WO2023085335A1 - Adhesive composition, adhesive sheet, optical laminate, image display panel, and image display device - Google Patents

Adhesive composition, adhesive sheet, optical laminate, image display panel, and image display device Download PDF

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Publication number
WO2023085335A1
WO2023085335A1 PCT/JP2022/041789 JP2022041789W WO2023085335A1 WO 2023085335 A1 WO2023085335 A1 WO 2023085335A1 JP 2022041789 W JP2022041789 W JP 2022041789W WO 2023085335 A1 WO2023085335 A1 WO 2023085335A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive composition
adhesive sheet
polymer
Prior art date
Application number
PCT/JP2022/041789
Other languages
French (fr)
Japanese (ja)
Inventor
寛大 小野
智之 木村
雄祐 外山
Original Assignee
日東電工株式会社
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Filing date
Publication date
Priority claimed from JP2021186028A external-priority patent/JP2023073161A/en
Priority claimed from JP2022169317A external-priority patent/JP2023073210A/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202280075716.0A priority Critical patent/CN118234826A/en
Publication of WO2023085335A1 publication Critical patent/WO2023085335A1/en

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to an adhesive composition, an adhesive sheet, an optical laminate, an image display panel and an image display device.
  • image display devices typified by liquid crystal display devices and electroluminescence (EL) display devices (eg, organic EL display devices and inorganic EL display devices) have rapidly spread.
  • EL electroluminescence
  • These various image display devices have a laminated structure of, for example, an image display cell such as a liquid crystal cell or an EL light emitting element, and an optical laminate including an optical film such as a polarizing plate and an adhesive sheet.
  • the pressure-sensitive adhesive sheet is mainly used for bonding between optical films included in the optical layered body and bonding between the image display cell and the optical layered body.
  • Patent Document 1 discloses a pressure-sensitive adhesive composition containing a (meth)acrylic polymer having a structural unit derived from a polar group-containing monomer such as 2-methoxyethyl acrylate, and a pressure-sensitive adhesive composition formed from the An adhesive sheet is disclosed.
  • static electricity is generated during manufacture, for example, when the optical laminate is attached to the image display cell via an adhesive sheet, or during use, for example, when the user touches the image display device. If the image display device is electrified by this static electricity, problems such as display failure may occur.
  • adhesive It is conceivable to adjust the surface resistance value of the pressure-sensitive adhesive sheet to a low value by adding a conductive agent to the agent composition.
  • the compounding amount of the conductive agent is excessively increased, the optical properties will deteriorate due to the deposition of the conductive agent and the durability of the adhesive sheet will decrease when the high temperature environment assumed in the inside of the vehicle in summer etc. is passed. etc. tend to occur.
  • the present invention provides a pressure-sensitive adhesive composition that achieves a low surface resistance value and is suitable for use in optical laminates in environments where high temperatures should be considered, and a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition. aim.
  • the present invention Containing a polymer (A) having a polyether structure as a main component, further comprising a conductive agent and a radical scavenger;
  • a pressure-sensitive adhesive composition which, when formed into a pressure-sensitive adhesive sheet, has a surface resistance value of 1 ⁇ 10 10 ⁇ / ⁇ or less.
  • the surface resistance value of the adhesive sheet is indicated by the measured value when the thickness of the adhesive sheet is 20 ⁇ m.
  • the present invention provides Containing a polymer (D) having a polyether structure as a main component, further comprising a conductive agent;
  • the pressure-sensitive adhesive sheet When the pressure-sensitive adhesive sheet is formed, the pressure-sensitive adhesive sheet has a radical generation amount RG 10 of 1.5 ⁇ 10 14 /g or less and a surface resistance value of 1 ⁇ 10 10 ⁇ / ⁇ or less.
  • the RG 10 is the amount of radicals generated from the pressure-sensitive adhesive sheet when heated at 105° C. for 10 minutes as evaluated by electron spin resonance method.
  • the present invention provides A pressure-sensitive adhesive sheet formed from the above pressure-sensitive adhesive composition is provided.
  • the present invention provides the above-mentioned adhesive sheet; an optical film;
  • An optical laminate comprising:
  • the present invention provides Provided is an image display panel comprising the above optical layered body.
  • the present invention provides Provided is an image display device comprising the above image display panel.
  • the present invention provides A pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a polymer (B), the dielectric constant of the polymer (B) at a frequency of 100 kHz is 5.0 or more; After heating the pressure-sensitive adhesive sheet at 105° C. for 120 hours, the pressure-sensitive adhesive sheet provides a pressure-sensitive adhesive sheet containing 1000 ppm or less of formic acid on a mass basis.
  • the present invention provides An optical laminate including an adhesive sheet and an optical film,
  • the optical film is a polarizing plate containing a polarizer, After heating the optical layered body at 105° C. for 120 hours, the polarizing plate provides an optical layered body containing 70 ppm or less of formic acid on a mass basis.
  • a pressure-sensitive adhesive composition that achieves a low surface resistance value and is suitable for use in an optical laminate under an environment where high temperatures should be considered, and a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition are provided. can provide.
  • FIG. 1 is a cross-sectional view schematically showing an example of the pressure-sensitive adhesive sheet of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an example of the optical layered body of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing an example of the optical layered body of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing an example of the optical layered body of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing an example of the optical layered body of the present invention.
  • FIG. 6 is a cross-sectional view schematically showing an example of the optical layered body of the present invention.
  • FIG. 7 is a cross-sectional view schematically showing an example of the image display panel of the invention.
  • FIG. 8 is a cross-sectional view schematically showing an example of the image display panel of the invention.
  • FIG. 9 is a cross-sectional view schematically showing an example of the image display panel of the invention.
  • the pressure-sensitive adhesive composition (I) of the present embodiment contains a polymer (A) having a polyether structure as a main component, and further contains a conductive agent. According to the studies of the present inventors, the polyether structure in the polymer (A) can promote the ionization of the conductive agent contained in the adhesive composition (I), and the ionization of the conductive agent It can contribute to the reduction of the surface resistance value of the pressure-sensitive adhesive sheet formed from the material.
  • Polyenation of PVA is a phenomenon in which multiple carbon-carbon unsaturated bonds occur in the main chain of PVA and the conjugated structure extends. is red).
  • the polyene formation of PVA can be explained as a phenomenon in which the cross-linked structure with boric acid disappears due to hydrolysis caused by heat, exposing many terminal OH groups of PVA, and the dehydration condensation reaction between the exposed OH groups proceeds. Moreover, this dehydration condensation reaction is presumed to be a radical reaction.
  • progress of radical reaction in the optical film at high temperature not limited to PVA in the polarizer, can cause changes in optical properties such as coloration to the optical film.
  • Radicals generated due to the polyether structure include radicals generated with the involvement of other components (e.g., polymerization initiators, cross-linking agents, antioxidants, etc.) starting from the radicals generated from the polyether structure. can be included.
  • the adhesive composition (I) further contains a radical scavenger.
  • the radical scavenger can limit the amount of radicals generated in the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (I) at high temperatures.
  • the pressure-sensitive adhesive composition (I), in which the amount of radicals generated at high temperatures is limited when made into a pressure-sensitive adhesive sheet, is suitable for use in optical laminates in environments where high temperatures should be considered.
  • the formed pressure-sensitive adhesive sheet has a surface resistance value of 1 ⁇ 10 10 ⁇ / ⁇ or less.
  • the surface resistance value is 5 ⁇ 10 9 ⁇ / ⁇ or less, 1 ⁇ 10 9 ⁇ / ⁇ or less, 8 ⁇ 10 8 ⁇ / ⁇ or less, 6 ⁇ 10 8 ⁇ / ⁇ or less, 5 ⁇ 10 8 ⁇ / ⁇ or less, It may be 4 ⁇ 10 8 ⁇ / ⁇ or less, 3 ⁇ 10 8 ⁇ / ⁇ or less, or even 2 ⁇ 10 8 ⁇ / ⁇ or less.
  • the lower limit of the surface resistance value is, for example, 1 ⁇ 10 6 ⁇ / ⁇ or more, and may be 1 ⁇ 10 7 ⁇ / ⁇ or more.
  • the pressure-sensitive adhesive composition (I) having a surface resistance value within the above range when formed into a pressure-sensitive adhesive sheet is suitable for use in an environment where static electricity is likely to occur, such as inside a vehicle.
  • polymer (A) examples are (meth)acrylic polymers, urethane polymers, silicone polymers and rubber polymers.
  • the polymer (A) is not limited to the above examples as long as it has a polyether structure.
  • Polymer (A) is preferably a (meth)acrylic polymer.
  • the pressure-sensitive adhesive composition (I) may contain a (meth)acrylic polymer as a main component.
  • the adhesive composition (I) may be an acrylic adhesive composition.
  • a main component means the component with the largest content rate in a composition.
  • the content of the main component is, for example, 50% by weight or more, and may be 60% by weight or more, 70% by weight or more, 75% by weight or more, or even 80% by weight or more.
  • the (meth)acrylic polymer means a polymer having structural units derived from (meth)acrylic monomers such as (meth)acrylate.
  • the content of structural units derived from (meth)acrylic monomers in the (meth)acrylic polymer is, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, and 80% by weight. % or more, 85 wt % or more, 90 wt % or more, or even 95 wt % or more.
  • the (meth)acrylic polymer may consist only of structural units derived from (meth)acrylic monomers.
  • (Meth)acrylic means acrylic and methacrylic.
  • (Meth)acrylate means acrylate and methacrylate.
  • the polymer (A) has a polyether structure.
  • a polyether structure is a structure containing at least two ether groups (--O--).
  • the polyether structure may be linear or branched.
  • An example of a polyether structure includes an alkyl group, which may be linear or branched, and at least two ether groups.
  • the polymer (A) may have a polyether structure in its main chain or in its side chains, preferably in its side chains.
  • the polymer (A) may be a (meth)acrylic polymer having polyether structures in side chains.
  • the polymer (A) may have structural units having a polyether structure.
  • the polyether structure may be positioned on the main chain or on the side chain, preferably on the side chain.
  • the polymer (A) may have a structural unit derived from a (meth)acrylic monomer having a polyether structure in its side chain.
  • R 1 in formula (1) is a hydrogen atom or a methyl group.
  • R 2 in formula (1) is an alkyl group that may be linear or branched, preferably a linear alkyl group. Examples of R 2 are methyl and ethyl groups.
  • n is an integer of 1-15, preferably an integer of 1-10, more preferably an integer of 1-5. When n is 1, the monomer of formula (1) contains two ether groups, including the "-O-" of the COO group.
  • the monomer of formula (1) is one type of (meth)acrylic monomer, more specifically, one type of (meth)acrylate monomer.
  • the monomer of formula (1) is also one type of alkoxy group-containing (meth)acrylate monomer.
  • a structural unit derived from the monomer of formula (1) has a polyether structure in its side chain.
  • Examples of monomers of formula (1) are 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate. ) acrylates and methoxypolyethylene glycol (meth)acrylates, preferably 2-methoxyethyl acrylate (MEA).
  • the structural unit derived from the monomer of formula (1) can particularly contribute to lowering the surface resistance of the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (I).
  • the content of structural units having a polyether structure (for example, structural units derived from the monomer of formula (1)) in the polymer (A) is, for example, 15% by weight or more, 20% by weight or more, and 25% by weight. Above, 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight 80% by weight or more, 85% by weight or more, 90% by weight or more, or even 95% by weight or more.
  • the upper limit of the content is, for example, 100% by weight or less, and may be 99.5% by weight or less, or even 99% by weight or less.
  • the polymer (A) may have one or more structural units derived from the following monomers (A2).
  • the monomer (A2) shown below can be copolymerized with the monomer of formula (1).
  • An example of the monomer (A2) is a (meth)acrylic monomer having an alkyl group with 1 to 30 carbon atoms in its side chain.
  • the alkyl group may be linear or branched.
  • Examples of (meth)acrylic monomers having alkyl groups in side chains include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate.
  • the content of the structural unit derived from the (meth)acrylic monomer having an alkyl group in the side chain in the polymer (A) is, for example, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight. % or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, or even 5 wt% or less, or even 0 wt% (without the structural unit even) good.
  • the hydroxyl group-containing monomer may be a hydroxyl group-containing (meth)acrylic monomer.
  • hydroxyl-containing monomers are 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl ( hydroxyalkyl (meth)acrylates such as meth)acrylates, 10-hydroxydecyl (meth)acrylate and 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate.
  • 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred, and 4-hydroxybutyl (meth) Acrylates are more preferred.
  • the content of structural units derived from hydroxyl group-containing monomers in the polymer (A) is, for example, 1 to 5% by weight, and may be 3% by weight or less, or even 2% by weight or less.
  • Polymer (A) may not have a structural unit derived from a hydroxyl group-containing monomer.
  • the monomer (A2) may be an aromatic ring-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, or an amide group-containing monomer.
  • the aromatic ring-containing monomer may be an aromatic ring-containing (meth)acrylic monomer.
  • aromatic ring-containing monomers include phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, hydroxyethylated ⁇ - naphthol (meth)acrylate and biphenyl (meth)acrylate.
  • carboxyl group-containing monomers examples include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid.
  • amino group-containing monomers are N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.
  • amide group-containing monomers are (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(meth)acrylamide, N- Butyl (meth)acrylamide, N-hexyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methylol-N-propane (meth)acrylamide, aminomethyl (meth)acrylamide, aminoethyl (meth)acrylamide, mercaptomethyl acrylamide-based monomers such as (meth)acrylamide and mercaptoethyl (meth)acrylamide; N-acryloyl heterocycles such as N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine and N-(meth)acryloylpyrrolidine and N-vinyl group-containing lactam monomers such as N-vinylpyrrolidon
  • the monomer (A2) may be a polyfunctional monomer.
  • multifunctional monomers are hexanediol di(meth)acrylate (1,6-hexanediol di(meth)acrylate), butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl (meth)acrylate ) polyfunctional acrylates such as acrylates, epoxy acrylates, polyester acrylates and urethane acrylates; and divinylbenzene.
  • Polyfunctional acrylates are preferably 1,6-hexanediol
  • the total content of structural units derived from the aromatic ring-containing monomer, carboxyl group-containing monomer, amino group-containing monomer, amide group-containing monomer and polyfunctional monomer in the polymer (A) is , preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 8% by weight or less.
  • the total content is, for example, 0.01% by weight or more, and may be 1% by weight or more, 2% by weight or more, or even 3% by weight or more.
  • Polymer (A) may not have these structural units.
  • the content of the structural unit derived from the carboxyl group-containing monomer may be less than 0.1% by weight, or even 0% by weight (if the structural unit is (even without it) is fine.
  • Examples of other monomers (A2) include nitrile group-containing (meth)acrylates such as (meth)acrylonitrile; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; vinyl sulfonic acid group-containing monomers such as sodium sulfonate; phosphate group-containing monomers; alicyclic hydrocarbon groups such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins such as ethylene, propylene, butadiene, isoprene and isobutylene, or dienes; vinyl ethers such as alkyl ethers; and vinyl chloride.
  • nitrile group-containing (meth)acrylates such as (me
  • the total content of structural units derived from the other monomer (A2) in the polymer (A) is, for example, 30% by weight or less, may be 10% by weight or less, or is 0% by weight (not have the structural unit).
  • the polymer (A) can be formed by polymerizing one or more of the above monomers by a known method.
  • a monomer and a partial polymer of the monomer may be polymerized.
  • Polymerization can be carried out, for example, by solution polymerization, emulsion polymerization, bulk polymerization, thermal polymerization, or active energy ray polymerization. Solution polymerization and active energy ray polymerization are preferred from the viewpoint of forming a pressure-sensitive adhesive sheet with excellent optical transparency.
  • Polymerization is preferably carried out while avoiding contact of the monomer and/or partial polymer with oxygen. Polymerization in shutdown can be employed.
  • the polymer (A) to be formed may be in any form such as a random copolymer, a block copolymer, a graft copolymer and the like.
  • the polymerization system forming the polymer (A) may contain one or more polymerization initiators.
  • the type of polymerization initiator can be selected depending on the polymerization reaction, and may be, for example, a thermal polymerization initiator or a photopolymerization initiator.
  • Solvents used for solution polymerization include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as methylcyclohexane; and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the solvent is not limited to the above examples.
  • the solvent may be a mixed solvent of two or more solvents.
  • Polymerization initiators used for solution polymerization are, for example, azo polymerization initiators, peroxide polymerization initiators, and redox polymerization initiators.
  • Peroxide polymerization initiators are, for example, dibenzoyl peroxide and t-butyl permaleate.
  • the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable.
  • the azo polymerization initiator for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2-methylpropion acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid.
  • AIBN 2,2'-azobisisobutyronitrile
  • 2,2'-azobis-2-methylbutyronitrile 2,2'-azobis (2-methylpropion acid) dimethyl
  • 4,4'-azobis-4-cyanovaleric acid is not limited to the above examples.
  • the active energy rays used for active energy ray polymerization are, for example, ionizing radiation such as ⁇ -rays, ⁇ -rays, ⁇ -rays, neutron beams and electron beams, and ultraviolet rays.
  • the active energy rays are preferably ultraviolet rays.
  • Polymerization by irradiation with ultraviolet rays is also called photopolymerization.
  • a polymerization system for active energy ray polymerization typically contains a photopolymerization initiator. Polymerization conditions for active energy polymerization are not limited as long as the polymer (A) is formed.
  • Photopolymerization initiators include, for example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, ⁇ -ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators. , a benzoin-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a ketal-based photopolymerization initiator, and a thioxanthone-based photopolymerization initiator.
  • the photopolymerization initiator is not limited to the above examples.
  • Benzoin ether-based photopolymerization initiators include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, anisolemethyl is ether.
  • Acetophenone-based photopolymerization initiators include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl)dichloro Acetophenone.
  • Examples of ⁇ -ketol photopolymerization initiators are 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one.
  • the aromatic sulfonyl chloride photopolymerization initiator is, for example, 2-naphthalenesulfonyl chloride.
  • a photoactive oxime-based photopolymerization initiator is, for example, 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
  • a benzoin-based photopolymerization initiator is, for example, benzoin.
  • a benzylic photopolymerization initiator is, for example, benzyl.
  • benzophenone-based photopolymerization initiators examples include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and ⁇ -hydroxycyclohexylphenyl ketone.
  • a ketal photopolymerization initiator is, for example, benzyl dimethyl ketal.
  • Thioxanthone-based photopolymerization initiators are, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
  • the amount of the photopolymerization initiator used is, for example, 0.01 to 1 part by weight, and may be 0.05 to 0.5 part by weight, based on 100 parts by weight of the total amount of the monomers.
  • the weight average molecular weight (Mw) of the polymer (A) is, for example, 1-3 million, preferably 1.8-3 million.
  • the weight average molecular weight (Mw) of the polymer in this specification is a value (converted to polystyrene) based on GPC (gel permeation chromatography) measurement.
  • the glass transition temperature (Tg) of the polymer (A) is, for example, -50°C or lower, preferably -52°C or lower, and more preferably -55°C or lower.
  • the lower limit of Tg of polymer (A) is, for example, -75°C.
  • the Tg of the polymer (A) is a value obtained by averaging the Tg of a homopolymer for each monomer that forms the structural unit of the polymer (A) and taking into account the content of the structural unit. is.
  • the content of the polymer (A) in the adhesive composition (I) is, for example, 50% by weight or more, 60% by weight or more, 70% by weight or more, 75% by weight or more, and further 80% by weight in terms of solid content. or more.
  • the upper limit of the content is, for example, 99% by weight or less, and may be 97% by weight or less, or even 95% by weight or less.
  • the adhesive composition (I) further contains a conductive agent (antistatic agent).
  • the pressure-sensitive adhesive composition (I) may contain one or more conductive agents.
  • conductive agents are ionic compounds such as salts.
  • the ionic compound may be an ionic liquid that is liquid at normal temperature (25° C.).
  • Examples of ionic compounds are inorganic cation salts and organic cation salts.
  • Examples of inorganic cation salts are inorganic cation-anion salts.
  • Examples of cations contained in inorganic cation salts are alkali metal ions.
  • Alkali metal ions are, for example, lithium ions, sodium ions, potassium ions, preferably lithium ions.
  • the inorganic cation salt may be a lithium salt.
  • Examples of anions contained in inorganic cation salts are 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 ) 3 C ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , (CN) 2 N ⁇ , C 4 F 9 SO 3 ⁇ , C 3 F 7 COO ⁇ , (CF 3 SO 2 )(CF 3 CO)N ⁇ , —O 3 S(CF 2 ) 3 SO 3 ⁇ , and the following general formula (a) is an anion represented by (d).
  • the anion contained in the inorganic cation salt is preferably a fluorine-containing anion, more preferably a fluorine-containing imide anion.
  • fluorine-containing imide anions are imide anions with perfluoroalkyl groups.
  • fluorine-containing imide anions are (CF 3 SO 2 )(CF 3 CO)N ⁇ and anions represented by the above general formulas (a), (b) or (d), Preferred are (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N — (perfluoroalkylsulfonyl) imides represented by the general formula (a), more preferably (CF 3 SO 2 ) bis(trifluoromethanesulfonyl)imide represented by 2N- .
  • An example of a preferred inorganic cation salt is lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).
  • An example of an organic cation salt is an organic cation-anion salt.
  • Examples of cations contained in organic cation salts are organic onium containing organic groups.
  • Examples of onium contained in organic onium include nitrogen-containing onium, sulfur-containing onium and phosphorus-containing onium, preferably nitrogen-containing onium and sulfur-containing onium.
  • Examples of nitrogen-containing oniums include ammonium cations, piperidinium cations, pyrrolidinium cations, pyridinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, imidazolium cations, tetrahydropyrimidinium cations, and dihydropyrimidinium cations.
  • organic onium examples include alkyl groups, alkoxyl groups, alkenyl groups. Specific examples of preferred organic oniums are tetraalkylammonium cations (eg, tributylmethylammonium cations), alkylpiperidinium cations, alkylpyrrolidinium cations.
  • Examples of anions contained in organic cation salts are the same as examples of anions contained in inorganic cation salts.
  • Examples of preferred organic cation salts are 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, trimethylbutylammonium bis(trifluoromethanesulfonyl)imide.
  • the conductive agent may be used in combination with an inorganic cation salt and an organic cation salt.
  • the amount of the conductive agent in the adhesive composition (I) is, for example, 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight or more, or 3 parts by weight or more with respect to 100 parts by weight of the polymer (A). , and may be 4 parts by weight or more.
  • the upper limit of the amount is, for example, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, less than 10 parts by weight, 9 parts by weight or less, 8 parts by weight or less, with respect to 100 parts by weight of the polymer (A). It may be 7 parts by weight or less, or even 6 parts by weight or less.
  • the adhesive composition (I) further contains a radical scavenger.
  • radical scavengers are various antioxidants such as hindered phenols, hindered amines, phosphites, phenols, thioethers, and blends of these.
  • Types of antioxidants are, for example, radical chain inhibitors and peroxide decomposers.
  • the antioxidant may be at least one selected from hindered phenol, hindered amine and phosphite.
  • the hindered phenol-based antioxidant may have a structure in which a tertiary butyl group is bonded to at least one carbon atom adjacent to the carbon atom on the aromatic ring to which the phenol OH group is bonded.
  • Examples of hindered phenolic antioxidants are dibutylhydroxytoluene (BHT); rganox 1135, Irganox 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 259 , Irganox3114, Irganox565 and Irganox295 (all trade names, manufactured by BASF).
  • BHT dibutylhydroxytoluene
  • the hindered amine antioxidant may have at least one hindered piperidine group in one molecule.
  • hindered amine antioxidants are Adekastab LA-63, Adekastab LA-63P, Adekastab LA-52 and Adekastab LA-57 (all trade names, manufactured by ADEKA).
  • phosphite-based antioxidants include triphenylphosphite, diphenylisodecylphosphite and phenyldiisodecylphosphite; and Adekastab 2112, Adekastab 2112RG, Adekastab 1178 and Adekastab 3010 (all trade names, manufactured by ADEKA). is.
  • phenolic antioxidants are monophenolic antioxidants, bisphenolic antioxidants and polymeric phenolic antioxidants.
  • monophenolic antioxidants are 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin- ⁇ -(3 , 5-di-t-butyl-4-hydroxyphenyl)propionate.
  • bisphenol antioxidants examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'- thiobis(3-methyl-6-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[ ⁇ -(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane.
  • polymeric phenolic antioxidants are 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane, Bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3',5'-di-t-butyl- 4′-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione and tocopherol.
  • thioether-based antioxidants examples include Adekastab AO-503 and Adekastab AO-26 (both trade names, manufactured by ADEKA).
  • the molecular weight of the radical scavenger may be 1000 or less, 900 or less, 850 or less, 800 or less, 700 or less, 600 or less, 500 or less, 450 or less, or even 400 or less. good.
  • the lower limit of the molecular weight is, for example, 100 or more. According to studies by the present inventors, a radical scavenger having a molecular weight within the above range is particularly suitable for suppressing the amount of radicals generated in a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (I).
  • the radical scavenger eg, antioxidant
  • the radical scavenger may be liquid at room temperature (25°C).
  • the content of the radical scavenger in the adhesive composition (I) is, for example, 0.1 parts by weight or more, 0.2 parts by weight or more, or 0.3 parts by weight or more with respect to 100 parts by weight of the polymer (A). , 0.4 parts by weight or more, or even 0.5 parts by weight or more.
  • the upper limit of the amount is, for example, 15 parts by weight or less, 10 parts by weight or less, 7 parts by weight or less, 5 parts by weight or less, less than 5 parts by weight, 4 parts by weight or less, with respect to 100 parts by weight of the polymer (A). It may be 3 parts by weight or less, or even 2 parts by weight or less.
  • the pressure-sensitive adhesive composition (I) may further contain materials other than the polymer (A), the conductive agent and the radical scavenger.
  • materials are additives.
  • additives include cross-linking agents, silane coupling agents, coloring agents such as pigments and dyes, UV absorbers, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, rework improvers, softening agents, agents, polymerization inhibitors, rust preventives, inorganic fillers, organic fillers, powders such as metal powders, particles, and foils.
  • Additives can be blended in a total amount of, for example, 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 3 parts by weight or less per 100 parts by weight of the polymer (A).
  • cross-linking agents are organic cross-linking agents and multifunctional metal chelates.
  • organic cross-linking agents are isocyanate cross-linking agents, peroxide cross-linking agents, epoxy cross-linking agents and imine cross-linking agents.
  • the organic cross-linking agent and polyfunctional metal chelate can be used for both the solvent-type and active energy ray-curable pressure-sensitive adhesive compositions (I).
  • the cross-linking agent is preferably a peroxide-based cross-linking agent or an isocyanate-based cross-linking agent.
  • a peroxide-based cross-linking agent and an isocyanate-based cross-linking agent may be used in combination.
  • the pressure-sensitive adhesive composition (I) may contain an isocyanate cross-linking agent, may contain a peroxide cross-linking agent, or may contain both an isocyanate cross-linking agent and a peroxide cross-linking agent. good too.
  • isocyanate cross-linking agents include aromatic isocyanate compounds such as tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate and polymethylene polyphenyl isocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, hydrogenated diphenylmethane diisocyanate and alicyclic isocyanate compounds such as isophorone diisocyanate; and aliphatic isocyanate compounds such as butylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate.
  • aromatic isocyanate compounds such as tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate and polymethylene polyphenyl isocyanate
  • the isocyanate-based cross-linking agent is a compound (adduct) obtained by adding the above-mentioned isocyanate compound to a polyhydric alcohol compound such as trimethylolpropane; A compound subjected to an addition reaction with a polyol; a derivative of the isocyanate compound such as an isocyanurate compound may be used.
  • derivatives include trimethylolpropane/tolylene diisocyanate trimer adduct (eg, Tosoh Corporation, Coronate L), trimethylolpropane/hexamethylene diisocyanate trimer adduct (eg, Tosoh Corporation, Coronate HL ), an isocyanurate of hexamethylene diisocyanate (eg, Coronate HX manufactured by Tosoh Corporation).
  • trimethylolpropane/tolylene diisocyanate trimer adduct eg, Tosoh Corporation, Coronate L
  • trimethylolpropane/hexamethylene diisocyanate trimer adduct eg, Tosoh Corporation, Coronate HL
  • an isocyanurate of hexamethylene diisocyanate eg, Coronate HX manufactured by Tosoh Corporation.
  • the amount thereof is, for example, 0.1 to 10 parts by weight and 0.2 to 5 parts by weight with respect to 100 parts by weight of the polymer (A). , 0.25 to 3 parts by weight, 0.3 to 1 part by weight, or even 0.3 to 0.5 parts by weight.
  • peroxide-based cross-linking agents examples include di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy Neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -ethylhexanoate, di(4-methylbenzoyl)peroxide, benzoylperoxide, t-butylperoxyisobutyrate, 1,1-di(t-hexylperoxy)cyclohexane.
  • the peroxide-based cross-linking agent may benzoyl peroxide because of its excellent cross-linking reaction efficiency.
  • the amount thereof is, for example, 0.005 to 5 parts by weight, and 0.01 to 3 parts by weight, relative to 100 parts by weight of the polymer (A). parts by weight, 0.05 to 2 parts by weight, 0.07 to 1 part by weight, 0.07 to 0.5 parts by weight, 0.07 to 0.3 parts by weight, further 0.07 to 0.2 parts by weight may be
  • silane coupling agents are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Epoxy group-containing silane coupling agents such as trimethoxysilane; 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3 -Dimethylbutylidene)propylamine, amino group-containing silane coupling agents such as N-phenyl- ⁇ -aminopropyltrimethoxysilane; ) acrylic group-containing silane coupling agents; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane.
  • the amount is, for example, 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, relative to 100 parts by weight of the polymer (A). It may be 0.5 parts by weight or less, 0.2 parts by weight or less, 0.1 parts by weight or less, or even 0.05 parts by weight or less.
  • the adhesive composition (I) may not contain a silane coupling agent.
  • Types of the pressure-sensitive adhesive composition (I) are, for example, emulsion type, solvent type (solution type), active energy ray-curable type (light-curing type), and heat-melting type (hot-melt type).
  • the PSA composition (I) may be solvent-based, active energy ray-curable, or solvent-based.
  • the solvent-based pressure-sensitive adhesive composition (I) may not contain a photocuring agent such as an ultraviolet curing agent.
  • the adhesive composition (I) can be used, for example, in optical laminates.
  • the pressure-sensitive adhesive composition (I) may be used for optical laminates.
  • the use of the pressure-sensitive adhesive composition (I) is not limited to the above examples.
  • the pressure-sensitive adhesive composition (II) of this embodiment contains the polymer (B).
  • the pressure-sensitive adhesive composition (II) may contain the polymer (B) as a main component.
  • "Principal component" has the meaning given above.
  • the polymer (B) has a dielectric constant of 5.0 or more at a frequency of 100 kHz.
  • the pressure-sensitive adhesive sheet contains 1000 ppm or less of formic acid on a mass basis. When the content of formic acid is as low as this, the optical layered body is less likely to be colored even after being subjected to a high-temperature environment.
  • formic acid on the polymer is polyene conversion of PVA contained in the polarizer. It is presumed that exposed OH groups in PVA are protonated by formic acid, and dehydration condensation reactions proceed. In addition, it is considered that the progress of the above-mentioned reaction due to formic acid in the optical film at high temperatures, not limited to PVA in the polarizer, can bring about changes in optical properties such as coloration of the optical film.
  • Optical laminate members in which formic acid can be generated include adhesive sheets, polarizing plates, OCA (optical clear adhesive) layers, and protective films.
  • the OCA layer is, for example, an adhesive layer formed on the surface of the polarizing plate opposite to the adhesive sheet in the optical laminate. In other words, the polarizing plate may be arranged between the adhesive sheet and the OCA layer.
  • the OCA layer is a layer containing an optically transparent adhesive.
  • the material of the adhesive contained in the OCA layer is not particularly limited. include.
  • a protective film is, for example, a film formed on the surface of a polarizer. Details of the protective film will be described later.
  • formic acid can be generated by hydrolysis of the protective film.
  • the content of formic acid contained in the pressure-sensitive adhesive sheet is, on a mass basis, 800 ppm or less, 500 ppm or less, 200 ppm or less, 100 ppm or less, It may be 70 ppm or less, 50 ppm or less, 25 ppm or less, 5 ppm or less, 2.5 ppm or less, or even less than 2.5 ppm.
  • the lower limit of the formic acid content is not particularly limited, and is, for example, 0 ppm or more on a mass basis.
  • the dielectric constant P of the polymer (B) at a frequency of 100 kHz is 5.0 or more.
  • the dielectric constant P is as high as this, even when an optical film with a low dielectric constant, especially a polarizing film and an adhesive sheet are used in combination, the sensitivity of the touch sensor included in the image display device is suppressed from deteriorating. tend to be able to
  • the dielectric constant P can be measured by the following method. First, a test piece with a thickness of 30 ⁇ m is produced, which is composed only of polymer. Regarding this test piece, the dielectric constant at a frequency of 100 kHz is measured by the automatic balancing bridge method (transformer bridge method) in accordance with JIS K6911:1995. The obtained measured value can be regarded as the dielectric constant P.
  • the details of the conditions for measuring the dielectric constant are as follows.
  • Measurement method Capacitance method (Apparatus: 4294A Precision Impedance Analyzer manufactured by Agilent Technologies) Electrode configuration: Aluminum plate with a diameter of 12.1 mm and a thickness of 0.5 mm Counter electrode: 3 oz copper plate Measurement environment: 23 ⁇ 1° C., 52 ⁇ 1% RH
  • the dielectric constant P may be 6.0 or more, 6.5 or more, 6.8 or more, 7.0 or more, 7.3 or more, or even 7.5 or more.
  • the upper limit of the dielectric constant P is not particularly limited, and is, for example, 10.0 or less.
  • the polymer (B) contained in the adhesive composition (II) may be, for example, the polymer (A) described in Embodiment 1.
  • the adhesive composition (II) may further contain a radical scavenger and a peroxide cross-linking agent.
  • the radical scavenger may be an antioxidant.
  • the radical scavenger for example, the radical scavenger described in Embodiment 1, that is, various antioxidants can be used.
  • the molecular weight of the radical scavenger eg antioxidant
  • the upper limit of the molecular weight is, for example, 1500 or less.
  • a radical scavenger having a molecular weight within the above range is particularly suitable for suppressing the amount of formic acid generated in a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (II).
  • the preferred blending amount of the radical scavenger in the pressure-sensitive adhesive composition (II) is as described in the first embodiment.
  • the peroxide-based cross-linking agent for example, the peroxide-based cross-linking agent described in Embodiment 1 can be used.
  • the preferred blending amount of the peroxide-based cross-linking agent in the pressure-sensitive adhesive composition (II) is as described in the first embodiment. Excessive blending of the peroxide-based cross-linking agent can promote polyenization of PVA contained in the polarizer. Polyenation may involve reactants of reactions involving peroxide-based crosslinkers, such as benzoic acid.
  • the pressure-sensitive adhesive composition (II) contains a peroxide-based cross-linking agent, it is particularly suitable for suppressing coloration if the blending amount is within the above range.
  • the pressure-sensitive adhesive composition (II) may further contain an isocyanate-based cross-linking agent in addition to the peroxide-based cross-linking agent.
  • an isocyanate-based cross-linking agent examples are as described in the first embodiment.
  • the preferred blending amount of the isocyanate-based cross-linking agent in the pressure-sensitive adhesive composition (II) is also as described in the first embodiment.
  • the adhesive composition (II) may further contain materials other than the polymer (B), the radical scavenger and the peroxide-based cross-linking agent.
  • conductive agents antistatic agents
  • the pressure-sensitive adhesive composition (II) may contain one or more conductive agents.
  • conductive agents are ionic compounds such as salts.
  • the ionic compound may be an ionic liquid that is liquid at normal temperature (25° C.).
  • the conductive agent described in Embodiment 1 can be used.
  • Examples of conductive agents are ionic compounds such as salts.
  • Examples of ionic compounds are inorganic and organic cation salts.
  • the conductive agent may contain an organic cationic salt.
  • the conductive agent may be an organic cationic salt.
  • the blending amount of the conductive agent in the adhesive composition (II) is as described in the first embodiment.
  • the adhesive composition (II) may further contain materials other than the polymer (B), radical scavenger, peroxide cross-linking agent and conductive agent. Examples of such materials are additives. Examples of additives are as described in the first embodiment.
  • Types of the adhesive composition (II) are, for example, emulsion type, solvent type (solution type), active energy ray-curable type (light-curing type), and heat-melting type (hot-melt type).
  • the PSA composition (II) may be solvent-based, active energy ray-curable, or solvent-based.
  • the solvent-based pressure-sensitive adhesive composition (II) may not contain a photocuring agent such as an ultraviolet curing agent.
  • the adhesive composition (II) can be used, for example, in optical laminates.
  • the pressure-sensitive adhesive composition (II) may be used for optical laminates.
  • the use of the pressure-sensitive adhesive composition (II) is not limited to the above examples.
  • the content of acetic acid contained in the adhesive sheet may be low.
  • the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (II) may contain 50 ppm or less of acetic acid on a mass basis.
  • the content of acetic acid is as low as this, the optical layered body is less likely to be colored even after being subjected to a high-temperature environment.
  • the content of acetic acid contained in the pressure-sensitive adhesive sheet is, on a mass basis, 30 ppm or less, 20 ppm or less, 15 ppm or less, 10 ppm or less, It may be 7 ppm or less, 5 ppm or less, 3 ppm or less, 2.8 ppm or less, or even less than 2.5 ppm.
  • the lower limit of the acetic acid content is not particularly limited, and is, for example, 0 ppm or more on a mass basis.
  • the pressure-sensitive adhesive composition (III) of this embodiment contains a polymer (D) having a polyether structure as a main component, and further contains a conductive agent. According to the studies of the present inventors, the polyether structure in the polymer (D) can promote the ionization of the conductive agent contained in the adhesive composition (III), and the ionization of the conductive agent It can contribute to the reduction of the surface resistance value of the pressure-sensitive adhesive sheet formed from the material.
  • Polyenation of PVA is a phenomenon in which multiple carbon-carbon unsaturated bonds occur in the main chain of PVA and the conjugated structure extends. is red).
  • the polyene formation of PVA can be explained as a phenomenon in which the cross-linked structure with boric acid disappears due to hydrolysis caused by heat, exposing many terminal OH groups of PVA, and the dehydration condensation reaction between the exposed OH groups proceeds. Moreover, this dehydration condensation reaction is presumed to be a radical reaction.
  • progress of radical reaction in the optical film at high temperature not limited to PVA in the polarizer, can cause changes in optical properties such as coloration to the optical film.
  • Radicals generated due to the polyether structure include radicals generated with the involvement of other components (e.g., polymerization initiators, cross-linking agents, antioxidants, etc.) starting from the radicals generated from the polyether structure. can be included.
  • the formed pressure-sensitive adhesive sheet has a radical generation rate RG 10 limited to 1.5 ⁇ 10 14 /g or less.
  • the radical generation amount RG 10 is the radical generation amount of the pressure-sensitive adhesive sheet when heated at 105° C. for 10 minutes, evaluated by an electron spin resonance method (hereinafter referred to as ESR).
  • ESR electron spin resonance method
  • Radical generation amount RG 10 is 1.3 ⁇ 10 14 /g or less, 1.0 ⁇ 10 14 /g or less, 9.0 ⁇ 10 13 /g or less, further 8.0 ⁇ 10 13 /g g or less.
  • the lower limit of the radical generation amount RG 10 is not limited, it is, for example, 1.0 ⁇ 10 10 /g or more.
  • the radical generation amount RG 20 in the formed pressure-sensitive adhesive sheet is, for example, 2.5 ⁇ 10 14 / g or less, 2.0 ⁇ 10 14 / g or less, 1.5 ⁇ 10 14 pieces/g or less, 1.2 ⁇ 10 14 pieces/g or less, or 1.0 ⁇ 10 14 pieces/g or less.
  • the lower limit of the radical generation amount RG 20 is not limited, it is, for example, 1.0 ⁇ 10 10 /g or more.
  • the radical generation amount RG 20 is the radical generation amount of the pressure-sensitive adhesive sheet when heated at 105° C. for 20 minutes, evaluated by ESR.
  • the pressure-sensitive adhesive composition (III) having a radical generation amount RG 20 in the pressure-sensitive adhesive sheet within the above range is particularly suitable for use in optical laminates under high-temperature environments.
  • the ratio of RG 20 to radical generation amount RG 10 is, for example, 1.7 or less, 1.5 or less, less than 1.5, 1.4 or less, 1.4. It may be less than or even 1.3 or less.
  • the lower limit of RG20 / RG10 is, for example, 0.8 or more.
  • the pressure-sensitive adhesive composition (III) having RG 20 /RG 10 within the above range when formed into a pressure-sensitive adhesive sheet is particularly suitable for use in optical laminates under environments where high temperatures should be considered.
  • the radical generation amount RG 30 in the formed pressure-sensitive adhesive sheet is, for example, 3.0 ⁇ 10 14 / g or less, 2.5 ⁇ 10 14 / g or less, 2.0 ⁇ 10 14 pieces/g or less, 1.7 ⁇ 10 14 pieces/g or less, 1.5 ⁇ 10 14 pieces/g or less, 1.4 ⁇ 10 14 pieces/g or less, 1.3 It may be 1.2 ⁇ 10 14 pieces/g or less, or 1.2 ⁇ 10 14 pieces/g or less.
  • the lower limit of the radical generation amount RG 30 is not limited, it is, for example, 1.0 ⁇ 10 10 /g or more.
  • the radical generation amount RG 30 is the radical generation amount of the pressure-sensitive adhesive sheet when heated at 105° C. for 30 minutes, evaluated by ESR.
  • the pressure-sensitive adhesive composition (I) having the radical generation amount RG 30 in the pressure-sensitive adhesive sheet within the above range is particularly suitable for use in optical laminates under high-temperature environments.
  • the ratio of RG 30 to radical generation amount RG 10 is, for example, 2.2 or less, 2.0 or less, 1.9 or less, less than 1.9, 1.7. 1.6 or less, or even 1.5 or less.
  • the lower limit of RG30 / RG10 is, for example, 0.8 or more.
  • the pressure-sensitive adhesive composition (I) having RG 30 /RG 10 in the above range when formed into a pressure-sensitive adhesive sheet is particularly suitable for use in optical laminates under environments where high temperatures should be considered.
  • the amount of generated radicals for the pressure-sensitive adhesive composition (III) can be evaluated as follows. First, a part of the adhesive sheet formed from the adhesive composition to be evaluated is collected, packed in the tip portion of the ESR sample tube, and the sample tube is sealed. The amount of the part contained in the sample tube is about 50 mg.
