０％以下）を達成できる観点から、本実施形態に係る粘着剤組成物（粘着剤組成物を１００質量％とした場合）において０．１質量％以上５質量％以下であることができ、０．２質量％以上１質量％以下であることが好ましい。 The content of the component (B) in the pressure-sensitive adhesive composition according to this embodiment is a pressure-sensitive adhesive composition (pressure-sensitive adhesive) according to this embodiment from the viewpoint of achieving a predetermined gel fraction (for example, 50% to 90%). In the case where the agent composition is 100% by mass), it can be 0.1% by mass or more and 5% by mass or less, and preferably 0.2% by mass or more and 1% by mass or less.
　１．４．１－３．その他の成分
　本実施形態に係る粘着剤組成物は、必要に応じて、（Ａ）成分および（Ｂ）成分以外の成分をさらに含むことができる。例えば、本実施形態に係る粘着剤組成物には、本発明の効果を損なわない範囲で、（Ｃ）シランカップリング剤（以下、単に「（Ｃ）成分」と記載することもある。）、（Ｄ）イオン性化合物（以下、単に「（Ｄ）成分」と記載する場合もある。）、酸化防止剤、紫外線吸収剤、粘着付与剤、可塑剤等が配合されていても良い。 1.4.1-3. Other Components The pressure-sensitive adhesive composition according to this embodiment can further contain components other than the component (A) and the component (B) as necessary. For example, the pressure-sensitive adhesive composition according to the present embodiment includes (C) a silane coupling agent (hereinafter sometimes simply referred to as “component (C)”), as long as the effects of the present invention are not impaired. (D) An ionic compound (hereinafter sometimes simply referred to as “component (D)”), an antioxidant, an ultraviolet absorber, a tackifier, a plasticizer, and the like may be blended.
　（１）（Ｃ）シランカップリング剤
　本実施形態に係る粘着剤組成物が（Ｃ）成分を含むことにより、本実施形態に係る粘着剤組成物を用いて被着体の表面に粘着剤層を形成した場合、被着体との接着を良好に保つことができる。（Ｃ）成分は例えば、ビニルトリメトキシシラン，ビニルトリエトキシシランおよびメタクリロキシプロピルトリメトキシシラン等の重合性不飽和基含有ケイ素化合物；３－グリシドキシプロピルトリメトキシシラン，３－グリシドキシプロピルメチルジメトキシシランおよび２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ構造を有するケイ素化合物；３－アミノプロピルトリメトキシシラン，Ｎ－（２－アミノエチル）３－アミノプロピルトリメトキシシランおよび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等のアミノ基含有ケイ素化合物；並びに３－クロロプロピルトリメトキシシラン；オリゴマー型シランカップリング剤等であってもよく、中でも、（メタ）アクリル系コポリマー（Ａ）中に含まれる官能基と反応する官能基を有しているシランカップリング剤が湿熱環境下でハガレを生じさせにくいという点で好ましい。 (1) (C) Silane coupling agent When the pressure-sensitive adhesive composition according to this embodiment contains the component (C), a pressure-sensitive adhesive layer is applied to the surface of the adherend using the pressure-sensitive adhesive composition according to this embodiment. When formed, adhesion with the adherend can be kept good. Component (C) is, for example, a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Silicon compounds having an epoxy structure such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane And amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents, etc. (Meth) acrylic Silane coupling agents having a functional group reactive with the functional group contained in the copolymer (A) is preferable because hardly cause peeling in wet heat environment.
　本実施形態に係る粘着剤組成物における（Ｃ）成分の含有量は、被着体との接着を良好に保つことができる観点から、本実施形態に係る粘着剤組成物（粘着剤組成物を１００質量％とした場合）に対して０．１質量％以上５質量％以下であることができ、０．２質量％以上１質量％以下であることが好ましい。 The content of the component (C) in the pressure-sensitive adhesive composition according to this embodiment is the pressure-sensitive adhesive composition (pressure-sensitive adhesive composition) according to this embodiment from the viewpoint of maintaining good adhesion with the adherend. 0.1 mass% or more and 5 mass% or less, and preferably 0.2 mass% or more and 1 mass% or less with respect to 100 mass%).
　（２）（Ｄ）イオン性化合物
　また、本実施形態に係る粘着剤組成物は、イオン性化合物（Ｄ）を含んでいてもよい。（Ｄ）成分としては、例えば、アニオンとカチオンとからなる、２５℃で液体状、または固体状のイオン性化合物が挙げられ、具体的には、アルカリ金属塩、イオン性液体（２５℃で液体状）、界面活性剤等が挙げられる。本実施形態に係る粘着剤組成物が（Ｄ）成分を含むことにより、（Ａ）成分を構成する（ａ１）成分由来のアルキレンオキシド鎖の酸素原子が、（Ｄ）成分を構成するカチオンに配位することにより、高い帯電防止性能を実現することができる。 (2) (D) Ionic compound Moreover, the adhesive composition which concerns on this embodiment may contain the ionic compound (D). Examples of the component (D) include an ionic compound that is composed of an anion and a cation and is liquid or solid at 25 ° C., specifically, an alkali metal salt, an ionic liquid (liquid at 25 ° C. Shape), surfactants and the like. When the pressure-sensitive adhesive composition according to this embodiment contains the component (D), the oxygen atom of the alkylene oxide chain derived from the component (a1) constituting the component (A) is distributed to the cation constituting the component (D). Therefore, high antistatic performance can be realized.
　上記アルカリ金属塩としては、リチウム、ナトリウム、カリウム等のアルカリ金属カチオンと、アニオンとからなる化合物が挙げられ、具体的には、塩化ナトリウム、塩化カリウム、塩化リチウム、過塩素酸リチウム、塩素酸カリウム、硝酸カリウム、硝酸ナトリウム、炭酸ナトリウム、チオシアン酸ナトリウム、ＬｉＢｒ、ＬｉＩ、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＳＣＮ、酢酸ナトリウム、アルギン酸ナトリウム、リグニンスルホン酸ナトリウム、トルエンスルホン酸ナトリウム、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、Ｌｉ（ＣＦ３ＳＯ２）ＩＮ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）２Ｎ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）ＩＮ、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ等が挙げられる。 Examples of the alkali metal salt include compounds comprising an alkali metal cation such as lithium, sodium and potassium and an anion. Specifically, sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, potassium chlorate , Potassium nitrate, sodium nitrate, sodium carbonate, sodium thiocyanate, LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) IN, Li (C 2 F 5 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) IN, Li (CF 3 SO 2 ) 3 C, and the like. It is done.
　上記イオン性液体を構成するカチオンとしては、ピペリジニウムカチオン、ピロリジニウムカチオン、ピロリン骨格を有するカチオン、ピロール骨格を有するカチオン、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオン等が挙げられ、上記イオン性液体を構成するアニオンとしては、Ｃｌ－、Ｂｒ－、Ｉ－、ＡｌＣｌ４ －、Ａｌ２Ｃｌ７ －、ＢＦ４ －、ＰＦ６ －、ＣｌＯ４ －、ＮＯ３ －、ＣＨ３ＣＯＯ－、ＣＦ３ＣＯＯ－、ＣＨ３ＳＯ３ －、ＣＦ３ＳＯ３ －、（ＣＦ３ＳＯ２）２Ｎ－、（ＣＦ３ＳＯ２）３Ｃ－、ＡｓＦ６ －、ＳｂＦ６ －、ＮｂＦ６ －、ＴａＦ６ －、Ｆ（ＨＦ）ｎ－（ｎ＝２～３）、（ＣＮ）２Ｎ－、Ｃ４Ｆ９ＳＯ３ －、（Ｃ２Ｆ５ＳＯ２）２Ｎ－、Ｃ３Ｆ７ＣＯＯ－、（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）Ｎ－等があげられる。 As the cation constituting the ionic liquid, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyra Zolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation and the like. Examples of anions constituting the ionic liquid include Cl − , Br − , I − , AlCl 4. − , Al 2 Cl 7 − , BF 4 − , PF 6 − , ClO 4 − , NO 3 − , CH 3 COO − , CF 3 COO − , CH 3 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , AsF 6 − , SbF 6 − , NbF 6 − , TaF 6 − , F (HF) n − (n = 2 to 3), (CN) 2 N − , C 4 F 9 SO 3 − , (C 2 F 5 SO 2 ) 2 N − , C 3 F 7 COO − , (CF 3 SO 2 ) (CF 3 CO) N − and the like.
　そして、上記イオン性化合物としては、これらのカチオンとアニオンとから構成され、２５℃で液状のイオン性化合物が挙げられる。このようなイオン性化合物としては、具体的には、２－メチル－１－ピロリンテトラフルオロボレート、１－エチル－２－フェニルインドールテトラフルオロボレート、１，２－ジメチルインドールテトラフルオロボレート、１－エチルカルバゾールテトラフルオロボレート、１－エチル－３－メチルイミダゾリウムテトラフルオロボレート、１－エチル－３－メチルイミダゾリウムアセテート、１－エチル－３－メチルイミダゾリウムトリフルオロアセテート、１－エチル－３－メチルイミダゾリウムヘプタフルオロブチレート、１－エチル－３－メチルイミダゾリウムトリフルオロメタンスルホネート、１－エチル－３－メチルイミダゾリウムペルフルオロブタンスルホネート、１－エチル－３－メチルイミダゾリウムジシアナミド、１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－エチル－３－メチルイミダゾリウムビス（ペンタフルオロエタンスルホニル）イミド、１－エチル－３－メチルイミダゾリウムトリス（トリフルオロメタンスルホニル）メチド、１－ブチル－３－メチルイミダゾリウムテトラフルオロボレート、１－ブチル－３－メチルイミダゾリウムヘキサフルオロホスフェート、１－ブチル－３－メチルイミダゾリウムトリフルオロアセテート、１－ブチル－３－メチルイミダゾリウムヘプタフルオロブチレート、１－ブチル－３－メチルイミダゾリウムトリフルオロメタンスルホネート、１－ブチル－３－メチルイミダゾリウムペルフルオロブタンスルホネート、１－ブチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－へキシル－３－メチルイミダゾリウムブロミド、１－へキシル－３－メチルイミダゾリウムクロライド、１－へキシル－３－メチルイミダゾリウムテトラフルオロボレート、１－へキシル－３－メチルイミダゾリウムヘキサフルオロホスフェート、１－へキシル－３－メチルイミダゾリウムトリフルオロメタンスルホネート、１－オクチル－３－メチルイミダゾリウムテトラフルオロボレート、１－オクチル－３－メチルイミダゾリウムヘキサフルオロホスフェート、１－へキシル－２，３－ジメチルイミダゾリウムテトラフルオロボレート、１，２－ジメチル－３－プロピルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－メチルピラゾリウムテトラフルオロボレート、３－メチルピラゾリウムテトラフルオロボレート、テトラヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、ジアリルジメチルアンモニウムテトラフルオロボレート、ジアリルジメチルアンモニウムトリフルオロメタンスルホネート、ジアリルジメチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、ジアリルジメチルアンモニウムビス（ペンタフルオロエタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムテトラフルオロボレート、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムトリフルオロメタンスルホネート、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムビス（ペンタフルオロエタンスルホニル）イミド、グリシジルトリメチルアンモニウムトリフルオロメタンスルホネート、グリシジルトリメチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、グリシジルトリメチルアンモニウムビス（ペンタフルオロエタンスルホニル）イミド、１－ブチルピリジニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、１－ブチル－３－メチルピリジニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、１－エチル－３－メチルイミダゾリウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、ジアリルジメチルアンモニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、グリシジルトリメチルアンモニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－プロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ブチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－へキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ノニルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ，Ｎ－ジプロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ブチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－ブチル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－ブチル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－ペンチル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ，Ｎ－ジヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリメチルヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－プロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリエチルプロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリエチルペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリエチルヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ－メチル－Ｎ－エチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ－メチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ－ブチル－Ｎ－へキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ，Ｎ－ジヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジブチル－Ｎ－メチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジブチル－Ｎ－メチル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリオクチルメチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ－メチル－Ｎ－エチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド等が挙げられる。 