WO2024019158A1 - Method for producing adhesive sheet and method for producing optical film including adhesive sheet - Google Patents

Method for producing adhesive sheet and method for producing optical film including adhesive sheet Download PDF

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Publication number
WO2024019158A1
WO2024019158A1 PCT/JP2023/026819 JP2023026819W WO2024019158A1 WO 2024019158 A1 WO2024019158 A1 WO 2024019158A1 JP 2023026819 W JP2023026819 W JP 2023026819W WO 2024019158 A1 WO2024019158 A1 WO 2024019158A1
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WIPO (PCT)
Prior art keywords
adhesive sheet
pressure
sensitive adhesive
producing
optical film
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PCT/JP2023/026819
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French (fr)
Japanese (ja)
Inventor
赳彦 三嶋
悟士 山本
智之 木村
普史 形見
Original Assignee
日東電工株式会社
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Publication of WO2024019158A1 publication Critical patent/WO2024019158A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • 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

Definitions

  • the present invention relates to a method of manufacturing a pressure-sensitive adhesive sheet and a method of manufacturing an optical film with a pressure-sensitive adhesive sheet.
  • 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 that is cured by polymerizing and crosslinking a group of monomers including acrylic monomers, silicone monomers, and the like.
  • Patent Document 1 discloses a method (photocuring method) of forming an adhesive sheet by irradiating a coating layer containing a photocurable composition with light. Further, Patent Document 1 discloses a method of reducing the amount of monomer remaining in a formed adhesive sheet by heating and drying.
  • the problem of odor will occur.
  • the anchoring force of the adhesive sheet to the object to be bonded may be reduced.
  • the present invention aims to provide a technology suitable for producing a pressure-sensitive adhesive sheet in which the amount of residual monomer is reduced and a decrease in anchoring force is suppressed.
  • the present invention By performing surface modification treatment using active energy rays on a first adhesive sheet containing a monomer polymer and residual monomer, the amount of the residual monomer is reduced compared to the first adhesive sheet.
  • a method for producing a pressure-sensitive adhesive sheet the method comprising: obtaining a second pressure-sensitive adhesive sheet, I will provide a.
  • the invention provides: A method for producing an optical film with a pressure-sensitive adhesive sheet, the method comprising forming an optical film with a pressure-sensitive adhesive sheet by disposing an optical film on the surface of the second pressure-sensitive adhesive sheet formed by the method for producing a pressure-sensitive adhesive sheet of the present invention; I will provide a.
  • 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 schematic diagram for explaining an example of a method for manufacturing a pressure-sensitive adhesive sheet of the present invention.
  • FIG. 3 is a schematic diagram for explaining an example of a method of forming a first adhesive sheet.
  • FIG. 3 is a schematic diagram for explaining an example of a method of forming a first adhesive sheet.
  • FIG. 3 is a schematic diagram for explaining an example of a method of forming a first adhesive sheet.
  • FIG. 3 is a schematic diagram for explaining an example of a method of forming a first adhesive sheet.
  • 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 an optical film with a pressure-sensitive adhesive sheet of the present invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram for demonstrating an example of the manufacturing method of the optical film with an adhesive sheet of this invention.
  • FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing an optical film with a pressure-sensitive adhesive sheet of the present invention.
  • the method for manufacturing a pressure-sensitive adhesive sheet according to the first aspect of the present invention includes: By performing surface modification treatment using active energy rays on a first adhesive sheet containing a monomer polymer and residual monomer, the amount of the residual monomer is reduced compared to the first adhesive sheet. and obtaining a second pressure-sensitive adhesive sheet.
  • the amount of the residual monomer in the second pressure-sensitive adhesive sheet is 5000 ppm (weight basis) or less.
  • the amount of the residual monomer in the first adhesive sheet is 6000 ppm or more (by weight).
  • the surface modification treatment includes corona treatment, plasma treatment, excimer UV light treatment, and flame treatment. at least one selected from the group consisting of processing.
  • the surface modification treatment is performed in an atmosphere with an oxygen concentration of 20% by volume or less.
  • the atmosphere is an inert gas atmosphere.
  • the surface modification treatment is performed on the exposed surface of the first pressure-sensitive adhesive sheet. do.
  • the first pressure-sensitive adhesive sheet is formed by a monomer group and/or a partial polymerization of the monomer group.
  • This is a pressure-sensitive adhesive sheet formed from a photocurable composition containing a substance.
  • the monomer group includes a (meth)acrylic monomer.
  • the first pressure-sensitive adhesive sheet is formed by polymerizing a monomer group and/or a partial polymerization of the monomer group.
  • the method further includes forming a coating layer containing a photocurable composition containing a substance by irradiating the coating layer with light.
  • the light is applied to the first pressure-sensitive adhesive sheet into a laminate including the base sheet, the coating layer, and the release liner in this order. Form by irradiating.
  • the light is different from the active energy ray.
  • the method for producing an optical film with a pressure-sensitive adhesive sheet according to the thirteenth aspect of the present invention includes: The method includes arranging an optical film on the surface of the second adhesive sheet formed by the manufacturing method according to any one of the first to twelfth aspects to form an optical film with an adhesive sheet.
  • the surface is the surface that has been subjected to the surface modification treatment.
  • the optical film comprises at least one film selected from the group consisting of a polarizing film and a retardation film. include.
  • the anchoring force of the second adhesive sheet with respect to the optical film is 12 N/
  • the optical film with the pressure-sensitive adhesive sheet having a thickness of 25 mm or more is formed.
  • the present inventor came up with the idea of reducing the amount of residual monomer by surface-modifying the adhesive sheet using active energy rays, conducted studies based on this idea, and completed the present invention. According to the surface modification treatment using active energy rays, it is possible to reduce the amount of residual monomer contained in the pressure-sensitive adhesive sheet, and it is also possible to suppress a decrease in anchoring force.
  • the second adhesive sheet 2 is formed by subjecting the first adhesive sheet 1 to surface modification treatment using active energy rays 21 .
  • the first pressure-sensitive adhesive sheet 1 contains a monomer polymer and residual monomer. Residual monomers are typically unreacted monomers in the polymerization reaction that forms the polymer. In the second adhesive sheet 2, the amount of residual monomer is reduced compared to the first adhesive sheet 1.
  • the surface modification treatment is actually performed on the surface 12 of the first pressure-sensitive adhesive sheet 1, which is the exposed surface. More specifically, the surface modification treatment is performed by irradiating the surface 12 with active energy rays 21 .
  • the aspect of the surface modification treatment is not limited to this example.
  • the surface modification treatment is performed on one surface 12 of the first pressure-sensitive adhesive sheet 1.
  • the surface modification treatment may be performed on both surfaces 12 and 13 of the first adhesive sheet 1.
  • the surface 12 that has been subjected to the surface modification treatment becomes a modification treated surface 14.
  • FIG. 2 Another example of the method for manufacturing the pressure-sensitive adhesive sheet of the present invention will be described with reference to FIG. 2.
  • a long first adhesive sheet 1 is subjected to surface modification treatment using active energy rays 21, and a second long adhesive sheet 2 is formed.
  • the surface modification treatment is performed when the first adhesive sheet 1 passes through the processing device 22. Further, the surface modification treatment is carried out while conveying the first adhesive sheet 1 and the second adhesive sheet 2 while being laminated on the elongated base sheet 11.
  • the method of FIG. 2 is particularly suitable for mass production of the second adhesive sheet 2.
  • the amount of residual monomer in the second adhesive sheet 2 may be 5000 ppm or less, 4500 ppm or less, 4000 ppm or less, 3500 ppm or less, 3000 ppm or less, 2500 ppm or less, 2000 ppm or less, 1500 ppm or less, or even 1000 ppm or less. good.
  • the lower limit of the amount of residual monomer is, for example, 30 ppm or more. In this specification, all "ppm" are based on weight.
  • the amount of residual monomer in the first adhesive sheet 1 is, for example, 6000 ppm or more, 8000 ppm or more, 10000 ppm or more, 13000 ppm or more, 15000 ppm or more, 18000 ppm or more, 20000 ppm or more, 25000 ppm or more, 30000 ppm or more, 35000 ppm or more, and even 40000 ppm or more. more than pm It may be.
  • the upper limit of the amount of residual monomer is, for example, 50,000 ppm or less.
  • the amount of residual monomer in the first adhesive sheet 1 and the second adhesive sheet 2 can be evaluated by gas chromatogram (GC) analysis.
  • GC gas chromatogram
  • the surface modification treatment is, for example, at least one selected from the group consisting of corona treatment, plasma treatment, excimer UV light treatment, and flame treatment, and may be corona treatment and/or plasma treatment. There may be.
  • the active energy ray 21 may be at least one selected from the group consisting of an electron beam, an ion beam, a plasma beam, and an ultraviolet ray.
  • Each surface modification treatment can be performed by a corresponding known treatment device 22.
  • the surface modification treatment can be carried out in an atmospheric atmosphere, it may also be carried out in an atmosphere in which the oxygen concentration is reduced compared to the atmosphere (oxygen concentration 20.9% by volume).
  • Surface modification treatment in an atmosphere with reduced oxygen concentration is particularly suitable for reducing the amount of residual monomer while limiting the degree of treatment.
  • the surface modification treatment is performed at an oxygen concentration of 20% by volume or less, 15% by volume or less, 10% by volume or less, 8% by volume or less, 6% by volume or less, 5% by volume or less, 3% by volume or less, 1% by volume or less, 0. It may be carried out in an atmosphere of 5% by volume or less, or even 0.3% by volume or less.
  • the lower limit of the oxygen concentration may be 0.01 volume % or more, 0.1 volume % or more, or even 0.5 volume % or more.
  • An example of an atmosphere with reduced oxygen concentration is a mixed atmosphere of oxygen and an inert gas. Examples of inert gases are argon and nitrogen. However, the inert gas is not limited to the above example.
  • the anchoring power of the modification treated surface 14 of the second pressure-sensitive adhesive sheet 2 can be improved compared to before the treatment.
  • Surface modification treatment in an atmosphere with a reduced oxygen concentration can reduce the anchorage of the modified surface 14, especially when the degree of treatment is increased (for example, when the discharge amount is 10 kJ/m 2 or more in corona treatment). Particularly suitable for increasing strength.
  • the anchoring force is, for example, an anchoring force on a resin film such as an optical film. Furthermore, depending on the type of surface modification treatment, the risk of fire can be reduced even when the degree of treatment is increased by performing it in an atmosphere with a reduced oxygen concentration.
  • the surface modification treatment may be performed in an atmosphere substantially free of oxygen.
  • substantially free of oxygen means that the oxygen concentration is less than 0.1% by volume, preferably less than 0.05% by volume, more preferably less than 0.01% by volume.
  • An example of a substantially oxygen-free atmosphere is an inert gas atmosphere.
  • the surface modification treatment may be performed in an inert gas atmosphere.
  • 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 .
  • An example of the base sheet 11 is the same as an example of a base sheet 31 described later that can be used to form the first adhesive sheet 1.
  • the base sheet 31 used to form the first adhesive sheet 1 may be used as the base sheet 11.
  • the first pressure-sensitive adhesive sheet 1 may be a pressure-sensitive adhesive sheet (photocurable pressure-sensitive adhesive sheet) formed from a photocurable composition containing a monomer group and/or a partial polymer of the monomer group.
  • the first adhesive sheet 1 is not limited to the above example as long as it contains a monomer polymer and a residual monomer.
  • the first adhesive sheet 1 may be an adhesive sheet (thermosetting adhesive sheet) formed from a thermosetting composition containing a monomer group and a solvent. Note that the amount of residual monomer contained tends to be larger in photocurable adhesive sheets than in thermosetting adhesive sheets.
  • the manufacturing method of the present invention is particularly advantageous when the first adhesive sheet 1 (and the second adhesive sheet 2 formed from the adhesive sheet) is of a photocurable type.
  • the first pressure-sensitive adhesive sheet 1, which is a photocurable type, is produced by, for example, irradiating light 35 onto a first laminate 34 that includes a base sheet 31, a coating layer 32 containing a photocurable composition, and a release liner 33 in this order.
  • the first adhesive sheet 1 is formed from the coating layer 32 by irradiation with the light 35 (FIG. 3C).
  • the formed first adhesive sheet 1 is sandwiched between the base sheet 31 and the release liner 33 and constitutes a part of the second laminate 36 until the release liner 33 is peeled off.
  • the light 35 is irradiated from the base sheet 31 side.
  • the light 35 passes through the base sheet 31, reaches the coating layer 32, and cures the coating layer 32.
  • the irradiation with the light 35 may be performed from the release liner 33 side, or from both sides of the release liner 33 and the base sheet 31 (FIG. 3B).
  • the manufacturing method of the present invention may further include the above step of forming the first adhesive sheet 1.
  • the first pressure-sensitive adhesive sheet 1 is prepared by irradiating the coating layer 32 containing the photocurable composition containing the monomer group and/or the partial polymer of the monomer group with the light 35. It may further include forming.
  • the first adhesive sheet 1 may be formed by irradiating the first laminate 34 including the base sheet 31, the coating layer 32, and the release liner 33 in this order with the light 35.
  • the step of forming the first adhesive sheet 1 and the surface modification treatment for the formed first adhesive sheet 1 may be performed continuously.
  • FIG. 4 An example of the manufacturing method of the present invention, which further includes a step of forming the first adhesive sheet 1, will be described with reference to FIG. 4.
  • a coating layer 32 of a photocurable composition is formed on one side of a long base sheet 31 fed out from a roll 41 using a coating device 42 .
  • the elongated release liner 33 unwound from the rolled body 43 is placed on the coating layer 32 to form the elongated first laminate 34 .
  • the first laminate 34 is irradiated with light 35 from the irradiation device 44 to form the elongated first adhesive sheet 1 .
  • the release liner 33 is peeled off from the second laminate 36 including the first adhesive sheet 1 and wound up into a roll 45 .
  • the above steps are performed while conveying the base sheet 31 and release liner 33.
  • the exposed surface (surface 12) of the first pressure-sensitive adhesive sheet 1 formed by peeling off the release liner 33 is subjected to surface modification treatment by the treatment device 22, and the second adhesive sheet having the modified surface 14 is An adhesive sheet 2 is formed.
  • the above steps after peeling off the release liner 33 are carried out while conveying the base sheet 31 (11).
  • the method of FIG. 4 is particularly suitable for mass production of the second adhesive sheet 2.
  • Liner base material An example of the base material of the release liner 33 (hereinafter referred to as "liner base material”) 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 33 may have a light 35 transmittance, or may have a light 35 transmittance comparable to that of the base sheet 31.
  • the thickness of the release liner 33 is, for example, 10 to 200 ⁇ m, and may be 25 to 150 ⁇ m.
  • the release liner 33 may include layers other than the liner base material.
  • the release liner 33 may include a release layer.
  • the release liner 33 includes, for example, a liner base material and a release layer formed on one surface of the liner base material. This release liner 33 can be used so that the release layer is on the coating layer 32 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 33 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 first 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 first 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 33 may be sheet-shaped or elongated.
  • Base material sheet An example of the base sheet 31 is a resin film. Examples of resins included in the base sheet 31 are the same as examples of resins that can be included in the liner base material.
  • the base sheet 31 has excellent transparency for light 35.
  • the thickness of the base sheet 31 is, for example, 10 to 200 ⁇ m, and may be 25 to 150 ⁇ m.
  • the base sheet 31 may include a release layer on the surface facing the coating layer 32.
  • Examples of the release layer that the base sheet 31 can include and its manufacturing method are the same as the examples of the release layer that the release liner 33 can include and its manufacturing method.
  • Both the release liner 33 and the base sheet 31 may include 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 31 may be thicker.
  • a sheet can usually be selected that has a greater peeling force with the first adhesive sheet 1 than the release liner 33.
  • the base sheet 31 may be sheet-shaped or elongated.
  • the photocurable composition is a composition from which the first pressure-sensitive adhesive sheet 1 can be formed from the coating layer 32 by irradiation with light 35 .
  • the photocurable composition includes, for example, a monomer group containing a (meth)acrylic monomer and/or a partial polymer of the monomer group.
  • 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 80% by weight. % or more.
  • an acrylic pressure-sensitive adhesive sheet 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 content of (meth)acrylic acid alkyl ester in the monomer group is, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight. % or more, and even 95% or more by weight.
  • 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 content of the carboxyl group-containing monomer in the monomer group is, for example, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5.5% by weight or less, and even 5% by weight or less. It may be less than % by weight.
  • the lower limit of the content may be, for example, 0.1% by weight or more, 0.5% by weight or more, or even 1% 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. Examples of hydroxy group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and (meth)acrylate.
  • the hydroxy group-containing monomer is preferably 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate.
  • the content of the hydroxy group-containing monomer in the monomer group 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, 0.8% by weight or less, 0.5% by weight or less. It may be less than 0.3% by weight, less than 0.2% by weight, and even less than 0.1% by weight.
  • the lower limit of the content may be, for example, 0.01% by weight or more, 0.03% by weight or more, and even 0.05% by weight or more.
  • the monomer group does not need to contain hydroxy group-containing monomers.
  • each of the above-mentioned monomers may be included as a partially polymerized product.
  • the partial polymer may be either a homopolymer or a copolymer.