  • a pressure-sensitive adhesive sheet is formed from the pressure-sensitive adhesive composition based on the method for producing a pressure-sensitive adhesive sheet described later, and the formed pressure-sensitive adhesive Take a portion of the sheet.
  • the sample tube was set in the ESR device and heated from room temperature (25 ⁇ 5°C) to 105°C at a heating rate of 30°C/min. , and 30 minutes, ESR measurements are performed.
  • the amount of radical generation can be quantitatively calculated from the signal intensity of the ESR signal observed by the measurement.
  • the ESR signal corresponding to the generated radicals can be selected based on the signal's g-value (the center position of the signal) and the splitting width.
  • ESR signals corresponding to radicals may be looked for by comparing them with profiles obtained by performing ESR measurements without heating.
  • the ESR signal corresponding to radicals may be a signal of radicals generated with the involvement of other components starting from radicals generated from the polyether structure.
  • the strongest signal can be selected from among the ESR signals corresponding to radicals. It is well known to those skilled in the art that ESR enables quantitative evaluation of radicals contained in substances. The amount of radicals generated in the pressure-sensitive adhesive sheet (cured product of the pressure-sensitive adhesive composition) can also be evaluated in detail according to known methods.
  • the amount of radicals generated in the adhesive composition is, for example, the composition of the adhesive composition, the composition and content of the polymer (D), the type and content of the conductive agent, the adhesive composition other than the polymer (D) and the conductive agent. It may change depending on the type, content and combination of materials blended in the adhesive sheet, the degree of curing of the adhesive sheet, and the like.
  • the degree of curing of the pressure-sensitive adhesive sheet for example, in the case of a solvent-based pressure-sensitive adhesive composition (III), the solid content concentration and viscosity of the solution containing the pressure-sensitive adhesive composition, the conditions for forming a coating film on the base film , conditions for drying the coating film, and when the device for drying the coating film (heating furnace, etc.) is a non-sealed type, the temperature and humidity of the atmosphere in which the device is placed may change.
  • a solvent-based pressure-sensitive adhesive composition (III) the solid content concentration and viscosity of the solution containing the pressure-sensitive adhesive composition, the conditions for forming a coating film on the base film , conditions for drying the coating film, and when the device for drying the coating film (heating furnace, etc.) is a non-sealed type, the temperature and humidity of the atmosphere in which the device is placed may change.
  • the formed pressure-sensitive adhesive sheet has a surface resistance value of 1 ⁇ 10 10 ⁇ / ⁇ or less.
  • the surface resistance value is 5 ⁇ 10 9 ⁇ / ⁇ or less, 1 ⁇ 10 9 ⁇ / ⁇ or less, 8 ⁇ 10 8 ⁇ / ⁇ or less, 6 ⁇ 10 8 ⁇ / ⁇ or less, 5 ⁇ 10 8 ⁇ / ⁇ or less, It may be 4 ⁇ 10 8 ⁇ / ⁇ or less, 3 ⁇ 10 8 ⁇ / ⁇ or less, or even 2 ⁇ 10 8 ⁇ / ⁇ or less.
  • the lower limit of the surface resistance value is, for example, 1 ⁇ 10 6 ⁇ / ⁇ or more, and may be 1 ⁇ 10 7 ⁇ / ⁇ or more.
  • the pressure-sensitive adhesive composition (III) having a surface resistance value within the above range when formed into a pressure-sensitive adhesive sheet is suitable for use in an environment where static electricity is likely to occur, such as inside a vehicle.
  • polymer (D) examples are (meth)acrylic polymers, urethane polymers, silicone polymers and rubber polymers.
  • the polymer (D) is not limited to the above examples as long as it has a polyether structure.
  • Polymer (D) is preferably a (meth)acrylic polymer.
  • the pressure-sensitive adhesive composition (III) may contain a (meth)acrylic polymer as a main component.
  • the adhesive composition (III) may be an acrylic adhesive composition.
  • Principal component has the meaning given above.
  • the polymer (D) may be the polymer (A) described in the first embodiment.
  • the adhesive composition (III) further contains a conductive agent (antistatic agent).
  • the pressure-sensitive adhesive composition (III) may contain one or more conductive agents.
  • conductive agents are ionic compounds such as salts.
  • the ionic compound may be an ionic liquid that is liquid at normal temperature (25° C.). Details of the conductive agent are as described in the first embodiment.
  • the adhesive composition (III) may further contain materials other than the polymer (D) and the conductive agent.
  • materials are additives.
  • additives include cross-linking agents, silane coupling agents, coloring agents such as pigments and dyes, UV absorbers, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, rework improvers, softening agents, agents, antioxidants, anti-aging agents, light stabilizers, polymerization inhibitors, rust inhibitors, inorganic fillers, organic fillers, powders such as metal powders, particles, and foils. Details of the additive are as described in the first embodiment.
  • Types of the pressure-sensitive adhesive composition (III) are, for example, emulsion type, solvent type (solution type), active energy ray-curable type (light-curing type), and heat-melting type (hot-melt type).
  • the PSA composition (III) may be solvent-based, active energy ray-curable, or solvent-based.
  • the solvent-based pressure-sensitive adhesive composition (III) may not contain a photocuring agent such as an ultraviolet curing agent.
  • the adhesive composition (III) can be used, for example, in optical laminates.
  • the pressure-sensitive adhesive composition (III) may be used for optical laminates.
  • the use of the pressure-sensitive adhesive composition (III) is not limited to the above examples.
  • a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (III) may have a radical generation amount RG 10 within the range described above.
  • the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (III) has at least radical generation amounts RG 20 and RG 30 within the ranges described above, and radical generation amount ratios RG 20 /RG 10 and RG 30 /RG 10 . It can have one property.
  • the pressure-sensitive adhesive sheet 1 in FIG. 1 is a sheet formed from the pressure-sensitive adhesive composition (I), a sheet formed from the pressure-sensitive adhesive composition (II), or a sheet formed from the pressure-sensitive adhesive composition (III).
  • the pressure-sensitive adhesive sheet 1 When the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (I), the pressure-sensitive adhesive sheet 1 may have a surface resistance value within the range described above in the description of the pressure-sensitive adhesive composition (I). When the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (II), the pressure-sensitive adhesive sheet may contain formic acid within the range described above in the description of the pressure-sensitive adhesive composition (II). When the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (III), the pressure-sensitive adhesive sheet 1 may have a radical generation amount RG 10 within the range described above in the description of the pressure-sensitive adhesive composition (III).
  • the pressure-sensitive adhesive sheet 1 when the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (III), the pressure-sensitive adhesive sheet 1 has radical generation amounts RG 20 and RG 30 within the ranges described above in the description of the pressure-sensitive adhesive composition (III), and radical generation It may have at least one characteristic selected from the quantitative ratios RG20 / RG10 and RG30 / RG10 .
  • the adhesive sheet 1 can be formed from the adhesive composition (I) or the adhesive composition (II) by the following method.
  • the method for forming the PSA sheet 1 from the PSA composition (I) is described below, and the PSA sheet 1 is formed by the same method for the PSA composition (II) and the PSA composition (III). can.
  • the pressure-sensitive adhesive composition (I) or a mixture of the pressure-sensitive adhesive composition (I) and a solvent is applied to a base film to form a coating film, and the formed coating film is dried. An adhesive sheet 1 is formed.
  • the pressure-sensitive adhesive composition (I) is thermally cured by heat during drying.
  • the active energy ray-curable type for example, a monomer (group) that becomes the polymer (A) by polymerization, and, if necessary, a partial polymer of the monomer (group), a polymerization initiator , an additive, a solvent, and the like are applied to a substrate film, and the formed coating film is irradiated with an active energy ray to form an adhesive sheet 1 .
  • the solvent may be removed by drying the coating film before irradiation with the active energy ray.
  • the base film may be a film (release liner) whose coating surface has been subjected to a release treatment.
  • the adhesive sheet 1 formed on the base film can be transferred to any layer.
  • the base film may be an optical film such as a polarizing plate, in which case an optical laminate including the adhesive sheet 1 and the optical film is obtained.
  • Coating is, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, extrusion coating using a die coater, or the like. can be implemented by
  • the drying temperature after coating is, for example, 40 to 200°C.
  • the drying time is, for example, 5 seconds to 20 minutes, and may be 5 seconds to 10 minutes, or even 10 seconds to 5 minutes.
  • the drying temperature and drying time when drying after coating may be within the above ranges.
  • composition and mixture to be applied to the base film preferably have a viscosity suitable for handling and coating. Therefore, for the active energy ray-curable type, the mixture to be applied preferably contains a partial polymer of the monomer (group).
  • the thickness of the adhesive sheet 1 is, for example, 2 ⁇ m to 55 ⁇ m, and may be 2 ⁇ m to 30 ⁇ m, 5 ⁇ m to 25 ⁇ m, or even 10 ⁇ m to 20 ⁇ m.
  • the adhesive sheet 1 can be used, for example, in an optical laminate.
  • the pressure-sensitive adhesive sheet 1 may be used for optical laminates.
  • the application of the adhesive sheet 1 is not limited to the above examples.
  • the optical laminate 10A of FIG. 2 includes the adhesive sheet 1 and an optical film.
  • the optical film in FIG. 2 is the polarizing plate 2 .
  • the polarizing plate 2 contains a polarizer.
  • the adhesive sheet 1 and the polarizing plate 2 are laminated together.
  • the optical layered body 10A can be attached to an object (for example, an image display panel) with the adhesive sheet 1 interposed therebetween.
  • the optical laminate 10A can be used as an optical film with an adhesive sheet, more specifically, as a polarizing plate with an adhesive sheet.
  • Examples of optical films other than the polarizing plate 2 are retardation films and laminated films containing polarizing plates and/or retardation films.
  • the optical film may be a circular polarizer. However, the optical film is not limited to the above examples.
  • the optical film may include a film made of glass.
  • the polarizing plate 2 is typically a laminate containing a polarizer and a protective film (transparent protective film).
  • the protective film is arranged, for example, in contact with the main surface of the polarizer (the surface with the widest area).
  • a polarizer may be placed between two protective films.
  • the optical laminate 10A may further include a protective film, and the protective film may be arranged on at least one surface of the polarizer.
  • the polarizer is not particularly limited.
  • a uniaxially stretched film obtained by adsorbing a dichroic substance such as a dye; and a polyene-based oriented film such as dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride.
  • a polarizer typically consists of a polyvinyl alcohol film (the polyvinyl alcohol film includes an ethylene/vinyl acetate copolymer-based partially saponified film) and a dichroic substance such as iodine.
  • the thickness of the polarizer is not particularly limited.
  • the lower limit of the thickness of the polarizer is not particularly limited.
  • a thin polarizer (for example, a thickness of 20 ⁇ m or less) is suppressed in dimensional change, and can contribute to an improvement in the durability of the optical layered body, especially at high temperatures.
  • thermoplastic resin that is excellent in transparency, mechanical strength, thermal stability, water barrier properties, isotropy, etc.
  • thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, cyclic Polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof can be used.
  • cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, cyclic Polyolefin resins (norbornene-based resins), polyarylate resins, polys
  • the material of the protective film may be a thermosetting resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, or silicone, or an ultraviolet curable resin.
  • a protective film made of a thermoplastic resin is attached to one main surface of the polarizer via an adhesive, and a thermosetting resin or ultraviolet curable resin is attached to the other main surface of the polarizer.
  • a protective film made of mold resin may be attached.
  • the protective film may contain one or more optional additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants and the like.
  • the moisture permeability of the protective film is not particularly limited, and may be 200 g/(m 2 ⁇ day) or less, or may be 50 g/(m 2 ⁇ day) or less.
  • moisture in the air can be prevented from entering the inside of the polarizing plate 2, and a change in the moisture content of the polarizing plate 2 can be suppressed.
  • a protective film whose moisture permeability is limited to the above range, when placed between the adhesive sheet 1 and the polarizer, can contribute to inhibition of movement of radicals from the adhesive sheet 1 at high temperatures. .
  • Examples of materials for forming protective films with low moisture permeability include polyester-based polymers, polycarbonate-based polymers, arylate-based polymers, amide-based polymers, olefin-based polymers, cyclic olefin-based polymers, (meth)acrylic-based polymers, and these mixtures.
  • the moisture permeability of the protective film can be measured by the following method according to JIS Z0208:1976 moisture permeability test (cup method).
  • the protective film is cut to a diameter of 60 mm to prepare a measurement sample.
  • a measurement sample is set in a moisture-permeable cup in which about 15 g of calcium chloride is placed.
  • This moisture permeable cup is placed in a constant temperature machine set at a temperature of 40° C. and a humidity of 92% RH, and left for 24 hours to conduct a moisture permeability test.
  • the moisture permeability of the protective film can be determined.
  • the thickness of the protective film can be determined as appropriate, it is generally about 10 to 200 ⁇ m in terms of strength, workability such as handleability, and thinness.
  • the polarizer and protective film are usually in close contact via a water-based adhesive or the like.
  • water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latexes, water-based polyurethanes, and water-based polyesters.
  • adhesives other than the adhesives described above include ultraviolet curing adhesives, electron beam curing adhesives, and the like. Electron beam curing adhesives for polarizing plates exhibit suitable adhesion to various protective films.
  • the adhesive may contain a metallic compound filler.
  • a retardation film or the like can be formed on the polarizer instead of the protective film. It is also possible to provide another protective film, a retardation film, etc. on the protective film.
  • a hard coat layer may be provided on the surface facing the surface adhered to the polarizer, and a treatment for the purpose of antireflection, antisticking, diffusion, antiglare, etc. may be applied. .
  • the light transmittance in the thickness direction of the optical layered body 10A before the heating test is defined as Tsa 0
  • Tsa 500 the light transmittance in the thickness direction of the optical layered body 10A after heating the optical layered body 10A at 95°C for 500 hours.
  • the light transmittance in the thickness direction of the optical layered body 10A before the heating test is defined as Tsb 0
  • Tsb 500 the light transmittance in the thickness direction of the optical layered body 10A after heating the optical layered body 10A at 105°C for 500 hours.
  • ⁇ Tsb may satisfy ⁇ Tsb>0%.
  • FIG. 3 Another example of the optical laminate of this embodiment is shown in FIG.
  • the optical layered body 10B of FIG. 3 has a layered structure in which a release liner 3, an adhesive sheet 1 and a polarizing plate 2 are layered in this order. By peeling off the release liner 3, the optical laminate 10B can be used as a polarizing plate with an adhesive sheet.
  • a release liner 3 By peeling off the release liner 3, the optical laminate 10B can be used as a polarizing plate with an adhesive sheet.
  • Materials constituting the release liner 3 include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films; porous materials such as paper, cloth, and nonwoven fabric; nets, foam sheets, metal foils, and laminates thereof.
  • plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
  • porous materials such as paper, cloth, and nonwoven fabric
  • nets, foam sheets, metal foils, and laminates thereof are preferably used because of its excellent surface smoothness.
  • the plastic film is not particularly limited as long as it is a film capable of protecting the adhesive sheet 1.
  • examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, and vinyl chloride copolymer. film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film and the like.
  • the thickness of the release liner 3 is usually about 5-200 ⁇ m, preferably about 5-100 ⁇ m.
  • the release liner 3 may be subjected, if necessary, to silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, release and antifouling treatment using silica powder, etc., coating type, kneading type, vapor deposition.
  • the mold may be subjected to antistatic treatment.
  • a release treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc.
  • the base film used when producing the adhesive sheet 1 may be used as the release liner 3.
  • the optical laminate 10C of FIG. 4 has a laminated structure in which a release liner 3, an adhesive sheet 1, a retardation film 5, an interlayer adhesive 4 and a polarizing plate 2 are laminated in this order. After peeling off the release liner 3, the optical layered body 10C can be used by attaching it to, for example, an image display cell.
  • the retardation film 5 a film obtained by stretching a polymer film or a film obtained by aligning and fixing a liquid crystal material can be used.
  • the retardation film 5 has birefringence in the plane and/or in the thickness direction, for example.
  • the retardation film 5 includes an antireflection retardation film (see JP 2012-133303 [0221], [0222], [0228]), a viewing angle compensation retardation film (JP 2012-133303 [ 0225], [0226]), an oblique orientation retardation film for viewing angle compensation (see JP-A-2012-133303 [0227]), and the like.
  • the specific configuration of the retardation film 5, such as retardation value, arrangement angle, three-dimensional birefringence, whether it is a single layer or multiple layers, is not particularly limited, and a known retardation film can be used.
  • the thickness of the retardation film 5 is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 1 to 9 ⁇ m, particularly preferably 3 to 8 ⁇ m.
  • the retardation film 5 may include, for example, a quarter-wave plate and/or a half-wave plate in which a liquid crystal material is aligned and fixed.
  • a known adhesive can be used for the interlayer adhesive 4 .
  • the adhesive sheet 1 may be used as the interlayer adhesive 4 .
  • the optical laminate 10D of FIG. 5 has a laminated structure in which a release liner 3, an adhesive sheet 1, a retardation film 5, an interlayer adhesive 4, a polarizing plate 2 and a protective film 6 are laminated in this order. After peeling off the release liner 3, the optical layered body 10D can be used by attaching it to, for example, an image display cell.
  • the protective film 6 has a function of protecting the polarizing plate 2, which is the outermost layer, during distribution and storage of the optical layered body 10D and when the optical layered body 10D is incorporated in an image display device. Moreover, it may be a protective film 6 that functions as a window to an external space when incorporated in an image display device.
  • Protective film 6 is typically a resin film.
  • the resin constituting the protective film 6 is, for example, polyester such as PET, polyolefin such as polyethylene and polypropylene, acrylic, cycloolefin, polyimide, and polyamide, preferably polyester.
  • the protective film 6 is not limited to the above example.
  • the protective film 6 may be a glass film or a laminated film containing a glass film.
  • the protective film 6 may be subjected to surface treatment such as antiglare, antireflection, and antistatic.
  • the protective film 6 may be bonded to the polarizing plate 2 with any adhesive. Bonding with the adhesive sheet 1 is also possible.
  • the optical layered body of the present embodiment can be distributed and stored, for example, as a wound body in which a strip-shaped optical layered body is wound, or as a sheet-shaped optical layered body.
  • the optical layered body of the present embodiment is suitable for use in image display devices, particularly in-vehicle displays, which are used in environments where static electricity is particularly likely to occur. Examples of in-vehicle displays include panels for car navigation systems, cluster panels, and mirror displays.
  • the cluster panel is a panel that displays the traveling speed of the vehicle, the number of revolutions of the engine, and the like.
  • an optical laminate includes an adhesive sheet and an optical film.
  • An optical film is a polarizing plate containing a polarizer. After heating the optical laminate at 105° C. for 120 hours, the polarizing plate contains 70 ppm or less formic acid on a mass basis. When the content of formic acid contained in the polarizing plate is as low as this, the optical layered body is less likely to be colored even after being subjected to a high-temperature environment.
  • the optical layered body 10E of FIG. 6 includes the adhesive sheet 7 and an optical film.
  • the optical film in FIG. 6 is the polarizing plate 8 .
  • the polarizing plate 8 contains a polarizer.
  • the adhesive sheet 7 and the polarizing plate 8 are laminated together.
  • the optical layered body 10E can be attached to an object (for example, an image display panel) via the adhesive sheet 7 .
  • the optical laminate 10E can be used as an optical film with an adhesive sheet, more specifically, as a polarizing plate with an adhesive sheet.
  • Examples of optical films other than the polarizing plate 8 are retardation films and laminated films containing polarizing plates and/or retardation films.
  • the optical film may be a circular polarizer. However, the optical film is not limited to the above examples.
  • the optical film may include a film made of glass.
  • the content of formic acid contained in the polarizing plate is 65 ppm or less, 60 ppm or less, 55 ppm or less, 50 ppm or less, 45 ppm or less, 40 ppm or less, 35 ppm or less, 30 ppm or less, and further may be 28 ppm or less.
  • the lower limit of the formic acid content is not particularly limited, and is, for example, 0 ppm or more.
  • the optical layered body tends to undergo unwanted coloring after being exposed to a high-temperature environment.
  • a possible cause of the coloring is the polyene conversion of PVA by an acid contained in the polarizing plate, such as formic acid.
  • the details of the polyene conversion of PVA with formic acid are as described in the second embodiment.
  • the adhesive sheet 7 is formed, for example, from the adhesive composition (IV).
  • the adhesive composition (IV) contains, for example, polymer (C) and a cross-linking agent.
  • the pressure-sensitive adhesive composition (IV) may contain the polymer (C) as a main component. "Principal component" has the meaning given above.
  • polymers (C) are (meth)acrylic polymers, urethane polymers, silicone polymers and rubber polymers.
  • Polymer (C) is preferably a (meth)acrylic polymer.
  • Polymer (C) can function, for example, as a base polymer for an acrylic pressure-sensitive adhesive.
  • Polymer (C) may be a polymer having a dielectric constant of 5.0 or higher at a frequency of 100 kHz.
  • the dielectric constant may be 6.0 or higher, 6.5 or higher, 6.8 or higher, 7.0 or higher, 7.3 or higher, or even 7.5 or higher.
  • the upper limit of the dielectric constant is not particularly limited, and is, for example, 10.0 or less.
  • the polymer (C) may have structural units derived from the monomers represented by formula (1) below.
  • R 1 in formula (1) is a hydrogen atom or a methyl group.
  • R 2 in formula (1) is an alkyl group that may be linear or branched, preferably a linear alkyl group. Examples of R 2 are methyl and ethyl groups.
  • n is an integer of 1-15, preferably an integer of 1-10, more preferably an integer of 1-5.
  • the content of structural units derived from the monomer represented by formula (1) is not particularly limited, and may be, for example, 15 to 99.5% by weight, or 30 to 99% by weight. 50 to 98% by weight, 50 to 80% by weight, or 50 to 70% by weight.
  • (meth)acrylic monomers having an alkyl group having 1 to 30 carbon atoms in the side chain hydroxyl group-containing monomers at least one monomer selected from the group consisting of monomers, aromatic ring-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, amide group-containing monomers and polyfunctional monomers. be done. These monomers can be used alone or in combination. Examples of these monomers are the same as the monomer (A2) described in Embodiment 1, so description thereof is omitted.
  • the content of structural units derived from monomers is not particularly limited, and may be, for example, 0.1 to 50% by weight, or may be 0.5 to 45% by weight. . In some cases, the content of structural units derived from monomers in the polymer (C) may be 1 to 5% by weight. In some cases, the content of structural units derived from monomers in the polymer (C) may be 20 to 45% by weight, 25 to 45% by weight, or 30 to 45% by weight. % by weight.
  • a (meth)acryloyl group in addition to the monomers represented by the formula (1) and the above monomers, for the purpose of improving the adhesiveness and heat resistance of the pressure-sensitive adhesive sheet, a (meth)acryloyl group, a vinyl group, or the like may be used. Other monomers having polymerizable functional groups containing unsaturated double bonds can be used. Other monomers can be used alone or in combination.
  • the content of structural units derived from the other monomer in the polymer (C) may be 30% by weight or less, and 10% by weight. It may be less than or equal to 0% by weight (not having the structural unit).
  • the weight average molecular weight (Mw) of the polymer (C) is, for example, 1 million to 3 million, may be 1.2 million to 2.5 million, or may be 1.5 million to 2.3 million.
  • Mw weight average molecular weight
  • the weight average molecular weight of the polymer (C) is 1,000,000 to 3,000,000, cracks in the pressure-sensitive adhesive sheet can be suppressed, and there is a tendency to suppress an increase in viscosity and occurrence of gelation.
  • the adhesive composition (IV) may contain the polymer (C) described above.
  • the pressure-sensitive adhesive composition (IV) may further contain a polymer other than the polymer (C).
  • the polymer (C) can be produced by known polymerization methods such as solution polymerization, radiation polymerization such as electron beam and UV, bulk polymerization, and various radical polymerizations such as emulsion polymerization.
  • the resulting polymer (C) may be any of random copolymers, block copolymers, graft copolymers and the like.
  • the method and polymerization conditions for forming the polymer (C) may be the same as the method and polymerization conditions for forming the polymer (A) described in Embodiment 1, respectively.
  • the type of solvent, the type of polymerization initiator, etc. used to form the polymer (C) can also be those described in the first embodiment.
  • cross-linking agents contained in the adhesive composition (IV) are isocyanate-based cross-linking agents and peroxide-based cross-linking agents.
  • a peroxide-based cross-linking agent and an isocyanate-based cross-linking agent may be used in combination.
  • the pressure-sensitive adhesive composition (IV) may contain an isocyanate cross-linking agent, may contain a peroxide cross-linking agent, or may contain both an isocyanate cross-linking agent and a peroxide cross-linking agent. good too.
  • the isocyanate-based cross-linking agent and the peroxide-based cross-linking agent the isocyanate-based cross-linking agent and the peroxide-based cross-linking agent described in the first embodiment can be used.
  • the adhesive sheet 7 may be an adhesive sheet formed from the adhesive composition (I) described in Embodiment 1, or an adhesive sheet formed from the adhesive composition (II) described in Embodiment 2. It may be a sheet, or it may be the pressure-sensitive adhesive composition (III) described in the third embodiment. Using these adhesive sheets as the adhesive sheet 7 in the optical layered body 10E is particularly suitable for reducing the content of formic acid contained in the polarizing plate 8. FIG.
  • the polarizing plate 8 may be the same as the polarizing plate 2 described in the fifth embodiment.
  • the polarizing plate 8 may contain a polarizer.
  • the optical layered body of this embodiment may be the same as the optical layered bodies 10A to 10D of Embodiment 5 except that the adhesive sheet 7 is used instead of the adhesive sheet 1.
  • FIG. 7 An example of the image display panel of this embodiment is shown in FIG.
  • An image display panel 11A in FIG. 7 includes an optical layered body 10A and further includes, for example, an image display cell 30A.
  • the optical laminate 10A is attached to the image display cell 30A with the adhesive sheet 1 interposed therebetween.
  • the optical laminate 10B, 10C or 10D shown in FIGS. 3 to 5 can also be used instead of the optical laminate 10A (except for the release liner 3).
  • the optical layered body 10E of FIG. 6 can also be used instead of the optical layered body 10A.
  • the image display cell 30A includes an image forming layer 32, a first transparent substrate 31 and a second transparent substrate 33, for example.
  • the image forming layer 32 is arranged, for example, between the first transparent substrate 31 and the second transparent substrate 33 and is in contact with the first transparent substrate 31 and the second transparent substrate 33 respectively.
  • the adhesive sheet 1 of the optical laminate 10A is, for example, in contact with the first transparent substrate 31 of the image display cell 30A.
  • the image forming layer 32 is, for example, a liquid crystal layer containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field.
  • a liquid crystal layer containing such liquid crystal molecules is suitable for an IPS (In-Plane-Switching) method.
  • the liquid crystal layer may be of TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, ⁇ type, VA (Vertical Alignment) type, or the like.
  • TN Transmission Nematic
  • STN Super Twisted Nematic
  • VA Very Alignment
  • an image display cell provided with a liquid crystal layer is sometimes referred to as a liquid crystal cell
  • an image display panel provided with a liquid crystal cell is sometimes referred to as a liquid crystal panel.
  • the image forming layer 32 may be an EL light emitting layer.
  • the thickness of the image forming layer 32 is, for example, 1.5 ⁇ m to 4 ⁇ m.
  • Examples of materials for the first transparent substrate 31 and the second transparent substrate 33 include glass and polymer.
  • a transparent substrate made of polymer is sometimes referred to as a polymer film.
  • Examples of polymers constituting the transparent substrate include polyethylene terephthalate, polycycloolefin, polycarbonate and the like.
  • the thickness of the transparent substrate made of glass is, for example, 0.1 mm to 1 mm.
  • the thickness of the transparent substrate made of polymer is, for example, 10 ⁇ m to 200 ⁇ m.
  • the image display cell 30A may further include layers other than the image forming layer 32, the first transparent substrate 31 and the second transparent substrate 33.
  • Other layers include, for example, a color filter, an easy-adhesion layer and a hard coat layer.
  • the color filter is arranged, for example, on the viewing side of the image forming layer 32, preferably between the first transparent substrate 31 and the adhesive sheet 1 of the optical layered body 10A.
  • the easy-adhesion layer and the hard coat layer are arranged on the surface of the first transparent substrate 31 or the second transparent substrate 33, for example.
  • the image display panel 11A may further include members other than the optical laminate 10A and the image display cell 30A.
  • the image display panel 11A may further include a conductive structure (not shown) electrically connected to the side surface of the optical laminate 10A.
  • the conductive structure may cover the entire side surface of the optical layered body 10A, or may partially cover the side surface of the optical layered body 10A.
  • the ratio of the area of the side surface of the optical layered body 10A covered with the conductive structure to the area of the entire side surface of the optical layered body 10A is, for example, 1% or more, preferably 3% or more.
  • Materials for the conductive structure include, for example, conductive pastes made of metals such as silver and gold; conductive adhesives; and other conductive materials.
  • the conductive structure may be a wiring extending from the side surface of the optical layered body 10A.
  • the image display panel 11A may further include an optical film other than the polarizing plate 2.
  • optical films include films used in image display devices such as polarizing plates, reflectors, anti-transmissive plates, viewing angle compensation films, and brightness enhancement films.
  • the image display panel 11A may include one or more of these optical films.
  • the polarizing plate is attached to the second transparent substrate 33 of the image display cell 30A, for example, via an adhesive sheet.
  • This polarizing plate has, for example, the configuration described above for the polarizing plate 2 .
  • the transmission axis (or absorption axis) of the polarizer is orthogonal to the transmission axis (or absorption axis) of the polarizer in the polarizing plate 2, for example.
  • the materials described above for the adhesive sheet 1 can be used as the material of the adhesive sheet for bonding the polarizing plate and the second transparent substrate 33 together.
  • the thickness of this adhesive sheet is not particularly limited, and is, for example, 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, still more preferably 5 to 35 ⁇ m.
  • the image display panel 11B of FIG. 8 further includes a conductive layer 40 arranged between the optical laminate 10A and the image display cell 30A.
  • the conductive layer 40 is, for example, a layer containing a conductive agent.
  • a conductive agent those mentioned above for the adhesive sheet 1 can be used.
  • the conductive agent is not limited to the above examples.
  • the conductive layer 40 is a composite of various conductive agents such as carbon nanotubes, ITO, ATO, and a conductive polymer (for example, a composite of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid). Bodies: PEDOT/PSS), etc.
  • the thickness of the conductive layer 40 is, for example, 5 nm to 180 nm.
  • the surface resistance value of the conductive layer 40 is, for example, 1.0 ⁇ 10 6 ⁇ /square to 1.0 ⁇ 10 10 ⁇ /square, preferably 1.0 ⁇ 10 8 ⁇ /square to 1.0 ⁇ 10 ⁇ /square. 9 ⁇ /square.
  • the image display panel 11C of FIG. 9 includes an image display cell 30B that further includes a touch sensing electrode portion 35. As shown in FIG. The touch sensing electrode portion 35 is arranged between the first transparent substrate 31 and the second transparent substrate 33 in the image display cell 30B.
  • the touch sensing electrode unit 35 has functions of touch sensor and touch drive.
  • the image display panel 11C is a so-called in-cell image display panel
  • the image display cell 30B is a so-called in-cell image display cell.
  • the touch sensing electrode section 35 has, for example, touch sensor electrodes 36 and touch drive electrodes 37 .
  • the touch sensor electrode 36 means a (receiving) electrode for touch detection.
  • the touch sensor electrodes 36 and the touch drive electrodes 37 can be independently formed in various patterns.
  • the touch sensor electrodes 36 and the touch drive electrodes 37 are provided independently in the X-axis direction and the Y-axis direction, respectively, and formed in a pattern in which they intersect at right angles. can be done.
  • the touch sensor electrodes 36 are arranged closer to the viewer than the touch drive electrodes 37 are.
  • the touch drive electrodes 37 may be arranged on the viewing side of the touch sensor electrodes 36 .
  • the touch sensor electrodes 36 and the touch drive electrodes 37 may be integrated.
  • the touch sensing electrode portion 35 is arranged between the image forming layer 32 and the first transparent substrate 31 (on the viewer side of the image forming layer 32).
  • the touch sensing electrode section 35 may be arranged between the image forming layer 32 and the second transparent substrate 33 (on the lighting system side of the image forming layer 32).
  • the touch sensor electrodes 36 and the touch drive electrodes 37 do not have to be in contact with each other.
  • the touch sensor electrodes 36 may be arranged between the image forming layer 32 and the first transparent substrate 31 and the touch drive electrodes 37 may be arranged between the image forming layer 32 and the second transparent substrate 33 .
  • the drive electrodes (touch drive electrodes 37 or electrodes in which the touch sensor electrodes 36 and the touch drive electrodes 37 are integrated) in the touch sensing electrode portion 35 can also serve as common electrodes for controlling the image forming layer 32 .
  • the touch sensor electrode 36 (capacitance sensor) and the touch drive electrode 37, which constitute the touch sensing electrode section 35, or an electrode formed by integrating these functions as a transparent conductive layer.
  • the material of this transparent conductive layer is not particularly limited. alloys and the like. Materials for the transparent conductive layer may be oxides of metals such as indium, tin, zinc, gallium, antimony, zirconium, and cadmium. Specific examples of this oxide include indium oxide, tin oxide, titanium oxide, cadmium oxide, and mixtures thereof.
  • the material of the transparent conductive layer may be a metal compound such as copper iodide.
  • the material of the transparent conductive layer is preferably indium oxide (ITO) containing tin oxide, tin oxide (ATO) containing antimony, or the like, and particularly preferably ITO.
  • ITO indium oxide
  • ATO tin oxide
  • the content of indium oxide in the transparent conductive layer is preferably 80 to 99% by weight and the content of tin oxide is preferably 1 to 20% by weight.
  • Electrodes constituting the touch sensing electrode portion 35 are always placed between the first transparent substrate 31 and the second transparent substrate 33. It can be formed as a transparent electrode pattern by the method. This transparent electrode pattern is electrically connected to, for example, a lead wire formed at the end of the transparent substrate. The lead-out line is connected to, for example, the controller IC.
  • the shape of the transparent electrode pattern any shape such as a comb shape, a stripe shape, a rhombus shape, or the like can be adopted according to the application.
  • the thickness of the transparent electrode pattern is, for example, 10 nm to 100 nm.
  • the width of the transparent electrode pattern is, for example, 0.1 mm to 5 mm.
  • the image display device of this embodiment includes, for example, an image display panel 11A and an illumination system.
  • the image display panels 11B and 11C of FIGS. 8 and 9 can also be used instead of the image display panel 11A.
  • the image display panel 11A is arranged, for example, on the viewing side of the lighting system.
  • the illumination system has, for example, a backlight or a reflector, and irradiates the image display panel 11A with light.
  • the image display device may be an organic EL display or a liquid crystal display. However, the image display device is not limited to this example.
  • the image display device may be an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED: Field Emission Display), or the like.
  • EL electroluminescence
  • PD plasma display
  • FED Field Emission Display
  • the image display device can be used for home appliances, vehicle applications, public information display (PID) applications, and the like, and is preferably an in-vehicle display.
  • (meth)acrylic polymer A1 A monomer containing 99 parts by weight of 2-methoxyethyl acrylate (MEA) and 1 part by weight of 4-hydroxybutyl acrylate (HBA) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser. The body mixture was charged. Furthermore, 0.1 part by weight of 2,2'-azobisisobutyronitrile (AIBN; manufactured by Kishida Chemical Co., Ltd.) as a polymerization initiator was added to 100 parts by weight of the monomer mixture together with 100 parts by weight of ethyl acetate. .
  • AIBN 2,2'-azobisisobutyronitrile
  • a solution of (meth)acrylic polymer A1 having a weight average molecular weight (Mw) of 1,800,000 and Mw/Mn of 4.4 was prepared by conducting a polymerization reaction for 8 hours while maintaining the liquid temperature in the flask at around 55°C. bottom.
  • Table 1 summarizes the monomers and amounts used to synthesize each (meth)acrylic polymer.
  • Example A1 (Meth) With respect to 100 parts by weight of the solid content of the acrylic polymer A1 solution, 0.35 parts by weight of an isocyanate cross-linking agent (Coronate L; trimethylolpropane tolylene diisocyanate manufactured by Tosoh Corporation), 5 parts by weight as a conductive agent Part of bis (trifluoromethanesulfonyl) imide lithium (LiTFSI; manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) and 1 part by weight of antioxidant (BASF Corporation, Irganox 1135, molecular weight 390) By further blending, A solution of a (meth)acrylic pressure-sensitive adhesive composition was prepared.
  • an isocyanate cross-linking agent Coronate L; trimethylolpropane tolylene diisocyanate manufactured by Tosoh Corporation
  • LiTFSI bis (trifluoromethanesulfonyl) imide lithium
  • antioxidant antioxidant
  • Example A2 Same as Example A1, except that 0.1 part by weight of a peroxide cross-linking agent (Niper BMT, manufactured by NOF CORPORATION) was further added, and the amount of the antioxidant was 0.5 parts by weight. Then, a solution of the (meth)acrylic pressure-sensitive adhesive composition of Example A2 was prepared.
  • a peroxide cross-linking agent Niper BMT, manufactured by NOF CORPORATION
  • Examples A3 to A8 As shown in Table 2 below, the isocyanate-based cross-linking agent, the peroxide-based cross-linking agent, the antioxidant and the conductive agent are blended with 100 parts by weight of the solid content of the (meth)acrylic polymer solution. to prepare solutions of the (meth)acrylic pressure-sensitive adhesive compositions of Examples A3 to A8.
  • the surface resistance value when forming a pressure-sensitive adhesive sheet was measured using the above-prepared pressure-sensitive adhesive sheet as a test sample, using Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd., at an applied voltage of 250 V, Measurement was performed under the condition of application time of 10 seconds. The measurement of the surface resistance value was carried out under an environment of a temperature of 25° C. ⁇ 5° C. and a relative humidity of 50 ⁇ 5%.
  • a polarizer having a thickness of 18 ⁇ m was obtained. Obtained.
  • a 30- ⁇ m-thick transparent protective film made of a modified acrylic polymer having a lactone ring structure was attached to one side of the polarizer with a polyvinyl alcohol-based adhesive.
  • a transparent protective film having a thickness of 47 ⁇ m which is a triacetyl cellulose film (KC4UY manufactured by Konica Minolta, KC4UY) formed with a hard coat layer (HC), was attached to the other surface of the polarizer with a polyvinyl alcohol-based adhesive.
  • a polarizing plate A was prepared by heat drying for 5 minutes in an oven set at 70°C.
  • the coloring of the optical layered body under high temperature was evaluated by the following method.
  • the produced optical layered body was cut into a size of 45 ⁇ 40 mm so that the absorption axis of the polarizer was on the long side.
  • the cut optical layered body was attached to a glass plate imitating the outermost layer of an image display panel via the adhesive sheet.
  • a glass plate imitating a front transparent member was placed on the exposed surface of the optical laminate on the polarizing plate side via an adhesive (manufactured by Nitto Denko Corporation, LUCIACS CS9821; acrylic acid monomer-free adhesive, thickness 200 ⁇ m). By sticking together, a laminate for evaluation imitating an image display device was produced.
  • the light transmittance was determined as a Y value (performing visibility correction) by a two-degree field of view XYZ system defined in JlS Z8701:1982 using a spectrophotometer (LPF-200, manufactured by Otsuka Electronics Co., Ltd.).
  • a C light source was used as the light source.
  • the measurement wavelength was 380 to 700 nm (every 10 nm).
  • the light transmittance of the laminate was measured near the center where the coloration was considered to be the most advanced.
  • the durability (high temperature durability) of the optical laminate was evaluated by the following method.
  • the produced optical layered body was fixed to the surface of a glass plate (Eagle XG manufactured by Corning) via the adhesive sheet. Fixation was performed in an atmosphere of 24° C. and 50% RH. Next, after treatment in an autoclave at 50°C and 5 atmospheres (absolute pressure) for 15 minutes, it was allowed to stand until it cooled to 24°C to stabilize the bonding of the optical laminate to the glass plate, followed by heating at 105°C. It was left in a heated atmosphere for 500 hours. After standing, the atmosphere was returned to 24° C.
  • the antistatic property of the optical layered body was evaluated by the following method (ESD test).
  • the produced optical layered body was fixed to the surface of the image display panel in FIG. 9 (surface on the viewing side) via the adhesive sheet.
  • the liquid crystal display panel to which the optical layered body was fixed was set on a backlight device, and static electricity was discharged with an applied voltage of 15 kV from an electrostatic discharge gun to the surface of the polarizing plate, which was the exposed surface on the viewing side.
  • the time from the time of ejection to the disappearance of white spots due to static electricity was measured, and the antistatic property was evaluated as follows. A: Disappears within 1 second B: Disappears within 10 seconds over 1 second C: Disappears over 10 seconds and within 60 seconds D: Disappears over 60 seconds
  • the pressure-sensitive adhesive sheet achieved a lower surface resistance value while suppressing coloration at high temperatures.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive sheet does not contain the polymer (A) having a polyether structure.
  • the surface resistance of the adhesive sheet increased.
  • (meth)acrylic polymer C The monomer mixture charged to the flask was 60 parts by weight of MEA, 20 parts by weight of ethyl acrylate, 14 parts by weight of n-butyl acrylate (BA), 5 parts by weight of phenoxyethyl acrylate, and 1 part by weight of HBA.
  • a solution of a (meth)acrylic polymer C having a weight average molecular weight (Mw) of 2,000,000 and Mw/Mn 3.9 was prepared in the same manner as the polymer A1.
  • (meth)acrylic pressure-sensitive adhesive composition (Sample b1) (Meth) with respect to 100 parts by weight of the solid content of the acrylic polymer B solution, 0.3 parts by weight of an isocyanate cross-linking agent (Mitsui Chemicals, Takenate D-110N; trimethylolpropane / xylylene diisocyanate adduct) And 5 parts by weight of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide (EMI-FSI; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Elexel AS-110) as a conductive agent was further added to obtain a sample b1.
  • a solution of a (meth)acrylic pressure-sensitive adhesive composition was prepared.
  • sample b2 Except that 0.1 parts by weight of a peroxide cross-linking agent (NOF Co., Ltd., Nyper BMT) and 0.5 parts by weight of an antioxidant (BASF, Irganox 1010, molecular weight 1178) were further added, the sample A solution of the (meth)acrylic pressure-sensitive adhesive composition of sample b2 was prepared in the same manner as b1.
  • a peroxide cross-linking agent NOF Co., Ltd., Nyper BMT
  • an antioxidant BASF, Irganox 1010, molecular weight 1178
  • sample b3 As shown in Table 4 below, the above-described isocyanate cross-linking agent, peroxide cross-linking agent and conductive agent are blended with respect to 100 parts by weight of the solid content of the solution of the (meth)acrylic polymer B, A solution of the (meth)acrylic pressure-sensitive adhesive composition of sample b3 was prepared.
