WO2018235510A1 - Adhesive composition for organic el display devices, adhesive layer for organic el display devices, polarizing film with adhesive layer for organic el display devices, and organic el display device - Google Patents

Adhesive composition for organic el display devices, adhesive layer for organic el display devices, polarizing film with adhesive layer for organic el display devices, and organic el display device Download PDF

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Publication number
WO2018235510A1
WO2018235510A1 PCT/JP2018/019819 JP2018019819W WO2018235510A1 WO 2018235510 A1 WO2018235510 A1 WO 2018235510A1 JP 2018019819 W JP2018019819 W JP 2018019819W WO 2018235510 A1 WO2018235510 A1 WO 2018235510A1
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Prior art keywords
organic
pressure
sensitive adhesive
adhesive layer
display device
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PCT/JP2018/019819
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French (fr)
Japanese (ja)
Inventor
昌邦 藤田
普史 形見
雄祐 外山
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201880036779.9A priority Critical patent/CN110710328B/en
Priority to CN202211531845.4A priority patent/CN115851177A/en
Priority to KR1020197030583A priority patent/KR102513736B1/en
Priority to KR1020227026287A priority patent/KR102668000B1/en
Publication of WO2018235510A1 publication Critical patent/WO2018235510A1/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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition for an organic EL (electroluminescence) display (OLED).
  • OLED organic EL
  • the present invention also relates to a pressure-sensitive adhesive layer for an organic EL display device formed from the pressure-sensitive adhesive composition for an organic EL display device, and a polarizing film with a pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer.
  • the present invention relates to an organic EL display device using the pressure-sensitive adhesive layer and / or the polarizing film.
  • organic EL display devices having an organic EL panel mounted are widely used in various applications such as mobile phones, car navigation devices, monitors for personal computers, and televisions.
  • a circularly polarizing plate (polarizing plate and polarizing plate) is usually formed on the surface of the organic EL panel to prevent external light from being reflected by the metal electrode (cathode) and viewed like a mirror surface. / 4 wave plate laminate etc.) is arranged.
  • a decoration panel etc. may be further laminated
  • the constituent members of the organic EL display device such as the circularly polarizing plate and the decorative panel are generally laminated via a bonding material such as a pressure-sensitive adhesive layer or an adhesive layer.
  • a component or the like in the image display apparatus may be degraded by incident ultraviolet light, and a layer containing an ultraviolet absorber to suppress the deterioration due to the ultraviolet light.
  • a layer containing an ultraviolet absorber to suppress the deterioration due to the ultraviolet light.
  • it has at least one ultraviolet absorbing layer, the light transmittance at a wavelength of 380 nm is 30% or less, and the visible light transmittance at a longer wavelength side than a wavelength of 430 nm is 80% or more Transparent double-sided pressure-sensitive adhesive sheets for image display devices (see, for example, Patent Document 1) are known.
  • the pressure-sensitive adhesive composition applied to the transparent double-sided pressure-sensitive adhesive sheet for image display contains, for example, a base polymer such as (meth) acrylic polymer.
  • the pressure-sensitive adhesive composition sometimes forms a radically crosslinked pressure-sensitive adhesive layer using a radical generator (for example, peroxide) as a crosslinking agent.
  • a radical generator for example, peroxide
  • the radical polymerization start in the said adhesive composition is started. Contains an agent.
  • the ultraviolet absorber when the ultraviolet absorber is contained in the pressure-sensitive adhesive composition containing the radical generating agent, the gel fraction of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition depending on the ultraviolet absorber (crosslinking Tend to decrease.
  • the decrease in gel fraction (crosslinking degree) of the pressure-sensitive adhesive layer becomes large, the pressure-sensitive adhesive layer has a defect such as a decrease in appearance yield due to glue marks or glue stain during processing, and generation of foaming in heating durability. was there.
  • An object of the present invention is to provide a pressure-sensitive adhesive composition for a display device.
  • the present invention provides a pressure-sensitive adhesive layer for an organic EL display device formed from the pressure-sensitive adhesive composition, and provides a polarizing film with a pressure-sensitive adhesive layer having a polarizing film and a pressure-sensitive adhesive layer for an organic EL display device.
  • An object of the present invention is to provide an organic EL display device including the pressure-sensitive adhesive layer and / or the polarizing film with the pressure-sensitive adhesive layer.
  • the base polymer, the radical generator, the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure, and the maximum absorption wavelength of the absorption spectrum in the wavelength region of 380 to 430 nm The present invention relates to a pressure-sensitive adhesive composition for an organic EL display device, which comprises at least one compound (A) selected from the dye compound (b).
  • the compound (A) contains both the ultraviolet absorber (a) and the dye compound (b).
  • the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) exists in a wavelength range of 300 to 400 nm.
  • a peroxide in the pressure-sensitive adhesive composition for an organic EL display device, a peroxide can be used as the radical generator.
  • a (meth) acrylic polymer can be used as the base polymer.
  • the radical generator is preferably contained in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the base polymer.
  • the compound (A) is preferably contained in an amount of 0.1 to 25 parts by weight with respect to 100 parts by weight of the base polymer.
  • the pressure-sensitive adhesive composition for an organic EL display may further contain an antioxidant.
  • the pressure-sensitive adhesive composition for an organic EL display may further contain a crosslinking agent.
  • the present invention also relates to a pressure-sensitive adhesive layer for an organic EL display device, which is formed from the pressure-sensitive adhesive composition for an organic EL display device.
  • the pressure-sensitive adhesive layer for an organic EL display device has an average transmittance of 12% or less at a wavelength of 300 to 400 nm, an average transmittance of 30% or less at a wavelength of 400 nm to 430 nm, and an average transmittance of 430 to 450 nm. It is preferable that it is 70% or more.
  • the pressure-sensitive adhesive layer for the organic EL display device has an average transmittance of 12% or less at a wavelength of 300 to 400 nm, an average transmittance of 400 nm to 430 nm at a wavelength of more than 30% and 95% or less.
  • the average transmittance is preferably 80% or more.
  • the present invention also relates to a polarizing film with a pressure-sensitive adhesive layer for an organic EL display characterized by having a polarizing film and the pressure-sensitive adhesive layer for the organic EL display.
  • the polarizing film is provided with a transparent protective film on one side of a polarizer and has a retardation film on the other side, and the organic EL It is preferable that a pressure-sensitive adhesive layer for a display device be provided on the surface of the retardation film opposite to the surface in contact with the polarizer and / or on the surface of the transparent protective film opposite to the surface in contact with the polarizer.
  • the polarizing film with a pressure-sensitive adhesive layer for an organic EL display device is an organic EL display device having a first pressure-sensitive adhesive layer, a transparent protective film, a polarizer, a second pressure-sensitive adhesive layer, a retardation film, and a third pressure-sensitive adhesive layer in this order.
  • a polarizing film with a pressure-sensitive adhesive layer It is preferable that at least one pressure-sensitive adhesive layer among the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer for the organic EL display device.
  • the retardation film is a 1 ⁇ 4 wavelength plate
  • the polarizing film is a circularly polarizing film.
  • the present invention also relates to an organic EL display device using at least one of the pressure-sensitive adhesive layer for the organic EL display device or the polarizing film with the pressure-sensitive adhesive layer for the organic EL display device.
  • the pressure-sensitive adhesive composition for an organic EL display device of the present invention contains an ultraviolet absorber (a) in addition to the base polymer.
  • the ultraviolet absorber (a) can suppress the deterioration due to the ultraviolet light and can suppress the deterioration of the organic EL element.
  • the maximum absorption wavelength of the absorption spectrum is 380 to 430 nm in place of the ultraviolet light absorber (a) or in combination with the ultraviolet light absorber (a) It contains a dye compound (b) present in the wavelength range. Also by the said pigment
  • the pressure-sensitive adhesive composition for an organic EL display device of the present invention contains a radical generator such as a peroxide.
  • the said radical generating agent functions as a crosslinking agent with respect to base polymers, such as (meth) acrylic-type polymer, for example, and controls the gel fraction of the adhesive layer formed from the said adhesive composition in a desired range. Can form a pressure-sensitive adhesive layer having a good appearance.
  • the ultraviolet absorber and / or the dye compound and the radical generating agent coexist, so that the gel fraction of the obtained pressure-sensitive adhesive layer decreases. I am concerned.
  • an ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure is selected and used as the ultraviolet absorber.
  • the decrease in gel fraction is due to the decrease in the degree of crosslinking due to the deactivation of the radical generated from the radical generator, and the cause of the deactivation of the radical is the ultraviolet absorber Considering that it is a hydrogen donating group, by suppressing the use of three or less UV absorbers (a) for the hydroxyl group related to the hydrogen donating group, the inhibition of crosslinking of the radical generator by the UV absorber is suppressed .
  • the pressure-sensitive adhesive composition for an organic EL display device of the present invention it is possible to obtain a pressure-sensitive adhesive layer for an organic EL display device capable of suppressing the decrease in appearance yield and the occurrence of foaming in heating durability. . Therefore, the organic EL display device using the pressure-sensitive adhesive layer-attached polarizing film including the pressure-sensitive adhesive layer for the organic EL display device and / or the pressure-sensitive adhesive layer for the organic EL display device of the present invention has excellent weathering deterioration resistance It is possible to extend the life.
  • FIG. 1 A) to (c) are cross-sectional views schematically showing an embodiment of a polarizing film with an adhesive layer for an organic EL display device of the present invention. It is a sectional view showing typically one embodiment of the organic EL display of the present invention. It is a sectional view showing typically one embodiment of the organic EL display of the present invention. It is a sectional view showing typically one embodiment of the organic EL display of the present invention. It is a sectional view showing typically one embodiment of the organic EL display of the present invention.
  • the pressure-sensitive adhesive composition for an organic EL display device comprises a base polymer, a radical generator, and a UV absorber having 0 to 3 hydroxyl groups in its molecular structure (a) And at least one compound (A) selected from the dye compounds (b) present in the wavelength range of 380 to 430 nm as the maximum absorption wavelength of the absorption spectrum.
  • the pressure-sensitive adhesive composition for an organic EL display device of the present invention contains a base polymer as a main component.
  • the main component refers to the component having the highest content of the total solids contained in the pressure-sensitive adhesive composition, and is, for example, a component that accounts for more than 50% by weight of the total solids contained in the pressure-sensitive adhesive composition , Or even components that account for more than 70% by weight.
  • a base polymer used by this invention it does not specifically limit as a base polymer used by this invention.
  • a rubber adhesive an acrylic adhesive, a silicone adhesive, a urethane adhesive, vinyl alkyl Ether pressure sensitive adhesives, polyvinyl alcohol pressure sensitive adhesives, polyvinyl pyrrolidone pressure sensitive adhesives, polyacrylamide pressure sensitive adhesives, cellulose pressure sensitive adhesives, etc.
  • acrylic pressure-sensitive adhesives are preferably used from the viewpoints of excellent optical transparency, showing appropriate adhesion, cohesiveness and adhesion properties of adhesion, and excellent in weather resistance, heat resistance, etc.
  • an acrylic pressure-sensitive adhesive composition containing a (meth) acrylic polymer as a base polymer is preferable.
  • the (meth) acrylic polymer usually contains, as a monomer unit, an alkyl (meth) acrylate as a main component.
  • (meth) acrylate is an acrylate and / or a methacrylate, and (meth) of this invention is the same meaning.
  • alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer examples include ones having 1 to 18 carbon atoms of a linear or branched alkyl group. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3 to 9.
  • alkyl (meth) acrylates containing an aromatic ring such as phenoxyethyl (meth) acrylate or benzyl (meth) acrylate are used be able to.
  • the (meth) acrylic polymer at least one type having a polymerizable functional group having an unsaturated double bond such as (meth) acryloyl group or vinyl group for the purpose of improving adhesiveness and heat resistance.
  • the copolymerized monomers of (1) can be introduced by copolymerization.
  • copolymerizable monomers include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid 6 -Hydroxyl-containing monomers such as -hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate
  • Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Group containing monomers; acrylic acid with caprolactone Styrene sulfonic
  • (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide and the like Monomers; (meth) acrylic acid alkylaminoalkyl monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate; (meth) acrylic (Meth) acrylate alkoxyalkyl monomers such as methoxyethyl acrylate and ethoxyethyl (meth) acrylate; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- ( Meta)
  • silane type monomer containing a silicon atom, etc. examples include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane 8-vinyloctyl triethoxysilane, 10-methacryloyloxydecyl trimethoxysilane, 10-acryloyloxydecyl trimethoxysilane, 10-methacryloyloxydecyl triethoxysilane, 10-acryloyloxydecyl triethoxysilane, and the like.
  • a copolymerizable monomer tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate And (meth) acryloyl esters of (meth) acrylic acid and polyhydric alcohol such as caprolactone modified with dipentaerythritol hexa (meth) acrylate Group, a poly(meth
  • the (meth) acrylic polymer has an alkyl (meth) acrylate as a main component in the weight ratio of all constituent monomers, and the proportion of the copolymerization monomer in the (meth) acrylic polymer is not particularly limited, but the above copolymer
  • the proportion of the polymerization monomer is preferably about 0 to about 20%, about 0.1 to about 15%, and more preferably about 0.1 to about 10% by weight of the total constituent monomers.
  • a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferably used from the viewpoint of adhesiveness and durability.
  • the hydroxyl group-containing monomer and the carboxyl group-containing monomer can be used in combination.
  • these copolymerizable monomers become reactive points with the crosslinking agent.
  • a hydroxyl group-containing monomer, a carboxyl group-containing monomer and the like are preferably used to improve the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer since they are highly reactive with the intermolecular crosslinking agent.
  • the hydroxyl group-containing monomer is preferable in terms of reworkability, and the carboxyl group-containing monomer is preferable in terms of achieving both durability and reworkability.
  • the ratio is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and further preferably 0.05 to 7% by weight. preferable.
  • the ratio is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and further 0.2 to 6% by weight. preferable.
  • the (meth) acrylic polymer of the present invention one having a weight average molecular weight of 500,000 to 3,000,000 is usually used. In consideration of durability, particularly heat resistance, it is preferable to use one having a weight average molecular weight of 700,000 to 2,700,000. Furthermore, 800,000 to 2,500,000 are preferable. When the weight average molecular weight is less than 500,000, it is not preferable in terms of heat resistance. Further, when the weight average molecular weight is larger than 3,000,000, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable because the cost is increased.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.
  • the production of such (meth) acrylic polymers can be appropriately selected from known production methods such as solution polymerization, radiation polymerization such as UV polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations.
  • the (meth) acrylic polymer to be obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
  • the reaction is carried out under a stream of an inert gas such as nitrogen, usually with the addition of a polymerization initiator, under reaction conditions of about 50 to 70 ° C. for about 5 to 30 hours.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
  • the weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount used can be appropriately adjusted according to the type of these.
  • radical polymerization initiator for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-) 2-Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutyramidine), 2, Azo initiators such as 2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), persulfates such as potassium persulfate and ammonium persulfate Salt, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-se -Butyl peroxy
  • the radical polymerization initiators may be used alone or in combination of two or more, but the total content is 0.005 to 1 weight per 100 weight parts of the monomer. It is preferably in the order of parts, and more preferably in the range of about 0.02 to 0.5 parts by weight.
  • chain transfer agents examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol and the like.
  • the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to.
  • an emulsifier used when carrying out the emulsion polymerization for example, anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, etc., polyoxy Nonionic emulsifiers, such as ethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, etc. are mentioned. These emulsifiers may be used alone or in combination of two or more.
  • a reactive emulsifier as an emulsifier into which a radically polymerizable functional group such as propenyl group or allyl ether group is introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE10N (manufactured by Asahi Denka Co., Ltd.), and the like.
  • Reactive emulsifiers are preferred because they are incorporated into the polymer chain after polymerization, which improves the water resistance.
  • the amount of the emulsifier used is preferably 0.3 to 5 parts by weight, more preferably 0.5 to 1 parts by weight from the viewpoint of polymerization stability and mechanical stability, based on 100 parts by weight of the total of the monomer components.
  • radical generating agent mix blended with the adhesive composition of this invention
  • peroxides are preferable as the radical generator to be blended in the pressure-sensitive adhesive composition.
  • the radical generator can generate radically active species by heating or light irradiation to promote crosslinking of the (meth) acrylic polymer in the pressure-sensitive adhesive composition.
  • a radical generating agent it is preferable to use a peroxide having a half-life temperature of 80 ° C. to 160 ° C., preferably 90 ° C. to 140 ° C., in consideration of workability and stability. It is more preferable to use.
  • peroxide examples include di (4-t-butylcyclohexyl) peroxydicarbonate (one-minute half-life temperature: 92.1 ° C.), di-sec-butylperoxydicarbonate (one-minute half-life temperature 92.4 ° C., t-butylperoxy neodecanoate (one-minute half-life temperature: 103.5 ° C.), t-hexyl peroxypivalate (one-minute half-life temperature: 109.1 ° C.), t -Butyl peroxypivalate (one-minute half-life temperature: 110.3 ° C), dilauroyl peroxide (one-minute half-life temperature: 116.4 ° C), di-n-octanoyl peroxide (one-minute half-life temperature 117.4 ° C., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (half-life temperature per minute: 124.3 ° C.
  • di (4-t-butylcyclohexyl) peroxydicarbonate one-minute half-life temperature: 92.1 ° C.
  • dilauroyl peroxide one-minute half-life temperature: 116. 4 ° C.
  • dibenzoyl peroxide one-minute half-life temperature: 130.0 ° C.
  • the half life of the peroxide is an index indicating the decomposition rate of the peroxide, and refers to the time until the remaining amount of the peroxide is halved.
  • the decomposition temperature for obtaining the half life at any time and the half life time at any temperature are described in the manufacturer catalog etc. For example, “Organic peroxide catalog 9th edition of Nippon Oil and Fats Co., Ltd. (May 2003) and the like.
  • the content of the radical generating agent (particularly peroxide) in the pressure-sensitive adhesive composition of the present invention is the adjustment of the processability, reworkability, crosslinking stability, releasability, etc. of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. Therefore, it is determined in consideration of the gel fraction etc. Increasing the content of the radical generating agent (especially peroxide) is preferable for securing the gel fraction (crosslinking degree) of the obtained pressure-sensitive adhesive layer, but if it is too much, the release applied to the pressure-sensitive adhesive layer The peeling force of the mold film (separator) tends to increase.
  • the content of the radical generator is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 parts by weight, based on 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). It is preferable that it is part by weight, more preferably 0.05 to 0.8 parts by weight, and still more preferably 0.1 to 0.6 parts by weight.
  • the radical polymerization initiator which was not used for the polymerization reaction in the case of preparation of the said (meth) acrylic-type polymer may remain.
  • the said residual radical generating agent can be used as a radical generating agent in the said adhesive composition. In that case, the amount of the residual radical generator can be quantified, and the radical generator can be appropriately blended according to the content of the residual radical generator.
  • the amount of peroxide decomposition remaining after the reaction can be measured, for example, by HPLC (high performance liquid chromatography).
  • each of the pressure-sensitive adhesive composition after reaction treatment is taken out, immersed in 10 mL of ethyl acetate, shaken and extracted at 120 rpm for 3 hours at 25 ° C. with a shaker, and then room temperature Let stand for 3 days. Then, add 10 mL of acetonitrile, shake at 120 rpm for 30 minutes at 25 ° C., filter through a membrane filter (0.45 ⁇ m), and inject about 10 ⁇ L of the extract into HPLC for analysis. The amount of peroxide can be used.
  • at least one compound (A) selected from Regarding the ultraviolet absorber (a) the fact that the number of hydroxyl groups in the molecular structure is 0 to 3 means that as described above, the number of hydrogen donating groups causing the deactivation of radicals is reduced to crosslink the radical generating agent It is effective in suppressing inhibition.
  • the fact that the number of hydroxyl groups is 0 to 3 is also preferable for suppressing the inhibition of crosslinking by the crosslinking agent when, for example, an isocyanate-based crosslinking agent having reactivity with the hydroxyl group is blended.
  • the said ultraviolet absorber (a) uses the compound which does not have a phenyl group in molecular structure as a hydrogen donor group which deactivates radicals other than a hydroxyl group.
  • the phenyl group which is not contained in the molecular structure means phenyl (—C 6 H 5 ) which does not have a substituent, and does not exclude a phenyl group having a substituent, a phenylene group and the like.
  • the dye compound (b) also has a small number of hydrogen donating groups such as a hydroxyl group and a phenyl group in the molecular structure from the viewpoint of preventing the inhibition of the crosslinking of the radical generator as in the ultraviolet absorber (a)
  • the hydroxyl group is preferably a compound having 0 to 3 or no hydroxyl group.
  • the compounding amount of the ultraviolet absorber (a) and / or the dye compound (b) as the compound (A) is 0.1 parts by weight with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer)
  • the amount is preferably about 25 parts by weight, more preferably about 0.5 to 20 parts by weight, and still more preferably about 2 to 10 parts by weight.
  • the ultraviolet absorbers (a) may be used alone or in combination of two or more.
  • the content of the ultraviolet absorber (a) as a whole is 100 parts by weight of the base polymer (for example, (meth) acrylic polymer) 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and 0.5 to 3 parts by weight Is more preferred.
  • the addition amount of the ultraviolet absorber (a) in the above range the ultraviolet absorbing function of the pressure-sensitive adhesive layer can be sufficiently exhibited, and in the case of performing the ultraviolet polymerization, the polymerization is not hindered. preferable.
  • the dye compounds (b) may be used alone or in combination of two or more.
  • the content of the dye compound (b) as a whole is 100 parts by weight of the base polymer (for example, (meth) acrylic polymer) 0.1 to 20 parts by weight is preferable, 0.1 to 10 parts by weight is preferable, 0.1 to 5 parts by weight is preferable, and 0.5 to 3 parts by weight More preferable.
  • the addition amount of the dye compound (b) in the above range light in a region not affecting light emission of the organic EL element can be sufficiently absorbed, and the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is used This is preferable because deterioration of the organic EL element can be suppressed.
  • the ultraviolet absorber (a) or the dye compound (b) can be used, it is preferable to use the ultraviolet absorber (a) and the dye compound (b) in combination.
  • the ultraviolet absorber (a) for example, a wavelength region (380 nm to 430 nm) on the shorter wavelength side than the light emitting region (longer wavelength side than 430 nm) of the organic EL element although it can absorb light of wavelength 380 nm Light is not sufficiently absorbed, and the transmitted light may cause deterioration.
  • the dye compound (b) can suppress the transmission of light having a wavelength (380 nm to 430 nm) shorter than the light emitting region (longer than 430 nm) of the organic EL element, and the ultraviolet absorber (a)
  • the combined use of the dye compound (b) and the dye compound (b) makes it possible to ensure sufficient transmittance of visible light in the light emitting region of the organic EL device.
  • the present invention by using such a dye compound (b) and the ultraviolet absorber (a2) in combination, light in a region (wavelength 380 nm to 430 nm) which does not affect light emission of the organic EL element is sufficiently absorbed.
  • the light emitting region (longer wavelength than 430 nm) of the organic EL element can be sufficiently transmitted, and as a result, deterioration of the organic EL element due to external light can be suppressed.
  • the total amount of the ultraviolet absorber (a) and the dye compound (b) is within the range of the compounding amount as the compound (A) It is preferable to control as follows.
  • the ultraviolet absorber (a) is preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). Is preferably 0.5 to 3 parts by weight.
  • the dye compound (b) is preferably about 0.1 to 10 parts by weight, and more preferably about 0.1 to 5 parts by weight, with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). And more preferably 0.5 to 3 parts by weight.
  • the UV absorber (a) is not particularly limited as long as it has 0 to 3 hydroxyl groups in the molecular structure, and for example, triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, oxybenzophenone
  • the ultraviolet absorbers include salicylic acid ester ultraviolet absorbers and cyanoacrylate ultraviolet absorbers. These may be used singly or in combination of two or more.
  • triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable, triazine-based UV absorbers having two or less hydroxyl groups in one molecule, and benzo having one benzotriazole skeleton in one molecule.
  • At least one UV absorber selected from the group consisting of triazole UV absorbers, which has good solubility in the monomers used to form the acrylic pressure-sensitive adhesive composition, and a wavelength near 380 nm Is preferred because of its high ability to absorb ultraviolet light.
  • triazine-based UV absorbers having two or less hydroxyl groups in one molecule include 2,4-bis-[ ⁇ 4- (4-ethylhexyloxy) -4-hydroxy ⁇ -phenyl] -6. -(4-Methoxyphenyl) -1,3,5-triazine (Tinosorb S, manufactured by BASF), 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) ) -1,3,5-Triazine (TINUVIN 460, manufactured by BASF Corp.), 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-) Reaction product of hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane (TINUVIN 400, manufactured by BASF), 2- [4, 6 Bis (2,4-dimethylphenyl) -1,3,5-
  • benzotriazole-based ultraviolet absorber having one benzotriazole skeleton in one molecule, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- is used.
  • examples of the benzophenone based ultraviolet absorber (benzophenone based compound) and the oxybenzophenone based ultraviolet absorber (oxybenzophenone based compound) include, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -Sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4, 4-dimethoxybenzophenone and the like can be mentioned.
  • salicylic acid ester type ultraviolet absorber for example, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (TINUVIN 120, manufactured by BASF AG) Etc. can be mentioned.
  • TINUVIN 120 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate
  • cyanoacrylate UV absorber examples include alkyl 2-cyanoacrylate, cycloalkyl 2-cyanoacrylate, alkoxyalkyl 2-cyanoacrylate, alkenyl 2-cyanoacrylate, and alkynyl Examples include 2-cyanoacrylate and the like.
  • the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) is preferably in the wavelength range of 300 to 400 nm, and more preferably in the wavelength range of 320 to 380 nm.
  • the method of measuring the maximum absorption wavelength is the same as the method of measuring the dye-based compound described later.
  • the dye compound (b) is not particularly limited as long as it is a compound which exists in the wavelength range of 380 to 430 nm in the maximum absorption wavelength of the absorption spectrum, but like the ultraviolet absorber (a), It is preferable that it is a compound which has few hydrogen donor groups, such as a hydroxyl group and a phenyl group, in a structure.
  • maximum absorption wavelength as used herein means an absorption maximum wavelength showing the maximum absorbance among a plurality of absorption maxima in the spectral absorption spectrum in the wavelength region of 300 to 460 nm.
  • the maximum absorption wavelength of the absorption spectrum of the dye compound (b) is more preferably in the wavelength range of 380 to 420 nm.
  • the dye compound (b) is not particularly limited as long as it has the above-mentioned wavelength characteristics, but a material which does not inhibit the display performance of the organic EL element and which does not have fluorescence and phosphorescence performance (photoluminescence) is preferable.
  • the half-width of the dye compound (b) is not particularly limited, but is preferably 80 nm or less, more preferably 5 to 70 nm, and still more preferably 10 to 60 nm.
  • the full width at half maximum of the dye compound is in the above range, it is possible to sufficiently transmit light in a region that does not affect the light emission of the organic EL element while transmitting sufficient light at wavelengths longer than 430 nm. Because it is preferable.
  • the measuring method of a half value width is based on the method as described below.
  • Examples of the dye compound (b) include organic dye compounds and inorganic dye compounds. Among them, from the viewpoint of maintaining the dispersibility in the resin component such as the base polymer and transparency, Organic dye compounds are preferred.
  • organic dye compounds examples include azomethine compounds, indole compounds, cinnamic acid compounds, pyrimidine compounds, porphyrin compounds and cyanine compounds.