  • the partial polymer can contribute to stable formation of the coating layer 32 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 100 parts by weight of the monomer group and its partial polymer. There may be.
  • the photocurable composition may contain a crosslinking agent.
  • a crosslinking agent is a polyfunctional monomer having two or more polymerizable functional groups in one molecule.
  • the polyfunctional monomer may be a (meth)acrylic monomer.
  • a monomer having a polymerizable functional group such as a methylol group.
  • the polyfunctional monomer is preferably a monomer having two or more C ⁇ C bonds in one molecule.
  • polyfunctional monomers are (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.); They are allyl (meth)acrylate, vinyl
  • the polyfunctional monomer is preferably a polyfunctional acrylate, more preferably trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.
  • the blending amount of the crosslinking agent varies depending on the molecular weight, the number of functional groups, etc., but is, for example, 5 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less per 100 parts by weight of the monomer group and its partial polymer.
  • the amount may be less than 1 part by weight, or even less than 0.5 part by weight.
  • 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, silane coupling agents, viscosity modifiers, tackifiers, plasticizers, softeners, anti-aging agents, fillers, colorants, antioxidants, surfactants, and antistatic agents. and an ultraviolet absorber.
  • 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 100 poise.
  • a photocurable composition having a viscosity within the above range is particularly suitable for forming the coating layer 32.
  • the first laminate 34 is, for example, formed by forming a coating layer 32 on a base sheet 31 (or a release liner 33), and disposing a release liner 33 (or a base sheet 31) on the formed coating layer 32. It can be formed by Further, a first laminate 34 is formed by pouring and applying the photocurable composition into the space between the base sheet 31 and the release liner 33 which are held at a predetermined interval so that their main surfaces face each other. You may.
  • the coating layer 32 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 32 can be adjusted depending on the desired thickness of the second adhesive sheet 2, and may be, for example, 5 to 100 ⁇ m, 5 to 50 ⁇ m, 5 to 25 ⁇ m, or even 5 to 20 ⁇ m. good.
  • the first laminate 34 may include further layers other than the base sheet 31, the coating layer 32, and the release liner 33.
  • the further layer may be arranged on the side of the base sheet 31 and/or release liner 33 opposite to the side of the coating layer 32.
  • the coating layer 32 is preferably in contact with the base sheet 31 and the release liner 33.
  • the light 35 irradiated to the first laminate 34 is, for example, visible light or ultraviolet light having a wavelength shorter than 450 nm.
  • the light 35 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 35 may be irradiated with short wavelength light having a wavelength of 200 nm or less, preferably 300 nm or less, which is cut by a filter or the like. Cutting the short wavelength light means that the base sheet 31 and/or release liner 33 are Suitable for suppressing deterioration of
  • the light source of the light 35 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 35 may be continuous or intermittent.
  • the irradiation intensity of the light 35 is, for example, 1 to 20 mW/cm 2 .
  • the irradiation time of the light 35 is, for example, 5 minutes to 5 hours.
  • the cumulative amount of light 35 to the first laminate 34 is, for example, 100 to 5000 mJ/cm 2 .
  • the light 35 may be different from the active energy ray 21.
  • the light 35 and the active energy ray 21 may be different in type.
  • the active energy rays 21 and the light 35 may have different wavelengths.
  • the wavelength may be 200 nm or less.
  • the polymerization rate of the monomer group in the first adhesive sheet 1 is preferably 90% or more.
  • the polymerization rate may be 95% or more, 96% or more, 97% or more, or even 98% or more.
  • the gel fraction of the first adhesive sheet 1 is, for example, 50% or more, and may be 75% or more, 80% or more, or even 85% or more.
  • the peeling force of the release liner 33 to the first adhesive sheet 1 may be smaller than the peeling force of the base sheet 31 to the first adhesive sheet 1.
  • the second adhesive sheet 2 may be of a photocurable type.
  • the thickness of the second adhesive sheet 2 is, for example, 2 to 70 ⁇ m, and may be 2 to 50 ⁇ m, 5 to 40 ⁇ m, 10 to 30 ⁇ m, 10 to 25 ⁇ m, or even 10 to 20 ⁇ m.
  • the gel fraction of the second adhesive sheet 2 is, for example, 50% or more, and may be 75% or more, 80% or more, or even 85% or more.
  • the second adhesive sheet 2 can be used, for example, in an optical laminate including an optical film.
  • the second adhesive sheet 2 may be used for optical laminates.
  • the optical laminate may be an optical film with an adhesive sheet.
  • the second adhesive sheet 2 may be used so that the modified surface 14 is on the optical film side, or may be used so that it is in contact with the optical film.
  • the purpose and method of using the second adhesive sheet 2 are not limited to the above example.
  • the optical film 3 is placed on the modified surface 14 of the second adhesive sheet 2 placed on the base sheet 11 to form the optical film 51 with the adhesive sheet.
  • the optical film with adhesive sheet 51 includes a base sheet 11, a second adhesive sheet 2, and an optical film 3 in this order.
  • the adhesive sheet-attached optical film 51 can be used as it is or after peeling off the base sheet 11, for example, as an optical laminate including the second adhesive sheet 2 and the optical film 3 in an image display device or the like.
  • the optical laminate may be bonded to an object (for example, an image forming panel) via the second adhesive sheet 2.
  • the use of the adhesive sheet-attached optical film 51 is not limited to the above example. Further members such as an optical film may be arranged on the exposed surface 37 formed by peeling the base sheet 11 from the optical film 51 with an adhesive sheet.
  • An optical film 52 with a pressure-sensitive adhesive sheet including the optical film 3B and the optical film 3B in this order can be formed (see FIG. 6).
  • the optical films 3A and 3B may be the same or different from each other.
  • the optical film 3 may be placed directly or indirectly on the modified surface 14 and the exposed surface 37. In other words, even if the optical film 3 is placed in contact with the modified surface 14 or the exposed surface 37, it is not placed with another layer sandwiched between the modified surface 14 or the exposed surface 37. You can.
  • the surface of the optical film 3 that comes into contact with the second pressure-sensitive adhesive sheet 2 may be a surface that has been subjected to surface modification treatment using active energy rays. This aspect is particularly suitable for improving the anchoring force between the second adhesive sheet 2 and the optical film 3.
  • Examples of the surface modification treatment for the optical film 3 are the same as those for the first pressure-sensitive adhesive sheet 1, including preferred examples.
  • FIG. 7 Another example of the method for manufacturing the optical film with adhesive sheet of the present invention will be described with reference to FIG. 7.
  • a long optical film 3 is placed on the modified surface 14 of the second adhesive sheet 2 formed by the method shown in FIG. 4 to form a long optical film 51 with adhesive sheet.
  • the optical film 3 is unwound from the roll 46 and placed on the modification treatment surface 14 .
  • the above steps are performed while conveying the base sheet 31 (11).
  • the formation of the second adhesive sheet 2 and the formation of the adhesive sheet-attached optical film 51 may be performed continuously.
  • the formation of the first adhesive sheet 1, the formation of the second adhesive sheet 2, and the formation of the adhesive sheet-attached optical film 51 may be performed continuously.
  • the method shown in FIG. 7 is particularly suitable for mass production of the optical film 51 with adhesive sheet.
  • the optical film 3 is, for example, a film containing at least one selected from the group consisting of a polarizing film and a retardation film.
  • the optical film 3 may be a laminated film including a polarizing film and/or a retardation film.
  • the optical film 3 may include a glass film.
  • the optical film 3 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 bonded to one main surface of a polarizer via an adhesive, and a protective film made of a thermosetting resin or 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.
  • 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-2012-133303 [0221], [0222], and [0228]) and a retardation film for viewing angle compensation (see JP-A 2012-133303 [0221], [0222], and [0228]). 0225], [0226]), an obliquely oriented retardation film for viewing angle compensation (see JP-A-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 of the second adhesive sheet 2 to the optical film 3 may be 10 N/25 mm or more, or 12 N/25 mm or more.
  • optical films 51 and 52 with adhesive sheets may be formed in which the anchoring force of the second adhesive sheet 2 with respect to the optical film 3 is 10 N/25 mm or more, further 12 N/25 mm or more.
  • the anchoring force may be 13 N/25 mm or more, 14 N/25 mm or more, 15 N/25 mm or more, 16 N/25 mm or more, or even 17 N/25 mm or more.
  • the upper limit of the anchoring force is, for example, 50 N/25 mm or less, and may be 30 N/25 mm or less.
  • a film containing (meth)acrylic resin as a main component may be used as the optical film 3 such as a protective film for a polarizer.
  • the adhesive strength between an acrylic film and an adhesive sheet generally tends to be low.
  • the second adhesive sheet 2 having a second anchoring force within the above range is particularly suitable for bonding to the optical film 3 which is an acrylic film.
  • the anchoring force of the second adhesive sheet 2 with respect to the optical film 3 can be measured by the following method.
  • the laminate of the optical film 3 and the second pressure-sensitive adhesive sheet 2 is cut into a piece having a width of 25 mm and a length of 150 mm to prepare a test piece.
  • the laminate may include other layers.
  • the entire surface of the optical film 3 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 second adhesive sheet 2 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 second adhesive sheet 2 during the test.
  • the evaluation sheet for example, an ITO film (125 Tetraite OES (manufactured by Oike Kogyo Co., Ltd.), etc.) can be used.
  • the second adhesive sheet 2 was peeled off from the optical film 3 at a peeling angle of 180° and a pulling speed of 300 mm/min while holding the evaluation sheet.
  • the average value of the force is specified as the anchoring force of the second adhesive sheet 2 with respect to the optical film 3.
  • the above test is conducted in an atmosphere of 23°C ⁇ 5°C.
  • An image display device may be formed using the optical films 51 and 52 with adhesive sheets.
  • the image display device can be formed by, for example, joining optical films 51 and 52 with adhesive sheets and an image display panel. The bonding may be performed using the second adhesive sheet 2.
  • 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.
  • Production of release liner B A release liner B having a release layer (thickness: 120 nm) on one side was produced in the same manner as Production Example 1 except that the coating thickness of the release agent composition on the liner base material was changed.
  • Retention - Sample preparation method 0.05 g of the sample (adhesive sheet) was collected in a screw bottle, 2.5 mL of ethyl acetate was added, and the mixture was shaken overnight. After filtering the obtained solution with a 0.45 ⁇ m membrane filter, 1 ⁇ L of the filtrate was injected into GC for analysis.
  • Release liner A and first adhesive sheet B were prepared in the same manner as in Production Example 2, except that photocurable composition C2 was used instead of photocurable composition C1 and the ultraviolet irradiation time was changed to 480 seconds. (thickness: 20 ⁇ m) and release liner B was formed. The polymerization rate of the first pressure-sensitive adhesive sheet B thus formed was 97.9%. Further, the amount of residual monomer in the first adhesive sheet B was 19,320 ppm.
  • Example 1 The release liner B was peeled off from the second laminate produced in Production Example 3, and one side of the first pressure-sensitive adhesive sheet A was exposed. Next, corona treatment was performed on the exposed surface of the first adhesive sheet A at a discharge rate of 14.6 kJ/m 2 in an atmosphere with an oxygen concentration of 0.1% by volume (oxygen-nitrogen mixed atmosphere, 1 atm). A second adhesive sheet was obtained. The amount of residual monomer in the obtained second pressure-sensitive adhesive sheet was 2990 ppm.
  • Example 2 to 9 Second adhesive sheets of Examples 2 to 9 were obtained in the same manner as in Example 1 except that the first adhesive sheets shown in Table 3 below were subjected to corona treatment under the conditions shown in Table 3. .
  • the processing atmosphere with oxygen concentrations of 1.0% by volume, 0.1% by volume, and 0.01% by volume was an oxygen-nitrogen mixed atmosphere.
  • the processing atmosphere with an oxygen concentration of 20.9% by volume was air. Note that the pressure of the processing atmosphere was 1 atm in all cases.
  • Comparative example 1 The first adhesive sheet A obtained by peeling off the release liner B from the second laminate produced in Production Example 2 was used as the adhesive sheet a of Comparative Example 1 without performing corona treatment.
  • An optical laminate was prepared by disposing a polarizing film D1 on the corona-treated surface of the second pressure-sensitive adhesive sheet produced in the example and on the exposed surface of the pressure-sensitive adhesive sheets a to c of the comparative examples.
  • the polarizing film D1 was arranged so that the surface on the side of the transparent protective film made of modified methacrylic resin was in contact with the adhesive sheet.
  • the anchoring force between the pressure-sensitive adhesive sheet and the polarizing film was measured by the method described above.
  • As the double-sided tape Nitto Denko Corporation's product name "No. 531" was used.
  • a SUS304 plate (width 40 mm x length 120 mm) was used as the stainless steel test plate.
  • An ITO film (125 Tetraite OES, manufactured by Oike Kogyo) was used as the evaluation sheet.
  • Autograph SHIMAZU AG-I 10KN (manufactured by Shimadzu Corporation) was used as a tensile tester.
  • Polarizing film D1 used for evaluation of anchoring force was produced as follows. A polyvinyl alcohol film having a thickness of 80 ⁇ m was stretched up to 3 times between rolls having different speed ratios while being dyed for 1 minute in an iodine solution having a concentration of 0.3% at a temperature of 30° C. Next, the film was stretched while being immersed for 0.5 minutes in an aqueous solution containing boric acid at a concentration of 4% and potassium iodide at a concentration of 10% at a temperature of 60°C until the total stretching ratio became 6 times.
  • a polarizer with a thickness of 28 ⁇ 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 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 using a polyvinyl alcohol adhesive.
  • a 47 ⁇ m thick transparent protective film made of a triacetyl cellulose film (manufactured by Konica Minolta, product name "KC4UY”) with a hard coat layer (HC) is attached using a polyvinyl alcohol adhesive.
  • Polarizing film D2 was produced by heating and drying for 5 minutes in an oven set at 70°C. Furthermore, the surface of the polarizing film D2 on the side of the transparent protective film made of a modified acrylic polymer was subjected to corona treatment at a discharge amount of 63 W/(m 2 ⁇ min) in the air atmosphere.
  • the productivity of the second pressure-sensitive adhesive sheet produced in the example and each pressure-sensitive adhesive sheet of the comparative example was determined as follows.
  • the time T is the treatment time required for the second adhesive sheet obtained by performing corona treatment until the amount of residual monomer reaches 10,000 ppm or less by the treatment
  • the time T is the treatment time required for the second adhesive sheet obtained without performing corona treatment.
  • this is the ultraviolet irradiation time required for the amount of residual monomer to reach 10,000 ppm or less when forming the second laminate from the first laminate.
  • the pressure-sensitive adhesive sheet obtained by the production method of the present invention can be used, for example, in optical laminates and image display devices.

Abstract

Provided is a method for producing an adhesive sheet, the method comprising subjecting a first adhesive sheet, comprising a polymer of a monomer and a remaining monomer, to a surface modification treatment in which an active energy ray is used, to obtain a second adhesive sheet in which the amount of the remaining monomer is reduced compared to the first adhesive sheet. The surface modification treatment is, for example, at least one treatment selected from the group consisting of a corona treatment, a plasma treatment, an excimer UV light treatment, and a flame treatment. This production method is suitable for producing an adhesive sheet in which a reduction in an anchoring force is suppressed while also having a reduced amount of a remaining monomer.

Description

粘着シートの製造方法及び粘着シート付き光学フィルムの製造方法Method for manufacturing adhesive sheet and optical film with adhesive sheet
　本発明は、粘着シートの製造方法及び粘着シート付き光学フィルムの製造方法に関する。 The present invention relates to a method of manufacturing a pressure-sensitive adhesive sheet and a method of manufacturing an optical film with a pressure-sensitive adhesive sheet.
　液晶表示装置及びエレクトロルミネセンス（ＥＬ）表示装置に代表される各種の画像表示装置は、一般に、偏光フィルム等の光学フィルムと粘着シートとを含む光学積層体を備えている。光学積層体に含まれる光学フィルム間の接合や、光学積層体と画像表示パネルとの接合には、通常、粘着シートが使用される。粘着シートとしては、アクリルモノマーやシリコーンモノマー等を含むモノマー群を重合及び架橋により硬化させたシートが典型的である。特許文献１には、光硬化性組成物を含む塗布層に光を照射して粘着シートを形成する方法（光硬化法）が開示されている。また、特許文献１には、形成した粘着シートに残存するモノマーの量を加熱乾燥によって低減させる方法が開示されている。 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 that is cured by polymerizing and crosslinking a group of monomers including acrylic monomers, silicone monomers, and the like. Patent Document 1 discloses a method (photocuring method) of forming an adhesive sheet by irradiating a coating layer containing a photocurable composition with light. Further, Patent Document 1 discloses a method of reducing the amount of monomer remaining in a formed adhesive sheet by heating and drying.
特許第４８２２０３４号Patent No. 4822034
　硬化後の粘着シートに含まれる残存モノマーの量が大きくなると、臭気（モノマー臭）の問題が生じる。例えば硬化条件を制御することで、残存モノマーの量を低減させることが考えられる。しかし、本発明者らの検討によれば、硬化条件の制御のみによって残存モノマーの量を低減させた場合には、接合対象物に対する粘着シートの投錨力が低下することがある。 If the amount of residual monomer contained in the adhesive sheet after curing increases, the problem of odor (monomer odor) will occur. For example, it is possible to reduce the amount of residual monomer by controlling the curing conditions. However, according to studies by the present inventors, when the amount of residual monomer is reduced only by controlling the curing conditions, the anchoring force of the adhesive sheet to the object to be bonded may be reduced.