  • sample b4 As shown in Table 4 below, the isocyanate-based cross-linking agent, the peroxide-based cross-linking agent and the conductive agent are blended with 100 parts by weight of the solid content of the solution of the (meth)acrylic polymer C, A solution of the (meth)acrylic pressure-sensitive adhesive composition of sample b4 was prepared.
  • the surface resistance value when forming a pressure-sensitive adhesive sheet was measured using the above-prepared pressure-sensitive adhesive sheet as a test sample, using Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd., at an applied voltage of 250 V, Measurement was performed under the condition of application time of 10 seconds. The measurement of the surface resistance value was carried out under an environment of a temperature of 25° C. ⁇ 5° C. and a relative humidity of 50 ⁇ 5%.
  • polarizer having a thickness of 28 ⁇ m was obtained in the same manner as the polarizing plate A except that the thickness and iodine concentration of the polyvinyl alcohol film used for the production of the polarizer were changed.
  • two types of transparent protective films were attached to the obtained polarizer in the same manner as in the preparation of the polarizing plate A to prepare a polarizing plate B.
  • Each pressure-sensitive adhesive sheet of Examples and Comparative Examples formed on a release liner was transferred to the polarizing plate prepared above to prepare a polarizing plate with the pressure-sensitive adhesive sheet.
  • the adhesive sheet was transferred to the surface of the polarizing plate on the side of the transparent protective film made of the modified acrylic polymer.
  • an OCA layer composed of an optically transparent adhesive (OCA) is formed on the surface of the polarizing plate opposite to the adhesive sheet, and the OCA layer, the polarizing plate, the adhesive sheet, and A laminate was produced in which the release liners were laminated in this order.
  • the OCA layer contained butyl acrylate as the base polymer.
  • the release liner was peeled off from this laminate.
  • glass was laminated on the surface of the pressure-sensitive adhesive sheet opposite to the polarizing plate and the surface of the OCA layer opposite to the polarizing plate.
  • optical laminates of Examples and Comparative Examples were produced, in which the glass, the OCA layer, the polarizing plate, the adhesive sheet, and the glass were laminated in this order.
  • ⁇ Durability (high temperature durability) B> The durability (high-temperature durability) of the optical laminate was evaluated by the same method as in ⁇ Durability (high-temperature durability) A> above, except that the optical laminates of Examples B1 to B4 and Comparative Example B1 were used. .
  • the content of formic acid contained in the adhesive sheet and the content of acetic acid contained in the adhesive sheet were determined by quantifying formate ions and acetate ions in the analysis solution by ion chromatography. ICS-3000 manufactured by Thermo Fisher Scientific was used for ion chromatographic measurement.
  • a heating test was conducted in which the optical layered bodies of Examples and Comparative Examples were allowed to stand in a hot air oven maintained at 105° C. for 120 hours. After the optical layered body after the heating test is immersed in liquid nitrogen and frozen, the glass formed on the surface of the OCA layer is peeled off from the optical layered body, and the OCA layer is scraped off to remove the layered body. Obtained. Next, for this laminate, the glass formed on the surface of the adhesive sheet was peeled off, and the adhesive sheet was physically removed from the polarizing plate. Thus, a polarizing plate was obtained from the optical laminate.
  • An analysis solution for ion chromatography measurement was prepared by the method described above, except that the obtained polarizing plate was used.
  • the content of formic acid contained in the polarizing plate was obtained by quantifying formate ions by ion chromatography.
  • the equipment used for ion chromatographic measurements is as described above.
  • Tables 5 and 6 show the evaluation results of each property of the pressure-sensitive adhesive sheets and optical laminates produced in Examples and Comparative Examples.
  • " ⁇ 2.5" indicates that the formic acid content or the acetic acid content was below the detection limit.
  • the content of formic acid contained in the pressure-sensitive adhesive sheet was 1000 ppm or less on a mass basis, compared with the optical layered body of Comparative Example B1. Coloration in was suppressed.
  • the content of formic acid contained in the polarizing plate was 70 ppm or less on a mass basis, and coloration at high temperatures was suppressed.
  • the content of acetic acid was small even after being subjected to a high-temperature environment.
  • Example d1 Preparation of (meth)acrylic polymer D1
  • MEA 2-methoxyethyl acrylate
  • 4-hydroxybutyl acrylate was placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser. I prepared.
  • 0.1 part by weight of 2,2'-azobisisobutyronitrile (AIBN; manufactured by Kishida Chemical Co., Ltd.) as a polymerization initiator was added to 100 parts by weight of the monomer mixture together with 100 parts by weight of ethyl acetate. .
  • AIBN 2,2'-azobisisobutyronitrile
  • (meth)acrylic polymer D1 having a weight average molecular weight (Mw) of 1,800,000 and Mw/Mn of 4.4 was prepared by conducting a polymerization reaction for 8 hours while maintaining the liquid temperature in the flask at around 55°C. bottom.
  • Example d2 A solution of the pressure-sensitive adhesive composition (sample d2) was prepared in the same manner as for sample d1, except that no peroxide-based cross-linking agent was added.
  • Example d3 A solution of the pressure-sensitive adhesive composition (sample d3) was prepared in the same manner as for sample d1, except that the amount of the peroxide-based cross-linking agent was changed to 0.1 parts by weight.
  • Example d4 (Meth) With respect to 100 parts by weight of the solid content of the acrylic polymer D1 solution, except that 1.0 parts by weight of an antioxidant (Irganox 1135, manufactured by BASF Japan) was further added, By the same method as sample d3, A solution of the adhesive composition (sample d4) was prepared.
  • an antioxidant Irganox 1135, manufactured by BASF Japan
  • Example d5 A solution of the pressure-sensitive adhesive composition (sample d5) was prepared in the same manner as for sample d1, except that the amount of the peroxide-based cross-linking agent was changed to 1.0 parts by weight.
  • composition of each adhesive composition of samples d1 to d5 is shown in Table 7 below.
  • the radical generation amounts RG 10 , RG 20 and RG 30 when forming pressure-sensitive adhesive sheets were evaluated by the methods described above.
  • the test piece (approximately 50 mg) housed in the ESR sample tube was taken from the pressure-sensitive adhesive sheet produced above.
  • the measurement apparatus and measurement conditions were as described below.
  • the g value (central magnetic field) of the ESR signal used to calculate the amount of radical generation was the highest among the radicals generated due to the polyether structure in the side chain of the (meth)acrylic polymer D1.
  • the surface resistance value when forming a pressure-sensitive adhesive sheet was measured using the above-prepared pressure-sensitive adhesive sheet as a test sample, using Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd., at an applied voltage of 250 V, Measurement was performed under the condition of application time of 10 seconds. The measurement of the surface resistance value was carried out under an environment of a temperature of 25° C. ⁇ 5° C. and a relative humidity of 50 ⁇ 5%.
  • polarizing plate B As the polarizing plate B, the polarizing plate B described above was used.
  • Example D1 The pressure-sensitive adhesive sheet of sample d11 formed on the release liner was transferred to the above polarizing plate A (polarizer thickness: 18 ⁇ m) to prepare an optical laminate (polarizing plate with pressure-sensitive adhesive sheet) of Example D1. The adhesive sheet was transferred to the surface of the polarizing plate on the side of the transparent protective film made of the modified acrylic polymer.
  • Example D2 An optical laminate of Example D2 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d12 was used instead of Sample d11.
  • Example D3 An optical laminate of Example D3 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d13 was used instead of Sample d11.
  • Example D4 An optical laminate of Example D4 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d14 was used instead of Sample d11.
  • Example D5 An optical laminate of Example D5 was produced in the same manner as in Example D1, except that the adhesive sheet of sample d13 was used instead of sample d11 and polarizing plate B was used instead of polarizing plate A.
  • Comparative Example D1 An optical laminate of Comparative Example D1 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d15 was used instead of Sample d11.
  • ⁇ Coloring B> A laminate for evaluation was prepared using the optical laminates according to Examples D1 to D5 and Comparative Example D1, and this laminate for evaluation was placed in a hot air oven maintained at 95 ° C. or 105 ° C. for 120 hours.
  • the coloring of the optical layered body at high temperatures was evaluated in the same manner as in ⁇ Coloring A> above, except that a heating test was performed.
  • the durability (high-temperature durability) of the optical laminate was evaluated by the same method as in ⁇ Durability (high-temperature durability) A> above, except that the optical laminates according to Examples D1 to D5 and Comparative Example D1 were used. bottom.
  • the pressure-sensitive adhesive sheet achieved a lower surface resistance value while suppressing coloration at high temperatures.
  • the pressure-sensitive adhesive composition of the present invention can be used, for example, in image display devices such as EL displays and liquid crystal displays.

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Abstract

The adhesive composition provided herein contains, as a main component, a polymer (A) having a polyether structure, and further contains a conductive agent and a radical scavenger. When an adhesive sheet is formed from said adhesive composition, the adhesive sheet has a surface resistance value of at most 1×1010 Ω/□. Moreover, the adhesive sheet provided herein is formed from an adhesive composition containing a polymer (B) having a relative permittivity of at least 5.0 at a frequency of 100 kHz, and the content of formic acid in the adhesive sheet, which has been heated at 105ºC for 120 hours, may be at most 1,000 ppm on a mass basis.

Description

粘着剤組成物、粘着シート、光学積層体、画像表示パネル及び画像表示装置Adhesive composition, adhesive sheet, optical laminate, image display panel and image display device
　本発明は、粘着剤組成物、粘着シート、光学積層体、画像表示パネル及び画像表示装置に関する。 The present invention relates to an adhesive composition, an adhesive sheet, an optical laminate, an image display panel and an image display device.
　近年、液晶表示装置及びエレクトロルミネセンス（ＥＬ）表示装置（例えば、有機ＥＬ表示装置、無機ＥＬ表示装置）に代表される画像表示装置が急速に普及している。これら各種の画像表示装置は、例えば、液晶セル、ＥＬ発光素子等の画像表示セルと、偏光板等の光学フィルム及び粘着シートを含む光学積層体と、の積層構造を有している。粘着シートは、主に、光学積層体に含まれる光学フィルム間の接合や、画像表示セルと光学積層体との接合に使用される。特許文献１には、２－メトキシエチルアクリレート等の極性基含有単量体に由来する構成単位を有する（メタ）アクリル系ポリマーを含んだ粘着剤組成物と、当該粘着剤組成物から形成された粘着シートとが開示されている。 In recent years, image display devices typified by liquid crystal display devices and electroluminescence (EL) display devices (eg, organic EL display devices and inorganic EL display devices) have rapidly spread. These various image display devices have a laminated structure of, for example, an image display cell such as a liquid crystal cell or an EL light emitting element, and an optical laminate including an optical film such as a polarizing plate and an adhesive sheet. The pressure-sensitive adhesive sheet is mainly used for bonding between optical films included in the optical layered body and bonding between the image display cell and the optical layered body. Patent Document 1 discloses a pressure-sensitive adhesive composition containing a (meth)acrylic polymer having a structural unit derived from a polar group-containing monomer such as 2-methoxyethyl acrylate, and a pressure-sensitive adhesive composition formed from the An adhesive sheet is disclosed.
特開２０１３－３２４２８号公報Japanese Unexamined Patent Application Publication No. 2013-32428
　画像表示装置では、その製造時、例えば粘着シートを介して光学積層体を画像表示セルに貼り合わせるとき、又は、使用時、例えば使用者が画像表示装置に触れるとき、に静電気が生じる。この静電気によって、画像表示装置が帯電すると、表示不良等の問題が生じうる。静電気が特に生じやすい環境、例えば車両の内部のように他の電子機器が周囲に存在する環境、で画像表示装置を用いる場合、画像表示装置の帯電による表示不良を十分に防止するために、粘着剤組成物に導電剤を配合することで粘着シートの表面抵抗値を低い値に調節することが考えられる。しかし、導電剤の配合量を過度に大きくした場合には、夏季の車両の内部等で想定される高温環境を経た場合に、導電剤の析出による光学特性の低下や粘着シートの耐久性の低下等が生じる傾向にある。 In the image display device, static electricity is generated during manufacture, for example, when the optical laminate is attached to the image display cell via an adhesive sheet, or during use, for example, when the user touches the image display device. If the image display device is electrified by this static electricity, problems such as display failure may occur. When using an image display device in an environment where static electricity is particularly likely to occur, for example, in an environment where there are other electronic devices around, such as inside a vehicle, to sufficiently prevent display defects due to charging of the image display device, adhesive It is conceivable to adjust the surface resistance value of the pressure-sensitive adhesive sheet to a low value by adding a conductive agent to the agent composition. However, if the compounding amount of the conductive agent is excessively increased, the optical properties will deteriorate due to the deposition of the conductive agent and the durability of the adhesive sheet will decrease when the high temperature environment assumed in the inside of the vehicle in summer etc. is passed. etc. tend to occur.
　本発明は、低い表面抵抗値が達成されながら、高温を考慮すべき環境下での光学積層体への使用に適した粘着剤組成物及び当該粘着剤組成物から形成された粘着シートの提供を目的とする。 The present invention provides a pressure-sensitive adhesive composition that achieves a low surface resistance value and is suitable for use in optical laminates in environments where high temperatures should be considered, and a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition. aim.
　本発明は、
　ポリエーテル構造を有するポリマー（Ａ）を主成分として含み、
　導電剤及びラジカル捕捉剤をさらに含み、
　粘着シートを形成したときに、前記粘着シートは１×１０１０Ω／□以下の表面抵抗値を有する、粘着剤組成物を提供する。 The present invention
Containing a polymer (A) having a polyether structure as a main component,
further comprising a conductive agent and a radical scavenger;
Provided is a pressure-sensitive adhesive composition which, when formed into a pressure-sensitive adhesive sheet, has a surface resistance value of 1×10 10 Ω/□ or less.
　本明細書において、粘着シートの表面抵抗値は、粘着シートの厚さが２０μｍのときの測定値により表示する。 In this specification, the surface resistance value of the adhesive sheet is indicated by the measured value when the thickness of the adhesive sheet is 20 μm.
　別の側面から、本発明は、
　ポリエーテル構造を有するポリマー（Ｄ）を主成分として含み、
　導電剤をさらに含み、
　粘着シートを形成したときに、前記粘着シートは、１．５×１０１４個／ｇ以下のラジカル発生量ＲＧ１０及び１×１０１０Ω／□以下の表面抵抗値を有する、粘着剤組成物を提供する。
　ただし、前記ＲＧ１０は、電子スピン共鳴法により評価した、１０５℃及び１０分の加熱時における前記粘着シートのラジカル発生量である。 From another aspect, the present invention provides
Containing a polymer (D) having a polyether structure as a main component,
further comprising a conductive agent;
When the pressure-sensitive adhesive sheet is formed, the pressure-sensitive adhesive sheet has a radical generation amount RG 10 of 1.5×10 14 /g or less and a surface resistance value of 1×10 10 Ω/□ or less. offer.
However, the RG 10 is the amount of radicals generated from the pressure-sensitive adhesive sheet when heated at 105° C. for 10 minutes as evaluated by electron spin resonance method.
　別の側面から、本発明は、
　上記の粘着剤組成物から形成された粘着シートを提供する。 From another aspect, the present invention provides
A pressure-sensitive adhesive sheet formed from the above pressure-sensitive adhesive composition is provided.
　別の側面から、本発明は、
　上記の粘着シートと、
　光学フィルムと、
　を含む、光学積層体を提供する。 From another aspect, the present invention provides
the above-mentioned adhesive sheet;
an optical film;
An optical laminate is provided, comprising:
　別の側面から、本発明は、
　上記の光学積層体を備える、画像表示パネルを提供する。 From another aspect, the present invention provides
Provided is an image display panel comprising the above optical layered body.
　別の側面から、本発明は、
　上記の画像表示パネルを備える、画像表示装置を提供する。 From another aspect, the present invention provides
Provided is an image display device comprising the above image display panel.
　別の側面から、本発明は、
　ポリマー（Ｂ）を含む粘着剤組成物から形成された粘着シートであって、
　周波数１００ｋＨｚにおける前記ポリマー（Ｂ）の比誘電率が５．０以上であり、
　前記粘着シートを１０５℃で１２０時間加熱した後に、前記粘着シートは、質量基準で１０００ｐｐｍ以下のギ酸を含有する、粘着シートを提供する。 From another aspect, the present invention provides
A pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a polymer (B),
the dielectric constant of the polymer (B) at a frequency of 100 kHz is 5.0 or more;
After heating the pressure-sensitive adhesive sheet at 105° C. for 120 hours, the pressure-sensitive adhesive sheet provides a pressure-sensitive adhesive sheet containing 1000 ppm or less of formic acid on a mass basis.
　別の側面から、本発明は、
　粘着シートと光学フィルムとを含む光学積層体であって、
　前記光学フィルムが、偏光子を含む偏光板であり、
　前記光学積層体を１０５℃で１２０時間加熱した後に、前記偏光板は、質量基準で７０ｐｐｍ以下のギ酸を含有する、光学積層体を提供する。 From another aspect, the present invention provides
An optical laminate including an adhesive sheet and an optical film,
The optical film is a polarizing plate containing a polarizer,
After heating the optical layered body at 105° C. for 120 hours, the polarizing plate provides an optical layered body containing 70 ppm or less of formic acid on a mass basis.
　本発明によれば、低い表面抵抗値が達成されながら、高温を考慮すべき環境下での光学積層体への使用に適した粘着剤組成物及び当該粘着剤組成物から形成された粘着シートを提供できる。 According to the present invention, a pressure-sensitive adhesive composition that achieves a low surface resistance value and is suitable for use in an optical laminate under an environment where high temperatures should be considered, and a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition are provided. can provide.
図１は、本発明の粘着シート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 the pressure-sensitive adhesive sheet of the present invention. 図２は、本発明の光学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 the optical layered body of the present invention. 図３は、本発明の光学積層体の一例を模式的に示す断面図である。FIG. 3 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. 図４は、本発明の光学積層体の一例を模式的に示す断面図である。FIG. 4 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. 図５は、本発明の光学積層体の一例を模式的に示す断面図である。FIG. 5 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. 図６は、本発明の光学積層体の一例を模式的に示す断面図である。FIG. 6 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. 図７は、本発明の画像表示パネルの一例を模式的に示す断面図である。FIG. 7 is a cross-sectional view schematically showing an example of the image display panel of the invention. 図８は、本発明の画像表示パネルの一例を模式的に示す断面図である。FIG. 8 is a cross-sectional view schematically showing an example of the image display panel of the invention. 図９は、本発明の画像表示パネルの一例を模式的に示す断面図である。FIG. 9 is a cross-sectional view schematically showing an example of the image display panel of the invention.
　以下に本発明を詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。 Although the present invention will be described in detail below, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
（実施形態１）
［粘着剤組成物］
　本実施形態の粘着剤組成物（Ｉ）は、ポリエーテル構造を有するポリマー（Ａ）を主成分として含み、導電剤をさらに含む。本発明者らの検討によれば、ポリマー（Ａ）中のポリエーテル構造は、粘着剤組成物（Ｉ）に含まれる導電剤の電離を促進しうると共に、導電剤の電離は、粘着剤組成物から形成した粘着シートの表面抵抗値の低下に寄与しうる。 (Embodiment 1)
[Adhesive composition]
The pressure-sensitive adhesive composition (I) of the present embodiment contains a polymer (A) having a polyether structure as a main component, and further contains a conductive agent. According to the studies of the present inventors, the polyether structure in the polymer (A) can promote the ionization of the conductive agent contained in the adhesive composition (I), and the ionization of the conductive agent It can contribute to the reduction of the surface resistance value of the pressure-sensitive adhesive sheet formed from the material.
　また、さらなる検討によれば、（ｉ）ポリエーテル構造を有するポリマー（Ａ）を主成分として含む粘着剤組成物から形成した粘着シートを光学積層体に使用すると、高温環境を経た後に、不要な着色、特に赤色の着色、が生じる傾向にあること、（ii）着色は、偏光板が光学積層体に含まれている場合に多くみられること、及び（iii）着色の原因として、高温によってポリエーテル構造に起因して生じたラジカルが光学フィルムに移動して、光学フィルムに含まれるポリマーに作用する機構が推定されること、が判明した。ラジカルによるポリマーへの作用としては、例えば、偏光子に含まれる典型的なポリマーであるポリビニルアルコール（ＰＶＡ）のポリエン化が考えられる。ＰＶＡのポリエン化とは、ＰＶＡの主鎖に複数の炭素－炭素不飽和結合が生じて共役構造が伸張する現象であり、共役構造の伸張によって可視光域に吸収が生じ、着色（典型的には赤色）を呈すると考えられる。ＰＶＡのポリエン化は、熱に起因する加水分解によってホウ酸との架橋構造が消失してＰＶＡの末端ＯＨ基が多く露出し、露出したＯＨ基間の脱水縮合反応が進む現象として説明できる。また、この脱水縮合反応は、ラジカル反応であると推定される。なお、偏光子中のＰＶＡに限られず、高温下の光学フィルム内でのラジカル反応の進行は、着色等の光学特性の変化を光学フィルムにもたらしうると考えられる。なお、ポリエーテル構造に起因して生じたラジカルには、ポリエーテル構造から生じたラジカルを起点として他の成分（例えば、重合開始剤、架橋剤、酸化防止剤等）が関与して発生したラジカルが含まれうる。 Further, according to further studies, when a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing (i) a polymer (A) having a polyether structure as a main component is used for an optical laminate, after passing through a high-temperature environment, unnecessary (ii) coloration is often observed when a polarizing plate is included in the optical layered body; It has been found that the mechanism is presumed that the radicals generated due to the ether structure migrate to the optical film and act on the polymer contained in the optical film. As an action of radicals on a polymer, for example, polyene conversion of polyvinyl alcohol (PVA), which is a typical polymer contained in polarizers, can be considered. Polyenation of PVA is a phenomenon in which multiple carbon-carbon unsaturated bonds occur in the main chain of PVA and the conjugated structure extends. is red). The polyene formation of PVA can be explained as a phenomenon in which the cross-linked structure with boric acid disappears due to hydrolysis caused by heat, exposing many terminal OH groups of PVA, and the dehydration condensation reaction between the exposed OH groups proceeds. Moreover, this dehydration condensation reaction is presumed to be a radical reaction. In addition, it is considered that progress of radical reaction in the optical film at high temperature, not limited to PVA in the polarizer, can cause changes in optical properties such as coloration to the optical film. Radicals generated due to the polyether structure include radicals generated with the involvement of other components (e.g., polymerization initiators, cross-linking agents, antioxidants, etc.) starting from the radicals generated from the polyether structure. can be included.
　粘着剤組成物（Ｉ）は、ラジカル捕捉剤をさらに含む。ラジカル捕捉剤によって、粘着剤組成物（Ｉ）から形成された粘着シートにおける、高温下でのラジカル発生量を制限できる。粘着シートとしたときに高温下でのラジカル発生量が制限された粘着剤組成物（Ｉ）は、高温を考慮すべき環境下での光学積層体への使用に適している。 The adhesive composition (I) further contains a radical scavenger. The radical scavenger can limit the amount of radicals generated in the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (I) at high temperatures. The pressure-sensitive adhesive composition (I), in which the amount of radicals generated at high temperatures is limited when made into a pressure-sensitive adhesive sheet, is suitable for use in optical laminates in environments where high temperatures should be considered.
　粘着剤組成物（Ｉ）から粘着シートを形成したときに、形成された粘着シートは１×１０１０Ω／□以下の表面抵抗値を有する。表面抵抗値は、５×１０９Ω／□以下、１×１０９Ω／□以下、８×１０８Ω／□以下、６×１０８Ω／□以下、５×１０８Ω／□以下、４×１０８Ω／□以下、３×１０８Ω／□以下、さらには２×１０８Ω／□以下であってもよい。表面抵抗値の下限は、例えば１×１０６Ω／□以上であり、１×１０７Ω／□以上であってもよい。粘着シートとしたときの表面抵抗値が上記範囲にある粘着剤組成物（Ｉ）は、静電気が生じやすい環境下、例えば車両の内部、における使用に適している。 When a pressure-sensitive adhesive sheet is formed from the pressure-sensitive adhesive composition (I), the formed pressure-sensitive adhesive sheet has a surface resistance value of 1×10 10 Ω/□ or less. The surface resistance value is 5×10 9 Ω/□ or less, 1×10 9 Ω/□ or less, 8×10 8 Ω/□ or less, 6×10 8 Ω/□ or less, 5× 10 8 Ω /□ or less, It may be 4×10 8 Ω/□ or less, 3×10 8 Ω/□ or less, or even 2×10 8 Ω/□ or less. The lower limit of the surface resistance value is, for example, 1×10 6 Ω/□ or more, and may be 1×10 7 Ω/□ or more. The pressure-sensitive adhesive composition (I) having a surface resistance value within the above range when formed into a pressure-sensitive adhesive sheet is suitable for use in an environment where static electricity is likely to occur, such as inside a vehicle.
　＜ポリマー（Ａ）＞
　ポリマー（Ａ）の例は、（メタ）アクリル系ポリマー、ウレタン系ポリマー、シリコーン系ポリマー及びゴム系ポリマーである。ただし、ポリマー（Ａ）は、ポリエーテル構造を有する限り、上記例に限定されない。ポリマー（Ａ）は、好ましくは、（メタ）アクリル系ポリマーである。換言すれば、粘着剤組成物（Ｉ）は（メタ）アクリル系ポリマーを主成分として含んでいてもよい。さらに換言すれば、粘着剤組成物（Ｉ）はアクリル系粘着剤組成物であってもよい。主成分とは、組成物において最も含有率の大きな成分を意味する。主成分の含有率は、例えば５０重量％以上であり、６０重量％以上、７０重量％以上、７５重量％以上、さらには８０重量％以上であってもよい。本明細書において（メタ）アクリル系ポリマーとは、（メタ）アクリレート等の（メタ）アクリル系単量体に由来する構成単位を有するポリマーを意味する。（メタ）アクリル系ポリマーにおける（メタ）アクリル系単量体に由来する構成単位の含有率は、例えば４０重量％以上であり、５０重量％以上、６０重量％以上、７０重量％以上、８０重量％以上、８５重量％以上、９０重量％以上、さらには９５重量％以上であってもよい。（メタ）アクリル系ポリマーは、（メタ）アクリル系単量体に由来する構成単位のみからなってもよい。（メタ）アクリルとは、アクリル及びメタクリルを意味する。（メタ）アクリレートとは、アクリレート及びメタクリレートを意味する。 <Polymer (A)>
Examples of polymer (A) are (meth)acrylic polymers, urethane polymers, silicone polymers and rubber polymers. However, the polymer (A) is not limited to the above examples as long as it has a polyether structure. Polymer (A) is preferably a (meth)acrylic polymer. In other words, the pressure-sensitive adhesive composition (I) may contain a (meth)acrylic polymer as a main component. Furthermore, in other words, the adhesive composition (I) may be an acrylic adhesive composition. A main component means the component with the largest content rate in a composition. The content of the main component is, for example, 50% by weight or more, and may be 60% by weight or more, 70% by weight or more, 75% by weight or more, or even 80% by weight or more. As used herein, the (meth)acrylic polymer means a polymer having structural units derived from (meth)acrylic monomers such as (meth)acrylate. The content of structural units derived from (meth)acrylic monomers in the (meth)acrylic polymer is, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, and 80% by weight. % or more, 85 wt % or more, 90 wt % or more, or even 95 wt % or more. The (meth)acrylic polymer may consist only of structural units derived from (meth)acrylic monomers. (Meth)acrylic means acrylic and methacrylic. (Meth)acrylate means acrylate and methacrylate.
　ポリマー（Ａ）は、ポリエーテル構造を有する。ポリエーテル構造は、少なくとも２つのエーテル基（－Ｏ－）を含む構造である。ポリエーテル構造は、直鎖状であっても分岐を有していてもよい。ポリエーテル構造の一例は、直鎖状であっても分岐を有していてもよいアルキル基と、少なくとも２つのエーテル基とを含む。ポリマー（Ａ）は、ポリエーテル構造を主鎖に有していても側鎖に有していてもよく、側鎖に有することが好ましい。ポリマー（Ａ）は、ポリエーテル構造を側鎖に有する（メタ）アクリル系ポリマーであってもよい。 The polymer (A) has a polyether structure. A polyether structure is a structure containing at least two ether groups (--O--). The polyether structure may be linear or branched. An example of a polyether structure includes an alkyl group, which may be linear or branched, and at least two ether groups. The polymer (A) may have a polyether structure in its main chain or in its side chains, preferably in its side chains. The polymer (A) may be a (meth)acrylic polymer having polyether structures in side chains.
　ポリマー（Ａ）は、ポリエーテル構造を有する構成単位を有していてもよい。当該構成単位においてポリエーテル構造は、主鎖に位置していても側鎖に位置していてもよく、側鎖に位置することが好ましい。ポリマー（Ａ）は、ポリエーテル構造を側鎖に有する（メタ）アクリル系単量体に由来する構成単位を有していてもよい。 The polymer (A) may have structural units having a polyether structure. In the structural unit, the polyether structure may be positioned on the main chain or on the side chain, preferably on the side chain. The polymer (A) may have a structural unit derived from a (meth)acrylic monomer having a polyether structure in its side chain.
　ポリエーテル構造を側鎖に有するポリマー（Ａ）の一例は、以下の式（１）に示す単量体に由来する構成単位を有する。式（１）のＲ１は、水素原子又はメチル基である。式（１）のＲ２は、直鎖状であっても分岐を有していてもよいアルキル基であり、好ましくは、直鎖状のアルキル基である。Ｒ２の例は、メチル基及びエチル基である。ｎは、１～１５の整数であり、好ましくは１～１０の整数であり、より好ましくは１～５の整数である。ｎが１のとき、式（１）の単量体は、ＣＯＯ基の「－Ｏ－」を含め、２つのエーテル基を含む。式（１）の単量体は、（メタ）アクリル系単量体の１種であり、より具体的には、（メタ）アクリレート単量体の１種である。側鎖末端のＲ２Ｏ基に着目すると、式（１）の単量体は、アルコキシ基含有（メタ）アクリレート単量体の１種でもある。式（１）の単量体に由来する構成単位は、ポリエーテル構造を側鎖に有する。
Figure JPOXMLDOC01-appb-C000005
 An example of the polymer (A) having a polyether structure in its side chain has a structural unit derived from a monomer represented by formula (1) below. R 1 in formula (1) is a hydrogen atom or a methyl group. R 2 in formula (1) is an alkyl group that may be linear or branched, preferably a linear alkyl group. Examples of R 2 are methyl and ethyl groups. n is an integer of 1-15, preferably an integer of 1-10, more preferably an integer of 1-5. When n is 1, the monomer of formula (1) contains two ether groups, including the "-O-" of the COO group. The monomer of formula (1) is one type of (meth)acrylic monomer, more specifically, one type of (meth)acrylate monomer. Focusing on the R 2 O group at the end of the side chain, the monomer of formula (1) is also one type of alkoxy group-containing (meth)acrylate monomer. A structural unit derived from the monomer of formula (1) has a polyether structure in its side chain.
Figure JPOXMLDOC01-appb-C000005
　式（１）の単量体の例は、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－（２－エトキシエトキシ）エチル（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート及びメトキシポリエチレングリコール（メタ）アクリレートであり、好ましくは２－メトキシエチルアクリレート（ＭＥＡ）である。式（１）の単量体に由来する構成単位は、粘着剤組成物（Ｉ）から形成された粘着シートにおける表面抵抗値の低下に特に寄与しうる。 Examples of monomers of formula (1) are 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate. ) acrylates and methoxypolyethylene glycol (meth)acrylates, preferably 2-methoxyethyl acrylate (MEA). The structural unit derived from the monomer of formula (1) can particularly contribute to lowering the surface resistance of the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (I).
　ポリマー（Ａ）におけるポリエーテル構造を有する構成単位（例えば、式（１）の単量体に由来する構成単位）の含有率は、例えば１５重量％以上であり、２０重量％以上、２５重量％以上、３０重量％以上、３５重量％以上、４０重量％以上、４５重量％以上、５０重量％以上、５５重量％以上、６０重量％以上、６５重量％以上、７０重量％以上、７５重量％以上、８０重量％以上、８５重量％以上、９０重量％以上、さらには９５重量％以上であってもよい。当該含有率の上限は、例えば１００重量％以下であり、９９．５重量％以下、さらには９９重量％以下であってもよい。 The content of structural units having a polyether structure (for example, structural units derived from the monomer of formula (1)) in the polymer (A) is, for example, 15% by weight or more, 20% by weight or more, and 25% by weight. Above, 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight 80% by weight or more, 85% by weight or more, 90% by weight or more, or even 95% by weight or more. The upper limit of the content is, for example, 100% by weight or less, and may be 99.5% by weight or less, or even 99% by weight or less.
　ポリマー（Ａ）は、以下の単量体（Ａ２）に由来する構成単位を１種又は２種以上有していてもよい。なお、以下に示す単量体（Ａ２）は、式（１）の単量体との共重合が可能である。 The polymer (A) may have one or more structural units derived from the following monomers (A2). The monomer (A2) shown below can be copolymerized with the monomer of formula (1).
　単量体（Ａ２）の例は、炭素数１～３０のアルキル基を側鎖に有する（メタ）アクリル系単量体である。アルキル基は、直鎖状であっても分岐を有していてもよい。アルキル基を側鎖に有する（メタ）アクリル系単量体の例は、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ｎ－へキシル（メタ）アクリレート、イソヘキシル（メタ）アクリレート、イソヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ドデシル（メタ）アクリレート（ラウリル（メタ）アクリレート）、ｎ－トリデシル（メタ）アクリレート、ｎ－テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート及びオクタデシル（メタ）アクリレートである。ポリマー（Ａ）におけるアルキル基を側鎖に有する（メタ）アクリル系単量体に由来する構成単位の含有率は、例えば８０重量％以下であり、７０重量％以下、６０重量％以下、５０重量％以下、４０重量％以下、３０重量％以下、２０重量％以下、１０重量％以下、さらには５重量％以下であってもよく、０重量％であっても（当該構成単位を有さなくても）よい。 An example of the monomer (A2) is a (meth)acrylic monomer having an alkyl group with 1 to 30 carbon atoms in its side chain. The alkyl group may be linear or branched. Examples of (meth)acrylic monomers having alkyl groups in side chains include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. , s-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth) Acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate Acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate (lauryl (meth)acrylate), n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate , heptadecyl (meth)acrylate and octadecyl (meth)acrylate. The content of the structural unit derived from the (meth)acrylic monomer having an alkyl group in the side chain in the polymer (A) is, for example, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight. % or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, or even 5 wt% or less, or even 0 wt% (without the structural unit even) good.
　単量体（Ａ２）の別の例は、水酸基含有単量体である。水酸基含有単量体は、水酸基含有（メタ）アクリル系単量体であってもよい。水酸基含有単量体の例は、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート及び１２－ヒドロキシラウリル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート、並びに（４－ヒドロキシメチルシクロヘキシル）－メチルアクリレートである。粘着剤組成物（Ｉ）から形成された粘着シートの耐久性を向上させる観点からは、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートが好ましく、４－ヒドロキシブチル（メタ）アクリレートがより好ましい。ポリマー（Ａ）における水酸基含有単量体に由来する構成単位の含有率は、例えば１～５重量％であり、３重量％以下、さらには２重量％以下であってもよい。ポリマー（Ａ）は、水酸基含有単量体に由来する構成単位を有さなくてもよい。 Another example of the monomer (A2) is a hydroxyl group-containing monomer. The hydroxyl group-containing monomer may be a hydroxyl group-containing (meth)acrylic monomer. Examples of hydroxyl-containing monomers are 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl ( hydroxyalkyl (meth)acrylates such as meth)acrylates, 10-hydroxydecyl (meth)acrylate and 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate. From the viewpoint of improving the durability of the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (I), 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred, and 4-hydroxybutyl (meth) Acrylates are more preferred. The content of structural units derived from hydroxyl group-containing monomers in the polymer (A) is, for example, 1 to 5% by weight, and may be 3% by weight or less, or even 2% by weight or less. Polymer (A) may not have a structural unit derived from a hydroxyl group-containing monomer.
　単量体（Ａ２）は、芳香環含有単量体、カルボキシル基含有単量体、アミノ基含有単量体、アミド基含有単量体であってもよい。芳香環含有単量体は、芳香環含有（メタ）アクリル系単量体であってもよい。芳香環含有単量体の例は、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、エチレンオキサイド変性ノニルフェノール（メタ）アクリレート、ヒドロキシエチル化β－ナフトール（メタ）アクリレート及びビフェニル（メタ）アクリレートである。カルボキシル基含有単量体の例は、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、イタコン酸、マレイン酸、フマール酸及びクロトン酸である。アミノ基含有単量体の例は、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート及びＮ，Ｎ－ジメチルアミノプロピル（メタ）アクリレートである。アミド基含有単量体の例は、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピルアクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メチロール－Ｎ－プロパン（メタ）アクリルアミド、アミノメチル（メタ）アクリルアミド、アミノエチル（メタ）アクリルアミド、メルカプトメチル（メタ）アクリルアミド及びメルカプトエチル（メタ）アクリルアミド等のアクリルアミド系単量体；Ｎ－（メタ）アクリロイルモルフォリン、Ｎ－（メタ）アクリロイルピペリジン及びＮ－（メタ）アクリロイルピロリジン等のＮ－アクリロイル複素環単量体；並びにＮ－ビニルピロリドン及びＮ－ビニル－ε－カプロラクタム等のＮ－ビニル基含有ラクタム系単量体である。 The monomer (A2) may be an aromatic ring-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, or an amide group-containing monomer. The aromatic ring-containing monomer may be an aromatic ring-containing (meth)acrylic monomer. Examples of aromatic ring-containing monomers include phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, hydroxyethylated β- naphthol (meth)acrylate and biphenyl (meth)acrylate. Examples of carboxyl group-containing monomers are (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid. Examples of amino group-containing monomers are N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate. Examples of amide group-containing monomers are (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(meth)acrylamide, N- Butyl (meth)acrylamide, N-hexyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methylol-N-propane (meth)acrylamide, aminomethyl (meth)acrylamide, aminoethyl (meth)acrylamide, mercaptomethyl acrylamide-based monomers such as (meth)acrylamide and mercaptoethyl (meth)acrylamide; N-acryloyl heterocycles such as N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine and N-(meth)acryloylpyrrolidine and N-vinyl group-containing lactam monomers such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam.
　単量体（Ａ２）は、多官能性単量体であってもよい。多官能性単量体の例は、ヘキサンジオールジ（メタ）アクリレート（１，６－ヘキサンジオールジ（メタ）アクリレート）、ブタンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、アリル（メタ）アクリレート、ビニル（メタ）アクリレート、エポキシアクリレート、ポリエステルアクリレート及びウレタンアクリレート等の多官能アクリレート；並びにジビニルベンゼンである。多官能アクリレートは、好ましくは１，６－ヘキサンジオールジアクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートである。 The monomer (A2) may be a polyfunctional monomer. Examples of multifunctional monomers are hexanediol di(meth)acrylate (1,6-hexanediol di(meth)acrylate), butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl (meth)acrylate ) polyfunctional acrylates such as acrylates, epoxy acrylates, polyester acrylates and urethane acrylates; and divinylbenzene. Polyfunctional acrylates are preferably 1,6-hexanediol diacrylate and dipentaerythritol hexa(meth)acrylate.
　ポリマー（Ａ）における芳香環含有単量体、カルボキシル基含有単量体、アミノ基含有単量体、アミド基含有単量体及び多官能性単量体に由来する構成単位の含有率の合計は、好ましくは２０重量％以下であり、より好ましくは１０重量％以下、さらに好ましくは８重量％以下である。ポリマー（Ａ）が当該構成単位を有する場合、含有率の合計は、例えば０．０１重量％以上であり、１重量％以上、２重量％以上、さらには３重量％以上であってもよい。ポリマー（Ａ）は、これらの構成単位を有さなくてもよい。特に、ポリマー（Ａ）において、カルボキシル基含有単量体に由来する構成単位の含有率は、０．１重量％未満であってもよく、０重量％であっても（当該構成単位を有さなくても）よい。 The total content of structural units derived from the aromatic ring-containing monomer, carboxyl group-containing monomer, amino group-containing monomer, amide group-containing monomer and polyfunctional monomer in the polymer (A) is , preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 8% by weight or less. When the polymer (A) has the structural unit, the total content is, for example, 0.01% by weight or more, and may be 1% by weight or more, 2% by weight or more, or even 3% by weight or more. Polymer (A) may not have these structural units. In particular, in the polymer (A), the content of the structural unit derived from the carboxyl group-containing monomer may be less than 0.1% by weight, or even 0% by weight (if the structural unit is (even without it) is fine.
　その他の単量体（Ａ２）の例は、（メタ）アクリロニトリル等のニトリル基含有（メタ）アクリレート；（メタ）アクリル酸グリシジル及び（メタ）アクリル酸メチルグリシジル等のエポキシ基含有単量体；ビニルスルホン酸ナトリウム等のスルホン酸基含有単量体；リン酸基含有単量体；（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル及び（メタ）アクリル酸イソボルニル等の脂環式炭化水素基を有する（メタ）アクリル酸エステル；酢酸ビニル及びプロピオン酸ビニル等のビニルエステル類；スチレン及びビニルトルエン等の芳香族ビニル化合物；エチレン、プロピレン、ブタジエン、イソプレン及びイソブチレン等のオレフィン類、又はジエン類；ビニルアルキルエーテル等のビニルエーテル類；並びに塩化ビニルである。 Examples of other monomers (A2) include nitrile group-containing (meth)acrylates such as (meth)acrylonitrile; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; vinyl sulfonic acid group-containing monomers such as sodium sulfonate; phosphate group-containing monomers; alicyclic hydrocarbon groups such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins such as ethylene, propylene, butadiene, isoprene and isobutylene, or dienes; vinyl ethers such as alkyl ethers; and vinyl chloride.
　ポリマー（Ａ）における上記その他の単量体（Ａ２）に由来する構成単位の含有率の合計は、例えば３０重量％以下であり、１０重量％以下であってもよく、０重量％である（当該構成単位を有さない）ことが好ましい。 The total content of structural units derived from the other monomer (A2) in the polymer (A) is, for example, 30% by weight or less, may be 10% by weight or less, or is 0% by weight ( not have the structural unit).
