WO2024019157A1 - Feuille adhésive et corps multicouche optique - Google Patents

Feuille adhésive et corps multicouche optique Download PDF

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Publication number
WO2024019157A1
WO2024019157A1 PCT/JP2023/026818 JP2023026818W WO2024019157A1 WO 2024019157 A1 WO2024019157 A1 WO 2024019157A1 JP 2023026818 W JP2023026818 W JP 2023026818W WO 2024019157 A1 WO2024019157 A1 WO 2024019157A1
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Prior art keywords
adhesive sheet
weight
less
monomer
film
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PCT/JP2023/026818
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English (en)
Japanese (ja)
Inventor
翔平 杉山
智之 木村
悟士 山本
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日東電工株式会社
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Publication of WO2024019157A1 publication Critical patent/WO2024019157A1/fr

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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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • 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
    • 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
    • H10K59/10—OLED displays

Definitions

  • the present invention relates to an adhesive sheet and an optical laminate.
  • Various image display devices typified by liquid crystal display devices and electroluminescent (EL) display devices, generally include an optical laminate that includes an optical film such as a polarizing film and an adhesive sheet.
  • Adhesive sheets are usually used for bonding between optical films included in an optical laminate and for bonding an optical laminate and an image display panel.
  • a typical pressure-sensitive adhesive sheet is a sheet obtained by curing a group of monomers including acrylic monomers, silicone monomers, etc. by polymerization and crosslinking.
  • Patent Document 1 discloses an example of an adhesive sheet.
  • a pressure-sensitive adhesive sheet is produced by irradiating a pressure-sensitive adhesive composition with light.
  • a typical pressure-sensitive adhesive sheet is manufactured, for example, by the following thermosetting method.
  • a crosslinking agent and the like are added to a polymer produced by polymerizing a polymerizable monomer in an organic solvent to prepare an adhesive composition.
  • This adhesive composition is applied to a base material such as a release liner, and the organic solvent is removed by heating to form a sheet.
  • a pressure-sensitive adhesive sheet can be manufactured by performing heat aging as necessary to complete crosslinking. In this manufacturing process, it is necessary to burn a large amount of fuel such as LNG in order to generate the thermal energy necessary for heat removal of the solvent and heat aging. Furthermore, if the organic solvent that has been removed by heating is released into the atmosphere as it is, it may have a significant negative impact on the surrounding environment.
  • organic solvents are often burned in a deodorizing furnace or the like before being released.
  • the organic solvent itself will also be converted into CO 2 and released into the atmosphere through combustion, resulting in a manufacturing process with extremely large CO 2 emissions. be.
  • the amount of energy and CO 2 emissions required for forming the pressure-sensitive adhesive sheet can be reduced compared to the above-mentioned thermosetting method.
  • the anchoring force between the pressure-sensitive adhesive sheet and the optical film is small, and peeling tends to occur between the pressure-sensitive adhesive sheet and the optical film.
  • the present invention provides a pressure-sensitive adhesive sheet suitable for adjusting the anchoring force with an optical film to a large value.
  • the present inventors further investigated based on the above findings, and found that if the amounts of the hydroxy group-containing monomer and the isocyanate crosslinking agent are appropriately adjusted, a pressure-sensitive adhesive sheet formed from a photocurable composition can be formed. Even in the case where the adhesive sheet is used, the curing of the adhesive sheet further progresses after it is bonded to the optical film, and the inventors have discovered that this allows the anchoring force with the optical film to be adjusted to a large value, leading to the completion of the present invention. .
  • the present invention A pressure-sensitive adhesive sheet formed from a photocurable composition containing a monomer group and/or a partial polymer of the monomer group, Out of 100 parts by weight of the monomer group, the amount of the hydroxy group-containing monomer is less than 5 parts by weight,
  • the photocurable composition includes an isocyanate crosslinking agent,
  • a pressure-sensitive adhesive sheet is provided, wherein the amount of the isocyanate crosslinking agent is 0.02 parts by weight or more based on 100 parts by weight of the monomer group and the partial polymer.
  • an optical laminate comprising:
  • a pressure-sensitive adhesive sheet suitable for adjusting the anchoring force with an optical film to a large value can be provided.
  • FIG. 1 is a cross-sectional view schematically showing an example of a pressure-sensitive adhesive sheet of the present invention.
  • FIG. 3 is a schematic diagram for explaining a method for measuring the amount of creep on a pressure-sensitive adhesive sheet.
  • FIG. 3 is a schematic diagram for explaining a method for measuring the amount of creep on a pressure-sensitive adhesive sheet.
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing a pressure-sensitive adhesive sheet of the present invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing a pressure-sensitive adhesive sheet of the present invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG.
  • FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing a pressure-sensitive adhesive sheet of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing an example of an optical laminate of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing an example of an optical laminate of the present invention.
  • the adhesive sheet according to the first aspect of the present invention is A pressure-sensitive adhesive sheet formed from a photocurable composition containing a monomer group and/or a partial polymer of the monomer group, Out of 100 parts by weight of the monomer group, the amount of the hydroxy group-containing monomer is less than 5 parts by weight,
  • the photocurable composition includes an isocyanate crosslinking agent, The blending amount of the isocyanate-based crosslinking agent is 0.02 parts by weight or more based on the total of 100 parts by weight of the monomer group and the partial polymer.
  • the amount of the isocyanate crosslinking agent is 0.000 parts by weight based on a total of 100 parts by weight of the monomer group and the partial polymer. It is 1 part by weight or more.
  • the amount of isocyanate present in the photocurable composition relative to the amount of hydroxy groups present in the photocurable composition is The ratio of the amounts of substances of the groups is 0.02 or more.
  • the isocyanate-based crosslinking agent contains an aliphatic isocyanate compound and/or a derivative of the aliphatic isocyanate compound.
  • the isocyanate-based crosslinking agent is a group consisting of a pentamethylene diisocyanate-based crosslinking agent and a hexamethylene diisocyanate-based crosslinking agent. At least one selected from
  • the content of the solvent in the photocurable composition is 5% by weight or less.
  • the monomer group includes a (meth)acrylic monomer.
  • the concentration of residual monomer is 16,000 ppm by weight or less.
  • the pressure-sensitive adhesive sheet according to any one of the first to eighth aspects has a surface that has been subjected to surface modification treatment.
  • the optical laminate according to the tenth aspect of the present invention is An adhesive sheet according to any one of the first to ninth aspects, an optical film containing at least one selected from the group consisting of a polarizing film and a retardation film; Equipped with.
  • the anchoring force between the adhesive sheet and the optical film is 10.0 N/25 mm or more.
  • the adhesive sheet 1 in FIG. 1 is formed from a photocurable composition containing a monomer group and/or a partial polymer of the monomer group.