And as said ionic compound, it is comprised from these cations and anions, and a liquid ionic compound is mentioned at 25 degreeC. Specific examples of such ionic compounds include 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, and 1-ethyl. Carbazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazole Lithium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1 Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluoro 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis ( Trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl- 3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1 -Hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3- Methyl pyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (penta Fluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethane Sulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethyl Ammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium ( Trifluoromethanesulfonyl) trifluoroacetamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) an Ni (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl-N-ethyl-N-propylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-he Ptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) ) Imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N -Dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- -Butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexyl Ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl- N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl -N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (Trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluorome Tansulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N -Dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoro) Romethanesulfonyl) imide and the like.
　上記界面活性剤としては、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤および両性界面活性剤の何れも使用することができる。 As the surfactant, any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used.
　上記ノニオン系界面活性剤としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニエルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエート等のソルビタン高級脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート等のポリオキシエチレンソルビタン高級脂肪酸エステル類、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレート等のポリオキシエチレン高級脂肪酸エステル類；例えば、オレイン酸モノグリセライド、ステアリン酸モノグリセライド等のグリセリン高級脂肪酸エステル類、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン等のポリオキシアルキレン類およびそれらのブロックコポリマーが挙げられる。 Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyls such as polyoxyethylene octylphenyl ether and polyoxyethylene nonielphenyl ether. Sorbitan higher fatty acid esters such as ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monostearate; for example, oleic acid monoglyceride, stearic acid monoglyceride Glycerine higher fatty acid esters such as id, polyoxyethylene, polyoxypropylene, polyoxyalkylenes and their block copolymers of polyoxybutylene and the like.
　上記カチオン系界面活性剤としては、塩化アルキルトリメチルアンモニウム、塩化ジアルキルジメチルアンモニウム、塩化ベンザルコニウム塩、アルキルジメチルアンモニウムエトサルフェート等が挙げられる。 Examples of the cationic surfactant include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, alkyldimethylammonium ethosulphate and the like.
　上記アニオン系界面活性剤としては、ラウリン酸ナトリウム、オレイン酸ナトリウム、Ｎ－アシル－Ｎ－メチルグリシンナトリウム塩、ポリオキシエチレンラウリルエーテルカルボン酸ナトリウム等のカルボン酸塩、ドデシルベンゼンスルフォン酸ナトリウム、ジアルキルスルホコハク酸エステル塩、ジメチル－５－スルホイソフタレートナトリウム等のスルホン酸塩、ラウリル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等の硫酸エステル塩、ポリオキシエチレンラウリル燐酸ナトリウム、ポリオキシエチレンノニルフェニルエーテルリン酸ナトリウム等の燐酸エステル塩等が挙げられる。 Examples of the anionic surfactant include sodium laurate, sodium oleate, N-acyl-N-methylglycine sodium salt, sodium carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium dodecylbenzenesulfonate, dialkylsulfosuccinate. Acid ester salts, sulfonates such as sodium dimethyl-5-sulfoisophthalate, sulfate salts such as sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, sodium polyoxyethylene lauryl phosphate And phosphoric acid ester salts such as sodium polyoxyethylene nonylphenyl ether phosphate.
　上記両性界面活性剤としては、カルボキシベタイン型界面活性剤、アミノカルボン酸塩、イミダゾリニウムペタイン、レシチン、アルキルアミンオキサイドが挙げられる。また、その他に、伝導性ポリマー、伝導性カーボン、塩化アンモニウム、塩化アルミニウム、塩化銅、塩化鉄、硫酸アンモニウム等を使用することができる。 Examples of the amphoteric surfactant include carboxybetaine surfactants, aminocarboxylates, imidazolinium petines, lecithins, and alkylamine oxides. In addition, conductive polymers, conductive carbon, ammonium chloride, aluminum chloride, copper chloride, iron chloride, ammonium sulfate, and the like can be used.
　このなかでも、アルカリ金属塩が好ましい。 Of these, alkali metal salts are preferred.
　本実施形態に係る粘着剤組成物が（Ｄ）成分を含む場合、本実施形態に係る粘着剤組成物における（Ｄ）成分の含有量は、本実施形態に係る粘着剤組成物（粘着剤組成物を１００質量％とした場合）に対して０．１質量％以上１０質量％以下であることができ、０．５質量％以上５質量％以下であることが好ましい。 When the adhesive composition which concerns on this embodiment contains (D) component, content of the (D) component in the adhesive composition which concerns on this embodiment is the adhesive composition (adhesive composition) which concerns on this embodiment. 0.1 mass% or more and 10 mass% or less, and preferably 0.5 mass% or more and 5 mass% or less with respect to 100% by mass of the product.
　１．４．１－４．（Ａ）成分の重合方法
　（Ａ）成分の重合方法は、特に制限されるものではなく、溶液重合、乳化重合、懸濁重合などの公知の方法により重合できるが、重合により得られた共重合体の混合物を用いて、本発明の粘着剤組成物を製造するにあたり、処理工程が比較的簡単でかつ短時間で行える観点から、溶液重合により重合することが好ましい。 1.4.1-4. (A) Polymerization Method of Component (A) The polymerization method of component (A) is not particularly limited and can be polymerized by known methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc. In producing the pressure-sensitive adhesive composition of the present invention using a mixture of coalesces, it is preferable to perform polymerization by solution polymerization from the viewpoint that the treatment process is relatively simple and can be performed in a short time.
　溶液重合は、一般に、重合槽内に所定の有機溶媒、各単量体、重合開始剤、および必要に応じて用いられる連鎖移動剤等を仕込み、窒素気流または有機溶媒の還流温度の下で、撹拌しながら数時間加熱反応させることにより行われる。 In solution polymerization, generally, a predetermined organic solvent, each monomer, a polymerization initiator, a chain transfer agent used as necessary, and the like are charged in a polymerization tank, under a nitrogen stream or a reflux temperature of the organic solvent, The reaction is carried out by heating for several hours with stirring.
　なお、この場合において、有機溶媒、単量体および／または重合開始剤の少なくとも一部を逐次添加してもよい。有機溶媒としては、例えば、ベンゼン、トルエン、エチルベンゼン、ｎ－プロピルベンゼン、ｔｅｒｔ－ブチルベンゼン、ｏ－キシレン、ｍ－キシレン、ｐ－キシレン、テトラリン、デカリン、芳香族ナフサなどの芳香族炭化水素類；例えば、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン、イソオクタン、ｎ－デカン、ジペンテン、石油スピリット、石油ナフサ、テレピン油などの脂肪系もしくは脂環族系炭化水素類；例えば、酢酸エチル、酢酸ｎ－ブチル、酢酸ｎ－アミル、酢酸２－ヒドロキシエチル、酢酸２－ブトキシエチル、酢酸３－メトキシブチル、安息香酸メチルなどのエステル類；例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、イソホロン、シクロヘキサノン、メチルシクロヘキサノンなどのケトン類；例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル類；例えば、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、ｓ－ブチルアルコール、ｔｅｒｔ－ブチルアルコールなどのアルコール類；などを挙げることができる。これらの有機溶媒はそれぞれ単独で、または２種以上混合して用いることができる。 In this case, at least a part of the organic solvent, the monomer and / or the polymerization initiator may be sequentially added. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha; For example, aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil; Esters such as butyl, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, methyl benzoate; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone Ketones such as For example, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl And alcohols such as alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and tert-butyl alcohol. These organic solvents can be used alone or in combination of two or more.
　これら重合用有機溶媒のうち、（Ａ）成分の重合に際しては、重合反応中に連鎖移動を生じにくい有機溶媒、例えば、エステル類、ケトン類を使用することが好ましく、特に、（Ａ）成分の溶解性、重合反応の容易さなどの点から、酢酸エチル、メチルエチルケトン、アセトンなどの使用が好ましい。 Among these organic solvents for polymerization, in the polymerization of the component (A), it is preferable to use an organic solvent that hardly causes chain transfer during the polymerization reaction, for example, esters and ketones. In view of solubility and ease of polymerization reaction, use of ethyl acetate, methyl ethyl ketone, acetone or the like is preferable.