  • organic dye compound commercially available ones can be suitably used.
  • indole compound BONASORB UA3911 (trade name, maximum absorption wavelength of absorption spectrum: 398 nm, half width: 48 nm, manufactured by Orient Chemical Industries, Ltd.)
  • SOM-5-0106 trade name, maximum absorption wavelength of absorption spectrum: 416 nm, half width: 50 nm, manufactured by Orient Chemical Industries Ltd.
  • porphyrin compound FDB-001 (Trade name, maximum absorption wavelength of absorption spectrum: 420 nm, half width: 14 nm, Yamada Chemical Industry Co., Ltd.)
  • cyanine compound merocyanine compound
  • polymethine compound trade name: DAA
  • An antioxidant to be blended into the pressure-sensitive adhesive composition of the present invention can be blended.
  • An antioxidant can prevent inhibition by oxygen of radicals generated from a radical generator, and can ensure a stable gel fraction (crosslinking degree), and a release film (separator applied to an adhesive layer) The gel fraction can be increased while suppressing the increase in the peeling force of
  • antioxidants examples include phenol type, phosphorus type, sulfur type and amine type antioxidants, and at least one selected from these is used. Among these, phenolic antioxidants are preferred.
  • phenolic antioxidant examples include, as a monocyclic phenol compound, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6- Dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-Dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl- 6-t-Hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL ⁇ -Tocopherol,
  • Phosphorus-containing phenolic compounds such as calcium (bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate)), bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel, etc. Can be mentioned.
  • the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tris tridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phos Phyto, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (Butoxyethyl) phosphite, tetratridecyl-4,4'-
  • 1,6-hexanediol diphosphite Hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) diphos Pheat, tris [4,4'-isopropylidene bis (2-t-butylphenol)] phosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 9,10-dihydro-9-phosphaphenanthrene -10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl.
  • dialkylthiodipropionate and polyhydric alcohol ester of alkylthiopropionic acid are preferable to use.
  • the dialkylthiodipropionate used herein is preferably a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms, and as the polyhydric alcohol ester of alkylthiopropionic acid, an alkyl having 4 to 20 carbon atoms Polyhydric alcohol esters of alkylthiopropionic acid having a group are preferred.
  • dialkyl thiodipropionates examples include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate.
  • polyhydric alcohol esters of alkylthiopropionic acid for example, glycerin tributyl thiopropionate, glycerin trioctyl thiopropionate, glycerin trilauryl thiopropionate, glycerin tristearyl thiopropionate, trimethylol ethane tributyl Thiopropionate, trimethylolethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate, trimethylol ethane tristearyl thiopropionate, pentaerythritol tetrabutyl thiopropionate, pentaerythritol tetraoctyl thiopro Peonate, pentaerythritol tetralauryl thiopropionate, pentaerythritol tetrastearyl thiopro Peonate, pen
  • amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2 , 6,6-Tetramethylpiperidine ethanol, Polycondensate of N, N ′, N ′, N ′ ′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6) , 6-Tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine ⁇ 1,3,5-triazine ⁇ N, N′-bis (Polycondensate of (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [ ⁇ 6- (1, 1, 3, 3 Tetra
  • the content of the antioxidant in the pressure-sensitive adhesive composition of the present invention is determined from the viewpoint of preventing the color fading of the dye by the radical generating agent.
  • the content of the antioxidant is preferably in the range of 0.03 parts by weight or more based on 100 parts by weight of the (meth) acrylic polymer.
  • the ratio of capturing radicals generated from the radical generator increases.
  • the crosslinking inhibition of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition tends to occur, and the gel fraction of the pressure-sensitive adhesive layer tends to decrease to cause appearance defects.
  • the content of the antioxidant is preferably 5 parts by weight or less, more preferably 1.5 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer.
  • the content of the above-mentioned antioxidant is preferably 0.05 to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer).
  • the amount is preferably 1.5 parts by weight, more preferably 0.1 to 1.0 parts by weight, and still more preferably 0.3 to 0.8 parts by weight.
  • the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent (excluding the above-mentioned radical generator).
  • a crosslinking agent excluding the above-mentioned radical generator.
  • an isocyanate-based crosslinking agent when used in combination as a crosslinking agent, three-dimensional crosslinking of the pressure-sensitive adhesive layer by the isocyanate-based crosslinking agent while effectively suppressing radical crosslinking inhibition by oxygen by the antioxidant.
  • a network can be formed efficiently. As a result, the occurrence of appearance abnormalities at the end of the polarizing film can be more effectively prevented.
  • Crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyl etherified melamine crosslinking agents, and metal chelate crosslinking agents. Agents are included.
  • the crosslinking agents can be used alone or in combination of two or more. Among these, an isocyanate type crosslinking agent is preferably used.
  • the said crosslinking agent may be used individually by 1 type and may be used in mixture of 2 or more types, content as a whole is a base polymer (for example, (meth) acrylic-type polymer) 100
  • the amount is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 4 parts by weight, and particularly preferably 0.02 to 3 parts by weight. .
  • An isocyanate type crosslinking agent refers to a compound having two or more isocyanate groups (including an isocyanate regenerated functional group in which an isocyanate group is temporarily protected by a blocking agent or quantification or the like) in one molecule.
  • aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate
  • alicyclic isocyanates such as isophorone diisocyanate
  • aliphatic isocyanates such as hexamethylene diisocyanate, etc.
  • lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
  • cycloaliphatic diisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate
  • Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenylisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene Is
  • the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent.
  • the compounding amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, with respect to 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. More preferred is 0.02 to 0.6 parts by weight.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxycyclohexyl) Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,1 Amino group-containing silane coupling agents such as 3-dimethylbutylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane Meta) Acrylic group containing Shira Coupling agents, such as isocyanate group-containing
  • the pressure-sensitive adhesive composition of the present invention may contain, in addition to the components described above, appropriate additives depending on the application.
  • tackifier for example, solid, semi-solid or liquid at room temperature consisting of rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenolic resin, etc.
  • Filler such as hollow glass balloon; Plasticizer; Inhibitors; light stabilizers (HALS); antioxidants etc.
  • HALS light stabilizers
  • the pressure-sensitive adhesive layer for an organic EL display device of the present invention is characterized in that it is formed from the pressure-sensitive adhesive composition for an organic EL display device.
  • the pressure-sensitive adhesive composition is applied to at least one surface of a substrate, and a coated film formed from the pressure-sensitive adhesive composition is dried and formed, or an active energy ray such as ultraviolet light is irradiated. Can be formed.
  • base material it does not specifically limit as said base material,
  • various base materials such as a release film and a transparent resin film base material, and the polarizing film mentioned later can also be used suitably as a base material.
  • constituent material of the release film examples include resin films such as polyethylene, polypropylene, polyethylene terephthalate and polyester film, porous materials such as paper, cloth and non-woven fabric, nets, foam sheets, metal foils, and laminates thereof Although an appropriate thin leaf etc. can be mentioned, a resin film is used suitably from the point which is excellent in surface smoothness.
  • the resin film for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene film -Vinyl acetate copolymer film etc. may be mentioned.
  • the thickness of the release film is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • the release film may be, if necessary, a release agent of silicone type, fluorine type, long chain alkyl type or fatty acid amide type, silica powder etc., release treatment and antifouling treatment, coating type, kneading type, It is also possible to carry out antistatic treatment such as deposition type.
  • antistatic treatment such as deposition type.
  • the releasability from the pressure-sensitive adhesive layer can be further enhanced by appropriately performing release treatment such as silicone treatment, long chain alkyl treatment, fluorine treatment and the like on the surface of the release film.
  • the transparent resin film substrate is not particularly limited, but various resin films having transparency are used.
  • the said resin film is formed of the film of one layer.
  • polyester resin such as polyethylene terephthalate and polyethylene naphthalate, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin
  • Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like can be mentioned.
  • polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
  • the thickness of the film substrate is preferably 15 to 200 ⁇ m, and more preferably 25 to 188 ⁇ m.
  • the method for applying the pressure-sensitive adhesive composition onto the substrate may be roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain
  • the drying conditions are not particularly limited, and the composition of the pressure-sensitive adhesive composition
  • the concentration can be set appropriately, for example, at about 60 to 170 ° C., preferably 60 to 150 ° C., for 1 to 60 minutes, preferably 2 to 30 minutes.
  • the coating film can be irradiated with ultraviolet light to form a pressure-sensitive adhesive layer.
  • the thickness of the pressure-sensitive adhesive layer is preferably 5 ⁇ m or more, more preferably 50 ⁇ m or more, still more preferably 100 ⁇ m or more, from the viewpoint of securing the function of absorbing light having a wavelength of less than 430 nm. It is particularly preferable to be the above.
  • the upper limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 mm or less. When the thickness of the pressure-sensitive adhesive layer exceeds 1 mm, the transmission of ultraviolet light becomes difficult, and it takes time to polymerize the monomer component, and problems occur in processability, winding up in steps and transportability, and productivity is poor. Not desirable because
  • the gel fraction of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 40% or more, more preferably 60% or more, and still more preferably 75% or more. Particularly preferred is 85% or more. When the gel fraction of the pressure-sensitive adhesive layer is small, the cohesion is inferior, and problems may occur in processability and handling.
  • the gel fraction immediately after forming the pressure-sensitive adhesive layer by heat drying or ultraviolet irradiation of the coating film of the pressure-sensitive adhesive composition is preferably 60% or more from the viewpoint of preventing appearance defects such as paste marks. Is more preferably 63% or more, still more preferably 66% or more, and particularly preferably 70% or more.
  • the pressure-sensitive adhesive layer preferably has a haze value measured at a thickness of 25 ⁇ m of 2% or less, more preferably 0 to 1.5%, and still more preferably 0 to 1%. It is preferable for the pressure-sensitive adhesive layer to have high transparency when the haze is in the above-mentioned range.
  • the average transmittance at a wavelength of 300 to 400 nm of the pressure-sensitive adhesive layer is preferably 12% or less, more preferably 5% or less, and more preferably 2% or less.
  • permeability of an adhesive layer is the said range can fully be absorbed, and degradation of an organic EL element can be suppressed.
  • the average transmittance at a wavelength of 430 to 450 nm of the pressure-sensitive adhesive layer is preferably 70% or more, more preferably 75% or more, and the average transmittance at a wavelength of 500 to 780 nm is preferably 80% or more And 85% or more.
  • the transmittance of the pressure-sensitive adhesive layer is in the above range, light can be sufficiently transmitted in the light emitting region (longer wavelength side than 430 nm) of the organic EL element, and the organic EL display using the pressure-sensitive adhesive layer The device can emit sufficient light.
  • the average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 to 430 nm or less can be designed in accordance with the characteristics required for the organic EL display device.
  • the average transmittance of the adhesive layer at a wavelength of 400 to 430 nm or less is It is preferably 30% or less, more preferably 20% or less.
  • the average transmittance of the pressure-sensitive adhesive layer is 400% to 430 nm or less and is more than 30% and 95% or less Is preferable, and more than 50% and 90% or less is more preferable.
  • the “average transmittance of wavelengths 300 to 400 nm” refers to the average value of the measured transmittances by measuring the transmittance at a pitch of 1 nm in a wavelength range of 300 to 400 nm. The same is true for the average transmittance in other wavelength regions.
  • the pressure-sensitive adhesive layer of the present invention can sufficiently absorb light in a region which does not affect light emission of the organic EL device by having the transmittance, and the light-emitting region (longer wavelength than 430 nm of the organic EL device) Side) can be sufficiently transmitted, and deterioration of the organic EL element due to external light can be suppressed.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until it is practically used.
  • Polarizing film with pressure-sensitive adhesive layer for organic EL display device The polarizing film with pressure-sensitive adhesive layer for an organic EL display device of the present invention is characterized by having a polarizing film and the pressure-sensitive adhesive layer for the organic EL display device.
  • the pressure-sensitive adhesive layer for an organic EL display device those described above can be suitably used.
  • the pressure-sensitive adhesive layer can be attached to the polarizing film and transferred.
  • the said release film can be used as a separator of the polarizing film with an adhesive layer as it is, and the simplification in a process surface can be performed.
  • Polarizer is not particularly limited, and various types of polarizers can be used.
  • a polarizer for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene / vinyl acetate copolymer-based partially saponified film, dichroism of iodine or a dichroic dye Examples thereof include those obtained by adsorbing a substance and uniaxially stretched, and dehydrated products of polyvinyl alcohol and dehydrochlorinated products of polyvinyl chloride such as polyene-based oriented films.
  • a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
  • the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
  • a polarizer obtained by staining a polyvinyl alcohol-based film with iodine and uniaxially stretching it can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine and then stretching it to 3 to 7 times its original length. It can also be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride and the like as required. Furthermore, before dyeing, the polyvinyl alcohol-based film may be dipped in water and rinsed if necessary.
  • the stretching may be performed after staining with iodine, may be stretching while staining, or may be stretched and then stained with iodine. It can also be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • a thin polarizer having a thickness of 10 ⁇ m or less can also be used.
  • the thickness is preferably 1 to 7 ⁇ m. It is preferable that such a thin polarizer has less thickness unevenness, excellent visibility, and less dimensional change, so it is excellent in durability, and further, thickness reduction as a polarizing film can be achieved.
  • Typical thin polarizers are disclosed in JP-A-51-069644, JP-A-2000-338329, WO 2010/100917, WO 2010/100917, or a patent.
  • thin polarizing films described in Japanese Patent No. 4751481 and Japanese Patent Application Laid-Open No. 2012-073563.
  • These thin polarizing films can be obtained by a manufacturing method including the steps of stretching a polyvinyl alcohol resin (hereinafter, also referred to as a PVA resin) layer and a stretching resin base material in the state of a laminate and dyeing.
  • a PVA resin polyvinyl alcohol resin
  • a stretching resin base material in the state of a laminate and dyeing.
  • WO 2010/100917 pamphlet or those obtained by the process including the step of stretching in an aqueous solution of boric acid as described in Japanese Patent No. 4751481 or Japanese Patent Application Laid-Open No. 2012-073563, particularly preferred It is preferable to use one obtained by a method including the step of auxiliary air stretching before stretching in a boric acid aqueous solution as described in the specification of 4751481 and JP-A-2012-073563.
  • Transparent Protective Film As the transparent protective film, those conventionally used can be appropriately used. Specifically, a transparent protective film formed of a material excellent in transparency, mechanical strength, thermal stability, water blocking property, isotropy, etc. is preferable.
  • polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate
  • cellulose based polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers such as polymethyl methacrylate
  • styrene based polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
  • AS resin acrylonitrile / styrene copolymer
  • polyolefins having polyethylene, polypropylene, cyclo-based or norbornene structure polyolefin-based polymers such as ethylene / propylene copolymer, vinyl chloride-based polymers, amide-based polymers such as nylon and aromatic polyamides, imide-based polymers, sulfone-based polymers , Polyethersulfone based polymer, polyetheretherketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol based polymer, vinylidene chloride based polymer, vinyl butyral based polymer, arylate based polymer, polyoxymethylene based polymer, epoxy based polymer, or Blends of the above polymers and the like are also mentioned as examples of the polymer forming the above transparent protective film.
  • the transparent protective film can also be formed as a cured layer of thermosetting resin such as acrylic resin, urethane resin, acrylic urethane resin, epoxy resin, and silicone resin, and ultraviolet curable resin
  • the thickness of the transparent protective film can be appropriately determined, but in general, it is about 1 to 500 ⁇ m from the viewpoints of strength, workability such as handleability, and thin film properties.
  • the polarizer and the transparent protective film are preferably in close contact with each other via a water-based adhesive or the like.
  • water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latexes, water-based polyurethanes, water-based polyesters, and the like.
  • an adhesive agent of a polarizer and a transparent protective film an ultraviolet curable adhesive, an electron beam curable adhesive, etc. are mentioned.
  • the adhesive for electron beam-curable polarizing film exhibits suitable adhesiveness to the above various viewing side transparent protective films.
  • the adhesive used in the present invention can contain a metal compound filler.
  • the surface of the transparent protective film to which the polarizer is not attached may be treated with a hard coat layer, an antireflective treatment, an antisticking treatment, or a treatment for diffusion or antiglare.
  • any one having retardation and capable of functioning as an optical compensation layer can be used.
  • the phase difference characteristic can be suitably adjusted to the value required for optical compensation.
  • a stretched film can be suitably used as such a retardation film.
  • nx ny includes not only cases in which nx and ny are completely identical but also cases in which nx and ny are substantially the same.
  • ny nz includes not only cases in which ny and nz are completely identical, but also cases in which ny and nz are substantially the same.
  • the retardation film has a front surface retardation of the transparent protective film of 1 ⁇ 4 wavelength (about 100 to 170 nm). Preferably, it is a quarter wave plate.
  • the installation place of the said adhesive layer is not specifically limited, It may be provided in the surface on the opposite side to the surface in contact with the polarizer of the said transparent protective film,
  • the polarizer of retardation film It may be provided on the side opposite to the side in contact with the surface, but from the viewpoint of suppressing the deterioration of the organic EL element, it is preferably provided on at least one side or both sides.
  • FIGS. 1 (a) to (c) An example of a specific configuration of the pressure-sensitive adhesive layer-attached polarizing film for an organic EL display device of the present invention is shown in FIGS. 1 (a) to (c).
  • adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 As shown in FIG. 1 (b), transparent protective film 3 / polarizer 4 / retardation
  • film 5 / adhesive layer 2 As shown in FIG. 1 (c), each layer is in this order as adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 2;
  • the laminated polarizing film 1 with an adhesive layer for organic EL display devices can be mentioned.
  • the pressure-sensitive adhesive layer 2 is the pressure-sensitive adhesive layer for the organic EL display device of the present invention
  • FIG. 1 (c) at least the two pressure-sensitive adhesive layers 2 are present.
  • One of them may be the pressure-sensitive adhesive layer for the organic EL display device of the present invention, and both of them may be the pressure-sensitive adhesive layer for the organic EL display device of the present invention.
  • the polarizing film 6 is a piece protection polarizing film comprised from the polarizer 4 and the transparent protective film 3, it is not limited to this, The polarizing film 4 and the retardation film 5 It may be both protective polarizing films further having a transparent protective film therebetween. Further, as described above, various functional layers such as a hard coat layer can be formed on the surface of the transparent protective film 3 which is not in contact with the polarizer 4.
  • the said adhesive layer may be an adhesive layer for organic EL display apparatuses of this invention. That is, the polarizing film with a pressure-sensitive adhesive layer for an organic EL display device has a first pressure-sensitive adhesive layer, a transparent protective film, a polarizer, a second pressure-sensitive adhesive layer, a retardation film, and a third pressure-sensitive adhesive layer in this order At least one pressure-sensitive adhesive layer of the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer may be the pressure-sensitive adhesive layer for the organic EL display device.
  • Organic EL Display Device uses at least one pressure-sensitive adhesive layer for an organic EL display device of the present invention and / or at least one polarizing film with an adhesive layer for an organic EL display device of the present invention. It features.
  • cover glass or cover plastic 7 / adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 2 / organic EL display panel (OLED element panel) 8 (FIG. 2); cover glass or cover plastic 7 / adhesive layer 9 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive Layer 2 / organic EL display panel 8 (FIG. 3); cover glass or cover plastic 7 / adhesive layer 2 / sensor layer 10 / adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive As in the layer 2 / organic EL display panel 8 (FIG.
  • an organic EL display in which each layer is laminated in this order can be mentioned.
  • At least one of the pressure-sensitive adhesive layers 2 in each configuration may be the pressure-sensitive adhesive layer of the present invention, and all the pressure-sensitive adhesive layers 2 may be the pressure-sensitive adhesive layer of the present invention.
  • the organic EL display device of the present invention may include various functional layers such as a protective film and a hard coat layer.
  • an adhesive layer and / or an adhesive layer can be appropriately used.
  • pressure-sensitive adhesive layers other than the pressure-sensitive adhesive layer of the present invention conventional pressure-sensitive adhesive layers used in the present field can be appropriately used.
  • benzoyl peroxide trade name: Naipar BMT, manufactured by Nippon Oil and Fats Co., Ltd.
  • Example 1 Preparation of pressure-sensitive adhesive composition
  • a radical generator Benzoyl peroxide, trade name Nyper BMT manufactured by NOF Corporation
  • an isocyanate crosslinking agent Takenate D110N, trade name of Mitsui Chemicals, Inc.
  • a UV absorber a
  • Tinosorb S manufactured by BASF
  • a silane coupling agent KBM 403 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the pressure-sensitive adhesive composition is applied onto a 38 ⁇ m thick separator (polyethylene terephthalate film with a surface subjected to peeling treatment: release film) so that the thickness after drying is 20 ⁇ m, and dried at 155 ° C. for 1 minute The solvent was removed by layering to obtain a pressure-sensitive adhesive layer (A).
  • a 38 ⁇ m thick separator polyethylene terephthalate film with a surface subjected to peeling treatment: release film
  • the separator on which the pressure-sensitive adhesive layer (A) is formed is formed of cycloolefin polymer film / polarizer / acrylic resin film / pressure-sensitive adhesive layer (B) / retardation film It was transferred to a polarizing film having a retardation film of the constitution to prepare a polarizing film with an adhesive layer.
  • the composition of the obtained polarizing film with a pressure-sensitive adhesive layer is cycloolefin polymer film / polarizer / acrylic resin film / pressure-sensitive adhesive layer (B) / retardation film / pressure-sensitive adhesive layer (A).
  • the cycloolefin polymer film and the acrylic resin film of the both sides of a polarizer were bonded using the polyvinyl alcohol-type adhesive agent, and the polarizing film was obtained.
  • the polarizing film and the retardation film were bonded together through an adhesive layer (B).
  • the structural member of the polarizing film which has retardation film is as follows.
  • Cycloolefin polymer film A cycloolefin polymer film (trade name: Zeonor Film, manufactured by Nippon Zeon Co., Ltd.) having a thickness of 25 ⁇ m was used.
  • a polarizer consisting of a 5 ⁇ m thick stretched polyvinyl alcohol film impregnated with iodine was used.
  • the single transmittance Y value of the polarizer (or the polarizing film laminated with the protective film) was 42.4%, and the degree of polarization was 99.995.
  • the resin pellet consisting of 100 parts by weight of the imidized MS resin described in Production Example 1 of JP-A-2010-284840 is dried at 100.5 kPa and 100 ° C. for 12 hours, and the die temperature is 270 ° C. in a single-screw extruder. And extruded from a T-die to form a film (thickness 80 ⁇ m). Furthermore, the film is stretched in an atmosphere of 150 ° C. in the transport direction (thickness 40 ⁇ m), and then stretched in an atmosphere of 150 ° C. in a direction perpendicular to the film transport direction, and an acrylic resin film of 20 ⁇ m thickness I got
  • a pressure-sensitive adhesive composition was prepared by adding 0.1 parts by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the pressure-sensitive adhesive composition (solution) is coated on a 38 ⁇ m-thick separator (polyethylene terephthalate film with release-treated surface: release film) to a dry thickness of 15 ⁇ m, 100 ° C. The mixture was dried for 3 minutes and the solvent was removed to obtain a pressure-sensitive adhesive layer (B).
  • Example 2 in preparing the pressure-sensitive adhesive composition, the type of (meth) acrylic polymer, the type or blending amount of the crosslinking agent, the type or blending amount of the ultraviolet light absorber, the type or blending amount of the dye compound, the antioxidant A pressure-sensitive adhesive layer was formed in the same manner as in Example 1 except that the compounding amount of A was changed as shown in Table 1. Further, in the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
  • the separator is peeled off from the pressure-sensitive adhesive layer (A) obtained in Examples and Comparative Examples, and the pressure-sensitive adhesive layer (A) is attached to a jig for measurement, and a spectrophotometer (product name: U4100, Hitachi High-Tech Co., Ltd.) Measured by Technologies).
  • the transmittance was measured in the wavelength range of 300 nm to 450 nm.
  • the average transmittances at wavelengths of 300 nm to 400 nm, wavelengths of 400 nm to 430 nm, and wavelengths of 430 nm to 450 nm are shown in Table 1.
  • the gel fraction is 0.2 g of the pressure-sensitive adhesive layer (A) and wrapped in a fluorine resin (TEMISH NTF-1122 manufactured by Nitto Denko Co., Ltd.) (Wa) whose weight is measured in advance so that the pressure-sensitive adhesive does not leak After binding, the weight (Wb) was measured and placed in a sample bottle. 40 cc of ethyl acetate was added and left for 7 days. Thereafter, the fluororesin was taken out, dried at 130 ° C. for 2 hours on an aluminum cup, the weight (Wc) of the fluororesin containing the sample was measured, and the gel fraction was determined by the following formula (I).
  • TEMISH NTF-1122 manufactured by Nitto Denko Co., Ltd.
  • Formula (I): gel fraction (Wc-Wa) / (Wb-Wa) x 100 (% by weight) The gel fraction was measured immediately after the pressure-sensitive adhesive layer (A) was formed (within 4 hours) and after it was left at room temperature (23 ° C.) for one week after the pressure-sensitive adhesive layer (A) was formed.
  • ⁇ Durability> The separator is peeled off from the obtained polarizing film with pressure-sensitive adhesive layer (290 mm long ⁇ 220 mm wide), and the pressure-sensitive adhesive layer (A) side is in a cross nicol state on both sides of an alkali-free glass plate with a thickness of 0.7 mm. Sticked to Next, the sample was autoclaved at 50 ° C. and 5 atm for 15 minutes to make the sample completely intimate. The samples were treated under the conditions of 85 for 500 hours, respectively, and then the state of foaming, peeling, and lifting was visually observed according to the following criteria. ⁇ ⁇ ⁇ ... no foaming, peeling, floating, etc. ⁇ : There is no problem in practical use, but the level is slightly worse visually. X ... There is a problem in practical use.
  • the separator peeling force is preferably 0.02 to 1.0 (N / 50 mm).
  • the separator peeling force of 0.02 (N / 50 mm) or more is preferable for suppressing appearance defects due to the floating of the separator during processing or handling.
  • the separator peeling force is more preferably 0.04 to 0.5 (N / 50 mm), still more preferably 0.06 to 0.2 (N / 50 mm), and particularly preferably 0.08 to 0.15 (N). / 50 mm).
  • the radical generating agent is benzoyl peroxide (trade name niper BMT manufactured by NOF Corporation); D110N is an isocyanate crosslinking agent (trade name Takenate D110N manufactured by Mitsui Chemicals, Inc.); C / L is an isocyanate crosslinking agent (trade name Coronate L manufactured by Tosoh Corporation);
  • the UV absorber a1 is 2,4-bis-[ ⁇ 4- (4-ethylhexyloxy) -4-hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (commodity Name: Tinosorb S, BASF Corporation);
  • the ultraviolet absorber a2 is 2,2 ′, 4,4 ′ tetrahydroxybenzophenone (trade name: SeeSorb 106, manufactured by Cipro Chemical Industries, Ltd.);
  • the dye compound b1 is a merocyanine compound (trade name: FDB-009, maximum absorption wavelength of absorption spectrum

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to an adhesive composition for organic EL display devices, which is characterized by containing a base polymer, a radical generator and at least one compound (A) that is selected from among ultraviolet absorbents (a), each of which has 0-3 hydroxyl groups in the molecular structure and dye compounds (b), each of which has the maximum absorption wavelength of absorption spectrum within the wavelength range of from 380 nm to 430 nm. An adhesive composition for organic EL display devices according to the present invention is capable of suppressing deterioration of an organic EL element if used for an organic EL display device, and is also capable of suppressing decrease in the appearance yield, the occurrence of foaming in terms of heating durability, and the like.

