WO2017110332A1 - Polarizing film with pressure-sensitive adhesive layer, and image display device - Google Patents

Polarizing film with pressure-sensitive adhesive layer, and image display device Download PDF

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Publication number
WO2017110332A1
WO2017110332A1 PCT/JP2016/084344 JP2016084344W WO2017110332A1 WO 2017110332 A1 WO2017110332 A1 WO 2017110332A1 JP 2016084344 W JP2016084344 W JP 2016084344W WO 2017110332 A1 WO2017110332 A1 WO 2017110332A1
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WO
WIPO (PCT)
Prior art keywords
adhesive layer
sensitive adhesive
pressure
polarizing film
film
Prior art date
Application number
PCT/JP2016/084344
Other languages
French (fr)
Japanese (ja)
Inventor
山本　真也
普史 形見
寛教 柳沼
淳 保井
Original Assignee
日東電工株式会社
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Filing date
Publication date
Priority claimed from JP2016095329A external-priority patent/JP2017120363A/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020187015835A priority Critical patent/KR20180097535A/en
Priority to SG11201804877QA priority patent/SG11201804877QA/en
Priority to CN202011114600.2A priority patent/CN112433287B/en
Priority to KR1020247011112A priority patent/KR20240050450A/en
Priority to CN201680072755.XA priority patent/CN108369305B/en
Publication of WO2017110332A1 publication Critical patent/WO2017110332A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • 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
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/08—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 light absorbing layer
    • G02F2201/086—UV absorbing
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • This invention relates to the polarizing film with an adhesive layer used for an image display apparatus. Moreover, this invention relates to the image display apparatus using the said polarizing film with an adhesive layer.
  • the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper.
  • liquid crystal display devices and organic EL display devices for example, in liquid crystal display devices, it is indispensable to dispose polarizing elements on both sides of the liquid crystal cell, and generally a polarizing film is attached. Has been.
  • various optical elements have been used for display panels such as liquid crystal panels and organic EL panels in order to improve the display quality of displays.
  • the polarizing film used in these image display devices generally has a configuration in which a polarizer is sandwiched between two protective films, and triacetyl cellulose (TAC) is widely used as the protective film.
  • TAC triacetyl cellulose
  • a double-sided pressure-sensitive adhesive sheet for integrating two members disposed between the surface protection panel in the image display device and the viewing side of the liquid crystal module Transparent double-sided pressure-sensitive adhesive for image display devices, having at least one ultraviolet absorbing layer, having a light transmittance of 380 nm or less and a visible light transmittance of 80% or more on a longer wavelength side than the wavelength of 430 nm
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a sheet for example, see Patent Document 1 or an acrylic polymer and a triazine-based ultraviolet absorber is known (for example, see Patent Document 2).
  • an ultraviolet absorbing ability can be imparted to the pressure-sensitive adhesive layer in a pressure-sensitive adhesive optical film in which a pressure-sensitive adhesive layer is provided on one or both sides of the optical film (see, for example, Patent Document 3).
  • Patent Documents 1 to 3 it is known to bond various members used in an image display device using a transparent adhesive having an ultraviolet absorbing function. There were problems in terms of occurrence, yield deterioration, and workability.
  • the polarizing film may be required to have a higher ultraviolet absorption function. Specifically, even when exposed to ultraviolet rays for a long time (specifically, about 300 hours) or when exposed to ultraviolet rays having a wide wavelength range, it is required that the optical characteristics do not change. Therefore, there has been a demand for a polarizing film that satisfies such a higher ultraviolet absorption function.
  • the present invention can solve the problem of yield reduction, and even when the polarizing film is thin, can provide a higher UV cut function and can suppress the occurrence of curling. It aims at providing the polarizing film with an adhesive layer. Another object of the present invention is to provide an image display device using the polarizing film with the pressure-sensitive adhesive layer.
  • the present invention is a polarizing film with a pressure-sensitive adhesive layer used on the viewing side from the image display unit in the image display device,
  • the polarizing film with the pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer on both sides of the polarizing film and the polarizing film,
  • the polarizing film has a transparent protective film on both sides of the polarizer and the polarizer, Polarized light with pressure-sensitive adhesive layer, wherein the transparent protective film on the viewing side of the polarizer has a transmittance at a wavelength of 380 nm of less than 6%, and the pressure-sensitive adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function Related to film.
  • the transparent protective film on the viewer side of the polarizer is at least one film selected from the group consisting of a triacetyl cellulose film, an acrylic film, a polyethylene terephthalate film, and a polyolefin film having a cyclo or norbornene structure, and The thickness is preferably 40 ⁇ m or less.
  • the thickness of the pressure-sensitive adhesive layer on the viewing side of the polarizing film is preferably at least twice the thickness of the pressure-sensitive adhesive layer on the image display unit side of the polarizing film.
  • the adhesive layer on the viewing side of the polarizing film preferably has a transmittance at a wavelength of 380 nm of 9% or less and a transmittance at a wavelength of 400 nm of 60% or more.
  • the b * value of the pressure-sensitive adhesive layer on the viewing side of the polarizing film is preferably 3.0 or less.
  • the adhesive layer on the viewing side of the polarizing film preferably has a transmittance of 380 nm at a wavelength of 9% or less and a transmittance at a wavelength of 420 nm of 75% or less.
  • the adhesive layer on the viewing side of the polarizing film contains an acrylic polymer as a base polymer.
  • the polarizing film with an adhesive layer of the present invention is preferably used for a liquid crystal display device or an organic EL display device.
  • the present invention also relates to an image display device characterized in that the polarizing film with an adhesive layer of the present invention is used on the viewing side from the image display unit.
  • the polarizing film with the pressure-sensitive adhesive layer of the present invention has a configuration in which the pressure-sensitive adhesive layer having an ultraviolet absorbing function is laminated in advance on the viewing side of the polarizing film, the problem of process deletion and yield reduction can be solved. And even if it is a case where a polarizing film is thin, a higher ultraviolet cut function can be provided and curling generation
  • the polarizing film with the pressure-sensitive adhesive layer of the present invention is used on the viewing side from the image display unit in the image display device,
  • the polarizing film with the pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer on both sides of the polarizing film and the polarizing film,
  • the polarizing film has a transparent protective film on both sides of the polarizer and the polarizer,
  • the transmittance of the transparent protective film on the viewing side of the polarizer at a wavelength of 380 nm is less than 6%
  • the adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function.
  • the polarizing film 1 with the pressure-sensitive adhesive layer of the present invention has a viewing-side pressure-sensitive adhesive layer 2 a / viewing-side transparent protective film 3 a / polarizer 4 / image display unit side transparent protective film 3 b / image display unit side.
  • Any structure including the pressure-sensitive adhesive layer 2b may be used, and a structure including a retardation film or the like may be used.
  • a structure such as a display unit side pressure-sensitive adhesive layer (not shown) may be used.
  • the polarizing film 5 includes a viewing-side transparent protective film 3a / a polarizer 4 / an image display unit-side transparent protective film 3b.
  • the viewing-side pressure-sensitive adhesive layer (viewing-side pressure-sensitive adhesive layer) of the polarizing film has an ultraviolet absorbing function.
  • the visible-side pressure-sensitive adhesive layer only needs to have an ultraviolet absorbing function, and the composition thereof is not particularly limited.
  • an appropriate pressure-sensitive adhesive can be used, and the type thereof is not particularly limited.
  • Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives.
  • acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate adhesiveness, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like.
  • the acrylic pressure-sensitive adhesive (composition) contains an acrylic polymer as a base polymer.
  • the acrylic pressure-sensitive adhesive composition preferably contains, for example, a partial polymer of a monomer component containing an alkyl (meth) acrylate and / or a (meth) acrylic polymer obtained from the monomer component and an ultraviolet absorber. .
  • the acrylic pressure-sensitive adhesive composition is obtained from a partially polymerized monomer component containing alkyl (meth) acrylate and / or the monomer component. (Meth) acrylic polymer.
  • alkyl (meth) acrylate examples include those having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester end.
  • Alkyl (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.
  • Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
  • the alkyl (meth) acrylate for example, the alkyl (meth) acrylate having 1 to 9 carbon atoms can be preferably exemplified.