  • the amount of the hydroxy group-containing monomer is less than 5 parts by weight out of 100 parts by weight of the monomer group.
  • the photocurable composition contains an isocyanate crosslinking agent, and the amount of the isocyanate crosslinking agent is 0.02 parts by weight or more based on 100 parts by weight of the monomer group and the partial polymer. .
  • this pressure-sensitive adhesive sheet 1 When this pressure-sensitive adhesive sheet 1 is bonded to an optical film, the curing of the pressure-sensitive adhesive sheet 1 tends to proceed further after bonding. By further progressing the curing of the adhesive sheet 1 on the surface of the optical film, the anchoring force between the adhesive sheet 1 and the optical film can be adjusted to a large value.
  • the adhesive sheet 1 has surfaces 1a and 1b facing each other.
  • the adhesive sheet 1 is attached to an optical film via the surface 1a, and the adhesive sheet 1 is attached to an image display panel via the surface 1b.
  • the surface 1a of the adhesive sheet 1 that contacts the optical film may or may not be subjected to a surface modification treatment.
  • the surface 1a subjected to the surface modification treatment there is a tendency that the anchoring force between the adhesive sheet 1 and the optical film can be improved.
  • the surface 1b of the adhesive sheet 1 is preferably not subjected to surface modification treatment. Examples of surface modification treatments include corona treatment, plasma treatment, excimer treatment, and flame treatment.
  • the surface 1a is preferably subjected to a corona treatment as a surface modification treatment.
  • the surface modification treatment may be performed in an inert gas atmosphere.
  • the risk of ignition of the remaining monomer can be reduced.
  • the content is more preferably 6% by volume or less, and even more preferably 3% by volume or less.
  • the oxygen concentration is preferably 0.01% by volume or more, and 0.1% by volume or more. More preferably, 0.5% by volume or more is particularly preferred.
  • the inert gas include nitrogen and argon.
  • the surface modification treatment may be carried out under normal pressure (1 atmosphere).
  • the conditions for the surface modification treatment are, for example, 0.6 to 100 kJ/m 2 in terms of discharge amount.
  • the lower limit of discharge amount is 1kJ/ m2 or more, 2kJ/ m2 or more, 5kJ/m2 or more, 7kJ/ m2 or more, 10kJ/ m2 or more, 13kJ/m2 or more, 15kJ/m2 or more, 20kJ/ m2 or more.
  • the upper limit of the discharge amount is 70 kJ/m 2 or less, 60 kJ/m 2 or less, 50 kJ/m 2 or less, 45 kJ/m 2 or less, 40 kJ/m 2 or less, 30 kJ/m 2 or less, 20 kJ/m 2 or less, and even It may be 18 kJ/m 2 or less.
  • the discharge amount may be 1 to 18 kJ/m 2 .
  • the discharge amount may be 1 to 60 kJ/m 2 .
  • the adhesive sheet 1 is formed from a photocurable composition.
  • the photocurable composition is an adhesive composition that forms the adhesive sheet 1 when irradiated with light.
  • the monomer group includes, for example, a (meth)acrylic monomer.
  • the content of the (meth)acrylic component in the photocurable composition that is, the (meth)acrylic monomer and its partial polymer, is 50% by weight or more, 60% by weight or more, 70% by weight or more, and even The content may be 80% by weight or more, and in this case, an acrylic pressure-sensitive adhesive sheet 1 containing a (meth)acrylic polymer and a crosslinked product thereof as main components can be formed.
  • the photocurable composition is not limited to the above example.
  • (meth)acrylic means acrylic and methacryl.
  • (Meth)acrylate means acrylate and methacrylate.
  • An example of the (meth)acrylic monomer is a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms in the side chain.
  • the number of carbon atoms in the alkyl group may be 7 or less, 6 or less, 5 or less, or even 4 or less.
  • the alkyl group may be linear or branched.
  • Examples of (meth)acrylic acid alkyl esters are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, 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, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate (lauryl (meth)acrylate), n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, pentadecyl
  • the amount of (meth)acrylic acid alkyl ester is, for example, 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, It may be 85 parts by weight or more, 90 parts by weight or more, or even 95 parts by weight or more.
  • the weight of the partially polymerized product is converted to the weight of each monomer before polymerization.
  • the monomer group may include a carboxyl group-containing monomer.
  • the carboxyl group-containing monomer may be a (meth)acrylic monomer, or in other words, the (meth)acrylic monomer may include a carboxyl group-containing monomer.
  • 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.
  • the amount of the carboxyl group-containing monomer is, for example, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less. It may be less than 4.8 parts by weight, less than 4 parts by weight, less than 3 parts by weight, less than 2 parts by weight, less than 1 part by weight, and even less than 0.5 parts by weight.
  • the lower limit of the blending amount is, for example, 0.1 part by weight or more, and in some cases may be 0.5 part by weight or more.
  • the monomer group does not need to contain carboxyl group-containing monomers.
  • the monomer group may include a hydroxy group-containing monomer.
  • the hydroxy group-containing monomer may be a (meth)acrylic monomer, or in other words, the (meth)acrylic monomer may include a hydroxy group-containing monomer.
  • the hydroxy group-containing monomer can contribute to improving the cohesive force of the pressure-sensitive adhesive sheet.
  • hydroxy group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, They are 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate.
  • the hydroxy group-containing monomer is preferably 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate.
  • the amount of the hydroxy group-containing monomer is less than 5 parts by weight.
  • the blending amount of the hydroxy group-containing monomer is preferably 4 parts by weight or less, and may be 3 parts by weight or less, 2 parts by weight or less, and even 1 part by weight or less.
  • the lower limit of the blending amount may be, for example, 0.01 part by weight or more, 0.03 part by weight or more, and even 0.05 part by weight or more.
  • the monomer group does not need to contain hydroxy group-containing monomers.
  • the monomer group may include an ether group-containing monomer.
  • the ether group-containing monomer may be a (meth)acrylic monomer, or in other words, the (meth)acrylic monomer may include an ether group-containing monomer.
  • the ether group-containing monomer can contribute to improving the anchoring force between the adhesive sheet 1 and the optical film.
  • the ether group-containing monomer is preferably an alkoxy group-containing monomer.
  • the alkoxy group-containing monomer include an alkylene oxide adduct represented by the following chemical formula (1).
  • R 1 in formula (1) is a hydrogen atom or a methyl group.
  • R 2 in formula (1) is an alkyl group.
  • the alkyl group may be linear or branched.
  • R 2 is preferably a linear alkyl group. Examples of R 2 are methyl and ethyl groups.
  • n in formula (1) is an integer of 1 to 30, preferably an integer of 1 to 12, and may be an integer of 1 to 5.