Description

有機ＥＬ表示装置用粘着剤組成物、有機ＥＬ表示装置用粘着剤層、有機ＥＬ表示装置用粘着剤層付き偏光フィルム、および有機ＥＬ表示装置Adhesive composition for organic EL display device, adhesive layer for organic EL display device, polarizing film with adhesive layer for organic EL display device, and organic EL display device
　本発明は、有機ＥＬ（エレクトロルミネッセンス）表示装置（ＯＬＥＤ）用粘着剤組成物に関する。また、本発明は、前記有機ＥＬ表示装置用粘着剤組成物から形成された有機ＥＬ表示装置用粘着剤層、当該粘着剤層を有する粘着剤層付き偏光フィルムに関する。さらに、本発明は、前記粘着剤層および／または前記偏光フィルムを用いた有機ＥＬ表示装置に関する。 The present invention relates to a pressure-sensitive adhesive composition for an organic EL (electroluminescence) display (OLED). The present invention also relates to a pressure-sensitive adhesive layer for an organic EL display device formed from the pressure-sensitive adhesive composition for an organic EL display device, and a polarizing film with a pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer. Furthermore, the present invention relates to an organic EL display device using the pressure-sensitive adhesive layer and / or the polarizing film.
　近年、有機ＥＬパネルを搭載した有機ＥＬ表示装置が、携帯電話、カーナビゲーション装置、パソコン用モニタ、テレビ等の各種用途において広く用いられるようになってきた。有機ＥＬ表示装置は、通常、外光が金属電極（陰極）で反射されて鏡面のように視認されることを抑止するために、有機ＥＬパネルの視認側表面に円偏光板（偏光板と１／４波長板の積層体等）が配置される。また、有機ＥＬパネルの視認側表面に積層された円偏光板には、さらに加飾パネル等が積層される場合がある。前記円偏光板や加飾パネル等の有機ＥＬ表示装置の構成部材は、通常、粘着剤層や接着剤層等の接合材料を介して積層される。 BACKGROUND In recent years, organic EL display devices having an organic EL panel mounted are widely used in various applications such as mobile phones, car navigation devices, monitors for personal computers, and televisions. In the organic EL display device, a circularly polarizing plate (polarizing plate and polarizing plate) is usually formed on the surface of the organic EL panel to prevent external light from being reflected by the metal electrode (cathode) and viewed like a mirror surface. / 4 wave plate laminate etc.) is arranged. Moreover, a decoration panel etc. may be further laminated | stacked on the circularly-polarizing plate laminated | stacked on the visual recognition side surface of an organic electroluminescent panel. The constituent members of the organic EL display device such as the circularly polarizing plate and the decorative panel are generally laminated via a bonding material such as a pressure-sensitive adhesive layer or an adhesive layer.
　有機ＥＬ表示装置等の画像表示装置においては、入射する紫外光により画像表示装置内の構成部材等が劣化する場合があり、当該紫外光による劣化を抑制するために、紫外線吸収剤を含有する層を設けることが知られている。具体的には、例えば、少なくとも１層の紫外線吸収層を有し、波長３８０ｎｍの光線透過率が３０％以下であり、かつ波長４３０ｎｍよりも長波長側における可視光透過率が８０％以上である画像表示装置用透明両面粘着シート（例えば、特許文献１参照）が知られている。 In an image display apparatus such as an organic EL display apparatus, a component or the like in the image display apparatus may be degraded by incident ultraviolet light, and a layer containing an ultraviolet absorber to suppress the deterioration due to the ultraviolet light. It is known to provide. Specifically, for example, it has at least one ultraviolet absorbing layer, the light transmittance at a wavelength of 380 nm is 30% or less, and the visible light transmittance at a longer wavelength side than a wavelength of 430 nm is 80% or more Transparent double-sided pressure-sensitive adhesive sheets for image display devices (see, for example, Patent Document 1) are known.
特開２０１２－２１１３０５号公報JP 2012-211305 A
　一般的に、画像表示装置用透明両面粘着シートに適用される粘着剤組成物は、例えば、（メタ）アクリル系ポリマー等のベースポリマーを含有する。また粘着剤組成物には、ベースポリマーの他に、架橋剤としてラジカル発生剤（例えば、過酸化物）を用いて、ラジカル架橋させた粘着剤層を形成することがある。また、前記ベースポリマーとして（メタ）アクリル系ポリマーを用いる場合には、当該（メタ）アクリル系ポリマー中にはモノマー成分を熱または放射線硬化により調製するため、前記粘着剤組成物中にラジカル重合開始剤が含有されている。 Generally, the pressure-sensitive adhesive composition applied to the transparent double-sided pressure-sensitive adhesive sheet for image display contains, for example, a base polymer such as (meth) acrylic polymer. In addition to the base polymer, the pressure-sensitive adhesive composition sometimes forms a radically crosslinked pressure-sensitive adhesive layer using a radical generator (for example, peroxide) as a crosslinking agent. Moreover, when using a (meth) acrylic-type polymer as said base polymer, in order to prepare a monomer component in the said (meth) acrylic-type polymer by heat or radiation curing, the radical polymerization start in the said adhesive composition is started. Contains an agent.
　しかし、前記ラジカル発生剤を含有する粘着剤組成物中に、紫外線吸収剤を含有させた場合には、紫外線吸収剤によっては当該粘着剤組成物から形成される粘着剤層のゲル分率（架橋度）の低下する傾向がある。前記粘着剤層のゲル分率（架橋度）の低下が大きくなると、当該粘着剤層は、糊打痕や加工時の糊汚れによる外観歩留り低下や、加熱耐久性での発泡の発生等の不具合があった。 However, when the ultraviolet absorber is contained in the pressure-sensitive adhesive composition containing the radical generating agent, the gel fraction of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition depending on the ultraviolet absorber (crosslinking Tend to decrease. When the decrease in gel fraction (crosslinking degree) of the pressure-sensitive adhesive layer becomes large, the pressure-sensitive adhesive layer has a defect such as a decrease in appearance yield due to glue marks or glue stain during processing, and generation of foaming in heating durability. was there.
　そこで、本発明は、有機ＥＬ表示装置に用いることで、有機ＥＬ素子の劣化を抑制することができ、かつ外観歩留り低下や、加熱耐久性での発泡の発生等を抑制することができる有機ＥＬ表示装置用粘着剤組成物を提供することを目的とする。 Therefore, the present invention can suppress the deterioration of the organic EL element by using it in the organic EL display device, and can suppress the decrease in appearance yield, the generation of the foaming in the heating durability, and the like. An object of the present invention is to provide a pressure-sensitive adhesive composition for a display device.
　また、本発明は前記粘着剤組成物から形成される有機ＥＬ表示装置用粘着剤層を提供すること、偏光フィルムおよび有機ＥＬ表示装置用粘着剤層を有する粘着剤層付き偏光フィルムを提供すること、前記粘着剤層および／または前記粘着剤層付き偏光フィルムを含む有機ＥＬ表示装置を提供することを目的とする。 Further, the present invention provides a pressure-sensitive adhesive layer for an organic EL display device formed from the pressure-sensitive adhesive composition, and provides a polarizing film with a pressure-sensitive adhesive layer having a polarizing film and a pressure-sensitive adhesive layer for an organic EL display device. An object of the present invention is to provide an organic EL display device including the pressure-sensitive adhesive layer and / or the polarizing film with the pressure-sensitive adhesive layer.
　本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、下記有機ＥＬ表示装置用粘着剤組成物を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found the following pressure-sensitive adhesive composition for an organic EL display device, and have completed the present invention.
　即ち、本発明は、ベースポリマー、ラジカル発生剤、並びに、分子構造中の水酸基が０～３個である紫外線吸収剤（ａ）および吸収スペクトルの最大吸収波長が３８０～４３０ｎｍの波長領域に存在する色素化合物（ｂ）から選ばれる少なくとも１種の化合物（Ａ）含むことを特徴とする有機ＥＬ表示装置用粘着剤組成物、に関する。 That is, according to the present invention, the base polymer, the radical generator, the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure, and the maximum absorption wavelength of the absorption spectrum in the wavelength region of 380 to 430 nm The present invention relates to a pressure-sensitive adhesive composition for an organic EL display device, which comprises at least one compound (A) selected from the dye compound (b).
　前記有機ＥＬ表示装置用粘着剤組成物において、前記化合物（Ａ）が、前記紫外線吸収剤（ａ）および前記色素化合物（ｂ）の両方を含むことが好ましい。 In the pressure-sensitive adhesive composition for an organic EL display device, it is preferable that the compound (A) contains both the ultraviolet absorber (a) and the dye compound (b).
　前記有機ＥＬ表示装置用粘着剤組成物において、前記紫外線吸収剤（ａ）の吸収スペクトルの最大吸収波長が、３００～４００ｎｍの波長領域に存在することが好ましい。 In the pressure-sensitive adhesive composition for an organic EL display device, it is preferable that the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) exists in a wavelength range of 300 to 400 nm.
　前記有機ＥＬ表示装置用粘着剤組成物において、前記ラジカル発生剤は、過酸化物を用いることができる。 In the pressure-sensitive adhesive composition for an organic EL display device, a peroxide can be used as the radical generator.
　前記有機ＥＬ表示装置用粘着剤組成物において、前記ベースポリマーは、（メタ）アクリル系ポリマーを用いることができる。 In the pressure-sensitive adhesive composition for an organic EL display device, a (meth) acrylic polymer can be used as the base polymer.
　前記有機ＥＬ表示装置用粘着剤組成物において、前記ラジカル発生剤を、前記ベースポリマー１００重量部に対して０．０１～２重量部含有することが好ましい。 In the pressure-sensitive adhesive composition for an organic EL display device, the radical generator is preferably contained in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the base polymer.
　前記有機ＥＬ表示装置用粘着剤組成物において、前記化合物（Ａ）を、前記ベースポリマー１００重量部に対して０．１～２５重量部含有することが好ましい。 In the pressure-sensitive adhesive composition for an organic EL display device, the compound (A) is preferably contained in an amount of 0.1 to 25 parts by weight with respect to 100 parts by weight of the base polymer.
　前記有機ＥＬ表示装置用粘着剤組成物は、さらに酸化防止剤を含むことができる。 The pressure-sensitive adhesive composition for an organic EL display may further contain an antioxidant.
　前記有機ＥＬ表示装置用粘着剤組成物は、さらに架橋剤を含むことができる。 The pressure-sensitive adhesive composition for an organic EL display may further contain a crosslinking agent.
　また本発明は、前記有機ＥＬ表示装置用粘着剤組成物から形成されることを特徴とする有機ＥＬ表示装置用粘着剤層、に関する。 The present invention also relates to a pressure-sensitive adhesive layer for an organic EL display device, which is formed from the pressure-sensitive adhesive composition for an organic EL display device.
　前記有機ＥＬ表示装置用粘着剤層は、波長３００～４００ｎｍの平均透過率が１２％以下であり、波長４００ｎｍ～４３０ｎｍの平均透過率が３０％以下であり、波長４３０～４５０ｎｍの平均透過率が７０％以上であることが好ましい。 The pressure-sensitive adhesive layer for an organic EL display device has an average transmittance of 12% or less at a wavelength of 300 to 400 nm, an average transmittance of 30% or less at a wavelength of 400 nm to 430 nm, and an average transmittance of 430 to 450 nm. It is preferable that it is 70% or more.
　前記有機ＥＬ表示装置用粘着剤層は、波長３００～４００ｎｍの平均透過率が１２％以下であり、波長４００ｎｍ～４３０ｎｍの平均透過率が３０％を超え９５％以下であり、波長４３０～４５０ｎｍの平均透過率が８０％以上であることが好ましい。 The pressure-sensitive adhesive layer for the organic EL display device has an average transmittance of 12% or less at a wavelength of 300 to 400 nm, an average transmittance of 400 nm to 430 nm at a wavelength of more than 30% and 95% or less. The average transmittance is preferably 80% or more.
　また本発明は、偏光フィルムと、前記有機ＥＬ表示装置用粘着剤層とを有することを特徴とする有機ＥＬ表示装置用粘着剤層付き偏光フィルム、に関する。 The present invention also relates to a polarizing film with a pressure-sensitive adhesive layer for an organic EL display characterized by having a polarizing film and the pressure-sensitive adhesive layer for the organic EL display.
　前記有機ＥＬ表示装置用粘着剤層付き偏光フィルムは、前記偏光フィルムが、偏光子の一方の面に透明保護フィルムが設けられ、他方の面に位相差フィルムを有するものであって、前記有機ＥＬ表示装置用粘着剤層が、前記位相差フィルムの偏光子と接する面と反対側の面、および／または、前記透明保護フィルムの偏光子と接する面と反対側の面に設けられることが好ましい。 In the polarizing film with an adhesive layer for an organic EL display device, the polarizing film is provided with a transparent protective film on one side of a polarizer and has a retardation film on the other side, and the organic EL It is preferable that a pressure-sensitive adhesive layer for a display device be provided on the surface of the retardation film opposite to the surface in contact with the polarizer and / or on the surface of the transparent protective film opposite to the surface in contact with the polarizer.
　前記有機ＥＬ表示装置用粘着剤層付き偏光フィルムは、第１粘着剤層、透明保護フィルム、偏光子、第２粘着剤層、位相差フィルム、第３粘着剤層をこの順に有する有機ＥＬ表示装置用粘着剤層付き偏光フィルムであって、
　前記第１粘着剤層、第２粘着剤層、および第３粘着剤層のうち、少なくとも一つの粘着剤層が、前記有機ＥＬ表示装置用粘着剤層であることが好ましい。 The polarizing film with a pressure-sensitive adhesive layer for an organic EL display device is an organic EL display device having a first pressure-sensitive adhesive layer, a transparent protective film, a polarizer, a second pressure-sensitive adhesive layer, a retardation film, and a third pressure-sensitive adhesive layer in this order. A polarizing film with a pressure-sensitive adhesive layer,
It is preferable that at least one pressure-sensitive adhesive layer among the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer for the organic EL display device.
　前記有機ＥＬ表示装置用粘着剤層付き偏光フィルムにおいて、前記位相差フィルムが１／４波長板であって、前記偏光フィルムが円偏光フィルムであることが好ましい。 In the pressure-sensitive adhesive layer-attached polarizing film for an organic EL display device, it is preferable that the retardation film is a 1⁄4 wavelength plate, and the polarizing film is a circularly polarizing film.
　また本発明は、前記有機ＥＬ表示装置用粘着剤層、または前記有機ＥＬ表示装置用粘着剤層付き偏光フィルムを少なくとも１つ用いたことを特徴とする有機ＥＬ表示装置、に関する。 The present invention also relates to an organic EL display device using at least one of the pressure-sensitive adhesive layer for the organic EL display device or the polarizing film with the pressure-sensitive adhesive layer for the organic EL display device.
　本発明の有機ＥＬ表示装置用粘着剤組成物は、ベースポリマーの他に、紫外線吸収剤（ａ）を含有する。紫外線吸収剤（ａ）によって、紫外光による劣化を抑制して、有機ＥＬ素子の劣化を抑制することができる。また、本発明の有機ＥＬ表示装置用粘着剤組成物は、前記紫外線吸収剤（ａ）の代わりに、または前記紫外線吸収剤（ａ）と併用して吸収スペクトルの最大吸収波長が３８０～４３０ｎｍの波長領域に存在する色素化合物（ｂ）を含有する。当該色素化合物（ｂ）によっても、紫外光による劣化を抑制して、有機ＥＬ素子の劣化を抑制することができる。 The pressure-sensitive adhesive composition for an organic EL display device of the present invention contains an ultraviolet absorber (a) in addition to the base polymer. The ultraviolet absorber (a) can suppress the deterioration due to the ultraviolet light and can suppress the deterioration of the organic EL element. In the pressure-sensitive adhesive composition for an organic EL display device of the present invention, the maximum absorption wavelength of the absorption spectrum is 380 to 430 nm in place of the ultraviolet light absorber (a) or in combination with the ultraviolet light absorber (a) It contains a dye compound (b) present in the wavelength range. Also by the said pigment | dye compound (b), deterioration by an ultraviolet light can be suppressed and deterioration of an organic EL element can be suppressed.
　また、本発明の有機ＥＬ表示装置用粘着剤組成物は、過酸化物等のラジカル発生剤を含有する。当該ラジカル発生剤は、例えば、（メタ）アクリル系ポリマー等のベースポリマーに対する架橋剤として機能して、前記粘着剤組成物から形成される粘着剤層のゲル分率を所望の範囲に制御することができ、良好な外観の粘着剤層を形成することができる。 The pressure-sensitive adhesive composition for an organic EL display device of the present invention contains a radical generator such as a peroxide. The said radical generating agent functions as a crosslinking agent with respect to base polymers, such as (meth) acrylic-type polymer, for example, and controls the gel fraction of the adhesive layer formed from the said adhesive composition in a desired range. Can form a pressure-sensitive adhesive layer having a good appearance.
　前記のように本発明の有機ＥＬ表示装置用粘着剤組成物中には、紫外線吸収剤および／または色素化合物と、ラジカル発生剤が併存するため、得られる粘着剤層のゲル分率の低下が懸念される。しかし、本発明の有機ＥＬ表示装置用粘着剤組成物では、紫外線吸収剤として、分子構造中の水酸基が０～３個である紫外線吸収剤（ａ）を選択して用いる。即ち、本発明では、ゲル分率の低下は、ラジカル発生剤から発生するラジカルが失活することによる架橋度の低下に起因しており、そのラジカルを失活させる原因が、紫外線吸収剤が有する水素供与性基であると考え、水素供与性基に係る水酸基は３個以下の紫外線吸収剤（ａ）を選択して用いることで、紫外線吸収剤によるラジカル発生剤の架橋阻害を抑制している。 As described above, in the pressure-sensitive adhesive composition for an organic EL display device according to the present invention, the ultraviolet absorber and / or the dye compound and the radical generating agent coexist, so that the gel fraction of the obtained pressure-sensitive adhesive layer decreases. I am concerned. However, in the pressure-sensitive adhesive composition for an organic EL display device of the present invention, an ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure is selected and used as the ultraviolet absorber. That is, in the present invention, the decrease in gel fraction is due to the decrease in the degree of crosslinking due to the deactivation of the radical generated from the radical generator, and the cause of the deactivation of the radical is the ultraviolet absorber Considering that it is a hydrogen donating group, by suppressing the use of three or less UV absorbers (a) for the hydroxyl group related to the hydrogen donating group, the inhibition of crosslinking of the radical generator by the UV absorber is suppressed .
　その結果、本発明の有機ＥＬ表示装置用粘着剤組成物によれば、外観歩留り低下や、加熱耐久性での発泡の発生等を抑制することができる有機ＥＬ表示装置用粘着剤層が得られる。従って、本発明の有機ＥＬ表示装置用粘着剤層および／または有機ＥＬ表示装置用粘着剤層を含む粘着剤層付き偏光フィルムを用いた有機ＥＬ表示装置は、優れた耐候劣化性を有し、長寿命化することができる。 As a result, according to the pressure-sensitive adhesive composition for an organic EL display device of the present invention, it is possible to obtain a pressure-sensitive adhesive layer for an organic EL display device capable of suppressing the decrease in appearance yield and the occurrence of foaming in heating durability. . Therefore, the organic EL display device using the pressure-sensitive adhesive layer-attached polarizing film including the pressure-sensitive adhesive layer for the organic EL display device and / or the pressure-sensitive adhesive layer for the organic EL display device of the present invention has excellent weathering deterioration resistance It is possible to extend the life.
（ａ）～（ｃ）本発明の有機ＥＬ表示装置用粘着剤層付き偏光フィルムの一実施形態を模式的に示す断面図である。(A) to (c) are cross-sectional views schematically showing an embodiment of a polarizing film with an adhesive layer for an organic EL display device of the present invention. 本発明の有機ＥＬ表示装置の一実施形態を模式的に示す断面図である。It is a sectional view showing typically one embodiment of the organic EL display of the present invention. 本発明の有機ＥＬ表示装置の一実施形態を模式的に示す断面図である。It is a sectional view showing typically one embodiment of the organic EL display of the present invention. 本発明の有機ＥＬ表示装置の一実施形態を模式的に示す断面図である。It is a sectional view showing typically one embodiment of the organic EL display of the present invention.
　１．有機ＥＬ表示装置用粘着剤組成物
　本発明の有機ＥＬ表示装置用粘着剤組成物は、ベースポリマー、ラジカル発生剤、並びに、分子構造中の水酸基が０～３個である紫外線吸収剤（ａ）および吸収スペクトルの最大吸収波長が３８０～４３０ｎｍの波長領域に存在する色素化合物（ｂ）から選ばれる少なくとも１種の化合物（Ａ）含むことを特徴とする。 1. Pressure-Sensitive Adhesive Composition for Organic EL Display Device The pressure-sensitive adhesive composition for an organic EL display device according to the present invention comprises a base polymer, a radical generator, and a UV absorber having 0 to 3 hydroxyl groups in its molecular structure (a) And at least one compound (A) selected from the dye compounds (b) present in the wavelength range of 380 to 430 nm as the maximum absorption wavelength of the absorption spectrum.
　本発明の有機ＥＬ表示装置用粘着剤組成物は、ベースポリマーを主成分として含む。主成分とは、粘着剤組成物に含まれる全固形分のうち最も含有割合の多い成分を指し、例えば、粘着剤組成物に含まれる全固形分のうち５０重量％より多くを占める成分であり、さらには７０重量％より多くを占める成分を指す。 The pressure-sensitive adhesive composition for an organic EL display device of the present invention contains a base polymer as a main component. The main component refers to the component having the highest content of the total solids contained in the pressure-sensitive adhesive composition, and is, for example, a component that accounts for more than 50% by weight of the total solids contained in the pressure-sensitive adhesive composition , Or even components that account for more than 70% by weight.
　本発明で用いるベースポリマーとしては、特に限定されるものではなく、粘着剤組成物の種類としては、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤等を挙げることができる。これら粘着剤の中でも、光学的透明性に優れ、適宜な密着性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性等に優れる点から、アクリル系粘着剤が好ましく使用される。本発明においては、（メタ）アクリル系ポリマーをベースポリマーとして含有するアクリル系粘着剤組成物であることが好ましい。 It does not specifically limit as a base polymer used by this invention, As a kind of adhesive composition, For example, a rubber adhesive, an acrylic adhesive, a silicone adhesive, a urethane adhesive, vinyl alkyl Ether pressure sensitive adhesives, polyvinyl alcohol pressure sensitive adhesives, polyvinyl pyrrolidone pressure sensitive adhesives, polyacrylamide pressure sensitive adhesives, cellulose pressure sensitive adhesives, etc. can be mentioned. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used from the viewpoints of excellent optical transparency, showing appropriate adhesion, cohesiveness and adhesion properties of adhesion, and excellent in weather resistance, heat resistance, etc. . In the present invention, an acrylic pressure-sensitive adhesive composition containing a (meth) acrylic polymer as a base polymer is preferable.
　＜（メタ）アクリル系ポリマー＞
　前記（メタ）アクリル系ポリマーは、通常、モノマー単位として、アルキル（メタ）アクリレートを主成分として含有する。なお、（メタ）アクリレートはアクリレートおよび／またはメタクリレートをいい、本発明の（メタ）とは同様の意味である。 <(Meth) acrylic polymer>
The (meth) acrylic polymer usually contains, as a monomer unit, an alkyl (meth) acrylate as a main component. In addition, (meth) acrylate is an acrylate and / or a methacrylate, and (meth) of this invention is the same meaning.
　前記（メタ）アクリル系ポリマーの主骨格を構成する、アルキル（メタ）アクリレートとしては、直鎖状または分岐鎖状のアルキル基の炭素数１～１８のものを例示できる。これらは単独であるいは組み合わせて使用することができる。これらアルキル基の平均炭素数は３～９であるのが好ましい。 Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer include ones having 1 to 18 carbon atoms of a linear or branched alkyl group. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3 to 9.
　また、粘着特性、耐久性、位相差の調整、屈折率の調整等の点から、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレートのような芳香族環を含有するアルキル（メタ）アクリレートを用いることができる。 In addition, in view of adhesion properties, durability, adjustment of retardation, adjustment of refractive index, etc., alkyl (meth) acrylates containing an aromatic ring such as phenoxyethyl (meth) acrylate or benzyl (meth) acrylate are used be able to.
　前記（メタ）アクリル系ポリマー中には、接着性や耐熱性の改善を目的に、（メタ）アクリロイル基またはビニル基等の不飽和二重結合を有する重合性の官能基を有する、１種類以上の共重合モノマーを共重合により導入することができる。そのような共重合モノマーの具体例としては、例えば、(メタ)アクリル酸２－ヒドロキシエチル、(メタ)アクリル酸３－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や（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等のヒドロキシル基含有モノマー；(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、クロトン酸等のカルボキシル基含有モノマー；無水マレイン酸、無水イタコン酸等の酸無水物基含有モノマー；アクリル酸のカプロラクトン付加物；スチレンスルホン酸やアリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸等のスルホン酸基含有モノマー；２－ヒドロキシエチルアクリロイルホスフェート等の燐酸基含有モノマー等が挙げられる。 In the (meth) acrylic polymer, at least one type having a polymerizable functional group having an unsaturated double bond such as (meth) acryloyl group or vinyl group for the purpose of improving adhesiveness and heat resistance. The copolymerized monomers of (1) can be introduced by copolymerization. Specific examples of such copolymerizable monomers include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid 6 -Hydroxyl-containing monomers such as -hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Group containing monomers; acrylic acid with caprolactone Styrene sulfonic acid or allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, (meth) acrylamidopropane sulfonic acid, sulfopropyl (meth) acrylate, sulfone such as (meth) acryloyloxynaphthalene sulfonic acid Acid group-containing monomers; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate and the like.
　また、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミドやＮ－メチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミド等の（Ｎ－置換）アミド系モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチル等の（メタ）アクリル酸アルキルアミノアルキル系モノマー；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル等の（メタ）アクリル酸アルコキシアルキル系モノマー；Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミドやＮ－（メタ）アクリロイル－６－オキシヘキサメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－８－オキシオクタメチレンスクシンイミド、Ｎ－アクリロイルモルホリン等のスクシンイミド系モノマー；Ｎ－シクロヘキシルマレイミドやＮ－イソプロピルマレイミド、Ｎ－ラウリルマレイミドやＮ－フェニルマレイミド等のマレイミド系モノマー；Ｎ－メチルイタコンイミド、Ｎ－エチルイタコンイミド、Ｎ－ブチルイタコンイミド、Ｎ－オクチルイタコンイミド、Ｎ－２－エチルヘキシルイタコンイミド、Ｎ－シクロヘキシルイタコンイミド、Ｎ－ラウリルイタコンイミド等のイタコンイミド系モノマー、等も改質目的のモノマー例として挙げられる。 Also, (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide and the like Monomers; (meth) acrylic acid alkylaminoalkyl monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate; (meth) acrylic (Meth) acrylate alkoxyalkyl monomers such as methoxyethyl acrylate and ethoxyethyl (meth) acrylate; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- ( Meta) Acryloyl-8- Succinimide based monomers such as xyoctamethylene succinimide and N-acryloyl morpholine; maleimide based monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide and N-phenyl maleimide; N-methyl itaconimide, N-ethyl itaconic Itaconimide based monomers such as imide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N-lauryl lutaconimide, etc. are also mentioned as examples of monomers for modification purpose .