  • the alkyl (meth) acrylate is preferable in terms of easily balancing the adhesive properties.
  • the alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms at the ester terminal is 40% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. It is preferably 50% by weight or more, more preferably 60% by weight or more.
  • the monomer component may contain a copolymerization monomer other than the alkyl (meth) acrylate as a monofunctional monomer component.
  • a copolymerization monomer can be used as the remainder of the said alkyl (meth) acrylate in a monomer component.
  • a cyclic nitrogen-containing monomer can be included.
  • a polymerizable functional group which has unsaturated double bonds such as a (meth) acryloyl group or a vinyl group
  • has a cyclic nitrogen structure can be especially used without a restriction
  • the cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure.
  • cyclic nitrogen-containing monomers examples include lactam vinyl monomers such as N-vinyl pyrrolidone, N-vinyl- ⁇ -caprolactam, and methyl vinyl pyrrolidone; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as imidazole, vinyl oxazole and vinyl morpholine. Moreover, the (meth) acryl monomer containing heterocyclic rings, such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, is mentioned.
  • N-acryloylmorpholine N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like.
  • lactam vinyl monomers are preferable.
  • the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by weight, and preferably 0.5 to 40% by weight, based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable, and 0.5 to 30% by weight is even more preferable.
  • the monomer component used in the present invention can contain a hydroxyl group-containing monomer as a monofunctional monomer component.
  • a hydroxyl group-containing monomer a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; -Hydroxyalkylcycloalkane (meth) acrylates such as -hydroxymethylcyclohexyl) methyl (meth) acrylate.
  • hydroxyethyl (meth) acrylamide examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. These can be used alone or in combination. Of these, hydroxyalkyl (meth) acrylate is preferred.
  • the hydroxyl group-containing monomer is preferably 1% by weight or more from the viewpoint of enhancing adhesive force and cohesive force with respect to the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, It is more preferably 2% by weight or more, and further preferably 3% by weight or more.
  • the amount of the hydroxyl group-containing monomer is too large, the pressure-sensitive adhesive layer becomes hard and the adhesive strength may decrease, and the viscosity of the pressure-sensitive adhesive may become too high or gel.
  • the hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 27% by weight or less, and more preferably 25% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable.
  • the monomer component that forms the (meth) acrylic polymer can contain other functional group-containing monomers as monofunctional monomers, such as carboxyl group-containing monomers and monomers having a cyclic ether group. It is done.
  • carboxyl group-containing monomer a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation.
  • the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Can be used alone or in combination. These anhydrides can be used for itaconic acid and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.
  • a carboxyl group-containing monomer can be arbitrarily used for the monomer component used for manufacture of the (meth) acrylic-type polymer of this invention, On the other hand, it is not necessary to use a carboxyl group-containing monomer.
  • a monomer having a cyclic ether group a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group.
  • the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like.
  • Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl-oxetanylmethyl (meth) acrylate and the like. These can be used alone or in combination.
  • the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, and 27% by weight. % Or less is more preferable, and 25% by weight or less is more preferable.
  • the monomer component forming the (meth) acrylic polymer of the present invention includes, for example, CH 2 ⁇ C (R 1 ) COOR 2 (wherein R 1 is hydrogen or a methyl group, and R 2 is the number of carbon atoms). And an alkyl (meth) acrylate represented by 1 to 3 substituted alkyl groups and cyclic cycloalkyl groups.
  • the substituent of the substituted alkyl group having 1 to 3 carbon atoms as R 2 is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms.
  • the aryl group is not limited, but is preferably a phenyl group.
  • Examples of such a monomer represented by CH 2 ⁇ C (R 1 ) COOR 2 include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl. (Meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned. These can be used alone or in combination.
  • the (meth) acrylate represented by CH 2 ⁇ C (R 1 ) COOR 2 is 50% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. 45% by weight or less is preferable, 40% by weight or less is more preferable, and 35% by weight or less is more preferable.
  • copolymerization monomers include vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; Monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers and the like can also be used. Moreover, as a copolymerization monomer, the monomer which has cyclic structures, such as terpene (meth) acrylate and dicyclopentanyl (meth) acrylate, can be used.
  • silane monomers containing silicon atoms examples include silane monomers containing silicon atoms.
  • examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
  • the monomer component that forms the (meth) acrylic polymer of the present invention contains a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive, in addition to the monofunctional monomer exemplified above. be able to.
  • the polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as (poly) ethylene glycol di (meth) acrylate, (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) acrylate Ester compounds of poly
  • trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used.
  • a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but it is preferably used at 3 parts by weight or less, more preferably 2 parts by weight or less, with respect to a total of 100 parts by weight of the monofunctional monomer. 1 part by weight or less is more preferable. Moreover, it does not specifically limit as a lower limit, However It is preferable that it is 0 weight part or more, and it is more preferable that it is 0.001 weight part or more. Adhesive force can be improved when the usage-amount of a polyfunctional monomer exists in the said range.
  • the production of the (meth) acrylic polymer can be appropriately selected from known production methods such as radiation polymerization such as solution polymerization and ultraviolet (UV) polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
  • a partial polymer of the monomer component can also be suitably used.
  • polymerization can be carried out by appropriately adding a polymerization initiator, a chain transfer agent, an emulsifier and the like used for radical polymerization to the monomer component.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used for the radical polymerization are not particularly limited and can be appropriately selected and used.
  • the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, and the usage-amount is suitably adjusted according to these kinds.
  • solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
  • the reaction is carried out in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
  • thermal polymerization initiators used for solution polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (2 -Methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 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′-dimethyleneisobutyl) Amidine), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, Wako Pure Chemical Industries, Ltd.) Azo initiators such as potassium persulfate, ammonium persulfate,
  • Examples include oxide initiators, redox initiators that combine a peroxide and a reducing agent, such as a combination of persulfate and sodium bisulfite, and a combination of peroxide and sodium ascorbate. It is not limited to.
  • the polymerization initiator may be used alone or in combination of two or more, but is preferably about 1 part by weight or less with respect to 100 parts by weight of the total amount of monomer components.
  • the amount is more preferably about 0.005 to 1 part by weight, and further preferably about 0.02 to 0.5 part by weight.
  • the amount of the polymerization initiator used is about 0.2 parts by weight or less with respect to 100 parts by weight of the total amount of monomer components.
  • the amount is preferably about 0.06 to 0.2 parts by weight.
  • chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
  • the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.3 parts by weight relative to 100 parts by weight of the total amount of monomer components. Less than or equal to
  • emulsifier used in emulsion polymerization examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer and the like can be mentioned. These emulsifiers may be used alone or in combination of two or more.
  • reactive emulsifiers as emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SE10N (manufactured by ADEKA), and the like.
  • the amount of the emulsifier used is preferably 5 parts by weight or less with respect to 100 parts by weight of the total amount of the monomer components.
  • the (meth) acrylic polymer when produced by radiation polymerization, it can be produced by polymerizing the monomer component by irradiating the monomer component with radiation such as an electron beam or ultraviolet (UV). Among these, ultraviolet polymerization is preferable.
  • ultraviolet polymerization which is a preferable embodiment in radiation polymerization will be described.
  • an ultraviolet curable acrylic pressure-sensitive adhesive containing a monomer component containing the alkyl (meth) acrylate and / or a partial polymer of the monomer component, an ultraviolet absorber, and a photopolymerization initiator. It is preferably formed by ultraviolet polymerization of the composition. Since the pressure-sensitive adhesive layer formed by ultraviolet polymerization of the ultraviolet curable acrylic pressure-sensitive adhesive composition can be formed to have a thickness of 150 ⁇ m or more, and a pressure-sensitive adhesive layer having a wide thickness can be formed. preferable.
  • the photopolymerization initiator includes a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more.
  • A photopolymerization initiator having an absorption band at a wavelength of 400 nm or more.
  • the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is preferable because it can be sufficiently polymerized even though it contains an ultraviolet absorber.
  • photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF), 2,4,6-trimethylbenzoyl- And diphenyl-phosphine oxide (LUCIRIN TPO, manufactured by BASF).
  • the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more may be used alone or in combination of two or more.