　前記重合開始剤としては、通常の溶液重合で使用できる有機過酸化物、アゾ化合物などを使用することが可能である。このような有機過酸化物としては、例えば、ｔｅｒｔ－ブチルハイドロパーオキサイド、クメンハイドロオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキシド、ラウロイルパーオキシド、カプロイルパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ｔｅｒｔ－ブチルパーオキシビバレート、２，２－ビス（４，４－ジ－ｔｅｒｔ－ブチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔｅｒｔ－アミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔｅｒｔ－オクチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－α－クミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔｅｒｔ－ブチルパーオキシシクロヘキシル）ブタン、２，２－ビス（４，４－ジ－ｔｅｒｔ－オクチルパーオキシシクロヘキシル）ブタンなどが挙げられ、アゾ化合物としては、例えば、２，２´－アゾビス－イソブチロニトリル、２，２´－アゾビス－２，４－ジメチルバレロニトリル、２，２´－アゾビス－４－メトキシ－２，４－ジメチルバレロニトリルなどを挙げることができる。 As the polymerization initiator, it is possible to use organic peroxides and azo compounds that can be used in ordinary solution polymerization. Examples of such organic peroxides include tert-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, diisopropyl peroxydicarbonate, and di-2. Ethyl hexyl peroxydicarbonate, tert-butyl peroxybivalate, 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, 2,2-bis (4,4-di-tert- Amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-tert-octylperoxycyclohexyl) propane, 2,2-bis (4,4-di-α-cumylperoxycyclohexyl) propane, 2 , 2-bis (4,4-di-te t-butylperoxycyclohexyl) butane, 2,2-bis (4,4-di-tert-octylperoxycyclohexyl) butane, and the like. Examples of the azo compound include 2,2′-azobis-isobuty Examples include rhonitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like.
　これら重合開始剤のうち、（Ａ）成分の重合反応中に、グラフト反応を起こさない重合開始剤が好ましく、特にアゾ系が好ましい。その使用量は、通常、単量体合計１００質量部に対して０．０１質量部以上２質量部以下であり、好ましくは０．１質量部以上１．０質量部以下である。 Among these polymerization initiators, polymerization initiators that do not cause a graft reaction during the polymerization reaction of component (A) are preferable, and azo-based compounds are particularly preferable. The amount used is usually 0.01 parts by mass or more and 2 parts by mass or less, preferably 0.1 parts by mass or more and 1.0 parts by mass or less, with respect to 100 parts by mass of the total amount of monomers.
　また、本発明の粘着剤組成物に含まれる（Ａ）成分の製造に際しては、連鎖移動剤を使用しないのが普通であるが、本発明の目的および効果を損なわない範囲で、必要に応じて使用することは可能である。 Further, in the production of the component (A) contained in the pressure-sensitive adhesive composition of the present invention, it is normal not to use a chain transfer agent, but as long as it does not impair the purpose and effect of the present invention. It is possible to use.
　このような連鎖移動剤としては、例えば、シアノ酢酸；シアノ酢酸の炭素原子数１以上８以下のアルキルエステル類；ブロモ酢酸；ブロモ酢酸の炭素原子数１以上８以下のアルキルエステル類；アントラセン、フェナントレン、フルオレン、９－フェニルフルオレンなどの芳香族化合物類；ｐ－ニトロアニリン、ニトロベンゼン、ジニトロベンゼン、ｐ－ニトロ安息香酸、ｐ－ニトロフェノール、ｐ－ニトロトルエンなどの芳香族ニトロ化合物類；ベンゾキノン、２，３，５，６－テトラメチル－ｐ－ベンゾキノンなどのベンゾキノン誘導体類；トリブチルボランなどのボラン誘導体；四臭化炭素、四塩化炭素、１，１，２，２－テトラブロモエタン、トリブロモエチレン、トリクロロエチレン、ブロモトリクロロメタン、トリブロモメタン、３－クロロ－１－プロペンなどのハロゲン化炭化水素類；クロラール、フラルデヒドなどのアルデヒド類：炭素原子数１以上１８以下のアルキルメルカプタン類；チオフェノール、トルエンメルカプタンなどの芳香族メルカプタン類；メルカプト酢酸、メルカプト酢酸の炭素原子数１以上１０以下のアルキルエステル類；炭素原子数１以上１２以下のヒドロキシアルキルメルカプタン類；ピネン、ターピノレンなどのテルペン類；などを挙げることができる。 Examples of such chain transfer agents include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene and phenanthrene. Aromatic compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene; benzoquinone, 2, Benzoquinone derivatives such as 3,5,6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, Trichlorethylene, bromotrichloromethane, tribromometa Halogenated hydrocarbons such as 3-chloro-1-propene; aldehydes such as chloral and furaldehyde; alkyl mercaptans having 1 to 18 carbon atoms; aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid And alkyl esters of mercaptoacetic acid having 1 to 10 carbon atoms; hydroxyalkyl mercaptans having 1 to 12 carbon atoms; terpenes such as pinene and terpinolene;
　（Ａ）成分の重合温度としては、一般に約３０℃以上１８０℃以下であり、好ましくは４０℃以上１５０℃以下であり、より好ましくは５０℃以上９０℃以下の範囲である。なお、溶液重合法などで得られた重合物中に未反応の単量体が含まれる場合は、該単量体を除くために、メタノールなどによる再沈澱法で精製することも可能である。 The polymerization temperature of the component (A) is generally about 30 ° C. or higher and 180 ° C. or lower, preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 90 ° C. or lower. When an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, it can be purified by a reprecipitation method using methanol or the like in order to remove the monomer.
　１．４．１－５．粘着剤組成物の製造
　本実施形態に係る粘着剤組成物は、通常、前記（Ａ）および（Ｂ）成分および必要に応じて任意成分を、同時にあるいは任意の順番で混合して調製される。また、（Ａ）成分と（Ｂ）成分とを混合するにあたり、（Ａ）成分を溶液重合により調製した場合は、重合完了後の（Ａ）成分を含む溶液に（Ｂ）成分を添加してもよく、（Ａ）成分を塊状重合により調製する場合は、重合完了後では均一混合が困難になるため、この重合の途中で（Ｂ）成分を添加して混合することが好ましい。 1.4.1-5. Manufacture of an adhesive composition The adhesive composition which concerns on this embodiment is normally prepared by mixing the said (A) and (B) component and arbitrary components as needed simultaneously or in arbitrary orders. Moreover, when mixing (A) component and (B) component, when preparing (A) component by solution polymerization, (B) component is added to the solution containing (A) component after the completion of polymerization. In addition, when the component (A) is prepared by bulk polymerization, uniform mixing becomes difficult after the completion of the polymerization. Therefore, it is preferable to add and mix the component (B) during the polymerization.
　１．４．１－６．粘着剤層の製造
　本実施形態に係る積層体を作製するにあたり、上記粘着剤層は、粘着剤層を剥離フィルム上に設け、これを上記被着体に転写して形成されるのが一般的である。また、粘着剤層の厚みは、通常は１μｍ以上５０μｍ以下、好ましくは５μｍ以上３０μｍ以下程度である。 1.4.1-6. Manufacture of an adhesive layer When producing the laminated body which concerns on this embodiment, the said adhesive layer is generally formed by providing an adhesive layer on a peeling film and transferring this to the said adherend. It is. The thickness of the pressure-sensitive adhesive layer is usually 1 μm or more and 50 μm or less, preferably about 5 μm or more and 30 μm or less.
　１．５．作用効果
　１．５．１．公知技術
　一般に、ポリシクロオレフィン系フィルムを構成するポリマーは主に、低極性の基から構成されることから、極性が低いため、ポリシクロオレフィン系フィルムにはアクリル系粘着剤が被着しにくい。このため、ポリシクロオレフィン系フィルムと粘着剤層との極性を合わせることで、ポリシクロオレフィン系フィルムと粘着剤層との密着性を高める試みがなされている。 1.5. Effect 1.5.1. Known Technology Generally, a polymer constituting a polycycloolefin-based film is mainly composed of a low-polar group, and therefore has a low polarity. Therefore, an acrylic pressure-sensitive adhesive is difficult to adhere to the polycycloolefin-based film. For this reason, attempts have been made to improve the adhesion between the polycycloolefin film and the pressure-sensitive adhesive layer by matching the polarities of the polycycloolefin film and the pressure-sensitive adhesive layer.
　例えば、低極性基（例えば、芳香族炭化水素基や脂環式炭化水素基）を有する重合体を含む粘着剤層が、ポリシクロオレフィン系フィルムの接着に用いられている（特許文献１および２参照）。しかしながら、例えば本願比較例４および５で示されるように、これらの低極性基を有する重合体を含む粘着剤組成物から得られる粘着剤層では、耐久性およびポリシクロオレフィン系フィルムとの接着性が十分でない場合がある。 For example, a pressure-sensitive adhesive layer containing a polymer having a low polarity group (for example, an aromatic hydrocarbon group or an alicyclic hydrocarbon group) is used for adhesion of a polycycloolefin film (Patent Documents 1 and 2). reference). However, as shown in Comparative Examples 4 and 5, for example, the pressure-sensitive adhesive layer obtained from a pressure-sensitive adhesive composition containing a polymer having these low polar groups has durability and adhesion to a polycycloolefin film. May not be enough.
　１．５．２．本発明の作用効果
　これに対して、本実施形態に係る積層体を構成する粘着剤層を形成するための粘着剤組成物では、該粘着剤組成物を形成するための単量体混合物中の（ａ１）成分が、粘着剤層に適度な弾性率および光漏れ防止効果をもたらす。すなわち、本発明は、（ａ１）成分であるアルキレンオキシド鎖含有単量体によって、ポリシクロオレフィン系フィルムに応じた弾性率を有する粘着剤層を得ることができるため、ポリシクロオレフィン系フィルムとの密着性を高めることができるうえに、光漏れ防止効果も得られるという、新規でかつ独創的な発想に基づくものである。 1.5.2. In contrast, in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer constituting the laminate according to the present embodiment, in the monomer mixture for forming the pressure-sensitive adhesive composition The component (a1) provides an appropriate elastic modulus and light leakage prevention effect to the pressure-sensitive adhesive layer. That is, in the present invention, an adhesive layer having an elastic modulus corresponding to a polycycloolefin film can be obtained from the alkylene oxide chain-containing monomer as the component (a1). This is based on a novel and original idea that the adhesion can be improved and the light leakage prevention effect can be obtained.