　ポリマー（Ａ）は、上述した１種又は２種以上の単量体を公知の方法により重合して形成できる。単量体と、単量体の部分重合物とを重合してもよい。重合は、例えば、溶液重合、乳化重合、塊状重合、熱重合、活性エネルギー線重合により実施できる。光学的透明性に優れる粘着シートを形成できる観点からは、溶液重合、活性エネルギー線重合が好ましい。重合は、単量体及び／又は部分重合物と酸素との接触を避けて実施することが好ましく、このために、例えば、窒素等の不活性ガス雰囲気下における重合、あるいは樹脂フィルム等により酸素を遮断した状態での重合を採用できる。形成するポリマー（Ａ）は、ランダム共重合体、ブロック共重合体、グラフト共重合体等のいずれの態様であってもよい。 The polymer (A) can be formed by polymerizing one or more of the above monomers by a known method. A monomer and a partial polymer of the monomer may be polymerized. Polymerization can be carried out, for example, by solution polymerization, emulsion polymerization, bulk polymerization, thermal polymerization, or active energy ray polymerization. Solution polymerization and active energy ray polymerization are preferred from the viewpoint of forming a pressure-sensitive adhesive sheet with excellent optical transparency. Polymerization is preferably carried out while avoiding contact of the monomer and/or partial polymer with oxygen. Polymerization in shutdown can be employed. The polymer (A) to be formed may be in any form such as a random copolymer, a block copolymer, a graft copolymer and the like.
　ポリマー（Ａ）を形成する重合系は、１種又は２種以上の重合開始剤を含んでいてもよい。重合開始剤の種類は、重合反応により選択でき、例えば、熱重合開始剤、光重合開始剤であってもよい。 The polymerization system forming the polymer (A) may contain one or more polymerization initiators. The type of polymerization initiator can be selected depending on the polymerization reaction, and may be, for example, a thermal polymerization initiator or a photopolymerization initiator.
　溶液重合に使用する溶媒は、例えば、酢酸エチル、酢酸ｎ－ブチル等のエステル類；トルエン、ベンゼン等の芳香族炭化水素類；ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類；メチルエチルケトン、メチルイソブチルケトン等のケトン類である。ただし、溶媒は上記例に限定されない。溶媒は、２種以上の溶媒の混合溶媒であってもよい。 Solvents used for solution polymerization include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as methylcyclohexane; and ketones such as methyl ethyl ketone and methyl isobutyl ketone. However, the solvent is not limited to the above examples. The solvent may be a mixed solvent of two or more solvents.
　溶液重合に使用する重合開始剤は、例えば、アゾ系重合開始剤、過酸化物系重合開始剤、レドックス系重合開始剤である。過酸化物系重合開始剤は、例えば、ジベンゾイルペルオキシド、ｔ－ブチルペルマレエートである。なかでも、特開２００２－６９４１１号公報に開示のアゾ系重合開始剤が好ましい。当該アゾ系重合開始剤は、例えば、２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２’－アゾビス－２－メチルブチロニトリル、２，２’－アゾビス（２－メチルプロピオン酸）ジメチル、４，４’－アゾビス－４－シアノバレリアン酸である。ただし、重合開始剤は上記例に限定されない。アゾ系重合開始剤の使用量は、例えば、単量体の全量１００重量部に対して０．０５～０．５重量部であり、０．１～０．３重量部であってもよい。 Polymerization initiators used for solution polymerization are, for example, azo polymerization initiators, peroxide polymerization initiators, and redox polymerization initiators. Peroxide polymerization initiators are, for example, dibenzoyl peroxide and t-butyl permaleate. Among them, the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable. The azo polymerization initiator, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2-methylpropion acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid. However, the polymerization initiator is not limited to the above examples. The amount of the azo polymerization initiator used is, for example, 0.05 to 0.5 parts by weight, and may be 0.1 to 0.3 parts by weight, per 100 parts by weight of the total amount of the monomers.
　活性エネルギー線重合に使用する活性エネルギー線は、例えば、α線、β線、γ線、中性子線、電子線等の電離性放射線、及び紫外線である。活性エネルギー線は、紫外線が好ましい。紫外線の照射による重合は、光重合とも称される。活性エネルギー線重合の重合系は、典型的には、光重合開始剤を含む。活性エネルギー重合の重合条件は、ポリマー（Ａ）が形成される限り、限定されない。 The active energy rays used for active energy ray polymerization are, for example, ionizing radiation such as α-rays, β-rays, γ-rays, neutron beams and electron beams, and ultraviolet rays. The active energy rays are preferably ultraviolet rays. Polymerization by irradiation with ultraviolet rays is also called photopolymerization. A polymerization system for active energy ray polymerization typically contains a photopolymerization initiator. Polymerization conditions for active energy polymerization are not limited as long as the polymer (A) is formed.
　光重合開始剤は、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α－ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤である。ただし、光重合開始剤は上記例に限定されない。 Photopolymerization initiators include, for example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators. , a benzoin-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a ketal-based photopolymerization initiator, and a thioxanthone-based photopolymerization initiator. However, the photopolymerization initiator is not limited to the above examples.
　ベンゾインエーテル系光重合開始剤は、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、アニソールメチルエーテルである。アセトフェノン系光重合開始剤は、例えば、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、４－フェノキシジクロロアセトフェノン、４－（ｔ－ブチル）ジクロロアセトフェノンである。α－ケトール系光重合開始剤は、例えば、２－メチル－２－ヒドロキシプロピオフェノン、１－［４－（２－ヒドロキシエチル）フェニル］－２－メチルプロパン－１－オンである。芳香族スルホニルクロリド系光重合開始剤は、例えば、２－ナフタレンスルホニルクロライドである。光活性オキシム系光重合開始剤は、例えば、１－フェニル－１，１－プロパンジオン－２－（ｏ－エトキシカルボニル）－オキシムである。ベンゾイン系光重合開始剤は、例えば、ベンゾインである。ベンジル系光重合開始剤は、例えば、ベンジルである。ベンゾフェノン系光重合開始剤は、例えば、ベンゾフェノン、ベンゾイル安息香酸、３，３’－ジメチル－４－メトキシベンゾフェノン、ポリビニルベンゾフェノン、α－ヒドロキシシクロヘキシルフェニルケトンである。ケタール系光重合開始剤は、例えば、ベンジルジメチルケタールである。チオキサントン系光重合開始剤は、例えば、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントンである。 Benzoin ether-based photopolymerization initiators include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, anisolemethyl is ether. Acetophenone-based photopolymerization initiators include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl)dichloro Acetophenone. Examples of α-ketol photopolymerization initiators are 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. The aromatic sulfonyl chloride photopolymerization initiator is, for example, 2-naphthalenesulfonyl chloride. A photoactive oxime-based photopolymerization initiator is, for example, 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. A benzoin-based photopolymerization initiator is, for example, benzoin. A benzylic photopolymerization initiator is, for example, benzyl. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenyl ketone. A ketal photopolymerization initiator is, for example, benzyl dimethyl ketal. Thioxanthone-based photopolymerization initiators are, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
　光重合開始剤の使用量は、例えば、単量体の全量１００重量部に対して０．０１～１重量部であり、０．０５～０．５重量部であってもよい。 The amount of the photopolymerization initiator used is, for example, 0.01 to 1 part by weight, and may be 0.05 to 0.5 part by weight, based on 100 parts by weight of the total amount of the monomers.
　ポリマー（Ａ）の重量平均分子量（Ｍｗ）は、例えば、１００万～３００万であり、好ましくは１８０万～３００万である。ポリマー（Ａ）の重量平均分子量が１００万～３００万であることによって、粘着シートのクラックを抑制できるとともに、粘度の上昇やゲル化の発生を抑制できる傾向がある。本明細書におけるポリマーの重量平均分子量（Ｍｗ）は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）の測定に基づく値（ポリスチレン換算）である。 The weight average molecular weight (Mw) of the polymer (A) is, for example, 1-3 million, preferably 1.8-3 million. When the weight-average molecular weight of the polymer (A) is 1,000,000 to 3,000,000, cracks in the pressure-sensitive adhesive sheet can be suppressed, and there is a tendency to suppress increase in viscosity and occurrence of gelation. The weight average molecular weight (Mw) of the polymer in this specification is a value (converted to polystyrene) based on GPC (gel permeation chromatography) measurement.
　ポリマー（Ａ）のガラス転移温度（Ｔｇ）は、例えば－５０℃以下であり、好ましくは－５２℃以下であり、より好ましくは－５５℃以下である。ポリマー（Ａ）のＴｇの下限値は、例えば－７５℃である。ポリマー（Ａ）のＴｇは、ポリマー（Ａ）の構成単位を形成する単量体ごとに、ホモポリマーとしたときのＴｇを求め、これらのＴｇを構成単位の含有率を考慮して平均した値である。 The glass transition temperature (Tg) of the polymer (A) is, for example, -50°C or lower, preferably -52°C or lower, and more preferably -55°C or lower. The lower limit of Tg of polymer (A) is, for example, -75°C. The Tg of the polymer (A) is a value obtained by averaging the Tg of a homopolymer for each monomer that forms the structural unit of the polymer (A) and taking into account the content of the structural unit. is.
　粘着剤組成物（Ｉ）におけるポリマー（Ａ）の含有率は、固形分比で、例えば５０重量％以上であり、６０重量％以上、７０重量％以上、７５重量％以上、さらには８０重量％以上であってもよい。含有率の上限は、例えば９９重量％以下であり、９７重量％以下、さらには９５重量％以下であってもよい。 The content of the polymer (A) in the adhesive composition (I) is, for example, 50% by weight or more, 60% by weight or more, 70% by weight or more, 75% by weight or more, and further 80% by weight in terms of solid content. or more. The upper limit of the content is, for example, 99% by weight or less, and may be 97% by weight or less, or even 95% by weight or less.
　＜導電剤＞
　粘着剤組成物（Ｉ）は、導電剤（帯電防止剤）をさらに含む。粘着剤組成物（Ｉ）は、１種又は２種以上の導電剤を含んでいてもよい。導電剤の例は、塩等のイオン性化合物である。イオン性化合物は、常温（２５℃）で液体のイオン液体であってもよい。 <Conductive agent>
The adhesive composition (I) further contains a conductive agent (antistatic agent). The pressure-sensitive adhesive composition (I) may contain one or more conductive agents. Examples of conductive agents are ionic compounds such as salts. The ionic compound may be an ionic liquid that is liquid at normal temperature (25° C.).
　イオン性化合物の例は、無機カチオン塩及び有機カチオン塩である。無機カチオン塩の例は、無機カチオン－アニオン塩である。無機カチオン塩に含まれるカチオンの例は、アルカリ金属イオンである。アルカリ金属イオンは、例えば、リチウムイオン、ナトリウムイオン、カリウムイオンであり、好ましくはリチウムイオンである。無機カチオン塩は、リチウム塩であってもよい。 Examples of ionic compounds are inorganic cation salts and organic cation salts. Examples of inorganic cation salts are inorganic cation-anion salts. Examples of cations contained in inorganic cation salts are alkali metal ions. Alkali metal ions are, for example, lithium ions, sodium ions, potassium ions, preferably lithium ions. The inorganic cation salt may be a lithium salt.
　無機カチオン塩に含まれるアニオンの例は、Ｃｌ－、Ｂｒ－、Ｉ－、ＡｌＣｌ４ －、Ａｌ２Ｃｌ７ －、ＢＦ４ －、ＰＦ６ －、ＣｌＯ４ －、ＮＯ３ －、ＣＨ３ＣＯＯ－、ＣＦ３ＣＯＯ－、ＣＨ３ＳＯ３ －、ＣＦ３ＳＯ３ －、（ＣＦ３ＳＯ２）３Ｃ－、ＡｓＦ６ －、ＳｂＦ６ －、ＮｂＦ６ －、ＴａＦ６ －、（ＣＮ）２Ｎ－、Ｃ４Ｆ９ＳＯ３ －、Ｃ３Ｆ７ＣＯＯ－、（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）Ｎ－、－Ｏ３Ｓ（ＣＦ２）３ＳＯ３ －、及び下記一般式（ａ）～（ｄ）で表されるアニオンである。
（ａ）　（ＣｎＦ２ｎ＋１ＳＯ２）２Ｎ－　（ｎは１～１０の整数）
（ｂ）　ＣＦ２（ＣｍＦ２ｍＳＯ２）２Ｎ－　（ｍは１～１０の整数）
（ｃ）　－Ｏ３Ｓ（ＣＦ２）ｌＳＯ３ －　（ｌは１～１０の整数）
（ｄ）　（ＣｐＦ２ｐ＋１ＳＯ２）Ｎ－（ＣｑＦ２ｑ＋１ＳＯ２）　（ｐ及びｑは、互いに独立して１～１０の整数） Examples of anions contained in inorganic cation salts are 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 ) 3 C − , AsF 6 − , SbF 6 − , NbF 6 − , TaF 6 − , (CN) 2 N − , C 4 F 9 SO 3 − , C 3 F 7 COO − , (CF 3 SO 2 )(CF 3 CO)N − , —O 3 S(CF 2 ) 3 SO 3 − , and the following general formula (a) is an anion represented by (d).
(a) (C n F 2n+1 SO 2 ) 2 N − (n is an integer of 1 to 10)
(b) CF 2 (C m F 2m SO 2 ) 2 N − (m is an integer of 1 to 10)
(c) — O 3 S(CF 2 ) l SO 3 — (l is an integer of 1 to 10)
(d) (C p F 2p+1 SO 2 )N − (C q F 2q+1 SO 2 ) (p and q are independently integers from 1 to 10)
　無機カチオン塩に含まれるアニオンは、好ましくはフッ素含有アニオンであり、より好ましくはフッ素含有イミドアニオンである。フッ素含有イミドアニオンの例は、ペルフルオロアルキル基を有するイミドアニオンである。フッ素含有イミドアニオンのより具体的な例は、（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）Ｎ－や、上記の一般式（ａ）、（ｂ）又は（ｄ）で表されるアニオンであり、好ましくは（ＣＦ３ＳＯ２）２Ｎ－、（Ｃ２Ｆ５ＳＯ２）２Ｎ－等の一般式（ａ）で表わされる（ペルフルオロアルキルスルホニル）イミドであり、より好ましくは（ＣＦ３ＳＯ２）２Ｎ－で表わされるビス（トリフルオロメタンスルホニル）イミドである。好ましい無機カチオン塩の例は、リチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）である。 The anion contained in the inorganic cation salt is preferably a fluorine-containing anion, more preferably a fluorine-containing imide anion. Examples of fluorine-containing imide anions are imide anions with perfluoroalkyl groups. More specific examples of fluorine-containing imide anions are (CF 3 SO 2 )(CF 3 CO)N − and anions represented by the above general formulas (a), (b) or (d), Preferred are (CF 3 SO 2 ) 2 N − , (C 2 F 5 SO 2 ) 2 N — (perfluoroalkylsulfonyl) imides represented by the general formula (a), more preferably (CF 3 SO 2 ) bis(trifluoromethanesulfonyl)imide represented by 2N- . An example of a preferred inorganic cation salt is lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).
　有機カチオン塩の例は、有機カチオン－アニオン塩である。有機カチオン塩に含まれるカチオンの例は、有機基を含む有機オニウムである。有機オニウムに含まれるオニウムの例は、含窒素オニウム、含硫黄オニウム、含リンオニウムであり、好ましくは、含窒素オニウム、含硫黄オニウムである。含窒素オニウムの例は、アンモニウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、ピ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である。含硫黄オニウムの例は、スルホニウムカチオンである。含リンオニウムの例は、ホスホニウムカチオンである。有機オニウムに含まれる有機基の例は、アルキル基、アルコキシル基、アルケニル基である。好ましい有機オニウムの具体例は、テトラアルキルアンモニウムカチオン（例えば、トリブチルメチルアンモニウムカチオン）、アルキルピペリジニウムカチオン、アルキルピロリジニウムカチオンである。 An example of an organic cation salt is an organic cation-anion salt. Examples of cations contained in organic cation salts are organic onium containing organic groups. Examples of onium contained in organic onium include nitrogen-containing onium, sulfur-containing onium and phosphorus-containing onium, preferably nitrogen-containing onium and sulfur-containing onium. Examples of nitrogen-containing oniums include ammonium cations, piperidinium cations, pyrrolidinium cations, pyridinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, imidazolium cations, tetrahydropyrimidinium cations, and dihydropyrimidinium cations. , pyrazolium cation, and pyrazolinium cation. An example of a sulfur-containing onium is the sulfonium cation. An example of a phosphorous onium is a phosphonium cation. Examples of organic groups contained in organic onium are alkyl groups, alkoxyl groups, alkenyl groups. Specific examples of preferred organic oniums are tetraalkylammonium cations (eg, tributylmethylammonium cations), alkylpiperidinium cations, alkylpyrrolidinium cations.
　有機カチオン塩に含まれるアニオンの例は、無機カチオン塩に含まれるアニオンの例と同じである。好ましい有機カチオン塩の例は、１－エチル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド、トリメチル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）イミドである。 Examples of anions contained in organic cation salts are the same as examples of anions contained in inorganic cation salts. Examples of preferred organic cation salts are 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, trimethylbutylammonium bis(trifluoromethanesulfonyl)imide.
　導電剤は、無機カチオン塩と有機カチオン塩とを組み合わせて用いてもよい。 The conductive agent may be used in combination with an inorganic cation salt and an organic cation salt.
　粘着剤組成物（Ｉ）における導電剤の配合量は、ポリマー（Ａ）１００重量部に対して、例えば０．５重量部以上であり、１重量部以上、２重量部以上、３重量部以上、さらには４重量部以上であってもよい。配合量の上限は、ポリマー（Ａ）１００重量部に対して、例えば２０重量部以下であり、１５重量部以下、１０重量部以下、１０重量部未満、９重量部以下、８重量部以下、７重量部以下、さらには６重量部以下であってもよい。 The amount of the conductive agent in the adhesive composition (I) is, for example, 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight or more, or 3 parts by weight or more with respect to 100 parts by weight of the polymer (A). , and may be 4 parts by weight or more. The upper limit of the amount is, for example, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, less than 10 parts by weight, 9 parts by weight or less, 8 parts by weight or less, with respect to 100 parts by weight of the polymer (A). It may be 7 parts by weight or less, or even 6 parts by weight or less.
　＜ラジカル捕捉剤＞
　粘着剤組成物（Ｉ）は、ラジカル捕捉剤をさらに含む。ラジカル捕捉剤の例は、ヒンダードフェノール系、ヒンダードアミン系、ホスファイト系、フェノール系及びチオエーテル系、並びにこれらの系統を混合したブレンド系等の各種の酸化防止剤である。 <Radical Scavenger>
The adhesive composition (I) further contains a radical scavenger. Examples of radical scavengers are various antioxidants such as hindered phenols, hindered amines, phosphites, phenols, thioethers, and blends of these.
　酸化防止剤の種類は、例えば、ラジカル連鎖禁止剤及び過酸化物分解剤である。 Types of antioxidants are, for example, radical chain inhibitors and peroxide decomposers.
　酸化防止剤は、ヒンダードフェノール系、ヒンダードアミン系及びホスファイト系から選ばれる少なくとも１種であってもよい。 The antioxidant may be at least one selected from hindered phenol, hindered amine and phosphite.
　ヒンダードフェノール系酸化防止剤は、フェノールのＯＨ基が結合した芳香環上の炭素原子に隣接した少なくとも１つの炭素原子に対してターシャリーブチル基が結合した構造を有していてもよい。ヒンダードフェノール系酸化防止剤の例は、ジブチルヒドロキシトルエン（ＢＨＴ）；並びにＩｒｇａｎｏｘ１０１０、Ｉｒｇａｎｏｘ１０１０ＦＦ、Ｉｒｇａｎｏｘ１０３５、Ｉｒｇａｎｏｘ１０３５ＦＦ、Ｉｒｇａｎｏｘ１０７６、Ｉｒｇａｎｏｘ１０７６ＦＤ、Ｉｒｇａｎｏｘ１０７６ＤＷＪ、Ｉｒｇａｎｏｘ１０９８、Ｉｒｇａｎｏｘ１１３５、Ｉｒｇａｎｏｘ１３３０、Ｉｒｇａｎｏｘ１７２６、Ｉｒｇａｎｏｘ１４２５ＷＬ、Ｉｒｇａｎｏｘ１５２０Ｌ、Ｉｒｇａｎｏｘ２４５、Ｉｒｇａｎｏｘ２４５ＦＦ、Ｉｒｇａｎｏｘ２５９、Ｉｒｇａｎｏｘ３１１４、Ｉｒｇａｎｏｘ５６５及びＩｒｇａｎｏｘ２９５（いずれも商品名であり、ＢＡＳＦ社製）である。 The hindered phenol-based antioxidant may have a structure in which a tertiary butyl group is bonded to at least one carbon atom adjacent to the carbon atom on the aromatic ring to which the phenol OH group is bonded. Examples of hindered phenolic antioxidants are dibutylhydroxytoluene (BHT); rganox 1135, Irganox 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 259 , Irganox3114, Irganox565 and Irganox295 (all trade names, manufactured by BASF).
　ヒンダードアミン系酸化防止剤は、一分子中に少なくとも１つのヒンダードピぺリジン基を有していてもよい。ヒンダードアミン系酸化防止剤の例は、アデカスタブＬＡ－６３、アデカスタブＬＡ－６３Ｐ、アデカスタブＬＡ－５２及びアデカスタブＬＡ－５７（いずれも商品名であり、ＡＤＥＫＡ社製）である。 The hindered amine antioxidant may have at least one hindered piperidine group in one molecule. Examples of hindered amine antioxidants are Adekastab LA-63, Adekastab LA-63P, Adekastab LA-52 and Adekastab LA-57 (all trade names, manufactured by ADEKA).
　ホスファイト系酸化防止剤の例は、トリフェニルホスファイト、ジフェニルイソデシルホスファイト及びフェニルジイソデシルホスファイト；並びにアデカスタブ２１１２、アデカスタブ２１１２ＲＧ、アデカスタブ１１７８及びアデカスタブ３０１０（いずれも商品名であり、ＡＤＥＫＡ社製）である。 Examples of phosphite-based antioxidants include triphenylphosphite, diphenylisodecylphosphite and phenyldiisodecylphosphite; and Adekastab 2112, Adekastab 2112RG, Adekastab 1178 and Adekastab 3010 (all trade names, manufactured by ADEKA). is.
　フェノール系酸化防止剤の例は、モノフェノール系酸化防止剤、ビスフェノール系酸化防止剤及び高分子型フェノール系酸化防止剤である。モノフェノール系酸化防止剤の例は、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－ブチル－４－エチルフェノール、ステアリン－β－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネートである。ビスフェノール系酸化防止剤の例は、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、３，９－ビス［１，１－ジメチル－２－［β－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］エチル］２，４，８，１０－テトラオキサスピロ［５，５］ウンデカンである。高分子型フェノール系酸化防止剤の例は、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、テトラキス－［メチレン－３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン、ビス［３，３’－ビス－（４’－ヒドロキシ－３’－ｔ－ブチルフェニル）ブチリックアシッド］グリコールエステル、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンジル）－Ｓ－トリアジン－２，４，６－（１Ｈ、３Ｈ、５Ｈ）トリオン及びトコフェノールである。 Examples of phenolic antioxidants are monophenolic antioxidants, bisphenolic antioxidants and polymeric phenolic antioxidants. Examples of monophenolic antioxidants are 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β-(3 , 5-di-t-butyl-4-hydroxyphenyl)propionate. Examples of bisphenol antioxidants are 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'- thiobis(3-methyl-6-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane. Examples of polymeric phenolic antioxidants are 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane, Bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3',5'-di-t-butyl- 4′-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione and tocopherol.
　チオエーテル系酸化防止剤の例は、アデカスタブＡＯ－５０３及びアデカスタブＡＯ－２６（いずれも商品名であり、ＡＤＥＫＡ社製）である。 Examples of thioether-based antioxidants are Adekastab AO-503 and Adekastab AO-26 (both trade names, manufactured by ADEKA).
　ラジカル捕捉剤（例えば酸化防止剤）の分子量は、１０００以下であってもよく、９００以下、８５０以下、８００以下、７００以下、６００以下、５００以下、４５０以下、さらには４００以下であってもよい。分子量の下限は、例えば１００以上である。本発明者らの検討によれば、分子量が上記範囲にあるラジカル捕捉剤は、粘着剤組成物（Ｉ）から形成された粘着シートにおけるラジカル発生量の抑制に特に適している。 The molecular weight of the radical scavenger (e.g., antioxidant) may be 1000 or less, 900 or less, 850 or less, 800 or less, 700 or less, 600 or less, 500 or less, 450 or less, or even 400 or less. good. The lower limit of the molecular weight is, for example, 100 or more. According to studies by the present inventors, a radical scavenger having a molecular weight within the above range is particularly suitable for suppressing the amount of radicals generated in a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (I).
　ラジカル捕捉剤（例えば酸化防止剤）は、常温（２５℃）で液体であってもよい。 The radical scavenger (eg, antioxidant) may be liquid at room temperature (25°C).
　粘着剤組成物（Ｉ）におけるラジカル捕捉剤の配合量は、ポリマー（Ａ）１００重量部に対して、例えば０．１重量部以上であり、０．２重量部以上、０．３重量部以上、０．４重量部以上、さらには０．５重量部以上であってもよい。配合量の上限は、ポリマー（Ａ）１００重量部に対して、例えば１５重量部以下であり、１０重量部以下、７重量部以下、５重量部以下、５重量部未満、４重量部以下、３重量部以下、さらには２重量部以下であってもよい。 The content of the radical scavenger in the adhesive composition (I) is, for example, 0.1 parts by weight or more, 0.2 parts by weight or more, or 0.3 parts by weight or more with respect to 100 parts by weight of the polymer (A). , 0.4 parts by weight or more, or even 0.5 parts by weight or more. The upper limit of the amount is, for example, 15 parts by weight or less, 10 parts by weight or less, 7 parts by weight or less, 5 parts by weight or less, less than 5 parts by weight, 4 parts by weight or less, with respect to 100 parts by weight of the polymer (A). It may be 3 parts by weight or less, or even 2 parts by weight or less.
　＜添加剤＞
　粘着剤組成物（Ｉ）は、ポリマー（Ａ）、導電剤及びラジカル捕捉剤以外の材料をさらに含んでいてもよい。当該材料の例は、添加剤である。添加剤の例は、架橋剤、シランカップリング剤、顔料及び染料等の着色剤、紫外線吸収剤、界面活性剤、可塑剤、粘着性付与剤、表面潤滑剤、レベリング剤、リワーク向上剤、軟化剤、重合禁止剤、防錆剤、無機充填材、有機充填材、金属粉等の粉体、粒子、及び箔状物である。添加剤は、ポリマー（Ａ）１００重量部に対して合計で、例えば１０重量部以下、好ましくは５重量部以下、より好ましくは３重量部以下の範囲で配合できる。 <Additive>
The pressure-sensitive adhesive composition (I) may further contain materials other than the polymer (A), the conductive agent and the radical scavenger. Examples of such materials are additives. Examples of additives include cross-linking agents, silane coupling agents, coloring agents such as pigments and dyes, UV absorbers, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, rework improvers, softening agents, agents, polymerization inhibitors, rust preventives, inorganic fillers, organic fillers, powders such as metal powders, particles, and foils. Additives can be blended in a total amount of, for example, 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 3 parts by weight or less per 100 parts by weight of the polymer (A).
　架橋剤の例は、有機系架橋剤及び多官能性金属キレートである。有機系架橋剤の例は、イソシアネート系架橋剤、過酸化物系架橋剤、エポキシ系架橋剤及びイミン系架橋剤である。有機系架橋剤及び多官能性金属キレートは、溶剤型及び活性エネルギー線硬化型のいずれの型の粘着剤組成物（Ｉ）に対しても使用できる。粘着剤組成物（Ｉ）が溶剤型である場合、架橋剤は、好ましくは過酸化物系架橋剤、イソシアネート系架橋剤である。過酸化物系架橋剤とイソシアネート系架橋剤とを併用してもよい。粘着剤組成物（Ｉ）は、イソシアネート系架橋剤を含んでいてもよく、過酸化物系架橋剤を含んでいてもよく、イソシアネート系架橋剤及び過酸化物系架橋剤の双方を含んでいてもよい。 Examples of cross-linking agents are organic cross-linking agents and multifunctional metal chelates. Examples of organic cross-linking agents are isocyanate cross-linking agents, peroxide cross-linking agents, epoxy cross-linking agents and imine cross-linking agents. The organic cross-linking agent and polyfunctional metal chelate can be used for both the solvent-type and active energy ray-curable pressure-sensitive adhesive compositions (I). When the pressure-sensitive adhesive composition (I) is a solvent type, the cross-linking agent is preferably a peroxide-based cross-linking agent or an isocyanate-based cross-linking agent. A peroxide-based cross-linking agent and an isocyanate-based cross-linking agent may be used in combination. The pressure-sensitive adhesive composition (I) may contain an isocyanate cross-linking agent, may contain a peroxide cross-linking agent, or may contain both an isocyanate cross-linking agent and a peroxide cross-linking agent. good too.
　イソシアネート系架橋剤の例は、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、ジフェニルメタンジイソシアネート、キシレンジイソシアネート及びポリメチレンポリフェニルイソシアネート等の芳香族イソシアネート化合物；シクロペンチレンジイソシアネート、シクロヘキシレ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及びイソホロンジイソシアネート等の脂環族イソシアネート化合物；ブチレンジイソシアネート、テトラメチレンジイソシアナート及びヘキサメチレンジイソシアネート等の脂肪族イソシアネート化合物である。イソシアネート系架橋剤は、上記イソシアネート化合物をトリメチロールプロパン等の多価アルコール化合物に付加した化合物（アダクト体）；上記イソシアネート化合物をポリエーテルポリオール、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及びポリイソプレンポリオール等のポリオールと付加反応させた化合物；イソシアヌレート化物等の上記イソシアネート化合物の誘導体であってもよい。誘導体の具体例は、トリメチロールプロパン／トリレンジイソシアネート３量体付加物（例えば、東ソー社製、コロネートＬ）、トリメチロールプロパン／ヘキサメチレンジイソシアネート３量体付加物（例えば、東ソー社製、コロネートＨＬ）、ヘキサメチレンジイソシアネートのイソシアヌレート体（例えば、東ソー社製、コロネートＨＸ）である。 Examples of isocyanate cross-linking agents include aromatic isocyanate compounds such as tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate and polymethylene polyphenyl isocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, hydrogenated diphenylmethane diisocyanate and alicyclic isocyanate compounds such as isophorone diisocyanate; and aliphatic isocyanate compounds such as butylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate. The isocyanate-based cross-linking agent is a compound (adduct) obtained by adding the above-mentioned isocyanate compound to a polyhydric alcohol compound such as trimethylolpropane; A compound subjected to an addition reaction with a polyol; a derivative of the isocyanate compound such as an isocyanurate compound may be used. Specific examples of derivatives include trimethylolpropane/tolylene diisocyanate trimer adduct (eg, Tosoh Corporation, Coronate L), trimethylolpropane/hexamethylene diisocyanate trimer adduct (eg, Tosoh Corporation, Coronate HL ), an isocyanurate of hexamethylene diisocyanate (eg, Coronate HX manufactured by Tosoh Corporation).
　粘着剤組成物（Ｉ）がイソシアネート系架橋剤を含む場合、その配合量は、ポリマー（Ａ）１００重量部に対して、例えば０．１～１０重量部であり、０．２～５重量部、０．２５～３重量部、０．３～１重量部、さらには０．３～０．５重量部であってもよい。 When the pressure-sensitive adhesive composition (I) contains an isocyanate-based cross-linking agent, the amount thereof is, for example, 0.1 to 10 parts by weight and 0.2 to 5 parts by weight with respect to 100 parts by weight of the polymer (A). , 0.25 to 3 parts by weight, 0.3 to 1 part by weight, or even 0.3 to 0.5 parts by weight.
　過酸化物系架橋剤の例は、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、ジラウロイルパーオキサイド、ジ－ｎ－オクタノイルパーオキサイド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジ（４－メチルベンゾイル）パーオキサイド、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシイソブチレート、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサンである。過酸化物系架橋剤は、架橋反応効率が優れることから、ベンゾイルパーオキサイドであってもよい。 Examples of peroxide-based cross-linking agents include di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy Neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -ethylhexanoate, di(4-methylbenzoyl)peroxide, benzoylperoxide, t-butylperoxyisobutyrate, 1,1-di(t-hexylperoxy)cyclohexane. The peroxide-based cross-linking agent may be benzoyl peroxide because of its excellent cross-linking reaction efficiency.
　粘着剤組成物（Ｉ）が過酸化物系架橋剤を含む場合、その配合量は、ポリマー（Ａ）１００重量部に対して、例えば０．００５～５重量部であり、０．０１～３重量部、０．０５～２重量部、０．０７～１重量部、０．０７～０．５重量部、０．０７～０．３重量部、さらには０．０７～０．２重量部であってもよい。 When the pressure-sensitive adhesive composition (I) contains a peroxide-based cross-linking agent, the amount thereof is, for example, 0.005 to 5 parts by weight, and 0.01 to 3 parts by weight, relative to 100 parts by weight of the polymer (A). parts by weight, 0.05 to 2 parts by weight, 0.07 to 1 part by weight, 0.07 to 0.5 parts by weight, 0.07 to 0.3 parts by weight, further 0.07 to 0.2 parts by weight may be
　シランカップリング剤の例は、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トリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、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基含有シランカップリング剤；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－アミノプロピルメチルジメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチルブチリデン）プロピルアミン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤；３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等の（メタ）アクリル基含有シランカップリング剤；３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤である。 Examples of silane coupling agents are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Epoxy group-containing silane coupling agents such as trimethoxysilane; 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3 -Dimethylbutylidene)propylamine, amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane; ) acrylic group-containing silane coupling agents; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane.
　粘着剤組成物（Ｉ）がシランカップリング剤を含む場合、その配合量は、ポリマー（Ａ）１００重量部に対して、例えば５重量部以下であり、３重量部以下、１重量部以下、０．５重量部以下、０．２重量部以下、０．１重量部以下、さらには０．０５重量部以下であってもよい。粘着剤組成物（Ｉ）は、シランカップリング剤を含まなくてもよい。 When the pressure-sensitive adhesive composition (I) contains a silane coupling agent, the amount is, for example, 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, relative to 100 parts by weight of the polymer (A). It may be 0.5 parts by weight or less, 0.2 parts by weight or less, 0.1 parts by weight or less, or even 0.05 parts by weight or less. The adhesive composition (I) may not contain a silane coupling agent.
　粘着剤組成物（Ｉ）の型は、例えば、エマルション型、溶剤型（溶液型）、活性エネルギー線硬化型（光硬化型）、熱溶融型（ホットメルト型）である。耐久性に優れる粘着シートを形成できる観点からは、粘着剤組成物（Ｉ）は、溶剤型又は活性エネルギー線硬化型であってもよく、溶剤型であってもよい。溶剤型の粘着剤組成物（Ｉ）は、紫外線硬化剤等の光硬化剤を含まなくてもよい。 Types of the pressure-sensitive adhesive composition (I) are, for example, emulsion type, solvent type (solution type), active energy ray-curable type (light-curing type), and heat-melting type (hot-melt type). From the viewpoint of forming a highly durable PSA sheet, the PSA composition (I) may be solvent-based, active energy ray-curable, or solvent-based. The solvent-based pressure-sensitive adhesive composition (I) may not contain a photocuring agent such as an ultraviolet curing agent.
　粘着剤組成物（Ｉ）は、例えば、光学積層体に使用できる。換言すれば、粘着剤組成物（Ｉ）は光学積層体用であってもよい。ただし、粘着剤組成物（Ｉ）の用途は、上記例に限定されない。 The adhesive composition (I) can be used, for example, in optical laminates. In other words, the pressure-sensitive adhesive composition (I) may be used for optical laminates. However, the use of the pressure-sensitive adhesive composition (I) is not limited to the above examples.
（実施形態２）
［粘着剤組成物］
　本実施形態の粘着剤組成物（II）は、ポリマー（Ｂ）を含む。粘着剤組成物（II）は、ポリマー（Ｂ）を主成分として含んでいてもよい。「主成分」は、上述した意味を有する。ここで、周波数１００ｋＨｚにおけるポリマー（Ｂ）の比誘電率は、５．０以上である。加えて、粘着剤組成物（II）から形成された粘着シートを１０５℃で１２０時間加熱した後に、粘着シートは、質量基準で１０００ｐｐｍ以下のギ酸を含有する。ギ酸の含有量がこの程度に低い場合、高温環境を経た後であっても、光学積層体に着色が生じにくい。 (Embodiment 2)
[Adhesive composition]
The pressure-sensitive adhesive composition (II) of this embodiment contains the polymer (B). The pressure-sensitive adhesive composition (II) may contain the polymer (B) as a main component. "Principal component" has the meaning given above. Here, the polymer (B) has a dielectric constant of 5.0 or more at a frequency of 100 kHz. In addition, after heating the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (II) at 105° C. for 120 hours, the pressure-sensitive adhesive sheet contains 1000 ppm or less of formic acid on a mass basis. When the content of formic acid is as low as this, the optical layered body is less likely to be colored even after being subjected to a high-temperature environment.
　本発明者らの検討によれば、（iv）周波数１００ｋＨｚにおける比誘電率が５．０以上であるポリマーを含む粘着剤組成物から形成した粘着シートを光学積層体に使用すると、高温環境を経た後に、不要な着色、特に赤色の着色、が生じる傾向にあること、及び（ｖ）着色は、偏光板が光学積層体に含まれている場合に多くみられること、が判明した。この原因として、例えば、粘着シートに含まれている酸が、光学フィルムに含まれるポリマーに作用することが判明した。加えて、本発明者らは、光学フィルムに含まれるポリマーに作用する酸がギ酸であることを見出した。ギ酸によるポリマーへの作用としては、例えば、偏光子に含まれるＰＶＡのポリエン化が考えられる。ＰＶＡにおいて、露出したＯＨ基がギ酸によってプロトン化され、脱水縮合反応が進行すると推定される。なお、偏光子中のＰＶＡに限られず、高温下の光学フィルム内でのギ酸による上記反応の進行は、着色等の光学特性の変化を光学フィルムにもたらしうると考えられる。 According to the study of the present inventors, (iv) when a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a polymer having a dielectric constant of 5.0 or more at a frequency of 100 kHz is used for an optical laminate, the pressure-sensitive adhesive sheet undergoes a high-temperature environment. It was later found that unwanted coloration, especially red coloration, tends to occur, and (v) coloration is more prevalent when polarizers are included in the optical stack. As a cause of this, for example, it was found that the acid contained in the adhesive sheet acts on the polymer contained in the optical film. In addition, the inventors have found that the acid acting on the polymer contained in the optical film is formic acid. An example of the action of formic acid on the polymer is polyene conversion of PVA contained in the polarizer. It is presumed that exposed OH groups in PVA are protonated by formic acid, and dehydration condensation reactions proceed. In addition, it is considered that the progress of the above-mentioned reaction due to formic acid in the optical film at high temperatures, not limited to PVA in the polarizer, can bring about changes in optical properties such as coloration of the optical film.
　上記したとおり、光学積層体を加熱することによって、光学積層体を構成する部材にギ酸が生じうる。ギ酸が生じうる光学積層体の部材として、粘着シート、偏光板、ＯＣＡ（optical clear adhesive）層、及び保護フィルムが挙げられる。ＯＣＡ層は、例えば、光学積層体において、偏光板の粘着シートとは反対側の面に形成された粘着剤層である。言い換えると、偏光板は、粘着シートとＯＣＡ層との間に配置されていてもよい。ＯＣＡ層は、光学透明粘着剤を含む層である。ＯＣＡ層に含まれる粘着剤の材料は、特に限定されず、例えば、（メタ）アクリル系ポリマー、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系ポリマー、ゴム系ポリマーなどをベースポリマーとして含む。保護フィルムは、例えば、偏光子の表面に形成されるフィルムである。保護フィルムの詳細は後述する。例えば、保護フィルムが加水分解されることによってギ酸が発生しうる。 As described above, formic acid can be generated in the members constituting the optical layered body by heating the optical layered body. Optical laminate members in which formic acid can be generated include adhesive sheets, polarizing plates, OCA (optical clear adhesive) layers, and protective films. The OCA layer is, for example, an adhesive layer formed on the surface of the polarizing plate opposite to the adhesive sheet in the optical laminate. In other words, the polarizing plate may be arranged between the adhesive sheet and the OCA layer. The OCA layer is a layer containing an optically transparent adhesive. The material of the adhesive contained in the OCA layer is not particularly limited. include. A protective film is, for example, a film formed on the surface of a polarizer. Details of the protective film will be described later. For example, formic acid can be generated by hydrolysis of the protective film.
　粘着剤組成物（II）から形成された粘着シートを１０５℃で１２０時間加熱した後に、粘着シートに含まれるギ酸の含有量は、質量基準で、８００ｐｐｍ以下、５００ｐｐｍ以下、２００ｐｐｍ以下、１００ｐｐｍ以下、７０ｐｐｍ以下、５０ｐｐｍ以下、２５ｐｐｍ以下、５ｐｐｍ以下、２．５ｐｐｍ以下、さらには２．５ｐｐｍ未満であってもよい。ギ酸の含有量の下限は、特に限定されず、例えば、質量基準で０ｐｐｍ以上である。 After heating the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (II) at 105° C. for 120 hours, the content of formic acid contained in the pressure-sensitive adhesive sheet is, on a mass basis, 800 ppm or less, 500 ppm or less, 200 ppm or less, 100 ppm or less, It may be 70 ppm or less, 50 ppm or less, 25 ppm or less, 5 ppm or less, 2.5 ppm or less, or even less than 2.5 ppm. The lower limit of the formic acid content is not particularly limited, and is, for example, 0 ppm or more on a mass basis.
　周波数１００ｋＨｚにおけるポリマー（Ｂ）の比誘電率Ｐは、５．０以上である。比誘電率Ｐがこの程度に高い場合、比誘電率が低い光学フィルム、特に偏光フィルムと粘着シートとを組み合わせて用いた場合であっても、画像表示装置が備えるタッチセンサの感度の低下を抑制できる傾向がある。 The dielectric constant P of the polymer (B) at a frequency of 100 kHz is 5.0 or more. When the dielectric constant P is as high as this, even when an optical film with a low dielectric constant, especially a polarizing film and an adhesive sheet are used in combination, the sensitivity of the touch sensor included in the image display device is suppressed from deteriorating. tend to be able to
　比誘電率Ｐは、次の方法によって測定できる。まず、ポリマーのみから構成された、厚さ３０μｍの試験片を作製する。この試験片について、ＪＩＳ　Ｋ６９１１：１９９５に準拠して、周波数１００ｋＨｚにおける比誘電率を自動平衡ブリッジ法（変成器ブリッジ法）により測定する。得られた測定値を比誘電率Ｐとみなすことができる。比誘電率の測定条件の詳細は、以下のとおりである。
・測定条件
　測定方法：容量法（装置：Agilent Technologies社製の4294A Precision Impedance Analyzer）
　電極構成：直径１２．１ｍｍ、厚さ０．５ｍｍのアルミニウム板
　対向電極：３ｏｚ　銅板
　測定環境：２３±１℃、５２±１％ＲＨ The dielectric constant P can be measured by the following method. First, a test piece with a thickness of 30 μm is produced, which is composed only of polymer. Regarding this test piece, the dielectric constant at a frequency of 100 kHz is measured by the automatic balancing bridge method (transformer bridge method) in accordance with JIS K6911:1995. The obtained measured value can be regarded as the dielectric constant P. The details of the conditions for measuring the dielectric constant are as follows.