  • alkylene oxide adducts shown in formula (1) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, and methoxytriethylene glycol.
  • the ether group-containing monomer is not limited to the above alkylene oxide adduct.
  • the ether group-containing monomer may have a ring structure, and the ring structure may have an ether group.
  • the ring structure having an ether group include a tetrahydrofuran ring and a dioxane ring.
  • Examples of ether group-containing monomers having a ring structure are cyclic trimethylolpropane formal (meth)acrylate and tetrahydrofurfuryl (meth)acrylate.
  • the amount of the ether group-containing monomer is, for example, 1 part by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more. It may be at least 40 parts by weight, at least 50 parts by weight, at least 60 parts by weight, at least 70 parts by weight, at least 80 parts by weight, and even at least 90 parts by weight.
  • the upper limit of the blending amount is, for example, 99 parts by weight or less, and may be 50 parts by weight or less depending on the case.
  • the monomer group does not need to contain ether group-containing monomers.
  • each of the above-mentioned monomers may be included as a partial polymer.
  • the partial polymer may be either a homopolymer or a copolymer.
  • the partial polymer can contribute to stable formation of the coating layer described below by appropriately increasing the viscosity of the photocurable composition.
  • the photocurable composition usually contains a photopolymerization initiator.
  • a photopolymerization initiator is a photoradical generator that generates radicals using visible light and/or ultraviolet light having a wavelength shorter than 450 nm.
  • photopolymerization initiators include benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; substituted benzoin ethers such as anisole methyl ether; 2,2-diethoxyacetophenone, 2,2-dimethoxy-2- Substituted acetophenones such as phenylacetophenone; ⁇ -hydroxyalkylphenones such as 1-hydroxycyclohexyl-phenylketone; substituted alphaketols such as 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; Photoactive oximes such as 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone
  • the amount of the photopolymerization initiator in the photocurable composition is, for example, 0.02 to 10 parts by weight, and 0.05 to 5 parts by weight, based on a total of 100 parts by weight of the monomer group and its partial polymer. It may be a department.
  • the photocurable composition contains an isocyanate-based crosslinking agent.
  • the isocyanate crosslinking agent a compound having at least two isocyanate groups (isocyanate compound) can be used.
  • the number of isocyanate groups contained in the isocyanate compound is preferably 3 or more.
  • the upper limit of the number of isocyanate groups is not particularly limited, and is, for example, 5.
  • the isocyanate compound include aromatic isocyanate compounds, alicyclic isocyanate compounds, and aliphatic isocyanate compounds.
  • aromatic isocyanate compounds include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'-toluidine.
  • aromatic isocyanate compounds include diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.
  • alicyclic isocyanate compounds include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tolylene diisocyanate. , hydrogenated tetramethylxylylene diisocyanate, and the like.
  • aliphatic isocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4 , 4-trimethylhexamethylene diisocyanate and the like.
  • isocyanate crosslinking agent examples include multimers (dimers, trimers, pentamers, etc.) of the above isocyanate compounds, adducts obtained by adding to polyhydric alcohols such as trimethylolpropane, urea modified products, Also included are urethane prepolymers obtained by adding to biuret modified products, allophanate modified products, isocyanurate modified products, carbodiimide modified products, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like.
  • the isocyanate-based crosslinking agent preferably contains an aliphatic isocyanate compound and/or a derivative of an aliphatic isocyanate compound.
  • the isocyanate-based crosslinking agent may be at least one selected from the group consisting of pentamethylene diisocyanate (PDI)-based crosslinking agents (PDI and its derivatives) and hexamethylene diisocyanate (HDI)-based crosslinking agents (HDI and its derivatives). Particularly preferred.
  • PDI-based crosslinking agent include isocyanurate-modified PDI.
  • Specific examples of HDI-based crosslinking agents include isocyanurate-modified HDI and biuret-modified products.
  • the amount of the isocyanate crosslinking agent is 0.02 parts by weight or more, preferably 0.05 parts by weight or more, based on 100 parts by weight of the monomer group and its partial polymer. , 0.1 parts by weight or more, 0.5 parts by weight or more, 1 parts by weight or more, 1.5 parts by weight or more, or even 2 parts by weight or more.
  • the upper limit of the blending amount is, for example, 5 parts by weight or less, and may be 3 parts by weight or less.
  • the amount of isocyanate groups present in the photocurable composition (especially the amount of hydroxy groups contained in the hydroxy group-containing monomer) relative to the amount of hydroxy groups present in the photocurable composition , the amount of isocyanate groups contained in the isocyanate crosslinking agent) is, for example, 0.02 or more, 0.05 or more, 0.1 or more, 0.5 or more, 1.0 or more, and may be 1.5 or more.
  • the upper limit of the ratio NCO/OH is, for example, 5.0 or less, and may be 1.0 or less depending on the case.
  • the photocurable composition may further contain a crosslinking agent other than the isocyanate-based crosslinking agent.
  • crosslinking agents include, for example, polyfunctional monomers having two or more polymerizable functional groups in one molecule.
  • the polyfunctional monomer may be a (meth)acrylic monomer.
  • the polyfunctional monomer is preferably a monomer having two or more C ⁇ C bonds in one molecule.
  • polyfunctional monomers examples include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol Tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol diacrylate (NDDA) , 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and other polyfunctional acrylates (ester compounds of polyhydric alcohol and (meth)acrylic acid, etc.) ); allyl (meth)acrylate,
  • the polyfunctional monomer is preferably a polyfunctional acrylate, more preferably trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.
  • the amount of other crosslinking agents in the photocurable composition varies depending on the molecular weight, the number of functional groups, etc., but is, for example, 5 parts by weight or less based on the total of 100 parts by weight of the monomer group and its partial polymer, The amount may be 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, 0.3 parts by weight or less, and even 0.1 parts by weight or less.
  • the lower limit of the blending amount is, for example, 0.01 part by weight or more, and may even be 0.05 part by weight or more.
  • the photocurable composition may contain additives other than those mentioned above.
  • additives are chain transfer agents, rework improvers, corrosion inhibitors, silane coupling agents, viscosity modifiers, tackifiers, plasticizers, softeners, anti-aging agents, fillers, colorants, antioxidants. , surfactants, antistatic agents and ultraviolet absorbers.
  • the content of the solvent in the photocurable composition is, for example, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, and even 0.5% by weight or less. You can.
  • the photocurable composition may be substantially free of solvent. "Substantially free of solvent” means that the content of solvents derived from additives etc. is, for example, 0.1% by weight or less, preferably 0.05% by weight or less, more preferably 0.01% by weight or less. The intention is to allow it.
  • the viscosity of the photocurable composition is preferably 5 to 150 poise.