  • the addition amount of the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is not particularly limited, but is preferably smaller than the addition amount of an ultraviolet absorber described later, (meta)
  • the amount is preferably about 0.005 to 1 part by weight and more preferably about 0.02 to 0.5 part by weight with respect to 100 parts by weight of the monofunctional monomer component forming the acrylic polymer. It is preferable that the amount of the photopolymerization initiator (A) added is in the above range because ultraviolet polymerization can sufficiently proceed.
  • the photopolymerization initiator can contain a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm. Moreover, it is preferable that a photoinitiator (B) does not have an absorption band in wavelength 400nm or more.
  • the photopolymerization initiator (B) is not particularly limited as long as it generates radicals by ultraviolet rays and starts photopolymerization and has an absorption band at a wavelength of less than 400 nm. Any initiator can be suitably used.
  • benzoin ether photopolymerization initiator acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone A photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or the like can be used.
  • examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- Examples thereof include 1-one and anisole methyl ether.
  • acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4-t-butyldichloroacetophenone. Etc.
  • Examples of ⁇ -ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy-2-methylpropan-1-one, and the like. Is mentioned.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.
  • benzoin photopolymerization initiator examples include benzoin.
  • benzyl photopolymerization initiator examples include benzyl and the like.
  • benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
  • Ketal photopolymerization initiators include benzyl dimethyl ketal and the like.
  • thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthioxanthone, dodecylthioxanthone and the like are included.
  • acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
  • the photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be used alone or in combination of two or more.
  • the photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be added within a range that does not impair the effects of the present invention, and the addition amount is a monofunctional that forms a (meth) acrylic polymer.
  • the amount is preferably about 0.005 to 0.5 part by weight, more preferably about 0.02 to 0.1 part by weight based on 100 parts by weight of the monomeric monomer component.
  • a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm is first added to the monomer component, and ultraviolet rays are irradiated to partially polymerize. It is preferable to perform ultraviolet polymerization by adding a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more and an ultraviolet absorber to a partial polymerization product (prepolymer composition) of a monomer component.
  • the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is added to the partial polymerization product (prepolymer composition) of the monomer component partially polymerized by ultraviolet irradiation, the photopolymerization is started. It is preferable to add the agent after dissolving it in the monomer.
  • the ultraviolet absorber contained in the acrylic pressure-sensitive adhesive composition is not particularly limited.
  • a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, An oxybenzophenone type ultraviolet absorber, a salicylic acid ester type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
  • triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable, triazine-based UV absorbers having 2 or less hydroxyl groups in one molecule, and benzones having one benzotriazole skeleton in one molecule.
  • triazine ultraviolet absorbers having 2 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), 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl And [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane reaction product (TINUVIN400, manufactured by BASF), 2- [4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazin-2-yl]
  • benzophenone ultraviolet absorber (benzophenone compound) and oxybenzophenone ultraviolet absorber (oxybenzophenone compound)
  • examples of the benzophenone ultraviolet absorber (benzophenone compound) and oxybenzophenone ultraviolet absorber (oxybenzophenone compound) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy.
  • -4-methoxybenzophenone-5-sulfonic acid anhydrous and trihydrate
  • 2-hydroxy-4-octyloxybenzophenone 4-dodecyloxy-2-hydroxybenzophenone
  • 4-benzyloxy-2-hydroxybenzophenone 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4-dimethoxybenzophenone and the like can be mentioned.
  • salicylic acid ester ultraviolet absorber examples include, for example, phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, and phenyl-2-acryloyloxy.
  • cyanoacrylate ultraviolet absorber examples include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl- Examples include 2-cyanoacrylate.
  • UV absorber examples include, for example, trade name “FDB-001” (manufactured by Yamada Chemical Co., Ltd.), trade name “SMP-122” (manufactured by Hayashibara), azomethine compound (trade name: BONASORB UA 3911, manufactured by Orient Chemical Industry Co., Ltd.), indole chemicals (trade name: BONASORB UA-3701, manufactured by Orient Chemical Industry Co., Ltd.), Disperse Yellow 54 (trade name: KAYASET YELLOW AG, manufactured by Nippon Kayaku Co., Ltd.) , Quinophthalone compound (trade name: MS YELLOW HD-137, manufactured by Yamada Chemical Co., Ltd.), Solvent Yellow91 (PLASTYELLOW 8000, manufactured by Arimoto Chemical Industry Co., Ltd.), Solvent Yellow 163 (KP Plastic Yellow MK, Kiwa Chemical Industries) Dye etc. made by Co., Ltd. can also be used.
  • FDB-001 trade name “FDB-001” (
  • the ultraviolet absorber may be used alone or in combination of two or more, but the total content is a monofunctional monomer component that forms a (meth) acrylic polymer.
  • the amount is preferably about 0.1 to 5 parts by weight, more preferably about 0.5 to 3 parts by weight with respect to 100 parts by weight.
  • the acrylic pressure-sensitive adhesive composition used in 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 based on 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 epoxy cyclohexyl).
  • Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, (3-dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane ( (Meth) acrylic group-containing sila Coupling agents, such as isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like.
  • the acrylic pressure-sensitive adhesive composition used in the present invention may contain a crosslinking agent.
  • crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Crosslinkers such as oxides are included.
  • a crosslinking agent can be used alone or in combination of two or more. Among these, an isocyanate type crosslinking agent is preferably used.
  • the crosslinking agent may be used alone or in combination of two or more, but the total content is a monofunctional monomer that forms a (meth) acrylic polymer.
  • 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 0.02 to 3 parts by weight with respect to 100 parts by weight of the component. It is preferable to obtain.
  • the isocyanate-based cross-linking agent refers to a compound having two or more isocyanate groups (including an isocyanate-regenerating functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification) in one molecule.
  • the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
  • lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
  • alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
  • 2,4-tolylene diisocyanate Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, 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.), hexamethyle Isocyan
  • the acrylic pressure-sensitive adhesive composition used in the present invention may contain appropriate additives in addition to the components described above, depending on the application.
  • tackifiers for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc., solid, semi-solid, or liquid at room temperature
  • fillers such as hollow glass balloons; plasticizers; aging Inhibitors; antioxidants and the like.
  • the acrylic pressure-sensitive adhesive composition is preferably adjusted to have a viscosity suitable for work such as coating on a substrate. Adjustment of the viscosity of the acrylic pressure-sensitive adhesive composition is performed, for example, by adding various polymers such as thickening additives, polyfunctional monomers, or the like, or by partially polymerizing monomer components in the acrylic pressure-sensitive adhesive composition. The partial polymerization may be performed before or after adding various polymers such as thickening additives, polyfunctional monomers, and the like.
  • the viscosity of the acrylic pressure-sensitive adhesive composition varies depending on the amount of the additive and the like, the polymerization rate when the monomer component in the acrylic pressure-sensitive adhesive composition is partially polymerized cannot be uniquely determined. It is preferably about 20% or less, more preferably about 3 to 20%, still more preferably about 5 to 15%. If it exceeds 20%, the viscosity becomes too high, so that it is difficult to apply to the substrate.
  • the viewing-side pressure-sensitive adhesive layer is formed by coating the acrylic pressure-sensitive adhesive composition on at least one side of the substrate and drying the coating film formed from the acrylic pressure-sensitive adhesive composition, or by ultraviolet rays or the like It can be formed by irradiation with active energy rays.
  • the substrate is not particularly limited, and for example, various substrates such as a release film and a transparent resin film substrate, and a polarizing film described later can also be suitably used as the substrate.
  • various substrates such as a release film and a transparent resin film substrate, and a polarizing film described later can also be suitably used as the substrate.
  • the viewing-side pressure-sensitive adhesive layer is formed on a substrate other than the polarizing film, the viewing-side pressure-sensitive adhesive layer can be attached to the polarizing film and transferred.
  • constituent material of the release film examples include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Suitable thin leaf bodies and the like can be mentioned, but a resin film is suitably used from the viewpoint of excellent surface smoothness.
  • the resin film examples include 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, and ethylene.
  • -Vinyl acetate copolymer film and the like examples include 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, and ethylene.
  • -Vinyl acetate copolymer film and the like examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthal
  • the thickness of the release film is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • release agent and antifouling treatment with silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed.
  • the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.
  • the transparent resin film substrate is not particularly limited, and various resin films having transparency are used.
  • the resin film is formed of a single layer film.