　本発明は、残存モノマーの量が低減され、かつ投錨力の低下が抑制された粘着シートの製造に適した技術の提供を目的とする。 The present invention aims to provide a technology suitable for producing a pressure-sensitive adhesive sheet in which the amount of residual monomer is reduced and a decrease in anchoring force is suppressed.
　本発明は、
　モノマーの重合体と残存モノマーとを含む第１の粘着シートに対して活性エネルギー線を用いた表面改質処理を実施することにより、前記第１の粘着シートに比べて前記残存モノマーの量を低減させた第２の粘着シートを得ることを含む、粘着シートの製造方法、
　を提供する。 The present invention
By performing surface modification treatment using active energy rays on a first adhesive sheet containing a monomer polymer and residual monomer, the amount of the residual monomer is reduced compared to the first adhesive sheet. A method for producing a pressure-sensitive adhesive sheet, the method comprising: obtaining a second pressure-sensitive adhesive sheet,
I will provide a.
　別の側面において、本発明は、
　上記本発明の粘着シートの製造方法によって形成された前記第２の粘着シートの表面に光学フィルムを配置して粘着シート付き光学フィルムを形成することを含む、粘着シート付き光学フィルムの製造方法、
　を提供する。 In another aspect, the invention provides:
A method for producing an optical film with a pressure-sensitive adhesive sheet, the method comprising forming an optical film with a pressure-sensitive adhesive sheet by disposing an optical film on the surface of the second pressure-sensitive adhesive sheet formed by the method for producing a pressure-sensitive adhesive sheet of the present invention;
I will provide a.
　本発明によれば、残存モノマーの量が低減され、かつ投錨力の低下が抑制された粘着シートの製造に適した技術を提供できる。 According to the present invention, it is possible to provide a technique suitable for manufacturing a pressure-sensitive adhesive sheet in which the amount of residual monomer is reduced and a decrease in anchoring force is suppressed.
本発明の粘着シートの製造方法の一例を説明するための模式図である。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. 本発明の粘着シートの製造方法の一例を説明するための模式図である。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. 第１の粘着シートを形成する方法の一例を説明するための模式図である。FIG. 3 is a schematic diagram for explaining an example of a method of forming a first adhesive sheet. 第１の粘着シートを形成する方法の一例を説明するための模式図である。FIG. 3 is a schematic diagram for explaining an example of a method of forming a first adhesive sheet. 第１の粘着シートを形成する方法の一例を説明するための模式図である。FIG. 3 is a schematic diagram for explaining an example of a method of forming a first adhesive sheet. 本発明の粘着シートの製造方法の一例を説明するための模式図である。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. 本発明の粘着シート付き光学フィルムの製造方法の一例を説明するための模式図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing an optical film with a pressure-sensitive adhesive sheet of the present invention. 本発明の粘着シート付き光学フィルムの製造方法の一例を説明するための模式図である。BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram for demonstrating an example of the manufacturing method of the optical film with an adhesive sheet of this invention. 本発明の粘着シート付き光学フィルムの製造方法の一例を説明するための模式図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram for explaining an example of a method for manufacturing an optical film with a pressure-sensitive adhesive sheet of the present invention.
　本発明の第１態様にかかる粘着シートの製造方法は、
　モノマーの重合体と残存モノマーとを含む第１の粘着シートに対して活性エネルギー線を用いた表面改質処理を実施することにより、前記第１の粘着シートに比べて前記残存モノマーの量を低減させた第２の粘着シートを得ることを含む。 The method for manufacturing a pressure-sensitive adhesive sheet according to the first aspect of the present invention includes:
By performing surface modification treatment using active energy rays on a first adhesive sheet containing a monomer polymer and residual monomer, the amount of the residual monomer is reduced compared to the first adhesive sheet. and obtaining a second pressure-sensitive adhesive sheet.
　本発明の第２態様において、例えば、第１態様にかかる粘着シートの製造方法では、前記第２の粘着シートにおける前記残存モノマーの量が５０００ｐｐｍ（重量基準）以下である。 In the second aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to the first aspect, the amount of the residual monomer in the second pressure-sensitive adhesive sheet is 5000 ppm (weight basis) or less.
　本発明の第３態様において、例えば、第１又は第２態様にかかる粘着シートの製造方法では、前記第１の粘着シートにおける前記残存モノマーの量が６０００ｐｐｍ（重量基準）以上である。 In the third aspect of the present invention, for example, in the method for producing an adhesive sheet according to the first or second aspect, the amount of the residual monomer in the first adhesive sheet is 6000 ppm or more (by weight).
　本発明の第４態様において、例えば、第１から第３態様のいずれか１つの態様にかかる粘着シートの製造方法では、前記表面改質処理が、コロナ処理、プラズマ処理、エキシマＵＶ光処理及びフレーム処理からなる群から選択される少なくとも１つである。 In a fourth aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to any one of the first to third aspects, the surface modification treatment includes corona treatment, plasma treatment, excimer UV light treatment, and flame treatment. at least one selected from the group consisting of processing.
　本発明の第５態様において、例えば、第１から第４態様のいずれか１つの態様にかかる粘着シートの製造方法では、前記表面改質処理を、酸素濃度２０体積％以下の雰囲気で実施する。 In the fifth aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to any one of the first to fourth aspects, the surface modification treatment is performed in an atmosphere with an oxygen concentration of 20% by volume or less.
　本発明の第６態様において、例えば、第５態様にかかる粘着シートの製造方法では、前記雰囲気が不活性ガス雰囲気である。 In the sixth aspect of the present invention, for example, in the method for manufacturing a pressure-sensitive adhesive sheet according to the fifth aspect, the atmosphere is an inert gas atmosphere.
　本発明の第７態様において、例えば、第１から第６態様のいずれか１つの態様にかかる粘着シートの製造方法では、前記表面改質処理を前記第１の粘着シートの露出面に対して実施する。 In a seventh aspect of the present invention, for example, in the method for manufacturing a pressure-sensitive adhesive sheet according to any one of the first to sixth aspects, the surface modification treatment is performed on the exposed surface of the first pressure-sensitive adhesive sheet. do.
　本発明の第８態様において、例えば、第１から第７態様のいずれか１つの態様にかかる粘着シートの製造方法では、前記第１の粘着シートが、モノマー群及び／又は前記モノマー群の部分重合物を含む光硬化性組成物から形成された粘着シートである。 In the eighth aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to any one of the first to seventh aspects, the first pressure-sensitive adhesive sheet is formed by a monomer group and/or a partial polymerization of the monomer group. This is a pressure-sensitive adhesive sheet formed from a photocurable composition containing a substance.
　本発明の第９態様において、例えば、第８態様にかかる粘着シートの製造方法では、前記モノマー群は（メタ）アクリル系モノマーを含む。 In the ninth aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to the eighth aspect, the monomer group includes a (meth)acrylic monomer.
　本発明の第１０態様において、例えば、第１から第９態様のいずれか１つの態様にかかる粘着シートの製造方法では、前記第１の粘着シートを、モノマー群及び／又は前記モノマー群の部分重合物を含む光硬化性組成物を含む塗布層に光を照射して形成することをさらに含む。 In the tenth aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to any one of the first to ninth aspects, the first pressure-sensitive adhesive sheet is formed by polymerizing a monomer group and/or a partial polymerization of the monomer group. The method further includes forming a coating layer containing a photocurable composition containing a substance by irradiating the coating layer with light.
　本発明の第１１態様において、例えば、第１０態様にかかる粘着シートの製造方法では、前記第１の粘着シートを、基材シート、前記塗布層及びはく離ライナーをこの順に含む積層体に前記光を照射して形成する。 In the eleventh aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to the tenth aspect, the light is applied to the first pressure-sensitive adhesive sheet into a laminate including the base sheet, the coating layer, and the release liner in this order. Form by irradiating.
　本発明の第１２態様において、例えば、第１０又は第１１態様にかかる粘着シートの製造方法では、前記光は、前記活性エネルギー線とは異なる。 In the twelfth aspect of the present invention, for example, in the method for producing a pressure-sensitive adhesive sheet according to the tenth or eleventh aspect, the light is different from the active energy ray.
　本発明の第１３態様にかかる粘着シート付き光学フィルムの製造方法は、
　第１から第１２態様のいずれか１つの態様にかかる製造方法によって形成された前記第２の粘着シートの表面に光学フィルムを配置して粘着シート付き光学フィルムを形成することを含む。 The method for producing an optical film with a pressure-sensitive adhesive sheet according to the thirteenth aspect of the present invention includes:
The method includes arranging an optical film on the surface of the second adhesive sheet formed by the manufacturing method according to any one of the first to twelfth aspects to form an optical film with an adhesive sheet.
　本発明の第１４態様において、例えば、第１３態様にかかる粘着シート付き光学フィルムの製造方法では、前記表面は前記表面改質処理がなされた面である。 In the fourteenth aspect of the present invention, for example, in the method for producing an optical film with a pressure-sensitive adhesive sheet according to the thirteenth aspect, the surface is the surface that has been subjected to the surface modification treatment.
　本発明の第１５態様において、例えば、第１３又は第１４態様にかかる粘着シート付き光学フィルムの製造方法では、前記光学フィルムが、偏光フィルム及び位相差フィルムからなる群から選ばれる少なくとも１つのフィルムを含む。 In a fifteenth aspect of the present invention, for example, in the method for producing an optical film with an adhesive sheet according to the thirteenth or fourteenth aspect, the optical film comprises at least one film selected from the group consisting of a polarizing film and a retardation film. include.
　本発明の第１６態様において、例えば、第１３から第１５態様のいずれか１つの態様にかかる粘着シート付き光学フィルムの製造方法では、前記光学フィルムに対する前記第２の粘着シートの投錨力が１２Ｎ／２５ｍｍ以上である前記粘着シート付き光学フィルムを形成する。 In a sixteenth aspect of the present invention, for example, in the method for manufacturing an optical film with an adhesive sheet according to any one of the thirteenth to fifteenth aspects, the anchoring force of the second adhesive sheet with respect to the optical film is 12 N/ The optical film with the pressure-sensitive adhesive sheet having a thickness of 25 mm or more is formed.
　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。 The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented with arbitrary modifications within the scope of the gist of the present invention.
　本発明者は、粘着シートに対する活性エネルギー線を用いた表面改質処理によって残存モノマーの量を低減させることを着想し、この着想に基づいて検討を進め、本発明を完成させた。活性エネルギー線を用いた表面改質処理によれば、粘着シートに含まれる残存モノマーの量を低減できると共に投錨力の低下を抑制できる。 The present inventor came up with the idea of reducing the amount of residual monomer by surface-modifying the adhesive sheet using active energy rays, conducted studies based on this idea, and completed the present invention. According to the surface modification treatment using active energy rays, it is possible to reduce the amount of residual monomer contained in the pressure-sensitive adhesive sheet, and it is also possible to suppress a decrease in anchoring force.
［粘着シートの製造方法］
　図１を参照して、本発明の粘着シートの製造方法の一例を説明する。この例では、第１の粘着シート１に対して活性エネルギー線２１を用いた表面改質処理を実施することにより、第２の粘着シート２を形成する。第１の粘着シート１は、モノマーの重合体と残存モノマーとを含む。残存モノマーは、典型的には、重合体を形成する重合反応における未反応モノマーである。第２の粘着シート２では、第１の粘着シート１に比べて、残存モノマーの量が低減されている。表面改質処理は、露出面である第１の粘着シート１の表面１２に対して実際される。より具体的には、表面改質処理は、表面１２に対する活性エネルギー線２１の照射により実施される。ただし、活性エネルギー線２１を用いる限り、表面改質処理の態様はこの例に限定されない。また、表面改質処理は、第１の粘着シート１の一方の表面１２に対して実施されている。ただし、表面改質処理は、第１の粘着シート１の双方の表面１２，１３に対して実施してもよい。表面改質処理がなされた表面１２は、改質処理面１４となる。 [Method for manufacturing adhesive sheet]
An example of the method for manufacturing a pressure-sensitive adhesive sheet of the present invention will be described with reference to FIG. In this example, the second adhesive sheet 2 is formed by subjecting the first adhesive sheet 1 to surface modification treatment using active energy rays 21 . The first pressure-sensitive adhesive sheet 1 contains a monomer polymer and residual monomer. Residual monomers are typically unreacted monomers in the polymerization reaction that forms the polymer. In the second adhesive sheet 2, the amount of residual monomer is reduced compared to the first adhesive sheet 1. The surface modification treatment is actually performed on the surface 12 of the first pressure-sensitive adhesive sheet 1, which is the exposed surface. More specifically, the surface modification treatment is performed by irradiating the surface 12 with active energy rays 21 . However, as long as the active energy rays 21 are used, the aspect of the surface modification treatment is not limited to this example. Moreover, the surface modification treatment is performed on one surface 12 of the first pressure-sensitive adhesive sheet 1. However, the surface modification treatment may be performed on both surfaces 12 and 13 of the first adhesive sheet 1. The surface 12 that has been subjected to the surface modification treatment becomes a modification treated surface 14.
　図２を参照して、本発明の粘着シートの製造方法の別の一例を説明する。この例では、長尺状の第１の粘着シート１に対して活性エネルギー線２１を用いた表面改質処理が実施され、長尺状の第２の粘着シート２が形成される。表面改質処理は、第１の粘着シート１が処理装置２２を通過する際に実施される。また、表面改質処理は、長尺状の基材シート１１に積層された状態で第１の粘着シート１及び第２の粘着シート２を搬送しながら実施される。図２の方法は、第２の粘着シート２の量産に特に適している。 Another example of the method for manufacturing the pressure-sensitive adhesive sheet of the present invention will be described with reference to FIG. 2. In this example, a long first adhesive sheet 1 is subjected to surface modification treatment using active energy rays 21, and a second long adhesive sheet 2 is formed. The surface modification treatment is performed when the first adhesive sheet 1 passes through the processing device 22. Further, the surface modification treatment is carried out while conveying the first adhesive sheet 1 and the second adhesive sheet 2 while being laminated on the elongated base sheet 11. The method of FIG. 2 is particularly suitable for mass production of the second adhesive sheet 2.
　第２の粘着シート２における残存モノマーの量は、５０００ｐｐｍ以下であってもよく、４５００ｐｐｍ以下、４０００ｐｐｍ以下、３５００ｐｐｍ以下、３０００ｐｐｍ以下、２５００ｐｐｍ以下、２０００ｐｐｍ以下、１５００ｐｐｍ以下、さらには１０００ｐｐｍ以下であってもよい。残存モノマーの量の下限は、例えば３０ｐｐｍ以上である。本明細書において「ｐｐｍ」は全て重量基準である。 The amount of residual monomer in the second adhesive sheet 2 may be 5000 ppm or less, 4500 ppm or less, 4000 ppm or less, 3500 ppm or less, 3000 ppm or less, 2500 ppm or less, 2000 ppm or less, 1500 ppm or less, or even 1000 ppm or less. good. The lower limit of the amount of residual monomer is, for example, 30 ppm or more. In this specification, all "ppm" are based on weight.
　第１の粘着シート１における残存モノマーの量は、例えば６０００ｐｐｍ以上であり、８０００ｐｐｍ以上、１００００ｐｐｍ以上、１３０００ｐｐｍ以上、１５０００ｐｐｍ以上、１８０００ｐｐｍ以上、２００００ｐｐｍ以上、２５０００ｐｐｍ以上、３００００ｐｐｍ以上、３５０００ｐｐｍ以上、さらには４００００ｐｐｍ以上であってもよい。残存モノマーの量の上限は、例えば５００００ｐｐｍ以下である。 The amount of residual monomer in the first adhesive sheet 1 is, for example, 6000 ppm or more, 8000 ppm or more, 10000 ppm or more, 13000 ppm or more, 15000 ppm or more, 18000 ppm or more, 20000 ppm or more, 25000 ppm or more, 30000 ppm or more, 35000 ppm or more, and even 40000 ppm or more. more than pm It may be. The upper limit of the amount of residual monomer is, for example, 50,000 ppm or less.
　第１の粘着シート１及び第２の粘着シート２における残存モノマーの量は、ガスクロマトグラム（ＧＣ）分析により評価できる。 The amount of residual monomer in the first adhesive sheet 1 and the second adhesive sheet 2 can be evaluated by gas chromatogram (GC) analysis.
　表面改質処理は、例えば、コロナ処理、プラズマ処理、エキシマＵＶ光処理及びフレーム処理からなる群から選択される少なくとも１つであり、コロナ処理及び／又はプラズマ処理であってもよく、コロナ処理であってもよい。換言すれば、活性エネルギー線２１は、電子線、イオン線、プラズマ線及び紫外線からなる群から選択される少なくとも１つであってもよい。各々の表面改質処理は、対応する公知の処理装置２２により実施できる。 The surface modification treatment is, for example, at least one selected from the group consisting of corona treatment, plasma treatment, excimer UV light treatment, and flame treatment, and may be corona treatment and/or plasma treatment. There may be. In other words, the active energy ray 21 may be at least one selected from the group consisting of an electron beam, an ion beam, a plasma beam, and an ultraviolet ray. Each surface modification treatment can be performed by a corresponding known treatment device 22.