・Measurement conditions Measurement method: Capacitance method (Apparatus: 4294A Precision Impedance Analyzer manufactured by Agilent Technologies)
Electrode configuration: Aluminum plate with a diameter of 12.1 mm and a thickness of 0.5 mm Counter electrode: 3 oz copper plate Measurement environment: 23±1° C., 52±1% RH
　比誘電率Ｐは、６．０以上、６．５以上、６．８以上、７．０以上、７．３以上、さらには７．５以上であってもよい。比誘電率Ｐの上限は、特に限定されず、例えば、１０．０以下である。 The dielectric constant P may be 6.0 or more, 6.5 or more, 6.8 or more, 7.0 or more, 7.3 or more, or even 7.5 or more. The upper limit of the dielectric constant P is not particularly limited, and is, for example, 10.0 or less.
　粘着剤組成物（II）に含まれるポリマー（Ｂ）は、例えば、実施形態１で説明したポリマー（Ａ）であってもよい。 The polymer (B) contained in the adhesive composition (II) may be, for example, the polymer (A) described in Embodiment 1.
　粘着剤組成物（II）は、ラジカル捕捉剤及び過酸化物系架橋剤をさらに含んでいてもよい。 The adhesive composition (II) may further contain a radical scavenger and a peroxide cross-linking agent.
　ラジカル捕捉剤は、酸化防止剤であってもよい。ラジカル捕捉剤として、例えば、実施形態１で説明したラジカル捕捉剤、すなわち、各種の酸化防止剤が使用できる。粘着剤組成物（II）において、ラジカル捕捉剤（例えば酸化防止剤）の分子量は、１０００以上であってもよい。分子量の上限は、例えば、１５００以下である。本発明者らの検討によれば、分子量が上記範囲にあるラジカル捕捉剤は、粘着剤組成物（II）から形成された粘着シートにおけるギ酸の発生量の抑制に特に適している。粘着剤組成物（II）におけるラジカル捕捉剤の好ましい配合量は、実施形態１で説明したとおりである。 The radical scavenger may be an antioxidant. As the radical scavenger, for example, the radical scavenger described in Embodiment 1, that is, various antioxidants can be used. In the adhesive composition (II), the molecular weight of the radical scavenger (eg antioxidant) may be 1000 or more. The upper limit of the molecular weight is, for example, 1500 or less. According to studies by the present inventors, a radical scavenger having a molecular weight within the above range is particularly suitable for suppressing the amount of formic acid generated in a pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (II). The preferred blending amount of the radical scavenger in the pressure-sensitive adhesive composition (II) is as described in the first embodiment.
　過酸化物系架橋剤は、例えば、実施形態１で説明した過酸化物系架橋剤を使用できる。粘着剤組成物（II）における過酸化物系架橋剤の好ましい配合量は、実施形態１で説明したとおりである。過酸化物系架橋剤の過剰な配合は、偏光子に含まれるＰＶＡのポリエン化を促進させうる。ポリエン化には、過酸化物系架橋剤の関与する反応の反応物、例えば、安息香酸が関与している可能性がある。粘着剤組成物（II）が過酸化物系架橋剤を含む場合、その配合量が上記した範囲であれば、着色の抑制に特に適している。 For the peroxide-based cross-linking agent, for example, the peroxide-based cross-linking agent described in Embodiment 1 can be used. The preferred blending amount of the peroxide-based cross-linking agent in the pressure-sensitive adhesive composition (II) is as described in the first embodiment. Excessive blending of the peroxide-based cross-linking agent can promote polyenization of PVA contained in the polarizer. Polyenation may involve reactants of reactions involving peroxide-based crosslinkers, such as benzoic acid. When the pressure-sensitive adhesive composition (II) contains a peroxide-based cross-linking agent, it is particularly suitable for suppressing coloration if the blending amount is within the above range.
　粘着剤組成物（II）は、過酸化物系架橋剤に加えてイソシアネート系架橋剤をさらに含んでいてもよい。イソシアネート系架橋剤の例は、実施形態１で説明したとおりである。粘着剤組成物（II）におけるイソシアネート系架橋剤の好ましい配合量も、実施形態１で説明したとおりである。 The pressure-sensitive adhesive composition (II) may further contain an isocyanate-based cross-linking agent in addition to the peroxide-based cross-linking agent. Examples of the isocyanate-based cross-linking agent are as described in the first embodiment. The preferred blending amount of the isocyanate-based cross-linking agent in the pressure-sensitive adhesive composition (II) is also as described in the first embodiment.
　粘着剤組成物（II）は、ポリマー（Ｂ）、ラジカル捕捉剤及び過酸化物系架橋剤以外の材料をさらに含んでいてもよい。当該材料の例は、導電剤（帯電防止剤）である。粘着剤組成物（II）は、１種又は２種以上の導電剤を含んでいてもよい。導電剤の例は、塩等のイオン性化合物である。イオン性化合物は、常温（２５℃）で液体のイオン液体であってもよい。導電剤として、実施形態１で説明した導電剤が使用できる。導電剤の例は、塩等のイオン性化合物である。イオン性化合物の例は、無機カチオン塩及び有機カチオン塩である。導電剤は、有機カチオン塩を含んでいてもよい。導電剤は、有機カチオン塩であってもよい。粘着剤組成物（II）における導電剤の配合量は、実施形態１で説明したとおりである。 The adhesive composition (II) may further contain materials other than the polymer (B), the radical scavenger and the peroxide-based cross-linking agent. Examples of such materials are conductive agents (antistatic agents). The pressure-sensitive adhesive composition (II) may contain one or more conductive agents. Examples of conductive agents are ionic compounds such as salts. The ionic compound may be an ionic liquid that is liquid at normal temperature (25° C.). As the conductive agent, the conductive agent described in Embodiment 1 can be used. Examples of conductive agents are ionic compounds such as salts. Examples of ionic compounds are inorganic and organic cation salts. The conductive agent may contain an organic cationic salt. The conductive agent may be an organic cationic salt. The blending amount of the conductive agent in the adhesive composition (II) is as described in the first embodiment.
　粘着剤組成物（II）は、ポリマー（Ｂ）、ラジカル捕捉剤、過酸化物系架橋剤及び導電剤以外の材料をさらに含んでいてもよい。当該材料の例は、添加剤である。添加剤の例は、実施形態１で説明したとおりである。 The adhesive composition (II) may further contain materials other than the polymer (B), radical scavenger, peroxide cross-linking agent and conductive agent. Examples of such materials are additives. Examples of additives are as described in the first embodiment.
　粘着剤組成物（II）の型は、例えば、エマルション型、溶剤型（溶液型）、活性エネルギー線硬化型（光硬化型）、熱溶融型（ホットメルト型）である。耐久性に優れる粘着シートを形成できる観点からは、粘着剤組成物（II）は、溶剤型又は活性エネルギー線硬化型であってもよく、溶剤型であってもよい。溶剤型の粘着剤組成物（II）は、紫外線硬化剤等の光硬化剤を含まなくてもよい。 Types of the adhesive composition (II) are, for example, emulsion type, solvent type (solution type), active energy ray-curable type (light-curing type), and heat-melting type (hot-melt type). From the viewpoint of being able to form a highly durable PSA sheet, the PSA composition (II) may be solvent-based, active energy ray-curable, or solvent-based. The solvent-based pressure-sensitive adhesive composition (II) may not contain a photocuring agent such as an ultraviolet curing agent.
　粘着剤組成物（II）は、例えば、光学積層体に使用できる。換言すれば、粘着剤組成物（II）は光学積層体用であってもよい。ただし、粘着剤組成物（II）の用途は、上記例に限定されない。 The adhesive composition (II) can be used, for example, in optical laminates. In other words, the pressure-sensitive adhesive composition (II) may be used for optical laminates. However, the use of the pressure-sensitive adhesive composition (II) is not limited to the above examples.
　なお、粘着剤組成物（II）から形成された粘着シートを加熱した後に、粘着シートに含まれる酢酸の含有量は、低くてもよい。粘着剤組成物（II）から形成された粘着シートを１０５℃で１２０時間加熱した後に、粘着シートは、質量基準で５０ｐｐｍ以下の酢酸を含有していてもよい。酢酸の含有量がこの程度に低い場合、高温環境を経た後であっても、光学積層体に着色がより生じにくい。 After heating the adhesive sheet formed from the adhesive composition (II), the content of acetic acid contained in the adhesive sheet may be low. After heating the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (II) at 105° C. for 120 hours, the pressure-sensitive adhesive sheet may contain 50 ppm or less of acetic acid on a mass basis. When the content of acetic acid is as low as this, the optical layered body is less likely to be colored even after being subjected to a high-temperature environment.
　粘着剤組成物（II）から形成された粘着シートを１０５℃で１２０時間加熱した後に、粘着シートに含まれる酢酸の含有量は、質量基準で、３０ｐｐｍ以下、２０ｐｐｍ以下、１５ｐｐｍ以下、１０ｐｐｍ以下、７ｐｐｍ以下、５ｐｐｍ以下、３ｐｐｍ以下、２．８ｐｐｍ以下、さらには２．５ｐｐｍ未満であってもよい。酢酸の含有量の下限は、特に限定されず、例えば、質量基準で０ｐｐｍ以上である。 After heating the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (II) at 105° C. for 120 hours, the content of acetic acid contained in the pressure-sensitive adhesive sheet is, on a mass basis, 30 ppm or less, 20 ppm or less, 15 ppm or less, 10 ppm or less, It may be 7 ppm or less, 5 ppm or less, 3 ppm or less, 2.8 ppm or less, or even less than 2.5 ppm. The lower limit of the acetic acid content is not particularly limited, and is, for example, 0 ppm or more on a mass basis.
（実施形態３）
［粘着剤組成物］
　本実施形態の粘着剤組成物（III）は、ポリエーテル構造を有するポリマー（Ｄ）を主成分として含み、導電剤をさらに含む。本発明者らの検討によれば、ポリマー（Ｄ）中のポリエーテル構造は、粘着剤組成物（III）に含まれる導電剤の電離を促進しうると共に、導電剤の電離は、粘着剤組成物から形成した粘着シートの表面抵抗値の低下に寄与しうる。 (Embodiment 3)
[Adhesive composition]
The pressure-sensitive adhesive composition (III) of this embodiment contains a polymer (D) having a polyether structure as a main component, and further contains a conductive agent. According to the studies of the present inventors, the polyether structure in the polymer (D) can promote the ionization of the conductive agent contained in the adhesive composition (III), and the ionization of the conductive agent It can contribute to the reduction of the surface resistance value of the pressure-sensitive adhesive sheet formed from the material.
　また、さらなる検討によれば、（vi）ポリエーテル構造を有するポリマー（Ｄ）を主成分として含む粘着剤組成物から形成した粘着シートを光学積層体に使用すると、高温環境を経た後に、不要な着色、特に赤色の着色、が生じる傾向にあること、（vii）着色は、偏光板が光学積層体に含まれている場合に多くみられること、及び（viii）着色の原因として、高温によってポリエーテル構造に起因して生じたラジカルが光学フィルムに移動して、光学フィルムに含まれるポリマーに作用する機構が推定されること、が判明した。ラジカルによるポリマーへの作用としては、例えば、偏光子に含まれる典型的なポリマーであるポリビニルアルコール（ＰＶＡ）のポリエン化が考えられる。ＰＶＡのポリエン化とは、ＰＶＡの主鎖に複数の炭素－炭素不飽和結合が生じて共役構造が伸張する現象であり、共役構造の伸張によって可視光域に吸収が生じ、着色（典型的には赤色）を呈すると考えられる。ＰＶＡのポリエン化は、熱に起因する加水分解によってホウ酸との架橋構造が消失してＰＶＡの末端ＯＨ基が多く露出し、露出したＯＨ基間の脱水縮合反応が進む現象として説明できる。また、この脱水縮合反応は、ラジカル反応であると推定される。なお、偏光子中のＰＶＡに限られず、高温下の光学フィルム内でのラジカル反応の進行は、着色等の光学特性の変化を光学フィルムにもたらしうると考えられる。なお、ポリエーテル構造に起因して生じたラジカルには、ポリエーテル構造から生じたラジカルを起点として他の成分（例えば、重合開始剤、架橋剤、酸化防止剤等）が関与して発生したラジカルが含まれうる。 Further, according to further studies, when a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing (vi) a polymer (D) having a polyether structure as a main component is used for an optical laminate, after passing through a high-temperature environment, unnecessary (vii) coloration is often observed when the polarizing plate is included in the optical laminate; It has been found that the mechanism is presumed that the radicals generated due to the ether structure migrate to the optical film and act on the polymer contained in the optical film. As an action of radicals on a polymer, for example, polyene conversion of polyvinyl alcohol (PVA), which is a typical polymer contained in polarizers, can be considered. Polyenation of PVA is a phenomenon in which multiple carbon-carbon unsaturated bonds occur in the main chain of PVA and the conjugated structure extends. is red). The polyene formation of PVA can be explained as a phenomenon in which the cross-linked structure with boric acid disappears due to hydrolysis caused by heat, exposing many terminal OH groups of PVA, and the dehydration condensation reaction between the exposed OH groups proceeds. Moreover, this dehydration condensation reaction is presumed to be a radical reaction. In addition, it is considered that progress of radical reaction in the optical film at high temperature, not limited to PVA in the polarizer, can cause changes in optical properties such as coloration to the optical film. Radicals generated due to the polyether structure include radicals generated with the involvement of other components (e.g., polymerization initiators, cross-linking agents, antioxidants, etc.) starting from the radicals generated from the polyether structure. can be included.
　粘着剤組成物（III）から粘着シートを形成したときに、形成された粘着シートでは、ラジカル発生量ＲＧ１０が１．５×１０１４個／ｇ以下に制限されている。ただし、ラジカル発生量ＲＧ１０は、電子スピン共鳴法（以下、ＥＳＲと記載）により評価した、１０５℃及び１０分の加熱時における粘着シートのラジカル発生量である。粘着シートとしたときに高温下でのラジカル発生量が制限された粘着剤組成物（III）は、高温を考慮すべき環境下での光学積層体への使用に適している。 When a pressure-sensitive adhesive sheet is formed from the pressure-sensitive adhesive composition (III), the formed pressure-sensitive adhesive sheet has a radical generation rate RG 10 limited to 1.5×10 14 /g or less. However, the radical generation amount RG 10 is the radical generation amount of the pressure-sensitive adhesive sheet when heated at 105° C. for 10 minutes, evaluated by an electron spin resonance method (hereinafter referred to as ESR). The pressure-sensitive adhesive composition (III), in which the amount of radicals generated at high temperatures is limited when made into a pressure-sensitive adhesive sheet, is suitable for use in optical laminates in environments where high temperatures should be considered.
　ラジカル発生量ＲＧ１０は、１．３×１０１４個／ｇ以下、１．０×１０１４個／ｇ以下、９．０×１０１３個／ｇ以下、さらには８．０×１０１３個／ｇ以下であってもよい。ラジカル発生量ＲＧ１０の下限は限定されないが、例えば、１．０×１０１０個／ｇ以上である。 Radical generation amount RG 10 is 1.3 × 10 14 /g or less, 1.0 × 10 14 /g or less, 9.0 × 10 13 /g or less, further 8.0 × 10 13 /g g or less. Although the lower limit of the radical generation amount RG 10 is not limited, it is, for example, 1.0×10 10 /g or more.
　粘着剤組成物（III）から粘着シートを形成したときに、形成された粘着シートにおけるラジカル発生量ＲＧ２０は、例えば、２．５×１０１４個／ｇ以下、２．０×１０１４個／ｇ以下、１．５×１０１４個／ｇ以下、１．２×１０１４個／ｇ以下、さらには１．０×１０１４個／ｇ以下であってもよい。ラジカル発生量ＲＧ２０の下限は限定されないが、例えば、１．０×１０１０個／ｇ以上である。ただし、ラジカル発生量ＲＧ２０は、ＥＳＲにより評価した、１０５℃及び２０分の加熱時における粘着シートのラジカル発生量である。粘着シートとしたときのラジカル発生量ＲＧ２０が上記範囲にある粘着剤組成物（III）は、高温を考慮すべき環境下での光学積層体への使用に特に適している。 When a pressure-sensitive adhesive sheet is formed from the pressure-sensitive adhesive composition (III), the radical generation amount RG 20 in the formed pressure-sensitive adhesive sheet is, for example, 2.5 × 10 14 / g or less, 2.0 × 10 14 / g or less, 1.5×10 14 pieces/g or less, 1.2×10 14 pieces/g or less, or 1.0×10 14 pieces/g or less. Although the lower limit of the radical generation amount RG 20 is not limited, it is, for example, 1.0×10 10 /g or more. However, the radical generation amount RG 20 is the radical generation amount of the pressure-sensitive adhesive sheet when heated at 105° C. for 20 minutes, evaluated by ESR. The pressure-sensitive adhesive composition (III) having a radical generation amount RG 20 in the pressure-sensitive adhesive sheet within the above range is particularly suitable for use in optical laminates under high-temperature environments.
　ラジカル発生量ＲＧ１０に対するＲＧ２０の比（ラジカル発生量比ＲＧ２０／ＲＧ１０）は、例えば、１．７以下であり、１．５以下、１．５未満、１．４以下、１．４未満、さらには１．３以下であってもよい。ＲＧ２０／ＲＧ１０の下限は、例えば、０．８以上である。粘着シートとしたときのＲＧ２０／ＲＧ１０が上記範囲にある粘着剤組成物（III）は、高温を考慮すべき環境下での光学積層体への使用に特に適している。 The ratio of RG 20 to radical generation amount RG 10 (radical generation amount ratio RG 20 /RG 10 ) is, for example, 1.7 or less, 1.5 or less, less than 1.5, 1.4 or less, 1.4. It may be less than or even 1.3 or less. The lower limit of RG20 / RG10 is, for example, 0.8 or more. The pressure-sensitive adhesive composition (III) having RG 20 /RG 10 within the above range when formed into a pressure-sensitive adhesive sheet is particularly suitable for use in optical laminates under environments where high temperatures should be considered.
　粘着剤組成物（III）から粘着シートを形成したときに、形成された粘着シートにおけるラジカル発生量ＲＧ３０は、例えば、３．０×１０１４個／ｇ以下、２．５×１０１４個／ｇ以下、２．０×１０１４個／ｇ以下、１．７×１０１４個／ｇ以下、１．５×１０１４個／ｇ以下、１．４×１０１４個／ｇ以下、１．３×１０１４個／ｇ以下、さらには１．２×１０１４個／ｇ以下であってもよい。ラジカル発生量ＲＧ３０の下限は限定されないが、例えば、１．０×１０１０個／ｇ以上である。ただし、ラジカル発生量ＲＧ３０は、ＥＳＲにより評価した、１０５℃及び３０分の加熱時における粘着シートのラジカル発生量である。粘着シートとしたときのラジカル発生量ＲＧ３０が上記範囲にある粘着剤組成物（Ｉ）は、高温を考慮すべき環境下での光学積層体への使用に特に適している。 When a pressure-sensitive adhesive sheet is formed from the pressure-sensitive adhesive composition (III), the radical generation amount RG 30 in the formed pressure-sensitive adhesive sheet is, for example, 3.0 × 10 14 / g or less, 2.5 × 10 14 / g or less, 2.0×10 14 pieces/g or less, 1.7×10 14 pieces/g or less, 1.5×10 14 pieces/g or less, 1.4×10 14 pieces/g or less, 1.3 It may be 1.2×10 14 pieces/g or less, or 1.2×10 14 pieces/g or less. Although the lower limit of the radical generation amount RG 30 is not limited, it is, for example, 1.0×10 10 /g or more. However, the radical generation amount RG 30 is the radical generation amount of the pressure-sensitive adhesive sheet when heated at 105° C. for 30 minutes, evaluated by ESR. The pressure-sensitive adhesive composition (I) having the radical generation amount RG 30 in the pressure-sensitive adhesive sheet within the above range is particularly suitable for use in optical laminates under high-temperature environments.
　ラジカル発生量ＲＧ１０に対するＲＧ３０の比（ラジカル発生量比ＲＧ３０／ＲＧ１０）は、例えば、２．２以下であり、２．０以下、１．９以下、１．９未満、１．７以下、１．６以下、さらには１．５以下であってもよい。ＲＧ３０／ＲＧ１０の下限は、例えば、０．８以上である。粘着シートとしたときのＲＧ３０／ＲＧ１０が上記範囲にある粘着剤組成物（Ｉ）は、高温を考慮すべき環境下での光学積層体への使用に特に適している。 The ratio of RG 30 to radical generation amount RG 10 (radical generation amount ratio RG 30 /RG 10 ) is, for example, 2.2 or less, 2.0 or less, 1.9 or less, less than 1.9, 1.7. 1.6 or less, or even 1.5 or less. The lower limit of RG30 / RG10 is, for example, 0.8 or more. The pressure-sensitive adhesive composition (I) having RG 30 /RG 10 in the above range when formed into a pressure-sensitive adhesive sheet is particularly suitable for use in optical laminates under environments where high temperatures should be considered.
　粘着剤組成物（III）について上記ラジカル発生量は、以下のように評価できる。まず、評価対象である粘着剤組成物から形成された粘着シートの一部を採取し、ＥＳＲ試料管の先端部分に詰めて試料管を密閉する。試料管に収容する上記一部の量は、５０ｍｇ程度とする。粘着剤組成物が粘着シートを形成する前の状態（一例として溶液状）である場合は、例えば、後述する粘着シートの作製方法に基づいて粘着剤組成物から粘着シートを形成し、形成した粘着シートの一部を採取する。次に、試料管をＥＳＲ装置にセットし、室温（２５±５℃）から昇温速度３０℃／分で１０５℃まで昇温させ、１０５℃に到達した時点を基準として、１０分、２０分、及び３０分の各時間が経過した時点でＥＳＲ測定を実施する。測定により観測されたＥＳＲ信号の信号強度から、ラジカル発生量を定量的に算出できる。発生したラジカルに対応するＥＳＲ信号は、信号のｇ値（信号の中心位置）及び***幅に基づいて選択できる。加熱することなくＥＳＲ測定を実施して得られたプロファイルと対比することで、ラジカルに対応するＥＳＲ信号を探してもよい。ラジカルに対応するＥＳＲ信号は、ポリエーテル構造から生じたラジカルを起点として他の成分が関与して発生したラジカルの信号であってもよい。ラジカルに対応するＥＳＲ信号のうち、最も強度の強い信号を選択できる。なお、ＥＳＲによって物質に含まれるラジカルの定量評価が可能であることは、当業者に周知である。粘着シート（粘着剤組成物の硬化物）におけるラジカル発生量についても、公知の手法に詳細を従って評価することが可能である。 The amount of generated radicals for the pressure-sensitive adhesive composition (III) can be evaluated as follows. First, a part of the adhesive sheet formed from the adhesive composition to be evaluated is collected, packed in the tip portion of the ESR sample tube, and the sample tube is sealed. The amount of the part contained in the sample tube is about 50 mg. When the pressure-sensitive adhesive composition is in a state before forming a pressure-sensitive adhesive sheet (as an example, in the form of a solution), for example, a pressure-sensitive adhesive sheet is formed from the pressure-sensitive adhesive composition based on the method for producing a pressure-sensitive adhesive sheet described later, and the formed pressure-sensitive adhesive Take a portion of the sheet. Next, the sample tube was set in the ESR device and heated from room temperature (25±5°C) to 105°C at a heating rate of 30°C/min. , and 30 minutes, ESR measurements are performed. The amount of radical generation can be quantitatively calculated from the signal intensity of the ESR signal observed by the measurement. The ESR signal corresponding to the generated radicals can be selected based on the signal's g-value (the center position of the signal) and the splitting width. ESR signals corresponding to radicals may be looked for by comparing them with profiles obtained by performing ESR measurements without heating. The ESR signal corresponding to radicals may be a signal of radicals generated with the involvement of other components starting from radicals generated from the polyether structure. The strongest signal can be selected from among the ESR signals corresponding to radicals. It is well known to those skilled in the art that ESR enables quantitative evaluation of radicals contained in substances. The amount of radicals generated in the pressure-sensitive adhesive sheet (cured product of the pressure-sensitive adhesive composition) can also be evaluated in detail according to known methods.
　粘着剤組成物におけるラジカル発生量は、例えば、粘着剤組成物の組成、ポリマー（Ｄ）の組成及び含有率、導電剤の種類及び含有率、ポリマー（Ｄ）及び導電剤以外に粘着剤組成物に配合されている材料の種類、含有率及び組み合わせ、並びに、粘着シートの硬化の程度等により変化しうる。粘着シートの硬化の程度は、例えば溶剤型の粘着剤組成物（III）である場合には、粘着剤組成物を含む溶液の固形分濃度及び粘度、基材フィルム上への塗布膜の形成条件、塗布膜の乾燥条件、並びに、塗布膜の乾燥を実施する装置（加熱炉等）が非密閉型であるときには当該装置が置かれた雰囲気の温度及び湿度等により変化しうる。 The amount of radicals generated in the adhesive composition is, for example, the composition of the adhesive composition, the composition and content of the polymer (D), the type and content of the conductive agent, the adhesive composition other than the polymer (D) and the conductive agent. It may change depending on the type, content and combination of materials blended in the adhesive sheet, the degree of curing of the adhesive sheet, and the like. The degree of curing of the pressure-sensitive adhesive sheet, for example, in the case of a solvent-based pressure-sensitive adhesive composition (III), the solid content concentration and viscosity of the solution containing the pressure-sensitive adhesive composition, the conditions for forming a coating film on the base film , conditions for drying the coating film, and when the device for drying the coating film (heating furnace, etc.) is a non-sealed type, the temperature and humidity of the atmosphere in which the device is placed may change.
　粘着剤組成物（III）から粘着シートを形成したときに、形成された粘着シートは１×１０１０Ω／□以下の表面抵抗値を有する。表面抵抗値は、５×１０９Ω／□以下、１×１０９Ω／□以下、８×１０８Ω／□以下、６×１０８Ω／□以下、５×１０８Ω／□以下、４×１０８Ω／□以下、３×１０８Ω／□以下、さらには２×１０８Ω／□以下であってもよい。表面抵抗値の下限は、例えば１×１０６Ω／□以上であり、１×１０７Ω／□以上であってもよい。粘着シートとしたときの表面抵抗値が上記範囲にある粘着剤組成物（III）は、静電気が生じやすい環境下、例えば車両の内部、における使用に適している。 When a pressure-sensitive adhesive sheet is formed from the pressure-sensitive adhesive composition (III), the formed pressure-sensitive adhesive sheet has a surface resistance value of 1×10 10 Ω/□ or less. The surface resistance value is 5×10 9 Ω/□ or less, 1×10 9 Ω/□ or less, 8×10 8 Ω/□ or less, 6×10 8 Ω/□ or less, 5×10 8 Ω/□ or less, It may be 4×10 8 Ω/□ or less, 3×10 8 Ω/□ or less, or even 2×10 8 Ω/□ or less. The lower limit of the surface resistance value is, for example, 1×10 6 Ω/□ or more, and may be 1×10 7 Ω/□ or more. The pressure-sensitive adhesive composition (III) having a surface resistance value within the above range when formed into a pressure-sensitive adhesive sheet is suitable for use in an environment where static electricity is likely to occur, such as inside a vehicle.
　＜ポリマー（Ｄ）＞
　ポリマー（Ｄ）の例は、（メタ）アクリル系ポリマー、ウレタン系ポリマー、シリコーン系ポリマー及びゴム系ポリマーである。ただし、ポリマー（Ｄ）は、ポリエーテル構造を有する限り、上記例に限定されない。ポリマー（Ｄ）は、好ましくは、（メタ）アクリル系ポリマーである。換言すれば、粘着剤組成物（III）は（メタ）アクリル系ポリマーを主成分として含んでいてもよい。さらに換言すれば、粘着剤組成物（III）はアクリル系粘着剤組成物であってもよい。「主成分」は、上述した意味を有する。 <Polymer (D)>
Examples of polymer (D) are (meth)acrylic polymers, urethane polymers, silicone polymers and rubber polymers. However, the polymer (D) is not limited to the above examples as long as it has a polyether structure. Polymer (D) is preferably a (meth)acrylic polymer. In other words, the pressure-sensitive adhesive composition (III) may contain a (meth)acrylic polymer as a main component. Furthermore, in other words, the adhesive composition (III) may be an acrylic adhesive composition. "Principal component" has the meaning given above.
　ポリマー（Ｄ）は、実施形態１で説明したポリマー（Ａ）であってもよい。 The polymer (D) may be the polymer (A) described in the first embodiment.
　＜導電剤＞
　粘着剤組成物（III）は、導電剤（帯電防止剤）をさらに含む。粘着剤組成物（III）は、１種又は２種以上の導電剤を含んでいてもよい。導電剤の例は、塩等のイオン性化合物である。イオン性化合物は、常温（２５℃）で液体のイオン液体であってもよい。導電剤の詳細は、実施形態１で説明したとおりである。 <Conductive agent>
The adhesive composition (III) further contains a conductive agent (antistatic agent). The pressure-sensitive adhesive composition (III) may contain one or more conductive agents. Examples of conductive agents are ionic compounds such as salts. The ionic compound may be an ionic liquid that is liquid at normal temperature (25° C.). Details of the conductive agent are as described in the first embodiment.
　＜添加剤＞
　粘着剤組成物（III）は、ポリマー（Ｄ）及び導電剤以外の材料をさらに含んでいてもよい。当該材料の例は、添加剤である。添加剤の例は、架橋剤、シランカップリング剤、顔料及び染料等の着色剤、紫外線吸収剤、界面活性剤、可塑剤、粘着性付与剤、表面潤滑剤、レベリング剤、リワーク向上剤、軟化剤、酸化防止剤、老化防止剤、光安定剤、重合禁止剤、防錆剤、無機充填材、有機充填材、金属粉等の粉体、粒子、及び箔状物である。添加剤の詳細は、実施形態１で説明したとおりである。 <Additive>
The adhesive composition (III) may further contain materials other than the polymer (D) and the conductive agent. Examples of such materials are additives. Examples of additives include cross-linking agents, silane coupling agents, coloring agents such as pigments and dyes, UV absorbers, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, rework improvers, softening agents, agents, antioxidants, anti-aging agents, light stabilizers, polymerization inhibitors, rust inhibitors, inorganic fillers, organic fillers, powders such as metal powders, particles, and foils. Details of the additive are as described in the first embodiment.
　粘着剤組成物（III）の型は、例えば、エマルション型、溶剤型（溶液型）、活性エネルギー線硬化型（光硬化型）、熱溶融型（ホットメルト型）である。耐久性に優れる粘着シートを形成できる観点からは、粘着剤組成物（III）は、溶剤型又は活性エネルギー線硬化型であってもよく、溶剤型であってもよい。溶剤型の粘着剤組成物（III）は、紫外線硬化剤等の光硬化剤を含まなくてもよい。 Types of the pressure-sensitive adhesive composition (III) are, for example, emulsion type, solvent type (solution type), active energy ray-curable type (light-curing type), and heat-melting type (hot-melt type). From the viewpoint of forming a highly durable PSA sheet, the PSA composition (III) may be solvent-based, active energy ray-curable, or solvent-based. The solvent-based pressure-sensitive adhesive composition (III) may not contain a photocuring agent such as an ultraviolet curing agent.
　粘着剤組成物（III）は、例えば、光学積層体に使用できる。換言すれば、粘着剤組成物（III）は光学積層体用であってもよい。ただし、粘着剤組成物（III）の用途は、上記例に限定されない。 The adhesive composition (III) can be used, for example, in optical laminates. In other words, the pressure-sensitive adhesive composition (III) may be used for optical laminates. However, the use of the pressure-sensitive adhesive composition (III) is not limited to the above examples.
　粘着剤組成物（III）から形成された粘着シートは、上述した範囲のラジカル発生量ＲＧ１０を有しうる。また、粘着剤組成物（III）から形成された粘着シートは、上述した範囲のラジカル発生量ＲＧ２０及びＲＧ３０、並びにラジカル発生量比ＲＧ２０／ＲＧ１０及びＲＧ３０／ＲＧ１０から選ばれる少なくとも１つの特性を有しうる。 A pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (III) may have a radical generation amount RG 10 within the range described above. In addition, the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition (III) has at least radical generation amounts RG 20 and RG 30 within the ranges described above, and radical generation amount ratios RG 20 /RG 10 and RG 30 /RG 10 . It can have one property.
（実施形態４）
［粘着シート］
　本実施形態の粘着シートの一例を図１に示す。図１の粘着シート１は、粘着剤組成物（Ｉ）から形成されたシート、粘着剤組成物（II）から形成されたシート、又は粘着剤組成物（III）から形成されたシートである。 (Embodiment 4)
[Adhesive sheet]
An example of the adhesive sheet of this embodiment is shown in FIG. The pressure-sensitive adhesive sheet 1 in FIG. 1 is a sheet formed from the pressure-sensitive adhesive composition (I), a sheet formed from the pressure-sensitive adhesive composition (II), or a sheet formed from the pressure-sensitive adhesive composition (III).
　粘着シート１が粘着剤組成物（Ｉ）から形成される場合、粘着シート１は、粘着剤組成物（Ｉ）の説明において上述した範囲の表面抵抗値を有しうる。粘着シート１が粘着剤組成物（II）から形成される場合、粘着シートは、粘着剤組成物（II）の説明において上述した範囲のギ酸を含有しうる。粘着シート１が粘着剤組成物（III）から形成される場合、粘着シート１は、粘着剤組成物（III）の説明において上述した範囲のラジカル発生量ＲＧ１０を有しうる。また、粘着シート１が粘着剤組成物（III）から形成される場合、粘着シート１は、粘着剤組成物（III）の説明において上述した範囲のラジカル発生量ＲＧ２０及びＲＧ３０、並びにラジカル発生量比ＲＧ２０／ＲＧ１０及びＲＧ３０／ＲＧ１０から選ばれる少なくとも１つの特性を有しうる。 When the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (I), the pressure-sensitive adhesive sheet 1 may have a surface resistance value within the range described above in the description of the pressure-sensitive adhesive composition (I). When the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (II), the pressure-sensitive adhesive sheet may contain formic acid within the range described above in the description of the pressure-sensitive adhesive composition (II). When the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (III), the pressure-sensitive adhesive sheet 1 may have a radical generation amount RG 10 within the range described above in the description of the pressure-sensitive adhesive composition (III). Further, when the pressure-sensitive adhesive sheet 1 is formed from the pressure-sensitive adhesive composition (III), the pressure-sensitive adhesive sheet 1 has radical generation amounts RG 20 and RG 30 within the ranges described above in the description of the pressure-sensitive adhesive composition (III), and radical generation It may have at least one characteristic selected from the quantitative ratios RG20 / RG10 and RG30 / RG10 .
　粘着シート１は、粘着剤組成物（Ｉ）又は粘着剤組成物（II）から以下の方法によって形成できる。以下は、粘着剤組成物（Ｉ）から粘着シート１を形成する方法を述べるが、粘着剤組成物（II）及び粘着剤組成物（III）の場合も、同様の方法により粘着シート１を形成できる。 The adhesive sheet 1 can be formed from the adhesive composition (I) or the adhesive composition (II) by the following method. The method for forming the PSA sheet 1 from the PSA composition (I) is described below, and the PSA sheet 1 is formed by the same method for the PSA composition (II) and the PSA composition (III). can.
　溶剤型については、例えば、粘着剤組成物（Ｉ）又は粘着剤組成物（Ｉ）と溶剤との混合物を基材フィルムに塗布して塗布膜を形成し、形成された塗布膜を乾燥して粘着シート１を形成する。乾燥時の熱により粘着剤組成物（Ｉ）は熱硬化する。活性エネルギー線硬化型（光硬化型）については、例えば、重合によりポリマー（Ａ）となる単量体（群）、並びに必要に応じて、単量体（群）の部分重合物、重合開始剤、添加剤及び溶剤等の混合物を基材フィルムに塗布し、形成された塗布膜に活性エネルギー線を照射して粘着シート１を形成する。活性エネルギー線の照射前に、塗布膜を乾燥して溶剤を除去してもよい。基材フィルムは、塗布面に剥離処理がなされたフィルム（はく離ライナー）であってもよい。 For the solvent type, for example, the pressure-sensitive adhesive composition (I) or a mixture of the pressure-sensitive adhesive composition (I) and a solvent is applied to a base film to form a coating film, and the formed coating film is dried. An adhesive sheet 1 is formed. The pressure-sensitive adhesive composition (I) is thermally cured by heat during drying. For the active energy ray-curable type (photocurable type), for example, a monomer (group) that becomes the polymer (A) by polymerization, and, if necessary, a partial polymer of the monomer (group), a polymerization initiator , an additive, a solvent, and the like are applied to a substrate film, and the formed coating film is irradiated with an active energy ray to form an adhesive sheet 1 . The solvent may be removed by drying the coating film before irradiation with the active energy ray. The base film may be a film (release liner) whose coating surface has been subjected to a release treatment.
　基材フィルム上に形成された粘着シート１は、任意の層に転写できる。また、基材フィルムは偏光板等の光学フィルムであってもよく、この場合、粘着シート１と光学フィルムとを含む光学積層体が得られる。 The adhesive sheet 1 formed on the base film can be transferred to any layer. Also, the base film may be an optical film such as a polarizing plate, in which case an optical laminate including the adhesive sheet 1 and the optical film is obtained.
　基材フィルムへの塗布には、公知の方法を採用できる。塗布は、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコートにより実施できる。 A known method can be adopted for application to the base film. Coating is, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, extrusion coating using a die coater, or the like. can be implemented by
　溶剤型について、塗布後の乾燥温度は、例えば４０～２００℃である。乾燥時間は、例えば５秒～２０分であり、５秒～１０分、さらには１０秒～５分であってもよい。活性エネルギー線硬化型について、塗布後の乾燥を行う場合の乾燥温度及び乾燥時間は、上記範囲にあってもよい。 For the solvent type, the drying temperature after coating is, for example, 40 to 200°C. The drying time is, for example, 5 seconds to 20 minutes, and may be 5 seconds to 10 minutes, or even 10 seconds to 5 minutes. For the active energy ray-curable type, the drying temperature and drying time when drying after coating may be within the above ranges.
　基材フィルムに塗布する組成物及び混合物は、取り扱い及び塗工に適した粘度を有することが好ましい。このため、活性エネルギー線硬化型については、塗布する混合物は、単量体（群）の部分重合物を含むことが好ましい。 The composition and mixture to be applied to the base film preferably have a viscosity suitable for handling and coating. Therefore, for the active energy ray-curable type, the mixture to be applied preferably contains a partial polymer of the monomer (group).
　粘着シート１の厚さは、例えば２μｍ～５５μｍであり、２μｍ～３０μｍ、５μｍ～２５μｍ、さらには１０μｍ～２０μｍであってもよい。 The thickness of the adhesive sheet 1 is, for example, 2 μm to 55 μm, and may be 2 μm to 30 μm, 5 μm to 25 μm, or even 10 μm to 20 μm.
　粘着シート１は、例えば、光学積層体に使用できる。換言すれば、粘着シート１は光学積層体用であってもよい。ただし、粘着シート１の用途は、上記例に限定されない。 The adhesive sheet 1 can be used, for example, in an optical laminate. In other words, the pressure-sensitive adhesive sheet 1 may be used for optical laminates. However, the application of the adhesive sheet 1 is not limited to the above examples.
（実施形態５）
［光学積層体］
　本実施形態の光学積層体の一例を図２に示す。図２の光学積層体１０Ａは、粘着シート１と光学フィルムとを含む。図２の光学フィルムは偏光板２である。偏光板２は、偏光子を含む。粘着シート１と偏光板２とは互いに積層されている。光学積層体１０Ａは、粘着シート１を介して、対象物（例えば、画像表示パネル）と貼り合わせることが可能である。光学積層体１０Ａは、粘着シート付き光学フィルム、より具体的には、粘着シート付き偏光板、として使用できる。偏光板２以外の光学フィルムの例は、位相差フィルム、並びに偏光板及び／又は位相差フィルムを含む積層フィルムである。光学フィルムは、円偏光板であってもよい。ただし、光学フィルムは上記例に限定されない。光学フィルムは、ガラス製のフィルムを含んでいてもよい。 (Embodiment 5)
[Optical laminate]
An example of the optical laminate of this embodiment is shown in FIG. The optical laminate 10A of FIG. 2 includes the adhesive sheet 1 and an optical film. The optical film in FIG. 2 is the polarizing plate 2 . The polarizing plate 2 contains a polarizer. The adhesive sheet 1 and the polarizing plate 2 are laminated together. The optical layered body 10A can be attached to an object (for example, an image display panel) with the adhesive sheet 1 interposed therebetween. The optical laminate 10A can be used as an optical film with an adhesive sheet, more specifically, as a polarizing plate with an adhesive sheet. Examples of optical films other than the polarizing plate 2 are retardation films and laminated films containing polarizing plates and/or retardation films. The optical film may be a circular polarizer. However, the optical film is not limited to the above examples. The optical film may include a film made of glass.
　＜偏光板＞
　偏光板２は、典型的には、偏光子及び保護フィルム（透明保護フィルム）を含む積層体である。保護フィルムは、例えば、偏光子の主面（最も広い面積を有する表面）に接して配置されている。偏光子は、２つの保護フィルムの間に配置されていてもよい。光学積層体１０Ａは保護フィルムをさらに含み、保護フィルムは、偏光子の少なくとも一方の面に配置されていてもよい。 <Polarizing plate>
The polarizing plate 2 is typically a laminate containing a polarizer and a protective film (transparent protective film). The protective film is arranged, for example, in contact with the main surface of the polarizer (the surface with the widest area). A polarizer may be placed between two protective films. The optical laminate 10A may further include a protective film, and the protective film may be arranged on at least one surface of the polarizer.
　偏光子としては、特に限定されず、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素、二色性染料等の二色性物質を吸着させて一軸延伸したもの；ポリビニルアルコールの脱水処理物、ポリ塩化ビニルの脱塩酸処理物等のポリエン系配向フィルム等が挙げられる。偏光子は、典型的には、ポリビニルアルコール系フィルム（ポリビニルアルコール系フィルムには、エチレン・酢酸ビニル共重合体系部分ケン化フィルムが含まれる）、及び、ヨウ素等の二色性物質からなる。 The polarizer is not particularly limited. A uniaxially stretched film obtained by adsorbing a dichroic substance such as a dye; and a polyene-based oriented film such as dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride. A polarizer typically consists of a polyvinyl alcohol film (the polyvinyl alcohol film includes an ethylene/vinyl acetate copolymer-based partially saponified film) and a dichroic substance such as iodine.