　より具体的には、本実施形態に係る積層体は、ガラス基板と、ポリシクロオレフィン系フィルムと、前記ガラス基板と前記ポリシクロオレフィン系フィルムとの間に設けられた粘着剤層と、を含み、前記粘着剤層を形成するための粘着剤組成物は、（Ａ）成分：上記（ａ１）成分、（ａ２）成分、（ａ３）成分、（ａ４）成分、および（ａ５）成分からなる単量体組成物の共重合体および（Ｂ）成分：イソシアネート系架橋剤を含み、かつ、上記（ａ１）成分、（ａ２）成分、（ａ３）成分、（ａ４）成分、および（ａ５）成分をそれぞれ所定の割合で含むことにより、上記（ａ１）成分が粘着剤層に適度な弾性率および光漏れ防止効果をもたらす。これにより、該粘着剤層の損失正接が高く、該粘着剤層が適度な弾性を有するため、該粘着剤層がポリシクロオレフィン系フィルムの表面になじみやすく、ガラス基板とポリシクロオレフィン系フィルムとの密着性を高めることができる。また、該粘着剤層は高温および多湿条件下で優れた耐久性を発揮し、かつ、光漏れを低減することができる。 More specifically, the laminate according to this embodiment includes a glass substrate, a polycycloolefin film, and an adhesive layer provided between the glass substrate and the polycycloolefin film. The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises a component (A): a single component comprising the component (a1), component (a2), component (a3), component (a4), and component (a5). The copolymer of the monomer composition and the component (B): an isocyanate-based crosslinking agent, and the component (a1), component (a2), component (a3), component (a4), and component (a5) By including each in a predetermined ratio, the component (a1) brings an appropriate elastic modulus and light leakage prevention effect to the pressure-sensitive adhesive layer. Thereby, since the loss tangent of the pressure-sensitive adhesive layer is high and the pressure-sensitive adhesive layer has an appropriate elasticity, the pressure-sensitive adhesive layer is easily adapted to the surface of the polycycloolefin-based film, and the glass substrate and the polycycloolefin-based film It is possible to improve the adhesion. In addition, the pressure-sensitive adhesive layer can exhibit excellent durability under high temperature and high humidity conditions, and can reduce light leakage.
　同様に、本実施形態に係る積層体は、第１のポリシクロオレフィン系フィルムと、第２のポリシクロオレフィン系フィルムと、前記第１のポリシクロオレフィン系フィルムと前記第２のポリシクロオレフィン系フィルムとの間に設けられた粘着剤層と、を有し、前記粘着剤層を形成するための粘着剤組成物は、（Ａ）成分：上記（ａ１）成分、（ａ２）成分、（ａ３）成分、（ａ４）成分、および（ａ５）成分からなる単量体組成物の共重合体および（Ｂ）成分：イソシアネート系架橋剤を含み、かつ、上記（ａ１）成分、（ａ２）成分、（ａ３）成分、（ａ４）成分、および（ａ５）成分をそれぞれ所定の割合で含むことにより、上記（ａ１）成分が粘着剤層に適度な弾性率および光漏れ防止効果をもたらす。これにより、該粘着剤層の損失正接が高く、該粘着剤層が適度な弾性を有するため、該粘着剤層がポリシクロオレフィン系フィルムの表面になじみやすく、ポリシクロオレフィン系フィルム同士の密着性を高めることができる。また、該粘着剤層は高温および多湿条件下で優れた耐久性を発揮し、かつ、光漏れを低減することができる。 Similarly, the laminate according to this embodiment includes a first polycycloolefin film, a second polycycloolefin film, the first polycycloolefin film, and the second polycycloolefin film. A pressure-sensitive adhesive layer provided between the film and the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises: (A) component: (a1) component, (a2) component, (a3) A copolymer of a monomer composition comprising the component (a), the component (a4), and the component (a5) and the component (B): an isocyanate-based crosslinking agent, and the component (a1), the component (a2), By including the (a3) component, the (a4) component, and the (a5) component at a predetermined ratio, the (a1) component brings an appropriate elastic modulus and light leakage prevention effect to the pressure-sensitive adhesive layer. Thereby, since the loss tangent of the pressure-sensitive adhesive layer is high and the pressure-sensitive adhesive layer has an appropriate elasticity, the pressure-sensitive adhesive layer is easily adapted to the surface of the polycycloolefin-based film, and the adhesion between the polycycloolefin-based films is Can be increased. In addition, the pressure-sensitive adhesive layer can exhibit excellent durability under high temperature and high humidity conditions, and can reduce light leakage.
　２．実施例
　以下、本発明を下記実施例に基づいて説明するが、本発明は実施例に限定されない。 2. EXAMPLES Hereinafter, the present invention will be described based on the following examples, but the present invention is not limited to the examples.
　２．１．（Ａ）成分（アクリル系重合体）の調製
　２．１．１．製造例１（アクリル系重合体１の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート６８質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル３０質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体１を得た。 2.1. Preparation of component (A) (acrylic polymer) 2.1.1. Production Example 1 (Production of acrylic polymer 1)
In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 68 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, 30 parts by mass of 2-methoxyethyl acrylate , And 140 parts by mass of ethyl acetate, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 1.
　得られたアクリル系重合体１の１０５℃での加熱残分（ｎＶ％）は２５．０％であった。また、得られたアクリル系重合体１についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は８９．９万であり、アクリル系重合体１の分散指数は１１であり、２３℃おける粘度は５．１(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 1 was 25.0%. Moreover, the weight average molecular weight measured by gel permeation chromatography (GPC) about the obtained acrylic polymer 1 is 89,990,000, the dispersion index of the acrylic polymer 1 is 11, and it can stand at 23 degreeC. The viscosity was 5.1 (Pa · s).
　２．１．２．製造例２（アクリル重合体２の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート４８質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル５０質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体２を得た。 2.1.2. Production Example 2 (Production of acrylic polymer 2)
In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 48 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, 50 parts by mass of 2-methoxyethyl acrylate , And 140 parts by mass of ethyl acetate, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 2.
　得られたアクリル系重合体２の１０５℃での加熱残分（ｎＶ％）は２４．９％であった。また、得られたアクリル系重合体２についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９０．３万であり、アクリル系重合体２の分散指数は１１であり、２３℃おける粘度は５．４(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 2 was 24.9%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 2 is 903,000, the dispersion index of the acrylic polymer 2 is 11, and it can stand at 23 degreeC. The viscosity was 5.4 (Pa · s).
　２．１．３．製造例３（アクリル重合体３の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート８質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル９０質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体３を得た。 2.1.3. Production Example 3 (Production of acrylic polymer 3)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 8 parts by weight of butyl acrylate, 1 part by weight of 2-hydroxyethyl acrylate, 1 part by weight of acrylamide, 90 parts by weight of 2-methoxyethyl acrylate , And 140 parts by mass of ethyl acetate, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 3.
　得られたアクリル系重合体３の１０５℃での加熱残分（ｎＶ％）は２５．２％であった。また、得られたアクリル系重合体３についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９０．２万であり、アクリル系重合体２の分散指数は１２であり、２３℃おける粘度は５．２(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 3 was 25.2%. Moreover, the weight average molecular weight measured by gel permeation chromatography (GPC) about the obtained acrylic polymer 3 is 902,000, the dispersion index of the acrylic polymer 2 is 12, and it can stand at 23 degreeC. The viscosity was 5.2 (Pa · s).
　２．１．４．製造例４（アクリル重合体２の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート６質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル９２質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体４を得た。 2.1.4. Production Example 4 (Production of acrylic polymer 2)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 6 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, 92 parts by mass of 2-methoxyethyl acrylate , And 140 parts by mass of ethyl acetate, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 4.
　得られたアクリル系重合体４の１０５℃での加熱残分（ｎＶ％）は２５．１％であった。また、得られたアクリル系重合体４についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９０．３万であり、アクリル系重合体４の分散指数は１１であり、２３℃おける粘度は５．１(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 4 was 25.1%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 4 is 903,000, the dispersion index of the acrylic polymer 4 is 11, and it can stand at 23 degreeC. The viscosity was 5.1 (Pa · s).
　２．１．５．製造例５（アクリル重合体５の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート４質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル９５質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体５を得た。 2.1.5. Production Example 5 (Production of acrylic polymer 5)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 4 parts by weight of butyl acrylate, 1 part by weight of 2-hydroxyethyl acrylate, 1 part by weight of acrylamide, 95 parts by weight of 2-methoxyethyl acrylate , And 140 parts by mass of ethyl acetate, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 5.
　得られたアクリル系重合体５の１０５℃での加熱残分（ｎＶ％）は２５．２％であった。また、得られたアクリル系重合体５についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９０．２万であり、アクリル系重合体５の分散指数は１１であり、２３℃おける粘度は４．８(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 5 was 25.2%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 5 is 902,000, the dispersion index of the acrylic polymer 5 is 11, and it can stand at 23 degreeC. The viscosity was 4.8 (Pa · s).
　２．１．６．製造例６（アクリル重合体６の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート４７質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル５０質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体６を得た。 2.1.6. Production Example 6 (Production of acrylic polymer 6)
In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 47 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, 50 parts by mass of 2-methoxyethyl acrylate , And 140 parts by mass of ethyl acetate, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 6.
　得られたアクリル系重合体６の１０５℃での加熱残分（ｎＶ％）は２５．０％であった。また、得られたアクリル系重合体６についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９１．５万であり、アクリル系重合体６の分散指数は１１であり、２３℃おける粘度は５．８(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 6 was 25.0%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 6 is 915,000, the dispersion index of the acrylic polymer 6 is 11, and it can stand at 23 degreeC. The viscosity was 5.8 (Pa · s).