  • the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins.
  • 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 acrylic pressure-sensitive adhesive composition onto the substrate is roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat. Any known appropriate method such as curtain coating, lip coating, or die coater can be used without particular limitation.
  • the drying conditions are not particularly limited, and the pressure-sensitive adhesive composition
  • the temperature can be appropriately set depending on the composition, concentration, etc., but is, for example, about 60 to 170 ° C., preferably 60 to 150 ° C. for 1 to 60 minutes, preferably 2 to 30 minutes.
  • the acrylic pressure-sensitive adhesive composition is an ultraviolet curable acrylic pressure-sensitive adhesive composition and is formed by irradiating a coating film formed from the ultraviolet-curable acrylic pressure-sensitive adhesive composition with ultraviolet rays
  • the ultraviolet rays to be irradiated The illuminance is preferably 5 mW / cm 2 or more.
  • the illuminance of the ultraviolet light is less than 5 mW / cm 2 , the polymerization reaction time becomes long and the productivity may be inferior.
  • the illuminance of the ultraviolet light is preferably 200 mW / cm 2 or less.
  • the photopolymerization initiator is consumed rapidly, so that the polymer has a low molecular weight, and the holding power particularly at high temperatures may be reduced.
  • the integrated quantity of ultraviolet light is preferably 100mJ / cm 2 ⁇ 5000mJ / cm 2.
  • the ultraviolet lamp used in the present invention is not particularly limited, but an LED lamp is preferable. Since the LED lamp has a lower emission heat than other ultraviolet lamps, the temperature during polymerization of the pressure-sensitive adhesive layer can be suppressed. Therefore, the molecular weight reduction of the polymer can be prevented, the cohesive strength of the pressure-sensitive adhesive layer can be prevented from being lowered, and the holding power at a high temperature when the pressure-sensitive adhesive sheet is used can be increased. It is also possible to combine a plurality of ultraviolet lamps. Further, it is possible to intermittently irradiate ultraviolet rays, and to provide a light period in which ultraviolet rays are irradiated and a dark period in which ultraviolet rays are not irradiated.
  • the final polymerization rate of the monomer component in the ultraviolet curable acrylic pressure-sensitive adhesive composition is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.
  • the peak wavelength of ultraviolet rays irradiated to the ultraviolet curable acrylic pressure-sensitive adhesive composition is preferably in the range of 200 to 500 nm, and more preferably in the range of 300 to 450 nm.
  • the peak wavelength of ultraviolet rays exceeds 500 nm, the photopolymerization initiator may not be decomposed and the polymerization reaction may not start.
  • the peak wavelength of the ultraviolet light is less than 200 nm, the polymer chain may be cut and the adhesive properties may be deteriorated.
  • a release film or the like is formed on the coating film formed from the ultraviolet curable acrylic pressure-sensitive adhesive composition to block oxygen, or the photopolymerization reaction is performed by nitrogen. It is preferable to carry out in an atmosphere.
  • the above-mentioned thing can be mentioned as a release film.
  • the said release film can be used as a separator of a polarizing film with an adhesive layer as it is.
  • the ultraviolet curable acrylic adhesive composition used by this invention contains a photoinitiator (B), the monomer component containing an alkyl (meth) acrylate and the said photoinitiator (B) (
  • the composition containing the “pre-added polymerization initiator” is irradiated with ultraviolet rays to form a partial polymer of the monomer component, and the partial polymerization product of the monomer component contains an ultraviolet absorber and a wavelength of 400 nm.
  • It is preferable to prepare a UV-curable acrylic pressure-sensitive adhesive composition by adding the photopolymerization initiator (A) having an absorption band (sometimes referred to as “post-addition polymerization initiator”).
  • the polymerization rate of the partially polymerized product is preferably about 20% or less, more preferably about 3 to 20%, and further preferably about 5 to 15%.
  • the ultraviolet irradiation conditions are as described above.
  • the pressure-sensitive adhesive layer is formed from the ultraviolet curable acrylic pressure-sensitive adhesive composition containing the photopolymerization initiator (B), the polymerization rate of the monomer component is increased by performing polymerization in the two steps as described above. In addition, the ultraviolet absorbing function of the finally produced pressure-sensitive adhesive layer can be improved.
  • the thickness of the visual recognition side pressure-sensitive adhesive layer is at least twice the thickness of the pressure-sensitive adhesive layer (image display part-side pressure-sensitive adhesive layer) on the image display part side of the polarizing film described later from the viewpoint of ensuring the ultraviolet absorption function. Preferably, it is 5 times or more, more preferably 10 times or more. Specifically, the thickness of the viewing-side pressure-sensitive adhesive layer is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, and further preferably 150 ⁇ m or more. Although the upper limit of the thickness of a visual recognition side adhesive layer is not specifically limited, It is preferable that it is 10 mm or less. If the thickness of the pressure-sensitive adhesive layer exceeds 10 mm, it is difficult to transmit ultraviolet rays, and it takes time to polymerize the monomer component, which may be inferior in productivity.
  • the gel fraction of the visual recognition side adhesive layer of this invention is not specifically limited, It is preferable that it is 35% or more, It is more preferable that it is 50% or more, It is further that it is 75% or more It is preferably 85% or more.
  • the cohesive force is inferior, and when it is too large, the adhesive force may be inferior.
  • the permeation b * value of the viewing side pressure-sensitive adhesive layer is not particularly limited, but is preferably 3.0 or less, more preferably 1.5 or less, and even more preferably 0.5 or less.
  • the b * value refers to the b * value (chromaticity) in the L * a * b * color system conforming to JIS Z8729.
  • a spectrophotometer product name: U4100, manufactured by Hitachi High-Technologies Corporation
  • the transmittance of the viewing side pressure-sensitive adhesive layer at a wavelength of 380 nm is preferably 9% or less, more preferably 7% or less, further preferably 5% or less, and more preferably 3% or less. Particularly preferred. Since the transmittance at a wavelength of 380 nm is within the above range, incident ultraviolet rays can be blocked to a higher degree, so that deterioration of optical members such as liquid crystal panels, organic EL elements, polarizers, etc. is remarkably suppressed. Can do.
  • the transmittance of the viewing-side pressure-sensitive adhesive layer at a wavelength of 400 nm is preferably 60% or more, preferably 70% or more, and more preferably 75% or more.
  • the transmittance at a wavelength of 400 nm is within the above range, it is preferable because the incident visible light can be sufficiently transmitted and sufficient visibility can be secured in the image display device.
  • permeability in wavelength 420nm of the said visual recognition side adhesive layer is 75% or less, and is 50% or less. More preferably, it is more preferably 40% or less.
  • the transmittance at a wavelength of 420 nm is in the above range, which is preferable from the viewpoint of protecting the light emitting element of the OLED.
  • the pressure-sensitive adhesive layer When the viewing-side pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until practical use.
  • the said release film can be used as a separator of a polarizing film with an adhesive layer as it is, and can simplify in a process surface.
  • Image display part side adhesive layer It does not specifically limit as an adhesive layer (image display part side adhesive layer) of the image display part side surface of a polarizing film, It is detailed in the said visual recognition side adhesive layer.
  • the same acrylic adhesive composition as described above may be used, and various adhesive layers that are usually used can be used.
  • An appropriate pressure-sensitive adhesive can be used for forming the pressure-sensitive adhesive layer on the image display unit side surface, and the type thereof is not particularly limited.
  • Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives.
  • acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate adhesiveness, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like. .
  • the acrylic adhesive is based on an acrylic polymer having a monomer unit of (meth) acrylic acid alkyl ester as a main skeleton.
  • examples of the (meth) acrylic acid alkyl ester constituting the main skeleton of the acrylic polymer may include the same ones as those used for the acrylic pressure-sensitive adhesive composition forming the viewing-side pressure-sensitive adhesive layer.
  • the same thing as what is used for the said acrylic adhesive composition can also be mentioned as a copolymerization monomer and its ratio.
  • the acrylic polymer can be produced by various known methods, for example, a radical polymerization method such as a bulk polymerization method, a solution polymerization method, or a suspension polymerization method can be appropriately selected.
  • a radical polymerization method such as a bulk polymerization method, a solution polymerization method, or a suspension polymerization method can be appropriately selected.