  • a photocurable composition having a viscosity within the above range is particularly suitable for forming the coating layer described below.
  • the concentration of the residual monomer, especially the hydroxy group-containing monomer is 16,000 ppm by weight or less. In this case, there is a tendency for the anchoring force between the adhesive sheet 1 and the optical film to be suppressed from decreasing.
  • the concentration of the residual monomer is preferably 15000 weight ppm or less, 12000 weight ppm or less, 10000 weight ppm or less, 8000 weight ppm or less, 7000 weight ppm or less, 6000 weight ppm or less, 5000 weight ppm or less, 4000 weight ppm or less, It may be 3500 weight ppm or less, 3000 weight ppm or less, 2500 weight ppm or less, 2000 weight ppm or less, or even 1500 weight ppm or less.
  • the lower limit of the concentration of the residual monomer is, for example, 300 ppm by weight or more.
  • the concentration of residual monomer in the adhesive sheet 1 can be evaluated by gas chromatogram (GC) analysis.
  • the polymerization rate of the monomer group in the adhesive sheet 1 is preferably 90% or more.
  • the polymerization rate may be 95% or more, 98% or more, or even 99% or more.
  • the gel fraction of the adhesive sheet 1 is, for example, 50% or more, and may be 75% or more, 80% or more, or even 85% or more.
  • the creep amount of the adhesive sheet 1 is, for example, 500 ⁇ m or less, and may be 300 ⁇ m or less, 180 ⁇ m or less, 160 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, or even 50 ⁇ m or less.
  • the lower limit of the creep amount may be, for example, 5 ⁇ m or more, 10 ⁇ m or more, or even 20 ⁇ m or more.
  • the amount of creep of the adhesive sheet 1 can be evaluated as follows (see FIGS. 2A and 2B).
  • a test piece 52 is obtained by cutting a laminate of the adhesive sheet 1 and the support film 51 to be evaluated into a strip of 10 mm x 50 mm.
  • the support film 51 is disposed for the purpose of suppressing deformation of the load-applied portion of the pressure-sensitive adhesive sheet 1 during a test, and thereby measuring the amount of creep with higher accuracy.
  • a resin film such as a polyethylene terephthalate (PET) film can be used.
  • PET polyethylene terephthalate
  • the support film 51 may be an optical film or a laminate including an optical film.
  • the thickness of the support film 51 may be such that it does not deform itself under the above load, and is, for example, 20 to 200 ⁇ m.
  • the test piece 52 is attached to the surface of the stainless steel test plate 53 using the adhesive sheet 1 at a joint surface measuring 10 mm in length and 10 mm in width.
  • FIG. 2B is a cross section BB in FIG. 2A.
  • the test piece 52 is attached to the test plate 53 so that air bubbles are not mixed between the test plate 53 and the adhesive sheet 1.
  • the test plate 53 and the adhesive sheet 1 are placed in an autoclave at 50° C. and 5 atm (absolute pressure) for 15 minutes to homogenize the bond between the test plate 53 and the adhesive sheet 1.
  • test plate 53 and the test piece 52 are held vertically with the test plate 53 facing upward and left in an atmosphere of 25°C for at least 5 minutes.
  • a weight with a mass of 500 g is fixed at the center of the lower end, and a load 54 of 500 gf is applied vertically downward.
  • the amount of creep (deviation amount) of the adhesive sheet 1 with respect to the test plate 53 at the time point 3600 seconds after the start of applying the load 54 is measured as the amount of fall of the weight.
  • a laser displacement meter can be used to measure the amount of weight fall.
  • the thickness of the adhesive sheet 1 is, for example, 500 ⁇ m or less, and may be 250 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, 25 ⁇ m or less, or even 20 ⁇ m or less.
  • the lower limit of the thickness of the adhesive sheet 1 is, for example, 2 ⁇ m or more, and may be 5 ⁇ m or more.
  • the adhesive sheet 1 can be manufactured, for example, by the following method. First, as shown in FIGS. 3A and 3B, a first laminate 15 including a base sheet 21, a coating layer 22 containing a photocurable composition, and a release liner 23 in this order is produced. The adhesive sheet 1 can be formed from the coating layer 22 by irradiating the first laminate 15 with the light 14 (FIG. 3C).
  • the first laminate 15 is typically irradiated with the light 14 from the base sheet 21 side (FIG. 3A). At this time, the light 14 passes through the base sheet 21, reaches the coating layer 22, and cures the coating layer 22. However, the irradiation with the light 14 may be performed from the release liner 23 side, or from both sides of the release liner 23 and the base sheet 21 (FIG. 3B).
  • the adhesive sheet 1 formed from the coating layer 22 is sandwiched between the base sheet 21 and the release liner 23 and constitutes a part of the second laminate 16 until the release liner 23 is peeled off.
  • the base material of the release liner 23 is a resin film.
  • resins that can be included in the liner base material are polyesters such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfones, polycarbonates, polyamides, polyimides, polyolefins, (meth)acrylic resins, polyvinyl chloride, polyvinylidene chloride. , polystyrene, polyvinyl alcohol, polyarylate, and polyphenylene sulfide.
  • the resin is preferably a polyester such as polyethylene terephthalate.
  • the release liner 23 may have a light 14 transmittance, or may have a light 14 transmittance comparable to that of the base sheet 21.
  • the thickness of the release liner 23 is, for example, 10 to 200 ⁇ m, and may be 25 to 150 ⁇ m.
  • the release liner 23 may include layers other than the liner base material.
  • the release liner 23 may include a release layer.
  • the release liner 23 includes, for example, a liner base material and a release layer formed on one surface of the liner base material. This release liner 23 can be used so that the release layer is on the coating layer 22 side.
  • the release layer is typically a cured layer of a release agent composition containing a release agent.
  • Various mold release agents can be used as the mold release agent, such as a silicone mold release agent, a fluorine mold release agent, a long chain alkyl mold release agent, a fatty acid amide mold release agent, and silica powder.
  • the release liner 23 may include a cured layer of a release agent composition containing a silicone release agent as a main component (hereinafter referred to as "silicone release layer").
  • the silicone release layer is particularly suitable for achieving both adhesion and releasability to the pressure-sensitive adhesive sheet 1.
  • the main component means the component with the largest content rate.
  • the silicone mold release agent is, for example, various types of curable silicone materials such as addition reaction type, condensation reaction type, ultraviolet curable type, electron beam curable type, and solvent-free type, with addition reaction curable silicone materials being preferred.
  • the addition reaction-curable silicone material is particularly suitable for forming a release layer that has both adhesion and releasability to the pressure-sensitive adhesive sheet 1.