　表面改質処理は、大気雰囲気で実施することが可能であるが、大気（酸素濃度２０．９体積％）に比べて酸素濃度が低減された雰囲気で実施してもよい。低減された酸素濃度の雰囲気での表面改質処理は、処理の程度を抑えながら残存モノマーの量を低減することに特に適している。表面改質処理は、酸素濃度２０体積％以下、１５体積％以下、１０体積％以下、８体積％以下、６体積％以下、５体積％以下、３体積％以下、１体積％以下、０．５体積％以下、さらには０．３体積％以下の雰囲気で実施してもよい。酸素濃度の下限は、０．０１体積％以上、０．１体積％以上、さらには０．５体積％以上であってもよい。酸素濃度が低減された雰囲気の例は、酸素及び不活性ガスの混合雰囲気である。不活性ガスの例は、アルゴン及び窒素である。ただし、不活性ガスは上記例に限定されない。表面改質処理によって、第２の粘着シート２における改質処理面１４の投錨力は処理前よりも向上しうる。低減された酸素濃度の雰囲気での表面改質処理は、とりわけ処理の程度を高くした場合（例えば、コロナ処理において放電量を１０ｋＪ／ｍ2以上とした場合）に、改質処理面１４の投錨力を高めることに特に適している。投錨力は、例えば、光学フィルム等の樹脂フィルムに対する投錨力である。また、表面改質処理の種類によっては、低減された酸素濃度の雰囲気での実施により、処理の程度を高くした場合にも火気リスクを低減できる。 Although the surface modification treatment can be carried out in an atmospheric atmosphere, it may also be carried out in an atmosphere in which the oxygen concentration is reduced compared to the atmosphere (oxygen concentration 20.9% by volume). Surface modification treatment in an atmosphere with reduced oxygen concentration is particularly suitable for reducing the amount of residual monomer while limiting the degree of treatment. The surface modification treatment is performed at an oxygen concentration of 20% by volume or less, 15% by volume or less, 10% by volume or less, 8% by volume or less, 6% by volume or less, 5% by volume or less, 3% by volume or less, 1% by volume or less, 0. It may be carried out in an atmosphere of 5% by volume or less, or even 0.3% by volume or less. The lower limit of the oxygen concentration may be 0.01 volume % or more, 0.1 volume % or more, or even 0.5 volume % or more. An example of an atmosphere with reduced oxygen concentration is a mixed atmosphere of oxygen and an inert gas. Examples of inert gases are argon and nitrogen. However, the inert gas is not limited to the above example. By the surface modification treatment, the anchoring power of the modification treated surface 14 of the second pressure-sensitive adhesive sheet 2 can be improved compared to before the treatment. Surface modification treatment in an atmosphere with a reduced oxygen concentration can reduce the anchorage of the modified surface 14, especially when the degree of treatment is increased (for example, when the discharge amount is 10 kJ/m 2 or more in corona treatment). Particularly suitable for increasing strength. The anchoring force is, for example, an anchoring force on a resin film such as an optical film. Furthermore, depending on the type of surface modification treatment, the risk of fire can be reduced even when the degree of treatment is increased by performing it in an atmosphere with a reduced oxygen concentration.
　表面改質処理は、酸素を実質的に含まない雰囲気で実施してもよい。酸素を実質的に含まないとは、酸素濃度が０．１体積％未満、好ましくは０．０５体積％未満、より好ましくは０．０１体積％未満であることを意味する。酸素を実質的に含まない雰囲気の例は、不活性ガス雰囲気である。換言すれば、表面改質処理は不活性ガス雰囲気で実施してもよい。表面改質処理は、常圧（１気圧）下で実施してもよい。 The surface modification treatment may be performed in an atmosphere substantially free of oxygen. Substantially free of oxygen means that the oxygen concentration is less than 0.1% by volume, preferably less than 0.05% by volume, more preferably less than 0.01% by volume. An example of a substantially oxygen-free atmosphere is an inert gas atmosphere. In other words, the surface modification treatment may be performed in an inert gas atmosphere. The surface modification treatment may be carried out under normal pressure (1 atmosphere).
　コロナ処理である表面改質処理の条件は、放電量により表して、例えば、０．６～１００ｋＪ／ｍ2である。放電量の下限は、１ｋＪ／ｍ2以上、２ｋＪ／ｍ2以上、５ｋＪ／ｍ2以上、７ｋＪ／ｍ2以上、１０ｋＪ／ｍ2以上、１３ｋＪ／ｍ2以上、１５ｋＪ／ｍ2以上、２０ｋＪ／ｍ2以上、２５ｋＪ／ｍ2以上、３０ｋＪ／ｍ2以上、さらには３５ｋＪ／ｍ2以上であってもよい。放電量の上限は、７０ｋＪ／ｍ2以下、６０ｋＪ／ｍ2以下、５０ｋＪ／ｍ2以下、４５ｋＪ／ｍ2以下、４０ｋＪ／ｍ2以下、３０ｋＪ／ｍ2以下、２０ｋＪ／ｍ2以下、さらには１８ｋＪ／ｍ2以下であってもよい。酸素濃度１０体積％以上２０．９体積％以下の雰囲気でコロナ処理を実施する場合は、放電量は１～１８ｋＪ／ｍ2であってもよい。酸素濃度０．０１体積％以上１０体積％未満の雰囲気でコロナ処理を実施する場合は、放電量は１～６０ｋＪ／ｍ2であってもよい。 The conditions for the surface modification treatment, which is corona 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. m 2 or more, 25 kJ/m 2 or more, 30 kJ/m 2 or more, or even 35 kJ/m 2 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. When performing corona treatment in an atmosphere with an oxygen concentration of 10% by volume or more and 20.9% by volume or less, the discharge amount may be 1 to 18 kJ/m 2 . When performing corona treatment in an atmosphere with an oxygen concentration of 0.01% by volume or more and less than 10% by volume, the discharge amount may be 1 to 60 kJ/m 2 .
　基材シート１１の例は、第１の粘着シート１の形成に用いうる後述の基材シート３１の例と同じである。第１の粘着シート１の形成に用いた基材シート３１を基材シート１１に用いてもよい。 An example of the base sheet 11 is the same as an example of a base sheet 31 described later that can be used to form the first adhesive sheet 1. The base sheet 31 used to form the first adhesive sheet 1 may be used as the base sheet 11.
　（第１の粘着シート）
　第１の粘着シート１は、モノマー群及び／又は当該モノマー群の部分重合物を含む光硬化性組成物から形成された粘着シート（光硬化型の粘着シート）であってもよい。ただし、第１の粘着シート１は、モノマーの重合体と残存モノマーとを含む限り、上記例に限定されない。第１の粘着シート１は、モノマー群と溶剤とを含む熱硬化性組成物から形成された粘着シート（熱硬化型の粘着シート）であってもよい。なお、含まれる残存モノマーの量は、熱硬化型粘着シートに比べて光硬化型粘着シートで多い傾向にある。これには、大気中の酸素によって、特にシートの表面近傍における光硬化型組成物の硬化が阻害されやすいことが影響している可能性がある。このため、光硬化型の粘着シートでは、粘着シートの外部、典型的には隣接する層、に残存モノマーが移動して悪影響を及ぼしやすい。悪影響の一例は、隣接する光学フィルムにおけるクラックの発生である。この観点からは、第１の粘着シート１（及び当該粘着シートから形成された第２の粘着シート２）が光硬化型である場合に、本発明の製造方法は特に有利である。 (First adhesive sheet)
The first pressure-sensitive adhesive sheet 1 may be a pressure-sensitive adhesive sheet (photocurable pressure-sensitive adhesive sheet) formed from a photocurable composition containing a monomer group and/or a partial polymer of the monomer group. However, the first adhesive sheet 1 is not limited to the above example as long as it contains a monomer polymer and a residual monomer. The first adhesive sheet 1 may be an adhesive sheet (thermosetting adhesive sheet) formed from a thermosetting composition containing a monomer group and a solvent. Note that the amount of residual monomer contained tends to be larger in photocurable adhesive sheets than in thermosetting adhesive sheets. This may be due to the fact that curing of the photocurable composition is likely to be inhibited by oxygen in the atmosphere, particularly near the surface of the sheet. For this reason, in photo-curable pressure-sensitive adhesive sheets, residual monomers tend to migrate to the outside of the pressure-sensitive adhesive sheet, typically to adjacent layers, and cause adverse effects. An example of an adverse effect is the occurrence of cracks in adjacent optical films. From this point of view, the manufacturing method of the present invention is particularly advantageous when the first adhesive sheet 1 (and the second adhesive sheet 2 formed from the adhesive sheet) is of a photocurable type.
　光硬化型である第１の粘着シート１は、例えば、基材シート３１、光硬化性組成物を含む塗布層３２及びはく離ライナー３３をこの順に含む第１の積層体３４に光３５を照射して形成できる（図３Ａ）。光３５の照射によって、塗布層３２から第１の粘着シート１が形成される（図３Ｃ）。形成された第１の粘着シート１は、はく離ライナー３３が剥離されるまでは、基材シート３１及びはく離ライナー３３によって挟持されて第２の積層体３６の一部を構成している。図３Ａの例では、光３５は基材シート３１の側から照射される。光３５は、基材シート３１を透過して塗布層３２に到達し、塗布層３２を硬化させる。ただし、光３５の照射は、はく離ライナー３３の側から実施してもよいし、はく離ライナー３３及び基材シート３１の双方の側から実施してもよい（図３Ｂ）。 The first pressure-sensitive adhesive sheet 1, which is a photocurable type, is produced by, for example, irradiating light 35 onto a first laminate 34 that includes a base sheet 31, a coating layer 32 containing a photocurable composition, and a release liner 33 in this order. (Figure 3A). The first adhesive sheet 1 is formed from the coating layer 32 by irradiation with the light 35 (FIG. 3C). The formed first adhesive sheet 1 is sandwiched between the base sheet 31 and the release liner 33 and constitutes a part of the second laminate 36 until the release liner 33 is peeled off. In the example of FIG. 3A, the light 35 is irradiated from the base sheet 31 side. The light 35 passes through the base sheet 31, reaches the coating layer 32, and cures the coating layer 32. However, the irradiation with the light 35 may be performed from the release liner 33 side, or from both sides of the release liner 33 and the base sheet 31 (FIG. 3B).
　本発明の製造方法は、第１の粘着シート１を形成する上記工程をさらに含んでいてもよい。換言すれば、本発明の製造方法は、第１の粘着シート１を、モノマー群及び／又は当該モノマー群の部分重合物を含む光硬化性組成物を含む塗布層３２に光３５を照射して形成することをさらに含んでいてもよい。このとき、第１の粘着シート１は、基材シート３１、塗布層３２及びはく離ライナー３３をこの順に含む第１の積層体３４に光３５を照射して形成してもよい。第１の粘着シート１を形成する工程と、形成した第１の粘着シート１に対する上記表面改質処理とは、連続して実施してもよい。 The manufacturing method of the present invention may further include the above step of forming the first adhesive sheet 1. In other words, in the manufacturing method of the present invention, the first pressure-sensitive adhesive sheet 1 is prepared by irradiating the coating layer 32 containing the photocurable composition containing the monomer group and/or the partial polymer of the monomer group with the light 35. It may further include forming. At this time, the first adhesive sheet 1 may be formed by irradiating the first laminate 34 including the base sheet 31, the coating layer 32, and the release liner 33 in this order with the light 35. The step of forming the first adhesive sheet 1 and the surface modification treatment for the formed first adhesive sheet 1 may be performed continuously.
　図４を参照して、第１の粘着シート１を形成する工程をさらに含む本発明の製造方法の一例を説明する。この例では、巻回体４１から繰り出した長尺状の基材シート３１の片面に対して、塗布装置４２により光硬化性組成物の塗布層３２を形成する。次に、塗布層３２の上に、巻回体４３から繰り出した長尺状のはく離ライナー３３を配置して、長尺状の第１の積層体３４を形成する。次に、照射装置４４から第１の積層体３４に光３５を照射して、長尺状の第１の粘着シート１を形成する。次に、第１の粘着シート１を含む第２の積層体３６からはく離ライナー３３を剥離して巻回体４５に巻き取る。以上の工程は、基材シート３１及びはく離ライナー３３を搬送しながら実施する。次に、はく離ライナー３３の剥離により形成された第１の粘着シート１の露出面（表面１２）に対して処理装置２２による表面改質処理を実施して、改質処理面１４を有する第２の粘着シート２を形成する。はく離ライナー３３を剥離した後の以上の工程は、基材シート３１（１１）を搬送しながら実施する。図４の方法は、第２の粘着シート２の量産に特に適している。 An example of the manufacturing method of the present invention, which further includes a step of forming the first adhesive sheet 1, will be described with reference to FIG. 4. In this example, a coating layer 32 of a photocurable composition is formed on one side of a long base sheet 31 fed out from a roll 41 using a coating device 42 . Next, the elongated release liner 33 unwound from the rolled body 43 is placed on the coating layer 32 to form the elongated first laminate 34 . Next, the first laminate 34 is irradiated with light 35 from the irradiation device 44 to form the elongated first adhesive sheet 1 . Next, the release liner 33 is peeled off from the second laminate 36 including the first adhesive sheet 1 and wound up into a roll 45 . The above steps are performed while conveying the base sheet 31 and release liner 33. Next, the exposed surface (surface 12) of the first pressure-sensitive adhesive sheet 1 formed by peeling off the release liner 33 is subjected to surface modification treatment by the treatment device 22, and the second adhesive sheet having the modified surface 14 is An adhesive sheet 2 is formed. The above steps after peeling off the release liner 33 are carried out while conveying the base sheet 31 (11). The method of FIG. 4 is particularly suitable for mass production of the second adhesive sheet 2.
　　＜はく離ライナー＞
　はく離ライナー３３の基材（以下、「ライナー基材」）の例は、樹脂フィルムである。ライナー基材に含まれうる樹脂の例は、ポリエチレンテレフタレート及びポリエチレンナフタレート等のポリエステル、アセテート樹脂、ポリエーテルスルホン、ポリカーボネート、ポリアミド、ポリイミド、ポリオレフィン、（メタ）アクリル樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリビニルアルコール、ポリアリレート、並びにポリフェニレンサルファイドである。樹脂は、好ましくは、ポリエチレンテレフタレート等のポリエステルである。 <Release liner>
An example of the base material of the release liner 33 (hereinafter referred to as "liner base material") is a resin film. Examples of 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.
　はく離ライナー３３は、光３５の透過性を有していてもよく、基材シート３１と同程度の光３５の透過性を有していてもよい。 The release liner 33 may have a light 35 transmittance, or may have a light 35 transmittance comparable to that of the base sheet 31.
　はく離ライナー３３の厚さは、例えば１０～２００μｍであり、２５～１５０μｍであってもよい。 The thickness of the release liner 33 is, for example, 10 to 200 μm, and may be 25 to 150 μm.
　はく離ライナー３３は、ライナー基材以外の層を備えていてもよい。はく離ライナー３３は、離型層を備えていてもよい。はく離ライナー３３は、例えば、ライナー基材と、ライナー基材の一方の面に形成された離型層とを備える。このはく離ライナー３３は、離型層が塗布層３２の側となるように使用できる。 The release liner 33 may include layers other than the liner base material. The release liner 33 may include a release layer. The release liner 33 includes, for example, a liner base material and a release layer formed on one surface of the liner base material. This release liner 33 can be used so that the release layer is on the coating layer 32 side.
　離型層は、典型的には、離型剤を含む離型剤組成物の硬化層である。離型剤には、シリコーン系離型剤、フッ素系離型剤、長鎖アルキル系離型剤、脂肪酸アミド系離型剤、シリカ粉等の種々の離型剤を使用できる。はく離ライナー３３は、シリコーン系離型剤を主成分として含む離型剤組成物の硬化層（以下「シリコーン離型層」）を備えていてもよい。シリコーン離型層は、第１の粘着シート１に対する密着性及び剥離性の両立に特に適している。なお、本明細書において主成分とは、最も含有率の大きな成分を意味する。 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 33 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 first pressure-sensitive adhesive sheet 1. In addition, in this specification, the main component means the component with the largest content rate.
　シリコーン系離型剤は、例えば、付加反応型、縮合反応型、紫外線硬化型、電子線硬化型、無溶媒型等の各種の硬化型シリコーン材料であり、付加反応硬化型シリコーン材料が好ましい。付加反応硬化型シリコーン材料は、第１の粘着シート１に対する密着性及び剥離性の両立した離型層の形成に特に適している。硬化型シリコーン材料は、ウレタン、エポキシ、アルキッド樹脂等の有機樹脂にグラフト重合等により反応性シリコーンを導入したシリコーン変性樹脂であってもよい。 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 first 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.