  • the radical polymerization initiator various known azo and peroxide initiators can be used.
  • the reaction temperature is usually about 50 to 80 ° C., and the reaction time is 1 to 8 hours.
  • the solution polymerization method is preferable, and ethyl acetate, toluene and the like are generally used as the solvent for the acrylic polymer.
  • the solution concentration is usually about 20 to 80% by weight.
  • the pressure-sensitive adhesive can be a pressure-sensitive adhesive composition containing a crosslinking agent.
  • a crosslinking agent Especially an isocyanate type crosslinking agent is preferable.
  • the blending ratio of the acrylic polymer and the crosslinking agent is not particularly limited, but it is usually preferably about 0.001 to 20 parts by weight of the crosslinking agent (solid content) with respect to 100 parts by weight of the acrylic polymer (solid content). About 0.01 to 15 parts by weight is more preferable.
  • the pressure-sensitive adhesive may include a tackifier, a plasticizer, glass fiber, glass beads, metal powder, other inorganic powders, a pigment, a colorant, a filler, an antioxidant, if necessary.
  • Various additives may be used as appropriate, such as an agent, an ultraviolet absorber, a silane coupling agent, and the like without departing from the object of the present invention.
  • it is good also as an adhesive layer etc. which contain microparticles
  • the silane coupling agent include those described above.
  • the image display unit side pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition to various substrates such as a polarizing film or a release film and drying.
  • the pressure-sensitive adhesive layer can be attached to a polarizing film and transferred.
  • Examples of the method for applying the pressure-sensitive adhesive and the various base materials include the same methods as those for applying the acrylic pressure-sensitive adhesive composition and various base materials.
  • the coating amount is controlled so that the formed pressure-sensitive adhesive layer has a predetermined thickness (thickness after drying).
  • the thickness of the image display unit side pressure-sensitive adhesive layer is not particularly limited, but is preferably 1/2 or less, more preferably 1/5 or less of the thickness of the visual recognition side pressure-sensitive adhesive layer. / 10 or less is preferable.
  • the thickness of the image display unit side pressure-sensitive adhesive layer is preferably about 1 to 100 ⁇ m, more preferably about 3 to 50 ⁇ m, and further preferably about 5 to 30 ⁇ m.
  • the applied pressure-sensitive adhesive is dried.
  • the drying temperature and drying time are not particularly limited and are set as appropriate.
  • the drying temperature and the drying time are about 80 to 200 ° C. and preferably 0.5 to 10 minutes.
  • the pressure-sensitive adhesive layer When the image display part side pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until practical use.
  • the said release film can be used as a separator of a polarizing film with an adhesive layer as it is, and can simplify in a process surface.
  • Polarizing film used in the present invention has a transparent protective film on both sides of the polarizer and the polarizer, and the transparent protective film on the viewing side of the polarizer (viewing side transparent protective film) transmits at a wavelength of 380 nm.
  • the rate is less than 6%.
  • the transmittance of the viewing-side transparent protective film used in the present invention at a wavelength of 380 nm is less than 6%, preferably 3% or less, and more preferably 2% or less. Preferably, it is 1% or less.
  • a higher UV absorption capability is achieved by combining a viewing-side transparent protective film having a transmittance of less than 6% at a wavelength of 380 nm and the viewing-side pressure-sensitive adhesive layer (containing an UV absorber). It is something that can be done.
  • permeability in wavelength 380nm of the visual recognition side transparent protective film is not specifically limited, The smaller is preferable from a viewpoint of an ultraviolet absorption function.
  • polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
  • cellulose polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers such as polymethyl methacrylate
  • styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
  • AS resin acrylonitrile / styrene copolymer
  • polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends.
  • the transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
  • the visible-side transparent protective film is selected from the group consisting of a triacetyl cellulose film, an acrylic film (a film using an acrylic polymer), a polyethylene terephthalate film, and a polyolefin film having a cyclo or norbornene structure. At least one film is preferable, and a triacetyl cellulose film is more preferable.
  • the thickness of the viewing-side transparent protective film is not particularly limited, but is preferably 40 ⁇ m or less, more preferably 35 ⁇ m or less, and further preferably 30 ⁇ m or less. Moreover, the lower limit value of the thickness of the viewing-side transparent protective film is not particularly limited, but is preferably 1 ⁇ m or more. It is preferable that the thickness of the viewing-side transparent protective film is in the above range because the polarizing film can be sufficiently thinned and the protective function of the polarizer is not impaired.
  • the polarizer and the viewing-side protective film described later are in close contact with each other via an aqueous adhesive or the like.
  • the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
  • examples of the adhesive between the polarizer and the viewing-side transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
  • the electron beam curable polarizing film adhesive exhibits suitable adhesiveness with respect to the various viewing-side transparent protective films.
  • the adhesive used in the present invention can contain a metal compound filler.
  • the surface of the viewing side transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
  • the polarizer is not particularly limited, and various types can be used.
  • polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
  • a polarizer composed 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 dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
  • the polyvinyl alcohol film In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even 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.
  • Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
  • the thin polarizer typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or a patent.
  • the thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned.
  • These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
  • PVA-based resin polyvinyl alcohol-based resin
  • International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing.
  • those obtained by a production method including a step of stretching in an aqueous boric acid solution as described in International Publication No. 2010/100917 pamphlet or Japanese Patent No. 47514881 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
  • Those obtained by a production method including a step of stretching in the air before stretching in a boric acid aqueous solution described in the specification of 4751481 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
  • a transparent protective film formed from a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable.
  • a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate
  • Cellulose polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers such as polymethyl methacrylate
  • styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
  • AS resin acrylonitrile / styrene copolymer
  • polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends.
  • the transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
  • the thickness of the protective film on the image display portion side can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoint of workability such as strength and handleability and thin film properties.
  • the polarizer and the image display unit side transparent protective film are also usually in close contact with each other through an aqueous adhesive or the like.
  • aqueous adhesive examples include those described above.
  • the surface of the image display portion side transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
  • the image display device of the present invention is characterized by using the polarizing film with an adhesive layer of the present invention.
  • a cover glass or cover plastic 6 / viewing side pressure-sensitive adhesive layer 2a / viewing side transparent protective film 3a / polarizer 4 / Image display unit side transparent protective film 3b / Image display unit side adhesive layer 2b / Liquid crystal display (LCD) or organic EL display unit (OLED) 7 (FIG.
  • the polarizing film 1 with the pressure-sensitive adhesive layer of the present invention is “viewing-side pressure-sensitive adhesive layer 2a / viewing-side transparent protective film 3a / polarizer 4 / image display unit-side transparent protective film 3b / image display unit-side pressure-sensitive adhesive”. It refers to the portion of the agent layer 2b "and may contain a retardation film or the like other than these.
  • a retardation film is included, specifically, the image display unit side adhesive layer 2b and a liquid crystal display device (LCD) or an organic EL display device (OLED) 7 are laminated via an adhesive layer. can do.
  • an adhesive layer and / or an adhesive layer can be used suitably.
  • Examples of the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper.
  • Production Example 1 (Production of acrylic pressure-sensitive adhesive composition (a-1)) Photopolymerization started on a monomer mixture composed of 78 parts by weight of 2-ethylhexyl acrylate (2EHA), 18 parts by weight of N-vinyl-2-pyrrolidone (NVP), and 4 parts by weight of 2-hydroxyethyl acrylate (HEA).
  • EHA 2-ethylhexyl acrylate
  • NDP N-vinyl-2-pyrrolidone
  • HSA 2-hydroxyethyl acrylate
  • 0.035 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, having an absorption band at a wavelength of 200 to 370 nm, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane-1 -ON (trade name: Irgacure 651, having an absorption band at a wavelength of 200 to 380 nm, manufactured by BASF) 0.035 parts by weight, and then viscosity (measurement conditions: BH viscometer No.
  • Production Example 2 (Production of acrylic pressure-sensitive adhesive composition (a-2)) Polymerized into a monomer mixture composed of 72 parts by weight of 2-ethylhexyl acrylate (2EHA), 1 part by weight of methacrylic acid acrylate (MMA), 12 parts by weight of N-vinylpyrrolidone (NVP), and 15 parts by weight of hydroxyethyl acrylate (HEA) As an initiator, 0.2 parts by weight of azobisbutylnitrile (AIBN) and 233 parts by weight of ethyl acetate were added and then reacted at 60 ° C. for 7 hours in a nitrogen atmosphere to partially polymerize the monomer components. A partially polymerized product was obtained.