　２．１．７．製造例７（アクリル重合体７の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート９８質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体７を得た。 2.1.7. Production Example 7 (Production of acrylic polymer 7)
A flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 98 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, and 140 parts by mass of ethyl acetate. The contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 7.
　得られたアクリル系重合体７の１０５℃での加熱残分（ｎＶ％）は２４．９％であった。また、得られたアクリル系重合体７についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９３．１万であり、アクリル系重合体７の分散指数は１１であり、２３℃おける粘度は４．９(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 7 was 24.9%. Moreover, the weight average molecular weight measured by gel permeation chromatography (GPC) about the obtained acrylic polymer 7 is 931,000, the dispersion index of the acrylic polymer 7 is 11, and it can stand at 23 degreeC. The viscosity was 4.9 (Pa · s).
　２．１．８．製造例８（アクリル重合体８の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート８質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル９０質量部、ｎ－ドデシルメルカプタン０．０４質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１３０部を添加して、アクリル重合体８を得た。 2.1.8. Production Example 8 (Production of acrylic polymer 8)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 8 parts by weight of butyl acrylate, 1 part by weight of 2-hydroxyethyl acrylate, 1 part by weight of acrylamide, 90 parts by weight of 2-methoxyethyl acrylate , 0.04 parts by mass of n-dodecyl mercaptan and 140 parts by mass of ethyl acetate were charged, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 130 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 8.
　得られたアクリル系重合体８の１０５℃での加熱残分（ｎＶ％）は３５．５％であった。また、得られたアクリル系重合体８についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は３６．０万であり、アクリル系重合体８の分散指数は１０であり、２３℃おける粘度は３．５(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 8 was 35.5%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 8 is 36.0 million, the dispersion index of the acrylic polymer 8 is 10, and it is 23 degreeC. The viscosity was 3.5 (Pa · s).
　２．１．９．製造例９（アクリル重合体９の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート６８質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸シクロヘキシル３０質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体９を得た。 2.1.9. Production Example 9 (Production of acrylic polymer 9)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 68 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, 30 parts by mass of cyclohexyl acrylate, and acetic acid 140 parts by mass of ethyl was charged, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 9.
　得られたアクリル系重合体９の１０５℃での加熱残分（ｎＶ％）は２５．０％であった。また、得られたアクリル系重合体９についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は８９．１万であり、アクリル系重合体９の分散指数は１１であり、２３℃おける粘度は５．３(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 9 was 25.0%. The acrylic polymer 9 obtained had a weight average molecular weight of 891,000 measured by gel permeation chromatography (GPC), and the acrylic polymer 9 had a dispersion index of 11 at 23 ° C. The viscosity was 5.3 (Pa · s).
　２．１．１０．製造例１０（アクリル重合体１０の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート６８質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸ベンジル３０質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合１０を得た。 2.1.10. Production Example 10 (Production of acrylic polymer 10)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 68 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, 30 parts by mass of benzyl acrylate, and acetic acid 140 parts by mass of ethyl was charged, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain acrylic polymerization 10.
　得られたアクリル系重合体１０の１０５℃での加熱残分（ｎＶ％）は２４．８％であった。また、得られたアクリル系重合体１０についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９０．８万であり、アクリル系重合体１０の分散指数は１３であり、２３℃おける粘度は５．４(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 10 was 24.8%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 10 is 908,000, the dispersion index of the acrylic polymer 10 is 13, and it can stand at 23 degreeC. The viscosity was 5.4 (Pa · s).
　２．１．１１．製造例１１（アクリル系重合体１１の製造）
　撹絆装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、ブチルアクリレート７３質量部、２－ヒドロキエチルアクリレート１質量部、アクリルアミド１質量部、アクリル酸２－メトキシエチル２５質量部、および酢酸エチル１４０質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を７０℃に加熱した。次いで、窒素ガスで十分に置換されたフラスコ内に、ＡＩＢＮ０．１質量部を撹絆下で添加した。フラスコ内の内容物の温度を７０℃に維持しながら８時間反応させた。８時間経過後の反応混合物に酢酸エチル１４０部を添加して、アクリル重合体１１を得た。 2.1.11. Production Example 11 (Production of acrylic polymer 11)
In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 73 parts by mass of butyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylamide, 25 parts by mass of 2-methoxyethyl acrylate , And 140 parts by mass of ethyl acetate, and the contents of the flask were heated to 70 ° C. while introducing nitrogen gas into the flask. Next, 0.1 part by weight of AIBN was added under stirring in a flask that was sufficiently replaced with nitrogen gas. The reaction was carried out for 8 hours while maintaining the temperature of the contents in the flask at 70 ° C. After 8 hours, 140 parts of ethyl acetate was added to the reaction mixture to obtain an acrylic polymer 11.
　得られたアクリル系重合体１の１０５℃での加熱残分（ｎＶ％）は２５．１％であった。また、得られたアクリル系重合体１についてゲルパーミエ一ションクロマトグラフィー(ＧＰＣ)により測定された重量平均分子量は９３．１万であり、アクリル系重合体１の分散指数は１２であり、２３℃おける粘度は５．１(Ｐａ・ｓ)であった。 The heating residue (nV%) at 105 ° C. of the obtained acrylic polymer 1 was 25.1%. Moreover, the weight average molecular weight measured by the gel permeation chromatography (GPC) about the obtained acrylic polymer 1 is 931,000, the dispersion index of the acrylic polymer 1 is 12, and it can stand at 23 degreeC. The viscosity was 5.1 (Pa · s).
　２．１．１２．製造例１２（積層体の作製）
　下記表２の配合比率にて各成分（（Ａ）成分～（Ｄ）成分）を配合して、よく混合した。泡抜け後、ドクターブレートを用いＰＥＴセパレータに塗工したらすぐに９０℃で３分間乾燥して厚さ２５ｍｍの粘着剤層を作製した。該粘着剤層を乾燥した後、ＣＯＰ層を一表面に有する偏光板のＣＯＰ面に貼り合わせ、室温２３℃、湿度６５％の条件下、１～７日間静置した。その後、この偏光板を適当な大きさに裁断して、ガラス板に貼り合わせて、実施例１ないし６および比較例１ないし５の積層体（ガラス板および粘着剤層付偏光板）を作製した。この積層体は、ガラス板と、粘着剤層と、偏光板とがこの順で積層されており、粘着剤層を介してガラス板と偏光板とが接着されている。この積層体について、８５℃／９５ＲＨ％、６０℃／９５ＲＨ％の２条件で５００時間の耐久試験、光漏れ測定試験、および表面抵抗値の測定を行った。 2.1.12. Production Example 12 (Production of laminate)
Each component (component (A) to component (D)) was blended at the blending ratio shown in Table 2 below and mixed well. After defoaming, it was dried at 90 ° C. for 3 minutes as soon as it was applied to a PET separator using a doctor blade, and a 25 mm thick adhesive layer was prepared. After the pressure-sensitive adhesive layer was dried, it was bonded to the COP surface of a polarizing plate having a COP layer on one surface, and allowed to stand for 1 to 7 days under conditions of room temperature 23 ° C. and humidity 65%. Thereafter, this polarizing plate was cut into an appropriate size and bonded to a glass plate to produce laminates (glass plate and polarizing plate with an adhesive layer) of Examples 1 to 6 and Comparative Examples 1 to 5. . In this laminate, a glass plate, an adhesive layer, and a polarizing plate are laminated in this order, and the glass plate and the polarizing plate are bonded via the adhesive layer. The laminate was subjected to a 500 hour durability test, a light leakage measurement test, and a surface resistance value measurement under two conditions of 85 ° C./95 RH% and 60 ° C./95 RH%.
　２．２．試験方法
　２．２．１．ゲル分率
　試料１ｇを酢酸エチル５０ｍｌに投入し、振盪機（型名ｓｈａｋｅｒ　ＳＡ－３００、ヤマト科学株式会社製）にかけた。ゲル分を２００メッシュのステンレス網にてろ過し、乾燥させた。その後、ろ過後の試料の質量をろ過前の試料の質量で除した値をゲル分率として算出した。 2.2. Test method 2.2.1. Gel fraction 1 g of a sample was placed in 50 ml of ethyl acetate and applied to a shaker (type name: Shaker SA-300, manufactured by Yamato Scientific Co., Ltd.). The gel content was filtered through a 200 mesh stainless steel net and dried. Then, the value which remove | divided the mass of the sample after filtration by the mass of the sample before filtration was computed as a gel fraction.
　２．２．２．耐久性（耐熱・耐湿試験）
　積層体（ガラス板および粘着剤層付偏光板）を１５０ｍｍ×２５０ｍｍの大きさに裁断し、ガラス板の片面にラミネーターロールを用いて貼着し、次いで、５０℃にて５気圧に調整されたオートクレーブに２０分間保持して試験板を作成した。同様の試験板を２枚作成し、それぞれ、６０℃でかつ湿度９５％ＲＨの条件下に５００時間放置し、および８０℃の条件下で５００時間放置し、以下の基準でガラス板－粘着剤層の界面のハガレ、発泡の発生等を目視で確認した。 2.2.2. Durability (heat and humidity resistance test)
The laminate (glass plate and polarizing plate with pressure-sensitive adhesive layer) was cut into a size of 150 mm × 250 mm, attached to one side of the glass plate using a laminator roll, and then adjusted to 5 atm at 50 ° C. A test plate was prepared by holding in an autoclave for 20 minutes. Two similar test plates were prepared and left for 500 hours under the conditions of 60 ° C. and 95% humidity, respectively, and left for 500 hours under the conditions of 80 ° C. The peeling of the interface of the layer, the occurrence of foaming, etc. were confirmed visually.
　（基準）
　○：ハガレ等の外観不良は観察されなかった。
　△：ハガレ等の外観不良が僅かに観察された。
　×：ハガレ等の外観不良が明らかに観察された。 (Standard)
○: Appearance defects such as peeling were not observed.
Δ: A slight appearance defect such as peeling was observed.
X: Appearance defects such as peeling were clearly observed.
　２．２．３．光漏れ試験