　偏光子の厚さは、特に限定されず、例えば８０μｍ以下であり、５０μｍ以下、３０μｍ以下、２５μｍ以下、さらには２０μｍ以下であってもよい。偏光子の厚さの下限は、特に限定されず、例えば１μｍ以上であり、５μｍ以上、１０μｍ以上、さらには１５μｍ以上であってもよい。薄型の偏光子（例えば、厚さ２０μｍ以下）は、寸法変化が抑制されており、光学積層体の耐久性、特に高温下の耐久性、の向上に寄与しうる。 The thickness of the polarizer is not particularly limited. The lower limit of the thickness of the polarizer is not particularly limited. A thin polarizer (for example, a thickness of 20 μm or less) is suppressed in dimensional change, and can contribute to an improvement in the durability of the optical layered body, especially at high temperatures.
　保護フィルムの材料としては、例えば、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れる熱可塑性樹脂が用いられる。このような熱可塑性樹脂の具体例としては、トリアセチルセルロース等のセルロース樹脂、ポリエステル樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリオレフィン樹脂、（メタ）アクリル樹脂、環状ポリオレフィン樹脂（ノルボルネン系樹脂）、ポリアリレート樹脂、ポリスチレン樹脂、ポリビニルアルコール樹脂、及び、これらの混合物が挙げられる。保護フィルムの材料は、（メタ）アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化性樹脂又は紫外線硬化型樹脂であってもよい。偏光板２が２つの保護フィルムを有する場合、２つの保護フィルムの材料は、互いに同じであってもよく、異なっていてもよい。例えば、偏光子の一方の主面に対して、接着剤を介して、熱可塑性樹脂で構成された保護フィルムが貼り合わされ、偏光子の他方の主面に対して、熱硬化性樹脂又は紫外線硬化型樹脂で構成された保護フィルムが貼り合わされていてもよい。保護フィルムは、任意の添加剤を１種類以上含んでいてもよい。添加剤としては、例えば、紫外線吸収剤、酸化防止剤、滑剤、可塑剤、離型剤、着色防止剤、難燃剤、核剤、帯電防止剤、顔料、着色剤等が挙げられる。 As a material for the protective film, for example, a thermoplastic resin that is excellent in transparency, mechanical strength, thermal stability, water barrier properties, isotropy, etc. is used. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, cyclic Polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof can be used. The material of the protective film may be a thermosetting resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, or silicone, or an ultraviolet curable resin. When the polarizing plate 2 has two protective films, the materials of the two protective films may be the same or different. For example, a protective film made of a thermoplastic resin is attached to one main surface of the polarizer via an adhesive, and a thermosetting resin or ultraviolet curable resin is attached to the other main surface of the polarizer. A protective film made of mold resin may be attached. The protective film may contain one or more optional additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants and the like.
　保護フィルムの透湿度は、特に限定されず、２００ｇ／（ｍ２・ｄａｙ）以下であってもよく、５０ｇ／（ｍ２・ｄａｙ）以下であってもよい。この場合、偏光板２の内部に空気中の水分が侵入することを抑制でき、偏光板２の水分率の変化を抑制できる。これにより、保存時等において、偏光板２のカールや寸法変化の発生を抑制できる。また、透湿度が上記範囲に制限されている保護フィルムは、粘着シート１と偏光子との間に配置された場合には、高温下における粘着シート１からのラジカルの移動の阻害に寄与しうる。透湿度が低い保護フィルムを形成する材料としては、例えば、ポリエステル系ポリマー、ポリカーボネート系ポリマー、アリレート系ポリマー、アミド系ポリマー、オレフィン系ポリマー、環状オレフィン系ポリマー、（メタ）アクリル系ポリマー、及びこれらの混合物が挙げられる。 The moisture permeability of the protective film is not particularly limited, and may be 200 g/(m 2 ·day) or less, or may be 50 g/(m 2 ·day) or less. In this case, moisture in the air can be prevented from entering the inside of the polarizing plate 2, and a change in the moisture content of the polarizing plate 2 can be suppressed. As a result, it is possible to prevent the polarizing plate 2 from curling or changing its dimension during storage or the like. In addition, a protective film whose moisture permeability is limited to the above range, when placed between the adhesive sheet 1 and the polarizer, can contribute to inhibition of movement of radicals from the adhesive sheet 1 at high temperatures. . Examples of materials for forming protective films with low moisture permeability include polyester-based polymers, polycarbonate-based polymers, arylate-based polymers, amide-based polymers, olefin-based polymers, cyclic olefin-based polymers, (meth)acrylic-based polymers, and these mixtures.
　保護フィルムの透湿度は、ＪＩＳ　Ｚ０２０８：１９７６の透湿度試験（カップ法）に準じて、以下の方法によって測定できる。まず、保護フィルムを直径６０ｍｍに切断し、測定サンプルを準備する。次に、約１５ｇの塩化カルシウムが配置された透湿カップに測定サンプルをセットする。この透湿カップを温度４０℃、湿度９２％ＲＨに設定された恒温機に配置し、２４時間放置することによって透湿度試験を行う。試験前後における塩化カルシウムの重量の増加量を測定することによって、保護フィルムの透湿度を特定できる。 The moisture permeability of the protective film can be measured by the following method according to JIS Z0208:1976 moisture permeability test (cup method). First, the protective film is cut to a diameter of 60 mm to prepare a measurement sample. Next, a measurement sample is set in a moisture-permeable cup in which about 15 g of calcium chloride is placed. This moisture permeable cup is placed in a constant temperature machine set at a temperature of 40° C. and a humidity of 92% RH, and left for 24 hours to conduct a moisture permeability test. By measuring the amount of increase in the weight of calcium chloride before and after the test, the moisture permeability of the protective film can be determined.
　保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄膜性等の点より１０～２００μｍ程度である。 Although the thickness of the protective film can be determined as appropriate, it is generally about 10 to 200 μm in terms of strength, workability such as handleability, and thinness.
　偏光子と保護フィルムとは通常、水系接着剤等を介して密着している。水系接着剤としては、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス、水系ポリウレタン、水系ポリエステル等を例示できる。上記の接着剤以外の他の接着剤としては、紫外線硬化型接着剤、電子線硬化型接着剤等が挙げられる。電子線硬化型偏光板用接着剤は、各種の保護フィルムに対して、好適な接着性を示す。接着剤は、金属化合物フィラーを含んでいてもよい。 The polarizer and protective film are usually in close contact via a water-based adhesive or the like. Examples of water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latexes, water-based polyurethanes, and water-based polyesters. Examples of adhesives other than the adhesives described above include ultraviolet curing adhesives, electron beam curing adhesives, and the like. Electron beam curing adhesives for polarizing plates exhibit suitable adhesion to various protective films. The adhesive may contain a metallic compound filler.
　偏光板では、保護フィルムに代えて、位相差フィルム等を偏光子上に形成することもできる。保護フィルム上には、さらに別の保護フィルムを設けること、位相差フィルム等を設けること等もできる。 In the polarizing plate, a retardation film or the like can be formed on the polarizer instead of the protective film. It is also possible to provide another protective film, a retardation film, etc. on the protective film.
　保護フィルムについて、偏光子と接着している表面と対向する表面には、ハードコート層が設けられていてもよく、反射防止、スティッキング防止、拡散、アンチグレア等を目的とした処理を施すこともできる。 Regarding the protective film, a hard coat layer may be provided on the surface facing the surface adhered to the polarizer, and a treatment for the purpose of antireflection, antisticking, diffusion, antiglare, etc. may be applied. .
　加熱試験前における光学積層体１０Ａの厚さ方向の光線透過率をＴｓａ０と定義し、９５℃で５００時間光学積層体１０Ａを加熱した後における、光学積層体１０Ａの厚さ方向の光線透過率をＴｓａ５００と定義する。このとき、加熱試験前後における光線透過率の差ΔＴｓａ＝Ｔｓａ５００－Ｔｓａ０は、例えば、ΔＴｓａ＞０％を満たす。これにより、光学積層体は、高温を考慮すべき環境下での使用により適している。加熱試験の詳細は、実施例の欄に記載する。 The light transmittance in the thickness direction of the optical layered body 10A before the heating test is defined as Tsa 0 , and the light transmittance in the thickness direction of the optical layered body 10A after heating the optical layered body 10A at 95°C for 500 hours. is defined as Tsa 500 . At this time, the difference in light transmittance ΔTsa=Tsa 500 −Tsa 0 before and after the heating test satisfies, for example, ΔTsa>0%. This makes the optical layered body more suitable for use in environments where high temperatures should be considered. The details of the heating test are described in the Examples section.
　加熱試験前における光学積層体１０Ａの厚さ方向の光線透過率をＴｓｂ０と定義し、１０５℃で５００時間光学積層体１０Ａを加熱した後における、光学積層体１０Ａの厚さ方向の光線透過率をＴｓｂ５００と定義する。このとき、加熱試験前後における光線透過率の差ΔＴｓｂ＝Ｔｓｂ５００－Ｔｓｂ０は、例えば、ΔＴｓｂ＞－１０％を満たす。ΔＴｓｂは、ΔＴｓｂ＞０％を満たしていてもよい。 The light transmittance in the thickness direction of the optical layered body 10A before the heating test is defined as Tsb 0 , and the light transmittance in the thickness direction of the optical layered body 10A after heating the optical layered body 10A at 105°C for 500 hours. is defined as Tsb 500 . At this time, the difference in light transmittance ΔTsb=Tsb 500 −Tsb 0 before and after the heating test satisfies, for example, ΔTsb>−10%. ΔTsb may satisfy ΔTsb>0%.
　本実施形態の光学積層体の別の一例を図３に示す。図３の光学積層体１０Ｂは、はく離ライナー３、粘着シート１及び偏光板２がこの順に積層された積層構造を有する。光学積層体１０Ｂは、はく離ライナー３を剥離することで、粘着シート付き偏光板として使用できる。以下の各例は、技術的に矛盾しない限り、相互に組み合わされてもよい。 Another example of the optical laminate of this embodiment is shown in FIG. The optical layered body 10B of FIG. 3 has a layered structure in which a release liner 3, an adhesive sheet 1 and a polarizing plate 2 are layered in this order. By peeling off the release liner 3, the optical laminate 10B can be used as a polarizing plate with an adhesive sheet. Each of the examples below may be combined with each other unless they are technically inconsistent.
　はく離ライナー３の構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔、及びこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。 Materials constituting the release liner 3 include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films; porous materials such as paper, cloth, and nonwoven fabric; nets, foam sheets, metal foils, and laminates thereof. However, a plastic film is preferably used because of its excellent surface smoothness.
　プラスチックフィルムとしては、粘着シート１を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 The plastic film is not particularly limited as long as it is a film capable of protecting the adhesive sheet 1. Examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, and vinyl chloride copolymer. film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film and the like.
　はく離ライナー３の厚さは、通常５～２００μｍ、好ましくは５～１００μｍ程度である。はく離ライナー３には、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型及び防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理が施されてもよい。特に、はく離ライナー３の表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜行うことにより、粘着シート１からの剥離性をより高めることができる。 The thickness of the release liner 3 is usually about 5-200 μm, preferably about 5-100 μm. The release liner 3 may be subjected, if necessary, to silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents, release and antifouling treatment using silica powder, etc., coating type, kneading type, vapor deposition. The mold may be subjected to antistatic treatment. In particular, by subjecting the surface of the release liner 3 to a release treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc., the releasability from the adhesive sheet 1 can be further enhanced.
　なお、上述のとおり、粘着シート１を作製するときに利用した基材フィルムをはく離ライナー３として用いてもよい。 Note that, as described above, the base film used when producing the adhesive sheet 1 may be used as the release liner 3.
　本実施形態の光学積層体の別の一例を図４に示す。図４の光学積層体１０Ｃは、はく離ライナー３、粘着シート１、位相差フィルム５、層間粘着剤４及び偏光板２がこの順に積層された積層構造を有する。光学積層体１０Ｃは、はく離ライナー３を剥離した後、例えば画像表示セルに貼付して使用できる。 Another example of the optical laminate of this embodiment is shown in FIG. The optical laminate 10C of FIG. 4 has a laminated structure in which a release liner 3, an adhesive sheet 1, a retardation film 5, an interlayer adhesive 4 and a polarizing plate 2 are laminated in this order. After peeling off the release liner 3, the optical layered body 10C can be used by attaching it to, for example, an image display cell.
　位相差フィルム５としては、高分子フィルムを延伸させて得られるものや液晶材料を配向、固定化させたものを用いることができる。位相差フィルム５は、例えば、面内及び／又は厚さ方向に複屈折を有する。 As the retardation film 5, a film obtained by stretching a polymer film or a film obtained by aligning and fixing a liquid crystal material can be used. The retardation film 5 has birefringence in the plane and/or in the thickness direction, for example.
　位相差フィルム５には、反射防止用位相差フィルム（特開２０１２－１３３３０３号公報〔０２２１〕、〔０２２２〕、〔０２２８〕参照）、視野角補償用相差フィルム（特開２０１２－１３３３０３号公報〔０２２５〕、〔０２２６〕参照）、視野角補償用の傾斜配向位相差フィルム（特開２０１２－１３３３０３号公報〔０２２７〕参照）等が含まれる。 The retardation film 5 includes an antireflection retardation film (see JP 2012-133303 [0221], [0222], [0228]), a viewing angle compensation retardation film (JP 2012-133303 [ 0225], [0226]), an oblique orientation retardation film for viewing angle compensation (see JP-A-2012-133303 [0227]), and the like.
　位相差フィルム５の具体的な構成、例えば、位相差値、配置角度、３次元複屈折率、単層か多層か等は特に限定されず、公知の位相差フィルムを使用することができる。 The specific configuration of the retardation film 5, such as retardation value, arrangement angle, three-dimensional birefringence, whether it is a single layer or multiple layers, is not particularly limited, and a known retardation film can be used.
　位相差フィルム５の厚さは、好ましくは２０μｍ以下であり、より好ましくは１０μｍ以下であり、さらに好ましくは１～９μｍであり、特に好ましくは３～８μｍである。 The thickness of the retardation film 5 is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 1 to 9 μm, particularly preferably 3 to 8 μm.
　位相差フィルム５は、例えば、液晶材料が配向、固定化された１／４波長板及び／又は１／２波長板を含んでいてもよい。 The retardation film 5 may include, for example, a quarter-wave plate and/or a half-wave plate in which a liquid crystal material is aligned and fixed.
　層間粘着剤４には公知の粘着剤を使用できる。粘着シート１を層間粘着剤４に使用してもよい。 A known adhesive can be used for the interlayer adhesive 4 . The adhesive sheet 1 may be used as the interlayer adhesive 4 .
　本実施形態の光学積層体の別の一例を図５に示す。図５の光学積層体１０Ｄは、はく離ライナー３、粘着シート１、位相差フィルム５、層間粘着剤４、偏光板２及び保護フィルム６がこの順に積層された積層構造を有する。光学積層体１０Ｄは、はく離ライナー３を剥離した後、例えば画像表示セルに貼付して使用できる。 Another example of the optical laminate of this embodiment is shown in FIG. The optical laminate 10D of FIG. 5 has a laminated structure in which a release liner 3, an adhesive sheet 1, a retardation film 5, an interlayer adhesive 4, a polarizing plate 2 and a protective film 6 are laminated in this order. After peeling off the release liner 3, the optical layered body 10D can be used by attaching it to, for example, an image display cell.
　保護フィルム６は、光学積層体１０Ｄの流通及び保管時、並びに光学積層体１０Ｄを画像表示装置に組み込んだ状態において、最外層である偏光板２を保護する機能を有する。また、画像表示装置に組み込んだ状態において、外部空間へのウィンドウとして機能する保護フィルム６であってもよい。保護フィルム６は、典型的には、樹脂フィルムである。保護フィルム６を構成する樹脂は、例えば、ＰＥＴ等のポリエステル、ポリエチレン及びポリプロピレン等のポリオレフィン、アクリル、シクロオレフィン、ポリイミド、並びにポリアミドであり、ポリエステルが好ましい。ただし、保護フィルム６は上記例に限定されない。保護フィルム６は、ガラス製のフィルム、又はガラス製のフィルムを含む積層フィルムであってもよい。保護フィルム６には、アンチグレア、反射防止、帯電防止等の表面処理が施されていてもよい。 The protective film 6 has a function of protecting the polarizing plate 2, which is the outermost layer, during distribution and storage of the optical layered body 10D and when the optical layered body 10D is incorporated in an image display device. Moreover, it may be a protective film 6 that functions as a window to an external space when incorporated in an image display device. Protective film 6 is typically a resin film. The resin constituting the protective film 6 is, for example, polyester such as PET, polyolefin such as polyethylene and polypropylene, acrylic, cycloolefin, polyimide, and polyamide, preferably polyester. However, the protective film 6 is not limited to the above example. The protective film 6 may be a glass film or a laminated film containing a glass film. The protective film 6 may be subjected to surface treatment such as antiglare, antireflection, and antistatic.
　保護フィルム６は、任意の粘着剤によって偏光板２に接合されていてもよい。粘着シート１による接合も可能である。 The protective film 6 may be bonded to the polarizing plate 2 with any adhesive. Bonding with the adhesive sheet 1 is also possible.
　本実施形態の光学積層体は、例えば、帯状の光学積層体を巻回した巻回体として、あるいは枚葉状の光学積層体として、流通及び保管が可能である。本実施形態の光学積層体は、静電気が特に生じやすい環境で用いられる画像表示装置、特に車載用ディスプレイ、の用途に適している。車載用ディスプレイとしては、例えば、カーナビゲーション装置用パネル、クラスタパネル、ミラーディスプレイ等が挙げられる。クラスタパネルは、車両の走行速度やエンジンの回転数等を表示するパネルである。 The optical layered body of the present embodiment can be distributed and stored, for example, as a wound body in which a strip-shaped optical layered body is wound, or as a sheet-shaped optical layered body. The optical layered body of the present embodiment is suitable for use in image display devices, particularly in-vehicle displays, which are used in environments where static electricity is particularly likely to occur. Examples of in-vehicle displays include panels for car navigation systems, cluster panels, and mirror displays. The cluster panel is a panel that displays the traveling speed of the vehicle, the number of revolutions of the engine, and the like.
（実施形態６）
［光学積層体］
　光学積層体の別の例は、粘着シートと光学フィルムとを含む。光学フィルムは、偏光子を含む偏光板である。光学積層体を１０５℃で１２０時間加熱した後に、偏光板は、質量基準で７０ｐｐｍ以下のギ酸を含有する。偏光板に含まれるギ酸の含有量がこの程度に低い場合、高温環境を経た後であっても、光学積層体に着色が生じにくい。 (Embodiment 6)
[Optical laminate]
Another example of an optical laminate includes an adhesive sheet and an optical film. An optical film is a polarizing plate containing a polarizer. After heating the optical laminate at 105° C. for 120 hours, the polarizing plate contains 70 ppm or less formic acid on a mass basis. When the content of formic acid contained in the polarizing plate is as low as this, the optical layered body is less likely to be colored even after being subjected to a high-temperature environment.
　本実施形態の光学積層体の別の一例を図６に示す。図６の光学積層体１０Ｅは、粘着シート７と光学フィルムとを含む。図６の光学フィルムは偏光板８である。偏光板８は、偏光子を含む。粘着シート７と偏光板８とは互いに積層されている。光学積層体１０Ｅは、粘着シート７を介して、対象物（例えば、画像表示パネル）と貼り合わせることが可能である。光学積層体１０Ｅは、粘着シート付き光学フィルム、より具体的には、粘着シート付き偏光板、として使用できる。偏光板８以外の光学フィルムの例は、位相差フィルム、並びに偏光板及び／又は位相差フィルムを含む積層フィルムである。光学フィルムは、円偏光板であってもよい。ただし、光学フィルムは上記例に限定されない。光学フィルムは、ガラス製のフィルムを含んでいてもよい。 Another example of the optical laminate of this embodiment is shown in FIG. The optical layered body 10E of FIG. 6 includes the adhesive sheet 7 and an optical film. The optical film in FIG. 6 is the polarizing plate 8 . The polarizing plate 8 contains a polarizer. The adhesive sheet 7 and the polarizing plate 8 are laminated together. The optical layered body 10E can be attached to an object (for example, an image display panel) via the adhesive sheet 7 . The optical laminate 10E can be used as an optical film with an adhesive sheet, more specifically, as a polarizing plate with an adhesive sheet. Examples of optical films other than the polarizing plate 8 are retardation films and laminated films containing polarizing plates and/or retardation films. The optical film may be a circular polarizer. However, the optical film is not limited to the above examples. The optical film may include a film made of glass.
　光学積層体１０Ｅを１０５℃で１２０時間加熱した後に、偏光板に含まれるギ酸の含有量は、６５ｐｐｍ以下、６０ｐｐｍ以下、５５ｐｐｍ以下、５０ｐｐｍ以下、４５ｐｐｍ以下、４０ｐｐｍ以下、３５ｐｐｍ以下、３０ｐｐｍ以下、さらには２８ｐｐｍ以下であってもよい。ギ酸の含有量の下限は、特に限定されず、例えば、０ｐｐｍ以上である。 After heating the optical laminate 10E at 105° C. for 120 hours, the content of formic acid contained in the polarizing plate is 65 ppm or less, 60 ppm or less, 55 ppm or less, 50 ppm or less, 45 ppm or less, 40 ppm or less, 35 ppm or less, 30 ppm or less, and further may be 28 ppm or less. The lower limit of the formic acid content is not particularly limited, and is, for example, 0 ppm or more.
　本発明者らの検討によれば、光学積層体において、高温環境を経た後に不要な着色が生じる傾向にあることが判明した。着色の原因として、偏光板に含まれる酸、例えばギ酸によるＰＶＡのポリエン化が考えられる。ギ酸によるＰＶＡのポリエン化の詳細は、実施形態２で説明したとおりである。 According to the studies of the present inventors, it has been found that the optical layered body tends to undergo unwanted coloring after being exposed to a high-temperature environment. A possible cause of the coloring is the polyene conversion of PVA by an acid contained in the polarizing plate, such as formic acid. The details of the polyene conversion of PVA with formic acid are as described in the second embodiment.
　粘着シート７は、例えば、粘着剤組成物（IV）から形成される。粘着剤組成物（IV）は、例えば、ポリマー（Ｃ）及び架橋剤を含む。粘着剤組成物（IV）は、ポリマー（Ｃ）を主成分として含んでいてもよい。「主成分」は、上述した意味を有する。 The adhesive sheet 7 is formed, for example, from the adhesive composition (IV). The adhesive composition (IV) contains, for example, polymer (C) and a cross-linking agent. The pressure-sensitive adhesive composition (IV) may contain the polymer (C) as a main component. "Principal component" has the meaning given above.
　ポリマー（Ｃ）の例は、（メタ）アクリル系ポリマー、ウレタン系ポリマー、シリコーン系ポリマー及びゴム系ポリマーである。ポリマー（Ｃ）は、好ましくは、（メタ）アクリル系ポリマーである。ポリマー（Ｃ）は、例えば、アクリル系粘着剤のベースポリマーとして機能しうる。ポリマー（Ｃ）は、周波数１００ｋＨｚにおける比誘電率が５．０以上のポリマーであってもよい。比誘電率は、６．０以上、６．５以上、６．８以上、７．０以上、７．３以上、さらには７．５以上であってもよい。比誘電率の上限は、特に限定されず、例えば、１０．０以下である。 Examples of polymers (C) are (meth)acrylic polymers, urethane polymers, silicone polymers and rubber polymers. Polymer (C) is preferably a (meth)acrylic polymer. Polymer (C) can function, for example, as a base polymer for an acrylic pressure-sensitive adhesive. Polymer (C) may be a polymer having a dielectric constant of 5.0 or higher at a frequency of 100 kHz. The dielectric constant may be 6.0 or higher, 6.5 or higher, 6.8 or higher, 7.0 or higher, 7.3 or higher, or even 7.5 or higher. The upper limit of the dielectric constant is not particularly limited, and is, for example, 10.0 or less.
　ポリマー（Ｃ）は、以下の式（１）に示す単量体に由来する構成単位を有していてもよい。
Figure JPOXMLDOC01-appb-C000006
 The polymer (C) may have structural units derived from the monomers represented by formula (1) below.
Figure JPOXMLDOC01-appb-C000006
　式（１）のＲ１は、水素原子又はメチル基である。式（１）のＲ２は、直鎖状であっても分岐を有していてもよいアルキル基であり、好ましくは、直鎖状のアルキル基である。Ｒ２の例は、メチル基及びエチル基である。ｎは、１～１５の整数であり、好ましくは１～１０の整数であり、より好ましくは１～５の整数である。 R 1 in formula (1) is a hydrogen atom or a methyl group. R 2 in formula (1) is an alkyl group that may be linear or branched, preferably a linear alkyl group. Examples of R 2 are methyl and ethyl groups. n is an integer of 1-15, preferably an integer of 1-10, more preferably an integer of 1-5.
　ポリマー（Ｃ）において、式（１）に示す単量体に由来する構成単位の含有率は、特に限定されず、例えば１５～９９．５重量％であってもよく、３０～９９重量％であってもよく、５０～９８重量％であってもよく、５０～８０重量％であってもよく、５０～７０重量％であってもよい。 In the polymer (C), the content of structural units derived from the monomer represented by formula (1) is not particularly limited, and may be, for example, 15 to 99.5% by weight, or 30 to 99% by weight. 50 to 98% by weight, 50 to 80% by weight, or 50 to 70% by weight.
　ポリマー（Ｃ）を構成する単量体としては、式（１）に示す単量体以外に、炭素数１～３０のアルキル基を側鎖に有する（メタ）アクリル系単量体、水酸基含有単量体、芳香環含有単量体、カルボキシル基含有単量体、アミノ基含有単量体アミド基含有単量体及び多官能性単量体からなる群より選ばれる少なくとも１つの単量体が挙げられる。これらの単量体は、単独で又は組み合わせて使用できる。これらの単量体の例は、実施形態１で説明した単量体（Ａ２）と同様であるため、説明を省略する。 As the monomers constituting the polymer (C), in addition to the monomers represented by the formula (1), (meth)acrylic monomers having an alkyl group having 1 to 30 carbon atoms in the side chain, hydroxyl group-containing monomers at least one monomer selected from the group consisting of monomers, aromatic ring-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, amide group-containing monomers and polyfunctional monomers. be done. These monomers can be used alone or in combination. Examples of these monomers are the same as the monomer (A2) described in Embodiment 1, so description thereof is omitted.
　ポリマー（Ｃ）において、単量体に由来する構成単位の含有率は、特に限定されず、例えば０．１～５０重量％であってもよく、０．５～４５重量％であってもよい。場合によっては、ポリマー（Ｃ）において、単量体に由来する構成単位の含有率は、１～５重量％であってもよい。また、場合によっては、ポリマー（Ｃ）において、単量体に由来する構成単位の含有率は、２０～４５重量％であってもよく、２５～４５重量％であってもよく、３０～４５重量％であってもよい。 In the polymer (C), the content of structural units derived from monomers is not particularly limited, and may be, for example, 0.1 to 50% by weight, or may be 0.5 to 45% by weight. . In some cases, the content of structural units derived from monomers in the polymer (C) may be 1 to 5% by weight. In some cases, the content of structural units derived from monomers in the polymer (C) may be 20 to 45% by weight, 25 to 45% by weight, or 30 to 45% by weight. % by weight.
　単量体成分としては、式（１）に示す単量体及び上記の単量体以外にも、粘着シートの接着性、耐熱性の改善を目的に、（メタ）アクリロイル基又はビニル基などの不飽和二重結合を含む重合性官能基を有する他の単量体を用いることができる。他の単量体は、単独で又は組み合わせて使用できる。 As a monomer component, in addition to the monomers represented by the formula (1) and the above monomers, for the purpose of improving the adhesiveness and heat resistance of the pressure-sensitive adhesive sheet, a (meth)acryloyl group, a vinyl group, or the like may be used. Other monomers having polymerizable functional groups containing unsaturated double bonds can be used. Other monomers can be used alone or in combination.
　単量体成分として、他の単量体を使用する場合、ポリマー（Ｃ）において、他の単量体に由来する構成単位の含有率は、３０重量％以下であってもよく、１０重量％以下であってもよく、０重量％（当該構成単位を有さない）であってもよい。 When another monomer is used as the monomer component, the content of structural units derived from the other monomer in the polymer (C) may be 30% by weight or less, and 10% by weight. It may be less than or equal to 0% by weight (not having the structural unit).
　ポリマー（Ｃ）の重量平均分子量（Ｍｗ）は、例えば、１００万～３００万であり、１２０万～２５０万であってもよく、１５０万～２３０万であってもよい。ポリマー（Ｃ）の重量平均分子量が１００万～３００万であることによって、粘着シートのクラックを抑制できるとともに、粘度の上昇やゲル化の発生を抑制できる傾向がある。 The weight average molecular weight (Mw) of the polymer (C) is, for example, 1 million to 3 million, may be 1.2 million to 2.5 million, or may be 1.5 million to 2.3 million. When the weight average molecular weight of the polymer (C) is 1,000,000 to 3,000,000, cracks in the pressure-sensitive adhesive sheet can be suppressed, and there is a tendency to suppress an increase in viscosity and occurrence of gelation.
　粘着剤組成物（IV）は、上記したポリマー（Ｃ）を含んでいてもよい。粘着剤組成物（IV）は、ポリマー（Ｃ）以外のポリマーをさらに含んでいてもよい。 The adhesive composition (IV) may contain the polymer (C) described above. The pressure-sensitive adhesive composition (IV) may further contain a polymer other than the polymer (C).
　ポリマー（Ｃ）は、溶液重合、電子線やＵＶなどの放射線重合、塊状重合、乳化重合などの各種ラジカル重合などの公知の重合方法によって作製できる。得られるポリマー（Ｃ）は、ランダム共重合体、ブロック共重合体、グラフト共重合体などのいずれでもよい。 The polymer (C) can be produced by known polymerization methods such as solution polymerization, radiation polymerization such as electron beam and UV, bulk polymerization, and various radical polymerizations such as emulsion polymerization. The resulting polymer (C) may be any of random copolymers, block copolymers, graft copolymers and the like.
　ポリマー（Ｃ）を形成する方法及び重合条件は、それぞれ、実施形態１で説明した、ポリマー（Ａ）を形成する方法及び重合条件と同じであってもよい。ポリマー（Ｃ）を形成するために使用される、溶媒の種類、重合開始剤の種類等も、実施形態１で説明したものを使用できる。 The method and polymerization conditions for forming the polymer (C) may be the same as the method and polymerization conditions for forming the polymer (A) described in Embodiment 1, respectively. The type of solvent, the type of polymerization initiator, etc. used to form the polymer (C) can also be those described in the first embodiment.
　粘着剤組成物（IV）に含まれる架橋剤の例は、イソシアネート系架橋剤及び過酸化物系架橋剤である。過酸化物系架橋剤とイソシアネート系架橋剤とを併用してもよい。粘着剤組成物（IV）は、イソシアネート系架橋剤を含んでいてもよく、過酸化物系架橋剤を含んでいてもよく、イソシアネート系架橋剤及び過酸化物系架橋剤の双方を含んでいてもよい。イソシアネート系架橋剤及び過酸化物系架橋剤は、実施形態１で説明した、イソシアネート系架橋剤及び過酸化物系架橋剤を使用できる。 Examples of cross-linking agents contained in the adhesive composition (IV) are isocyanate-based cross-linking agents and peroxide-based cross-linking agents. A peroxide-based cross-linking agent and an isocyanate-based cross-linking agent may be used in combination. The pressure-sensitive adhesive composition (IV) may contain an isocyanate cross-linking agent, may contain a peroxide cross-linking agent, or may contain both an isocyanate cross-linking agent and a peroxide cross-linking agent. good too. As the isocyanate-based cross-linking agent and the peroxide-based cross-linking agent, the isocyanate-based cross-linking agent and the peroxide-based cross-linking agent described in the first embodiment can be used.
　なお、粘着シート７は、実施形態１で説明した粘着剤組成物（Ｉ）から形成された粘着シートであってもよく、実施形態２で説明した粘着剤組成物（II）から形成された粘着シートであってもよく、実施形態３で説明した粘着剤組成物（III）であってもよい。光学積層体１０Ｅにおいて、粘着シート７としてこれらの粘着シートを使用することは、偏光板８に含まれるギ酸の含有量の低減に特に適している。 The adhesive sheet 7 may be an adhesive sheet formed from the adhesive composition (I) described in Embodiment 1, or an adhesive sheet formed from the adhesive composition (II) described in Embodiment 2. It may be a sheet, or it may be the pressure-sensitive adhesive composition (III) described in the third embodiment. Using these adhesive sheets as the adhesive sheet 7 in the optical layered body 10E is particularly suitable for reducing the content of formic acid contained in the polarizing plate 8. FIG.
　偏光板８は、実施形態５で説明した偏光板２と同様であってもよい。偏光板８は、偏光子を含んでいてもよい。 The polarizing plate 8 may be the same as the polarizing plate 2 described in the fifth embodiment. The polarizing plate 8 may contain a polarizer.
　本実施形態の光学積層体は、粘着シート１に代えて粘着シート７を使用する点を除き、実施形態５の光学積層体１０Ａ～１０Ｄと同様であってもよい。 The optical layered body of this embodiment may be the same as the optical layered bodies 10A to 10D of Embodiment 5 except that the adhesive sheet 7 is used instead of the adhesive sheet 1.
（実施形態７）
［画像表示パネル］
　本実施形態の画像表示パネルの一例を図７に示す。図７の画像表示パネル１１Ａは、光学積層体１０Ａを備え、例えば画像表示セル３０Ａをさらに備える。詳細には、粘着シート１を介して、光学積層体１０Ａが画像表示セル３０Ａに貼り合わされている。なお、光学積層体１０Ａに代えて、図３～５の光学積層体１０Ｂ，１０Ｃ又は１０Ｄも使用可能である（ただし、はく離ライナー３を除く）。加えて、光学積層体１０Ａに代えて、図６の光学積層体１０Ｅも使用可能である。 (Embodiment 7)
[Image display panel]
An example of the image display panel of this embodiment is shown in FIG. An image display panel 11A in FIG. 7 includes an optical layered body 10A and further includes, for example, an image display cell 30A. Specifically, the optical laminate 10A is attached to the image display cell 30A with the adhesive sheet 1 interposed therebetween. The optical laminate 10B, 10C or 10D shown in FIGS. 3 to 5 can also be used instead of the optical laminate 10A (except for the release liner 3). In addition, the optical layered body 10E of FIG. 6 can also be used instead of the optical layered body 10A.
　画像表示セル３０Ａは、例えば、画像形成層３２、第１透明基板３１及び第２透明基板３３を備えている。画像形成層３２は、例えば、第１透明基板３１及び第２透明基板３３の間に配置されており、第１透明基板３１及び第２透明基板３３のそれぞれに接している。光学積層体１０Ａの粘着シート１は、例えば、画像表示セル３０Ａの第１透明基板３１に接している。 The image display cell 30A includes an image forming layer 32, a first transparent substrate 31 and a second transparent substrate 33, for example. The image forming layer 32 is arranged, for example, between the first transparent substrate 31 and the second transparent substrate 33 and is in contact with the first transparent substrate 31 and the second transparent substrate 33 respectively. The adhesive sheet 1 of the optical laminate 10A is, for example, in contact with the first transparent substrate 31 of the image display cell 30A.
　画像形成層３２は、例えば、電界が存在しない状態でホモジニアス配向した液晶分子を含む液晶層である。このような液晶分子を含む液晶層は、ＩＰＳ（In-Plane-Switching）方式に適している。ただし、液晶層は、ＴＮ（Twisted Nematic）型、ＳＴＮ（Super Twisted Nematic）型、π型、ＶＡ（Vertical Alignment）型等に用いられてもよい。本明細書では、液晶層を備えた画像表示セルを液晶セルと呼び、液晶セルを備えた画像表示パネルを液晶パネルと呼ぶことがある。なお、画像形成層３２は、ＥＬ発光層であってもよい。 The image forming layer 32 is, for example, a liquid crystal layer containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field. A liquid crystal layer containing such liquid crystal molecules is suitable for an IPS (In-Plane-Switching) method. However, the liquid crystal layer may be of TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, π type, VA (Vertical Alignment) type, or the like. In this specification, an image display cell provided with a liquid crystal layer is sometimes referred to as a liquid crystal cell, and an image display panel provided with a liquid crystal cell is sometimes referred to as a liquid crystal panel. Note that the image forming layer 32 may be an EL light emitting layer.
　画像形成層３２の厚さは、例えば、１．５μｍ～４μｍである。 The thickness of the image forming layer 32 is, for example, 1.5 μm to 4 μm.
　第１透明基板３１及び第２透明基板３３の材料としては、例えば、ガラス及びポリマーが挙げられる。本明細書では、ポリマーで構成された透明基板をポリマーフィルムと呼ぶことがある。透明基板を構成するポリマーとしては、例えば、ポリエチレンテレフタレート、ポリシクロオレフィン、ポリカーボネート等が挙げられる。ガラスで構成された透明基板の厚さは、例えば、０．１ｍｍ～１ｍｍである。ポリマーで構成された透明基板の厚さは、例えば、１０μｍ～２００μｍである。 Examples of materials for the first transparent substrate 31 and the second transparent substrate 33 include glass and polymer. In this specification, a transparent substrate made of polymer is sometimes referred to as a polymer film. Examples of polymers constituting the transparent substrate include polyethylene terephthalate, polycycloolefin, polycarbonate and the like. The thickness of the transparent substrate made of glass is, for example, 0.1 mm to 1 mm. The thickness of the transparent substrate made of polymer is, for example, 10 μm to 200 μm.
　画像表示セル３０Ａは、画像形成層３２、第１透明基板３１及び第２透明基板３３以外の他の層をさらに含んでいてもよい。他の層としては、例えば、カラーフィルタ、易接着層及びハードコート層が挙げられる。カラーフィルタは、例えば、画像形成層３２よりも視認側に配置されており、好ましくは第１透明基板３１と光学積層体１０Ａの粘着シート１との間に位置する。易接着層及びハードコート層は、例えば、第１透明基板３１又は第２透明基板３３の表面上に配置されている。 The image display cell 30A may further include layers other than the image forming layer 32, the first transparent substrate 31 and the second transparent substrate 33. Other layers include, for example, a color filter, an easy-adhesion layer and a hard coat layer. The color filter is arranged, for example, on the viewing side of the image forming layer 32, preferably between the first transparent substrate 31 and the adhesive sheet 1 of the optical layered body 10A. The easy-adhesion layer and the hard coat layer are arranged on the surface of the first transparent substrate 31 or the second transparent substrate 33, for example.
　画像表示パネル１１Ａは、光学積層体１０Ａ及び画像表示セル３０Ａ以外の他の部材をさらに備えていてもよい。例えば、画像表示パネル１１Ａは、光学積層体１０Ａの側面に電気的に接続している導通構造（図示せず）をさらに備えていてもよい。導通構造をアースに接続すれば、光学積層体１０Ａが静電気によって帯電することを抑制しやすい。導通構造は、光学積層体１０Ａの側面全体を覆っていてもよく、光学積層体１０Ａの側面を部分的に覆っていてもよい。光学積層体１０Ａの側面全体の面積に対する導通構造によって覆われた光学積層体１０Ａの側面の面積の比率は、例えば１％以上であり、好ましくは３％以上である。 The image display panel 11A may further include members other than the optical laminate 10A and the image display cell 30A. For example, the image display panel 11A may further include a conductive structure (not shown) electrically connected to the side surface of the optical laminate 10A. By connecting the conductive structure to the ground, it is easy to suppress the optical layered body 10A from being charged with static electricity. The conductive structure may cover the entire side surface of the optical layered body 10A, or may partially cover the side surface of the optical layered body 10A. The ratio of the area of the side surface of the optical layered body 10A covered with the conductive structure to the area of the entire side surface of the optical layered body 10A is, for example, 1% or more, preferably 3% or more.
　導通構造の材料としては、例えば銀、金等の金属で構成された導電性ペースト；導電性接着剤；他の導電材料が挙げられる。導通構造は、光学積層体１０Ａの側面から伸びる配線であってもよい。 Materials for the conductive structure include, for example, conductive pastes made of metals such as silver and gold; conductive adhesives; and other conductive materials. The conductive structure may be a wiring extending from the side surface of the optical layered body 10A.
　画像表示パネル１１Ａは、偏光板２以外の他の光学フィルムをさらに備えていてもよい。他の光学フィルムとしては、例えば、偏光板、反射板、反透過板、視野角補償フィルム、輝度向上フィルム等の画像表示装置に用いられるフィルムが挙げられる。画像表示パネル１１Ａは、これらの１種又は２種以上の他の光学フィルムを備えていてもよい。 The image display panel 11A may further include an optical film other than the polarizing plate 2. Examples of other optical films include films used in image display devices such as polarizing plates, reflectors, anti-transmissive plates, viewing angle compensation films, and brightness enhancement films. The image display panel 11A may include one or more of these optical films.
　他の光学フィルムが偏光板である場合、当該偏光板は、例えば、粘着シートを介して、画像表示セル３０Ａの第２透明基板３３と貼り合わされる。この偏光板は、例えば、偏光板２について上述した構成を有する。他の光学フィルムとしての偏光板において、偏光子の透過軸（又は吸収軸）は、例えば、偏光板２における偏光子の透過軸（又は吸収軸）と直交している。偏光板と第２透明基板３３とを貼り合わせるための粘着シートの材料としては、粘着シート１について上述したものを用いることができる。この粘着シートの厚さは、特に限定されず、例えば１～１００μｍであり、好ましくは２～５０μｍであり、より好ましくは２～４０μｍであり、さらに好ましくは５～３５μｍである。 When the other optical film is a polarizing plate, the polarizing plate is attached to the second transparent substrate 33 of the image display cell 30A, for example, via an adhesive sheet. This polarizing plate has, for example, the configuration described above for the polarizing plate 2 . In the polarizing plate as another optical film, the transmission axis (or absorption axis) of the polarizer is orthogonal to the transmission axis (or absorption axis) of the polarizer in the polarizing plate 2, for example. As the material of the adhesive sheet for bonding the polarizing plate and the second transparent substrate 33 together, the materials described above for the adhesive sheet 1 can be used. The thickness of this adhesive sheet is not particularly limited, and is, for example, 1 to 100 μm, preferably 2 to 50 μm, more preferably 2 to 40 μm, still more preferably 5 to 35 μm.