　付加反応硬化型シリコーン材料の例は、ビニル基又はアルケニル基を分子内に有するポリオルガノシロキサンである。付加反応硬化型シリコーン材料は、ヒドロシリル基を有さなくてもよい。アルケニル基の例は、３－ブテニル基、４－ペンテニル基、５－ヘキセニル基、６－ヘプテニル基、７－オクテニル基、８－ノネニル基、９－デセニル基、１０－ウンデセニル基、及び１１－ドデセニル基である。ポリオルガノシロキサンの例は、ポリジメチルシロキサン、ポリジエチルシロキサン及びポリメチルエチルシロキサン等のポリアルキルアルキルシロキサン、ポリアルキルアリールシロキサン、並びにポリ（ジメチルシロキサン－ジエチルシロキサン）等の複数種のＳｉ原子含有モノマーの共重合体である。ポリオルガノシロキサンは、好ましくはポリジメチルシロキサンである。 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. Examples of 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. Examples of polyorganosiloxanes 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.
　シリコーン系離型剤を主成分として含む離型剤組成物（以下「シリコーン離型剤組成物」）は、通常、架橋剤を含む。架橋剤の例は、ヒドロシリル基を有するポリオルガノシロキサンである。架橋剤は、一分子中に２以上のヒドロシリル基を有していてもよい。 A mold release agent composition containing a silicone mold release agent as a main component (hereinafter referred to as "silicone mold release agent composition") usually contains a crosslinking agent. Examples of crosslinking agents are polyorganosiloxanes containing hydrosilyl groups. The crosslinking agent may have two or more hydrosilyl groups in one molecule.
　シリコーン離型剤組成物は、硬化触媒を含んでいてもよい。硬化触媒の例は、白金系触媒である。白金系触媒の例は、塩化白金酸、白金のオレフィン錯体、塩化白金酸のオレフィン錯体である。白金系触媒の使用量は、組成物の全固形分に対して、例えば１０～１０００ｐｐｍ（重量基準、白金換算）である。 The silicone mold release agent composition may contain a curing catalyst. An example of a curing catalyst is a platinum-based catalyst. Examples of 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.
　シリコーン離型剤組成物は、添加剤を含んでいてもよい。添加剤の例は、剥離コントロール剤及び密着性向上剤である。剥離コントロール剤の例は未反応性のシリコーン樹脂であり、より具体的な例は、オクタメチルシクロテトラシロキサン等のオルガノシロキサン、及びＭＱレジンである。剥離コントロール剤及び密着性向上剤の使用量は、組成物の全固形分に対して合計で、例えば１～３０重量％である。添加剤のさらなる例は、充填剤、帯電防止剤、酸化防止剤、紫外線吸収剤、可塑剤及び着色剤である。さらなる添加剤の使用量は、組成物の全固形分に対して合計で、例えば１０重量％以下である。 The silicone mold release agent composition may contain additives. Examples of additives are release control agents and adhesion promoters. Examples of 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.
　シリコーン離型剤組成物は、有機溶媒を含んでいてもよい。有機溶媒の例は、シクロヘキサン、ｎ－ヘキサン、ｎ－ヘプタン等の炭化水素系溶媒；トルエン、キシレン等の芳香族系溶媒；酢酸エチル、酢酸メチル等のエステル系溶媒；アセトン、メチルエチルケトン等のケトン系溶媒；メタノール、エタノール、ブタノール等のアルコール系溶媒である。２種以上の有機溶媒が含まれていてもよい。有機溶媒の使用量は、好ましくは、シリコーン離型剤組成物の８０～９９．９重量％である。 The silicone mold release agent composition may contain an organic solvent. Examples of 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.
　離型層は、例えば、ライナー基材上に形成した離型剤組成物を含む塗布膜を加熱及び乾燥して形成できる。離型剤組成物の塗布には、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、ダイコート等の各種の塗布方法を適用できる。加熱及び乾燥には、例えば熱風乾燥を適用できる。加熱温度及び時間は、ライナー基材の耐熱性により異なるが、通常、８０～１５０℃及び１０秒～１０分程度である。必要に応じて、紫外線等の活性エネルギー線の照射を併用してもよい。 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.
　離型層の厚さは、例えば１０～３００ｎｍである。厚さの上限は、２００ｎｍ以下、１５０ｎｍ以下、１２０ｎｍ以下、１１０ｎｍ以下、１００ｎｍ以下、１００ｎｍ未満、９０ｎｍ以下、８０ｎｍ以下、７０ｎｍ以下、７０ｎｍ未満、さらには６５ｎｍ以下であってもよい。厚さの下限は、１５ｎｍ以上、２０ｎｍ以上、２５ｎｍ以上、３０ｎｍ以上、３５ｎｍ以上、４０ｎｍ以上、４５ｎｍ以上、さらには５０ｎｍ以上であってもよい。 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.
　はく離ライナー３３は、枚葉状であっても長尺状であってもよい。 The release liner 33 may be sheet-shaped or elongated.
　　＜基材シート＞
　基材シート３１の例は、樹脂フィルムである。基材シート３１に含まれる樹脂の例は、ライナー基材に含まれうる樹脂の例と同じである。 <Base material sheet>
An example of the base sheet 31 is a resin film. Examples of resins included in the base sheet 31 are the same as examples of resins that can be included in the liner base material.
　基材シート３１は、光３５の透過性に優れることが好ましい。 It is preferable that the base sheet 31 has excellent transparency for light 35.
　基材シート３１の厚さは、例えば１０～２００μｍであり、２５～１５０μｍであってもよい。 The thickness of the base sheet 31 is, for example, 10 to 200 μm, and may be 25 to 150 μm.
　基材シート３１は、塗布層３２の側の面に離型層を備えていてもよい。基材シート３１が備えうる離型層及びその製法の例は、はく離ライナー３３が備えうる離型層及びその製法の例と同じである。はく離ライナー３３及び基材シート３１の双方が離型層を備えていてもよい。この場合、双方の離型層は、同じ離型剤を主成分として含む離型剤組成物から形成されていてもよい。また、双方の離型層の厚さは異なっていてもよく、例えば、基材シート３１が備える離型層の方が厚くてもよい。 The base sheet 31 may include a release layer on the surface facing the coating layer 32. Examples of the release layer that the base sheet 31 can include and its manufacturing method are the same as the examples of the release layer that the release liner 33 can include and its manufacturing method. Both the release liner 33 and the base sheet 31 may include a release layer. In this case, 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 31 may be thicker.
　基材シート３１には、通常、第１の粘着シート１との剥離力がはく離ライナー３３に比べて大きなシートを選択できる。 As the base sheet 31, a sheet can usually be selected that has a greater peeling force with the first adhesive sheet 1 than the release liner 33.
　基材シート３１は、枚葉状であっても長尺状であってもよい。 The base sheet 31 may be sheet-shaped or elongated.
　　＜光硬化性組成物＞
　光硬化性組成物は、光３５の照射によって塗布層３２から第１の粘着シート１が形成されうる組成物である。光硬化性組成物は、例えば、（メタ）アクリル系モノマーを含むモノマー群及び／又は当該モノマー群の部分重合物を含む。光硬化性組成物における（メタ）アクリル系成分、すなわち（メタ）アクリル系モノマー及びその部分重合物、の含有率は、５０重量％以上、６０重量％以上、７０重量％以上、さらには８０重量％以上であってもよい。この場合、（メタ）アクリル重合体及びその架橋物を主成分とするアクリル系の粘着シートを形成できる。ただし、光硬化性組成物は上記例に限定されない。本明細書において（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。 <Photocurable composition>
The photocurable composition is a composition from which the first pressure-sensitive adhesive sheet 1 can be formed from the coating layer 32 by irradiation with light 35 . The photocurable composition includes, for example, a monomer group containing a (meth)acrylic monomer and/or a partial polymer of the monomer group. 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 80% by weight. % or more. In this case, an acrylic pressure-sensitive adhesive sheet containing a (meth)acrylic polymer and a crosslinked product thereof as main components can be formed. However, the photocurable composition is not limited to the above example. In this specification, (meth)acrylic means acrylic and methacryl. (Meth)acrylate means acrylate and methacrylate.
　（メタ）アクリル系モノマーの例は、炭素数１～２０のアルキル基を側鎖に有する（メタ）アクリル酸アルキルエステルである。アルキル基の炭素数は、７以下、６以下、５以下、さらには４以下であってもよい。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。（メタ）アクリル酸アルキルエステルの例は、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。（メタ）アクリル酸アルキルエステルは、ｎ－ブチル（メタ）アクリレートであってもよい。 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 (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate and octadecyl (meth)acrylate. The (meth)acrylic acid alkyl ester may be n-butyl (meth)acrylate.
　モノマー群における（メタ）アクリル酸アルキルエステルの含有率は、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。なお、含有率の計算にあたり、部分重合物の重量は、重合前の各モノマーとしての重量に換算する。 The content of (meth)acrylic acid alkyl ester in the monomer group is, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight. % or more, and even 95% or more by weight. In calculating the content, the weight of the partially polymerized product is converted to the weight of each monomer before polymerization.
　モノマー群は、カルボキシル基含有モノマーを含んでいてもよい。カルボキシル基含有モノマーは（メタ）アクリル系モノマーであってもよく、換言すれば、（メタ）アクリル系モノマーがカルボキシル基含有モノマーを含んでいてもよい。カルボキシル基含有モノマーの例は、（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。モノマー群におけるカルボキシル基含有モノマーの含有率は、例えば１０重量％以下であり、９重量％以下、８重量％以下、７重量％以下、６重量％以下、５．５重量％以下、さらには５重量％以下であってもよい。含有率の下限は、例えば０．１重量％以上であり、０．５重量％以上、さらには１重量％以上であってもよい。モノマー群は、カルボキシル基含有モノマーを含んでいなくてもよい。 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 content of the carboxyl group-containing monomer in the monomer group is, for example, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5.5% by weight or less, and even 5% by weight or less. It may be less than % by weight. The lower limit of the content may be, for example, 0.1% by weight or more, 0.5% by weight or more, or even 1% by weight or more. The monomer group does not need to contain carboxyl group-containing monomers.
　モノマー群は、ヒドロキシ基含有モノマーを含んでいてもよい。ヒドロキシ基含有モノマーは（メタ）アクリル系モノマーであってもよく、換言すれば、（メタ）アクリル系モノマーがヒドロキシ基含有モノマーを含んでいてもよい。ヒドロキシ基含有モノマーは、粘着シートの凝集力向上に寄与しうる。ヒドロキシ基含有モノマーの例は、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル及び（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。ヒドロキシ基含有モノマーは、好ましくは、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸４－ヒドロキシブチルである。モノマー群におけるヒドロキシ基含有モノマーの含有率は、例えば５重量％以下であり、４重量％以下、３重量％以下、２重量％以下、１重量％以下、０．８重量％以下、０．５重量％以下、０．３重量％以下、０．２重量％以下、さらには０．１重量％以下であってもよい。含有率の下限は、例えば０．０１重量％以上であり、０．０３重量％以上、さらには０．０５重量％以上であってもよい。モノマー群は、ヒドロキシ基含有モノマーを含んでいなくてもよい。 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. Examples of hydroxy group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and (meth)acrylate. ) 8-hydroxyoctyl 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 content of the hydroxy group-containing monomer in the monomer group 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, 0.8% by weight or less, 0.5% by weight or less. It may be less than 0.3% by weight, less than 0.2% by weight, and even less than 0.1% by weight. The lower limit of the content may be, for example, 0.01% by weight or more, 0.03% by weight or more, and even 0.05% by weight or more. The monomer group does not need to contain hydroxy group-containing monomers.
　光硬化性組成物において、上述した各モノマーは部分重合物として含まれていてもよい。部分重合物は、単一重合体及び共重合体のいずれであってもよい。部分重合物は、光硬化性組成物の粘度を適度に増大させることで、塗布層３２の安定した形成に寄与しうる。 In the photocurable composition, each of the above-mentioned monomers may be included as a partially polymerized product. The partial polymer may be either a homopolymer or a copolymer. The partial polymer can contribute to stable formation of the coating layer 32 by appropriately increasing the viscosity of the photocurable composition.
　光硬化性組成物は、通常、光重合開始剤を含有する。光重合開始剤の例は、波長４５０ｎｍよりも短い波長の可視光及び／又は紫外線によりラジカルを発生する光ラジカル発生剤である。 The photocurable composition usually contains a photopolymerization initiator. An example of the photopolymerization initiator is a photoradical generator that generates radicals using visible light and/or ultraviolet light having a wavelength shorter than 450 nm.
　光重合開始剤の例は、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジメチルケタール等のベンゾインエーテル類；アニソールメチルエーテル等の置換ベンゾインエーテル；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等の置換アセトフェノン；１－ヒドロキシシクロヘキシル－フェニルケトン等のα－ヒドロキシアルキルフェノン；２－メチル－２－ヒドロキシプロピオフェノン等の置換アルファーケトール；２－ナフタレンスルホニルクロライド等の芳香族スルホニルクロライド；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）－オキシム等の光活性オキシム；ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’，４，４’－テトラ（ｔ－ブチルパーオキシカルボニル）ベンゾフェノン等のベンゾフェノン系化合物；チオキサントン、２－クロルチオキサントン、２－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、２，４－ジエチルチオキサントン等のチオキサントン系化合物；２，４，６－トリクロロ－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－トリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ピペロニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－スチリル－ｓ－トリアジン、２－（ナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシ－ナフト－１－イル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－トリクロロメチル－（ピペロニル）－６－トリアジン、２，４－トリクロロメチル－（４’－メトキシスチリル）－６－トリアジン等のトリアジン系化合物；１，２－オクタンジオン，１－〔４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）〕、Ｏ－（アセチル）－Ｎ－（１－フェニル－２－オキソ－２－（４’－メトキシ－ナフチル）エチリデン）ヒドロキシルアミン等のオキシムエステル系化合物；ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド等のホスフィン系化合物；９，１０－フェナンスレンキノン、カンファーキノン、エチルアントラキノン等のキノン系化合物；ボレート系化合物；カルバゾール系化合物；イミダゾール系化合物；並びにチタノセン系化合物である。光硬化性組成物は、１種又は２種以上の光重合開始剤を含んでいてもよい。 Examples of 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; α-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, acrylated benzophenone, Benzophenone compounds such as 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl Thioxanthone compounds such as thioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl- 4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl )-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2 , 4-trichloromethyl-(4'-methoxystyryl)-6-triazine and other triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], Oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene) hydroxylamine; bis(2,4,6-trimethylbenzoyl)phenyl Phosphine compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone; Borate compounds; Carbazole compounds; Imidazole compounds compounds; and titanocene compounds. The photocurable composition may contain one or more photopolymerization initiators.
　光硬化性組成物における光重合開始剤の配合量は、モノマー群及びその部分重合物の合計１００重量部に対して、例えば０．０２～１０重量部であり、０．０５～５重量部であってもよい。 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 100 parts by weight of the monomer group and its partial polymer. There may be.
　光硬化性組成物は、架橋剤を含んでいてもよい。架橋剤の例は、１分子中に２以上の重合性官能基を有する多官能モノマーである。多官能モノマーは（メタ）アクリル系モノマーであってもよい。多官能モノマーの例は、１分子中に２以上のＣ＝Ｃ結合を有するモノマー、及び１分子中に１以上のＣ＝Ｃ結合と、１以上のエポキシ基、アジリジン基、オキサゾリン基、ヒドラジン基、メチロール基等の重合性官能基とを有するモノマーである。多官能モノマーは、好ましくは、１分子中に２以上のＣ＝Ｃ結合を有するモノマーである。 The photocurable composition may contain a crosslinking agent. An example of a crosslinking agent is a polyfunctional monomer having two or more polymerizable functional groups in one molecule. The polyfunctional monomer may be a (meth)acrylic monomer. Examples of polyfunctional monomers include monomers having two or more C=C bonds in one molecule, and one or more C=C bonds and one or more epoxy groups, aziridine groups, oxazoline groups, and hydrazine groups in one molecule. , a monomer having a polymerizable functional group such as a methylol group. The polyfunctional monomer is preferably a monomer having two or more C═C bonds in one molecule.
　多官能モノマーの例は、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、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、１，２－エチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジアクリレート（ＮＤＤＡ）、１，１２－ドデカンジオールジ（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、テトラメチロールメタントリ（メタ）アクリレート等の多官能アクリレート（多価アルコールと（メタ）アクリル酸とのエステル化合物等）；アリル（メタ）アクリレート、ビニル（メタ）アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ブチルジ（メタ）アクリレート、ヘキシルジ（メタ）アクリレートである。多官能モノマーは、好ましくは、多官能アクリレートであり、より好ましくは、トリメチロールプロパントリ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートである。 Examples of polyfunctional monomers are (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.); They are allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di(meth)acrylate, and hexyl di(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.
　架橋剤の配合量は、分子量や官能基数等により異なるが、モノマー群及びその部分重合物の合計１００重量部あたり、例えば５重量部以下であり、３重量部以下、２重量部以下、１重量部以下、さらには０．５重量部以下であってもよい。配合量の下限は、例えば０．０１重量部以上であり、さらには０．０５重量部以上であってもよい。 The blending amount of the crosslinking agent varies depending on the molecular weight, the number of functional groups, etc., but is, for example, 5 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less per 100 parts by weight of the monomer group and its partial polymer. The amount may be less than 1 part by weight, or even less than 0.5 part by weight. 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.