  • 2EHA 2-ethylhexyl acrylate
  • MMA methacrylic acid acrylate
  • NDP N-vinylpyrrolidone
  • HOA hydroxyethyl acrylate
  • AIBN azobisbutylnitrile
  • Production Example 3 (Production of image display part side adhesive layer (B-1))
  • a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube 95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 part by weight of azobisisobutyronitrile as a polymerization initiator, and After 233 parts by weight of ethyl acetate was added, nitrogen gas was passed, and nitrogen substitution 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.
  • Mw weight average molecular weight
  • a pressure-sensitive adhesive composition (solution) was prepared by adding 0.1 part by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the obtained pressure-sensitive adhesive composition solution was applied onto a 38 ⁇ m thick separator (polyethylene terephthalate film whose surface was peeled) so that the thickness after drying was 12 ⁇ m, and dried at 100 ° C. for 3 minutes.
  • the solvent was removed by layering to obtain an adhesive layer.
  • the crosslinking process was performed by heating at 50 degreeC for 48 hours.
  • this pressure-sensitive adhesive layer is referred to as “image display portion side pressure-sensitive adhesive layer (B-1)”.
  • Production Example 4 (Production of image display part side adhesive layer (B-2))
  • the pressure-sensitive adhesive composition solution obtained in Production Example 3 was applied on a 38 ⁇ m-thick separator (polyethylene terephthalate film whose surface was release-treated) so that the thickness after drying was 15 ⁇ m.
  • the solvent was removed by drying at 3 ° C. for 3 minutes to obtain a pressure-sensitive adhesive layer.
  • the crosslinking process was performed by heating at 50 degreeC for 48 hours.
  • this pressure-sensitive adhesive layer is referred to as “image display portion side pressure-sensitive adhesive layer (B-2)”.
  • Example 1 Manufacture of pressure-sensitive adhesive composition with ultraviolet absorption function
  • 2,4-bis-[ ⁇ 4- (4-ethylhexyloxy) -4-hydroxy dissolved in butyl acrylate to a solid content of 15% in the obtained acrylic pressure-sensitive adhesive composition (a-1) ⁇ -Phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, “UV absorber 1” in Tables 1 and 2, manufactured by BASF Japan Ltd.)
  • 1.4 weight And 0.2 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, having absorption resistance at wavelengths of 200 to 450 nm, manufactured by BASF Japan Ltd.)
  • the pressure-sensitive adhesive composition with an ultraviolet absorbing function is applied on the release-treated film so that the thickness after forming the pressure-sensitive adhesive layer is 150 ⁇ m, and then the surface of the pressure-sensitive adhesive composition layer A release film was bonded to the substrate. Thereafter, UV irradiation was performed under the conditions of illuminance: 6.5 mW / cm 2 , light quantity: 1500 mJ / cm 2 , peak wavelength: 350 nm, and the pressure-sensitive adhesive composition layer was photocured, whereby the visible-side pressure-sensitive adhesive layer (A-1 ) Was formed.
  • polarizing film (Manufacture of polarizing film (P-1)) A 25 ⁇ m thick cycloolefin polymer (COP) film is bonded to the viewing side of a polarizer composed of a 5 ⁇ m thick stretched polyvinyl alcohol film impregnated with iodine using a polyvinyl alcohol-based adhesive to display an image of the polarizer.
  • a polarizing film (P-1) was obtained by laminating an acrylic film with a thickness of 20 ⁇ m using a polyvinyl alcohol-based adhesive on the part-side surface. The polarization degree of the polarizing film was 99.995.
  • the viewing-side pressure-sensitive adhesive layer (A-1) was laminated on the viewing side of the polarizing film (P-1) (that is, the surface of a cycloolefin polymer (COP) film having a thickness of 25 ⁇ m).
  • An image display unit side pressure-sensitive adhesive layer (B-1) is laminated on the image display unit side surface of the polarizing film (P-1) (that is, the surface of an acrylic film having a thickness of 20 ⁇ m), and a retardation film ( Thickness: 56 ⁇ m, material: polycarbonate) and an image display part side pressure-sensitive adhesive layer (B-2) were laminated to form a polarizing film with a pressure-sensitive adhesive layer.
  • the obtained polarizing film with the pressure-sensitive adhesive layer is: viewing-side pressure-sensitive adhesive layer (A-1) / polarizing film (P-1) / image-displaying part-side pressure-sensitive adhesive layer (B-1) / retardation film / image-displaying part. It had the structure of a side pressure-sensitive adhesive layer (B-2).
  • the pressure-sensitive adhesive layer was the same as in Example 1 except that the type of the acrylic pressure-sensitive adhesive composition, the addition amount of the ultraviolet absorber 1, and the thickness after forming the visible-side pressure-sensitive adhesive layer were as shown in Table 1. An attached polarizing film was formed.
  • Example 4 A pressure-sensitive adhesive layer was attached in the same manner as in Example 1 except that the visual-side pressure-sensitive adhesive layer (A-1) was changed to the visual-side pressure-sensitive adhesive layer (A-2) obtained below. A polarizing film was formed.
  • the pressure-sensitive adhesive composition with an ultraviolet absorbing function was applied on the release film of the release film so that the thickness after forming the pressure-sensitive adhesive layer was 150 ⁇ m, and 2 minutes at 60 ° C. and 2 minutes at 120 ° C. After partial drying, the peel-side film was bonded to form a viewing side pressure-sensitive adhesive layer (A-2).
  • Examples 5-6 A polarizing film with a pressure-sensitive adhesive layer was formed in the same manner as in Example 4 except that the thickness after forming the viewing-side pressure-sensitive adhesive layer and the image display part-side pressure-sensitive adhesive layer were as shown in Table 1.
  • Example 7 Manufacture of viewing side adhesive layer (A-3)) 2,4-bis-[ ⁇ 4- (4-ethylhexyloxy) dissolved in butyl acrylate to a solid content of 15% in the acrylic pressure-sensitive adhesive composition (a-1) obtained in Production Example 1 -4-hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, manufactured by BASF Japan Ltd.) 0.7 part by weight, Solvent Yellow 163 (KP Plas Yellow MK)
  • “UV absorber 2”, manufactured by Kiwa Chemical Industry Co., Ltd. 0.2 parts by weight, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, wavelength)
  • a pressure-sensitive adhesive composition with an ultraviolet absorption function is obtained by adding 0.2 parts by weight of BASF Japan, which has an absorption resistance at 200 to 450 nm, and stirring. .
  • the pressure-sensitive adhesive composition with an ultraviolet absorbing function is applied on the release-treated film so that the thickness after forming the pressure-sensitive adhesive layer is 150 ⁇ m, and then the surface of the pressure-sensitive adhesive composition layer A release film was bonded to the substrate. Thereafter, illuminance: 6.5 mW / cm 2, light quantity: 3000 mJ / cm 2, the peak wavelength irradiated with ultraviolet rays under the condition of 350 nm, the pressure-sensitive adhesive composition layer by light-curing, the visible side pressure-sensitive adhesive layer (A-3 ) was formed.
  • a pressure-sensitive adhesive layer was attached in the same manner as in Example 1 except that the visual-side pressure-sensitive adhesive layer (A-1) was changed to the visual-side pressure-sensitive adhesive layer (A-3) obtained above. A polarizing film was formed.
  • Comparative Example 1 A polarizing film with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the viewing-side pressure-sensitive adhesive layer (A-1), the retardation film, and the image display unit-side pressure-sensitive adhesive layer (B-2) were not formed. Formed.
  • Comparative Example 2 A polarizing film with a pressure-sensitive adhesive layer was formed in the same manner as in Example 1 except that the viewing-side pressure-sensitive adhesive layer (A-1) was not formed.
  • Comparative Examples 3 and 4 A polarizing film with an adhesive was formed in the same manner as in Examples 1 and 4 except that no ultraviolet absorber was added to the viewing-side adhesive layers (A-1) and (A-2).