  • the curable silicone material may be a silicone-modified resin in which reactive silicone is introduced into an organic resin such as urethane, epoxy, or alkyd resin by graft polymerization or the like.
  • An example of an addition reaction-curable silicone material is a polyorganosiloxane having a vinyl group or an alkenyl group in the molecule.
  • the addition reaction curable silicone material does not need to have a hydrosilyl group.
  • alkenyl groups are 3-butenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, 7-octenyl, 8-nonenyl, 9-decenyl, 10-undecenyl, and 11-dodecenyl. It is the basis.
  • polyorganosiloxanes examples include polyalkylalkylsiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polymethylethylsiloxane, polyalkylarylsiloxanes, and a plurality of Si atom-containing monomers such as poly(dimethylsiloxane-diethylsiloxane). It is a copolymer.
  • the polyorganosiloxane is preferably polydimethylsiloxane.
  • a mold release agent composition containing a silicone mold release agent as a main component usually contains a crosslinking agent.
  • crosslinking agents are polyorganosiloxanes containing hydrosilyl groups.
  • the crosslinking agent may have two or more hydrosilyl groups in one molecule.
  • the silicone mold release agent composition may contain a curing catalyst.
  • a curing catalyst is a platinum-based catalyst.
  • platinum-based catalysts are chloroplatinic acid, olefin complexes of platinum, and olefin complexes of chloroplatinic acid.
  • the amount of the platinum-based catalyst used is, for example, 10 to 1000 ppm (by weight, in terms of platinum) based on the total solid content of the composition.
  • the silicone mold release agent composition may contain additives.
  • additives are release control agents and adhesion promoters.
  • release control agents are unreacted silicone resins, and more specific examples are organosiloxanes such as octamethylcyclotetrasiloxane, and MQ resins.
  • the total amount of the peel control agent and adhesion improver used is, for example, 1 to 30% by weight based on the total solid content of the composition.
  • Further examples of additives are fillers, antistatic agents, antioxidants, UV absorbers, plasticizers and colorants.
  • the amount of further additives used is, for example, up to 10% by weight in total, based on the total solids content of the composition.
  • the silicone mold release agent composition may contain an organic solvent.
  • organic solvents include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone.
  • Solvent Alcohol solvent such as methanol, ethanol, butanol. Two or more types of organic solvents may be included. The amount of organic solvent used is preferably 80 to 99.9% by weight of the silicone mold release agent composition.
  • the release layer can be formed, for example, by heating and drying a coating film containing a release agent composition formed on a liner base material.
  • Application of the release agent composition includes 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, and die coating.
  • Various coating methods can be applied. For example, hot air drying can be used for heating and drying.
  • the heating temperature and time vary depending on the heat resistance of the liner base material, but are usually about 80 to 150°C and about 10 seconds to 10 minutes. If necessary, irradiation with active energy rays such as ultraviolet rays may be used in combination.
  • the thickness of the release layer is, for example, 10 to 300 nm.
  • the upper limit of the thickness may be 200 nm or less, 150 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, less than 100 nm, 90 nm or less, 80 nm or less, 70 nm or less, less than 70 nm, or even 65 nm or less.
  • the lower limit of the thickness may be 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, or even 50 nm or more.
  • the release liner 23 may be sheet-shaped or elongated.
  • An example of the base sheet 21 is a resin film.
  • Examples of resins included in the base sheet 21 are the same as examples of resins that can be included in the liner base material.
  • the base sheet 21 has excellent transparency for the light 14.
  • the thickness of the base sheet 21 is, for example, 10 to 200 ⁇ m, and may be 25 to 150 ⁇ m.
  • the base sheet 21 may include a release layer on the surface facing the coating layer 22.
  • Examples of the release layer that the base sheet 21 can include and its manufacturing method are the same as the examples of the release layer that the release liner 23 can include and its manufacturing method.
  • Both the release liner 23 and the base sheet 21 may be provided with a release layer.
  • both mold release layers may be formed from mold release agent compositions containing the same mold release agent as a main component. Further, the thicknesses of both release layers may be different, and for example, the release layer included in the base sheet 21 may be thicker.
  • a sheet can usually be selected that has a greater peeling force with the adhesive sheet 1 than the release liner 23.
  • the base sheet 21 may be sheet-shaped or elongated.
  • the first laminate 15 is constructed by, for example, forming a coating layer 22 on a base sheet 21 (or a release liner 23), and disposing a release liner 23 (or a base sheet 21) on the formed coating layer 22. It can be formed by Further, the first laminate 15 is formed by pouring and applying the photocurable composition into the space between the base sheet 21 and the release liner 23 which are held at a predetermined interval so that their main surfaces face each other. You may.
  • the coating layer 22 can be formed using a roll coat, a kiss roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, a dip roll coat, a bar coat, a knife coat, an air knife coat, a curtain coat, a lip coat, a die coat, etc.
  • Various application methods can be applied.
  • the thickness of the coating layer 22 can be adjusted depending on the desired thickness of the adhesive sheet 1, and is, for example, 5 to 500 ⁇ m, 5 to 250 ⁇ m, 5 to 150 ⁇ m, 5 to 100 ⁇ m, 5 to 50 ⁇ m, 5 to 30 ⁇ m, It may be 5 to 25 ⁇ m, or even 5 to 20 ⁇ m.
  • the light 14 irradiated onto the first laminate 15 is, for example, visible light or ultraviolet light having a wavelength shorter than 450 nm.
  • the light 14 may include light with a wavelength in the same region as the absorption wavelength of the photopolymerization initiator included in the photocurable composition.
  • the light 14 may be irradiated by cutting short wavelength light with a wavelength of 300 nm or less using a filter or the like, and cutting off the short wavelength light is suitable for suppressing deterioration of the base sheet 21 due to the light 14.
  • the light source of the light 14 is, for example, a light irradiation device including an ultraviolet irradiation lamp.
  • ultraviolet irradiation lamps examples include ultraviolet LEDs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, extra-high-pressure mercury lamps, metal halide lamps, xenon lamps, microwave-excited mercury lamps, black light lamps, chemical lamps, germicidal lamps, and low-pressure discharge mercury lamps. , an excimer laser. Two or more ultraviolet irradiation lamps may be combined.
  • Irradiation of the light 14 may be continuous or intermittent.
  • the illuminance of the light 14 is, for example, 1 to 20 mW/cm 2 .
  • the irradiation time of the light 14 is, for example, 5 minutes to 5 hours.
  • the cumulative amount of light 14 to the first laminate 15 is, for example, 100 to 5000 mJ/cm 2 .
  • the release liner 23 may be peeled off from the second laminate 16 to expose the surface (for example, the surface 1a) of the adhesive sheet 1, and the surface may be subjected to surface modification treatment.