　光硬化性組成物は、上述した以外の添加剤を含んでいてもよい。添加剤の例は、連鎖移動剤、シランカップリング剤、粘度調整剤、粘着付与剤、可塑剤、軟化剤、老化防止剤、充填剤、着色剤、酸化防止剤、界面活性剤、帯電防止剤及び紫外線吸収剤である。 The photocurable composition may contain additives other than those mentioned above. Examples of additives are chain transfer agents, silane coupling agents, viscosity modifiers, tackifiers, plasticizers, softeners, anti-aging agents, fillers, colorants, antioxidants, surfactants, and antistatic agents. and an ultraviolet absorber.
　光硬化性組成物における溶剤の含有率は、例えば５重量％以下であり、４重量％以下、３重量％以下、２重量％以下、１重量％以下、さらには０．５重量％以下であってもよい。光硬化性組成物は、溶剤を実質的に含まなくてもよい。溶剤を実質的に含まないとは、添加剤等に由来する溶剤等を、例えば０．１重量％以下、好ましくは０．０５重量％以下、より好ましくは０．０１重量％以下の含有率で許容する趣旨である。 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.
　光硬化性組成物の粘度は、好ましくは、５～１００ポイズである。上記範囲の粘度を有する光硬化性組成物は、塗布層３２の形成に特に適している。 The viscosity of the photocurable composition is preferably 5 to 100 poise. A photocurable composition having a viscosity within the above range is particularly suitable for forming the coating layer 32.
　　＜第１の積層体＞
　第１の積層体３４は、例えば、基材シート３１（又ははく離ライナー３３）の上に塗布層３２を形成し、形成した塗布層３２の上にはく離ライナー３３（又は基材シート３１）を配置して形成できる。また、互いの主面が向き合うように所定の間隔に保持された基材シート３１及びはく離ライナー３３の間の空間に光硬化性組成物を流しこむように塗布して第１の積層体３４を形成してもよい。 <First laminate>
The first laminate 34 is, for example, formed by forming a coating layer 32 on a base sheet 31 (or a release liner 33), and disposing a release liner 33 (or a base sheet 31) on the formed coating layer 32. It can be formed by Further, a first laminate 34 is formed by pouring and applying the photocurable composition into the space between the base sheet 31 and the release liner 33 which are held at a predetermined interval so that their main surfaces face each other. You may.
　塗布層３２の形成には、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、ダイコート等の各種の塗布方法を適用できる。 The coating layer 32 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.
　塗布層３２の厚さは、目的とする第２の粘着シート２の厚さに応じて調整でき、例えば５～１００μｍであり、５～５０μｍ、５～２５μｍ、さらには５～２０μｍであってもよい。 The thickness of the coating layer 32 can be adjusted depending on the desired thickness of the second adhesive sheet 2, and may be, for example, 5 to 100 μm, 5 to 50 μm, 5 to 25 μm, or even 5 to 20 μm. good.
　第１の積層体３４は、基材シート３１、塗布層３２及びはく離ライナー３３以外のさらなる層を含んでいてもよい。上記さらなる層は、基材シート３１及び／又ははく離ライナー３３における塗布層３２の側とは反対側に配置されていてもよい。塗布層３２は、基材シート３１及びはく離ライナー３３と接していることが好ましい。 The first laminate 34 may include further layers other than the base sheet 31, the coating layer 32, and the release liner 33. The further layer may be arranged on the side of the base sheet 31 and/or release liner 33 opposite to the side of the coating layer 32. The coating layer 32 is preferably in contact with the base sheet 31 and the release liner 33.
　　＜光の照射＞
　第１の積層体３４に照射する光３５は、例えば、波長４５０ｎｍよりも短い波長を有する可視光又は紫外線である。光３５は、光硬化性組成物が含む光重合開始剤の吸収波長と同じ領域の波長の光を含んでいてもよい。波長２００ｎｍ以下、好ましくは波長３００ｎｍ以下の短波長光をフィルター等でカットした光３５を照射してもよく、短波長光をカットすることは、光３５による基材シート３１及び／又ははく離ライナー３３の劣化の抑制に適している。光３５の光源は、例えば紫外線照射ランプを備える光照射装置である。紫外線照射ランプの例は、紫外光ＬＥＤ、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、キセノンランプ、マイクロウエーブ励起水銀灯、ブラックライトランプ、ケミカルランプ、殺菌ランプ、低圧放電水銀ランプ、エキシマレーザーである。２以上の紫外線照射ランプが組み合わされていてもよい。 <Light irradiation>
The light 35 irradiated to the first laminate 34 is, for example, visible light or ultraviolet light having a wavelength shorter than 450 nm. The light 35 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 35 may be irradiated with short wavelength light having a wavelength of 200 nm or less, preferably 300 nm or less, which is cut by a filter or the like. Cutting the short wavelength light means that the base sheet 31 and/or release liner 33 are Suitable for suppressing deterioration of The light source of the light 35 is, for example, a light irradiation device including an ultraviolet irradiation lamp. Examples of ultraviolet irradiation lamps 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.
　光３５の照射は、連続的であっても断続的であってもよい。 Irradiation of the light 35 may be continuous or intermittent.
　光３５の照射強度は、例えば１～２０ｍＷ／ｃｍ2である。光３５の照射時間は、例えば５分～５時間である。第１の積層体３４に対する光３５の積算光量は、例えば１００～５０００ｍＪ／ｃｍ2である。 The irradiation intensity of the light 35 is, for example, 1 to 20 mW/cm 2 . The irradiation time of the light 35 is, for example, 5 minutes to 5 hours. The cumulative amount of light 35 to the first laminate 34 is, for example, 100 to 5000 mJ/cm 2 .
　光３５は、活性エネルギー線２１とは異なっていてもよい。例えば、光３５と活性エネルギー線２１とは、その種類において異なっていてもよい。光である活性エネルギー線２１と、光３５とは、その波長において異なっていてもよい。活性エネルギー線２１が紫外線であるとき、波長は２００ｎｍ以下であってもよい。 The light 35 may be different from the active energy ray 21. For example, the light 35 and the active energy ray 21 may be different in type. The active energy rays 21 and the light 35 may have different wavelengths. When the active energy rays 21 are ultraviolet rays, the wavelength may be 200 nm or less.
　第１の粘着シート１におけるモノマー群の重合率は、好ましくは９０％以上である。重合率は、９５％以上、９６％以上、９７％以上、さらには９８％以上であってもよい。 The polymerization rate of the monomer group in the first adhesive sheet 1 is preferably 90% or more. The polymerization rate may be 95% or more, 96% or more, 97% or more, or even 98% or more.
　第１の粘着シート１のゲル分率は、例えば５０％以上であり、７５％以上、８０％以上、さらには８５％以上であってもよい。 The gel fraction of the first adhesive sheet 1 is, for example, 50% or more, and may be 75% or more, 80% or more, or even 85% or more.
　第１の粘着シート１に対するはく離ライナー３３の剥離力は、第１の粘着シート１に対する基材シート３１の剥離力に比べて小さくてもよい。 The peeling force of the release liner 33 to the first adhesive sheet 1 may be smaller than the peeling force of the base sheet 31 to the first adhesive sheet 1.
　（第２の粘着シート）
　第２の粘着シート２は、光硬化型であってもよい。 (Second adhesive sheet)
The second adhesive sheet 2 may be of a photocurable type.
　第２の粘着シート２の厚さは、例えば２～７０μｍであり、２～５０μｍ、５～４０μｍ、１０～３０μｍ、１０～２５μｍ、さらには１０～２０μｍであってもよい。 The thickness of the second adhesive sheet 2 is, for example, 2 to 70 μm, and may be 2 to 50 μm, 5 to 40 μm, 10 to 30 μm, 10 to 25 μm, or even 10 to 20 μm.
　第２の粘着シート２のゲル分率は、例えば５０％以上であり、７５％以上、８０％以上、さらには８５％以上であってもよい。 The gel fraction of the second adhesive sheet 2 is, for example, 50% or more, and may be 75% or more, 80% or more, or even 85% or more.
　第２の粘着シート２は、例えば、光学フィルムを含む光学積層体に使用できる。換言すれば、第２の粘着シート２は光学積層体用であってもよい。光学積層体は、粘着シート付き光学フィルムであってもよい。第２の粘着シート２は、改質処理面１４が光学フィルム側となるように使用してもよく、光学フィルムと接するように使用してもよい。ただし、第２の粘着シート２の用途及び使用方法は上記例に限定されない。 The second adhesive sheet 2 can be used, for example, in an optical laminate including an optical film. In other words, the second adhesive sheet 2 may be used for optical laminates. The optical laminate may be an optical film with an adhesive sheet. The second adhesive sheet 2 may be used so that the modified surface 14 is on the optical film side, or may be used so that it is in contact with the optical film. However, the purpose and method of using the second adhesive sheet 2 are not limited to the above example.
［粘着シート付き光学フィルムの製造方法］
　図５を参照して、本発明の粘着シート付き光学フィルムの製造方法の一例を説明する。この例では、基材シート１１上に配置された第２の粘着シート２の改質処理面１４に光学フィルム３を配置して、粘着シート付き光学フィルム５１を形成する。粘着シート付き光学フィルム５１は、基材シート１１、第２の粘着シート２及び光学フィルム３をこの順で含む。粘着シート付き光学フィルム５１は、そのまま又は基材シート１１を剥離した後に、例えば、第２の粘着シート２と光学フィルム３とを備える光学積層体として画像表示装置等に使用できる。光学積層体は、第２の粘着シート２を介して対象物（例えば画像形成パネル）に貼り合わせてもよい。ただし、粘着シート付き光学フィルム５１の用途は、上記例に限定されない。粘着シート付き光学フィルム５１から基材シート１１を剥離して形成された露出面３７には、光学フィルム等のさらなる部材を配置してもよく、一例として、光学フィルム３Ａ、第２の粘着シート２及び光学フィルム３Ｂをこの順で含む粘着シート付き光学フィルム５２を形成できる（図６参照）。光学フィルム３Ａ，３Ｂは、互いに同一であっても異なっていてもよい。 [Method for manufacturing optical film with adhesive sheet]
An example of the method for producing an optical film with a pressure-sensitive adhesive sheet of the present invention will be described with reference to FIG. In this example, the optical film 3 is placed on the modified surface 14 of the second adhesive sheet 2 placed on the base sheet 11 to form the optical film 51 with the adhesive sheet. The optical film with adhesive sheet 51 includes a base sheet 11, a second adhesive sheet 2, and an optical film 3 in this order. The adhesive sheet-attached optical film 51 can be used as it is or after peeling off the base sheet 11, for example, as an optical laminate including the second adhesive sheet 2 and the optical film 3 in an image display device or the like. The optical laminate may be bonded to an object (for example, an image forming panel) via the second adhesive sheet 2. However, the use of the adhesive sheet-attached optical film 51 is not limited to the above example. Further members such as an optical film may be arranged on the exposed surface 37 formed by peeling the base sheet 11 from the optical film 51 with an adhesive sheet. For example, an optical film 3A, a second adhesive sheet 2 An optical film 52 with a pressure-sensitive adhesive sheet including the optical film 3B and the optical film 3B in this order can be formed (see FIG. 6). The optical films 3A and 3B may be the same or different from each other.
　改質処理面１４及び露出面３７への光学フィルム３の配置は、直接的であっても間接的であってもよい。換言すれば、光学フィルム３は、改質処理面１４又は露出面３７に接するように配置されても、改質処理面１４又は露出面３７との間に他の層を挟んだ状態で配置されてもよい。 The optical film 3 may be placed directly or indirectly on the modified surface 14 and the exposed surface 37. In other words, even if the optical film 3 is placed in contact with the modified surface 14 or the exposed surface 37, it is not placed with another layer sandwiched between the modified surface 14 or the exposed surface 37. You can.
　光学フィルム３における第２の粘着シート２と接する面は、活性エネルギー線による表面改質処理がなされた面であってもよい。この態様は、第２の粘着シート２と光学フィルム３との間の投錨力の向上に特に適している。光学フィルム３に対する表面改質処理の例は、好ましい例を含め、第１の粘着シート１に対する表面改質処理の例と同じである。 The surface of the optical film 3 that comes into contact with the second pressure-sensitive adhesive sheet 2 may be a surface that has been subjected to surface modification treatment using active energy rays. This aspect is particularly suitable for improving the anchoring force between the second adhesive sheet 2 and the optical film 3. Examples of the surface modification treatment for the optical film 3 are the same as those for the first pressure-sensitive adhesive sheet 1, including preferred examples.
　図７を参照して、本発明の粘着シート付き光学フィルムの製造方法の別の一例を説明する。この例では、図４の方法により形成された第２の粘着シート２の改質処理面１４に長尺状の光学フィルム３を配置して、長尺状の粘着シート付き光学フィルム５１を形成する。光学フィルム３は、巻回体４６から繰り出されて改質処理面１４に配置される。以上の工程は、基材シート３１（１１）を搬送しながら実施される。図７に示すように、第２の粘着シート２の形成と粘着シート付き光学フィルム５１の形成とを連続して実施してもよい。また、第１の粘着シート１の形成と、第２の粘着シート２の形成と、粘着シート付き光学フィルム５１の形成とを連続して実施してもよい。図７の方法は、粘着シート付き光学フィルム５１の量産に特に適している。 Another example of the method for manufacturing the optical film with adhesive sheet of the present invention will be described with reference to FIG. 7. In this example, a long optical film 3 is placed on the modified surface 14 of the second adhesive sheet 2 formed by the method shown in FIG. 4 to form a long optical film 51 with adhesive sheet. . The optical film 3 is unwound from the roll 46 and placed on the modification treatment surface 14 . The above steps are performed while conveying the base sheet 31 (11). As shown in FIG. 7, the formation of the second adhesive sheet 2 and the formation of the adhesive sheet-attached optical film 51 may be performed continuously. Further, the formation of the first adhesive sheet 1, the formation of the second adhesive sheet 2, and the formation of the adhesive sheet-attached optical film 51 may be performed continuously. The method shown in FIG. 7 is particularly suitable for mass production of the optical film 51 with adhesive sheet.
　光学フィルム３は、例えば、偏光フィルム及び位相差フィルムからなる群から選ばれる少なくとも１つを含むフィルムである。光学フィルム３は、偏光フィルム及び／又は位相差フィルムを含む積層フィルムであってもよい。光学フィルム３は、ガラス製のフィルムを含んでいてもよい。ただし、光学フィルム３は上記例に限定されない。 The optical film 3 is, for example, a film containing at least one selected from the group consisting of a polarizing film and a retardation film. The optical film 3 may be a laminated film including a polarizing film and/or a retardation film. The optical film 3 may include a glass film. However, the optical film 3 is not limited to the above example.
　偏光フィルムは、偏光子を含む。偏光フィルムは、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。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。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。 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.
　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, 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.
　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, and may be, for example, 80 μm or less, 50 μm or less, 30 μm or less, 25 μm or less, or even 20 μm or less. The lower limit of the thickness of the polarizer is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, 10 μm or more, or even 15 μm or more. A thin polarizer (for example, 20 μm 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.
　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。偏光フィルムが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 the material for the protective film, for example, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc. is used. Specific examples of such 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. When the polarizing film 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 bonded to one main surface of a polarizer via an adhesive, and a protective film made of a thermosetting resin or 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.
　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。 The thickness of the protective film can be determined as appropriate, but is generally about 10 to 200 μm from the viewpoint of strength, workability such as handleability, thin film property, etc.
　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。 A polarizer and a protective film are usually attached to each other via a water-based adhesive or the like. Examples of water-based adhesives include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latex, water-based polyurethanes, and water-based polyesters. Examples of 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.
　偏光フィルムでは、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 film, 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.
　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 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. .
　偏光フィルムは、円偏光フィルムであってもよい。 The polarizing film may be a circularly polarizing film.
　位相差フィルムとしては、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, 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.
　位相差フィルムには、反射防止用位相差フィルム（特開２０１２－１３３３０３号公報〔０２２１〕、〔０２２２〕、〔０２２８〕参照）、視野角補償用位相差フィルム（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 includes a retardation film for antireflection (see JP-A-2012-133303 [0221], [0222], and [0228]) and a retardation film for viewing angle compensation (see JP-A 2012-133303 [0221], [0222], and [0228]). 0225], [0226]), an obliquely oriented retardation film for viewing angle compensation (see JP-A-2012-133303 [0227]), and the like.
　位相差フィルムの具体的な構成、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 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.
　位相差フィルムの厚さは、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 is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 1 to 9 μm, particularly preferably 3 to 8 μm.
　位相差フィルムは、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 may include, for example, a quarter-wave plate and/or a half-wave plate in which a liquid crystal material is oriented and fixed.