　本実施形態の画像表示パネルの別の一例を図８に示す。図８の画像表示パネル１１Ｂは、光学積層体１０Ａ及び画像表示セル３０Ａの間に配置された導電層４０をさらに備えている。 Another example of the image display panel of this embodiment is shown in FIG. The image display panel 11B of FIG. 8 further includes a conductive layer 40 arranged between the optical laminate 10A and the image display cell 30A.
　導電層４０は、例えば、導電剤を含む層である。導電剤としては、粘着シート１について上述したものを用いることができる。ただし、導電剤は上記例に限定されない。導電層４０は各種の導電剤、例えば、カーボンナノチューブ、ＩＴＯ、ＡＴＯ、ドーパントとの複合体である導電性ポリマー（一例として、ポリ（３，４－エチレンジオキシチオフェン）とポリスチレンスルホン酸との複合体：ＰＥＤＯＴ／ＰＳＳ）等、を含みうる。導電層４０の厚さは、例えば、５ｎｍ～１８０ｎｍである。導電層４０の表面抵抗値は、例えば、１．０×１０６Ω／□～１．０×１０１０Ω／□であり、好ましくは１．０×１０８Ω／□～１．０×１０９Ω／□である。 The conductive layer 40 is, for example, a layer containing a conductive agent. As the conductive agent, those mentioned above for the adhesive sheet 1 can be used. However, the conductive agent is not limited to the above examples. The conductive layer 40 is a composite of various conductive agents such as carbon nanotubes, ITO, ATO, and a conductive polymer (for example, a composite of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid). Bodies: PEDOT/PSS), etc. The thickness of the conductive layer 40 is, for example, 5 nm to 180 nm. The surface resistance value of the conductive layer 40 is, for example, 1.0×10 6 Ω/square to 1.0×10 10 Ω/square, preferably 1.0×10 8 Ω/square to 1.0×10 Ω/square. 9 Ω/square.
　本実施形態の画像表示パネルの別の一例を図９に示す。図９の画像表示パネル１１Ｃは、タッチセンシング電極部３５をさらに含む画像表示セル３０Ｂを備えている。画像表示セル３０Ｂにおいて、タッチセンシング電極部３５は、第１透明基板３１と第２透明基板３３との間に配置されている。タッチセンシング電極部３５は、タッチセンサ及びタッチ駆動の機能を有する。画像表示パネル１１Ｃは、いわゆるインセル型画像表示パネルであり、画像表示セル３０Ｂは、いわゆるインセル型画像表示セルである。 Another example of the image display panel of this embodiment is shown in FIG. The image display panel 11C of FIG. 9 includes an image display cell 30B that further includes a touch sensing electrode portion 35. As shown in FIG. The touch sensing electrode portion 35 is arranged between the first transparent substrate 31 and the second transparent substrate 33 in the image display cell 30B. The touch sensing electrode unit 35 has functions of touch sensor and touch drive. The image display panel 11C is a so-called in-cell image display panel, and the image display cell 30B is a so-called in-cell image display cell.
　タッチセンシング電極部３５は、例えば、タッチセンサ電極３６及びタッチ駆動電極３７を有する。タッチセンサ電極３６とは、タッチ検出用の（受信）電極を意味する。タッチセンサ電極３６及びタッチ駆動電極３７は、それぞれ独立して各種パターンにより形成することができる。例えば、画像表示セル３０Ｂが平板状である場合、タッチセンサ電極３６及びタッチ駆動電極３７をそれぞれＸ軸方向及びＹ軸方向に独立して設け、これらが直角に交差するようなパターンに形成することができる。図９では、タッチセンシング電極部３５において、タッチセンサ電極３６がタッチ駆動電極３７よりも視認側に配置されている。ただし、タッチ駆動電極３７がタッチセンサ電極３６よりも視認側に配置されていてもよい。タッチセンシング電極部３５において、タッチセンサ電極３６及びタッチ駆動電極３７は、一体化されていてもよい。 The touch sensing electrode section 35 has, for example, touch sensor electrodes 36 and touch drive electrodes 37 . The touch sensor electrode 36 means a (receiving) electrode for touch detection. The touch sensor electrodes 36 and the touch drive electrodes 37 can be independently formed in various patterns. For example, when the image display cell 30B has a flat plate shape, the touch sensor electrodes 36 and the touch drive electrodes 37 are provided independently in the X-axis direction and the Y-axis direction, respectively, and formed in a pattern in which they intersect at right angles. can be done. In FIG. 9 , in the touch sensing electrode portion 35 , the touch sensor electrodes 36 are arranged closer to the viewer than the touch drive electrodes 37 are. However, the touch drive electrodes 37 may be arranged on the viewing side of the touch sensor electrodes 36 . In the touch sensing electrode section 35, the touch sensor electrodes 36 and the touch drive electrodes 37 may be integrated.
　図９において、タッチセンシング電極部３５は、画像形成層３２と第１透明基板３１との間（画像形成層３２よりも視認側）に配置されている。ただし、タッチセンシング電極部３５は、画像形成層３２と第２透明基板３３との間（画像形成層３２よりも照明システム側）に配置されていてもよい。 In FIG. 9, the touch sensing electrode portion 35 is arranged between the image forming layer 32 and the first transparent substrate 31 (on the viewer side of the image forming layer 32). However, the touch sensing electrode section 35 may be arranged between the image forming layer 32 and the second transparent substrate 33 (on the lighting system side of the image forming layer 32).
　タッチセンシング電極部３５において、タッチセンサ電極３６及びタッチ駆動電極３７は、互いに接していなくてもよい。例えば、タッチセンサ電極３６が画像形成層３２と第１透明基板３１との間に配置され、タッチ駆動電極３７が画像形成層３２と第２透明基板３３との間に配置されていてもよい。 In the touch sensing electrode section 35, the touch sensor electrodes 36 and the touch drive electrodes 37 do not have to be in contact with each other. For example, the touch sensor electrodes 36 may be arranged between the image forming layer 32 and the first transparent substrate 31 and the touch drive electrodes 37 may be arranged between the image forming layer 32 and the second transparent substrate 33 .
　タッチセンシング電極部３５における駆動電極（タッチ駆動電極３７、又は、タッチセンサ電極３６とタッチ駆動電極３７とが一体化された電極）は、画像形成層３２を制御する共通電極を兼ねることができる。 The drive electrodes (touch drive electrodes 37 or electrodes in which the touch sensor electrodes 36 and the touch drive electrodes 37 are integrated) in the touch sensing electrode portion 35 can also serve as common electrodes for controlling the image forming layer 32 .
　タッチセンシング電極部３５を構成するタッチセンサ電極３６（静電容量センサー）、タッチ駆動電極３７、又は、これらを一体化して形成した電極は、透明導電層として機能する。この透明導電層の材料は、特に限定されず、例えば、金、銀、銅、白金、パラジウム、アルミニウム、ニッケル、クロム、チタン、鉄、コバルト、錫、マグネシウム、タングステン等の金属、及び、これらの合金等が挙げられる。透明導電層の材料は、インジウム、スズ、亜鉛、ガリウム、アンチモン、ジルコニウム、カドミウム等の金属の酸化物であってもよい。この酸化物としては、具体的には、酸化インジウム、酸化スズ、酸化チタン、酸化カドミウム及びこれらの混合物等が挙げられる。透明導電層の材料は、ヨウ化銅等の金属化合物であってもよい。透明導電層の材料は、酸化スズを含有する酸化インジウム（ＩＴＯ）、アンチモンを含有する酸化スズ（ＡＴＯ）等が好ましく、ＩＴＯが特に好ましい。透明導電層の材料がＩＴＯである場合、透明導電層における酸化インジウムの含有率が８０～９９重量％であり、かつ酸化スズの含有率が１～２０重量％であることが好ましい。 The touch sensor electrode 36 (capacitance sensor) and the touch drive electrode 37, which constitute the touch sensing electrode section 35, or an electrode formed by integrating these functions as a transparent conductive layer. The material of this transparent conductive layer is not particularly limited. alloys and the like. Materials for the transparent conductive layer may be oxides of metals such as indium, tin, zinc, gallium, antimony, zirconium, and cadmium. Specific examples of this oxide include indium oxide, tin oxide, titanium oxide, cadmium oxide, and mixtures thereof. The material of the transparent conductive layer may be a metal compound such as copper iodide. The material of the transparent conductive layer is preferably indium oxide (ITO) containing tin oxide, tin oxide (ATO) containing antimony, or the like, and particularly preferably ITO. When the material of the transparent conductive layer is ITO, the content of indium oxide in the transparent conductive layer is preferably 80 to 99% by weight and the content of tin oxide is preferably 1 to 20% by weight.
　タッチセンシング電極部３５を構成する電極（タッチセンサ電極３６、タッチ駆動電極３７、又は、これらを一体化して形成した電極）は、第１透明基板３１と第２透明基板３３との間において、常法により透明電極パターンとして形成することができる。この透明電極パターンは、例えば、透明基板の端部に形成された引き回し線に電気的に接続されている。引き回し線は、例えば、コントローラＩＣと接続されている。透明電極パターンの形状としては、櫛状、ストライプ状、ひし形状等、用途に応じて任意の形状を採用することができる。透明電極パターンの厚さは、例えば１０ｎｍ～１００ｎｍである。透明電極パターンの幅は、例えば０．１ｍｍ～５ｍｍである。 Electrodes (touch sensor electrodes 36, touch drive electrodes 37, or electrodes formed by integrating them) constituting the touch sensing electrode portion 35 are always placed between the first transparent substrate 31 and the second transparent substrate 33. It can be formed as a transparent electrode pattern by the method. This transparent electrode pattern is electrically connected to, for example, a lead wire formed at the end of the transparent substrate. The lead-out line is connected to, for example, the controller IC. As the shape of the transparent electrode pattern, any shape such as a comb shape, a stripe shape, a rhombus shape, or the like can be adopted according to the application. The thickness of the transparent electrode pattern is, for example, 10 nm to 100 nm. The width of the transparent electrode pattern is, for example, 0.1 mm to 5 mm.
（実施形態８）
［画像表示装置］
　本実施形態の画像表示装置は、例えば、画像表示パネル１１Ａ及び照明システムを備えている。なお、画像表示パネル１１Ａに代えて、図８～９の画像表示パネル１１Ｂ及び１１Ｃも使用可能である。画像表示装置において、画像表示パネル１１Ａは、例えば、照明システムよりも視認側に配置されている。照明システムは、例えば、バックライト又は反射板を有し、画像表示パネル１１Ａに光を照射する。 (Embodiment 8)
[Image display device]
The image display device of this embodiment includes, for example, an image display panel 11A and an illumination system. The image display panels 11B and 11C of FIGS. 8 and 9 can also be used instead of the image display panel 11A. In the image display device, the image display panel 11A is arranged, for example, on the viewing side of the lighting system. The illumination system has, for example, a backlight or a reflector, and irradiates the image display panel 11A with light.
　画像表示装置は、有機ＥＬディスプレイであってもよく、液晶ディスプレイであってもよい。ただし、画像表示装置はこの例に限定されない。画像表示装置は、エレクトロルミネッセンス（ＥＬ）ディスプレイ、プラズマディスプレイ（ＰＤ）、電界放出ディスプレイ（ＦＥＤ：Field Emission Display）等であってもよい。画像表示装置は、家電用途、車載用途、パブリックインフォメーションディスプレイ（ＰＩＤ）用途等に用いることができ、車載用ディスプレイであることが好ましい。 The image display device may be an organic EL display or a liquid crystal display. However, the image display device is not limited to this example. The image display device may be an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED: Field Emission Display), or the like. The image display device can be used for home appliances, vehicle applications, public information display (PID) applications, and the like, and is preferably an in-vehicle display.
　以下、実施例により、本発明をさらに詳細に説明する。本発明は、以下に示す実施例に限定されない。 The present invention will be described in more detail below with reference to examples. The invention is not limited to the examples shown below.
　＜（メタ）アクリル系ポリマーの重量平均分子量＞
　（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定した。（メタ）アクリル系ポリマーのＭｗ／Ｍｎについても、同様に測定した。
・分析装置：東ソー社製、ＨＬＣ－８１２０ＧＰＣ
・カラム：東ソー社製、Ｇ７０００ＨＸＬ＋ＧＭＨＸＬ＋ＧＭＨＸＬ
・カラムサイズ：各７．８ｍｍφ×３０ｃｍ　計９０ｃｍ
・カラム温度：４０℃
・流量：０．８ｍＬ／ｍｉｎ
・注入量：１００μＬ
・溶離液：テトラヒドロフラン
・検出器：示差屈折計（ＲＩ）
・標準試料：ポリスチレン <Weight average molecular weight of (meth)acrylic polymer>
The weight average molecular weight (Mw) of the (meth)acrylic polymer was measured by GPC (gel permeation chromatography). The Mw/Mn of the (meth)acrylic polymer was also measured in the same manner.
・ Analyzer: HLC-8120GPC manufactured by Tosoh Corporation
・Column: G7000H XL +GMH XL +GMH XL manufactured by Tosoh Corporation
・Column size: 7.8 mmφ×30 cm each, 90 cm in total
・Column temperature: 40°C
・Flow rate: 0.8mL/min
・Injection volume: 100 μL
・ Eluent: Tetrahydrofuran ・ Detector: Differential refractometer (RI)
・Standard sample: polystyrene
［（メタ）アクリル系ポリマーＡ１の調製］
　攪拌羽根、温度計、窒素ガス導入管及び冷却器を備えた４つ口フラスコに、２－メトキシエチルアクリレート（ＭＥＡ）９９重量部及び４－ヒドロキシブチルアクリレート（ＨＢＡ）１重量部を含有する単量体混合物を仕込んだ。さらに、単量体混合物１００重量部に対して、重合開始剤として２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ；キシダ化学社製）０．１重量部を酢酸エチル１００重量部と共に仕込んだ。混合物を緩やかに攪拌しながら、フラスコ内について窒素ガスを導入して窒素置換した。フラスコ内の液温を５５℃付近に維持して８時間重合反応を行うことによって、重量平均分子量（Ｍｗ）１８０万、Ｍｗ／Ｍｎ＝４．４の（メタ）アクリル系ポリマーＡ１の溶液を調製した。 [Preparation of (meth)acrylic polymer A1]
A monomer containing 99 parts by weight of 2-methoxyethyl acrylate (MEA) and 1 part by weight of 4-hydroxybutyl acrylate (HBA) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser. The body mixture was charged. Furthermore, 0.1 part by weight of 2,2'-azobisisobutyronitrile (AIBN; manufactured by Kishida Chemical Co., Ltd.) as a polymerization initiator was added to 100 parts by weight of the monomer mixture together with 100 parts by weight of ethyl acetate. . While gently stirring the mixture, nitrogen gas was introduced into the flask to replace it with nitrogen. A solution of (meth)acrylic polymer A1 having a weight average molecular weight (Mw) of 1,800,000 and Mw/Mn of 4.4 was prepared by conducting a polymerization reaction for 8 hours while maintaining the liquid temperature in the flask at around 55°C. bottom.
［（メタ）アクリル系ポリマーＡ２の調製］
　フラスコに仕込む単量体混合物を、ＭＥＡ６０重量部、ｎ－ブチルアクリレート（ＢＡ）３９重量部及びＨＢＡ１重量部とした以外は、（メタ）アクリル系ポリマーＡ１の調製と同様にして、重量平均分子量（Ｍｗ）１７５万、Ｍｗ／Ｍｎ＝３．５の（メタ）アクリル系ポリマーＡ２の溶液を調製した。 [Preparation of (meth) acrylic polymer A2]
The weight average molecular weight ( A solution of (meth)acrylic polymer A2 having Mw) of 1,750,000 and Mw/Mn of 3.5 was prepared.
［（メタ）アクリル系ポリマーＡ３の調製］
　フラスコに仕込む単量体混合物を、ＢＡ９９重量部及びＨＢＡ１重量部とした以外は、（メタ）アクリル系ポリマーＡ１の調製と同様にして、重量平均分子量（Ｍｗ）２００万、Ｍｗ／Ｍｎ＝４．５の（メタ）アクリル系ポリマーＡ３の溶液を調製した。 [Preparation of (meth) acrylic polymer A3]
A weight-average molecular weight (Mw) of 2,000,000 and Mw/Mn=4 was obtained in the same manner as in the preparation of (meth)acrylic polymer A1, except that the monomer mixture charged into the flask was 99 parts by weight of BA and 1 part by weight of HBA. A solution of (meth)acrylic polymer A3 of No. 5 was prepared.
　各（メタ）アクリル系ポリマーの合成に使用した単量体及び仕込み量を以下の表１にまとめる。 Table 1 below summarizes the monomers and amounts used to synthesize each (meth)acrylic polymer.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
［（メタ）アクリル系粘着剤組成物の調製］
（実施例Ａ１）
　（メタ）アクリル系ポリマーＡ１の溶液の固形分１００重量部に対して、０．３５重量部のイソシアネート系架橋剤（東ソー社製、コロネートＬ；トリメチロールプロパントリレンジイソシアネート）、導電剤として５重量部のビス（トリフルオロメタンスルホニル）イミドリチウム（ＬｉＴＦＳＩ；三菱マテリアル電子化成社製）、及び１重量部の酸化防止剤（ＢＡＳＦ社製、Ｉｒｇａｎｏｘ１１３５、分子量３９０）をさらに配合することによって、実施例Ａ１の（メタ）アクリル系粘着剤組成物の溶液を調製した。 [Preparation of (meth)acrylic pressure-sensitive adhesive composition]
(Example A1)
(Meth) With respect to 100 parts by weight of the solid content of the acrylic polymer A1 solution, 0.35 parts by weight of an isocyanate cross-linking agent (Coronate L; trimethylolpropane tolylene diisocyanate manufactured by Tosoh Corporation), 5 parts by weight as a conductive agent Part of bis (trifluoromethanesulfonyl) imide lithium (LiTFSI; manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) and 1 part by weight of antioxidant (BASF Corporation, Irganox 1135, molecular weight 390) By further blending, A solution of a (meth)acrylic pressure-sensitive adhesive composition was prepared.
（実施例Ａ２）
　０．１重量部の過酸化物系架橋剤（日本油脂社製、ナイパーＢＭＴ）をさらに配合すると共に、酸化防止剤の配合量を０．５重量部としたことを除き、実施例Ａ１と同様にして、実施例Ａ２の（メタ）アクリル系粘着剤組成物の溶液を調製した。 (Example A2)
Same as Example A1, except that 0.1 part by weight of a peroxide cross-linking agent (Niper BMT, manufactured by NOF CORPORATION) was further added, and the amount of the antioxidant was 0.5 parts by weight. Then, a solution of the (meth)acrylic pressure-sensitive adhesive composition of Example A2 was prepared.
（実施例Ａ３～Ａ８）
　以下の表２に示すように、（メタ）アクリル系ポリマーの溶液の固形分１００重量部に対して、上記イソシアネート系架橋剤、上記過酸化物系架橋剤、酸化防止剤及び導電剤を配合して、実施例Ａ３～Ａ８の（メタ）アクリル系粘着剤組成物の溶液を調製した。 (Examples A3 to A8)
As shown in Table 2 below, the isocyanate-based cross-linking agent, the peroxide-based cross-linking agent, the antioxidant and the conductive agent are blended with 100 parts by weight of the solid content of the (meth)acrylic polymer solution. to prepare solutions of the (meth)acrylic pressure-sensitive adhesive compositions of Examples A3 to A8.
（比較例Ａ１，Ａ２）
　以下の表２に示すように、（メタ）アクリル系ポリマーの溶液の固形分１００重量部に対して、上記イソシアネート系架橋剤、上記過酸化物系架橋剤及び導電剤を配合して、比較例Ａ１，Ａ２の（メタ）アクリル系粘着剤組成物の溶液を調製した。 (Comparative Examples A1 and A2)
As shown in Table 2 below, the isocyanate-based cross-linking agent, the peroxide-based cross-linking agent and the conductive agent were blended with respect to 100 parts by weight of the solid content of the (meth)acrylic polymer solution. Solutions of A1 and A2 (meth)acrylic pressure-sensitive adhesive compositions were prepared.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
［粘着シートの作製］
　各粘着剤組成物の溶液を、シリコーン系剥離剤で表面処理されたポリエチレンテレフタレートフィルム（はく離ライナー；三菱化学ポリエステルフィルム社製、ＭＲＦ３８）の片面に、乾燥後の粘着シートの厚さが２０μｍになるように塗布した。得られた塗布膜を１５５℃で１分間乾燥させることによって、はく離ライナーの表面に粘着シートを形成した。 [Production of adhesive sheet]
A solution of each adhesive composition was applied to one side of a polyethylene terephthalate film (release liner; manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) surface-treated with a silicone-based release agent, and the thickness of the adhesive sheet after drying was 20 μm. was applied as follows. The obtained coating film was dried at 155° C. for 1 minute to form an adhesive sheet on the surface of the release liner.
　＜表面抵抗値の測定＞
　各粘着剤組成物について、粘着シートを形成したときの表面抵抗値は、上記作製した粘着シートを試験サンプルとして使用し、三菱ケミカルアナリテック社製、ハイレスタＭＣＰ－ＨＴ４５０を用いて、印加電圧２５０Ｖ、印加時間１０秒の条件で測定した。表面抵抗値の測定は、温度２５℃±５℃及び相対湿度５０±５％の環境下で実施した。 <Measurement of surface resistance>
For each pressure-sensitive adhesive composition, the surface resistance value when forming a pressure-sensitive adhesive sheet was measured using the above-prepared pressure-sensitive adhesive sheet as a test sample, using Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd., at an applied voltage of 250 V, Measurement was performed under the condition of application time of 10 seconds. The measurement of the surface resistance value was carried out under an environment of a temperature of 25° C.±5° C. and a relative humidity of 50±5%.
［光学積層体の作製］
＜偏光板Ａの作製＞
　ポリビニルアルコールフィルムを、速度比の異なるロール間において、温度３０℃、濃度０．３重量％のヨウ素溶液中で１分間染色しながら、３倍まで延伸した。次に、濃度４重量％でホウ酸を含み、かつ濃度１０重量％でヨウ化カリウムを含む、温度６０℃の水溶液中に０．５分間浸漬しながら、総合延伸倍率が６倍になるまで延伸した。次に、濃度１．５重量％でヨウ化カリウムを含む、温度３０℃の水溶液中に１０秒間浸漬させて洗浄した後、５０℃で４分間乾燥を行うことによって、厚さ１８μｍの偏光子を得た。当該偏光子の片面に、ラクトン環構造を有する変性アクリル系ポリマーからなる厚さ３０μｍの透明保護フィルムをポリビニルアルコール系接着剤により貼り合せた。さらに、偏光子の他方の面に、トリアセチルセルロースフィルム（コニカミノルタ社製、ＫＣ４ＵＹ）にハードコート層（ＨＣ）を形成した厚さ４７μｍの透明保護フィルムをポリビニルアルコール系接着剤により貼り合せた。７０℃に設定されたオーブン内で５分間加熱乾燥させることによって偏光板Ａを作製した。 [Preparation of optical laminate]
<Preparation of polarizing plate A>
A polyvinyl alcohol film was stretched up to 3 times while being dyed in an iodine solution having a concentration of 0.3% by weight at a temperature of 30° C. for 1 minute between rolls having different speed ratios. Next, while being immersed in an aqueous solution containing boric acid at a concentration of 4% by weight and potassium iodide at a concentration of 10% by weight at a temperature of 60° C. for 0.5 minutes, it is stretched to a total draw ratio of 6 times. bottom. Next, after washing by immersing for 10 seconds in an aqueous solution containing potassium iodide at a concentration of 1.5% by weight at a temperature of 30° C. and drying at 50° C. for 4 minutes, a polarizer having a thickness of 18 μm was obtained. Obtained. A 30-μm-thick transparent protective film made of a modified acrylic polymer having a lactone ring structure was attached to one side of the polarizer with a polyvinyl alcohol-based adhesive. Furthermore, a transparent protective film having a thickness of 47 μm, which is a triacetyl cellulose film (KC4UY manufactured by Konica Minolta, KC4UY) formed with a hard coat layer (HC), was attached to the other surface of the polarizer with a polyvinyl alcohol-based adhesive. A polarizing plate A was prepared by heat drying for 5 minutes in an oven set at 70°C.
＜光学積層体の作製＞
　次に、はく離ライナー上に形成した実施例及び比較例の各粘着シートを上記作製した偏光板に転写して、光学積層体（粘着シート付き偏光板）を作製した。なお、粘着シートは、変性アクリル系ポリマーからなる透明保護フィルム側の偏光板の表面に転写した。 <Preparation of optical laminate>
Next, the pressure-sensitive adhesive sheets of Examples and Comparative Examples formed on the release liner were transferred to the polarizing plate prepared above to prepare an optical laminate (polarizing plate with pressure-sensitive adhesive sheet). The adhesive sheet was transferred to the surface of the polarizing plate on the side of the transparent protective film made of the modified acrylic polymer.
　＜着色Ａ＞
　高温下における光学積層体の着色は、以下の方法により評価した。作製した光学積層体を、偏光子の吸収軸が長辺となるように４５×４０ｍｍのサイズに切断した。次に、切断した光学積層体を、その粘着シートを介して、画像表示パネルの最外層を模したガラス板に貼り合わせた。次に、光学積層体における偏光板側の露出面に、粘着剤（日東電工社製、ＬＵＣＩＡＣＳ　ＣＳ９８２１；アクリル酸モノマーフリー粘着剤、厚さ２００μｍ）を介して、前面透明部材を模したガラス板を貼り合わせて、画像表示装置を模した評価用の積層体を作製した。次に、評価用の積層体を１０５℃に保持した熱風オーブンに１２０時間静置する加熱試験を実施し、加熱試験の前後における積層体の厚さ方向の光線透過率を測定した。光線透過率は、分光光度計（大塚電子社製、ＬＰＦ－２００）を用いて、ＪｌＳ　Ｚ８７０１：１９８２に定められた２度視野ＸＹＺ系によるＹ値（視感度補正を実施）として求めた。光源には、Ｃ光源を用いた。測定波長は、３８０～７００ｎｍ（１０ｎｍ毎）とした。積層体における光線透過率の測定部位は、最も着色が進んでいると考えられる中央付近とした。加熱試験前の光線透過率をＴｓ０、加熱試験後の光線透過率をＴｓ１２０として、その差ΔＴｓ＝Ｔｓ１２０－Ｔｓ０の値に基づいて、高温下における光学積層体の着色の程度を評価した。
　Ａ：ΔＴｓが０％超
　Ｂ：ΔＴｓが０％以下－３％超
　Ｃ：ΔＴｓが－３％以下－１０％超
　Ｄ：ΔＴｓが－１０％以下 <Coloring A>
The coloring of the optical layered body under high temperature was evaluated by the following method. The produced optical layered body was cut into a size of 45×40 mm so that the absorption axis of the polarizer was on the long side. Next, the cut optical layered body was attached to a glass plate imitating the outermost layer of an image display panel via the adhesive sheet. Next, a glass plate imitating a front transparent member was placed on the exposed surface of the optical laminate on the polarizing plate side via an adhesive (manufactured by Nitto Denko Corporation, LUCIACS CS9821; acrylic acid monomer-free adhesive, thickness 200 μm). By sticking together, a laminate for evaluation imitating an image display device was produced. Next, a heating test was performed in which the laminate for evaluation was placed in a hot air oven maintained at 105° C. for 120 hours, and the light transmittance in the thickness direction of the laminate was measured before and after the heating test. The light transmittance was determined as a Y value (performing visibility correction) by a two-degree field of view XYZ system defined in JlS Z8701:1982 using a spectrophotometer (LPF-200, manufactured by Otsuka Electronics Co., Ltd.). A C light source was used as the light source. The measurement wavelength was 380 to 700 nm (every 10 nm). The light transmittance of the laminate was measured near the center where the coloration was considered to be the most advanced. Assuming that the light transmittance before the heating test is Ts 0 and the light transmittance after the heating test is Ts 120 , the degree of coloring of the optical layered body at high temperature is evaluated based on the value of the difference ΔTs=Ts 120 -Ts 0 . bottom.
A: ΔTs is over 0% B: ΔTs is 0% or less -3% or more C: ΔTs is -3% or less -10% or more D: ΔTs is -10% or less
　＜耐久性（高温耐久性）Ａ＞
　光学積層体の耐久性（高温耐久性）は、以下の方法により評価した。作製した光学積層体を、その粘着シートを介してガラス板（コーニング製、イーグルＸＧ）の表面に固定した。固定は、２４℃及び５０％ＲＨの雰囲気で実施した。次に、５０℃及び５気圧（絶対圧）のオートクレーブにて１５分処理した後、２４℃に冷えるまで放置して、ガラス板への光学積層体への接合を安定させた後、１０５℃の加熱雰囲気に５００時間放置した。放置後、２４℃及び５０％ＲＨの雰囲気に戻し、ガラス板からの偏光板の剥がれや、ガラス板と偏光板との間に発泡が生じていないかを目視により確認して、以下のように、耐久性を評価した。
　Ａ：発泡や剥がれ等の外観上の変化がみられない。
　Ｂ：端部において、単独の剥がれ又は発泡がわずかにみられるが、実用上、問題ない範囲にある。
　Ｃ：端部において、連続した剥がれ又は発泡がわずかにみられるが、実用上、問題ない範囲にある。
　Ｄ：端部に著しい剥がれ又は発泡がみられ、実用上、問題がある。 <Durability (high temperature durability) A>
The durability (high temperature durability) of the optical laminate was evaluated by the following method. The produced optical layered body was fixed to the surface of a glass plate (Eagle XG manufactured by Corning) via the adhesive sheet. Fixation was performed in an atmosphere of 24° C. and 50% RH. Next, after treatment in an autoclave at 50°C and 5 atmospheres (absolute pressure) for 15 minutes, it was allowed to stand until it cooled to 24°C to stabilize the bonding of the optical laminate to the glass plate, followed by heating at 105°C. It was left in a heated atmosphere for 500 hours. After standing, the atmosphere was returned to 24° C. and 50% RH, and the polarizing plate was visually checked for peeling from the glass plate and bubbles between the glass plate and the polarizing plate. , to evaluate the durability.
A: No change in appearance such as foaming or peeling is observed.
B: Single peeling or foaming is slightly observed at the edge, but within a practically acceptable range.
C: Slight continuous peeling or foaming is observed at the edge, but within a practically acceptable range.
D: Significant peeling or foaming is observed at the edge, which is problematic in practice.
　＜帯電防止性＞
　光学積層体の帯電防止性は、以下の方法（ＥＳＤ試験）により評価した。作製した光学積層体を、その粘着シートを介して、図９の画像表示パネルの表面（視認側の表面）に固定した。次に、光学積層体を固定した液晶表示パネルをバックライト装置上にセットして、視認側の露出面である偏光板の表面に対して静電気放電銃により静電気を印加電圧１５ｋＶにて発射した。発射した時点から、静電気によって白抜けした部分が消失するまでの時間を測定し、以下のように帯電防止性を評価した。
　Ａ：１秒以内に消失
　Ｂ：１秒を超え１０秒以内に消失
　Ｃ：１０秒を超え６０秒以内に消失
　Ｄ：６０秒を超えて消失 <Antistatic property>
The antistatic property of the optical layered body was evaluated by the following method (ESD test). The produced optical layered body was fixed to the surface of the image display panel in FIG. 9 (surface on the viewing side) via the adhesive sheet. Next, the liquid crystal display panel to which the optical layered body was fixed was set on a backlight device, and static electricity was discharged with an applied voltage of 15 kV from an electrostatic discharge gun to the surface of the polarizing plate, which was the exposed surface on the viewing side. The time from the time of ejection to the disappearance of white spots due to static electricity was measured, and the antistatic property was evaluated as follows.
A: Disappears within 1 second B: Disappears within 10 seconds over 1 second C: Disappears over 10 seconds and within 60 seconds D: Disappears over 60 seconds
　実施例及び比較例の各光学積層体の評価結果を、各光学積層体に使用した粘着シートの表面抵抗値と共に、以下の表３に示す。なお、各光学積層体における高温下での着色（赤色化）は、主に偏光子に生じていた。 The evaluation results of each optical layered body of Examples and Comparative Examples are shown in Table 3 below together with the surface resistance value of the adhesive sheet used for each optical layered body. Note that the coloring (reddening) in each optical layered body at high temperatures mainly occurred in the polarizer.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表３に示すように、実施例の光学積層体では比較例Ａ２の光学積層体に比べて、粘着シートの低い表面抵抗値が達成されながら、高温下における着色が抑制された。なお、比較例Ａ１の光学積層体は、粘着シートを構成する粘着剤組成物がポリエーテル構造を有するポリマー（Ａ）を含まないため、実施例に比べて導電剤の配合量が多いにもかかわらず、粘着シートの表面抵抗値は高くなった。また、導電剤の配合量が多いために、光学積層体としての耐久性が低下したと考えられた。 As shown in Table 3, in the optical layered body of Example, compared with the optical layered body of Comparative Example A2, the pressure-sensitive adhesive sheet achieved a lower surface resistance value while suppressing coloration at high temperatures. In the optical laminate of Comparative Example A1, the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive sheet does not contain the polymer (A) having a polyether structure. However, the surface resistance of the adhesive sheet increased. In addition, it was considered that the durability as an optical layered body was lowered due to the large amount of the conductive agent.
［（メタ）アクリル系ポリマーＢの調製］
　フラスコに仕込む単量体混合物を、ＭＥＡ９８重量部、ｎ－ブチルアクリレート（ＢＡ）１重量部及びＨＢＡ１重量部とした以外は、（メタ）アクリル系ポリマーＡ１の調製と同様にして、重量平均分子量（Ｍｗ）１８０万、Ｍｗ／Ｍｎ＝３．５の（メタ）アクリル系ポリマーＢの溶液を調製した。 [Preparation of (meth) acrylic polymer B]
The weight average molecular weight ( A solution of (meth)acrylic polymer B having Mw) of 1,800,000 and Mw/Mn of 3.5 was prepared.
［（メタ）アクリル系ポリマーＣの調製］
　フラスコに仕込む単量体混合物を、ＭＥＡ６０重量部、エチルアクリレート２０重量部、ｎ－ブチルアクリレート（ＢＡ）１４重量部、フェノキシエチルアクリレート５重量部及びＨＢＡ１重量部とした以外は、（メタ）アクリル系ポリマーＡ１の調製と同様にして、重量平均分子量（Ｍｗ）２００万、Ｍｗ／Ｍｎ＝３．９の（メタ）アクリル系ポリマーＣの溶液を調製した。 [Preparation of (meth)acrylic polymer C]
The monomer mixture charged to the flask was 60 parts by weight of MEA, 20 parts by weight of ethyl acrylate, 14 parts by weight of n-butyl acrylate (BA), 5 parts by weight of phenoxyethyl acrylate, and 1 part by weight of HBA. A solution of a (meth)acrylic polymer C having a weight average molecular weight (Mw) of 2,000,000 and Mw/Mn=3.9 was prepared in the same manner as the polymer A1.
［（メタ）アクリル系粘着剤組成物の調製］
（サンプルｂ１）
　（メタ）アクリル系ポリマーＢの溶液の固形分１００重量部に対して、０．３重量部のイソシアネート系架橋剤（三井化学社製、タケネートＤ－１１０Ｎ；トリメチロールプロパン／キシリレンジイソシアネート付加物）及び導電剤として５重量部の１－エチル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド（ＥＭＩ－ＦＳＩ；第一工業製薬社製、エレクセルＡＳ－１１０）をさらに配合することによって、サンプルｂ１の（メタ）アクリル系粘着剤組成物の溶液を調製した。 [Preparation of (meth)acrylic pressure-sensitive adhesive composition]
(Sample b1)
(Meth) with respect to 100 parts by weight of the solid content of the acrylic polymer B solution, 0.3 parts by weight of an isocyanate cross-linking agent (Mitsui Chemicals, Takenate D-110N; trimethylolpropane / xylylene diisocyanate adduct) And 5 parts by weight of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide (EMI-FSI; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Elexel AS-110) as a conductive agent was further added to obtain a sample b1. A solution of a (meth)acrylic pressure-sensitive adhesive composition was prepared.
（サンプルｂ２）
　０．１重量部の過酸化物系架橋剤（日本油脂社製、ナイパーＢＭＴ）及び０．５重量部の酸化防止剤（ＢＡＳＦ社製、Ｉｒｇａｎｏｘ１０１０、分子量１１７８）をさらに配合したことを除き、サンプルｂ１と同様にして、サンプルｂ２の（メタ）アクリル系粘着剤組成物の溶液を調製した。 (Sample b2)
Except that 0.1 parts by weight of a peroxide cross-linking agent (NOF Co., Ltd., Nyper BMT) and 0.5 parts by weight of an antioxidant (BASF, Irganox 1010, molecular weight 1178) were further added, the sample A solution of the (meth)acrylic pressure-sensitive adhesive composition of sample b2 was prepared in the same manner as b1.
（サンプルｂ３）
　以下の表４に示すように、（メタ）アクリル系ポリマーＢの溶液の固形分１００重量部に対して、上記した、イソシアネート系架橋剤、過酸化物系架橋剤及び導電剤を配合して、サンプルｂ３の（メタ）アクリル系粘着剤組成物の溶液を調製した。 (Sample b3)
As shown in Table 4 below, the above-described isocyanate cross-linking agent, peroxide cross-linking agent and conductive agent are blended with respect to 100 parts by weight of the solid content of the solution of the (meth)acrylic polymer B, A solution of the (meth)acrylic pressure-sensitive adhesive composition of sample b3 was prepared.
（サンプルｂ４）
　以下の表４に示すように、（メタ）アクリル系ポリマーＣの溶液の固形分１００重量部に対して、上記した、イソシアネート系架橋剤、過酸化物系架橋剤及び導電剤を配合して、サンプルｂ４の（メタ）アクリル系粘着剤組成物の溶液を調製した。 (Sample b4)
As shown in Table 4 below, the isocyanate-based cross-linking agent, the peroxide-based cross-linking agent and the conductive agent are blended with 100 parts by weight of the solid content of the solution of the (meth)acrylic polymer C, A solution of the (meth)acrylic pressure-sensitive adhesive composition of sample b4 was prepared.
　＜比誘電率の測定＞
　実施例及び比較例の（メタ）アクリル系ポリマーＢ及びＣについて、上述の方法によって、周波数１００ｋＨｚにおける比誘電率Ｐを測定した。 <Measurement of dielectric constant>
For (meth)acrylic polymers B and C of Examples and Comparative Examples, the dielectric constant P at a frequency of 100 kHz was measured by the method described above.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
［粘着シートの作製］
　各粘着剤組成物の溶液を、シリコーン系剥離剤で表面処理されたポリエチレンテレフタレートフィルム（はく離ライナー；三菱化学ポリエステルフィルム社製、ＭＲＦ３８）の片面に、乾燥後の粘着シートの厚さが２０μｍになるように塗布した。得られた塗布膜を１５５℃で１分間乾燥させることによって、はく離ライナーの表面に粘着シートを形成した。 [Production of adhesive sheet]
A solution of each adhesive composition was applied to one side of a polyethylene terephthalate film (release liner; manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) surface-treated with a silicone-based release agent, and the thickness of the adhesive sheet after drying was 20 μm. was applied as follows. The obtained coating film was dried at 155° C. for 1 minute to form an adhesive sheet on the surface of the release liner.
　＜表面抵抗値の測定＞
　各粘着剤組成物について、粘着シートを形成したときの表面抵抗値は、上記作製した粘着シートを試験サンプルとして使用し、三菱ケミカルアナリテック社製、ハイレスタＭＣＰ－ＨＴ４５０を用いて、印加電圧２５０Ｖ、印加時間１０秒の条件で測定した。表面抵抗値の測定は、温度２５℃±５℃及び相対湿度５０±５％の環境下で実施した。 <Measurement of surface resistance>
For each pressure-sensitive adhesive composition, the surface resistance value when forming a pressure-sensitive adhesive sheet was measured using the above-prepared pressure-sensitive adhesive sheet as a test sample, using Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd., at an applied voltage of 250 V, Measurement was performed under the condition of application time of 10 seconds. The measurement of the surface resistance value was carried out under an environment of a temperature of 25° C.±5° C. and a relative humidity of 50±5%.
＜偏光板Ａの作製＞
　偏光板Ａは、上述の偏光板Ａを使用した。 <Preparation of polarizing plate A>
As the polarizing plate A, the polarizing plate A described above was used.
＜偏光板Ｂの作製＞
　偏光子の作製に用いたポリビニルアルコールフィルムの厚さ及びヨウ素濃度を変更した以外は偏光板Ａの作製と同様にして、厚さ２８μｍの偏光子を得た。次に、得られた偏光子に対して、偏光板Ａの作製と同様にして２種類の透明保護フィルムを貼り合わせて、偏光板Ｂを作製した。 <Preparation of polarizing plate B>
A polarizer having a thickness of 28 μm was obtained in the same manner as the polarizing plate A except that the thickness and iodine concentration of the polyvinyl alcohol film used for the production of the polarizer were changed. Next, two types of transparent protective films were attached to the obtained polarizer in the same manner as in the preparation of the polarizing plate A to prepare a polarizing plate B.
＜光学積層体の作製＞
　はく離ライナー上に形成した、実施例及び比較例の各粘着シートを、上記で作製した偏光板に転写して、粘着シート付き偏光板を作製した。なお、粘着シートは、変性アクリル系ポリマーからなる透明保護フィルム側の偏光板の表面に転写した。その後、粘着シート付き偏光板において、偏光板の粘着シートとは反対側の面に、光学透明粘着剤（ＯＣＡ）から構成されたＯＣＡ層を形成して、ＯＣＡ層、偏光板、粘着シート、及びはく離ライナーがこの順に積層された積層体を作製した。ＯＣＡ層は、ベースポリマーとしてブチルアクリレートを含んでいた。 <Preparation of optical laminate>
Each pressure-sensitive adhesive sheet of Examples and Comparative Examples formed on a release liner was transferred to the polarizing plate prepared above to prepare a polarizing plate with the pressure-sensitive adhesive sheet. The adhesive sheet was transferred to the surface of the polarizing plate on the side of the transparent protective film made of the modified acrylic polymer. After that, in the polarizing plate with an adhesive sheet, an OCA layer composed of an optically transparent adhesive (OCA) is formed on the surface of the polarizing plate opposite to the adhesive sheet, and the OCA layer, the polarizing plate, the adhesive sheet, and A laminate was produced in which the release liners were laminated in this order. The OCA layer contained butyl acrylate as the base polymer.
　次に、この積層体から、はく離ライナーをはく離させた。はく離ライナーをはく離した積層体において、粘着シートの偏光板とは反対側の表面及びＯＣＡ層の偏光板とは反対側の表面にガラスを積層させた。これにより、ガラス、ＯＣＡ層、偏光板、粘着シート、及びガラスがこの順に積層された、実施例及び比較例の光学積層体を作製した。 Next, the release liner was peeled off from this laminate. In the laminate from which the release liner was removed, glass was laminated on the surface of the pressure-sensitive adhesive sheet opposite to the polarizing plate and the surface of the OCA layer opposite to the polarizing plate. As a result, optical laminates of Examples and Comparative Examples were produced, in which the glass, the OCA layer, the polarizing plate, the adhesive sheet, and the glass were laminated in this order.