  • the optical laminate 10 in FIG. 4 includes the adhesive sheet 1 described above and at least one optical film 2 selected from the group consisting of a polarizing film and a retardation film. It is preferable that the adhesive sheet 1 is in direct contact with the optical film 2. In the example of FIG. 4, the surface 1a of the adhesive sheet 1 is in contact with the optical film 2.
  • the optical laminate 10 may have a structure in which the base sheet used in producing the adhesive sheet 1 is laminated on the adhesive sheet 1.
  • the optical laminate 10 can be used as an optical film with an adhesive sheet.
  • Optical film 2 has a surface 2 a facing adhesive sheet 1 .
  • the surface 2a is in contact with the surface 1a of the adhesive sheet 1.
  • the surface 2a of the optical film 2 may be subjected to a surface modification treatment. According to the surface 2a subjected to the surface modification treatment, there is a tendency that the anchoring force between the adhesive sheet 1 and the optical film 2 can be improved. Examples of the surface modification treatment include those described above for the adhesive sheet 1.
  • the surface 2a is preferably subjected to corona treatment as surface modification treatment.
  • conditions such as the amount of discharge can be adjusted as appropriate within the range described above for the adhesive sheet 1, for example.
  • the optical film 2 includes at least one selected from the group consisting of a polarizing film and a retardation film.
  • the optical film 2 may be a laminated film including a polarizing film and/or a retardation film.
  • the optical film 2 may include a glass film.
  • the optical film 2 is not limited to the above example.
  • the polarizing film includes a polarizer.
  • a polarizing film typically includes a polarizer and a protective film (transparent protective film).
  • the protective film is placed, for example, in contact with the main surface (the surface with the widest area) of the polarizer.
  • a polarizer may be placed between two protective films.
  • the protective film may be placed on at least one surface of the polarizer.
  • the polarizer is not particularly limited, and examples include hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, partially saponified ethylene/vinyl acetate copolymer films, iodine, and dichroism. Examples include those obtained by adsorbing dichroic substances such as dyes and uniaxially stretched; polyene-based oriented films such as dehydrated polyvinyl alcohol and dehydrochloric acid treated polyvinyl chloride.
  • a polarizer typically consists of a polyvinyl alcohol film (polyvinyl alcohol films include partially saponified ethylene/vinyl acetate copolymer films) and a dichroic substance such as iodine.
  • the thickness of the polarizer is not particularly limited, and may be, for example, 80 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, 25 ⁇ m or less, or even 20 ⁇ m or less.
  • the lower limit of the thickness of the polarizer is not particularly limited, and may be, for example, 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, or even 15 ⁇ m or more.
  • a thin polarizer (for example, 20 ⁇ m or less in thickness) has suppressed dimensional changes and can contribute to improving the durability of the optical laminate, especially the durability under high temperatures.
  • thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc.
  • thermoplastic resins include cellulose resins such as triacetylcellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, and cyclic resins.
  • examples include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
  • the material of the protective film may be a thermosetting resin or an ultraviolet curing resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, or silicone.
  • the materials of the two protective films may be the same or different.
  • a protective film made of a thermoplastic resin is attached to one main surface of a polarizer via an adhesive
  • a protective film made of a thermosetting resin or an ultraviolet curable resin is attached to the other main surface of the polarizer.
  • a protective film made of molded resin may be attached.
  • the protective film may contain one or more types of arbitrary additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like.
  • films containing (meth)acrylic resin tend to have low adhesive strength with adhesive sheets.
  • the anchoring force with the optical film 2 can be adjusted to a sufficiently high value even when it is in contact with the surface of the protective film containing (meth)acrylic resin. be able to.
  • the thickness of the protective film can be determined as appropriate, but is generally about 10 to 200 ⁇ m from the viewpoint of strength, workability such as handleability, thin film property, etc.
  • a polarizer and a protective film are usually attached to each other via a water-based adhesive or the like.
  • water-based adhesives include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latex, water-based polyurethanes, and water-based polyesters.
  • adhesives other than the above adhesives include ultraviolet curable adhesives and electron beam curable adhesives.
  • Electron beam-curable adhesives for polarizing plates exhibit suitable adhesion to various types of protective films.
  • the adhesive may include a metal compound filler.
  • a retardation film or the like can also 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 opposite to the surface bonded to the polarizer, and treatments for the purpose of anti-reflection, anti-sticking, diffusion, anti-glare, etc. can also be applied. .
  • the polarizing film may be a circularly polarizing film.
  • the retardation film one obtained by stretching a polymer film or one obtained by aligning and fixing a liquid crystal material can be used.
  • the retardation film has, for example, birefringence in the plane and/or in the thickness direction.
  • the retardation film includes a retardation film for antireflection (see JP-A No. 2012-133303 [0221], [0222], and [0228]) and a retardation film for viewing angle compensation (see JP-A No. 2012-133303 [0221], [0222], and [0228]). 0225], [0226]), an obliquely oriented retardation film for viewing angle compensation (see JP-A No. 2012-133303 [0227]), and the like.
  • the specific structure of the retardation film for example, retardation value, arrangement angle, three-dimensional birefringence, single layer or multilayer, etc., is not particularly limited, and any known retardation film can be used.
  • the thickness of the retardation film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 1 to 9 ⁇ m, particularly preferably 3 to 8 ⁇ m.
  • the retardation film may include, for example, a quarter-wave plate and/or a half-wave plate in which a liquid crystal material is oriented and fixed.
  • the anchoring force F between the adhesive sheet 1 and the optical film 2 tends to be large.
  • the anchoring force F is, for example, 10.0 N/25 mm or more, 11.0 N/25 mm or more, 12.0 N/25 mm or more, 13.0 N/25 mm or more, 14.0 N/25 mm or more, 15.0 N/25 mm or more, It may be 16.0 N/25 mm or more, 17.0 N/25 mm or more, 18.0 N/25 mm or more, 19.0 N/25 mm or more, or even 20.0 N/25 mm or more. It is preferable that the anchoring force F is greater than 16.0 N/25 mm.
  • the upper limit of the anchoring force F is not particularly limited, and may be, for example, 50 N/25 mm or less, and may be 30 N/25 mm or less.
  • the anchoring force F between the adhesive sheet 1 and the optical film 2 can be measured by the following method.
  • the optical laminate 10 to be evaluated is cut out into a piece having a width of 25 mm and a length of 150 mm to form a test piece.
  • the entire surface of the optical film 2 included in the test piece was superimposed on a stainless steel test plate via double-sided tape, and a 2 kg roller was moved back and forth once to press them together.
  • the adhesive sheet 1 included in the test piece is superimposed on the evaluation sheet, and a 2 kg roller is moved back and forth once to press them together.