　粘着シート付き光学フィルム５１，５２において、光学フィルム３に対する第２の粘着シート２の投錨力は、１０Ｎ／２５ｍｍ以上であってもよく、１２Ｎ／２５ｍｍ以上であってもよい。換言すれば、光学フィルム３に対する第２の粘着シート２の投錨力が１０Ｎ／２５ｍｍ以上、さらには１２Ｎ／２５ｍｍ以上である粘着シート付き光学フィルム５１，５２を形成してもよい。投錨力は、１３Ｎ／２５ｍｍ以上、１４Ｎ／２５ｍｍ以上、１５Ｎ／２５ｍｍ以上、１６Ｎ／２５ｍｍ以上、さらには１７Ｎ／２５ｍｍ以上であってもよい。投錨力の上限は、例えば５０Ｎ／２５ｍｍ以下であり、３０Ｎ／２５ｍｍ以下であってもよい。なお、偏光子の保護フィルム等の光学フィルム３において（メタ）アクリル樹脂を主成分として含むフィルム（以下、「アクリルフィルム」）が使用されることがある。アクリルフィルムと粘着シートとの接着強度は、一般に小さい傾向がある。この観点から、第２の投錨力が上記範囲にある第２の粘着シート２は、アクリルフィルムである光学フィルム３との接合に特に適している。 In the optical films 51 and 52 with adhesive sheets, the anchoring force of the second adhesive sheet 2 to the optical film 3 may be 10 N/25 mm or more, or 12 N/25 mm or more. In other words, optical films 51 and 52 with adhesive sheets may be formed in which the anchoring force of the second adhesive sheet 2 with respect to the optical film 3 is 10 N/25 mm or more, further 12 N/25 mm or more. The anchoring force may be 13 N/25 mm or more, 14 N/25 mm or more, 15 N/25 mm or more, 16 N/25 mm or more, or even 17 N/25 mm or more. The upper limit of the anchoring force is, for example, 50 N/25 mm or less, and may be 30 N/25 mm or less. Note that a film containing (meth)acrylic resin as a main component (hereinafter referred to as "acrylic film") may be used as the optical film 3 such as a protective film for a polarizer. The adhesive strength between an acrylic film and an adhesive sheet generally tends to be low. From this point of view, the second adhesive sheet 2 having a second anchoring force within the above range is particularly suitable for bonding to the optical film 3 which is an acrylic film.
　光学フィルム３に対する第２の粘着シート２の投錨力は、次の方法により測定できる。光学フィルム３と第２の粘着シート２との積層体を幅２５ｍｍ×長さ１５０ｍｍに切り出して試験片とする。光学フィルム３と第２の粘着シート２とが接している限り、積層体は他の層を含んでいてもよい。次に、両面テープを介して、試験片が備える光学フィルム３の表面全体をステンレス製試験板に重ね合わせ、２ｋｇのローラを１往復させて、これらを圧着させる。次に、試験片が備える第２の粘着シート２を評価用シートに重ね合わせ、２ｋｇのローラを１往復させて、これらを圧着させる。評価用シートは、幅３０ｍｍ×長さ１５０ｍｍのサイズを有し、試験中に第２の粘着シート２から剥離しないものである限り特に限定されない。評価用シートとしては、例えば、ＩＴＯフィルム（１２５テトライトＯＥＳ（尾池工業社製）等）を用いることができる。次に、市販の引張試験機を用いて、評価用シートを把持した状態で、剥離角度１８０°、引張速度３００ｍｍ／分で第２の粘着シート２を光学フィルム３から引きはがした際の剥離力の平均値を光学フィルム３に対する第２の粘着シート２の投錨力として特定する。上記の試験は、２３℃±５℃の雰囲気で行う。 The anchoring force of the second adhesive sheet 2 with respect to the optical film 3 can be measured by the following method. The laminate of the optical film 3 and the second pressure-sensitive adhesive sheet 2 is cut into a piece having a width of 25 mm and a length of 150 mm to prepare a test piece. As long as the optical film 3 and the second adhesive sheet 2 are in contact with each other, the laminate may include other layers. Next, the entire surface of the optical film 3 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. Next, the second adhesive sheet 2 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 second adhesive sheet 2 during the test. As the evaluation sheet, for example, an ITO film (125 Tetraite OES (manufactured by Oike Kogyo Co., Ltd.), etc.) can be used. Next, using a commercially available tensile tester, the second adhesive sheet 2 was peeled off from the optical film 3 at a peeling angle of 180° and a pulling speed of 300 mm/min while holding the evaluation sheet. The average value of the force is specified as the anchoring force of the second adhesive sheet 2 with respect to the optical film 3. The above test is conducted in an atmosphere of 23°C±5°C.
　粘着シート付き光学フィルム５１，５２を用いて、画像表示装置を形成してもよい。画像表示装置は、例えば、粘着シート付き光学フィルム５１，５２と画像表示パネルとを接合して形成できる。接合は、第２の粘着シート２により行ってもよい。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、画像表示装置は上記例に限定されない。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る。 An image display device may be formed using the optical films 51 and 52 with adhesive sheets. The image display device can be formed by, for example, joining optical films 51 and 52 with adhesive sheets and an image display panel. The bonding may be performed using the second adhesive sheet 2. 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. The image display device can be used for household appliances, in-vehicle applications, public information displays (PID), and the like.
　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。 Hereinafter, the present invention will be explained in more detail with reference to Examples. The invention is not limited to the examples shown below.
［モノマーシロップの作製］
　（合成例１）
　ｎ－ブチルアクリレート（ＢＡ）９９重量部、及び４－ヒドロキシブチルアクリレート（ＨＢＡ）１重量部と、光重合開始剤としてＯｍｎｉｒａｄ１８４（１－ヒドロキシシクロヘキシル－フェニルケトン、ＩＧＭ　Ｒｅｓｉｎｓ製）を０．０５重量部、Ｏｍｎｉｒａｄ６５１（２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、ＩＧＭ　Ｒｅｓｉｎｓ製）を０．０５重量部とを４つロフラスコに投入し、窒素雰囲気下で紫外線を照射することによって、部分的に光重合したモノマーシロップＡ１を得た。紫外線の照射は、フラスコ内の液体の粘度（計測条件：ＢＨ粘度計Ｎｏ．５ローター、１０ｒｐｍ、測定温度３０℃）が約２０Ｐａ・ｓになるまで実施した。 [Preparation of monomer syrup]
(Synthesis example 1)
99 parts by weight of n-butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate (HBA), and 0.05 parts by weight of Omnirad 184 (1-hydroxycyclohexyl-phenyl ketone, manufactured by IGM Resins) as a photopolymerization initiator. , 0.05 parts by weight of Omnirad 651 (2,2-dimethoxy-1,2-diphenylethane-1-one, manufactured by IGM Resins) were placed in a flask and irradiated with ultraviolet rays under a nitrogen atmosphere. A partially photopolymerized monomer syrup A1 was obtained. The ultraviolet irradiation was carried out until the viscosity of the liquid in the flask (measurement conditions: BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30° C.) reached approximately 20 Pa·s.
　（合成例２）
　使用するモノマーを表１のように変更したことを除き、モノマーシロップＡ１と同様にして、モノマーシロップＡ２を調製した。なお、表１中の「ＡＡ」は、アクリル酸である。 (Synthesis example 2)
Monomer syrup A2 was prepared in the same manner as monomer syrup A1, except that the monomers used were changed as shown in Table 1. In addition, "AA" in Table 1 is acrylic acid.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［光硬化性組成物の作製］
　以下の表２に示す組成となるように、モノマーシロップ及び架橋剤を混合して、光硬化性組成物Ｃ１，Ｃ２を得た。なお、表２中の「ＮＤＤＡ」は、１，９－ノナンジオールジアクリレートである。 [Preparation of photocurable composition]
Monomer syrup and a crosslinking agent were mixed to obtain photocurable compositions C1 and C2 having the compositions shown in Table 2 below. Note that "NDDA" in Table 2 is 1,9-nonanediol diacrylate.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［第１の粘着シートの作製］
　（製造例１：はく離ライナーＡの作製）
　付加反応硬化型シリコーン（ヘキセニル基含有ポリオルガノシロキサンを含むＬＴＣ７６１、３０重量％トルエン溶液、東レ・ダウコーニング製）３０重量部、剥離コントロール剤（未反応性シリコーン樹脂を含むＢＹ２４－８５６、東レ・ダウコーニング製）０．９重量部、及び硬化触媒（白金触媒を含むＳＲＸ２１２、東レ・ダウコーニング製）２重量部、及び希釈溶媒としてトルエン／ヘキサン混合溶媒（体積比１：１）を混合して、シリコーン系離型剤組成物を得た。離型剤組成物におけるシリコーン固形分の濃度は、１．０重量％であった。次に、ライナー基材（ポリエステルフィルムであるルミラーＸＤ５００Ｐ、厚さ７５μｍ）の片面に離型剤組成物をワイヤーバーにより塗布し、１３０℃で１分間加熱して、離型層（厚さ６０ｎｍ）を片面に備えるはく離ライナーＡを作製した。 [Preparation of first adhesive sheet]
(Production Example 1: Production of release liner A)
Addition reaction curing silicone (LTC761 containing hexenyl group-containing polyorganosiloxane, 30% by weight toluene solution, manufactured by Toray Dow Corning), 30 parts by weight, release control agent (BY24-856 containing unreactive silicone resin, Toray Dow) (manufactured by Corning), 2 parts by weight of a curing catalyst (SRX212 containing platinum catalyst, manufactured by Dow Corning Toray), and a mixed solvent of toluene/hexane (volume ratio 1:1) as a diluting solvent. A silicone mold release agent composition was obtained. The concentration of silicone solids in the mold release agent composition was 1.0% by weight. Next, a mold release agent composition was applied to one side of the liner base material (Lumirror Release liner A was prepared, which had one side of the release liner A.
　（製造例２：はく離ライナーＢの作製）
　ライナー基材に対する離型剤組成物の塗布厚みを変更した以外は製造例１と同様にして、離型層（厚さ１２０ｎｍ）を片面に備えるはく離ライナーＢを作製した。 (Production Example 2: Production of release liner B)
A release liner B having a release layer (thickness: 120 nm) on one side was produced in the same manner as Production Example 1 except that the coating thickness of the release agent composition on the liner base material was changed.
　（製造例３：第１の粘着シートＡの作製）
　光硬化性組成物Ｃ１を製造例１で作製したはく離ライナーＡ及び製造例２で作製したはく離ライナーＢによって挟持するようにアプリケーターにより塗布して、はく離ライナーＡ、塗布層及びはく離ライナーＢからなる第１の積層体を得た。はく離ライナーＡ，Ｂは、いずれも、離型層が塗布層に接するように使用した。次に、第１の積層体におけるはく離ライナーＡの側から、照射強度２．５ｍＷ／ｃｍ2、照射時間６４０秒の条件で紫外線（Ｂｌａｃｋ　ｌｉｇｈｔ光源）を照射し、塗布層を光硬化させて、はく離ライナーＡ、第１の粘着シートＡ（厚さ２０μｍ）及びはく離ライナーＢにより構成される第２の積層体を形成した。形成した第１の粘着シートＡにおける重合率は９８．１％であった。形成した第１の粘着シートＡにおける残存モノマーの量は、１８２３０ｐｐｍであった。残存モノマーの量は、ＧＣ分析により評価した。以降の第１の粘着シート及び第２の粘着シートにおける残存モノマーの量も同様に評価した。ＧＣ分析に用いた装置及び測定条件を以下に示す。
　・使用装置：ＧＣ７８９０Ａ（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ製）
　・カラム：ＨＰ－１（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ製）
　・検出器：水素炎イオン化検出器（ＦＩＤ）
　・注入口温度：２５０℃
　・測定温度条件：以下の（１）から（４）を順に実施。（１）０℃で３分保持、（２）昇温速度１０℃／分で昇温、（３）１２０℃に到達後、昇温速度２０℃／分で昇温、（４）３００℃で保持
　・試料調整方法：試料（粘着シート）０．０５ｇをスクリュー瓶に採取し、酢酸エチル２．５ｍＬを加えて一晩振とうした。得られた溶液を０．４５μｍメンブレンフィルターで濾過後、濾過液１μＬをＧＣに注入して分析した。 (Production Example 3: Production of first adhesive sheet A)
The photocurable composition C1 is applied using an applicator so as to be sandwiched between the release liner A prepared in Production Example 1 and the release liner B prepared in Production Example 2, thereby forming a third layer consisting of the release liner A, the coating layer, and the release liner B. A laminate of No. 1 was obtained. Both release liners A and B were used so that the release layer was in contact with the coating layer. Next, from the side of the release liner A in the first laminate, ultraviolet rays (black light light source) are irradiated with an irradiation intensity of 2.5 mW/cm 2 and an irradiation time of 640 seconds to photocure the coating layer, A second laminate consisting of release liner A, first adhesive sheet A (thickness: 20 μm), and release liner B was formed. The polymerization rate of the first pressure-sensitive adhesive sheet A thus formed was 98.1%. The amount of residual monomer in the first pressure-sensitive adhesive sheet A thus formed was 18,230 ppm. The amount of residual monomer was evaluated by GC analysis. The amount of residual monomer in the subsequent first adhesive sheet and second adhesive sheet was also evaluated in the same manner. The apparatus and measurement conditions used for GC analysis are shown below.
・Equipment used: GC7890A (manufactured by Agilent Technologies)
・Column: HP-1 (manufactured by Agilent Technologies)
・Detector: Flame ionization detector (FID)
・Inlet temperature: 250℃
・Measurement temperature conditions: Perform the following (1) to (4) in order. (1) Hold at 0℃ for 3 minutes, (2) Raise the temperature at a rate of 10℃/min, (3) After reaching 120℃, increase the temperature at a rate of 20℃/min, (4) At 300℃. Retention - Sample preparation method: 0.05 g of the sample (adhesive sheet) was collected in a screw bottle, 2.5 mL of ethyl acetate was added, and the mixture was shaken overnight. After filtering the obtained solution with a 0.45 μm membrane filter, 1 μL of the filtrate was injected into GC for analysis.
　（製造例４：第１の粘着シートＢの作製）
　光硬化性組成物Ｃ１の代わりに光硬化性組成物Ｃ２を用いるとともに、紫外線の照射時間を４８０秒に変更した以外は、製造例２と同様にして、はく離ライナーＡ、第１の粘着シートＢ（厚さ２０μｍ）及びはく離ライナーＢにより構成される第２の積層体を形成した。形成した第１の粘着シートＢの重合率は９７．９％であった。また、第１の粘着シートＢにおける残存モノマーの量は、１９３２０ｐｐｍであった。 (Production Example 4: Production of first adhesive sheet B)
Release liner A and first adhesive sheet B were prepared in the same manner as in Production Example 2, except that photocurable composition C2 was used instead of photocurable composition C1 and the ultraviolet irradiation time was changed to 480 seconds. (thickness: 20 μm) and release liner B was formed. The polymerization rate of the first pressure-sensitive adhesive sheet B thus formed was 97.9%. Further, the amount of residual monomer in the first adhesive sheet B was 19,320 ppm.
　（製造例５：第１の粘着シートＣの作製）
　紫外線の照射時間を２０００秒に変更した以外は製造例２と同様にして、はく離ライナーＡ、第１の粘着シートＣ（厚さ２０μｍ）及びはく離ライナーＢにより構成される第２の積層体を形成した。形成した第１の粘着シートＣの重合率は９７．７％であった。また、第１の粘着シートＣにおける残存モノマーの量は、１５００ｐｐｍであった。 (Production Example 5: Production of first adhesive sheet C)
A second laminate composed of release liner A, first adhesive sheet C (thickness 20 μm), and release liner B was formed in the same manner as in Production Example 2 except that the ultraviolet irradiation time was changed to 2000 seconds. did. The polymerization rate of the first adhesive sheet C thus formed was 97.7%. Further, the amount of residual monomer in the first pressure-sensitive adhesive sheet C was 1500 ppm.
［第２の粘着シートの作製］
　（実施例１）
　製造例３で作製した第２の積層体からはく離ライナーＢを剥離し、第１の粘着シートＡの片面を露出させた。次に、第１の粘着シートＡの露出面に対して、酸素濃度０．１体積％の雰囲気（酸素－窒素混合雰囲気、１気圧）下、放電量１４．６ｋＪ／ｍ2でコロナ処理を行って、第２の粘着シートを得た。得られた第２の粘着シートにおける残存モノマーの量は２９９０ｐｐｍであった。 [Preparation of second adhesive sheet]
(Example 1)
The release liner B was peeled off from the second laminate produced in Production Example 3, and one side of the first pressure-sensitive adhesive sheet A was exposed. Next, corona treatment was performed on the exposed surface of the first adhesive sheet A at a discharge rate of 14.6 kJ/m 2 in an atmosphere with an oxygen concentration of 0.1% by volume (oxygen-nitrogen mixed atmosphere, 1 atm). A second adhesive sheet was obtained. The amount of residual monomer in the obtained second pressure-sensitive adhesive sheet was 2990 ppm.
　（実施例２～９）
　以下の表３に示す第１の粘着シートに対して、表３に示す条件でコロナ処理を実施した以外は実施例１と同様にして、実施例２～９の第２の粘着シートを得た。なお、酸素濃度１．０体積％、０．１体積％及び０．０１体積％の処理雰囲気は、酸素－窒素混合雰囲気とした。酸素濃度２０．９体積％の処理雰囲気は、大気雰囲気とした。なお、処理雰囲気の圧力は全て１気圧であった。 (Examples 2 to 9)
Second adhesive sheets of Examples 2 to 9 were obtained in the same manner as in Example 1 except that the first adhesive sheets shown in Table 3 below were subjected to corona treatment under the conditions shown in Table 3. . Note that the processing atmosphere with oxygen concentrations of 1.0% by volume, 0.1% by volume, and 0.01% by volume was an oxygen-nitrogen mixed atmosphere. The processing atmosphere with an oxygen concentration of 20.9% by volume was air. Note that the pressure of the processing atmosphere was 1 atm in all cases.