　さらに改質モノマーとして、酢酸ビニル、プロピオン酸ビニル、Ｎ－ビニルピロリドン、メチルビニルピロリドン、ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、Ｎ－ビニルカルボン酸アミド類、スチレン、α－メチルスチレン、Ｎ－ビニルカプロラクタム等のビニル系モノマー；アクリロニトリル、メタクリロニトリル等のシアノアクリレート系モノマー；（メタ）アクリル酸グリシジル等のエポキシ基含有アクリル系モノマー；（メタ）アクリル酸ポリエチレングリコール、（メタ）アクリル酸ポリプロピレングリコール、（メタ）アクリル酸メトキシエチレングリコール、（メタ）アクリル酸メトキシポリプロピレングリコール等のグリコール系アクリルエステルモノマー；（メタ）アクリル酸テトラヒドロフルフリル、フッ素（メタ）アクリレート、シリコーン（メタ）アクリレートや２－メトキシエチルアクリレート等のアクリル酸エステル系モノマー等も使用することができる。さらには、イソプレン、ブタジエン、イソブチレン、ビニルエーテル等が挙げられる。 Further, as modifying monomers, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N- Vinyl monomers such as vinyl carboxylic acid amides, styrene, α-methylstyrene, N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy ethylene glycol (meth) acrylate, methoxy (meth) acrylate It is also possible to use glycol-based acrylic ester monomers such as propylene glycol; acrylic acid ester-based monomers such as (meth) acrylic acid tetrahydrofurfuryl, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate, etc. it can. Furthermore, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.
　さらに、上記以外の共重合可能なモノマーとして、ケイ素原子を含有するシラン系モノマー等が挙げられる。シラン系モノマーとしては、例えば、３－アクリロキシプロピルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、４－ビニルブチルトリメトキシシラン、４－ビニルブチルトリエトキシシラン、８－ビニルオクチルトリメトキシシラン、８－ビニルオクチルトリエトキシシラン、１０－メタクリロイルオキシデシルトリメトキシシラン、１０－アクリロイルオキシデシルトリメトキシシラン、１０－メタクリロイルオキシデシルトリエトキシシラン、１０－アクリロイルオキシデシルトリエトキシシラン等が挙げられる。 Furthermore, as a copolymerizable monomer other than the above, the silane type monomer containing a silicon atom, etc. are mentioned. Examples of silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane 8-vinyloctyl triethoxysilane, 10-methacryloyloxydecyl trimethoxysilane, 10-acryloyloxydecyl trimethoxysilane, 10-methacryloyloxydecyl triethoxysilane, 10-acryloyloxydecyl triethoxysilane, and the like.
　また、共重合モノマーとしては、トリプロピレングリコールジ（メタ）アクリレート、テトラ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、ビスフェノールＡジグリシジルエーテルジ（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、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（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、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステル化物等の（メタ）アクリロイル基、ビニル基等の不飽和二重結合を２個以上有する多官能性モノマーや、ポリエステル、エポキシ、ウレタン等の骨格にモノマー成分と同様の官能基として（メタ）アクリロイル基、ビニル基等の不飽和二重結合を２個以上付加したポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等を用いることもできる。 Further, as a copolymerizable monomer, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate And (meth) acryloyl esters of (meth) acrylic acid and polyhydric alcohol such as caprolactone modified with dipentaerythritol hexa (meth) acrylate Group, a polyfunctional monomer having two or more unsaturated double bonds such as vinyl group, or a skeleton such as polyester, epoxy, urethane etc. as a functional group similar to the monomer component and an unfunctionalized group such as (meth) acryloyl group or vinyl group It is also possible to use polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate or the like in which two or more saturated double bonds are added.
　前記（メタ）アクリル系ポリマーは、全構成モノマーの重量比率において、アルキル（メタ）アクリレートを主成分とし、（メタ）アクリル系ポリマー中の前記共重合モノマーの割合は、特に制限されないが、前記共重合モノマーの割合は、全構成モノマーの重量比率において、０～２０％程度、０．１～１５％程度、さらには０．１～１０％程度であるのが好ましい。 The (meth) acrylic polymer has an alkyl (meth) acrylate as a main component in the weight ratio of all constituent monomers, and the proportion of the copolymerization monomer in the (meth) acrylic polymer is not particularly limited, but the above copolymer The proportion of the polymerization monomer is preferably about 0 to about 20%, about 0.1 to about 15%, and more preferably about 0.1 to about 10% by weight of the total constituent monomers.
　これら共重合モノマーの中でも、接着性、耐久性の点から、ヒドロキシル基含有モノマー、カルボキシル基含有モノマーが好ましく用いられる。ヒドロキシル基含有モノマーおよびカルボキシル基含有モノマーは併用することができる。これら共重合モノマーは、粘着剤組成物が架橋剤を含有する場合に、架橋剤との反応点になる。ヒドロキシル基含有モノマー、カルボキシル基含有モノマー等は分子間架橋剤との反応性に富むため、得られる粘着剤層の凝集性や耐熱性の向上のために好ましく用いられる。ヒドロキシル基含有モノマーはリワーク性の点で好ましく、またカルボキシル基含有モノマーは耐久性とリワーク性を両立させる点で好ましい。 Among these copolymerizable monomers, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferably used from the viewpoint of adhesiveness and durability. The hydroxyl group-containing monomer and the carboxyl group-containing monomer can be used in combination. When the pressure-sensitive adhesive composition contains a crosslinking agent, these copolymerizable monomers become reactive points with the crosslinking agent. A hydroxyl group-containing monomer, a carboxyl group-containing monomer and the like are preferably used to improve the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer since they are highly reactive with the intermolecular crosslinking agent. The hydroxyl group-containing monomer is preferable in terms of reworkability, and the carboxyl group-containing monomer is preferable in terms of achieving both durability and reworkability.
　前記共重合モノマーとして、ヒドロキシル基含有モノマーを含有する場合、その割合は、０．０１～１５重量％が好ましく、０．０３～１０重量％がより好ましく、さらには０．０５～７重量％が好ましい。前記共重合モノマーとして、カルボキシル基含有モノマーを含有する場合、その割合は、０．０５～１０重量％が好ましく、０．１～８重量％がより好ましく、さらには０．２～６重量％が好ましい。 When the hydroxyl group-containing monomer is contained as the copolymerization monomer, the ratio is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and further preferably 0.05 to 7% by weight. preferable. When the carboxyl group-containing monomer is contained as the copolymerization monomer, the ratio is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and further 0.2 to 6% by weight. preferable.
　本発明の（メタ）アクリル系ポリマーは、通常、重量平均分子量が５０万～３００万の範囲のものが用いられる。耐久性、特に耐熱性を考慮すれば、重量平均分子量は７０万～２７０万であるものを用いることが好ましい。さらには８０万～２５０万であることが好ましい。重量平均分子量が５０万よりも小さいと、耐熱性の点で好ましくない。また、重量平均分子量が３００万よりも大きくなると、塗工するための粘度に調整するために多量の希釈溶剤が必要となり、コストアップとなることから好ましくない。なお、重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定し、ポリスチレン換算により算出された値をいう。 As the (meth) acrylic polymer of the present invention, one having a weight average molecular weight of 500,000 to 3,000,000 is usually used. In consideration of durability, particularly heat resistance, it is preferable to use one having a weight average molecular weight of 700,000 to 2,700,000. Furthermore, 800,000 to 2,500,000 are preferable. When the weight average molecular weight is less than 500,000, it is not preferable in terms of heat resistance. Further, when the weight average molecular weight is larger than 3,000,000, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable because the cost is increased. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.
　このような（メタ）アクリル系ポリマーの製造は、溶液重合、ＵＶ重合等の放射線重合、塊状重合、乳化重合、各種ラジカル重合などの公知の製造方法を適宜選択できる。また、得られる（メタ）アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト共重合体などいずれでもよい。 The production of such (meth) acrylic polymers can be appropriately selected from known production methods such as solution polymerization, radiation polymerization such as UV polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations. In addition, the (meth) acrylic polymer to be obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
　なお、溶液重合においては、重合溶媒として、例えば、酢酸エチル、トルエンなどが用いられる。具体的な溶液重合例としては、反応は窒素などの不活性ガス気流下で、重合開始剤を加え、通常、５０～７０℃程度で、５～３０時間程度の反応条件で行われる。 In solution polymerization, for example, ethyl acetate, toluene or the like is used as a polymerization solvent. As a specific example of solution polymerization, the reaction is carried out under a stream of an inert gas such as nitrogen, usually with the addition of a polymerization initiator, under reaction conditions of about 50 to 70 ° C. for about 5 to 30 hours.
　ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤などは特に限定されず適宜選択して使用することができる。なお、（メタ）アクリル系ポリマーの重量平均分子量は、重合開始剤、連鎖移動剤の使用量、反応条件により制御可能であり、これらの種類に応じて適宜のその使用量が調整される。 The polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used. The weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount used can be appropriately adjusted according to the type of these.
　ラジカル重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロライド、２，２’－アゾビス［２－（５－メチル－２－イミダゾリン－２－イル）プロパン］ジヒドロクロライド、２，２’－アゾビス（２－メチルプロピオンアミジン）二硫酸塩、２，２’－アゾビス（Ｎ，Ｎ’－ジメチレンイソブチルアミジン）、２，２’－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］ハイドレート（和光純薬社製、ＶＡ－０５７）などのアゾ系開始剤、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、ジラウロイルパーオキシド、ジ－ｎ－オクタノイルパーオキシド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジ（４－メチルベンゾイル）パーオキシド、ジベンゾイルパーオキシド、ｔ－ブチルパーオキシイソブチレート、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、ｔ－ブチルハイドロパーオキシド、過酸化水素などの過酸化物系開始剤、過硫酸塩と亜硫酸水素ナトリウムの組み合わせ、過酸化物とアスコルビン酸ナトリウムの組み合わせなどの過酸化物と還元剤とを組み合わせたレドックス系開始剤などを挙げることができるが、これらに限定されるものではない。 As a radical polymerization initiator, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-) 2-Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutyramidine), 2, Azo initiators such as 2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057), persulfates such as potassium persulfate and ammonium persulfate Salt, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-se -Butyl peroxy dicarbonate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1 , 3,3-Tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoylperoxide, t-butylperoxyisobutyrate, 1,1-di (t-hexyl) Peroxy) Peroxide initiators such as peroxidase initiators such as cyclohexane, t-butyl hydroperoxide and hydrogen peroxide, combinations of persulfates and sodium bisulfite, and combinations of peroxides and sodium ascorbate Although the redox type initiator etc. which combined the agent are mentioned, The present invention is not limited to these.
　前記ラジカル重合開始剤は、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量はモノマー１００重量部に対して、０．００５～１重量部程度であることが好ましく、０．０２～０．５重量部程度であることがより好ましい。 The radical polymerization initiators may be used alone or in combination of two or more, but the total content is 0.005 to 1 weight per 100 weight parts of the monomer. It is preferably in the order of parts, and more preferably in the range of about 0.02 to 0.5 parts by weight.
　連鎖移動剤としては、例えば、ラウリルメルカプタン、グリシジルメルカプタン、メルカプト酢酸、２－メルカプトエタノール、チオグリコール酸、チオグルコール酸２－エチルヘキシル、２，３－ジメルカプト－１－プロパノールなどが挙げられる。連鎖移動剤は、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量はモノマー成分の全量１００重量部に対して、０．１重量部程度以下である。 Examples of chain transfer agents include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol and the like. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to.
　また、乳化重合する場合に用いる乳化剤としては、例えば、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウムなどのアニオン系乳化剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン－ポリオキシプロピレンブロックポリマーなどのノニオン系乳化剤などが挙げられる。これらの乳化剤は、単独で用いてもよく２種以上を併用してもよい。 Moreover, as an emulsifier used when carrying out the emulsion polymerization, for example, anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, etc., polyoxy Nonionic emulsifiers, such as ethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, etc. are mentioned. These emulsifiers may be used alone or in combination of two or more.
　さらに、反応性乳化剤として、プロペニル基、アリルエーテル基などのラジカル重合性官能基が導入された乳化剤として、具体的には、例えば、アクアロンＨＳ－１０、ＨＳ－２０、ＫＨ－１０、ＢＣ－０５、ＢＣ－１０、ＢＣ－２０（以上、いずれも第一工業製薬社製）、アデカリアソープＳＥ１０Ｎ（旭電化工社製）などがある。反応性乳化剤は、重合後にポリマー鎖に取り込まれるため、耐水性がよくなり好ましい。乳化剤の使用量は、モノマー成分の全量１００重量部に対して、０．３～５重量部、重合安定性や機械的安定性から０．５～１重量部がより好ましい。 Furthermore, as a reactive emulsifier, as an emulsifier into which a radically polymerizable functional group such as propenyl group or allyl ether group is introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE10N (manufactured by Asahi Denka Co., Ltd.), and the like. Reactive emulsifiers are preferred because they are incorporated into the polymer chain after polymerization, which improves the water resistance. The amount of the emulsifier used is preferably 0.3 to 5 parts by weight, more preferably 0.5 to 1 parts by weight from the viewpoint of polymerization stability and mechanical stability, based on 100 parts by weight of the total of the monomer components.
　＜ラジカル発生剤＞
　本発明の粘着剤組成物に配合されるラジカル発生剤としては、前記（メタ）アクリル系ポリマーの製造の際に用いたラジカル重合開始剤を例示することができる。前記ラジカル重合開始剤のなかでも、粘着剤組成物に配合されるラジカル発生剤は過酸化物が好ましい。 <Radical generator>
As a radical generating agent mix | blended with the adhesive composition of this invention, the radical polymerization initiator used in the case of manufacture of the said (meth) acrylic-type polymer can be illustrated. Among the above-mentioned radical polymerization initiators, peroxides are preferable as the radical generator to be blended in the pressure-sensitive adhesive composition.
　ラジカル発生剤は、加熱または光照射によりラジカル活性種を発生して粘着剤組成物中の（メタ）アクリル系ポリマーの架橋を進行させることができる。ラジカル発生剤としては、作業性や安定性を勘案して、１分間半減期温度が８０℃～１６０℃である過酸化物を使用することが好ましく、９０℃～１４０℃である過酸化物を使用することがより好ましい。 The radical generator can generate radically active species by heating or light irradiation to promote crosslinking of the (meth) acrylic polymer in the pressure-sensitive adhesive composition. As a radical generating agent, it is preferable to use a peroxide having a half-life temperature of 80 ° C. to 160 ° C., preferably 90 ° C. to 140 ° C., in consideration of workability and stability. It is more preferable to use.
　前記過酸化物としては、例えば、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート（１分間半減期温度：９２．１℃）、ジ－ｓｅｃ－ブチルパーオキシジカーボネート（１分間半減期温度：９２．４℃）、ｔ－ブチルパーオキシネオデカノエート（１分間半減期温度：１０３．５℃）、ｔ－ヘキシルパーオキシピバレート（１分間半減期温度：１０９．１℃）、ｔ－ブチルパーオキシピバレート（１分間半減期温度：１１０．３℃）、ジラウロイルパーオキシド（１分間半減期温度：１１６．４℃）、ジ－ｎ－オクタノイルパーオキシド（１分間半減期温度：１１７．４℃）、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート（１分間半減期温度：１２４．３℃）、ジ（４－メチルベンゾイル）パーオキシド（１分間半減期温度：１２８．２℃）、ジベンゾイルパーオキシド（１分間半減期温度：１３０．０℃）、ｔ－ブチルパーオキシイソブチレート（１分間半減期温度：１３６．１℃）、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン（１分間半減期温度：１４９．２℃）等が挙げられる。なかでも特に架橋反応効率が優れることから、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート（１分間半減期温度：９２．１℃）、ジラウロイルパーオキシド（１分間半減期温度：１１６．４℃）、ジベンゾイルパーオキシド（１分間半減期温度：１３０．０℃）等が好ましく用いられる。 Examples of the peroxide include di (4-t-butylcyclohexyl) peroxydicarbonate (one-minute half-life temperature: 92.1 ° C.), di-sec-butylperoxydicarbonate (one-minute half-life temperature 92.4 ° C., t-butylperoxy neodecanoate (one-minute half-life temperature: 103.5 ° C.), t-hexyl peroxypivalate (one-minute half-life temperature: 109.1 ° C.), t -Butyl peroxypivalate (one-minute half-life temperature: 110.3 ° C), dilauroyl peroxide (one-minute half-life temperature: 116.4 ° C), di-n-octanoyl peroxide (one-minute half-life temperature 117.4 ° C., 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (half-life temperature per minute: 124.3 ° C.), di (4-methylbenzoyl) -Oxide (one-minute half-life temperature: 128.2 ° C), dibenzoyl peroxide (one-minute half-life temperature: 130.0 ° C), t-butyl peroxyisobutyrate (one-minute half-life temperature: 136.1 ° C And 1,1-di (t-hexylperoxy) cyclohexane (one-minute half-life temperature: 149.2 ° C.). Among them, since the crosslinking reaction efficiency is particularly excellent, di (4-t-butylcyclohexyl) peroxydicarbonate (one-minute half-life temperature: 92.1 ° C.), dilauroyl peroxide (one-minute half-life temperature: 116. 4 ° C.), dibenzoyl peroxide (one-minute half-life temperature: 130.0 ° C.), etc. are preferably used.
　前記過酸化物の半減期とは、過酸化物の分解速度を表す指標であり、過酸化物の残存量が半分になるまでの時間をいう。任意の時間で半減期を得るための分解温度や、任意の温度での半減期時間に関しては、メーカーカタログなどに記載されており、たとえば、日本油脂株式会社の「有機過酸化物カタログ第９版（２００３年５月）」などに記載されている。 The half life of the peroxide is an index indicating the decomposition rate of the peroxide, and refers to the time until the remaining amount of the peroxide is halved. The decomposition temperature for obtaining the half life at any time and the half life time at any temperature are described in the manufacturer catalog etc. For example, “Organic peroxide catalog 9th edition of Nippon Oil and Fats Co., Ltd. (May 2003) and the like.
　本発明の粘着剤組成物におけるラジカル発生剤（特に過酸化物）の含有量は、前記粘着剤組成物から形成される粘着剤層の加工性、リワーク性、架橋安定性、剥離性等の調整の為に、ゲル分率等を考慮して決定される。ラジカル発生剤（特に過酸化物）の含有量を多くすれば、得られる粘着剤層のゲル分率（架橋度）を確保するうえでは好ましいが、多くなり過ぎると、粘着剤層に適用する離型フィルム（セパレータ）の剥離力が上昇する傾向がある。通常、前記ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対して、ラジカル発生剤の含有量は、０．０１～２重量部であることが好ましく、さらには０．０１～１重量部であることが好ましく、さらには０．０５～０．８重量部が好ましく、さらには０．１～０．６重量部が好ましい。 The content of the radical generating agent (particularly peroxide) in the pressure-sensitive adhesive composition of the present invention is the adjustment of the processability, reworkability, crosslinking stability, releasability, etc. of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. Therefore, it is determined in consideration of the gel fraction etc. Increasing the content of the radical generating agent (especially peroxide) is preferable for securing the gel fraction (crosslinking degree) of the obtained pressure-sensitive adhesive layer, but if it is too much, the release applied to the pressure-sensitive adhesive layer The peeling force of the mold film (separator) tends to increase. In general, the content of the radical generator is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 parts by weight, based on 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). It is preferable that it is part by weight, more preferably 0.05 to 0.8 parts by weight, and still more preferably 0.1 to 0.6 parts by weight.
　なお、前記（メタ）アクリル系ポリマー中には、当該（メタ）アクリル系ポリマーの調製の際に重合反応に使用されなかったラジカル重合開始剤（ラジカル発生剤）が残存する場合がある。当該残存ラジカル発生剤は、前記粘着剤組成物中のラジカル発生剤として使用することができる。その場合は残存ラジカル発生剤の量を定量し、残存ラジカル発生剤の含有量に応じて、ラジカル発生剤を適宜に配合することができる。 In addition, in the said (meth) acrylic-type polymer, the radical polymerization initiator (radical generator) which was not used for the polymerization reaction in the case of preparation of the said (meth) acrylic-type polymer may remain. The said residual radical generating agent can be used as a radical generating agent in the said adhesive composition. In that case, the amount of the residual radical generator can be quantified, and the radical generator can be appropriately blended according to the content of the residual radical generator.
　なお、反応処理後の残存した過酸化物分解量は、例えば、ＨＰＬＣ（高速液体クロマトグラフィー）により測定することができる。 The amount of peroxide decomposition remaining after the reaction can be measured, for example, by HPLC (high performance liquid chromatography).
　より具体的には、例えば、反応処理後の粘着剤組成物を約０．２ｇずつ取り出し、酢酸エチル１０ｍＬに浸漬し、振とう機で２５℃下、１２０ｒｐｍで３時間振とう抽出した後、室温で３日間静置する。次いで、アセトニトリル１０ｍＬ加えて、２５℃下、１２０ｒｐｍで３０分振とうし、メンブランフィルター（０．４５μｍ）によりろ過して得られた抽出液約１０μＬをＨＰＬＣに注入して分析し、反応処理後の過酸化物量とすることができる。 More specifically, for example, about 0.2 g each of the pressure-sensitive adhesive composition after reaction treatment is taken out, immersed in 10 mL of ethyl acetate, shaken and extracted at 120 rpm for 3 hours at 25 ° C. with a shaker, and then room temperature Let stand for 3 days. Then, add 10 mL of acetonitrile, shake at 120 rpm for 30 minutes at 25 ° C., filter through a membrane filter (0.45 μm), and inject about 10 μL of the extract into HPLC for analysis. The amount of peroxide can be used.
　＜化合物（Ａ）＞
　本発明の粘着剤組成物には、分子構造中の水酸基が０～３個である紫外線吸収剤（ａ）および吸収スペクトルの最大吸収波長が３８０～４３０ｎｍの波長領域に存在する色素化合物（ｂ）から選ばれる少なくとも１種の化合物（Ａ）を配合する。前記紫外線吸収剤（ａ）に関して、分子構造中の水酸基が０～３個であることは、前述のように、ラジカルを失活させる原因の水素供与性基を少なくして、ラジカル発生剤の架橋阻害を抑制するうえで有効である。また、水酸基が０～３個であることは、例えば、水酸基と反応性を有するイソシアネート系架橋剤等を配合する場合には、当該架橋剤による架橋阻害を抑制するうえでも好ましい。また、前記紫外線吸収剤（ａ）は、水酸基以外のラジカルを失活させる水素供与性基として、フェニル基を分子構造中に有さない化合物を使用することが好ましい。なお、分子構造中に有しないフェニル基は、置換基を有しないフェニル（－Ｃ６Ｈ５）を示し、置換基を有するフェニル基やフェニレン基等を排除するものではない。また、前記色素化合物（ｂ）についても、前記紫外線吸収剤（ａ）と同様に、ラジカル発生剤の架橋阻害を防ぐ観点で、分子構造中に水酸基やフェニル基などの水素供与性基が少ない（水酸基は０～３個）または有しない化合物であることが好ましい。 <Compound (A)>
In the pressure-sensitive adhesive composition of the present invention, an ultraviolet light absorber (a) having 0 to 3 hydroxyl groups in the molecular structure and a dye compound (b) having a maximum absorption wavelength of 380 to 430 nm in the absorption spectrum And at least one compound (A) selected from Regarding the ultraviolet absorber (a), the fact that the number of hydroxyl groups in the molecular structure is 0 to 3 means that as described above, the number of hydrogen donating groups causing the deactivation of radicals is reduced to crosslink the radical generating agent It is effective in suppressing inhibition. In addition, the fact that the number of hydroxyl groups is 0 to 3 is also preferable for suppressing the inhibition of crosslinking by the crosslinking agent when, for example, an isocyanate-based crosslinking agent having reactivity with the hydroxyl group is blended. Moreover, it is preferable that the said ultraviolet absorber (a) uses the compound which does not have a phenyl group in molecular structure as a hydrogen donor group which deactivates radicals other than a hydroxyl group. The phenyl group which is not contained in the molecular structure means phenyl (—C 6 H 5 ) which does not have a substituent, and does not exclude a phenyl group having a substituent, a phenylene group and the like. Further, the dye compound (b) also has a small number of hydrogen donating groups such as a hydroxyl group and a phenyl group in the molecular structure from the viewpoint of preventing the inhibition of the crosslinking of the radical generator as in the ultraviolet absorber (a) The hydroxyl group is preferably a compound having 0 to 3 or no hydroxyl group.
　前記紫外線吸収剤（ａ）および／または色素化合物（ｂ）に係る前記化合物（Ａ）としての配合量は、ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対して、０．１～２５重量部であることが好ましく、０．５～２０重量部程度であることが好ましく、さらには２～１０重量部程度であることがより好ましい。 The compounding amount of the ultraviolet absorber (a) and / or the dye compound (b) as the compound (A) is 0.1 parts by weight with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer) The amount is preferably about 25 parts by weight, more preferably about 0.5 to 20 parts by weight, and still more preferably about 2 to 10 parts by weight.
　前記紫外線吸収剤（ａ）は、単独で使用してもよく、また２種以上を混合して使用してもよい。前記化合物（Ａ）として前記紫外線吸収剤（ａ）のみを用いる場合、前記紫外線吸収剤（ａ）の全体としての含有量は、ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対して、０．１～２０重量部であることが好ましく、０．１～１０重量部であることが好ましく、０．１～５重量部であることが好ましく、０．５～３重量部であることがより好ましい。紫外線吸収剤（ａ）の添加量を前記範囲とすることで、粘着剤層の紫外線吸収機能を十分に発揮することでき、かつ、紫外線重合をする場合は、当該重合の妨げとはならないため、好ましい。 The ultraviolet absorbers (a) may be used alone or in combination of two or more. When only the ultraviolet absorber (a) is used as the compound (A), the content of the ultraviolet absorber (a) as a whole is 100 parts by weight of the base polymer (for example, (meth) acrylic polymer) 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and 0.5 to 3 parts by weight Is more preferred. By setting the addition amount of the ultraviolet absorber (a) in the above range, the ultraviolet absorbing function of the pressure-sensitive adhesive layer can be sufficiently exhibited, and in the case of performing the ultraviolet polymerization, the polymerization is not hindered. preferable.
　前記色素化合物（ｂ）は、単独で使用してもよく、また２種以上を混合して使用してもよい。前記化合物（Ａ）として前記色素化合物（ｂ）のみを用いる場合、前記色素化合物（ｂ）の全体としての含有量は、ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対して、０．１～２０重量部であることが好ましく、０．１～１０重量部であることが好ましく、０．１～５重量部であることが好ましく、０．５～３重量部であることがより好ましい。色素化合物（ｂ）の添加量を前記範囲とすることで、有機ＥＬ素子の発光に影響しない領域の光を十分に吸収することができ、当該粘着剤組成物から形成される粘着剤層を用いることで、有機ＥＬ素子の劣化を抑制することができるため、好ましい。 The dye compounds (b) may be used alone or in combination of two or more. When only the dye compound (b) is used as the compound (A), the content of the dye compound (b) as a whole is 100 parts by weight of the base polymer (for example, (meth) acrylic polymer) 0.1 to 20 parts by weight is preferable, 0.1 to 10 parts by weight is preferable, 0.1 to 5 parts by weight is preferable, and 0.5 to 3 parts by weight More preferable. By setting the addition amount of the dye compound (b) in the above range, light in a region not affecting light emission of the organic EL element can be sufficiently absorbed, and the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is used This is preferable because deterioration of the organic EL element can be suppressed.