　２枚の積層体（ガラス板および粘着剤層付偏光板）を互いに直交するように重ね合わせた状態で８０ｍｍ×１４０ｍｍの大きさに裁断し、ガラス板の両側に互いに直交するようにラミネ一ターロールを用いて貼着し、次いで、５０℃かつ５気圧に調整されたオートクレーブに２０分間保持して、試験板を作成した。この試験板を８０℃の条件下に５００時間放置して、以下の基準で光漏れの観察を行った。 2.2.3. Light Leakage Test Two laminated bodies (glass plate and polarizing plate with adhesive layer) are cut to a size of 80 mm × 140 mm in a state where they are perpendicular to each other, so that they are perpendicular to each other on both sides of the glass plate. A test plate was prepared by sticking using a laminator roll and then holding it in an autoclave adjusted to 50 ° C. and 5 atm for 20 minutes. This test plate was allowed to stand for 500 hours at 80 ° C., and light leakage was observed according to the following criteria.
　（基準）
　○：光漏れは観察されなかった。
　△：光漏れが僅かに観察された。
　×：光漏れが明らかに観察された。 (Standard)
○: No light leakage was observed.
Δ: Slight light leakage was observed.
X: Light leakage was clearly observed.
　２．２．４．表面抵抗値
　９０ｍｍ×９０ｍｍに裁断した積層体（ガラス板および粘着剤層付偏光板）に関して、株式会社エ一ディーシー社製Ｒ８２５２デジタルエレクトロメータを用いて表面抵抗値を測定した。 2.2.4. Surface resistance value With respect to the laminate (glass plate and polarizing plate with an adhesive layer) cut to 90 mm × 90 mm, the surface resistance value was measured using an R8252 digital electrometer manufactured by EDC Corporation.
　２．２．５．損失正接
　５０μｍ厚に塗布した粘着シートを積層させ、約１ｍｍ厚のサンプルシート（粘着剤層）を作製した。このシートを用いて、アントンパール（AntonPaar）社製のモジュラーコンパクトレオメーターＭＣＲ３００を用いて測定した。測定周波数は１Ｈｚを用いた。 2.2.5. Loss tangent A pressure-sensitive adhesive sheet applied to a thickness of 50 μm was laminated to prepare a sample sheet (adhesive layer) having a thickness of about 1 mm. Using this sheet, measurement was performed using a modular compact rheometer MCR300 manufactured by Anton Paar. The measurement frequency was 1 Hz.
　２．２．６．偏光板（ＣＯＰ）への密着性
　上記耐久試験の条件において、偏光板（ＣＯＰ）－粘着剤層の界面の密着を目視で確認して、以下の基準で評価した。 2.2.6. Adhesiveness to polarizing plate (COP) Under the conditions of the durability test, the adhesion at the polarizing plate (COP) -adhesive layer interface was visually confirmed and evaluated according to the following criteria.
　（基準）
　◎：ハガレ等の外観不良は観察されなかった。
　○：ハガレ等の外観不良が僅かに観察された。
　△：ハガレ等の外観不良が部分的に観察された。
　×：ハガレ等の外観不良が顕著に観察された。 (Standard)
(Double-circle): Appearance defects, such as peeling, were not observed.
○: A slight appearance defect such as peeling was observed.
(Triangle | delta): Appearance defects, such as peeling, were partially observed.
X: Appearance defects such as peeling were remarkably observed.
　２．２．７．ＩＴＯ腐食性
　１０ｍｍ×１００ｍｍにカットしたＩＴＯ蒸着ＰＥＴフィルムに、実施例１ないし６および比較例１ないし５で得られた積層体（ガラス板および粘着剤層付偏光板）を１０ｍｍ×６０ｍｍにカットして貼り付け、５０℃×５ａｔｍで２０分間オートクレーブ処理を行った。次いで、１時間室温で静置した後、６０℃でかつ９０％ＲＨの環境下に５００時間置き、２３℃でかつ湿度６５％ＲＨの条件下に１時間静置した後、ＩＴＯ蒸着フィルムの抵抗値を測定し、あらかじめ測定しておいた試験前の抵抗値と比較し、試験前の抵抗値に対する抵抗値の変化率を求めた。試験前の抵抗値に対する抵抗値の変化率が大きいほど、ＩＴＯ腐食性が高いといえる。なお、抵抗値の測定には、テスター（三和電気計器（株）製、デジタルマルチメーターＰＣ５１０)を用いた。 2.2.7. ITO corrosivity The laminated body (glass plate and polarizing plate with adhesive layer) obtained in Examples 1 to 6 and Comparative Examples 1 to 5 was cut to 10 mm × 60 mm on an ITO vapor-deposited PET film cut to 10 mm × 100 mm. And then autoclaved at 50 ° C. × 5 atm for 20 minutes. Next, after standing at room temperature for 1 hour, placing it in an environment of 60 ° C. and 90% RH for 500 hours, standing at 23 ° C. and humidity of 65% RH for 1 hour, then the resistance of the ITO deposited film The value was measured and compared with the resistance value before the test measured in advance, and the rate of change of the resistance value with respect to the resistance value before the test was obtained. It can be said that the higher the rate of change of the resistance value relative to the resistance value before the test, the higher the ITO corrosivity. Note that a tester (manufactured by Sanwa Denki Keiki Co., Ltd., Digital Multimeter PC510) was used for measuring the resistance value.
　２．２．８．酸価
　酸価の測定は、JIS-K0070「化学製品の酸価，けん化価，エステル価，よう素価，水酸基価および不けん化物の試験方法」に準拠して行った。自動滴定装置（平沼産業社製、ＣＯＭ－１６００）を用いて電位差滴定法によって中和滴定反応を行い、下記式より酸価を求めた。Ａ＝｛Ｙ×ｆ×５．６１｝／Ｓ・Ａ：酸価・Ｙ：滴定に用いた滴定溶液の量（ｍｌ）・ｆ：滴定溶液のファクター・Ｓ：ポリマーサンプルの重量（ｇ）。 2.2.8. Acid value The acid value was measured in accordance with JIS-K0070 “Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. Neutralization titration was performed by potentiometric titration using an automatic titrator (COM-1600, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value was determined from the following formula. A = {Y × f × 5.61} / S · A: acid value • Y: amount of titration solution used for titration (ml) • f: factor of titration solution • S: weight of polymer sample (g)
　測定条件は下記の通りである。・サンプル溶液：ポリマーサンプル約０．５ｇを混合溶媒（トルエン／エタノール＝２／１　容積比）５０ｍｌに溶解してサンプル溶液とした。・滴定溶液：０．１ｍｏｌ／ｌ、エタノール性水酸化カリウム溶液・電極：ガラス電極、比較電極；カロメル電極 Measurement conditions are as follows. Sample solution: About 0.5 g of a polymer sample was dissolved in 50 ml of a mixed solvent (toluene / ethanol = 2/1 volume ratio) to obtain a sample solution. -Titration solution: 0.1 mol / l, ethanolic potassium hydroxide solution-Electrode: glass electrode, comparative electrode; calomel electrode
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　なお、表２における略語は以下の意味である。
　ＢＡ：ｎ－ブチルアクリリレート
　ＣＨＡ：シクロヘキシルアクリリレート
　ＢｚＡ：ベンジルアクリリレート
　ＭＥＡ：２－メトキシエチルアクリリレート
　ＡＡ：アクリル酸
　ＨＥＡ：２－ヒドロキエチルアクリリレート
　ＡＭ：アクリルアミド
　Ｌｉ・ＴＦＳＩ：リチウムビス（トリフルオロスルホニルイミド）
　Ｌ－４５：ＴＤＩ系硬化剤（綜研化学社製）
　Ａ－５０：シランカップリング剤（綜研化学社製） In addition, the abbreviation in Table 2 has the following meaning.
BA: n-butyl acrylate CHA: cyclohexyl acrylate BzA: benzyl acrylate MEA: 2-methoxyethyl acrylate AA: acrylic acid HEA: 2-hydroxyethyl acrylate AM: acrylamide Li · TFSI: lithium bis (trifluorosulfonyl) Imide)
L-45: TDI curing agent (manufactured by Soken Chemical Co., Ltd.)
A-50: Silane coupling agent (manufactured by Soken Chemical)
　表３の結果から、上記実施例１ないし６の積層体は、粘着剤層が、上記（Ａ）成分および上記（Ｂ）成分を含む粘着剤組成物から形成され、該（Ａ）成分の重量平均分子量が４０万以上２００万以下であり、かつ、酸価が１以下であることにより、粘着剤層を介してガラス基板とポリシクロオレフィン系フィルムとの接着性およびポリシクロオレフィン系フィルム同士の接着性に優れ、高い耐久性を実現し、かつ、光漏れを低減することができることが理解できる。 From the results of Table 3, in the laminates of Examples 1 to 6, the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing the component (A) and the component (B), and the weight of the component (A). When the average molecular weight is 400,000 or more and 2 million or less, and the acid value is 1 or less, the adhesiveness between the glass substrate and the polycycloolefin-based film and the polycycloolefin-based film between the pressure-sensitive adhesive layers It can be understood that the adhesiveness is excellent, high durability is realized, and light leakage can be reduced.
　これに対して、上記比較例１の積層体は、（Ａ）成分の酸価が１を超えるため、ＩＴＯへの腐食が生じたことが理解できる。また、上記比較例２の積層体は、（Ａ）成分の原料である粘着剤組成物中に（ａ１）成分を含まないため、耐久性および光漏れ防止性能が劣り、かつ、ＣＯＰへの密着性も低いことが理解できる。また、上記比較例３の積層体は、分子量が低いため、耐久性に劣ることが理解できる。また、上記比較例４の積層体は、（Ａ）成分の原料である粘着剤組成物中に、（ａ１）成分の代わりに（ａ４）成分としてベンジルアクリレートを３０質量％使用した例であり、耐久性およびＣＯＰへの密着性が良好でないうえに、光漏れ防止性能に劣ることが理解できる。また、上記比較例５の積層体は、（Ａ）成分の原料である粘着剤組成物中に、（ａ１）成分の代わりに（ａ５）成分としてシクロヘキシルアクリレートを３０質量％使用した例であり、耐久性が良好でないうえに、ＣＯＰへの密着性に劣ることが理解できる。また、上記比較例６の積層体は、（Ａ）成分の原料である粘着剤組成物中の（ａ１）成分の含有量が３０質量％未満である例であり、光漏れ防止性能およびＣＯＰへの密着性が良好でないことが理解できる。 In contrast, it can be understood that the laminate of Comparative Example 1 was corroded to ITO because the acid value of the component (A) exceeded 1. In addition, the laminate of Comparative Example 2 does not contain the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A), so that the durability and light leakage prevention performance are inferior, and the adhesion to the COP It can be understood that the property is also low. Moreover, since the laminated body of the said comparative example 3 has low molecular weight, it can be understood that it is inferior to durability. The laminate of Comparative Example 4 is an example in which 30% by mass of benzyl acrylate is used as the component (a4) instead of the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A). It can be understood that the durability and adhesion to the COP are not good and the light leakage prevention performance is poor. The laminate of Comparative Example 5 is an example in which 30% by mass of cyclohexyl acrylate is used as the component (a5) instead of the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A). It can be understood that the durability is not good and the adhesion to the COP is inferior. Further, the laminate of Comparative Example 6 is an example in which the content of the component (a1) in the pressure-sensitive adhesive composition that is the raw material of the component (A) is less than 30% by mass. It can be understood that the adhesion is not good.
　［符号の説明］
　１０　ガラス基板
　２０，２２　粘着剤層
　３０，１３０　偏光フィルム
　３２　位相差フィルム（ポリシクロオレフィン系フィルム）
　３４　ポリビニルアルコール（ＰＶＡ）フィルム
　３６　ＴＡＣフィルム
　３８　ポリシクロオレフィン系フィルムまたはＴＡＣフィルム
　１００，２００　積層体 [Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Glass substrate 20,22 Adhesive layer 30,130 Polarizing film 32 Retardation film (polycycloolefin type film)
34 Polyvinyl alcohol (PVA) film 36 TAC film 38 Polycycloolefin film or TAC film 100,200 Laminate