　（比較例１）
　製造例２で作製した第２の積層体からはく離ライナーＢを剥離して得た第１の粘着シートＡに対してコロナ処理を実施することなく、そのまま比較例１の粘着シートａとした。 (Comparative example 1)
The first adhesive sheet A obtained by peeling off the release liner B from the second laminate produced in Production Example 2 was used as the adhesive sheet a of Comparative Example 1 without performing corona treatment.
　（比較例２）
　製造例４で作製した第２の積層体からはく離ライナーＢを剥離して得た第１の粘着シートＣに対してコロナ処理を実施することなく、そのまま比較例２の粘着シートｂとした。 (Comparative example 2)
The first adhesive sheet C obtained by peeling off the release liner B from the second laminate produced in Production Example 4 was used as the adhesive sheet b of Comparative Example 2 without performing corona treatment.
　（比較例３）
　製造例３で作製した第２の積層体からはく離ライナーＢを剥離して得た第１の粘着シートＢに対してコロナ処理を実施することなく、そのまま比較例３の粘着シートｃとした。 (Comparative example 3)
The first adhesive sheet B obtained by peeling off the release liner B from the second laminate produced in Production Example 3 was used as the adhesive sheet c of Comparative Example 3 without performing corona treatment.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
［投錨力］
　実施例で作製した第２の粘着シートのコロナ処理面、及び比較例の粘着シートａ～ｃの露出面に偏光フィルムＤ１を配置して、光学積層体を作製した。偏光フィルムＤ１は、変性メタクリル樹脂からなる透明保護フィルム側の表面が粘着シートに接するように配置した。次に、作製した光学積層体について、上述の方法によって、粘着シートと偏光フィルムとの投錨力を測定した。両面テープには、日東電工社製の商品名「Ｎｏ．５３１」を用いた。ステンレス製試験板には、ＳＵＳ３０４の板（幅４０ｍｍ×長さ１２０ｍｍ）を用いた。評価用シートには、ＩＴＯフィルム（１２５テトライトＯＥＳ、尾池工業製）を用いた。引張試験機には、オートグラフＳＨＩＭＡＺＵ　ＡＧ-Ｉ　１０ＫＮ（島津製作所製）を用いた。 [Anchoring power]
An optical laminate was prepared by disposing a polarizing film D1 on the corona-treated surface of the second pressure-sensitive adhesive sheet produced in the example and on the exposed surface of the pressure-sensitive adhesive sheets a to c of the comparative examples. The polarizing film D1 was arranged so that the surface on the side of the transparent protective film made of modified methacrylic resin was in contact with the adhesive sheet. Next, for the produced optical laminate, the anchoring force between the pressure-sensitive adhesive sheet and the polarizing film was measured by the method described above. As the double-sided tape, Nitto Denko Corporation's product name "No. 531" was used. A SUS304 plate (width 40 mm x length 120 mm) was used as the stainless steel test plate. An ITO film (125 Tetraite OES, manufactured by Oike Kogyo) was used as the evaluation sheet. Autograph SHIMAZU AG-I 10KN (manufactured by Shimadzu Corporation) was used as a tensile tester.
　投錨力の評価に使用した偏光フィルムＤ１は、以下のように作製した。厚さ８０μｍの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％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％でホウ酸を含み、かつ濃度１０％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％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２８μｍ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（コニカミノルタ製、商品名「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フィルムＤ２を作製した。さらに、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フィルムＤ２の表面に対して、大気雰囲気下、放電量６３Ｗ／（ｍ2・分）でコロナ処理を行った。 Polarizing film D1 used for evaluation of anchoring force was produced as follows. A polyvinyl alcohol film having a thickness of 80 μm was stretched up to 3 times between rolls having different speed ratios while being dyed for 1 minute in an iodine solution having a concentration of 0.3% at a temperature of 30° C. Next, the film was stretched while being immersed for 0.5 minutes in an aqueous solution containing boric acid at a concentration of 4% and potassium iodide at a concentration of 10% at a temperature of 60°C until the total stretching ratio became 6 times. Next, a polarizer with a thickness of 28 μm 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. 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 using a polyvinyl alcohol adhesive. Furthermore, on the other side of the polarizer, a 47 μm thick transparent protective film made of a triacetyl cellulose film (manufactured by Konica Minolta, product name "KC4UY") with a hard coat layer (HC) is attached using a polyvinyl alcohol adhesive. Combined. Polarizing film D2 was produced by heating and drying for 5 minutes in an oven set at 70°C. Furthermore, the surface of the polarizing film D2 on the side of the transparent protective film made of a modified acrylic polymer was subjected to corona treatment at a discharge amount of 63 W/(m 2 ·min) in the air atmosphere.
［臭気］
　実施例で作製した第２の粘着シート及び比較例の各粘着シートに対する臭気の評価を以下のように実施した。 [Odor]
The second pressure-sensitive adhesive sheet produced in the example and each pressure-sensitive adhesive sheet of the comparative example were evaluated for odor as follows.
　評価対象の粘着シート４ｃｍ2をアルミカップに入れ、加熱装置（ＭＡＲＫＥＳ製、Ｔ－ＣＴＥ２５０）を用いて窒素ガス気流下にて４０℃で１０分加熱した。加熱により発生したガスは、全て吸着剤に通して捕集した。ガスを捕集した後の吸着剤をＧＣ／ＭＳ装置に直結した加熱脱着装置（ＭＡＲＫＥＳ製、ＴＤ－１００）により加熱し、捕集した成分を遊離させた。遊離させた成分をＧＣ／ＭＳのカラムに導入し、カラムにより分離したガスを嗅いだときに臭いを感じるかについての官能試験（においかぎＧＣ／ＭＳ試験）を３人のパネリストにより実施した。臭いを感じると判定したパネリストが３人の場合をＣ、２人の場合をＢ、１人の場合をＡ、０人の場合をＡＡとした。また、臭いを感じたときに臭いがピークとなる保持時間をパネリストにより特定し、当該ピークをもたらした成分をＧＣ／ＭＳ解析により特定した。ピークをもたらした成分は、臭気の評価がＡ、Ｂ又はＣとなった全ての粘着シートにおいてｎ－ブチルアクリレート（ＢＡ）であった。 4 cm 2 of the adhesive sheet to be evaluated was placed in an aluminum cup and heated at 40° C. for 10 minutes under a nitrogen gas stream using a heating device (manufactured by MARKES, T-CTE250). All gases generated by heating were collected through an adsorbent. After capturing the gas, the adsorbent was heated using a thermal desorption device (manufactured by MARKES, TD-100) directly connected to a GC/MS device to liberate the captured components. The liberated components were introduced into a GC/MS column, and a sensory test (smell GC/MS test) was conducted by three panelists to determine whether they could smell the gas separated by the column. The case where 3 panelists judged that they could smell the odor was rated C, the case where 2 panelists judged it to be B, the case where 1 panelist judged it as A, and the case where 0 panelists judged it to be AA. In addition, the panelists identified the retention time at which the odor reached its peak when the odor was perceived, and the component that caused the peak was identified by GC/MS analysis. The component that caused the peak was n-butyl acrylate (BA) in all pressure-sensitive adhesive sheets with odor ratings of A, B, or C.
［生産性］
　実施例で作製した第２の粘着シート及び比較例の各粘着シートの生産性を以下のように判定した。
　Ａ：残存モノマー量が１００００ｐｐｍ以下に達するのに要した時間Ｔが４８０秒以下である場合をＡとした。
　Ｂ：残存モノマー量が１００００ｐｐｍ以下に達するのに要した時間Ｔが４８０秒を超え９６０秒以下である場合をＢとした。
　Ｃ：残存モノマー量が１００００ｐｐｍ以下に達するのに要した時間Ｔが９６０秒を超える場合、又は残存モノマー量が１００００ｐｐｍを超えている場合をＣとした。
　なお、時間Ｔは、コロナ処理を実施して得た第２の粘着シートについては当該処理によって残存モノマー量が１００００ｐｐｍ以下に達するまでに要した処理時間であり、コロナ処理を実施することなく得た比較例２の粘着シートについては、第１の積層体から第２の積層体を形成する際に残存モノマー量が１００００ｐｐｍ以下に達するのに要した紫外線の照射時間である。 [Productivity]
The productivity of the second pressure-sensitive adhesive sheet produced in the example and each pressure-sensitive adhesive sheet of the comparative example was determined as follows.
A: A case where the time T required for the amount of residual monomer to reach 10,000 ppm or less was 480 seconds or less.
B: A case where the time T required for the amount of residual monomer to reach 10,000 ppm or less was more than 480 seconds and less than 960 seconds was designated as B.
C: Cases where the time T required for the amount of residual monomer to reach 10,000 ppm or less exceeded 960 seconds, or cases where the amount of residual monomer exceeded 10,000 ppm were designated as C.
Note that the time T is the treatment time required for the second adhesive sheet obtained by performing corona treatment until the amount of residual monomer reaches 10,000 ppm or less by the treatment, and the time T is the treatment time required for the second adhesive sheet obtained without performing corona treatment. For the adhesive sheet of Comparative Example 2, this is the ultraviolet irradiation time required for the amount of residual monomer to reach 10,000 ppm or less when forming the second laminate from the first laminate.
　評価結果を、コロナ処理の条件及び第２の粘着シートにおける残存モノマー量と共に、以下の表４に示す。 The evaluation results are shown in Table 4 below, along with the corona treatment conditions and the amount of residual monomer in the second pressure-sensitive adhesive sheet.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明の製造方法により得た粘着シートは、例えば、光学積層体や画像表示装置に使用できる。
  The pressure-sensitive adhesive sheet obtained by the production method of the present invention can be used, for example, in optical laminates and image display devices.

Claims (16)

  1. 　モノマーの重合体と残存モノマーとを含む第１の粘着シートに対して活性エネルギー線を用いた表面改質処理を実施することにより、前記第１の粘着シートに比べて前記残存モノマーの量を低減させた第２の粘着シートを得ることを含む、粘着シートの製造方法。 By performing surface modification treatment using active energy rays on a first adhesive sheet containing a monomer polymer and residual monomer, the amount of the residual monomer is reduced compared to the first adhesive sheet. A method for producing a pressure-sensitive adhesive sheet, the method comprising: obtaining a second pressure-sensitive adhesive sheet.
  2. 　前記第２の粘着シートにおける前記残存モノマーの量が５０００ｐｐｍ（重量基準）以下である、請求項１に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 1, wherein the amount of the residual monomer in the second pressure-sensitive adhesive sheet is 5000 ppm (weight basis) or less.
  3. 　前記第１の粘着シートにおける前記残存モノマーの量が６０００ｐｐｍ（重量基準）以上である、請求項１に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 1, wherein the amount of the residual monomer in the first pressure-sensitive adhesive sheet is 6000 ppm (weight basis) or more.
  4. 　前記表面改質処理が、コロナ処理、プラズマ処理、エキシマＵＶ光処理及びフレーム処理からなる群から選択される少なくとも１つである、請求項１に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 1, wherein the surface modification treatment is at least one selected from the group consisting of corona treatment, plasma treatment, excimer UV light treatment, and flame treatment.
  5. 　前記表面改質処理を、酸素濃度２０体積％以下の雰囲気で実施する、請求項１に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 1, wherein the surface modification treatment is performed in an atmosphere with an oxygen concentration of 20% by volume or less.
  6. 　前記雰囲気が不活性ガス雰囲気である、請求項５に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 5, wherein the atmosphere is an inert gas atmosphere.
  7. 　前記表面改質処理を前記第１の粘着シートの露出面に対して実施する、請求項１に記載の粘着シートの製造方法。 The method for manufacturing a pressure-sensitive adhesive sheet according to claim 1, wherein the surface modification treatment is performed on an exposed surface of the first pressure-sensitive adhesive sheet.
  8. 　前記第１の粘着シートが、モノマー群及び／又は前記モノマー群の部分重合物を含む光硬化性組成物から形成された粘着シートである、請求項１に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 1, wherein the first pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet formed from a photocurable composition containing a monomer group and/or a partial polymer of the monomer group.
  9. 　前記モノマー群は（メタ）アクリル系モノマーを含む、請求項８に記載の粘着シート。 The adhesive sheet according to claim 8, wherein the monomer group includes a (meth)acrylic monomer.
  10. 　前記第１の粘着シートを、モノマー群及び／又は前記モノマー群の部分重合物を含む光硬化性組成物を含む塗布層に光を照射して形成することをさらに含む、請求項１に記載の粘着シートの製造方法。 The method according to claim 1, further comprising forming the first pressure-sensitive adhesive sheet by irradiating a coating layer containing a photocurable composition containing a monomer group and/or a partial polymer of the monomer group with light. Method for manufacturing adhesive sheets.
  11. 　前記第１の粘着シートを、基材シート、前記塗布層及びはく離ライナーをこの順に含む積層体に前記光を照射して形成する、請求項１０に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 10, wherein the first pressure-sensitive adhesive sheet is formed by irradiating the light onto a laminate including a base sheet, the coating layer, and a release liner in this order.
  12. 　前記光は、前記活性エネルギー線とは異なる、請求項１０に記載の粘着シートの製造方法。 The method for producing a pressure-sensitive adhesive sheet according to claim 10, wherein the light is different from the active energy ray.
  13. 　請求項１～１２のいずれか１項に記載の製造方法によって形成された前記第２の粘着シートの表面に光学フィルムを配置して粘着シート付き光学フィルムを形成することを含む、粘着シート付き光学フィルムの製造方法。 An optical film with a pressure-sensitive adhesive sheet, the method comprising forming an optical film with a pressure-sensitive adhesive sheet by disposing an optical film on the surface of the second pressure-sensitive adhesive sheet formed by the manufacturing method according to any one of claims 1 to 12. Film manufacturing method.
  14. 　前記表面は前記表面改質処理がなされた面である、請求項１３に記載の粘着シート付き光学フィルムの製造方法。 The method for producing an optical film with a pressure-sensitive adhesive sheet according to claim 13, wherein the surface is a surface that has been subjected to the surface modification treatment.
  15. 　前記光学フィルムが、偏光フィルム及び位相差フィルムからなる群から選ばれる少なくとも１つのフィルムを含む、請求項１３に記載の粘着シート付き光学フィルムの製造方法。 The method for producing an optical film with a pressure-sensitive adhesive sheet according to claim 13, wherein the optical film includes at least one film selected from the group consisting of a polarizing film and a retardation film.
  16. 　前記光学フィルムに対する前記第２の粘着シートの投錨力が１２Ｎ／２５ｍｍ以上である前記粘着シート付き光学フィルムを形成する、請求項１３に記載の粘着シート付き光学フィルムの製造方法。 The method for producing an optical film with a pressure-sensitive adhesive sheet according to claim 13, wherein the optical film with a pressure-sensitive adhesive sheet is formed in which the anchoring force of the second pressure-sensitive adhesive sheet with respect to the optical film is 12 N/25 mm or more.
PCT/JP2023/026819 2022-07-22 2023-07-21 Method for producing adhesive sheet and method for producing optical film including adhesive sheet WO2024019158A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0260981A (en) * 1988-08-29 1990-03-01 Sekisui Chem Co Ltd Production of acrylic pressure-sensitive tape or sheet
JP2000026805A (en) * 1998-06-11 2000-01-25 Minnesota Mining & Mfg Co <3M> Pressure sensitive adhesive composition and preparation thereof
JP2005514476A (en) * 2001-12-21 2005-05-19 スリーエム イノベイティブ プロパティズ カンパニー Multistage irradiation method for producing acrylic-based adhesives
JP2005132962A (en) * 2003-10-30 2005-05-26 Soken Chem & Eng Co Ltd Method for producing (meth)acrylic polymer
JP2013241516A (en) * 2012-05-21 2013-12-05 Showa Denko Packaging Co Ltd Method of producing adhesive sheet
JP2014111715A (en) * 2012-10-31 2014-06-19 Nitto Denko Corp Method for producing tacky-adhesive sheet having ultraviolet-curable acrylic tacky adhesive layer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0260981A (en) * 1988-08-29 1990-03-01 Sekisui Chem Co Ltd Production of acrylic pressure-sensitive tape or sheet
JP2000026805A (en) * 1998-06-11 2000-01-25 Minnesota Mining & Mfg Co <3M> Pressure sensitive adhesive composition and preparation thereof
JP2005514476A (en) * 2001-12-21 2005-05-19 スリーエム イノベイティブ プロパティズ カンパニー Multistage irradiation method for producing acrylic-based adhesives
JP2005132962A (en) * 2003-10-30 2005-05-26 Soken Chem & Eng Co Ltd Method for producing (meth)acrylic polymer
JP2013241516A (en) * 2012-05-21 2013-12-05 Showa Denko Packaging Co Ltd Method of producing adhesive sheet
JP2014111715A (en) * 2012-10-31 2014-06-19 Nitto Denko Corp Method for producing tacky-adhesive sheet having ultraviolet-curable acrylic tacky adhesive layer

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