  • Comparative Example 5 Manufacture of polarizing film (P-2)
  • P-2 Manufacture of polarizing film (P-2)
  • a 25 ⁇ m thick triacetylcellulose film is bonded to the viewing side of a polarizer made of a stretched polyvinyl alcohol film having a thickness of 12 ⁇ m impregnated with iodine, using a polyvinyl alcohol-based adhesive, and the image display side surface of the polarizer
  • a polarizing film (P-2) was obtained by laminating an acrylic film having a thickness of 20 ⁇ m using a polyvinyl alcohol-based adhesive.
  • the polarization degree of the polarizing film was 99.995.
  • Example 2 a polarizing film with an adhesive was formed in the same manner as in Example 2 except that the polarizing film (P-1) was changed to the polarizing film (P-2).
  • the following evaluation was performed about the obtained adhesive layer and a polarizing film with an adhesive layer.
  • ⁇ Polymerization rate> The release film of the viewing-side pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, and only the viewing-side pressure-sensitive adhesive layer was placed on the weighed aluminum petri dish. The weight of (aluminum petri dish + viewing side pressure-sensitive adhesive layer) was measured, and the weight of the pressure-sensitive adhesive layer before drying was determined. After drying at 130 ° C. for 2 hours and cooling at room temperature for about 20 minutes, the weight of (aluminum petri dish + adhesive) was measured again, and the weight of the viewing-side adhesive layer after drying was determined. The polymerization rate was determined by the following calculation formula.
  • a visible-side pressure-sensitive adhesive layer wrapped with a tetrafluoroethylene sheet and tied with a kite string (referred to as “sample”) was placed in a 50 mL container filled with ethyl acetate and allowed to stand at 23 ° C. for 7 days. Thereafter, a sample (after ethyl acetate treatment) was taken out from the container, transferred to an aluminum cup, dried in a dryer at 130 ° C. for 2 hours to remove ethyl acetate, and then weighed (Xg). The weight was defined as the weight after immersion.
  • ⁇ Residual stress> From the viewing-side pressure-sensitive adhesive layers obtained in the examples and comparative examples, a test piece was prepared by cutting out a width of 30 mm and a length of 50 mm and forming a cylinder. This was installed with 20 mm between chucks, and the test piece was pulled 60 mm (300%) at a pulling speed of 200 mm / min (80 mm between the chucks after tension). At a position pulled 60 mm, it was fixed (held) for 300 seconds, and the stress value (N) after 300 seconds was measured. The residual stress was determined by the following formula. Residual stress after 300 seconds Stress value after 300 seconds (N) / (4 ⁇ thickness of test piece / 10)
  • the viewing-side pressure-sensitive adhesive layers obtained in Examples 1 to 7 and Comparative Examples 3 to 5 were bonded to the COP film of the polarizing film (P-1) used in Example 1. Furthermore, a 56 ⁇ m phase difference film with a 15 ⁇ m adhesive (manufactured by Nitto Denko Corporation) was bonded to the opposite side (acrylic film side) of the polarizing film to which the viewing-side pressure-sensitive adhesive layer was bonded.
  • Both surfaces of the sample were bonded with glass (trade name: S200200, thickness: 1.3 mm, size: 45 mm ⁇ 50 mm, manufactured by Matsunami Glass Industry Co., Ltd.), and autoclaved (atmospheric pressure: 0.5 MPa, temperature: 50 ° C.) for 15 minutes. Thereafter, the sample was charged under the following various reliability conditions, and the transmittance was measured with a spectral transmittance meter (product name: DOT-3, manufactured by Murakami Color Research Laboratory Co., Ltd.). The change in transmittance from the initial stage was determined. Evaluation was performed according to the following evaluation criteria. (Various reliability conditions) (Condition 1) 85 ° C.
  • ⁇ Glue stain, dimensional accuracy, end appearance> The polarizing film with an adhesive layer obtained in Examples and Comparative Examples was cut into a size of 25 mm ⁇ 30 mm with a super cutter. Thereafter, the end surface processing machine (manufactured by Megaro Technica Co., Ltd.) was used to cut the four side surfaces of the cut piece by 0.05 mm to obtain a sample. Regarding the glue stain, the side surface of the sample was visually confirmed to check for the presence or absence of glue stain. The dimensional accuracy and edge appearance were observed with an optical microscope and evaluated according to the following evaluation criteria. (Dimensional accuracy) ⁇ : Within ⁇ 0.3mm ⁇ : Over ⁇ 0.3mm (External appearance) ⁇ : When there is no stickiness at the end when touched by hand ⁇ : When there is stickiness at the end when touched by hand
  • P-1 is the polarizing film (P-1)
  • P-2 is the polarizing film (P-2)
  • a-1 is the acrylic pressure-sensitive adhesive composition obtained in Production Example 1.
  • A-1 is the acrylic pressure-sensitive adhesive composition (a-2) obtained in Production Example 2
  • the ultraviolet absorber 1 is 2,4-bis-[ ⁇ 4- (4 -Ethylhexyloxy) -4-hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, manufactured by BASF Japan Ltd.)
  • UV absorber 2 is Solvent Yellow 163 (KP Last Yellow MK, manufactured by Kiwa Chemical Industry Co., Ltd.)
  • B-1 is the image display part side adhesive layer (B-1) obtained in Production Example 3
  • B-2 is Production Example The image display part side pressure-sensitive adhesive layer (B-2) obtained in 4 is shown.

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Abstract

A polarizing film with a pressure-sensitive adhesive layer according to the present invention is to be used at a portion located more toward the visible side than an image display unit in an image display device. The polarizing film with a pressure-sensitive adhesive layer includes a polarizing film and a pressure-sensitive adhesive layer on both sides of the polarizing film. The polarizing film has a polarizer and a transparent protective film on both sides of the polarizer. The transparent protective film located on the visible side of the polarizer has a transmittance of less than 6% at the wavelength of 380 nm, and the pressure-sensitive adhesive layer on the visible side of the polarizing film has an ultraviolet absorption function. The present invention can solve the problem regarding a low process yield, and can provide a polarizing film with a pressure-sensitive adhesive layer capable of providing a sufficient ultraviolet protection function and inhibiting the occurrence of curling, even when the polarizing film is of a thin type.

Description

粘着剤層付き偏光フィルム、及び画像表示装置Polarizing film with adhesive layer and image display device
　本発明は、画像表示装置に用いる粘着剤層付き偏光フィルムに関する。また、本発明は、前記粘着剤層付き偏光フィルムを用いた画像表示装置に関する。画像表示装置としては、液晶表示装置、有機ＥＬ（エレクトロルミネッセンス）表示装置、ＰＤＰ（プラズマディスプレイパネル）、電子ペーパー等が挙げられる。 This invention relates to the polarizing film with an adhesive layer used for an image display apparatus. Moreover, this invention relates to the image display apparatus using the said polarizing film with an adhesive layer. Examples of the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper.
　液晶表示装置及び有機ＥＬ表示装置等は、その画像形成方式から、例えば、液晶表示装置では、液晶セルの両側に偏光素子を配置することが必要不可欠であり、一般的には偏光フィルムが貼着されている。また液晶パネル及び有機ＥＬパネル等の表示パネルには偏光フィルムの他に、ディスプレイの表示品位を向上させるために様々な光学素子が用いられるようになってきている。 In liquid crystal display devices and organic EL display devices, for example, in liquid crystal display devices, it is indispensable to dispose polarizing elements on both sides of the liquid crystal cell, and generally a polarizing film is attached. Has been. In addition to polarizing films, various optical elements have been used for display panels such as liquid crystal panels and organic EL panels in order to improve the display quality of displays.
　これらの画像表示装置に用いられる偏光フィルムは、一般に偏光子を２枚の保護フィルムで挟持する構成を有しており、保護フィルムとしてはトリアセチルセルロース（ＴＡＣ）が広く用いられている。 The polarizing film used in these image display devices generally has a configuration in which a polarizer is sandwiched between two protective films, and triacetyl cellulose (TAC) is widely used as the protective film.