Claims (12)

  1. 　ガラス基板と、
    　ポリシクロオレフィン系フィルムと、
    　前記ガラス基板と前記ポリシクロオレフィン系フィルムとの間に設けられた粘着剤層と、
    を含み、
    　前記粘着剤層は、（Ａ）下記単量体（ａ１）、単量体（ａ２）、単量体（ａ３）、単量体（ａ４）成分および単量体（ａ５）からなる単量体組成物の共重合体および（Ｂ）イソシアネート系架橋剤を含む粘着剤組成物から形成され、前記共重合体は、重量平均分子量が４０万以上２００万以下であり、かつ、酸価が１以下である、積層体。
    　（ａ１）アルキレンオキシド鎖含有単量体３０質量％以上９８．８質量％以下：
    　（ａ２）水酸基含有単量体０．１質量％以上１０質量％以下：
    　（ａ３）アミド基またはアミノ基含有単量体０．１質量％以上１０質量％以下：
    　（ａ４）（メタ）アクリル酸アルキルエステル単量体１質量％以上６９．８質量％以下：
    　（ａ５）前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分以外の共重合性単量体０質量％以上３０質量％以下：ただし、前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分、および前記単量体（ａ５）を足し合わせて１００質量％である。     A glass substrate;
    A polycycloolefin-based film;
    An adhesive layer provided between the glass substrate and the polycycloolefin-based film;
    Including
    The pressure-sensitive adhesive layer comprises (A) a monomer comprising the following monomer (a1), monomer (a2), monomer (a3), monomer (a4) component and monomer (a5) The copolymer is formed from a pressure-sensitive adhesive composition containing a copolymer of the composition and (B) an isocyanate-based crosslinking agent, and the copolymer has a weight average molecular weight of 400,000 or more and 2 million or less, and an acid value of 1 or less. A laminate.
    (A1) Alkylene oxide chain-containing monomer 30% by mass or more and 98.8% by mass or less:
    (A2) Hydroxyl group-containing monomer 0.1 mass% or more and 10 mass% or less:
    (A3) Amide group or amino group-containing monomer 0.1% by mass or more and 10% by mass or less:
    (A4) (Meth) acrylic acid alkyl ester monomer 1 mass% or more and 69.8 mass% or less:
    (A5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less: However, the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5) are added together. 100% by mass.
  2. 　前記ガラス基板および前記ポリシクロオレフィン系フィルムは、前記粘着剤層を介して接着されている、請求項１に記載の積層体。 The laminate according to claim 1, wherein the glass substrate and the polycycloolefin-based film are bonded via the pressure-sensitive adhesive layer.
  3. 　偏光フィルムをさらに含み、
    　前記偏光フィルムは、前記ポリシクロオレフィン系フィルムを含む、請求項１または２に記載の積層体。     Further comprising a polarizing film;
    The said polarizing film is a laminated body of Claim 1 or 2 containing the said polycycloolefin type film.
  4. 　位相差フィルムをさらに含み、
    　前記位相差フィルムは、前記ポリシクロオレフィン系フィルムを含む、請求項１または２に記載の積層体。     A retardation film;
    The laminate according to claim 1, wherein the retardation film includes the polycycloolefin-based film.
  5. 　前記ガラス基板は、画像表示装置に用いられるガラス基板である、請求項１ないし４のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the glass substrate is a glass substrate used in an image display device.
  6. 　第１のポリシクロオレフィン系フィルムと、
    　第２のポリシクロオレフィン系フィルムと、
    　前記第１のポリシクロオレフィン系フィルムと前記第２のポリシクロオレフィン系フィルムとの間に設けられた粘着剤層と、を含み、
    　前記粘着剤層は、（Ａ）下記単量体（ａ１）、単量体（ａ２）、単量体（ａ３）、および単量体（ａ４）成分、および単量体（ａ５）からなる単量体組成物の共重合体および（Ｂ）イソシアネート系架橋剤を含む粘着剤組成物から形成され、
    　（ａ１）アルキレンオキシド鎖含有単量体３０質量％以上９８．８質量％以下：
    　（ａ２）水酸基含有単量体０．１質量％以上１０質量％以下：
    　（ａ３）アミド基またはアミノ基含有単量体０．１質量％以上１０質量％以下：
    　（ａ４）（メタ）アクリル酸アルキルエステル単量体１質量％以上６９．８質量％以下：
    　（ａ５）前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分以外の共重合性単量体０質量％以上３０質量％以下：ただし、前記単量体（ａ１）、前記単量体（ａ２）、前記単量体（ａ３）、および前記単量体（ａ４）成分、および前記単量体（ａ５）を足し合わせて１００質量％である。
    　前記共重合体は、重量平均分子量が４０万以上２００万以下であり、かつ、酸価が１以下である、積層体。     A first polycycloolefin-based film;
    A second polycycloolefin-based film;
    An adhesive layer provided between the first polycycloolefin-based film and the second polycycloolefin-based film,
    The pressure-sensitive adhesive layer comprises (A) a monomer (a1), a monomer (a2), a monomer (a3), a monomer (a4) component, and a monomer (a5). A pressure-sensitive adhesive composition comprising a copolymer of a monomer composition and (B) an isocyanate-based crosslinking agent;
    (A1) Alkylene oxide chain-containing monomer 30% by mass or more and 98.8% by mass or less:
    (A2) Hydroxyl group-containing monomer 0.1 mass% or more and 10 mass% or less:
    (A3) Amide group or amino group-containing monomer 0.1% by mass or more and 10% by mass or less:
    (A4) (Meth) acrylic acid alkyl ester monomer 1 mass% or more and 69.8 mass% or less:
    (A5) Copolymerizable monomer other than the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) component 0% by mass to 30% by mass % Or less: However, the monomer (a1), the monomer (a2), the monomer (a3), the monomer (a4) component, and the monomer (a5) are added together. 100% by mass.
    The copolymer is a laminate having a weight average molecular weight of 400,000 or more and 2 million or less and an acid value of 1 or less.
  7. 　前記粘着剤層の損失正接が０．２以上である、請求項１ないし６のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 6, wherein a loss tangent of the pressure-sensitive adhesive layer is 0.2 or more.
  8. 　前記粘着剤組成物のゲル分率が５０％以上９０％以下である、請求項１ないし７のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive composition has a gel fraction of 50% or more and 90% or less.
  9. 　前記粘着剤組成物における前記（Ｂ）イソシアネート系架橋剤の含有量が０．１質量％以上５質量％以下である、請求項１ないし８のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 8, wherein the content of the (B) isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is 0.1 mass% or more and 5 mass% or less.
  10. 　前記粘着剤組成物における前記（Ｃ）シランカップリング剤の含有量が０．１質量％以上５質量％以下である、請求項１ないし９のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 9, wherein a content of the (C) silane coupling agent in the pressure-sensitive adhesive composition is 0.1 mass% or more and 5 mass% or less.
  11. 　前記粘着剤組成物における前記（Ｄ）帯電防止剤の含有量が０質量％以上１０質量％以下である、請求項１ないし１０のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 10, wherein the content of the antistatic agent (D) in the pressure-sensitive adhesive composition is 0% by mass or more and 10% by mass or less.
  12. 　前記共重合体は、脂環式炭化水素基および／または芳香族炭化水素基を有する単量体の含有量が３０質量％以下である、請求項１ないし１１のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive according to any one of claims 1 to 11, wherein the copolymer has a content of a monomer having an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group of 30% by mass or less. Agent composition.
PCT/JP2014/060290 2013-04-11 2014-04-09 Laminate WO2014168178A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2015511282A JP6283355B2 (en) 2013-04-11 2014-04-09 Laminate
KR1020157032057A KR102071103B1 (en) 2013-04-11 2014-04-09 Laminate
CN201480020669.5A CN105121157B (en) 2013-04-11 2014-04-09 Laminated body