　前記紫外線吸収剤（ａ）、色素化合物（ｂ）はいずれか一方を用いることができるが、前記紫外線吸収剤（ａ）および色素化合物（ｂ）を併用することが好ましい。紫外線吸収剤（ａ）によれば、例えば、波長３８０ｎｍの光を吸収することができるものの、有機ＥＬ素子の発光領域（４３０ｎｍよりも長波長側）より短波長側の波長領域（３８０ｎｍ～４３０ｎｍ）の光が十分に吸収されておらず、当該透過光により劣化が生じる場合がある。前記色素化合物（ｂ）は、有機ＥＬ素子の発光領域（４３０ｎｍよりも長波長側）より短波長側の波長（３８０ｎｍ～４３０ｎｍ）の光の透過を抑制することができ、前記紫外線吸収剤（ａ）および色素化合物（ｂ）を併用することにより、前記有機ＥＬ素子の発光領域における可視光の透過率を十分に確保できる。
本発明においては、このような色素化合物（ｂ）と前記紫外線吸収剤（ａ２）を組み合わせて用いることで、有機ＥＬ素子の発光に影響しない領域（波長３８０ｎｍ～４３０ｎｍ）の光を十分に吸収することができ、かつ、有機ＥＬ素子の発光領域（４３０ｎｍよりも長波長側）は十分に透過することができるものであり、その結果、有機ＥＬ素子の外光による劣化を抑制することができる。前記紫外線吸収剤（ａ）および色素化合物（ｂ）を併用する場合には、前記紫外線吸収剤（ａ）および色素化合物（ｂ）の合計量が前記化合物（Ａ）としての配合量の範囲内なるように制御するのが好ましい。前記紫外線吸収剤（ａ）は、ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対して、０．１～１０重量部であることが好ましく、０．１～５重量部であることが好ましく、０．５～３重量部であることがより好ましい。前記色素化合物（ｂ）は、ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対して、０．１～１０重量部程度であることが好ましく、０．１～５重量部程度であることがより好ましく、０．５～３重量部であることがより好ましい。 Although either the ultraviolet absorber (a) or the dye compound (b) can be used, it is preferable to use the ultraviolet absorber (a) and the dye compound (b) in combination. According to the ultraviolet absorber (a), for example, a wavelength region (380 nm to 430 nm) on the shorter wavelength side than the light emitting region (longer wavelength side than 430 nm) of the organic EL element although it can absorb light of wavelength 380 nm Light is not sufficiently absorbed, and the transmitted light may cause deterioration. The dye compound (b) can suppress the transmission of light having a wavelength (380 nm to 430 nm) shorter than the light emitting region (longer than 430 nm) of the organic EL element, and the ultraviolet absorber (a) The combined use of the dye compound (b) and the dye compound (b) makes it possible to ensure sufficient transmittance of visible light in the light emitting region of the organic EL device.
In the present invention, by using such a dye compound (b) and the ultraviolet absorber (a2) in combination, light in a region (wavelength 380 nm to 430 nm) which does not affect light emission of the organic EL element is sufficiently absorbed. In addition, the light emitting region (longer wavelength than 430 nm) of the organic EL element can be sufficiently transmitted, and as a result, deterioration of the organic EL element due to external light can be suppressed. When the ultraviolet absorber (a) and the dye compound (b) are used in combination, the total amount of the ultraviolet absorber (a) and the dye compound (b) is within the range of the compounding amount as the compound (A) It is preferable to control as follows. The ultraviolet absorber (a) is preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). Is preferably 0.5 to 3 parts by weight. The dye compound (b) is preferably about 0.1 to 10 parts by weight, and more preferably about 0.1 to 5 parts by weight, with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). And more preferably 0.5 to 3 parts by weight.
　＜紫外線吸収剤（ａ）＞
　紫外線吸収剤（ａ）は、分子構造中の水酸基が０～３個であれば、特に限定されないが、例えば、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、オキシベンゾフェノン系紫外線吸収剤、サリチル酸エステル系紫外線吸収剤、シアノアクリレート系紫外線吸収剤等を挙げることができ、これらを１種単独でまたは２種以上を組み合わせて用いることができる。これらの中でも、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤が好ましく、１分子中にヒドロキシル基を２個以下有するトリアジン系紫外線吸収剤、および、１分子中にベンゾトリアゾール骨格を１個有するベンゾトリアゾール系紫外線吸収剤からなる群から選択される少なくとも１種の紫外線吸収剤であることが、アクリル系粘着剤組成物の形成に用いられるモノマーへの溶解性が良好であり、かつ、波長３８０ｎｍ付近での紫外線吸収能力が高いため好ましい。 <UV absorber (a)>
The UV absorber (a) is not particularly limited as long as it has 0 to 3 hydroxyl groups in the molecular structure, and for example, triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, oxybenzophenone Examples of the ultraviolet absorbers include salicylic acid ester ultraviolet absorbers and cyanoacrylate ultraviolet absorbers. These may be used singly or in combination of two or more. Among these, triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable, triazine-based UV absorbers having two or less hydroxyl groups in one molecule, and benzo having one benzotriazole skeleton in one molecule. At least one UV absorber selected from the group consisting of triazole UV absorbers, which has good solubility in the monomers used to form the acrylic pressure-sensitive adhesive composition, and a wavelength near 380 nm Is preferred because of its high ability to absorb ultraviolet light.
　１分子中にヒドロキシル基を２個以下有するトリアジン系紫外線吸収剤としては、具体的には、２，４－ビス－［｛４－（４－エチルヘキシルオキシ）－４－ヒドロキシ｝－フェニル］－６－（４－メトキシフェニル）－１,３,５－トリアジン（Ｔｉｎｏｓｏｒｂ　Ｓ、ＢＡＳＦ社製）、２，４－ビス［２－ヒドロキシ－４－ブトキシフェニル］－６－（２，４－ジブトキシフェニル）－１,３,５－トリアジン（ＴＩＮＵＶＩＮ　４６０、ＢＡＳＦ社製）、２－（４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル）－５－ヒドロキシフェニルと［（Ｃ１０－Ｃ１６（主としてＣ１２－Ｃ１３）アルキルオキシ）メチル］オキシランとの反応生成物（ＴＩＮＵＶＩＮ４００、ＢＡＳＦ社製）、２－［４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル］－５－［３－（ドデシルオキシ）－２－ヒドロキシプロポキシ］フェノール）、２－（２，４－ジヒドロキシフェニル）－４，６－ビス－（２，４－ジメチルフェニル）－１，３，５－トリアジンと（２－エチルヘキシル）－グリシド酸エステルの反応生成物（ＴＩＮＵＶＩＮ４０５、ＢＡＳＦ社製）、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［（ヘキシル）オキシ］－フェノール（ＴＩＮＵＶＩＮ１５７７、ＢＡＳＦ社製）、２－（４，６－ジフェニルー１，３，５－トリアジン－２－イル）－５－［２－（２－エチルヘキサノイルオキシ）エトキシ］－フェノール（ＡＤＫ　ＳＴＡＢ　ＬＡ４６、ＡＤＥＫＡ製）、２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジン（ＴＩＮＵＶＩＮ４７９、ＢＡＳＦ社製）等を挙げることができる。 Specific examples of triazine-based UV absorbers having two or less hydroxyl groups in one molecule include 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6. -(4-Methoxyphenyl) -1,3,5-triazine (Tinosorb S, manufactured by BASF), 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) ) -1,3,5-Triazine (TINUVIN 460, manufactured by BASF Corp.), 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-) Reaction product of hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane (TINUVIN 400, manufactured by BASF), 2- [4, 6 Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) )-4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester reaction product (TINUVIN 405, manufactured by BASF), 2- (4) , 6-Diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (TINUVIN 1577, manufactured by BASF), 2- (4,6-diphenyl-1,3,5) Triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol (ADK STAB LA46, manufactured by ADEKA), 2- (2-hydrido) Carboxymethyl-4- [1- octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (TINUVIN 479, manufactured by BASF), and the like.
　また、１分子中にベンゾトリアゾール骨格を１個有するベンゾトリアゾール系紫外線吸収剤としては、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール（ＴＩＮＵＶＩＮ　９２８、ＢＡＳＦ社製）、２－（２－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）－２Ｈ－ベンゾトリアゾール（ＴＩＮＵＶＩＮ　ＰＳ、ＢＡＳＦ社製）、ベンゼンプロパン酸および３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－（１，１－ジメチルエチル）－４－ヒドロキシ（Ｃ７－９側鎖および直鎖アルキル）のエステル化合物（ＴＩＮＵＶＩＮ３８４－２、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール（ＴＩＮＵＶＩＮ９００、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール（ＴＩＮＵＶＩＮ９２８、ＢＡＳＦ社製）、メチル－３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート／ポリエチレングリコール３００の反応生成物（ＴＩＮＵＶＩＮ１１３０、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－クレゾール（ＴＩＮＵＶＩＮ　Ｐ、ＢＡＳＦ社製）、２（２Ｈ－ベンゾトリアゾール－２－イル）－４－６－ビス（１－メチル－１－フェニルエチル）フェノール（ＴＩＮＵＶＩＮ２３４、ＢＡＳＦ社製）、２－〔５－クロロ（２Ｈ）－ベンゾトリアゾール－２－イル〕－４－メチル－６－（ｔｅｒｔ－ブチル）フェノール（ＴＩＮＵＶＩＮ３２６、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノール（ＴＩＮＵＶＩＮ３２８、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール（ＴＩＮＵＶＩＮ３２９、ＢＡＳＦ社製）、メチル３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネートとポリエチレングリコール３００との反応生成物（ＴＩＮＵＶＩＮ２１３、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール（ＴＩＮＵＶＩＮ５７１、ＢＡＳＦ社製）、２－［２－ヒドロキシ－３－（３、４、５，６－テトラヒドロフタルイミドーメチル）－５－メチルフェニル］ベンゾトリアゾール（Ｓｕｍｉｓｏｒｂ２５０、住友化学工業（株）製）等を挙げることができる。 Further, as a benzotriazole-based ultraviolet absorber having one benzotriazole skeleton in one molecule, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- is used. (1,1,3,3-Tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF), 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (TINUVIN PS, manufactured by BASF) , Ester compounds of benzenepropanoic acid and 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) (TINUVIN 384-2 (Manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl) 1-phenylethyl) phenol (TINUVIN 900, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3 -Tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF Corp.), Reaction of methyl-3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 Product (TINUVIN 1130, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -p-cresol (TINUVIN, manufactured by BASF), 2 (2H-benzotriazol-2-yl) -4-6 -Bis (1-methyl-1-phenylethyl) phenol (TINUVIN 234, BA F), 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (TINUVIN 326, manufactured by BASF), 2- (2H-benzotriazole) -2-yl) -4,6-di-tert-pentylphenol (TINUVIN 328, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl) Butyl) phenol (TINUVIN 329, manufactured by BASF), a reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 ( TINUVIN 213, manufactured by BASF, 2- (2H-benzotriazol-2-yl) -6-dode Sil-4-methylphenol (TINUVIN571, manufactured by BASF), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole (Sumisorb 250, Sumitomo Chemical Co., Ltd. Industrial Co., Ltd. product etc. can be mentioned.
　また、前記ベンゾフェノン系紫外線吸収剤（ベンゾフェノン系化合物）、オキシベンゾフェノン系紫外線吸収剤（オキシベンゾフェノン系化合物）としては、例えば、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン－５－スルホン酸（無水および三水塩）、２－ヒドロキシ－４－オクチルオキシベンゾフェノン、４－ドデシルオキシ－２－ヒドロキシベンゾフェノン、４－ベンジルオキシ－２－ヒドロキシベンゾフェノン、２，２´－ジヒドロキシ－４，４－ジメトキシベンゾフェノン等を挙げることができる。 Further, examples of the benzophenone based ultraviolet absorber (benzophenone based compound) and the oxybenzophenone based ultraviolet absorber (oxybenzophenone based compound) include, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -Sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4, 4-dimethoxybenzophenone and the like can be mentioned.
　また前記サリチル酸エステル系紫外線吸収剤（サリチル酸エステル系化合物）としては、例えば、２，４－ジ－ｔｅｒｔ－ブチルフェニル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゾエート（ＴＩＮＵＶＩＮ１２０、ＢＡＳＦ社製）等を挙げることができる。 Moreover, as said salicylic acid ester type ultraviolet absorber (salicylic acid ester type compound), for example, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (TINUVIN 120, manufactured by BASF AG) Etc. can be mentioned.
　前記シアノアクリレート系紫外線吸収剤（シアノアクリレート系化合物）としては、例えば、アルキル－２－シアノアクリレート、シクロアルキル－２－シアノアクリレート、アルコキシアルキル－２－シアノアクリレート、アルケニル－２－シアノアクリレート、アルキニル－２－シアノアクリレート等を挙げることができる。 Examples of the cyanoacrylate UV absorber (cyanoacrylate compound) include alkyl 2-cyanoacrylate, cycloalkyl 2-cyanoacrylate, alkoxyalkyl 2-cyanoacrylate, alkenyl 2-cyanoacrylate, and alkynyl Examples include 2-cyanoacrylate and the like.
　前記紫外線吸収剤（ａ）の吸収スペクトルの最大吸収波長は、３００～４００ｎｍの波長領域に存在することが好ましく、３２０～３８０ｎｍの波長領域に存在することがより好ましい。最大吸収波長の測定方法は、後述する色素系化合物の測定方法と同様である。 The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) is preferably in the wavelength range of 300 to 400 nm, and more preferably in the wavelength range of 320 to 380 nm. The method of measuring the maximum absorption wavelength is the same as the method of measuring the dye-based compound described later.
　＜色素化合物（ｂ）＞
　色素化合物（ｂ）は、吸収スペクトルの最大吸収波長が３８０～４３０ｎｍの波長領域に存在する化合物であればよく、特に限定されるものではないが、前記紫外線吸収剤（ａ）と同様に、分子構造中に水酸基やフェニル基などの水素供与性基が少ないまたは有しない化合物であることが好ましい。なお、最大吸収波長とは、３００～４６０ｎｍの波長領域での分光吸収スペクトルにおいて、複数の吸収極大が存在する場合には、その中で最大の吸光度を示す吸収極大波長を意味するものである。 <Pigment compound (b)>
The dye compound (b) is not particularly limited as long as it is a compound which exists in the wavelength range of 380 to 430 nm in the maximum absorption wavelength of the absorption spectrum, but like the ultraviolet absorber (a), It is preferable that it is a compound which has few hydrogen donor groups, such as a hydroxyl group and a phenyl group, in a structure. The term “maximum absorption wavelength” as used herein means an absorption maximum wavelength showing the maximum absorbance among a plurality of absorption maxima in the spectral absorption spectrum in the wavelength region of 300 to 460 nm.
　色素化合物（ｂ）の吸収スペクトルの最大吸収波長は、３８０～４２０ｎｍの波長領域に存在することがより好ましい。また、色素化合物（ｂ）は前記波長特性を有するものであれば特に限定されないが、有機ＥＬ素子の表示性を阻害しないような、蛍光および燐光性能（フォトルミネセンス）を有しない材料が好ましい。 The maximum absorption wavelength of the absorption spectrum of the dye compound (b) is more preferably in the wavelength range of 380 to 420 nm. The dye compound (b) is not particularly limited as long as it has the above-mentioned wavelength characteristics, but a material which does not inhibit the display performance of the organic EL element and which does not have fluorescence and phosphorescence performance (photoluminescence) is preferable.
　また、前記色素化合物（ｂ）の半値幅は、特に限定されるものではないが、８０ｎｍ以下であることが好ましく、５～７０ｎｍであることがより好ましく、１０～６０ｎｍであることがさらに好ましい。色素化合物の半値幅が、前記範囲にあることで、有機ＥＬ素子の発光に影響しない領域の光を十分に吸収しつつ、４３０ｎｍよりも長波長側の光は十分に透過するコントロールが可能となるため好ましい。なお、半値幅の測定方法は、以下に記載の方法による。
＜半値幅の測定方法＞
　色素化合物（ｂ）の半値幅は、紫外可視分光光度計（Ｕ－４１００、（株）日立ハイテクサイエンス製）を使用し、以下の条件で色素化合物の溶液の透過吸光スペクトルから測定した。最大吸収波長の吸光度が１．０となるよう濃度を調整して測定した分光スペクトルから、ピーク値の５０％になる２点間の波長の間隔（半値全幅）をその色素化合物の半値幅とした。
　（測定条件）
　溶媒：トルエンまたはクロロホルム
　セル：石英セル
　光路長：１０ｍｍ The half-width of the dye compound (b) is not particularly limited, but is preferably 80 nm or less, more preferably 5 to 70 nm, and still more preferably 10 to 60 nm. When the full width at half maximum of the dye compound is in the above range, it is possible to sufficiently transmit light in a region that does not affect the light emission of the organic EL element while transmitting sufficient light at wavelengths longer than 430 nm. Because it is preferable. In addition, the measuring method of a half value width is based on the method as described below.
<Method of measuring half width>
The full width at half maximum of the dye compound (b) was measured from the transmission absorption spectrum of the solution of the dye compound under the following conditions using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science Co., Ltd.). From the spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength is 1.0, the distance (full width at half maximum) between the two points at 50% of the peak value is taken as the half width of the dye compound .
(Measurement condition)
Solvent: toluene or chloroform Cell: quartz cell Optical path length: 10 mm
　前記色素化合物（ｂ）としては、例えば、有機系色素化合物や無機系色素化合物を挙げることができるが、これらの中でも、ベースポリマー等の樹脂成分への分散性と透明性の維持の観点から、有機系色素化合物が好ましい。 Examples of the dye compound (b) include organic dye compounds and inorganic dye compounds. Among them, from the viewpoint of maintaining the dispersibility in the resin component such as the base polymer and transparency, Organic dye compounds are preferred.
　前記有機系色素化合物としては、アゾメチン系化合物、インドール系化合物、けい皮酸系化合物、ピリミジン系化合物、ポルフィリン系化合物、シアニン系化合物等を挙げることができる。 Examples of the organic dye compounds include azomethine compounds, indole compounds, cinnamic acid compounds, pyrimidine compounds, porphyrin compounds and cyanine compounds.
　前記有機色素化合物としては、市販されているものを好適に用いることができ、具体的には、前記インドール系化合物としては、ＢＯＮＡＳＯＲＢ　ＵＡ３９１１（商品名、吸収スペクトルの最大吸収波長：３９８ｎｍ、半値幅：４８ｎｍ、オリエント化学工業（株）製）を、
けい皮酸系化合物としては、ＳＯＭ－５－０１０６（商品名、吸収スペクトルの最大吸収波長：４１６ｎｍ、半値幅：５０ｎｍ、オリエント化学工業（株）製）を、ポルフィリン系化合物としては、ＦＤＢ－００１（商品名、吸収スペクトルの最大吸収波長：４２０ｎｍ、半値幅：１４ｎｍ、山田化学工業（株）製）を、シアニン系化合物としては、メロシアニン化合物（商品名：ＦＤＢ－００９、吸収スペクトルの最大吸収波長：３９４ｎｍ、半値幅：４３ｎｍ、山田化学工業（株）製）、ポリメチン化合物（商品名：ＤＡＡ－２４７、吸収スペクトルの最大吸収波長：３８９ｎｍ、半値幅：４９．５ｎｍ、山田化学工業（株）製）等を挙げることができ、中でも、架橋阻害抑制と光学信頼性の観点から、前記シアニン系化合物が好ましく、ポリメチン化合物が特に好ましい。 As the organic dye compound, commercially available ones can be suitably used. Specifically, as the indole compound, BONASORB UA3911 (trade name, maximum absorption wavelength of absorption spectrum: 398 nm, half width: 48 nm, manufactured by Orient Chemical Industries, Ltd.),
As a cinnamic acid compound, SOM-5-0106 (trade name, maximum absorption wavelength of absorption spectrum: 416 nm, half width: 50 nm, manufactured by Orient Chemical Industries Ltd.), and as a porphyrin compound, FDB-001 (Trade name, maximum absorption wavelength of absorption spectrum: 420 nm, half width: 14 nm, Yamada Chemical Industry Co., Ltd.), and as a cyanine compound, merocyanine compound (trade name: FDB-009, maximum absorption wavelength of absorption spectrum) : 394 nm, full width at half maximum: 43 nm, manufactured by Yamada Chemical Industry Co., Ltd., polymethine compound (trade name: DAA-247, absorption maximum wavelength of absorption spectrum: 389 nm, full width at half maximum: 49.5 nm, manufactured by Yamada Chemical Industry Co., Ltd. And the like, and among them, from the viewpoint of inhibition of crosslinking inhibition and optical reliability, the above-mentioned cyanine compound is preferable. Polymethine compounds are particularly preferred.
　＜酸化防止剤＞
　本発明の粘着剤組成物に配合される酸化防止剤を配合することができる。酸化防止剤は、ラジカル発生剤から発生するラジカルの酸素による阻害を防止して、安定なゲル分率（架橋度）を確保することができ、また、粘着剤層に適用する離型フィルム（セパレータ）の剥離力の上昇を抑制しながら、ゲル分率を上昇させることができる。 <Antioxidant>
An antioxidant to be blended into the pressure-sensitive adhesive composition of the present invention can be blended. An antioxidant can prevent inhibition by oxygen of radicals generated from a radical generator, and can ensure a stable gel fraction (crosslinking degree), and a release film (separator applied to an adhesive layer) The gel fraction can be increased while suppressing the increase in the peeling force of
　前記酸化防止剤としては、例えば、フェノール系、リン系、イオウ系およびアミン系の酸化防止剤があげられ、これらから選ばれるいずれか少なくとも１種を用いる。これらの中でも、フェノール系酸化防止剤が好ましい。 Examples of the antioxidant include phenol type, phosphorus type, sulfur type and amine type antioxidants, and at least one selected from these is used. Among these, phenolic antioxidants are preferred.
　フェノール系酸化防止剤の具体例としては、単環フェノール化合物として、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、２，６－ジ－ｔ－ブチル－４－エチルフェノール、２，６－ジシクロヘキシル－４－メチルフェノール、２，６－ジイソプロピル－４－エチルフェノール、２，６－ジ－ｔ－アミル－４－メチルフェノール、２，６－ジ－ｔ－オクチル－４－ｎ－プロピルフェノール、２，６－ジシクロヘキシル－４－ｎ－オクチルフェノール、２－イソプロピル－４－メチル－６－ｔ－ブチルフェノール、２－ｔ－ブチル－４－エチル－６－ｔ－オクチルフェノール、２－イソブチル－４－エチル－６－ｔ－ヘキシルフェノール、２－シクロヘキシル－４－ｎ－ブチル－６－イソプロピルフェノール、スチレン化混合クレゾール、ＤＬ－α－トコフェロール、ステアリルβ－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネートなどを、２環フェノール化合物として、２，２´－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、４，４´－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、４，４´－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２´－チオビス（４－メチル－６－ｔ－ブチルフェノール）、４，４´－メチレンビス（２，６－ジ－ｔ－ブチルフェノール）、２，２´－メチレンビス［６－（１－メチルシクロヘキシル）－ｐ－クレゾール］、２，２´－エチリデンビス（４，６－ジ－ｔ－ブチルフェノール）、２，２´－ブチリデンビス（２－ｔ－ブチル－４－メチルフェノール）、３，６－ジオキサオクタメチレンビス［３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート］、トリエチレングリコールビス［３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］、１，６－ヘキサンジオール　ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，２´－チオジエチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］などを、３環フェノール化合物として、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，３，５－トリス（２，６－ジメチル－３－ヒドロキシ－４－ｔ－ブチルベンジル）イソシアヌレート、１，３，５－トリス［（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、トリス（４－ｔ－ブチル－２，６－ジメチル－３－ヒドロキシベンジル）イソシアヌレート、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼンなどを、４環フェノール化合物として、テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタンなどを、リン含有フェノール化合物として、ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）カルシウム、ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）ニッケルなどを挙げることができる。 Specific examples of the phenolic antioxidant include, as a monocyclic phenol compound, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6- Dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-Dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl- 6-t-Hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL α-Tocopherol, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc. as a bicyclic phenol compound, 2,2′-methylenebis (4-methyl-6-t-butylphenol) 4,4'-Butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-thiobis (4-methyl-6-) t-Butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidene Bis (4,6-di-t-butylphenol), 2,2′-butylidenebis (2-t-butyl-4-methylphenol), 3,6-dioxaoctame Tylene bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1 , 6-Hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylene bis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] etc. as a tricyclic phenol compound, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (2) , 6-Dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyl) Phenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5 Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane etc. as a tetracyclic phenol compound, etc., with -di-t-butyl-4-hydroxybenzyl) benzene etc. Phosphorus-containing phenolic compounds such as calcium (bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate)), bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel, etc. Can be mentioned.
　リン系酸化防止剤の具体例としては、トリオクチルホスファイト、トリラウリルホスファイト、トリストリデシルホスファイト、トリスイソデシルホスファイト、フェニルジイソオクチルホスファイト、フェニルジイソデシルホスファイト、フェニルジ（トリデシル）ホスファイト、ジフェニルイソオクチルホスファイト、ジフェニルイソデシルホスファイト、ジフェニルトリデシルホスファイト、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト、トリス（ブトキシエチル）ホスファイト、テトラトリデシル－４，４´－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）－ジホスファイト、４，４´－イソプロピリデン－ジフェノールアルキルホスファイト（ただし、アルキルは炭素数１２～１５程度）、４，４´－イソプロピリデンビス（２－ｔ－ブチルフェノール）・ジ（ノニルフェニル）ホスファイト、トリス（ビフェニル）ホスファイト、テトラ（トリデシル）－１，１，３－トリス（２－メチル－５－ｔ－ブチル－４－ヒドロキシフェニル）ブタンジホスファイト、トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）ホスファイト、水素化－４，４´－イソプロピリデンジフェノールポリホスファイト、ビス（オクチルフェニル）・ビス［４，４´－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）］・１，６－ヘキサンジオールジホスファイト、ヘキサトリデシル－１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェノール）ジホスファイト、トリス［４，４´－イソプロピリデンビス（２－ｔ－ブチルフェノール）］ホスファイト、トリス（１，３－ジステアロイルオキシイソプロピル）ホスファイト、９，１０－ジヒドロ－９－ホスファフェナンスレン－１０－オキシド、テトラキス（２，４－ジ－ｔ－ブチルフェニル）－４，４´－ビフェニレンジホスホナイト、ジステアリルペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、フェニル・４，４´－イソプロピリデンジフェノール・ペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジ－ｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト及びフェニルビスフェノール－Ａ－ペンタエリスリトールジホスファイトなどが挙げられる。 Specific examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tris tridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phos Phyto, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (Butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4,4'-isopropylidene-diphenol alkylphos Phyto (however, alkyl has about 12 to 15 carbon atoms), 4,4'-isopropylidene bis (2-t-butylphenol), di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl)- 1,1,3-Tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated -4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) .bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)]. 1,6-hexanediol diphosphite Hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) diphos Pheat, tris [4,4'-isopropylidene bis (2-t-butylphenol)] phosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 9,10-dihydro-9-phosphaphenanthrene -10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl. 4,4'-isopropylidene diphenol pentaerythritol diphosphite bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite bis (2,6-di-tert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite and phenyl bis Such as phenol -A- pentaerythritol diphosphite, and the like.