　＜着色ａ＞
　評価用の積層体を９５℃に保持した熱風オーブンに５００時間静置する加熱試験を実施したことを除き、上記＜着色Ａ＞と同じ方法により高温下における光学積層体の着色を評価した。なお、積層体における光線透過率の測定部位は、最も着色が進んでいると考えられる中央付近とした。加熱試験前の光線透過率をＴｓａ０、加熱試験後の光線透過率をＴｓａ５００として、その差ΔＴｓａ＝Ｔｓａ５００－Ｔｓａ０の値に基づいて、高温下における光学積層体の着色の程度を評価した。
　Ａ：ΔＴｓａが０％超
　Ｂ：ΔＴｓａが０％以下－３％超
　Ｃ：ΔＴｓａが－３％以下－１０％超
　Ｄ：ΔＴｓａが－１０％以下 <Coloring a>
Coloring of the optical layered body at high temperature was evaluated in the same manner as in <Coloring A> above, except that the layered body for evaluation was placed in a hot air oven maintained at 95°C for 500 hours in a heating test. The light transmittance of the laminate was measured near the center where the coloration was considered to be the most advanced. Assuming that the light transmittance before the heating test is Tsa 0 and the light transmittance after the heating test is Tsa 500 , the degree of coloring of the optical layered body at high temperatures is evaluated based on the difference ΔTsa=Tsa 500 -Tsa 0 . bottom.
A: ΔTsa is over 0% B: ΔTsa is 0% or less -3% or more C: ΔTsa is -3% or less -10% or more D: ΔTsa is -10% or less
　＜着色ｂ＞
　評価用の積層体を１０５℃に保持した熱風オーブンに５００時間静置する加熱試験を実施したことを除き、上記＜着色Ａ＞と同じ方法により高温下における光学積層体の着色を評価した。なお、積層体における光線透過率の測定部位は、最も着色が進んでいると考えられる中央付近とした。加熱試験前の光線透過率をＴｓｂ０、加熱試験後の光線透過率をＴｓｂ５００として、その差ΔＴｓｂ＝Ｔｓｂ５００－Ｔｓｂ０の値に基づいて、高温下における光学積層体の着色の程度を評価した。
　Ａ：ΔＴｓｂが０％超
　Ｂ：ΔＴｓｂが０％以下－３％超
　Ｃ：ΔＴｓｂが－３％以下－１０％超
　Ｄ：ΔＴｓｂが－１０％以下 <Coloring b>
Coloring of the optical layered body at high temperature was evaluated in the same manner as in <Coloring A> above, except that the evaluation layered body was placed in a hot air oven maintained at 105°C for 500 hours in a heating test. The light transmittance of the laminate was measured near the center where the coloration was considered to be the most advanced. Assuming that the light transmittance before the heating test is Tsb 0 and the light transmittance after the heating test is Tsb 500 , the degree of coloring of the optical laminate at high temperatures is evaluated based on the difference ΔTsb=Tsb 500 −Tsb 0 . bottom.
A: ΔTsb is over 0% B: ΔTsb is 0% or less -3% or more C: ΔTsb is -3% or less -10% or more D: ΔTsb is -10% or less
　＜耐久性（高温耐久性）Ｂ＞
　実施例Ｂ１～Ｂ４及び比較例Ｂ１の光学積層体を使用したことを除き、光学積層体の耐久性（高温耐久性）は、上記＜耐久性（高温耐久性）Ａ＞と同じ方法により評価した。 <Durability (high temperature durability) B>
The durability (high-temperature durability) of the optical laminate was evaluated by the same method as in <Durability (high-temperature durability) A> above, except that the optical laminates of Examples B1 to B4 and Comparative Example B1 were used. .
＜粘着シートにおける、ギ酸の含有量及び酢酸の含有量の測定＞
　まず、はく離ライナー上に形成した、実施例及び比較例の各粘着シートを、１０５℃に保持した熱風オーブンに１２０時間静置させる加熱試験を実施した。 <Measurement of formic acid content and acetic acid content in adhesive sheet>
First, a heating test was conducted in which each pressure-sensitive adhesive sheet of Examples and Comparative Examples formed on a release liner was allowed to stand in a hot air oven maintained at 105° C. for 120 hours.
　加熱試験後の粘着シート約０．１ｇを秤量してＰＰ容器に加えた。このＰＰ容器に純水５０ｍＬをさらに加えてＰＰ容器に蓋をした。そして、ＰＰ容器を乾燥機に入れて、１２０℃で１時間加温して抽出を行った。得られた抽出液をメンブレンフィルターにてろ過してろ液を得た。得られたろ液について、固相抽出カートリッジにて有機物を除去することによって、イオンクロマトグラフ測定用の分析溶液を調製した。この分析溶液をイオンクロマトグラフ測定（ＩＣ測定）に使用した。分析溶液について、ギ酸イオン及び酢酸イオンをイオンクロマトグラフで定量することにより、粘着シートに含まれるギ酸の含有量及び粘着シートに含まれる酢酸の含有量を求めた。イオンクロマトグラフ測定には、Ｔｈｅｒｍｏ　Ｆｉｓｈｅｒ　Ｓｃｉｅｎｔｉｆｉｃ社製のＩＣＳ－３０００を使用した。 About 0.1 g of the adhesive sheet after the heating test was weighed and added to the PP container. 50 mL of pure water was further added to this PP container, and the PP container was capped. Then, the PP container was placed in a dryer and heated at 120° C. for 1 hour for extraction. The resulting extract was filtered through a membrane filter to obtain a filtrate. An analysis solution for ion chromatography was prepared by removing organic substances from the obtained filtrate with a solid-phase extraction cartridge. This analytical solution was used for ion chromatography measurements (IC measurements). The content of formic acid contained in the adhesive sheet and the content of acetic acid contained in the adhesive sheet were determined by quantifying formate ions and acetate ions in the analysis solution by ion chromatography. ICS-3000 manufactured by Thermo Fisher Scientific was used for ion chromatographic measurement.
＜偏光板におけるギ酸の含有量の測定＞
　まず、実施例及び比較例の光学積層体を、１０５℃に保持した熱風オーブンに１２０時間静置させる加熱試験を実施した。加熱試験後の光学積層体を液体窒素に浸漬して凍結させた後、ＯＣＡ層の表面に形成されているガラスを光学積層体からはく離させ、さらに、ＯＣＡ層を削り取って除去して積層体を得た。次にこの積層体について、粘着シートの表面に形成されているガラスをはく離させ、さらに粘着シートを偏光板から物理的に除去した。このようにして、光学積層体から偏光板を得た。得られた偏光板を使用したことを除き、上記した方法によりイオンクロマトグラフ測定用の分析溶液を調製した。ギ酸イオンをイオンクロマトグラフで定量することにより、偏光板に含まれるギ酸の含有量を求めた。イオンクロマトグラフ測定に使用した装置は上記したとおりである。 <Measurement of formic acid content in polarizing plate>
First, a heating test was conducted in which the optical layered bodies of Examples and Comparative Examples were allowed to stand in a hot air oven maintained at 105° C. for 120 hours. After the optical layered body after the heating test is immersed in liquid nitrogen and frozen, the glass formed on the surface of the OCA layer is peeled off from the optical layered body, and the OCA layer is scraped off to remove the layered body. Obtained. Next, for this laminate, the glass formed on the surface of the adhesive sheet was peeled off, and the adhesive sheet was physically removed from the polarizing plate. Thus, a polarizing plate was obtained from the optical laminate. An analysis solution for ion chromatography measurement was prepared by the method described above, except that the obtained polarizing plate was used. The content of formic acid contained in the polarizing plate was obtained by quantifying formate ions by ion chromatography. The equipment used for ion chromatographic measurements is as described above.
　実施例及び比較例で作製した、粘着シート及び光学積層体について、各特性の評価結果を表５及び表６に示す。表５において、「＜２．５」は、ギ酸の含有量又は酢酸の含有量が検出限界未満であったことを示す。 Tables 5 and 6 show the evaluation results of each property of the pressure-sensitive adhesive sheets and optical laminates produced in Examples and Comparative Examples. In Table 5, "<2.5" indicates that the formic acid content or the acetic acid content was below the detection limit.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表５及び表６に示すように、各実施例の光学積層体では、比較例Ｂ１の光学積層体に比べて、粘着シートに含まれるギ酸の含有量が質量基準で１０００ｐｐｍ以下であり、高温下における着色が抑制された。加えて、表５に示すように、各実施例の光学積層体では、偏光板に含まれるギ酸の含有量が質量基準で７０ｐｐｍ以下であり、高温下における着色が抑制された。なお、実施例及び比較例の光学積層体では、高温環境を経た後でも酢酸の含有量は少なかった。 As shown in Tables 5 and 6, in the optical layered body of each example, the content of formic acid contained in the pressure-sensitive adhesive sheet was 1000 ppm or less on a mass basis, compared with the optical layered body of Comparative Example B1. Coloration in was suppressed. In addition, as shown in Table 5, in the optical laminate of each example, the content of formic acid contained in the polarizing plate was 70 ppm or less on a mass basis, and coloration at high temperatures was suppressed. In the optical laminates of Examples and Comparative Examples, the content of acetic acid was small even after being subjected to a high-temperature environment.
（サンプルｄ１）
［（メタ）アクリル系ポリマーＤ１の調製］
　攪拌羽根、温度計、窒素ガス導入管及び冷却器を備えた４つ口フラスコに、２－メトキシエチルアクリレート（ＭＥＡ）９９重量部及び４－ヒドロキシブチルアクリレート１重量部を含有する単量体混合物を仕込んだ。さらに、単量体混合物１００重量部に対して、重合開始剤として２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ；キシダ化学社製）０．１重量部を酢酸エチル１００重量部と共に仕込んだ。混合物を緩やかに攪拌しながら、フラスコ内について窒素ガスを導入して窒素置換した。フラスコ内の液温を５５℃付近に維持して８時間重合反応を行うことによって、重量平均分子量（Ｍｗ）１８０万、Ｍｗ／Ｍｎ＝４．４の（メタ）アクリル系ポリマーＤ１の溶液を調製した。 (Sample d1)
[Preparation of (meth)acrylic polymer D1]
A monomer mixture containing 99 parts by weight of 2-methoxyethyl acrylate (MEA) and 1 part by weight of 4-hydroxybutyl acrylate was placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser. I prepared. Furthermore, 0.1 part by weight of 2,2'-azobisisobutyronitrile (AIBN; manufactured by Kishida Chemical Co., Ltd.) as a polymerization initiator was added to 100 parts by weight of the monomer mixture together with 100 parts by weight of ethyl acetate. . While gently stirring the mixture, nitrogen gas was introduced into the flask to replace it with nitrogen. A solution of (meth)acrylic polymer D1 having a weight average molecular weight (Mw) of 1,800,000 and Mw/Mn of 4.4 was prepared by conducting a polymerization reaction for 8 hours while maintaining the liquid temperature in the flask at around 55°C. bottom.
［（メタ）アクリル系粘着剤組成物の調製］
　次に、（メタ）アクリル系ポリマーＤ１の溶液の固形分１００重量部に対して、０．３５重量部のイソシアネート系架橋剤（東ソー社製、コロネートＬ；トリメチロールプロパントリレンジイソシアネート）、０．０１重量部の過酸化物系架橋剤（日本油脂社製、ナイパーＢＭＴ）、及び導電剤として５重量部のビス（トリフルオロメタンスルホニル）イミドリチウム（ＬｉＴＦＳＩ；三菱マテリアル電子化成社製）をさらに配合することによって、（メタ）アクリル系粘着剤組成物（サンプルｄ１）の溶液を調製した。 [Preparation of (meth)acrylic pressure-sensitive adhesive composition]
Next, 0.35 parts by weight of an isocyanate cross-linking agent (Coronate L; trimethylolpropane tolylene diisocyanate manufactured by Tosoh Corporation), 0.35 parts by weight of an isocyanate-based cross-linking agent (Coronate L; trimethylolpropane tolylene diisocyanate, manufactured by Tosoh Corporation), are added to 100 parts by weight of the solid content of the solution of the (meth)acrylic polymer D1. 01 parts by weight of a peroxide cross-linking agent (Niper BMT, manufactured by NOF Corporation) and 5 parts by weight of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI; manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) as a conductive agent are further blended. Thus, a solution of a (meth)acrylic pressure-sensitive adhesive composition (sample d1) was prepared.
（サンプルｄ２）
　過酸化物系架橋剤を配合しなかったことを除き、サンプルｄ１と同じ方法によって、粘着剤組成物（サンプルｄ２）の溶液を調製した。 (Sample d2)
A solution of the pressure-sensitive adhesive composition (sample d2) was prepared in the same manner as for sample d1, except that no peroxide-based cross-linking agent was added.
（サンプルｄ３）
　過酸化物系架橋剤の配合量を０．１重量部に変更したことを除き、サンプルｄ１と同じ方法によって、粘着剤組成物（サンプルｄ３）の溶液を調製した。 (Sample d3)
A solution of the pressure-sensitive adhesive composition (sample d3) was prepared in the same manner as for sample d1, except that the amount of the peroxide-based cross-linking agent was changed to 0.1 parts by weight.
（サンプルｄ４）
　（メタ）アクリル系ポリマーＤ１の溶液の固形分１００重量部に対して、酸化防止剤（ＢＡＳＦジャパン社製、Irganox1135）１．０重量部をさらに配合したことを除き、サンプルｄ３と同じ方法によって、粘着剤組成物（サンプルｄ４）の溶液を調製した。 (Sample d4)
(Meth) With respect to 100 parts by weight of the solid content of the acrylic polymer D1 solution, except that 1.0 parts by weight of an antioxidant (Irganox 1135, manufactured by BASF Japan) was further added, By the same method as sample d3, A solution of the adhesive composition (sample d4) was prepared.
（サンプルｄ５）
　過酸化物系架橋剤の配合量を１．０重量部に変更したことを除き、サンプルｄ１と同じ方法によって、粘着剤組成物（サンプルｄ５）の溶液を調製した。 (Sample d5)
A solution of the pressure-sensitive adhesive composition (sample d5) was prepared in the same manner as for sample d1, except that the amount of the peroxide-based cross-linking agent was changed to 1.0 parts by weight.
　サンプルｄ１～ｄ５の各粘着剤組成物の組成を以下の表７に示す。 The composition of each adhesive composition of samples d1 to d5 is shown in Table 7 below.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
［粘着シートの作製］
　各粘着剤組成物の溶液を、シリコーン系剥離剤で表面処理されたポリエチレンテレフタレートフィルム（はく離ライナー；三菱化学ポリエステルフィルム社製、ＭＲＦ３８）の片面に、乾燥後の粘着シートの厚さが２０μｍになるように塗布した。得られた塗布膜を１５５℃で１分間乾燥させることによって、はく離ライナーの表面に粘着シート（サンプルｄ１～ｄ５の各サンプルにそれぞれ対応するサンプルｄ１１～ｄ１５）を形成した。 [Production of adhesive sheet]
A solution of each adhesive composition was applied to one side of a polyethylene terephthalate film (release liner; manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) surface-treated with a silicone-based release agent, and the thickness of the adhesive sheet after drying was 20 μm. was applied as follows. The resulting coating film was dried at 155° C. for 1 minute to form an adhesive sheet (samples d11 to d15 corresponding to samples d1 to d5, respectively) on the surface of the release liner.
　＜ラジカル発生量の定量＞
　各粘着剤組成物について、粘着シートを形成したときのラジカル発生量ＲＧ１０、ＲＧ２０及びＲＧ３０の評価は、上述の方法により実施した。ただし、ＥＳＲ試料管に収容する試験片（約５０ｍｇ）は、上記作製した粘着シートから採取した。測定装置及び測定条件は以下に記載するとおりとした。ラジカル発生量の算出に使用したＥＳＲ信号のｇ値（中心磁場）は、（メタ）アクリル系ポリマーＤ１が側鎖に有するポリエーテル構造に起因して生じたラジカルの中でＥＳＲ信号の強度が最も大きく、偏光板に含まれるＰＶＡのポリエン化への寄与が大きいと考えられるＮＯ（ニトロキシド）ラジカルに対応した３３５２Ｇ（ガウス）付近とした。
・測定装置：ＥＭＸｐｌｕｓ（ＢＲＵＫＥＲ社）
・測定条件
　　測定温度　　　　　１０５℃
　　磁場掃引範囲　　　２００Ｇ
　　変調　　　　　　　１００ｋＨｚ、５Ｇ
　　マイクロ波　　　　９．４０ＧＨｚ、１ｍＷ
　　掃引時間　　　　　８０秒×４回
　　時定数　　　　　　３２７．６８ミリ秒
　　データポイント数　１０００ｐｏｉｎｔｓ
　　キャビティ　　　　Ｓｕｐｅｒ－ｈｉｇｈ－Ｑ <Quantification of amount of radicals generated>
For each pressure-sensitive adhesive composition, the radical generation amounts RG 10 , RG 20 and RG 30 when forming pressure-sensitive adhesive sheets were evaluated by the methods described above. However, the test piece (approximately 50 mg) housed in the ESR sample tube was taken from the pressure-sensitive adhesive sheet produced above. The measurement apparatus and measurement conditions were as described below. The g value (central magnetic field) of the ESR signal used to calculate the amount of radical generation was the highest among the radicals generated due to the polyether structure in the side chain of the (meth)acrylic polymer D1. It was set to around 3352 G (gauss) corresponding to NO (nitroxide) radicals, which are large and considered to greatly contribute to the polyene conversion of PVA contained in the polarizing plate.
・Measuring device: EMXplus (BRUKER)
・Measurement conditions Measurement temperature 105℃
Magnetic field sweep range 200G
Modulation 100kHz, 5G
Microwave 9.40GHz, 1mW
Sweep time 80 seconds x 4 times Time constant 327.68 milliseconds Number of data points 1000 points
Cavity Super-high-Q
　＜表面抵抗値の測定＞
　各粘着剤組成物について、粘着シートを形成したときの表面抵抗値は、上記作製した粘着シートを試験サンプルとして使用し、三菱ケミカルアナリテック社製、ハイレスタＭＣＰ－ＨＴ４５０を用いて、印加電圧２５０Ｖ、印加時間１０秒の条件で測定した。表面抵抗値の測定は、温度２５℃±５℃及び相対湿度５０±５％の環境下で実施した。 <Measurement of surface resistance>
For each pressure-sensitive adhesive composition, the surface resistance value when forming a pressure-sensitive adhesive sheet was measured using the above-prepared pressure-sensitive adhesive sheet as a test sample, using Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd., at an applied voltage of 250 V, Measurement was performed under the condition of application time of 10 seconds. The measurement of the surface resistance value was carried out under an environment of a temperature of 25° C.±5° C. and a relative humidity of 50±5%.
［光学積層体の作製］
＜偏光板Ａの作製＞
　偏光板Ａは、上述の偏光板Ａを使用した。 [Preparation of optical laminate]
<Preparation of polarizing plate A>
As the polarizing plate A, the polarizing plate A described above was used.
＜偏光板Ｂの作製＞
　偏光板Ｂは、上述の偏光板Ｂを使用した。 <Preparation of polarizing plate B>
As the polarizing plate B, the polarizing plate B described above was used.
（実施例Ｄ１）
　はく離ライナー上に形成したサンプルｄ１１の粘着シートを上述の偏光板Ａ（偏光子の厚さ１８μｍ）に転写して、実施例Ｄ１の光学積層体（粘着シート付き偏光板）を作製した。なお、粘着シートは、変性アクリル系ポリマーからなる透明保護フィルム側の偏光板の表面に転写した。 (Example D1)
The pressure-sensitive adhesive sheet of sample d11 formed on the release liner was transferred to the above polarizing plate A (polarizer thickness: 18 μm) to prepare an optical laminate (polarizing plate with pressure-sensitive adhesive sheet) of Example D1. The adhesive sheet was transferred to the surface of the polarizing plate on the side of the transparent protective film made of the modified acrylic polymer.
（実施例Ｄ２）
　サンプルｄ１１の代わりにサンプルｄ１２の粘着シートを使用したことを除き、実施例Ｄ１と同様にして、実施例Ｄ２の光学積層体を作製した。 (Example D2)
An optical laminate of Example D2 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d12 was used instead of Sample d11.
（実施例Ｄ３）
　サンプルｄ１１の代わりにサンプルｄ１３の粘着シートを使用したことを除き、実施例Ｄ１と同様にして、実施例Ｄ３の光学積層体を作製した。 (Example D3)
An optical laminate of Example D3 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d13 was used instead of Sample d11.
（実施例Ｄ４）
　サンプルｄ１１の代わりにサンプルｄ１４の粘着シートを使用したことを除き、実施例Ｄ１と同様にして、実施例Ｄ４の光学積層体を作製した。 (Example D4)
An optical laminate of Example D4 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d14 was used instead of Sample d11.
（実施例Ｄ５）
　サンプルｄ１１の代わりにサンプルｄ１３の粘着シートを使用すると共に、偏光板Ａの代わりに偏光板Ｂを使用したことを除き、実施例Ｄ１と同様にして、実施例Ｄ５の光学積層体を作製した。 (Example D5)
An optical laminate of Example D5 was produced in the same manner as in Example D1, except that the adhesive sheet of sample d13 was used instead of sample d11 and polarizing plate B was used instead of polarizing plate A.
（比較例Ｄ１）
　サンプルｄ１１の代わりにサンプルｄ１５の粘着シートを使用したことを除き、実施例Ｄ１と同様にして、比較例Ｄ１の光学積層体を作製した。 (Comparative Example D1)
An optical laminate of Comparative Example D1 was produced in the same manner as in Example D1, except that the pressure-sensitive adhesive sheet of Sample d15 was used instead of Sample d11.
　＜着色Ｂ＞
　実施例Ｄ１～Ｄ５及び比較例Ｄ１に係る光学積層体を使用して評価用の積層体を作製したことと、この評価用の積層体を９５℃又は１０５℃に保持した熱風オーブンに１２０時間静置する加熱試験を実施したこととを除き、上記＜着色Ａ＞と同じ方法により、高温下における光学積層体の着色を評価した。
　＜耐久性（高温耐久性）Ｃ＞
　実施例Ｄ１～Ｄ５及び比較例Ｄ１に係る光学積層体を使用したことを除き、光学積層体の耐久性（高温耐久性）は、上記＜耐久性（高温耐久性）Ａ＞と同じ方法により評価した。 <Coloring B>
A laminate for evaluation was prepared using the optical laminates according to Examples D1 to D5 and Comparative Example D1, and this laminate for evaluation was placed in a hot air oven maintained at 95 ° C. or 105 ° C. for 120 hours. The coloring of the optical layered body at high temperatures was evaluated in the same manner as in <Coloring A> above, except that a heating test was performed.
<Durability (high temperature durability) C>
The durability (high-temperature durability) of the optical laminate was evaluated by the same method as in <Durability (high-temperature durability) A> above, except that the optical laminates according to Examples D1 to D5 and Comparative Example D1 were used. bottom.
　実施例及び比較例の各光学積層体の評価結果を、各光学積層体に使用した粘着シートの評価結果と共に、以下の表８に示す。なお、各光学積層体における高温下での着色（赤色化）は、主に偏光子に生じていた。 The evaluation results of each optical layered body of Examples and Comparative Examples are shown in Table 8 below together with the evaluation results of the adhesive sheet used in each optical layered body. Note that the coloring (reddening) in each optical layered body at high temperatures mainly occurred in the polarizer.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　表８に示すように、実施例の光学積層体では比較例の光学積層体に比べて、粘着シートの低い表面抵抗値が達成されながら、高温下における着色が抑制された。 As shown in Table 8, in the optical layered bodies of Examples, compared to the optical layered bodies of Comparative Examples, the pressure-sensitive adhesive sheet achieved a lower surface resistance value while suppressing coloration at high temperatures.
　本発明の粘着剤組成物は、例えば、ＥＬディスプレイ、液晶ディスプレイ等の画像表示装置に使用できる。
 
  The pressure-sensitive adhesive composition of the present invention can be used, for example, in image display devices such as EL displays and liquid crystal displays.

Claims (67)

  1. 　ポリエーテル構造を有するポリマー（Ａ）を主成分として含み、
    　導電剤及びラジカル捕捉剤をさらに含み、
    　粘着シートを形成したときに、前記粘着シートは１×１０１０Ω／□以下の表面抵抗値を有する、粘着剤組成物。     Containing a polymer (A) having a polyether structure as a main component,
    further comprising a conductive agent and a radical scavenger;
    A pressure-sensitive adhesive composition, wherein when the pressure-sensitive adhesive sheet is formed, the pressure-sensitive adhesive sheet has a surface resistance value of 1×10 10 Ω/□ or less.
  2. 　前記ポリマー（Ａ）が（メタ）アクリル系ポリマーである、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the polymer (A) is a (meth)acrylic polymer.
  3. 　前記ポリマー（Ａ）が前記ポリエーテル構造を側鎖に有する、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the polymer (A) has the polyether structure in its side chain.
  4. 　前記ポリマー（Ａ）が以下の式（１）に示す単量体に由来する構成単位を有する、請求項１に記載の粘着剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     　前記式（１）において、Ｒ１は、水素原子又はメチル基であり、Ｒ２は、直鎖状であっても分岐を有していてもよいアルキル基であり、ｎは、１～１５の整数である。     2. The pressure-sensitive adhesive composition according to claim 1, wherein the polymer (A) has structural units derived from monomers represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     In the above formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group which may be linear or branched, and n is 1 to 15. is an integer.
  5. 　前記ポリマー（Ａ）における前記構成単位の含有率が２５重量％以上である、請求項４に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 4, wherein the content of the structural unit in the polymer (A) is 25% by weight or more.
  6. 　前記表面抵抗値が１×１０９Ω／□以下である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the surface resistance value is 1×10 9 Ω/□ or less.
  7. 　前記ラジカル捕捉剤が酸化防止剤である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the radical scavenger is an antioxidant.
  8. 　前記ラジカル捕捉剤の分子量が１０００以下である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the radical scavenger has a molecular weight of 1000 or less.
  9. 　前記粘着剤組成物における前記ラジカル捕捉剤の配合量が、前記ポリマー（Ａ）１００重量部に対して５重量部未満である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the content of the radical scavenger in the pressure-sensitive adhesive composition is less than 5 parts by weight with respect to 100 parts by weight of the polymer (A).
  10. 　前記粘着剤組成物における前記導電剤の配合量が、前記ポリマー（Ａ）１００重量部に対して８重量部以下である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the amount of the conductive agent compounded in the pressure-sensitive adhesive composition is 8 parts by weight or less with respect to 100 parts by weight of the polymer (A).
  11. 　前記粘着剤組成物がイソシアネート系架橋剤をさらに含む、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, further comprising an isocyanate-based cross-linking agent.
  12. 　前記粘着剤組成物が過酸化物系架橋剤をさらに含む、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, further comprising a peroxide-based cross-linking agent.
  13. 　溶剤型である、請求項１に記載の粘着剤組成物。 The adhesive composition according to claim 1, which is solvent-based.
  14. 　光学積層体用である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, which is for optical laminates.
  15. 　請求項１に記載の粘着剤組成物から形成された粘着シート。 A pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition according to claim 1.
  16. 　請求項１５に記載の粘着シートと、
    　光学フィルムと、
    　を含む、光学積層体。     The pressure-sensitive adhesive sheet according to claim 15;
    an optical film;
    An optical stack comprising:
  17. 　前記光学フィルムが、偏光子を含む偏光板である、請求項１６に記載の光学積層体。 The optical laminate according to claim 16, wherein the optical film is a polarizing plate containing a polarizer.
  18. 　保護フィルムをさらに含み、
    　前記保護フィルムは、前記偏光子の少なくとも一方の面に配置されている、請求項１７に記載の光学積層体。     further comprising a protective film;
    18. The optical laminate according to claim 17, wherein the protective film is arranged on at least one surface of the polarizer.
  19. 　請求項１６に記載の光学積層体を備える、画像表示パネル。 An image display panel comprising the optical laminate according to claim 16.
  20. 　請求項１９に記載の画像表示パネルを備える、画像表示装置。 An image display device comprising the image display panel according to claim 19.
  21. 　ポリマー（Ｂ）を含む粘着剤組成物から形成された粘着シートであって、
    　周波数１００ｋＨｚにおける前記ポリマー（Ｂ）の比誘電率が５．０以上であり、
    　前記粘着シートを１０５℃で１２０時間加熱した後に、前記粘着シートは、質量基準で１０００ｐｐｍ以下のギ酸を含有する、粘着シート。     A pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a polymer (B),
    the dielectric constant of the polymer (B) at a frequency of 100 kHz is 5.0 or more;
    A pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive sheet contains 1000 ppm or less of formic acid on a mass basis after heating the pressure-sensitive adhesive sheet at 105°C for 120 hours.
  22. 　前記粘着シートを１０５℃で１２０時間加熱した後に、前記粘着シートは、質量基準で１００ｐｐｍ以下のギ酸を含有する、請求項２１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 21, wherein the pressure-sensitive adhesive sheet contains 100 ppm or less of formic acid on a mass basis after heating the pressure-sensitive adhesive sheet at 105°C for 120 hours.
  23. 　前記ポリマー（Ｂ）が（メタ）アクリル系ポリマーである、請求項２１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 21, wherein the polymer (B) is a (meth)acrylic polymer.
  24. 　前記ポリマー（Ｂ）は、ポリエーテル構造を側鎖に有する、請求項２１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 21, wherein the polymer (B) has a polyether structure in its side chain.
  25. 　前記ポリマー（Ｂ）が以下の式（１）に示す単量体に由来する構成単位を有する、請求項２１に記載の粘着シート。
    Figure JPOXMLDOC01-appb-C000002
     　前記式（１）において、Ｒ１は、水素原子又はメチル基であり、Ｒ２は、直鎖状であっても分岐を有していてもよいアルキル基であり、ｎは、１～１５の整数である。     The pressure-sensitive adhesive sheet according to claim 21, wherein the polymer (B) has a structural unit derived from a monomer represented by formula (1) below.
    Figure JPOXMLDOC01-appb-C000002
     In the above formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group which may be linear or branched, and n is 1 to 15. is an integer.
  26. 　前記粘着剤組成物が、過酸化物系架橋剤及びラジカル捕捉剤をさらに含む、請求項２１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 21, wherein the pressure-sensitive adhesive composition further contains a peroxide cross-linking agent and a radical scavenger.
  27. 　前記ラジカル捕捉剤が酸化防止剤である、請求項２６に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 26, wherein the radical scavenger is an antioxidant.
  28. 　前記粘着剤組成物がイソシアネート系架橋剤をさらに含む、請求項２１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 21, wherein the pressure-sensitive adhesive composition further contains an isocyanate-based cross-linking agent.
  29. 　光学積層体用である、請求項２１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 21, which is for an optical laminate.
  30. 　請求項２１に記載の粘着シートと、
    　光学フィルムと、
    　を含む、光学積層体。     The pressure-sensitive adhesive sheet according to claim 21;
    an optical film;
    An optical stack comprising:
  31. 　前記光学フィルムが、偏光子を含む偏光板である、請求項３０に記載の光学積層体。 The optical laminate according to claim 30, wherein the optical film is a polarizing plate containing a polarizer.
  32. 　前記光学積層体を１０５℃で１２０時間加熱した後に、前記偏光板は、質量基準で７０ｐｐｍ以下のギ酸を含有する、請求項３１に記載の光学積層体。 The optical layered body according to claim 31, wherein the polarizing plate contains 70 ppm or less of formic acid on a mass basis after heating the optical layered body at 105°C for 120 hours.
  33. 　前記光学積層体を９５℃で５００時間加熱した加熱試験後の光線透過率をＴｓａ５００と定義し、前記加熱試験前の前記光学積層体の光線透過率をＴｓａ０と定義したとき、ΔＴｓａ＝Ｔｓａ５００－Ｔｓａ０がΔＴｓａ＞０％を満たす、請求項３０に記載の光学積層体。 When the light transmittance after the heating test in which the optical layered body is heated at 95° C. for 500 hours is defined as Tsa 500 , and the light transmittance of the optical layered body before the heating test is defined as Tsa 0 , ΔTsa=Tsa 31. The optical stack of claim 30, wherein 500 -Tsa 0 satisfies ΔTsa>0%.
  34. 　保護フィルムをさらに含み、
    　前記保護フィルムは、前記偏光子の少なくとも一方の面に配置されている、請求項３１に記載の光学積層体。     further comprising a protective film;
    32. The optical laminate according to Claim 31, wherein said protective film is disposed on at least one surface of said polarizer.
  35. 　請求項３０に記載の光学積層体を備える、画像表示パネル。 An image display panel comprising the optical laminate according to claim 30.
  36. 　請求項３５に記載の画像表示パネルを備える、画像表示装置。 An image display device comprising the image display panel according to claim 35.
  37. 　粘着シートと光学フィルムとを含む光学積層体であって、
    　前記光学フィルムが、偏光子を含む偏光板であり、
    　前記光学積層体を１０５℃で１２０時間加熱した後に、前記偏光板は、質量基準で７０ｐｐｍ以下のギ酸を含有する、光学積層体。     An optical laminate including an adhesive sheet and an optical film,
    The optical film is a polarizing plate containing a polarizer,
    The optical laminate, wherein the polarizing plate contains 70 ppm or less of formic acid on a mass basis after the optical laminate is heated at 105° C. for 120 hours.
  38. 　前記偏光子の厚みが２０μｍ以下である、請求項３７に記載の光学積層体。 The optical laminate according to claim 37, wherein the polarizer has a thickness of 20 µm or less.
  39. 　前記粘着シートは、ポリマー（Ｃ）を含む粘着剤組成物から形成された粘着シートであって、周波数１００ｋＨｚにおける前記ポリマー（Ｃ）の比誘電率が５．０以上である、請求項３７に記載の光学積層体。 38. The pressure-sensitive adhesive sheet according to claim 37, wherein the pressure-sensitive adhesive sheet is formed from a pressure-sensitive adhesive composition containing a polymer (C), and the relative permittivity of the polymer (C) at a frequency of 100 kHz is 5.0 or more. optical laminate.
  40. 　前記ポリマー（Ｃ）が（メタ）アクリル系ポリマーである、請求項３９に記載の光学積層体。 The optical laminate according to claim 39, wherein the polymer (C) is a (meth)acrylic polymer.
  41. 　前記ポリマー（Ｃ）は、ポリエーテル構造を側鎖に有する、請求項３９に記載の光学積層体。 The optical laminate according to claim 39, wherein the polymer (C) has a polyether structure in its side chain.
  42. 　前記ポリマー（Ｃ）が以下の式（１）に示す単量体に由来する構成単位を有する、請求項３９に記載の光学積層体。
    Figure JPOXMLDOC01-appb-C000003
     　前記式（１）において、Ｒ１は、水素原子又はメチル基であり、Ｒ２は、直鎖状であっても分岐を有していてもよいアルキル基であり、ｎは、１～１５の整数である。     40. The optical laminate according to claim 39, wherein the polymer (C) has a structural unit derived from a monomer represented by formula (1) below.
    Figure JPOXMLDOC01-appb-C000003
     In the above formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group which may be linear or branched, and n is 1 to 15. is an integer.
  43. 　前記粘着剤組成物が、過酸化物系架橋剤及びラジカル捕捉剤をさらに含む、請求項３９に記載の光学積層体。 The optical laminate according to claim 39, wherein the pressure-sensitive adhesive composition further contains a peroxide-based cross-linking agent and a radical scavenger.
  44. 　前記ラジカル捕捉剤が酸化防止剤である、請求項４３記載の光学積層体。 The optical laminate according to claim 43, wherein the radical scavenger is an antioxidant.
  45. 　前記粘着剤組成物がイソシアネート系架橋剤をさらに含む、請求項３９に記載の光学積層体。 The optical laminate according to claim 39, wherein the pressure-sensitive adhesive composition further contains an isocyanate-based cross-linking agent.
  46. 　請求項３７に記載の光学積層体を備える、画像表示パネル。 An image display panel comprising the optical laminate according to claim 37.
  47. 　請求項４６に記載の画像表示パネルを備える、画像表示装置。 An image display device comprising the image display panel according to claim 46.
  48. 　ポリエーテル構造を有するポリマー（Ｄ）を主成分として含み、
    　導電剤をさらに含み、
    　粘着シートを形成したときに、前記粘着シートは、１．５×１０１４個／ｇ以下のラジカル発生量ＲＧ１０及び１×１０１０Ω／□以下の表面抵抗値を有する、粘着剤組成物。
    　ただし、前記ＲＧ１０は、電子スピン共鳴法により評価した、１０５℃及び１０分の加熱時における前記粘着シートのラジカル発生量である。     Containing a polymer (D) having a polyether structure as a main component,
    further comprising a conductive agent;
    A pressure-sensitive adhesive composition, wherein when the pressure-sensitive adhesive sheet is formed, the pressure-sensitive adhesive sheet has a radical generation rate RG 10 of 1.5×10 14 radicals/g or less and a surface resistance value of 1×10 10 Ω/□ or less.
    However, the RG 10 is the amount of radicals generated from the pressure-sensitive adhesive sheet when heated at 105° C. for 10 minutes as evaluated by electron spin resonance method.
  49. 　前記ポリマー（Ｄ）が（メタ）アクリル系ポリマーである、請求項４８に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 48, wherein the polymer (D) is a (meth)acrylic polymer.
  50. 　前記ポリマー（Ｄ）が前記ポリエーテル構造を側鎖に有する、請求項４８に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 48, wherein the polymer (D) has the polyether structure in its side chain.
  51. 　前記ポリマー（Ｄ）が以下の式（１）に示す単量体に由来する構成単位を有する、請求項４８に記載の粘着剤組成物。
    Figure JPOXMLDOC01-appb-C000004
     　前記式（１）において、Ｒ１は、水素原子又はメチル基であり、Ｒ２は、直鎖状であっても分岐を有していてもよいアルキル基であり、ｎは、１～１５の整数である。     49. The pressure-sensitive adhesive composition according to claim 48, wherein the polymer (D) has a structural unit derived from a monomer represented by formula (1) below.
    Figure JPOXMLDOC01-appb-C000004
     In the above formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group which may be linear or branched, and n is 1 to 15. is an integer.
  52. 　前記ポリマー（Ｄ）における前記構成単位の含有率が２５重量％以上である、請求項５１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 51, wherein the content of said structural unit in said polymer (D) is 25% by weight or more.
  53. 　前記表面抵抗値が１×１０９Ω／□以下である、請求項４８に記載の粘着剤組成物。 49. The pressure-sensitive adhesive composition according to claim 48, wherein the surface resistance value is 1 x 10 <9> [Omega]/square or less.
  54. 　ラジカル発生量比ＲＧ２０／ＲＧ１０が１．５未満である、請求項４８に記載の粘着剤組成物。
    　ただし、前記ＲＧ２０は、電子スピン共鳴法により評価した、１０５℃及び２０分の加熱時における前記粘着シートのラジカル発生量である。     49. The pressure-sensitive adhesive composition according to claim 48, wherein the radical generation amount ratio RG20 / RG10 is less than 1.5.
    However, RG 20 is the amount of radicals generated from the pressure-sensitive adhesive sheet when heated at 105° C. for 20 minutes, as evaluated by an electron spin resonance method.
  55. 　ラジカル発生量比ＲＧ３０／ＲＧ１０が１．９未満である、請求項４８に記載の粘着剤組成物。
    　ただし、前記ＲＧ３０は、電子スピン共鳴法により評価した、１０５℃及び３０分の加熱時における前記粘着シートのラジカル発生量である。     49. The pressure-sensitive adhesive composition according to claim 48, wherein the radical generation amount ratio RG30 / RG10 is less than 1.9.
    However, the RG 30 is the amount of radicals generated from the pressure-sensitive adhesive sheet when heated at 105° C. for 30 minutes as evaluated by an electron spin resonance method.
  56. 　前記粘着剤組成物における前記導電剤の配合量が、前記ポリマー（Ｄ）１００重量部に対して８重量部以下である、請求項４８に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 48, wherein the amount of the conductive agent in the pressure-sensitive adhesive composition is 8 parts by weight or less with respect to 100 parts by weight of the polymer (D).
  57. 　前記粘着剤組成物がイソシアネート系架橋剤をさらに含む、請求項４８に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 48, wherein the pressure-sensitive adhesive composition further contains an isocyanate-based cross-linking agent.
  58. 　前記粘着剤組成物が過酸化物系架橋剤をさらに含む、請求項４８に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 48, wherein the pressure-sensitive adhesive composition further contains a peroxide-based cross-linking agent.
  59. 　溶剤型である、請求項４８に記載の粘着剤組成物。 The adhesive composition according to claim 48, which is solvent-based.
  60. 　光学積層体用である、請求項４８に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 48, which is for optical laminates.
  61. 　請求項４８に記載の粘着剤組成物から形成された粘着シート。 A pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition according to claim 48.
  62. 　請求項６１に記載の粘着シートと、
    　光学フィルムと、
    　を含む、光学積層体。     An adhesive sheet according to claim 61;
    an optical film;
    An optical stack comprising:
  63. 　前記光学フィルムが、偏光子を含む偏光板である、請求項６２に記載の光学積層体。 The optical laminate according to claim 62, wherein the optical film is a polarizing plate containing a polarizer.
  64. 　保護フィルムをさらに含み、
    　前記保護フィルムは、前記偏光子の少なくとも一方の面に配置されている、請求項６３に記載の光学積層体。     further comprising a protective film;
    64. The optical stack of Claim 63, wherein the protective film is disposed on at least one side of the polarizer.
  65. 　前記偏光子の厚さが２０μｍ以下である、請求項６３に記載の光学積層体。 The optical laminate according to claim 63, wherein the polarizer has a thickness of 20 µm or less.
  66. 　請求項６２に記載の光学積層体を備える、画像表示パネル。 An image display panel comprising the optical laminate according to claim 62.
  67. 　請求項６６に記載の画像表示パネルを備える、画像表示装置。
     
          An image display device comprising the image display panel according to claim 66 .
PCT/JP2022/041789 2021-11-15 2022-11-09 Adhesive composition, adhesive sheet, optical laminate, image display panel, and image display device WO2023085335A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013032438A (en) * 2011-08-02 2013-02-14 Nichias Corp Seal material
WO2021065075A1 (en) * 2019-09-30 2021-04-08 日東電工株式会社 Set of polarizing plates, and image display device including said set

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013032438A (en) * 2011-08-02 2013-02-14 Nichias Corp Seal material
WO2021065075A1 (en) * 2019-09-30 2021-04-08 日東電工株式会社 Set of polarizing plates, and image display device including said set

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