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013083258 2013-04-11
JP2013-083258 2013-04-11

Publications (1)

Publication Number Publication Date
WO2014168178A1 true WO2014168178A1 (en) 2014-10-16

Family

ID=51689584

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/060290 WO2014168178A1 (en) 2013-04-11 2014-04-09 Laminate

Country Status (5)

Country Link
JP (1) JP6283355B2 (en)
KR (1) KR102071103B1 (en)
CN (1) CN105121157B (en)
TW (1) TWI625231B (en)
WO (1) WO2014168178A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016166316A (en) * 2015-03-03 2016-09-15 リンテック株式会社 Adhesive, adhesive sheet and optical film with adhesive layer
JP2016166317A (en) * 2015-03-03 2016-09-15 リンテック株式会社 Adhesive composition, adhesive, adhesive sheet and optical film with adhesive layer
JP2016186054A (en) * 2015-03-27 2016-10-27 リンテック株式会社 Tacky composition, pressure-sensitive adhesive agent, pressure-sensitive adhesive sheet, and optical film with pressure-sensitive adhesive layer
JP2018090802A (en) * 2016-12-02 2018-06-14 三菱ケミカル株式会社 Adhesive resin composition and adhesive sheet
WO2021153636A1 (en) * 2020-01-30 2021-08-05 日東電工株式会社 Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016059979A1 (en) * 2014-10-15 2016-04-21 綜研化学株式会社 Adhesive layer, and polarizing plate and laminate having adhesive layer
SG11201800572XA (en) * 2016-01-27 2018-02-27 Nitto Denko Corp Stress distributing film, optical member, and electronic member
JP7055003B2 (en) * 2017-11-01 2022-04-15 日東電工株式会社 Adhesive composition for optical film, adhesive layer for optical film, and optical film with adhesive layer
FR3075800B1 (en) * 2017-12-21 2020-10-09 Arkema France ANTI-STICK COATS FOR TRANSFER PRINTING PROCESSES
JP7326958B2 (en) * 2019-07-22 2023-08-16 コニカミノルタ株式会社 LAMINATED FILM AND METHOD FOR MANUFACTURING THE SAME

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011225764A (en) * 2010-04-22 2011-11-10 Sumitomo Chemical Co Ltd Resin film with adhesive and optical laminate using the same
WO2012121122A1 (en) * 2011-03-10 2012-09-13 住友化学株式会社 Optical film having adhesive agent, and optical laminated body in which same is used
JP2013142124A (en) * 2012-01-11 2013-07-22 Soken Chem & Eng Co Ltd Adhesive tape for conductive film and laminate for touch panel

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100446664B1 (en) * 2002-02-20 2004-09-04 주식회사 엘지화학 Acrylic pressure sensitive adhesive composition for the polarizing firm
JP4521520B2 (en) 2003-08-06 2010-08-11 綜研化学株式会社 Adhesive for low polarity film
JP3996940B2 (en) 2005-05-11 2007-10-24 日東電工株式会社 Polarizing plate with optical compensation layer and image display device using the same
CN1884415B (en) * 2005-06-24 2011-09-07 东洋油墨制造株式会社 Antistatic acroleic acid binding agent
WO2007034533A1 (en) * 2005-09-20 2007-03-29 Soken Chemical & Engineering Co., Ltd. Pressure-sensitive adhesive composition for polarizing plate and polarizing plate with pressure-sensitive adhesive layer
JP4491422B2 (en) 2006-02-23 2010-06-30 セイコーエプソン株式会社 Clock dial and clock
CN101097269A (en) * 2006-06-26 2008-01-02 力特光电科技股份有限公司 Polarized plate structure
JP4942171B2 (en) * 2006-09-14 2012-05-30 綜研化学株式会社 Adhesive composition and adhesive sheet
KR101082450B1 (en) 2008-01-14 2011-11-11 주식회사 엘지화학 Acrylic pressure-sensitive adhesive compositions
CN101918886B (en) * 2008-01-18 2013-01-23 Lg化学株式会社 Optical film, preparation method of the same, and liquid crystal display comprising the same
JP5455362B2 (en) * 2008-12-25 2014-03-26 チェイル インダストリーズ インコーポレイテッド Adhesive composition and optical member using the same
JP5665700B2 (en) * 2011-09-08 2015-02-04 綜研化学株式会社 Adhesive sheet for conductive film and method for producing adhesive sheet for conductive film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011225764A (en) * 2010-04-22 2011-11-10 Sumitomo Chemical Co Ltd Resin film with adhesive and optical laminate using the same
WO2012121122A1 (en) * 2011-03-10 2012-09-13 住友化学株式会社 Optical film having adhesive agent, and optical laminated body in which same is used
JP2013142124A (en) * 2012-01-11 2013-07-22 Soken Chem & Eng Co Ltd Adhesive tape for conductive film and laminate for touch panel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016166316A (en) * 2015-03-03 2016-09-15 リンテック株式会社 Adhesive, adhesive sheet and optical film with adhesive layer
JP2016166317A (en) * 2015-03-03 2016-09-15 リンテック株式会社 Adhesive composition, adhesive, adhesive sheet and optical film with adhesive layer
JP2016186054A (en) * 2015-03-27 2016-10-27 リンテック株式会社 Tacky composition, pressure-sensitive adhesive agent, pressure-sensitive adhesive sheet, and optical film with pressure-sensitive adhesive layer
JP2018090802A (en) * 2016-12-02 2018-06-14 三菱ケミカル株式会社 Adhesive resin composition and adhesive sheet
JP7106848B2 (en) 2016-12-02 2022-07-27 三菱ケミカル株式会社 Adhesive resin composition and adhesive sheet
WO2021153636A1 (en) * 2020-01-30 2021-08-05 日東電工株式会社 Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet

Also Published As

Publication number Publication date
CN105121157A (en) 2015-12-02
CN105121157B (en) 2017-08-08
TW201446501A (en) 2014-12-16
KR102071103B1 (en) 2020-01-29
JP6283355B2 (en) 2018-02-21
KR20150140790A (en) 2015-12-16
JPWO2014168178A1 (en) 2017-02-16
TWI625231B (en) 2018-06-01

Similar Documents

Publication Publication Date Title
JP6283355B2 (en) Laminate
JP5887404B2 (en) Adhesive composition for optical film, adhesive optical film, and laminate
US20180267351A1 (en) Liquid crystal panel with touch sensing function and liquid crystal display device
CN115731778A (en) Transparent resin layer
JP6517150B2 (en) Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive optical film and laminate
TWI735614B (en) Adhesive composition, adhesive layer, optical film with adhesive layer, image display panel and liquid crystal display device
KR102153560B1 (en) Adhesive layer, and polarizing plate and laminate having adhesive layer
JP6748279B2 (en) Liquid crystal panel with touch sensing function, liquid crystal display device, and polarizing film with adhesive layer
TW201903090A (en) Polarizing film with adhesive layer, and image display device
JP6321629B2 (en) Adhesive composition for optical film and adhesive optical film
WO2014163003A1 (en) Adhesive composition for optics, adhesive sheet for optics, and method for producing adhesive sheet for optics
JP6563566B2 (en) Liquid crystal panel with touch sensing function and liquid crystal display device
WO2023224004A1 (en) In-cell-type liquid crystal panel
JP2018141989A (en) Liquid crystal panel with touch sensing function and liquid crystal display
JP6648183B2 (en) Polarizing film with adhesive layer for LCD panel with built-in touch sensing function
JP2020077389A (en) Transparent resin layer, polarization film with adhesive layer, and image display device
JP2019200423A (en) Liquid crystal panel with touch sensing function and liquid crystal display
JP2018151637A (en) Transparent resin layer, polarizing film with adhesive layer, and image display device
JP2018141990A (en) Liquid crystal panel with touch sensing function and liquid crystal display

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14782825

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015511282

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20157032057

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 14782825

Country of ref document: EP

Kind code of ref document: A1