  • the evaluation sheet has a size of 30 mm width x 150 mm length, and is not particularly limited as long as it does not peel off from the adhesive sheet 1 during the test.
  • an ITO film 125 Tetraite OES (manufactured by Oike Kogyo Co., Ltd.), etc.
  • the adhesive sheet 1 was peeled off from the optical film 2 at a peeling angle of 180° and a pulling speed of 300 mm/min while holding the evaluation sheet.
  • the value is specified as the anchoring force F between the adhesive sheet 1 and the optical film 2. Note that the above test is conducted in an atmosphere at 23°C.
  • the optical laminate 11 in FIG. 5 has a laminated structure in which an adhesive sheet 1A, an optical film 2A, an adhesive sheet 1B, and an optical film 2B are laminated in this order.
  • the optical laminate 11 may have a structure in which the base sheet used in producing the adhesive sheet 1A is laminated on the adhesive sheet 1A.
  • the optical film 2A is a retardation film
  • the optical film 2B is a polarizing film.
  • the adhesive sheet 1B functions as an interlayer adhesive between the optical films 2A and 2B.
  • the adhesive sheet 1B may be one using a known adhesive.
  • the optical laminate of this embodiment can be distributed and stored, for example, as a roll of a band-shaped optical laminate or as a sheet-shaped optical laminate.
  • the optical laminate of this embodiment is typically used in an image display device.
  • the image display device can be formed by, for example, joining the optical laminate 10 or 11 and an image display panel. The bonding is performed using the adhesive sheet 1, for example.
  • the image display device may be an organic EL display or a liquid crystal display. However, the image display device is not limited to the above example.
  • the image display device may be an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED), or the like.
  • EL electroluminescence
  • PD plasma display
  • FED field emission display
  • the image display device can be used for household appliances, in-vehicle applications, public information displays (PID), and the like.
  • Polyvinyl alcohol (PVA) resin film manufactured by Kuraray Co., Ltd., product name "PE3000" with a thickness of 30 ⁇ m is subjected to swelling, dyeing, crosslinking, and washing treatments while being uniaxially stretched, and then subjected to a drying treatment.
  • a polarizer with a thickness of 12 ⁇ m was obtained.
  • the uniaxial stretching was performed using a roll stretching machine so that the stretching ratio in the longitudinal direction was 5.9 times. Specifically, in the swelling treatment, the film was stretched to 2.2 times while being treated with pure water at 20°C. In the dyeing treatment, the film was stretched 1.4 times while being treated at 30° C.
  • the weight ratio of iodine and potassium iodide was 1:7.
  • a two-stage crosslinking treatment was adopted as the crosslinking treatment, and in the first crosslinking treatment, the film was stretched 1.2 times while being treated in a boric acid/potassium iodide aqueous solution at 40°C.
  • the boric acid content of this aqueous solution was 5.0%, and the potassium iodide content was 3.0%.
  • the film was stretched 1.6 times while being treated in a boric acid/potassium iodide aqueous solution at 65°C.
  • the boric acid content of this aqueous solution was 4.3%, and the potassium iodide content was 5.0%.
  • the cleaning treatment a 20° C. potassium iodide aqueous solution was used.
  • the potassium iodide content of the aqueous cleaning solution was 2.6%.
  • the drying process was carried out at 70°C for 5 minutes.
  • the TAC film side surface of a 32 ⁇ m thick TAC-HC film having a hard coat (HC) layer on one side of the triacetyl cellulose (TAC) film was coated with a PVA adhesive. It was pasted together by Furthermore, an unstretched cycloolefin polymer (COP) film with a thickness of 13 ⁇ m was bonded to the other surface of the polarizer using a PVA adhesive. As a result, a polarizing film D1 having a configuration of TAC protective layer/PVA polarizer/COP protective layer was produced. Further, the surface of the polarizing film D1 on the COP film side was subjected to corona treatment at a discharge amount of 63 W/m 2 ⁇ min.
  • HC hard coat
  • TAC triacetyl cellulose
  • [Polarizing film D2] (40 ⁇ m TAC film with HC) Add the solution to a resin solution (manufactured by DIC Corporation, product name: Unidic 17-806, solid content concentration: 80%) in which an ultraviolet curable resin monomer or oligomer containing urethane acrylate as the main component is dissolved in butyl acetate.
  • a resin solution manufactured by DIC Corporation, product name: Unidic 17-806, solid content concentration: 80%
  • an ultraviolet curable resin monomer or oligomer containing urethane acrylate as the main component is dissolved in butyl acetate.
  • a photopolymerization initiator manufactured by BASF Corporation, trade name: IRGACURE907
  • a leveling agent manufactured by DIC Corporation, trade name: GRANDIC PC4100 Part by weight was added.
  • cyclopentanone and propylene glycol monomethyl ether were added to the solution at a ratio of 45:55 so that the solid content concentration in the obtained solution was 36% to prepare a hard coat layer forming material.
  • the produced hard coat layer forming material was applied onto a triacetyl cellulose (TAC) film (manufactured by Fuji Film, TJ40UL, thickness: 40 ⁇ m) so that the thickness of the hard coat layer after curing was 7 ⁇ m to form a coating film. was formed.
  • TAC triacetyl cellulose
  • the coating film was further cured by irradiating the coating film with ultraviolet rays with a cumulative light intensity of 300 mJ/cm 2 using a high-pressure mercury lamp to form a hard coat layer (HC).
  • HC hard coat layer
  • t-butylperoxyisopropyl carbonate (Kaya Carbon BIC-7, manufactured by Kayaku Akzo Co., Ltd.) was added as a polymerization initiator, and 10.0g of t-butylperoxyisopropyl carbonate was added.
  • Solution polymerization was carried out at about 105° C. to 120° C. under reflux while a solution consisting of 230 g of MIBK was added dropwise over 4 hours, and ripening was further carried out over 4 hours.
  • stearyl phosphate/distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the obtained polymer solution, and the mixture was heated at about 90°C to 120°C for 5 hours under reflux. , a cyclization condensation reaction was performed.
  • the obtained polymer solution was subjected to vent type screw twin-screw extrusion at a barrel temperature of 260°C, a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), and a rear vent number of 1 and a fore vent number of 4.
  • a cyclization condensation reaction and devolatilization were further performed in the extruder, and transparent pellets of the lactone ring-containing polymer were obtained by extrusion.
  • the obtained pellets and acrylonitrile-styrene (AS) resin (Toyo ASAS20, manufactured by Toyo Styrene Co., Ltd.) were kneaded and extruded at a mass ratio of 90/10 using a single screw extruder (screw 30 mm ⁇ ).
  • AS acrylonitrile-styrene
  • a transparent pellet was obtained.