　硫黄系酸化防止剤としては、ジアルキルチオジプロピオネート及びアルキルチオプロピオン酸の多価アルコールエステルを用いることが好ましい。ここで使用されるジアルキルチオジプロピオネートとしては、炭素数６～２０のアルキル基を有するジアルキルチオジプロピオネートが好ましく、またアルキルチオプロピオン酸の多価アルコールエステルとしては、炭素数４～２０のアルキル基を有するアルキルチオプロピオン酸の多価アルコールエステルが好ましい。この場合に多価アルコールエステルを構成する多価アルコールの例としては、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール及びトリスヒドロキシエチルイソシアヌレートなどを挙げることができる。このようなジアルキルチオジプロピオネートとしては、例えば、ジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート及びジステアリルチオジプロピオネートなどを挙げることができる。一方、アルキルチオプロピオン酸の多価アルコールエステルとしては、例えば、グリセリントリブチルチオプロピオネート、グリセリントリオクチルチオプロピオネート、グリセリントリラウリルチオプロピオネート、グリセリントリステアリルチオプロピオネート、トリメチロールエタントリブチルチオプロピオネート、トリメチロールエタントリオクチルチオプロピオネート、トリメチロールエタントリラウリルチオプロピオネート、トリメチロールエタントリステアリルチオプロピオネート、ペンタエリスリトールテトラブチルチオプロピオネート、ペンタエリスリトールテトラオクチルチオプロピオネート、ペンタエリスリトールテトララウリルチオプロピオネート、ペンタエリスリトールテトラステアリルチオプロピオネートなどを挙げることができる。 As the sulfur-based antioxidant, it is preferable to use dialkylthiodipropionate and polyhydric alcohol ester of alkylthiopropionic acid. The dialkylthiodipropionate used herein is preferably a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms, and as the polyhydric alcohol ester of alkylthiopropionic acid, an alkyl having 4 to 20 carbon atoms Polyhydric alcohol esters of alkylthiopropionic acid having a group are preferred. In this case, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, tris hydroxyethyl isocyanurate etc. can be mentioned as an example of polyhydric alcohol which constitutes polyhydric alcohol ester. Examples of such dialkyl thiodipropionates include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate. On the other hand, as polyhydric alcohol esters of alkylthiopropionic acid, for example, glycerin tributyl thiopropionate, glycerin trioctyl thiopropionate, glycerin trilauryl thiopropionate, glycerin tristearyl thiopropionate, trimethylol ethane tributyl Thiopropionate, trimethylolethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate, trimethylol ethane tristearyl thiopropionate, pentaerythritol tetrabutyl thiopropionate, pentaerythritol tetraoctyl thiopro Peonate, pentaerythritol tetralauryl thiopropionate, pentaerythritol tetrastearyl thiopropionate, etc. It can be mentioned.
　アミン系酸化防止剤の具体例としては、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、コハク酸ジメチルと１－（２－ヒドロキシエチル）－４－ヒドロキシ－２，２，６，６－テトラメチルピペリジンエタノールの重縮合物、Ｎ，Ｎ´，Ｎ´´，Ｎ´´´－テトラキス－（４，６－ビス－（ブチル－（Ｎ－メチル－２，２，６，６－テトラメチルピペリジン－４－イル）アミノ）－トリアジン－２－イル）－４，７－ジアザデカン－１，１０－ジアミン、ジブチルアミン・１，３，５－トリアジン・Ｎ，Ｎ´－ビス（２，２，６，６－テトラメチル－４－ピペリジル－１，６－ヘキサメチレンジアミンとＮ－（２，２，６，６－テトラメチル－４－ピペリジル）ブチルアミンの重縮合物、ポリ［｛６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル｝｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝］、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、２，２，６，６－テトラメチル－４－ピペリジルベンゾエート、ビス－（１，２，６，６－ペンタメチル－４－ペピリジル）－２－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－２－ｎ－ブチルマロネート、ビス－（Ｎ－メチル－２，２，６，６－テトラメチル－４－ピペリジル）セバケート、１，１´－（１，２－エタンジイル）ビス（３，３，５，５－テトラメチルピペラジノン）、（ミックスト２，２，６，６－テトラメチル－４－ピペリジル／トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、（ミックスト１，２，２，６，６－ペンタメチル－４－ピペリジル／トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ミックスト［２，２，６，６－テトラメチル－４－ピペリジル／β，β，β´，β´－テトラメチル－３，９－［２，４，８，１０－テトラオキサスピロ（５，５）ウンデカン］ジエチル］－１，２，３，４－ブタンテトラカルボキシレート、ミックスト［１，２，２，６，６－ペンタメチル－４－ピペリジル／β，β，β´，β´－テトラメチル－３，９－［２，４，８，１０－テトラオキサスピロ（５，５）ウンデカン］ジエチル］－１，２，３，４－ブタンテトラカルボキシレート、Ｎ，Ｎ´－ビス（３－アミノプロピル）エチレンジアミン－２，４－ビス［Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ］－６－クロロ－１，３，５－トリアジン縮合物、ポリ［６－Ｎ－モルホリル－１，３，５－トリアジン－２，４－ジイル］［（２，２，６，６－テトラメチル－４－ピペリジル）イミノ］ヘキサメチレン［（２，２，６，６－テトラメチル－４－ピペリジル）イミド］、Ｎ，Ｎ´－ビス（２，２，６，６－テトラメチル－４－ピペリジル）ヘキサメチレンジアミンと１，２－ジブロモエタンとの縮合物、［Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）－２－メチル－２－（２，２，６，６－テトラメチル－４－ピペリジル）イミノ］プロピオンアミドなどを挙げることができる。 Specific examples of amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2 , 6,6-Tetramethylpiperidine ethanol, Polycondensate of N, N ′, N ′, N ′ ′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6) , 6-Tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine · 1,3,5-triazine · N, N′-bis (Polycondensate of (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [ {6- (1, 1, 3, 3 Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6) -Tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6,6 -Tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-pepyridyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n- Butyl malonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-) Tetramethyl piperazinone), Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-) Piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3 , 9- [2,4,8,10-Tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6 -Pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2, 3,4-butanetetracarboxylate N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6- Chloro-1,3,5-triazine condensate, poly [6-N-morpholine-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl] ) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine A condensation product of it with 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl- 4-piperidyl) imino] propionamide etc. Door can be.
　本発明の粘着剤組成物における酸化防止剤の含有量は、前記ラジカル発生剤による色素の退色を防止する観点から決定される。通常、前記（メタ）アクリル系ポリマー１００重量部に対して、酸化防止剤の含有量は、０．０３重量部以上の範囲とするのが好ましい。一方、前記酸化防止剤の含有量が多くなると、ラジカル発生剤から生じるラジカルを捕捉する割合が多くなる。その結果、前記粘着剤組成物から形成される粘着剤層の架橋阻害が起こしやすくなって、粘着剤層のゲル分率が低下して、外観不良を生じる傾向がある。かかる観点からは、前記（メタ）アクリル系ポリマー１００重量部に対して、酸化防止剤の含有量は、５重量部以下、さらには１．５重量部以下の範囲とするのが好ましい。上記のゲル分率の確保と色素の退色防止を両立させる観点から、ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対して、前記酸化防止剤の含有量は、０．０５～１．５重量部であることが好ましく、さらには０．１～１．０重量部が好ましく、さらには０．３～０．８重量部が好ましい。 The content of the antioxidant in the pressure-sensitive adhesive composition of the present invention is determined from the viewpoint of preventing the color fading of the dye by the radical generating agent. In general, the content of the antioxidant is preferably in the range of 0.03 parts by weight or more based on 100 parts by weight of the (meth) acrylic polymer. On the other hand, when the content of the antioxidant increases, the ratio of capturing radicals generated from the radical generator increases. As a result, the crosslinking inhibition of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition tends to occur, and the gel fraction of the pressure-sensitive adhesive layer tends to decrease to cause appearance defects. From this viewpoint, the content of the antioxidant is preferably 5 parts by weight or less, more preferably 1.5 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer. From the viewpoint of achieving both the above gel fraction securement and the prevention of color fading, the content of the above-mentioned antioxidant is preferably 0.05 to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). The amount is preferably 1.5 parts by weight, more preferably 0.1 to 1.0 parts by weight, and still more preferably 0.3 to 0.8 parts by weight.
　＜架橋剤＞
　さらに、本発明の粘着剤組成物は、架橋剤（前記ラジカル発生剤を除く）を含有することができる。本発明においては、架橋剤として、イソシアネート系架橋剤を併用した場合には、酸素によるラジカル架橋阻害を酸化防止剤により効果的に抑制しつつ、イソシアネート系架橋剤により、粘着剤層の三次元架橋ネットワークを効率良く形成することができる。その結果、偏光フィルム端部での外観異常の発生をさらに効果的に防止することができる。 <Crosslinking agent>
Furthermore, the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent (excluding the above-mentioned radical generator). In the present invention, when an isocyanate-based crosslinking agent is used in combination as a crosslinking agent, three-dimensional crosslinking of the pressure-sensitive adhesive layer by the isocyanate-based crosslinking agent while effectively suppressing radical crosslinking inhibition by oxygen by the antioxidant. A network can be formed efficiently. As a result, the occurrence of appearance abnormalities at the end of the polarizing film can be more effectively prevented.
　架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤の架橋剤が含まれる。架橋剤は１種を単独でまたは２種以上を組み合わせることができる。これらの中でも、イソシアネート系架橋剤が好ましく用いられる。 Crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyl etherified melamine crosslinking agents, and metal chelate crosslinking agents. Agents are included. The crosslinking agents can be used alone or in combination of two or more. Among these, an isocyanate type crosslinking agent is preferably used.
　上記架橋剤は１種を単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は、ベースポリマー（例えば、（メタ）アクリル系ポリマー）１００重量部に対し、５重量部以下であることが好ましく、０．０１～５重量部であることがより好ましく、０．０１～４重量部がさらに好ましく、０．０２～３重量部が特に好ましい。 Although the said crosslinking agent may be used individually by 1 type and may be used in mixture of 2 or more types, content as a whole is a base polymer (for example, (meth) acrylic-type polymer) 100 The amount is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 4 parts by weight, and particularly preferably 0.02 to 3 parts by weight. .
　イソシアネート系架橋剤は、イソシアネート基（イソシアネート基をブロック剤または数量体化等により一時的に保護したイソシアネート再生型官能基を含む）を１分子中に２つ以上有する化合物をいう。イソシアネート系架橋剤としては、トリレンジイソシアネート、キシレンジイソシアネート等の芳香族イソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート、ヘキサメチレンジイソシアネート等の脂肪族イソシアネート等が挙げられる。 An isocyanate type crosslinking agent refers to a compound having two or more isocyanate groups (including an isocyanate regenerated functional group in which an isocyanate group is temporarily protected by a blocking agent or quantification or the like) in one molecule. As an isocyanate type crosslinking agent, aromatic isocyanates, such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates, such as isophorone diisocyanate, aliphatic isocyanates, such as hexamethylene diisocyanate, etc. are mentioned.
　より具体的には、例えば、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート類、２，４－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、ポリメチレンポリフェニルイソシアネート等の芳香族ジイソシアネート類、トリメチロールプロパン／トリレンジイソシアネート３量体付加物（商品名：コロネートＬ、日本ポリウレタン工業（株）製）、トリメチロールプロパン／ヘキサメチレンジイソシアネート３量体付加物（商品名：コロネートＨＬ、日本ポリウレタン工業（株）製）、ヘキサメチレンジイソシアネートのイソシアヌレート体（商品名：コロネートＨＸ、日本ポリウレタン工業（株）製）等のイソシアネート付加物、キシリレンジイソシアネートのトリメチロールプロパン付加物（商品名：Ｄ１１０Ｎ、三井化学（株）製）、ヘキサメチレンジイソシアネートのトリメチロールプロパン付加物（商品名：Ｄ１６０Ｎ、三井化学（株）製）；ポリエーテルポリイソシアネート、ポリエステルポリイソシアネート、ならびにこれらと各種のポリオールとの付加物、イソシアヌレート結合、ビューレット結合、アロファネート結合等で多官能化したポリイソシアネート等を挙げることができる。 More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cycloaliphatic diisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenylisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene Isocyanate adducts of isocyanurate of diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals, Inc.), hexa Trimethylolpropane adduct of methylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals, Inc.); polyether polyisocyanate, polyester polyisocyanate, adducts of these with various polyols, isocyanurate bond, buret bond, The polyisocyanate etc. which were polyfunctionalized by the allophanate coupling etc. can be mentioned.
　さらに、本発明の粘着剤組成物にはシランカップリング剤を含有することができる。シランカップリング剤の配合量は、（メタ）アクリル系ポリマーを形成する単官能性モノマー成分１００重量部に対して１重量部以下であるのが好ましく、０．０１～１重量部がより好ましく、０．０２～０．６重量部がさらに好ましい。 Furthermore, the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent. The compounding amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, with respect to 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. More preferred is 0.02 to 0.6 parts by weight.
　前記シランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ基含有シランカップリング剤、３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチルブチリデン）プロピルアミン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤、３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等の（メタ）アクリル基含有シランカップリング剤、３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤等が挙げられる。 Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxycyclohexyl) Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,1 Amino group-containing silane coupling agents such as 3-dimethylbutylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane Meta) Acrylic group containing Shira Coupling agents, such as isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like.
　本発明の粘着剤組成物には、前記成分の他に、用途に応じて、適宜な添加剤が含まれていてもよい。例えば、粘着付与剤（例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂等からなる常温で固体、半固体、あるいは液状のもの）；中空ガラスバルーン等の充填剤；可塑剤；老化防止剤；光安定剤（ＨＡＬＳ）；酸化防止剤等が挙げられる。 The pressure-sensitive adhesive composition of the present invention may contain, in addition to the components described above, appropriate additives depending on the application. For example, tackifier (for example, solid, semi-solid or liquid at room temperature consisting of rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenolic resin, etc.); Filler such as hollow glass balloon; Plasticizer; Inhibitors; light stabilizers (HALS); antioxidants etc. may be mentioned.
　２．有機ＥＬ表示装置用粘着剤層
　本発明の有機ＥＬ表示装置用粘着剤層は、前記有機ＥＬ表示装置用粘着剤組成物から形成されることを特徴とする。 2. Pressure-Sensitive Adhesive Layer for Organic EL Display Device The pressure-sensitive adhesive layer for an organic EL display device of the present invention is characterized in that it is formed from the pressure-sensitive adhesive composition for an organic EL display device.
　粘着剤層の形成方法としては、特に限定されるものではなく、通常本分野において用いられる方法により形成することができる。具体的には、前記粘着剤組成物を基材の少なくとも片面に塗工し、当該粘着剤組成物から形成される塗布膜を乾燥して形成するか、または、紫外線等の活性エネルギー線を照射して形成することができる。 It does not specifically limit as a formation method of an adhesive layer, It can form by the method generally used in this field | area. Specifically, the pressure-sensitive adhesive composition is applied to at least one surface of a substrate, and a coated film formed from the pressure-sensitive adhesive composition is dried and formed, or an active energy ray such as ultraviolet light is irradiated. Can be formed.
　前記基材としては、特に限定されるものではなく、例えば、離型フィルム、透明樹脂フィルム基材等の各種基材や、後述する偏光フィルムも基材として好適に用いることができる。 It does not specifically limit as said base material, For example, various base materials, such as a release film and a transparent resin film base material, and the polarizing film mentioned later can also be used suitably as a base material.
　前記離型フィルムの構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等の樹脂フィルム、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔、およびこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点から樹脂フィルムが好適に用いられる。 Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate and polyester film, porous materials such as paper, cloth and non-woven fabric, nets, foam sheets, metal foils, and laminates thereof Although an appropriate thin leaf etc. can be mentioned, a resin film is used suitably from the point which is excellent in surface smoothness.
　その樹脂フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 As the resin film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene film -Vinyl acetate copolymer film etc. may be mentioned.
　前記離型フィルムの厚さは、通常５～２００μｍであり、好ましくは５～１００μｍ程度である。前記離型フィルムには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型および防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理をすることもできる。特に、前記離型フィルムの表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜行うことにより、前記粘着剤層からの剥離性をより高めることができる。 The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. The release film may be, if necessary, a release agent of silicone type, fluorine type, long chain alkyl type or fatty acid amide type, silica powder etc., release treatment and antifouling treatment, coating type, kneading type, It is also possible to carry out antistatic treatment such as deposition type. In particular, the releasability from the pressure-sensitive adhesive layer can be further enhanced by appropriately performing release treatment such as silicone treatment, long chain alkyl treatment, fluorine treatment and the like on the surface of the release film.
　前記透明樹脂フィルム基材としては、特に制限されないが、透明性を有する各種の樹脂フィルムが用いられる。当該樹脂フィルムは１層のフィルムにより形成されている。例えば、その材料として、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂、アセテート系樹脂、ポリエーテルスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、（メタ）アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、ポリアリレート系樹脂、ポリフェニレンサルファイド系樹脂等が挙げられる。これらの中で特に好ましいのは、ポリエステル系樹脂、ポリイミド系樹脂およびポリエーテルスルホン系樹脂である。 The transparent resin film substrate is not particularly limited, but various resin films having transparency are used. The said resin film is formed of the film of one layer. For example, as the material, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like can be mentioned. Among these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
　前記フィルム基材の厚さは、１５～２００μｍであることが好ましく、２５～１８８μｍであることがより好ましい。 The thickness of the film substrate is preferably 15 to 200 μm, and more preferably 25 to 188 μm.
　上記粘着剤組成物を上記基材上に塗布する方法は、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、ダイコーター等公知適宜な方法を用いることができ、特に制限されない。 The method for applying the pressure-sensitive adhesive composition onto the substrate may be roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain Well-known appropriate methods, such as a coat, a lip coat, a die coater, can be used, and it does not restrict | limit in particular.
　前記粘着剤層は、前記粘着剤組成物から形成される塗布膜を乾燥して形成する場合、その乾燥条件（温度、時間）は、特に限定されるものではなく、粘着剤組成物の組成、濃度等により適宜設定することができるが、例えば、６０～１７０℃程度、好ましくは６０～１５０℃で、１～６０分間、好ましくは２～３０分間である。その他、前記粘着剤組成物が紫外線硬化型粘着剤組成物の場合には、塗布膜に紫外線を照射して粘着剤層を形成することができる。 When the pressure-sensitive adhesive layer is formed by drying a coating film formed of the pressure-sensitive adhesive composition, the drying conditions (temperature, time) are not particularly limited, and the composition of the pressure-sensitive adhesive composition The concentration can be set appropriately, for example, at about 60 to 170 ° C., preferably 60 to 150 ° C., for 1 to 60 minutes, preferably 2 to 30 minutes. In addition, when the pressure-sensitive adhesive composition is an ultraviolet-curable pressure-sensitive adhesive composition, the coating film can be irradiated with ultraviolet light to form a pressure-sensitive adhesive layer.
　粘着剤層の厚さは、波長４３０ｎｍ未満の光を吸収する機能を確保する観点から、５μｍ以上であることが好ましく、５０μｍ以上であることがより好ましく、１００μｍ以上であることがさらに好ましく、１５０μｍ以上であることが特に好ましい。粘着剤層の厚さの上限値は特に限定されないが、１ｍｍ以下であることが好ましい。粘着剤層の厚さが１ｍｍを超えると紫外線の透過が困難になり、モノマー成分の重合に時間がかかる他、加工性や工程での巻き取り、搬送性に問題を生じ、生産性が劣る場合があるため、好ましくない。 The thickness of the pressure-sensitive adhesive layer is preferably 5 μm or more, more preferably 50 μm or more, still more preferably 100 μm or more, from the viewpoint of securing the function of absorbing light having a wavelength of less than 430 nm. It is particularly preferable to be the above. The upper limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 mm or less. When the thickness of the pressure-sensitive adhesive layer exceeds 1 mm, the transmission of ultraviolet light becomes difficult, and it takes time to polymerize the monomer component, and problems occur in processability, winding up in steps and transportability, and productivity is poor. Not desirable because
　本発明の粘着剤層のゲル分率は、特に限定されるものではないが、４０％以上であることが好ましく、６０％以上であることがより好ましく、７５％以上であることがさらに好ましく、８５％以上であることが特に好ましい。粘着剤層のゲル分率が小さい場合には凝集力に劣り、加工性やハンドリング性に問題が出る場合がある。また、粘着剤組成物の塗布膜を加熱乾燥や紫外線照射により粘着剤層を形成した直後のゲル分率は、糊打痕等の外観不具合を防止する観点から、６０％以上であることが好ましく、６３％以上であることがより好ましく、６６％以上であることがさらに好ましく、７０％以上であることが特に好ましい。 The gel fraction of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 40% or more, more preferably 60% or more, and still more preferably 75% or more. Particularly preferred is 85% or more. When the gel fraction of the pressure-sensitive adhesive layer is small, the cohesion is inferior, and problems may occur in processability and handling. The gel fraction immediately after forming the pressure-sensitive adhesive layer by heat drying or ultraviolet irradiation of the coating film of the pressure-sensitive adhesive composition is preferably 60% or more from the viewpoint of preventing appearance defects such as paste marks. Is more preferably 63% or more, still more preferably 66% or more, and particularly preferably 70% or more.
　前記粘着剤層は、厚さ２５μｍで測定したヘイズ値が２％以下であることが好ましく、０～１．５％であることがより好ましく、０～１％であることがさらに好ましい。ヘイズが前記範囲にあることで、粘着剤層が高い透明性を有するため好ましい。 The pressure-sensitive adhesive layer preferably has a haze value measured at a thickness of 25 μm of 2% or less, more preferably 0 to 1.5%, and still more preferably 0 to 1%. It is preferable for the pressure-sensitive adhesive layer to have high transparency when the haze is in the above-mentioned range.
　前記粘着剤層の波長３００～４００ｎｍの平均透過率は１２％以下であることが好ましく、さらには５％以下であることが好ましく、２％以下であることがより好ましい。粘着剤層の透過率が前記範囲であると、有機ＥＬ素子の発光に影響しない領域の光を十分に吸収できており、有機ＥＬ素子の劣化を抑制することができる。 The average transmittance at a wavelength of 300 to 400 nm of the pressure-sensitive adhesive layer is preferably 12% or less, more preferably 5% or less, and more preferably 2% or less. The light of the area | region which does not influence light emission of an organic EL element as the transmittance | permeability of an adhesive layer is the said range can fully be absorbed, and degradation of an organic EL element can be suppressed.
　前記粘着剤層の波長４３０～４５０ｎｍの平均透過率が７０％以上であることが好ましく、７５％以上であることがより好ましく、波長５００～７８０ｎｍの平均透過率が８０％以上であることが好ましく、８５％以上であることがより好ましい。粘着剤層の透過率が前記範囲にあると、有機ＥＬ素子の発光領域（４３０ｎｍよりも長波長側）において十分に光を透過することができており、当該粘着剤層を用いた有機ＥＬ表示装置は十分な発光をすることができる。 The average transmittance at a wavelength of 430 to 450 nm of the pressure-sensitive adhesive layer is preferably 70% or more, more preferably 75% or more, and the average transmittance at a wavelength of 500 to 780 nm is preferably 80% or more And 85% or more. When the transmittance of the pressure-sensitive adhesive layer is in the above range, light can be sufficiently transmitted in the light emitting region (longer wavelength side than 430 nm) of the organic EL element, and the organic EL display using the pressure-sensitive adhesive layer The device can emit sufficient light.
　また、前記粘着剤層の波長４００～４３０ｎｍ以下の平均透過率は、有機ＥＬ表示装置に求められる特性に応じて設計することができる。例えば、有機ＥＬ素子の発光に影響しない領域の光を十分に吸収して、有機ＥＬ素子の劣化を抑制し、保護する観点からは、前記粘着剤層の波長４００～４３０ｎｍ以下の平均透過率は３０％以下であることが好ましく、２０％以下であることがより好ましい。一方、有機ＥＬ素子を紫外光から保護しつつ、有機ＥＬ素子の着色を抑制する観点からは、前記粘着剤層の波長４００～４３０ｎｍ以下の平均透過率は３０％を超え９５％以下であることが好ましく、５０％を超え９０％以下であることがより好ましい。 The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 to 430 nm or less can be designed in accordance with the characteristics required for the organic EL display device. For example, from the viewpoint of sufficiently absorbing the light of the region that does not affect the light emission of the organic EL element to suppress the deterioration of the organic EL element and protecting the same, the average transmittance of the adhesive layer at a wavelength of 400 to 430 nm or less is It is preferably 30% or less, more preferably 20% or less. On the other hand, from the viewpoint of suppressing coloring of the organic EL element while protecting the organic EL element from ultraviolet light, the average transmittance of the pressure-sensitive adhesive layer is 400% to 430 nm or less and is more than 30% and 95% or less Is preferable, and more than 50% and 90% or less is more preferable.
　ここで、前記「波長３００～４００ｎｍの平均透過率」とは、波長３００～４００ｎｍの領域において１ｎｍピッチで透過率を計測し、当該計測した透過率の平均値のことをいう。他の波長領域のおける平均透過率も同様である。 Here, the “average transmittance of wavelengths 300 to 400 nm” refers to the average value of the measured transmittances by measuring the transmittance at a pitch of 1 nm in a wavelength range of 300 to 400 nm. The same is true for the average transmittance in other wavelength regions.
　本発明の粘着剤層は、前記透過率を有することで、有機ＥＬ素子の発光に影響しない領域の光を十分に吸収することができ、かつ、有機ＥＬ素子の発光領域（４３０ｎｍよりも長波長側）は十分に透過することができ、有機ＥＬ素子の外光による劣化を抑制することができる。 The pressure-sensitive adhesive layer of the present invention can sufficiently absorb light in a region which does not affect light emission of the organic EL device by having the transmittance, and the light-emitting region (longer wavelength than 430 nm of the organic EL device) Side) can be sufficiently transmitted, and deterioration of the organic EL element due to external light can be suppressed.
　前記粘着剤層が露出する場合には、実用に供されるまで離型フィルムで粘着剤層を保護してもよい。 When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until it is practically used.
　３．有機ＥＬ表示装置用粘着剤層付き偏光フィルム
　本発明の有機ＥＬ表示装置用粘着剤層付き偏光フィルムは、偏光フィルムと、前記有機ＥＬ表示装置用粘着剤層とを有することを特徴とする。 3. Polarizing film with pressure-sensitive adhesive layer for organic EL display device The polarizing film with pressure-sensitive adhesive layer for an organic EL display device of the present invention is characterized by having a polarizing film and the pressure-sensitive adhesive layer for the organic EL display device.
　有機ＥＬ表示装置用粘着剤層としては、前述したものを好適に用いることができる。また、粘着剤層を偏光フィルム以外の基材に形成した場合には、当該粘着剤層は偏光フィルムに貼り合せて転写することができる。また、前記離型フィルムは、そのまま粘着剤層付き偏光フィルムのセパレータとして用いることができ、工程面における簡略化ができる。 As the pressure-sensitive adhesive layer for an organic EL display device, those described above can be suitably used. When the pressure-sensitive adhesive layer is formed on a substrate other than the polarizing film, the pressure-sensitive adhesive layer can be attached to the polarizing film and transferred. Moreover, the said release film can be used as a separator of the polarizing film with an adhesive layer as it is, and the simplification in a process surface can be performed.
　前記偏光フィルムとしては、特に限定されるものではないが、偏光子と当該偏光子の少なくとも片面に透明保護フィルムを有するものを挙げることができる。 Although it does not specifically limit as said polarizing film, What has a transparent protective film in at least single side | surface of a polarizer and the said polarizer can be mentioned.
　（１）偏光子
　偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、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、ヨウ素や二色性染料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やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素等の二色性物質からなる偏光子が好適である。これらの偏光子の厚さは特に制限されないが、一般的に５～８０μｍ程度である。 (1) Polarizer The polarizer is not particularly limited, and various types of polarizers can be used. As a polarizer, for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene / vinyl acetate copolymer-based partially saponified film, dichroism of iodine or a dichroic dye Examples thereof include those obtained by adsorbing a substance and uniaxially stretched, and dehydrated products of polyvinyl alcohol and dehydrochlorinated products of polyvinyl chloride such as polyene-based oriented films. Among these, a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.
　ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、例えば、ポリビニルアルコールをヨウ素の水溶液に浸漬することによって染色し、元長の３～７倍に延伸することで作製することができる。必要に応じてホウ酸や硫酸亜鉛、塩化亜鉛等を含んでいても良いヨウ化カリウム等の水溶液に浸漬することもできる。さらに必要に応じて染色前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール系フィルム表面の汚れやブロッキング防止剤を洗浄することができるほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラ等の不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸しても良いし、また延伸してからヨウ素で染色しても良い。ホウ酸やヨウ化カリウム等の水溶液や水浴中でも延伸することができる。 A polarizer obtained by staining a polyvinyl alcohol-based film with iodine and uniaxially stretching it can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine and then stretching it to 3 to 7 times its original length. It can also be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride and the like as required. Furthermore, before dyeing, the polyvinyl alcohol-based film may be dipped in water and rinsed if necessary. In addition to being able to wash the stains and antiblocking agents on the surface of the polyvinyl alcohol film by washing the polyvinyl alcohol film with water, it is also possible to prevent unevenness such as uneven dyeing by swelling the polyvinyl alcohol film. is there. The stretching may be performed after staining with iodine, may be stretching while staining, or may be stretched and then stained with iodine. It can also be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
　また、本発明においては、厚さが１０μｍ以下の薄型偏光子も用いることができる。薄型化の観点から言えば当該厚さは１～７μｍであるのが好ましい。このような薄型の偏光子は、厚みムラが少なく、視認性が優れており、また寸法変化が少ないため耐久性に優れ、さらには偏光フィルムとしての厚さも薄型化が図れる点が好ましい。 In the present invention, a thin polarizer having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. It is preferable that such a thin polarizer has less thickness unevenness, excellent visibility, and less dimensional change, so it is excellent in durability, and further, thickness reduction as a polarizing film can be achieved.
　薄型の偏光子としては、代表的には、特開昭５１－０６９６４４号公報や特開２０００－３３８３２９号公報や、国際公開第２０１０／１００９１７号パンフレット、国際公開第２０１０／１００９１７号パンフレット、または特許４７５１４８１号明細書や特開２０１２－０７３５６３号公報に記載されている薄型偏光膜を挙げることができる。これら薄型偏光膜は、ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂ともいう）層と延伸用樹脂基材を積層体の状態で延伸する工程と染色する工程を含む製法による得ることができる。この製法であれば、ＰＶＡ系樹脂層が薄くても、延伸用樹脂基材に支持されていることにより延伸による破断等の不具合なく延伸することが可能となる。 Typical thin polarizers are disclosed in JP-A-51-069644, JP-A-2000-338329, WO 2010/100917, WO 2010/100917, or a patent. There can be mentioned thin polarizing films described in Japanese Patent No. 4751481 and Japanese Patent Application Laid-Open No. 2012-073563. These thin polarizing films can be obtained by a manufacturing method including the steps of stretching a polyvinyl alcohol resin (hereinafter, also referred to as a PVA resin) layer and a stretching resin base material in the state of a laminate and dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it is possible to stretch without any problems such as breakage due to stretching by being supported by the stretching resin base material.
　前記薄型偏光膜としては、積層体の状態で延伸する工程と染色する工程を含む製法の中でも、高倍率に延伸できて偏光性能を向上させることのできる点で、国際公開第２０１０／１００９１７号パンフレット、国際公開第２０１０／１００９１７号パンフレット、または特許４７５１４８１号明細書や特開２０１２－０７３５６３号公報に記載のあるようなホウ酸水溶液中で延伸する工程を含む製法で得られるものが好ましく、特に特許４７５１４８１号明細書や特開２０１２－０７３５６３号公報に記載のあるホウ酸水溶液中で延伸する前に補助的に空中延伸する工程を含む製法により得られるものが好ましい。 Among the thin polarizing films described above, among the process of drawing in the state of a laminate and the process of dyeing, it can be drawn at a high magnification and the polarization performance can be improved. WO 2010/100917 pamphlet, or those obtained by the process including the step of stretching in an aqueous solution of boric acid as described in Japanese Patent No. 4751481 or Japanese Patent Application Laid-Open No. 2012-073563, particularly preferred It is preferable to use one obtained by a method including the step of auxiliary air stretching before stretching in a boric acid aqueous solution as described in the specification of 4751481 and JP-A-2012-073563.
　（２）透明保護フィルム
　透明保護フィルムについては、従来から用いられているものを適宜用いることができる。具体的には、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れる材料から形成される透明保護フィルムが好ましく、例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体（ＡＳ樹脂）等のスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体等のポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、または、前記ポリマーのブレンド物等も前記透明保護フィルムを形成するポリマーの例として挙げられる。透明保護フィルムは、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型、紫外線硬化型の樹脂の硬化層として形成することもできる。 (2) Transparent Protective Film As the transparent protective film, those conventionally used can be appropriately used. Specifically, a transparent protective film formed of a material excellent in transparency, mechanical strength, thermal stability, water blocking property, isotropy, etc. is preferable. For example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate And cellulose based polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene based polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin), polycarbonate based polymers and the like. In addition, polyolefins having polyethylene, polypropylene, cyclo-based or norbornene structure, polyolefin-based polymers such as ethylene / propylene copolymer, vinyl chloride-based polymers, amide-based polymers such as nylon and aromatic polyamides, imide-based polymers, sulfone-based polymers , Polyethersulfone based polymer, polyetheretherketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol based polymer, vinylidene chloride based polymer, vinyl butyral based polymer, arylate based polymer, polyoxymethylene based polymer, epoxy based polymer, or Blends of the above polymers and the like are also mentioned as examples of the polymer forming the above transparent protective film. The transparent protective film can also be formed as a cured layer of thermosetting resin such as acrylic resin, urethane resin, acrylic urethane resin, epoxy resin, and silicone resin, and ultraviolet curable resin.
　透明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１～５００μｍ程度である。 The thickness of the transparent protective film can be appropriately determined, but in general, it is about 1 to 500 μm from the viewpoints of strength, workability such as handleability, and thin film properties.
　前記偏光子と透明保護フィルムとは、水系接着剤等を介して密着することが好ましい。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系、水系ポリウレタン、水系ポリエステル等を例示できる。上記の他、偏光子と透明保護フィルムとの接着剤としては、紫外硬化型接着剤、電子線硬化型接着剤等が挙げられる。電子線硬化型偏光フィルム用接着剤は、上記各種の視認側透明保護フィルムに対して、好適な接着性を示す。また本発明で用いる接着剤には、金属化合物フィラーを含有させることができる。 The polarizer and the transparent protective film are preferably in close contact with each other via a water-based adhesive or the like. Examples of water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latexes, water-based polyurethanes, water-based polyesters, and the like. In addition to the above, as an adhesive agent of a polarizer and a transparent protective film, an ultraviolet curable adhesive, an electron beam curable adhesive, etc. are mentioned. The adhesive for electron beam-curable polarizing film exhibits suitable adhesiveness to the above various viewing side transparent protective films. The adhesive used in the present invention can contain a metal compound filler.
　前記透明保護フィルムの偏光子を接着させない面には、ハードコート層や反射防止処理、スティッキング防止や、拡散ないしアンチグレアを目的とした処理を施したものであっても良い。 The surface of the transparent protective film to which the polarizer is not attached may be treated with a hard coat layer, an antireflective treatment, an antisticking treatment, or a treatment for diffusion or antiglare.
　また、前記透明保護フィルムとして、位相差を有し、光学補償層として機能し得るもののいずれも用いることができる。位相差を有する透明保護フィルムを用いる場合、その位相差特性は、光学補償に必要とされる値に適宜調整することができる。かかる位相差フィルムとしては、延伸フィルムを好適に用いることができる。前記位相差フィルムは、遅相軸方向の屈折率をｎｘ、面内の進相軸方向の屈折率をｎｙ、厚み方向の屈折率をｎｚとした場合に、ｎｘ＝ｎｙ＞ｎｚ、ｎｘ＞ｎｙ＞ｎｚ、ｎｘ＞ｎｙ＝ｎｚ、ｎｘ＞ｎｚ＞ｎｙ、ｎｚ＝ｎｘ＞ｎｙ、ｎｚ＞ｎｘ＞ｎｙ、ｎｚ＞ｎｘ＝ｎｙ、の関係を満足するものが、各種用途に応じて選択して用いられる。なお、ｎｘ＝ｎｙとは、ｎｘとｎｙが完全に同一である場合だけでなく、実質的にｎｘとｎｙが同じ場合も含む。また、ｎｙ＝ｎｚとは、ｎｙとｎｚが完全に同一である場合だけでなく、実質的にｎｙとｎｚが同じ場合も含む。 Further, as the transparent protective film, any one having retardation and capable of functioning as an optical compensation layer can be used. When using the transparent protective film which has a phase difference, the phase difference characteristic can be suitably adjusted to the value required for optical compensation. As such a retardation film, a stretched film can be suitably used. The retardation film has a refractive index in the slow axis direction of nx, a refractive index in the in-plane fast axis direction of ny, and a refractive index in the thickness direction of nz: nx = ny> nz, nx> ny Those satisfying the relationship of> nz, nx> ny = nz, nx> nz> ny, nz = nx> ny, nz> nx> ny, nz> nx = ny are selected and used according to various applications. Be Note that nx = ny includes not only cases in which nx and ny are completely identical but also cases in which nx and ny are substantially the same. Also, ny = nz includes not only cases in which ny and nz are completely identical, but also cases in which ny and nz are substantially the same.
　本発明で用いる偏光フィルムを有機ＥＬ表示装置の反射防止用の円偏光板として用いる場合は、前記位相差フィルムは、透明保護フィルムの正面レターデーションを１／４波長（約１００～１７０ｎｍ）とした１／４波長板であることが好ましい。 When the polarizing film used in the present invention is used as a circularly polarizing plate for preventing reflection of an organic EL display device, the retardation film has a front surface retardation of the transparent protective film of 1⁄4 wavelength (about 100 to 170 nm). Preferably, it is a quarter wave plate.
　透明保護フィルムとして位相差フィルムを使用する場合、偏光子の一方の面に透明保護フィルムが設けられ、他方の面に位相差フィルムを有するものを好適に用いることができる。また、その場合、前記粘着剤層の設置場所は特に限定されるものではなく、前記透明保護フィルムの偏光子と接する面と反対側の面に設けられていてもよく、位相差フィルムの偏光子と接する面と反対側の面に設けられていてもよいが、有機ＥＬ素子の劣化抑制の観点からは、少なくとも一方の面、若しくは両方の面に設けられている事が好ましい。 When using a retardation film as a transparent protective film, what has a transparent protective film in one side of a polarizer, and has a retardation film in the other side can be used suitably. Moreover, in that case, the installation place of the said adhesive layer is not specifically limited, It may be provided in the surface on the opposite side to the surface in contact with the polarizer of the said transparent protective film, The polarizer of retardation film It may be provided on the side opposite to the side in contact with the surface, but from the viewpoint of suppressing the deterioration of the organic EL element, it is preferably provided on at least one side or both sides.
　本発明の有機ＥＬ表示装置用粘着剤層付き偏光フィルムの具体的な構成の一例を、図１（ａ）～（ｃ）に示す。図１（ａ）に示すように、粘着剤層２／透明保護フィルム３／偏光子４／位相差フィルム５、図１（ｂ）に示すように、透明保護フィルム３／偏光子４／位相差フィルム５／粘着剤層２、図１（ｃ）に示すように、粘着剤層２／透明保護フィルム３／偏光子４／位相差フィルム５／粘着剤層２；のように、各層がこの順に積層された有機ＥＬ表示装置用粘着剤層付き偏光フィルム１を挙げることができる。前記図１（ａ）および（ｂ）においては、粘着剤層２が本発明の有機ＥＬ表示装置用粘着剤層であり、図１（ｃ）においては、２つある粘着剤層２のうち少なくとも１つが本発明の有機ＥＬ表示装置用粘着剤層であればよく、２つとも本発明の有機ＥＬ表示装置用粘着剤層であってもよい。また、図１においては、偏光フィルム６は、偏光子４と透明保護フィルム３から構成される片保護偏光フィルムであるが、これに限定されるものではなく、偏光子４と位相差フィルム５の間にさらに透明保護フィルムを有する両保護偏光フィルムであってもよい。また、前述の通り、透明保護フィルム３の偏光子４と接していない面には、ハードコート層等の各種機能層等を形成することもできる。 An example of a specific configuration of the pressure-sensitive adhesive layer-attached polarizing film for an organic EL display device of the present invention is shown in FIGS. 1 (a) to (c). As shown in FIG. 1 (a), adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5, as shown in FIG. 1 (b), transparent protective film 3 / polarizer 4 / retardation As shown in film 5 / adhesive layer 2, as shown in FIG. 1 (c), each layer is in this order as adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 2; The laminated polarizing film 1 with an adhesive layer for organic EL display devices can be mentioned. In FIGS. 1 (a) and 1 (b), the pressure-sensitive adhesive layer 2 is the pressure-sensitive adhesive layer for the organic EL display device of the present invention, and in FIG. 1 (c), at least the two pressure-sensitive adhesive layers 2 are present. One of them may be the pressure-sensitive adhesive layer for the organic EL display device of the present invention, and both of them may be the pressure-sensitive adhesive layer for the organic EL display device of the present invention. Moreover, in FIG. 1, although the polarizing film 6 is a piece protection polarizing film comprised from the polarizer 4 and the transparent protective film 3, it is not limited to this, The polarizing film 4 and the retardation film 5 It may be both protective polarizing films further having a transparent protective film therebetween. Further, as described above, various functional layers such as a hard coat layer can be formed on the surface of the transparent protective film 3 which is not in contact with the polarizer 4.
　また、前記位相差フィルムが、粘着剤層を介して偏光子に積層される場合、当該粘着剤層が、本発明の有機ＥＬ表示装置用粘着剤層であってもよい。すなわち、有機ＥＬ表示装置用粘着剤層付き偏光フィルムが、第１粘着剤層、透明保護フィルム、偏光子、第２粘着剤層、位相差フィルム、第３粘着剤層をこの順に有し、
　前記第１粘着剤層、第２粘着剤層、および第３粘着剤層のうち、少なくとも一つの粘着剤層が、前記有機ＥＬ表示装置用粘着剤層であればよい。 Moreover, when the said retardation film is laminated | stacked on a polarizer through the adhesive layer, the said adhesive layer may be an adhesive layer for organic EL display apparatuses of this invention. That is, the polarizing film with a pressure-sensitive adhesive layer for an organic EL display device has a first pressure-sensitive adhesive layer, a transparent protective film, a polarizer, a second pressure-sensitive adhesive layer, a retardation film, and a third pressure-sensitive adhesive layer in this order
At least one pressure-sensitive adhesive layer of the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer may be the pressure-sensitive adhesive layer for the organic EL display device.
４．有機ＥＬ表示装置
　本発明の有機ＥＬ表示装置は、本発明の有機ＥＬ表示装置用粘着剤層、および／または本発明の有機ＥＬ表示装置用粘着剤層付き偏光フィルムを少なくとも１つ用いたことを特徴とする。 4. Organic EL Display Device The organic EL display device of the present invention uses at least one pressure-sensitive adhesive layer for an organic EL display device of the present invention and / or at least one polarizing film with an adhesive layer for an organic EL display device of the present invention. It features.
　有機ＥＬ表示装置の具体的な構成の一例としては、例えば、図２～図４に示すように、カバーガラスまたはカバープラスチック７／粘着剤層２／透明保護フィルム３／偏光子４／位相差フィルム５／粘着剤層２／有機ＥＬ表示パネル（ＯＬＥＤ素子パネル）８（図２）；カバーガラスまたはカバープラスチック７／接着剤層９／透明保護フィルム３／偏光子４／位相差フィルム５／粘着剤層２／有機ＥＬ表示パネル８（図３）；カバーガラスまたはカバープラスチック７／粘着剤層２／センサー層１０／粘着剤層２／透明保護フィルム３／偏光子４／位相差フィルム５／粘着剤層２／有機ＥＬ表示パネル８（図４）；のように、各層がこの順に積層された有機ＥＬ表示装置を挙げることができる。前記各構成における粘着剤層２のうち、少なくとも１つが本発明の粘着剤層であればよく、全ての粘着剤層２が本発明の粘着剤層であってもよい。また、本発明の有機ＥＬ表示装置は、前記以外にも保護フィルム、ハードコート層等の各種機能層等を含んでいてもよい。また、各層の積層において、適宜粘着剤層および／または接着剤層を用いることができる。本発明の粘着剤層以外の粘着剤層としては、本分野において用いられる通常の粘着剤層を適宜用いることができる。 As an example of a specific structure of an organic electroluminescence display, as shown in FIGS. 2-4, for example, cover glass or cover plastic 7 / adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 2 / organic EL display panel (OLED element panel) 8 (FIG. 2); cover glass or cover plastic 7 / adhesive layer 9 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive Layer 2 / organic EL display panel 8 (FIG. 3); cover glass or cover plastic 7 / adhesive layer 2 / sensor layer 10 / adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive As in the layer 2 / organic EL display panel 8 (FIG. 4), an organic EL display in which each layer is laminated in this order can be mentioned. At least one of the pressure-sensitive adhesive layers 2 in each configuration may be the pressure-sensitive adhesive layer of the present invention, and all the pressure-sensitive adhesive layers 2 may be the pressure-sensitive adhesive layer of the present invention. In addition to the above, the organic EL display device of the present invention may include various functional layers such as a protective film and a hard coat layer. Moreover, in lamination of each layer, an adhesive layer and / or an adhesive layer can be appropriately used. As pressure-sensitive adhesive layers other than the pressure-sensitive adhesive layer of the present invention, conventional pressure-sensitive adhesive layers used in the present field can be appropriately used.
　以下に、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。なお、各例中の部および％はいずれも重量基準である。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples. All parts and% in each example are based on weight.
　＜（メタ）アクリル系ポリマーの重量平均分子量の測定＞
　（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定した。Ｍｗ／Ｍｎについても、同様に測定した。
・分析装置：東ソー社製、ＨＬＣ－８１２０ＧＰＣ
・カラム：東ソー社製、Ｇ７０００ＨＸＬ＋ＧＭＨＸＬ＋ＧＭＨＸＬ
・カラムサイズ：各７．８ｍｍφ×３０ｃｍ　計９０ｃｍ
・カラム温度：４０℃
・流量：０．８ｍＬ／ｍｉｎ
・注入量：１００μＬ
・溶離液：テトラヒドロフラン
・検出器：示差屈折計（ＲＩ）
・標準試料：ポリスチレン <Measurement of weight average molecular weight of (meth) acrylic polymer>
The weight average molecular weight (Mw) of the (meth) acrylic polymer was measured by GPC (gel permeation chromatography). The Mw / Mn was also measured in the same manner.
・ Analyzer: HLC-8120 GPC made by Tosoh Corporation
・ Column: Tosoh Corporation G7000 HXL + GMH XL + GMH XL
・ Column size: Each 7.8mmφ × 30cm in total 90cm
・ Column temperature: 40 ° C
・ Flow rate: 0.8mL / min
Injection volume: 100 μL
Eluent: Tetrahydrofuran Detector: Differential Refractometer (RI)
Standard sample: polystyrene
　＜（メタ）アクリル系ポリマー（１）の調製＞
　冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器にアクリル酸ブチル（ＢＡ）９９部、およびアクリル酸４－ヒドロキシブチル（ＨＢＡ）１部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物１００部に対して、重合開始剤として２，２’－アゾビスイソブチロニトリル０．１部を酢酸エチル１００部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を５５℃付近に保って８時間重合反応を行って、重量平均分子量（Ｍｗ）１８０万、Ｍｗ／Ｍｎ＝４．１のアクリル系ポリマーの溶液（固形分濃度３０重量％）を調製した。 <Preparation of (meth) acrylic polymer (1)>
A monomer mixture containing 99 parts of butyl acrylate (BA) and 1 part of 4-hydroxybutyl acrylate (HBA) was charged into a reaction vessel equipped with a condenser, a nitrogen introduction pipe, a thermometer and a stirrer. Furthermore, 0.1 part of 2,2'-azobisisobutyro nitrile as a polymerization initiator is charged together with 100 parts of ethyl acetate to 100 parts of the monomer mixture, and nitrogen gas is introduced while gently stirring to introduce nitrogen. After substitution, the solution temperature in the flask is maintained at around 55 ° C. and polymerization reaction is carried out for 8 hours, and a solution of acrylic polymer having a weight average molecular weight (Mw) of 1.8 million and Mw / Mn = 4.1 (solids concentration 30% by weight) was prepared.
　＜（メタ）アクリル系ポリマー（２）の調製＞
　冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器にアクリル酸ブチル（ＢＡ）９４.８部、アクリル酸（ＡＡ）５部、およびアクリル酸２－ヒドロキシエチル（ＨＥＡ）０．２部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物１００部に対して、重合開始剤としてベンゾイルパーオキサイド（日本油脂社製の商品名ナイパーＢＭＴ）０．３部を酢酸エチル１００部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を５５℃付近に保って８時間重合反応を行って、重量平均分子量（Ｍｗ）２２０万、Ｍｗ／Ｍｎ＝４．１のアクリル系ポリマーの溶液（固形分濃度３０重量％）を調製した。 <Preparation of (meth) acrylic polymer (2)>
94.8 parts of butyl acrylate (BA), 5 parts of acrylic acid (AA), and 2-hydroxyethyl acrylate (HEA) 0.2 in a reaction vessel equipped with a condenser, nitrogen inlet, thermometer and stirrer. A monomer mixture containing parts was charged. Furthermore, 0.3 part of benzoyl peroxide (trade name: Naipar BMT, manufactured by Nippon Oil and Fats Co., Ltd.) is added to 100 parts of the monomer mixture together with 100 parts of ethyl acetate, and nitrogen gas is introduced while gently stirring. And carry out polymerization reaction for 8 hours while keeping the liquid temperature in the flask at around 55 ° C., to obtain a solution of acrylic polymer having a weight average molecular weight (Mw) of 220,000 and Mw / Mn = 4.1 ( A solid concentration of 30% by weight was prepared.
　＜（メタ）アクリル系ポリマー（３）の調製＞
　冷却管、窒素導入管、温度計および撹拌装置を備えた反応容器に、ブチルアクリレート（ＢＡ）７３．３部、フェノキシエチルアクリレート（ＰＥＡ）２１部、Ｎ－ビニルピロリドン（ＮＶＰ）５部、アクリル酸（ＡＡ）０．３部、４－ヒドロキシブチルアクリレート（ＨＢＡ）０．４部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物（固形分）１００部に対して、重合開始剤として２，２’－アゾビスイソブチロニトリル０．１部を酢酸エチル１００部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を５５℃付近に保って８時間重合反応を行って、重量平均分子量（Ｍｗ）１６０万、Ｍｗ／Ｍｎ＝３．８のアクリル系ポリマーの溶液（固形分濃度２８重量％）を調製した。 <Preparation of (meth) acrylic polymer (3)>
73.3 parts of butyl acrylate (BA), 21 parts of phenoxyethyl acrylate (PEA), 5 parts of N-vinylpyrrolidone (NVP), acrylic acid in a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer A monomer mixture containing 0.3 parts of (AA) and 0.4 parts of 4-hydroxybutyl acrylate (HBA) was charged. Furthermore, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator is charged together with 100 parts of ethyl acetate with 100 parts of the monomer mixture (solid content), and nitrogen gas is added while being gently stirred. After introducing and nitrogen substitution, the solution temperature in the flask is kept at around 55 ° C and polymerization reaction is carried out for 8 hours, and a solution of acrylic polymer having a weight average molecular weight (Mw) of 1.60000 and Mw / Mn = 3.8. A solid concentration of 28% by weight was prepared.
　実施例１
　（粘着剤組成物の調製）
　上記で製造したアクリル系ポリマー（１）の溶液の固形分１００部に対して、
　ラジカル発生剤（ベンゾイルパーオキサイド，日本油脂社製の商品名ナイパーＢＭＴ）を０．３部、
　イソシアネート系架橋剤（三井化学社製の商品名タケネートＤ１１０Ｎ）０．１部、
　紫外線吸収剤（ａ）として、２，４－ビス－[｛４－（４－エチルヘキシルオキシ）－４－ヒドロキシ｝－フェニル]－６－（４－メトキシフェニル）－１，３，５-トリアジン（商品名：Ｔｉｎｏｓｏｒｂ　Ｓ，ＢＡＳＦ社製）２部、および
　シランカップリング剤（信越化学工業（株）製のＫＢＭ４０３）０．１部を配合して、粘着剤組成物を得た。 Example 1
(Preparation of pressure-sensitive adhesive composition)
With respect to 100 parts of solid content of the solution of the acrylic polymer (1) manufactured above,
0.3 part of a radical generator (Benzoyl peroxide, trade name Nyper BMT manufactured by NOF Corporation),
0.1 part of an isocyanate crosslinking agent (Takenate D110N, trade name of Mitsui Chemicals, Inc.),
As a UV absorber (a), 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine ( Trade name: Tinosorb S (manufactured by BASF) 2 parts, and 0.1 part of a silane coupling agent (KBM 403 manufactured by Shin-Etsu Chemical Co., Ltd.) were blended to obtain a pressure-sensitive adhesive composition.
　（粘着剤層の作製）
　前記粘着剤組成物を厚さ３８μｍのセパレータ（表面が剥離処理されたポリエチレンテレフタレート系フィルム：離型フィルム）上に、乾燥後の厚さが２０μｍとなるように塗布し、１５５℃で１分間乾燥層させて溶媒を除去し、粘着剤層（Ａ）を得た。 (Preparation of adhesive layer)
The pressure-sensitive adhesive composition is applied onto a 38 μm thick separator (polyethylene terephthalate film with a surface subjected to peeling treatment: release film) so that the thickness after drying is 20 μm, and dried at 155 ° C. for 1 minute The solvent was removed by layering to obtain a pressure-sensitive adhesive layer (A).
　前記粘着剤層（Ａ）を形成した、直後、前記粘着剤層（Ａ）を形成したセパレータを、シクロオレフィンポリマーフィルム／偏光子／アクリル系樹脂フィルム／粘着剤層（Ｂ）／位相差フィルムの構成の位相差フィルムを有する偏光フィルムに移着させて、粘着剤層付き偏光フィルムを作製した。得られた粘着剤層付き偏光フィルムの構成は、シクロオレフィンポリマーフィルム／偏光子／アクリル系樹脂フィルム／粘着剤層（Ｂ）／位相差フィルム／粘着剤層（Ａ）、である。 Immediately after forming the pressure-sensitive adhesive layer (A), the separator on which the pressure-sensitive adhesive layer (A) is formed is formed of cycloolefin polymer film / polarizer / acrylic resin film / pressure-sensitive adhesive layer (B) / retardation film It was transferred to a polarizing film having a retardation film of the constitution to prepare a polarizing film with an adhesive layer. The composition of the obtained polarizing film with a pressure-sensitive adhesive layer is cycloolefin polymer film / polarizer / acrylic resin film / pressure-sensitive adhesive layer (B) / retardation film / pressure-sensitive adhesive layer (A).