  • This pellet was melt-extruded through a coat hanger type T die with a width of 400 mm using a 50 mm ⁇ single screw extruder to produce a film with a thickness of 120 ⁇ m.
  • the produced film was stretched 2.0 times vertically and 2.0 times horizontally at a temperature of 150° C. using a biaxial stretching device to obtain a stretched film (30 ⁇ m acrylic film) with a thickness of 30 ⁇ m. Obtained.
  • a polarizer with a thickness of 18 ⁇ m was obtained by immersing it in an aqueous solution containing potassium iodide at a concentration of 1.5% and washing it for 10 seconds at a temperature of 30°C, and then drying it at 50°C for 4 minutes. Ta.
  • the TAC film side surface of the HC-attached 40 ⁇ m TAC film was bonded to one surface of the obtained polarizer using a PVA adhesive. Furthermore, the above 30 ⁇ m acrylic film was bonded to the other surface of the polarizer using a PVA adhesive. As a result, a polarizing film D2 having a configuration of TAC film/PVA polarizer/acrylic film was produced. Further, the surface of the polarizing film D2 on the acrylic film side was subjected to corona treatment at a discharge amount of 63 W/m 2 ⁇ min.
  • Release liner B which has a release layer (thickness: 120 nm) on one side, was prepared by the same method as release liner A, except that the thickness of the release agent composition applied to the liner base material was changed.
  • n-butyl acrylate HBA 4-hydroxybutyl acrylate
  • Omnirad184 1-hydroxycyclohexyl-phenyl ketone (Omnirad184, manufactured by IGM Resins BV)
  • Omnirad651 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad651, manufactured by IGM Resins BV)
  • NDDA 1,9-nonanediol diacrylate
  • D177N Isocyanurate modified product of hexamethylene diisocyanate (Mitsui Chemicals, Takenate D-177N)
  • D376N Isocyanurate modified product of pentamethylene diisocyanate (Stabio D-376N, manufactured by Mitsui Chemicals)
  • D165N Biuret modified product of hexamethylene diisocyanate (Mitsui Chemicals, Takenate D-165N)
  • TKA100 Isocyanurate modified product of hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation, Duranate TKA-100)
  • Photocurable composition C1 was applied to the surface of the release layer of release liner A using an applicator to form a coating layer (thickness: 20 ⁇ m).
  • the above-mentioned release liner was placed on the formed coating layer to obtain a first laminate.
  • Release liner B was arranged so that the release layer was in contact with the coating layer.
  • ultraviolet rays black light source
  • ultraviolet rays black light source
  • release liner A A second laminate consisting of an adhesive sheet (thickness: 20 ⁇ m) and release liner B was formed.
  • the release liner B was peeled off from the second laminate, and the above-mentioned polarizing film D1 was placed on the exposed surface of the adhesive sheet to obtain the optical laminate of Example 1.
  • the polarizing film D1 was arranged so that the surface on the COP film side was in contact with the adhesive sheet.
  • Example 2 to 6 and Comparative Example 1 Optical laminates of Examples 2 to 6 and Comparative Example 1 were obtained by the same method as Example 1, except that the photocurable composition used was changed as shown in Table 3.
  • Example 7 An optical laminate of Example 7 was obtained by the same method as Example 1 except that polarizing film D2 was used instead of polarizing film D1. In addition, the polarizing film D2 was arranged so that the surface on the acrylic film side was in contact with the adhesive sheet.
  • Example 8 10 to 13, 15, 16 and Comparative Examples 2 to 5 The optical laminates of Examples 8, 10 to 13, 15, 16 and Comparative Examples 2 to 5 were prepared by the same method as in Example 7, except that the photocurable composition used was changed as shown in Table 3. Obtained.
  • Example 9 After peeling off the release liner B from the second laminate and performing corona treatment on the exposed surface of the adhesive sheet at a discharge amount of 61 W/m 2 ⁇ min, the polarizing film D2 was placed on the exposed surface.
  • An optical laminate of Example 9 was obtained by the same method as Example 8 except for the following.
  • Example 14 After peeling off the release liner B from the second laminate and performing corona treatment on the exposed surface of the adhesive sheet at a discharge amount of 61 W/m 2 ⁇ min, the polarizing film D2 was placed on the exposed surface.
  • An optical laminate of Example 14 was obtained by the same method as Example 13 except for the following.
  • anchoring force F between the adhesive sheet and the polarizing film was measured by the method described above.
  • product name "No. 531" manufactured by Nitto Denko Corporation was used.
  • stainless steel test plate a SUS304 plate (width 40 mm x length 120 mm) was used.
  • an ITO film 125 Tetraite OES, manufactured by Oike Kogyo
  • Autograph SHIMAZU AG-I 10KN was used.
  • the pressure-sensitive adhesive sheet of the present invention can be used, for example, in optical laminates and image display devices.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention concerne une feuille adhésive qui est appropriée pour ajuster la puissance d'ancrage entre elle-même et un film optique à une grande valeur. Une feuille adhésive 1 selon la présente invention est formée d'une composition photodurcissable qui contient un groupe monomère et/ou un produit de polymérisation partielle du groupe monomère. Par rapport à cette feuille adhésive 1, la quantité ajoutée d'un monomère contenant un groupe hydroxy est inférieure à 5 parties en poids pour 100 parties en poids du groupe monomère. La composition photodurcissable contient en outre un agent de réticulation à base d'isocyanate ; et la quantité ajoutée de l'agent de réticulation à base d'isocyanate est de 0,02 partie en poids ou plus par rapport à un total de 100 parties en poids du groupe monomère et du produit de polymérisation partielle.
PCT/JP2023/026818 2022-07-22 2023-07-21 Feuille adhésive et corps multicouche optique WO2024019157A1 (fr)

Applications Claiming Priority (2)

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JP2022117588A JP2024014622A (ja) 2022-07-22 2022-07-22 粘着シート及び光学積層体
JP2022-117588 2022-07-22

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WO2024019157A1 true WO2024019157A1 (fr) 2024-01-25

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007084762A (ja) * 2005-09-26 2007-04-05 Nitto Denko Corp 光学用粘着剤組成物、光学用粘着剤層、粘着剤層付光学部材、その製造方法および画像表示装置
JP2020101814A (ja) * 2020-02-13 2020-07-02 日東電工株式会社 両面粘着剤層付偏光フィルムおよび画像表示装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007084762A (ja) * 2005-09-26 2007-04-05 Nitto Denko Corp 光学用粘着剤組成物、光学用粘着剤層、粘着剤層付光学部材、その製造方法および画像表示装置
JP2020101814A (ja) * 2020-02-13 2020-07-02 日東電工株式会社 両面粘着剤層付偏光フィルムおよび画像表示装置

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