　なお、偏光子の両側のシクロオレフィンポリマーフィルム及びアクリル系樹脂フィルムは、ポリビニルアルコール系接着剤を用いて貼り合せて偏光フィルムを得た。位相差フィルムを有する粘着剤層付き偏光フィルムの作製にあたっては、粘着剤層（Ｂ）を介して、偏光フィルムと位相差フィルムを貼り合わせた。 In addition, the cycloolefin polymer film and the acrylic resin film of the both sides of a polarizer were bonded using the polyvinyl alcohol-type adhesive agent, and the polarizing film was obtained. In preparation of the polarizing film with an adhesive layer which has a retardation film, the polarizing film and the retardation film were bonded together through an adhesive layer (B).
　なお、位相差フィルムを有する偏光フィルムの構成部材は下記のとおりである。 In addition, the structural member of the polarizing film which has retardation film is as follows.
　（シクロオレフィンポリマーフィルム）
　厚さ２５μｍのシクロオレフィンポリマーフィルム（商品名ゼオノアフィルム，日本ゼオン株式会社製）を用いた。 (Cycloolefin polymer film)
A cycloolefin polymer film (trade name: Zeonor Film, manufactured by Nippon Zeon Co., Ltd.) having a thickness of 25 μm was used.
　（偏光子の製造）
　ヨウ素が含浸された厚さ５μｍの延伸ポリビニルアルコールフィルムからなる偏光子を用いた。偏光子（または保護フィルムを貼り合わせた偏光フィルム）の単体透過率Ｙ値は、４２．４％、偏光度は９９．９９５であった。 (Manufacture of polarizer)
A polarizer consisting of a 5 μm thick stretched polyvinyl alcohol film impregnated with iodine was used. The single transmittance Y value of the polarizer (or the polarizing film laminated with the protective film) was 42.4%, and the degree of polarization was 99.995.
　（アクリル系樹脂フィルム）
　特開２０１０－２８４８４０号公報の製造例１に記載のイミド化ＭＳ樹脂１００重量部からなる樹脂ペレットを、１００．５ｋＰａ、１００℃で１２時間乾燥させ、単軸の押出機にてダイス温度２７０℃でＴダイから押出してフィルム状に成形した（厚さ８０μｍ）。さらに当該フィルムを、その搬送方向に１５０℃の雰囲気下に延伸し（厚さ４０μｍ）、次いでフィルム搬送方向と直交する方向に１５０℃の雰囲気下に延伸して、厚さ２０μｍのアクリル系樹脂フィルムを得た。 (Acrylic resin film)
The resin pellet consisting of 100 parts by weight of the imidized MS resin described in Production Example 1 of JP-A-2010-284840 is dried at 100.5 kPa and 100 ° C. for 12 hours, and the die temperature is 270 ° C. in a single-screw extruder. And extruded from a T-die to form a film (thickness 80 μm). Furthermore, the film is stretched in an atmosphere of 150 ° C. in the transport direction (thickness 40 μm), and then stretched in an atmosphere of 150 ° C. in a direction perpendicular to the film transport direction, and an acrylic resin film of 20 μm thickness I got
　（位相差フィルム）
　厚み５６μｍのポリカーボネートフィルム（日東電工株式会社製「ＮＲＦ」、面内位相差Ｒｅ（５５０）：１３５ｎｍ）を用いた。 (Retardation film)
A polycarbonate film (“NRF” manufactured by Nitto Denko Corporation, in-plane retardation Re (550): 135 nm) having a thickness of 56 μm was used.
　（粘着剤層（Ｂ）を形成する粘着剤組成物の調製）
　温度計、攪拌機、還流冷却管及び窒素ガス導入管を備えたセパラブルフラスコに、ブチルアクリレート９５重量部、アクリル酸５重量部、重合開始剤としてアゾビスイソブチロニトリル０．２重量部、及び酢酸エチル２３３重量部を投入した後、窒素ガスを流し、攪拌しながら約１時間窒素置換を行った。その後、６０℃にフラスコを加熱し、７時間反応させて、重量平均分子量（Ｍｗ）１１０万のアクリル系ポリマーを得た。上記アクリル系ポリマー溶液（固形分を１００重量部とする）に、イソシアネート系架橋剤として、トリメチロールプロパントリレンジイソシアネート（商品名：コロネートＬ，日本ポリウレタン工業（株）製）０．８重量部、シランカップリング剤（商品名：ＫＢＭ－４０３、信越化学工業（株）製）０．１重量部を加えて粘着剤組成物（溶液）を調製した。 (Preparation of pressure-sensitive adhesive composition forming pressure-sensitive adhesive layer (B))
In a separable flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet, 95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, After charging 233 parts by weight of ethyl acetate, nitrogen gas was flowed, and nitrogen replacement was performed for about 1 hour while stirring. Thereafter, the flask was heated to 60 ° C. and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million. 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent in the above acrylic polymer solution (solid content is 100 parts by weight), A pressure-sensitive adhesive composition (solution) was prepared by adding 0.1 parts by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
　（粘着剤層（Ｂ）の製造）
　前記粘着剤組成物（溶液）を、厚さ３８μｍのセパレータ（表面が剥離処理されたポリエチレンテレフタレート系フィルム：離型フィルム）上に、乾燥後の厚さが１５μｍとなるように塗布し、１００℃で３分間乾燥層させて溶媒を除去し、粘着剤層（Ｂ）を得た。 (Production of pressure-sensitive adhesive layer (B))
The pressure-sensitive adhesive composition (solution) is coated on a 38 μm-thick separator (polyethylene terephthalate film with release-treated surface: release film) to a dry thickness of 15 μm, 100 ° C. The mixture was dried for 3 minutes and the solvent was removed to obtain a pressure-sensitive adhesive layer (B).
　実施例２～１３、比較例１～３
　実施例１において、粘着剤組成物の調製にあたり、（メタ）アクリル系ポリマーの種類、架橋剤の種類または配合量、紫外線吸収剤の種類または配合量、色素化合物の種類または配合量、酸化防止剤の配合量を表１に示すように変えたこと以外は、実施例１と同様にして、粘着剤層を形成した。また、実施例１と同様にして粘着剤層付き偏光フィルムを作製した。 Examples 2 to 13 and Comparative Examples 1 to 3
In Example 1, in preparing the pressure-sensitive adhesive composition, the type of (meth) acrylic polymer, the type or blending amount of the crosslinking agent, the type or blending amount of the ultraviolet light absorber, the type or blending amount of the dye compound, the antioxidant A pressure-sensitive adhesive layer was formed in the same manner as in Example 1 except that the compounding amount of A was changed as shown in Table 1. Further, in the same manner as in Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced.
　上記実施例および比較例で得られた粘着剤層（Ａ）、粘着剤層付き偏光フィルムについて、以下の評価を行った。評価結果を表１に示す。 The following evaluation was performed about the adhesive layer (A) obtained by the said Example and comparative example, and the polarizing film with an adhesive layer. The evaluation results are shown in Table 1.
　＜粘着剤層の透過率の測定＞
　実施例および比較例で得られた粘着剤層（Ａ）からセパレータを剥離して、粘着剤層（Ａ）を測定用治具に取り付け、分光光度計（製品名：Ｕ４１００、（株）日立ハイテクノロジーズ製）で測定した。透過率は、波長３００ｎｍ～４５０ｎｍの範囲における透過率を測定した。波長３００ｎｍ～４００ｎｍ、波長４００ｎｍ～４３０ｎｍ、波長４３０ｎｍ～４５０ｎｍの平均透過率を表１に示す。 <Measurement of Permeability of Adhesive Layer>
The separator is peeled off from the pressure-sensitive adhesive layer (A) obtained in Examples and Comparative Examples, and the pressure-sensitive adhesive layer (A) is attached to a jig for measurement, and a spectrophotometer (product name: U4100, Hitachi High-Tech Co., Ltd.) Measured by Technologies). The transmittance was measured in the wavelength range of 300 nm to 450 nm. The average transmittances at wavelengths of 300 nm to 400 nm, wavelengths of 400 nm to 430 nm, and wavelengths of 430 nm to 450 nm are shown in Table 1.
　＜ゲル分率の測定＞
　ゲル分率は、前記粘着剤層（Ａ）を０．２ｇとり、あらかじめ重量を測定したフッ素樹脂（ＴＥＭＩＳＨ 　ＮＴＦ－１１２２日東電工（株）製）（Ｗａ）に包み、粘着剤が漏れないように縛った後、重量（Ｗｂ）を測定し、サンプル瓶にいれた。酢酸エチルを４０ｃｃ加えて７日間放置した。その後、フッ素樹脂を取り出し、アルミカップ上で１３０℃、２時間乾燥させ、サンプルを含むフッ素樹脂の重量（Ｗｃ）を測定し、次式（Ｉ）によりゲル分率を求めた。
　式（Ｉ）：ゲル分率＝（Ｗｃ－Ｗａ）／（Ｗｂ－Ｗａ）×１００（重量％）
　ゲル分率の測定は、粘着剤層（Ａ）を形成した直後（４時間以内）と、粘着剤層（Ａ）を形成した後、室温（２３℃）で１週間放置した後について行った。 <Measurement of gel fraction>
The gel fraction is 0.2 g of the pressure-sensitive adhesive layer (A) and wrapped in a fluorine resin (TEMISH NTF-1122 manufactured by Nitto Denko Co., Ltd.) (Wa) whose weight is measured in advance so that the pressure-sensitive adhesive does not leak After binding, the weight (Wb) was measured and placed in a sample bottle. 40 cc of ethyl acetate was added and left for 7 days. Thereafter, the fluororesin was taken out, dried at 130 ° C. for 2 hours on an aluminum cup, the weight (Wc) of the fluororesin containing the sample was measured, and the gel fraction was determined by the following formula (I).
Formula (I): gel fraction = (Wc-Wa) / (Wb-Wa) x 100 (% by weight)
The gel fraction was measured immediately after the pressure-sensitive adhesive layer (A) was formed (within 4 hours) and after it was left at room temperature (23 ° C.) for one week after the pressure-sensitive adhesive layer (A) was formed.
　＜外観歩留まり＞
　得られた粘着剤層付き偏光フィルムを一辺の長さが２７０ｍｍの正方形に打ち抜いたものについて、粘着剤層（Ａ）の糊打痕、端部の糊欠け、端部の糊汚れを以下の基準で評価した。
　○・・・問題なし。
　△・・・糊かけ、糊汚れ、糊打痕による一部外観不良がある。
　×・・・糊かけ、糊汚れ、糊打痕による外観不良が著しい。 <Appearance yield>
About the obtained adhesive film with a pressure-sensitive adhesive layer punched into a square with a side length of 270 mm, the following criteria were applied for the adhesive mark of the adhesive layer (A), the adhesive chipping of the end, and the adhesive stain of the end It evaluated by.
○ ... no problem.
Δ: Some appearance defects due to paste, paste stain, paste strike.
X · · · Poor appearance due to glueing, glue stains, glue marks, is remarkable.
　＜耐久性＞
　得られた粘着剤層付き偏光フィルム（縦２９０ｍｍ×横２２０ｍｍ）からセパレータを剥離し、粘着剤層（Ａ）側を、厚さ０．７ｍｍの無アルカリガラス板の両面にクロスニコル状態になるように貼着した。次いで、５０℃、５ａｔｍで１５分間オートクレーブ処理を施し、完全に密着させてサンプルを調製した。当該サンプルを８５の条件下でそれぞれ５００時間処理した後、発泡・剥れ・浮きの状態を以下の基準で目視観察した。
　〇・・・発泡・剥れ・浮きなどがない。
　△・・・実用上問題は無いレベルだが、目視でわずかにレベルが悪い。
　×・・・実用上問題がある。 <Durability>
The separator is peeled off from the obtained polarizing film with pressure-sensitive adhesive layer (290 mm long × 220 mm wide), and the pressure-sensitive adhesive layer (A) side is in a cross nicol state on both sides of an alkali-free glass plate with a thickness of 0.7 mm. Sticked to Next, the sample was autoclaved at 50 ° C. and 5 atm for 15 minutes to make the sample completely intimate. The samples were treated under the conditions of 85 for 500 hours, respectively, and then the state of foaming, peeling, and lifting was visually observed according to the following criteria.
・ ・ ・ ... no foaming, peeling, floating, etc.
Δ: There is no problem in practical use, but the level is slightly worse visually.
X ... There is a problem in practical use.
　＜剥離力＞
　得られた粘着剤層付き偏光フィルムから、長さ１００ｍｍ、幅５０ｍｍのシート片を切り出したものをサンプルとした。得られたサンプルについて、引張試験機（装置名：オートグラフ ＡＧ－ＩＳ、（株）島津製作所製）を用い、ＪＩＳ Ｚ０２３７に準拠して、２３℃、５０％Ｒ．Ｈ．の雰囲気下、引張速度３００ｍｍ／分、剥離角度１８０°の条件でサンプルからセパレータを引きはがし、１８０°引き剥がし剥離力（Ｎ／５０ｍｍ）を測定した。 <Peeling force>
What cut out the sheet piece of length 100 mm and width 50 mm from the obtained polarizing film with an adhesive layer was made into the sample. About the obtained sample, using a tensile tester (apparatus name: Autograph AG-IS, manufactured by Shimadzu Corporation), in accordance with JIS Z0237, 23 ° C., 50% R.H. H. The separator was peeled off from the sample under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 ° in an atmosphere of 1, and the 180 ° peeling peel force (N / 50 mm) was measured.
　前記セパレータ剥離力は、０．０２～１．０（Ｎ／５０ｍｍ）が好ましい。前記セパレータ剥離力が０．０２（Ｎ／５０ｍｍ）以上であることは、加工時やハンドリングにおいてセパレータの浮きによる外観不具合を抑えるうえで好ましい。一方、前記セパレータ剥離力が１．０（Ｎ／５０ｍｍ）以下であることは、セパレータの剥離不良を抑えるうえで好ましい。前記セパレータ剥離力は、より好ましくは０．０４～０．５（Ｎ／５０ｍｍ）、さらに好ましくは０．０６～０．２（Ｎ／５０ｍｍ）、特に好ましくは０．０８～０．１５（Ｎ／５０ｍｍ）である。 The separator peeling force is preferably 0.02 to 1.0 (N / 50 mm). The separator peeling force of 0.02 (N / 50 mm) or more is preferable for suppressing appearance defects due to the floating of the separator during processing or handling. On the other hand, it is preferable in order to suppress the peeling defect of a separator that the said separator peeling force is 1.0 (N / 50 mm) or less. The separator peeling force is more preferably 0.04 to 0.5 (N / 50 mm), still more preferably 0.06 to 0.2 (N / 50 mm), and particularly preferably 0.08 to 0.15 (N). / 50 mm).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１中、
　ラジカル発生剤は、ベンゾイルパーオキサイド（日本油脂社製の商品名ナイパーＢＭＴ）；
　Ｄ１１０Ｎは、イソシアネート系架橋剤（三井化学社製の商品名タケネートＤ１１０Ｎ）；
　Ｃ／Ｌは、イソシアネート系架橋剤（東ソー社製の商品名コロネートＬ）；
　紫外線吸収剤のａ１は、２，４－ビス－[｛４－（４－エチルヘキシルオキシ）－４－ヒドロキシ｝－フェニル]－６－（４－メトキシフェニル）－１，３，５-トリアジン（商品名：Ｔｉｎｏｓｏｒｂ　Ｓ，ＢＡＳＦ社製）；
　紫外線吸収剤のａ２は、２，２’，４，４’テトラヒドロキシベンゾフェノン（商品名：ＳｅｅＳｏｒｂ１０６，シプロ化成社製）；
　色素化合物のｂ１は、メロシアニン系化合物（商品名：ＦＤＢ－００９，吸収スペクトルの最大吸収波長：３９４ｎｍ，半値幅：４３ｎｍ，山田化学工業（株）製）；
　色素化合物のｂ２は、ポリメチン化合物（商品名：ＤＡＡ－２４７、吸収スペクトルの最大吸収波長：３８９ｎｍ、半値幅：４９．５ｎｍ、山田化学工業（株）製）；
　色素化合物のｂ３は、アルキルフェニルインドールシアノアクリナート誘導体（インドール化合物）（商品名：ＢＯＮＡＳＯＲＢ　ＵＡ３９１２，吸収スペクトルの最大吸収波長：３８６ｎｍ，半値幅：５３ｎｍ，オリエント化学工業（株）製）；
　酸化防止剤は、フェノール系酸化防止剤（ＢＡＳＦジャパン社製の商品名ＩＲＧＡＮＯＸ １０１０）；を示す。 In Table 1,
The radical generating agent is benzoyl peroxide (trade name niper BMT manufactured by NOF Corporation);
D110N is an isocyanate crosslinking agent (trade name Takenate D110N manufactured by Mitsui Chemicals, Inc.);
C / L is an isocyanate crosslinking agent (trade name Coronate L manufactured by Tosoh Corporation);
The UV absorber a1 is 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (commodity Name: Tinosorb S, BASF Corporation);
The ultraviolet absorber a2 is 2,2 ′, 4,4 ′ tetrahydroxybenzophenone (trade name: SeeSorb 106, manufactured by Cipro Chemical Industries, Ltd.);
The dye compound b1 is a merocyanine compound (trade name: FDB-009, maximum absorption wavelength of absorption spectrum: 394 nm, full width at half maximum: 43 nm, Yamada Chemical Industry Co., Ltd.);
The pigment compound b2 is a polymethine compound (trade name: DAA-247, maximum absorption wavelength of absorption spectrum: 389 nm, half width: 49.5 nm, manufactured by Yamada Chemical Industry Co., Ltd.);
B3 of the dye compound is an alkylphenylindole cyanoacrylate derivative (indole compound) (trade name: BONASORB UA3912, absorption maximum wavelength of absorption spectrum: 386 nm, half width: 53 nm, manufactured by Orient Chemical Industries, Ltd.);
The antioxidant refers to a phenolic antioxidant (trade name IRGANOX 1010 manufactured by BASF Japan Ltd.).
　　１　　有機ＥＬ表示装置用粘着剤層付き偏光フィルム
　　２　　粘着剤層
　　３　　透明保護フィルム
　　４　　偏光子
　　５　　位相差フィルム
　　６　　偏光フィルム
　　７　　カバーガラスまたはカバープラスチック
　　８　　有機ＥＬパネル
　　９　　接着剤層
　１０　　センサー層
 
 
　 1 Polarized film with adhesive layer for organic EL display 2 Adhesive layer 3 Transparent protective film 4 Polarizer 5 Retardation film 6 Polarized film 7 Cover glass or cover plastic 8 Organic EL panel 9 Adhesive layer 10 Sensor layer

Claims (17)

  1. 　ベースポリマー、ラジカル発生剤、並びに、分子構造中の水酸基が０～３個である紫外線吸収剤（ａ）および吸収スペクトルの最大吸収波長が３８０～４３０ｎｍの波長領域に存在する色素化合物（ｂ）から選ばれる少なくとも１種の化合物（Ａ）含むことを特徴とする有機ＥＬ表示装置用粘着剤組成物。 Base polymer, radical generator, UV absorber (a) having 0 to 3 hydroxyl groups in the molecular structure, and dye compound (b) having a maximum absorption wavelength of 380 to 430 nm in absorption spectrum A pressure-sensitive adhesive composition for an organic EL display device, comprising at least one selected compound (A).
  2. 　前記化合物（Ａ）が、前記紫外線吸収剤（ａ）および前記色素化合物（ｂ）の両方を含むことを特徴とする請求項１に記載の有機ＥＬ表示装置用粘着剤組成物。 The pressure-sensitive adhesive composition for an organic EL display device according to claim 1, wherein the compound (A) contains both the ultraviolet light absorber (a) and the dye compound (b).
  3. 　前記紫外線吸収剤（ａ）の吸収スペクトルの最大吸収波長が、３００～４００ｎｍの波長領域に存在することを特徴とする請求項１または２記載の有機ＥＬ表示装置用粘着剤組成物。 3. The pressure-sensitive adhesive composition for an organic EL display device according to claim 1, wherein the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) is in a wavelength range of 300 to 400 nm.
  4. 　前記ラジカル発生剤が、過酸化物であることを特徴とする請求項１～３のいずれかに記載の有機ＥＬ表示装置用粘着剤組成物。 The pressure-sensitive adhesive composition for an organic EL display device according to any one of claims 1 to 3, wherein the radical generator is a peroxide.
  5. 　前記ベースポリマーが、（メタ）アクリル系ポリマーであることを特徴とする請求項１～４のいずれかに記載の有機ＥＬ表示装置用粘着剤組成物。 The pressure-sensitive adhesive composition for an organic EL display device according to any one of claims 1 to 4, wherein the base polymer is a (meth) acrylic polymer.
  6. 　前記ラジカル発生剤を、前記ベースポリマー１００重量部に対して０．０１～２重量部含有することを特徴とする請求項１～５のいずれかに記載の有機ＥＬ表示装置用粘着剤組成物。 The pressure-sensitive adhesive composition for an organic EL display device according to any one of claims 1 to 5, wherein the radical generating agent is contained in 0.01 to 2 parts by weight with respect to 100 parts by weight of the base polymer.
  7. 　前記化合物（Ａ）を、前記ベースポリマー１００重量部に対して０．１～２５重量部含有することを特徴とする請求項１～６のいずれかに記載の有機ＥＬ表示装置用粘着剤組成物。 The pressure-sensitive adhesive composition for an organic EL display device according to any one of claims 1 to 6, wherein the compound (A) is contained in an amount of 0.1 to 25 parts by weight with respect to 100 parts by weight of the base polymer. .
  8. 　さらに酸化防止剤を含むことを特徴とする請求項１～７のいずれかに記載の有機ＥＬ表示装置用粘着剤組成物。 The pressure-sensitive adhesive composition for an organic EL display device according to any one of claims 1 to 7, further comprising an antioxidant.
  9. 　さらに、架橋剤を含有することを特徴とする請求項１～８のいずれかに有機ＥＬ表示装置用粘着剤組成物。 The pressure-sensitive adhesive composition for an organic EL display according to any one of claims 1 to 8, further comprising a crosslinking agent.
  10. 　請求項１～９のいずれかに記載の有機ＥＬ表示装置用粘着剤組成物から形成されることを特徴とする有機ＥＬ表示装置用粘着剤層。 A pressure-sensitive adhesive layer for an organic EL display device, which is formed from the pressure-sensitive adhesive composition for an organic EL display device according to any one of claims 1 to 9.
  11. 　波長３００～４００ｎｍの平均透過率が１２％以下であり、波長４００ｎｍ～４３０ｎｍの平均透過率が３０％以下であり、波長４３０～４５０ｎｍの平均透過率が７０％以上であることを特徴とする請求項１０に記載の有機ＥＬ表示装置用粘着剤層。 The average transmittance of wavelengths 300 to 400 nm is 12% or less, the average transmittance of wavelengths 400 nm to 430 nm is 30% or less, and the average transmittance of wavelengths 430 to 450 nm is 70% or more. Item 11. The pressure-sensitive adhesive layer for an organic EL display device according to item 10.
  12. 　波長３００～４００ｎｍの平均透過率が１２％以下であり、波長４００ｎｍ～４３０ｎｍの平均透過率が３０％を超え９５％以下であり、波長４３０～４５０ｎｍの平均透過率が８０％以上であることを特徴とする請求項１０に記載の有機ＥＬ表示装置用粘着剤層。 Average transmittance of wavelengths 300 to 400 nm is 12% or less, average transmittance of wavelengths 400 nm to 430 nm is more than 30% and 95% or less, and average transmittance of wavelengths 430 to 450 nm is 80% or more. The adhesive layer for organic electroluminescent display devices of Claim 10 characterized by the above-mentioned.
  13. 　偏光フィルムと、請求項１０～１２のいずれかに記載の有機ＥＬ表示装置用粘着剤層とを有することを特徴とする有機ＥＬ表示装置用粘着剤層付き偏光フィルム。 A polarizing film with a pressure-sensitive adhesive layer for an organic EL display device, comprising: a polarizing film; and the pressure-sensitive adhesive layer for an organic EL display device according to any one of claims 10 to 12.
  14. 　前記偏光フィルムが、偏光子の一方の面に透明保護フィルムが設けられ、他方の面に位相差フィルムを有するものであって、前記有機ＥＬ表示装置用粘着剤層が、前記位相差フィルムの偏光子と接する面と反対側の面、および／または、前記透明保護フィルムの偏光子と接する面と反対側の面に設けられることを特徴とする請求項１３に記載の有機ＥＬ表示装置用粘着剤層付き偏光フィルム。 The polarizing film is provided with a transparent protective film on one side of a polarizer and has a retardation film on the other side, and the pressure-sensitive adhesive layer for an organic EL display device is the polarization of the retardation film. The adhesive for an organic EL display device according to claim 13, characterized in that it is provided on the side opposite to the side in contact with the child and / or on the side opposite to the side in contact with the polarizer of the transparent protective film. Layered polarizing film.
  15. 　第１粘着剤層、透明保護フィルム、偏光子、第２粘着剤層、位相差フィルム、第３粘着剤層をこの順に有する有機ＥＬ表示装置用粘着剤層付き偏光フィルムであって、
    　前記第１粘着剤層、第２粘着剤層、および第３粘着剤層のうち、少なくとも一つの粘着剤層が、前記有機ＥＬ表示装置用粘着剤層であることを特徴とする請求項１３に記載の有機ＥＬ表示装置用粘着剤層付き偏光フィルム。     A polarizing film with a pressure-sensitive adhesive layer for an organic EL display device, comprising a first pressure-sensitive adhesive layer, a transparent protective film, a polarizer, a second pressure-sensitive adhesive layer, a retardation film, and a third pressure-sensitive adhesive layer in this order,
    14. The device according to claim 13, wherein at least one adhesive layer among the first adhesive layer, the second adhesive layer, and the third adhesive layer is the adhesive layer for the organic EL display device. The polarizing film with the adhesive layer for organic electroluminescence display as described in it.
  16. 　前記位相差フィルムが１／４波長板であって、前記偏光フィルムが円偏光フィルムであることを特徴とする請求項１４または１５に記載の有機ＥＬ表示装置用粘着剤層付き偏光フィルム。 The pressure-sensitive adhesive layer-attached polarizing film for an organic EL display device according to claim 14 or 15, wherein the retardation film is a quarter wavelength plate, and the polarizing film is a circular polarizing film.
  17. 　請求項１０～１２のいずれかに記載の有機ＥＬ表示装置用粘着剤層、または請求項１３～１６のいずれかに記載の有機ＥＬ表示装置用粘着剤層付き偏光フィルムを少なくとも１つ用いたことを特徴とする有機ＥＬ表示装置。
     
          A pressure-sensitive adhesive layer for an organic EL display device according to any one of claims 10 to 12, or at least one polarizing film with an adhesive layer for an organic EL display device according to any one of claims 13 to 16. An organic EL display device characterized by

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