　近年、画像表示装置の軽量化、薄膜化の流れに伴い、画像表示装置に使用される各部材について薄膜化が要求されており、偏光フィルムの保護フィルムについても薄膜化が要求されている。前記保護フィルムの厚さが薄くなると、画像表示装置に入射する紫外線を十分にカットできなくなり、偏光子のみならず、画像表示装置に用いられる液晶パネル、有機ＥＬ素子等をはじめとする各種光学部材の紫外線による劣化を早めるといった問題があった。 In recent years, with the trend of reducing the weight and thickness of image display devices, it is required to reduce the thickness of each member used in the image display device, and also to reduce the thickness of the protective film of the polarizing film. When the thickness of the protective film is reduced, the ultraviolet light incident on the image display device cannot be sufficiently cut, and not only the polarizer but also various optical members such as liquid crystal panels and organic EL elements used in the image display device. There was a problem that the deterioration due to ultraviolet rays was accelerated.
　このような問題を解消するために、例えば、画像表示装置における表面保護パネルと液晶モジュールの視認側との間に配設して、２つの部材を一体化させるための両面粘着シートであって、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）や、アクリル系ポリマー及びトリアジン系紫外線吸収剤を含有する粘着剤層を有する粘着シートが知られている（例えば、特許文献２参照）。また、光学フィルムの片面又は両面に粘着剤層が設けられている粘着型光学フィルムにおいて、前記粘着剤層に紫外線吸収能を付与できることが知られている（例えば、特許文献３参照）。 In order to solve such a problem, for example, a double-sided pressure-sensitive adhesive sheet for integrating two members disposed between the surface protection panel in the image display device and the viewing side of the liquid crystal module, Transparent double-sided pressure-sensitive adhesive for image display devices, having at least one ultraviolet absorbing layer, having a light transmittance of 380 nm or less and a visible light transmittance of 80% or more on a longer wavelength side than the wavelength of 430 nm A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a sheet (for example, see Patent Document 1) or an acrylic polymer and a triazine-based ultraviolet absorber is known (for example, see Patent Document 2). Further, it is known that an ultraviolet absorbing ability can be imparted to the pressure-sensitive adhesive layer in a pressure-sensitive adhesive optical film in which a pressure-sensitive adhesive layer is provided on one or both sides of the optical film (see, for example, Patent Document 3).
特開２０１２－２１１３０５号公報JP 2012-211305 A 特開２０１３－７５９７８号公報JP 2013-75978 A 特許第４２０８１８７号公報Japanese Patent No. 4208187
　近年、特許文献１～３に記載されているように、紫外線吸収機能を有する透明粘着剤を用いて画像表示装置に用いる各種部材を貼り合わせることが知られているが、この場合、厚みムラが生じたり、歩留まり悪化、作業性といった観点で課題があった。 In recent years, as described in Patent Documents 1 to 3, it is known to bond various members used in an image display device using a transparent adhesive having an ultraviolet absorbing function. There were problems in terms of occurrence, yield deterioration, and workability.
　また、偏光フィルムの用途によっては、偏光フィルムに、より高い紫外線吸収機能が要求される場合がある。具体的には、長時間（具体的には３００時間程度）紫外線に曝された場合や、幅広い波長領域を有する紫外線に曝された場合であっても、光学特性が変化しないことが要求されており、そのようなより高い紫外線吸収機能を満足する偏光フィルムが望まれていた。 Also, depending on the application of the polarizing film, the polarizing film may be required to have a higher ultraviolet absorption function. Specifically, even when exposed to ultraviolet rays for a long time (specifically, about 300 hours) or when exposed to ultraviolet rays having a wide wavelength range, it is required that the optical characteristics do not change. Therefore, there has been a demand for a polarizing film that satisfies such a higher ultraviolet absorption function.
　また、偏光フィルムの偏光子や保護フィルムの薄膜化により、得られる偏光フィルムにカールが生じるといった問題もあった。 Also, there has been a problem that curling occurs in the obtained polarizing film due to the thinning of the polarizer and the protective film of the polarizing film.
　そこで、本発明は、歩留まり低下の課題を解決することができ、かつ、偏光フィルムが薄型の場合であっても、より高い紫外線カット機能を付与することができ、カール発生を抑制することができる粘着剤層付き偏光フィルムを提供すること目的とする。また、本発明は、前記粘着剤層付き偏光フィルムを用いた画像表示装置を提供することも目的とする。 Therefore, the present invention can solve the problem of yield reduction, and even when the polarizing film is thin, can provide a higher UV cut function and can suppress the occurrence of curling. It aims at providing the polarizing film with an adhesive layer. Another object of the present invention is to provide an image display device using 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、下記粘着剤層付き偏光フィルムを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found the following polarizing film with a pressure-sensitive adhesive layer and have completed the present invention.
　すなわち、本発明は、画像表示装置において画像表示部より視認側に用いられる粘着剤層付き偏光フィルムであって、
　前記粘着剤層付き偏光フィルムは、偏光フィルムと当該偏光フィルムの両面に粘着剤層を有し、
　前記偏光フィルムは、偏光子と当該偏光子の両面に透明保護フィルムを有し、
　前記偏光子の視認側の透明保護フィルムの波長３８０ｎｍにおける透過率が６％未満であり、かつ
　前記偏光フィルムの視認側の粘着剤層が紫外線吸収機能を有することを特徴とする粘着剤層付き偏光フィルムに関する。 That is, the present invention is a polarizing film with a pressure-sensitive adhesive layer used on the viewing side from the image display unit in the image display device,
The polarizing film with the pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer on both sides of the polarizing film and the polarizing film,
The polarizing film has a transparent protective film on both sides of the polarizer and the polarizer,
Polarized light with pressure-sensitive adhesive layer, wherein the transparent protective film on the viewing side of the polarizer has a transmittance at a wavelength of 380 nm of less than 6%, and the pressure-sensitive adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function Related to film.
　前記偏光子の視認側の透明保護フィルムが、トリアセチルセルロースフィルム、アクリルフィルム、ポリエチレンテレフタレートフィルム、及び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フィルムからなる群から選択される少なくとも１種のフィルムであり、かつ厚さが４０μｍ以下であることが好ましい。 The transparent protective film on the viewer side of the polarizer is at least one film selected from the group consisting of a triacetyl cellulose film, an acrylic film, a polyethylene terephthalate film, and a polyolefin film having a cyclo or norbornene structure, and The thickness is preferably 40 μm or less.
　前記偏光フィルムの視認側の粘着剤層の厚さが、前記偏光フィルムの画像表示部側の粘着剤層の厚さの２倍以上であることが好ましい。 The thickness of the pressure-sensitive adhesive layer on the viewing side of the polarizing film is preferably at least twice the thickness of the pressure-sensitive adhesive layer on the image display unit side of the polarizing film.
　前記偏光フィルムの視認側の粘着剤層が、波長３８０ｎｍの透過率が９％以下であり、かつ、波長４００ｎｍの透過率が６０％以上であることが好ましい。 The adhesive layer on the viewing side of the polarizing film preferably has a transmittance at a wavelength of 380 nm of 9% or less and a transmittance at a wavelength of 400 nm of 60% or more.
　前記偏光フィルムの視認側の粘着剤層のｂ＊値が３．０以下であることが好ましい。 The b * value of the pressure-sensitive adhesive layer on the viewing side of the polarizing film is preferably 3.0 or less.
　前記偏光フィルムの視認側の粘着剤層が、波長３８０ｎｍの透過率が９％以下であり、かつ、波長４２０ｎｍの透過率が７５％以下であることが好ましい。 The adhesive layer on the viewing side of the polarizing film preferably has a transmittance of 380 nm at a wavelength of 9% or less and a transmittance at a wavelength of 420 nm of 75% or less.
　前記偏光フィルムの視認側の粘着剤層が、アクリル系ポリマーをベースポリマーとして含有していることが好ましい。 It is preferable that the adhesive layer on the viewing side of the polarizing film contains an acrylic polymer as a base polymer.
　本発明の粘着剤層付き偏光フィルムは、液晶表示装置又は有機ＥＬ表示装置に用いることが好ましい。 The polarizing film with an adhesive layer of the present invention is preferably used for a liquid crystal display device or an organic EL display device.
　また、本発明は、本発明の粘着剤層付き偏光フィルムを画像表示部より視認側に用いたことを特徴とする画像表示装置に関する。 The present invention also relates to an image display device characterized in that the polarizing film with an adhesive layer of the present invention is used on the viewing side from the image display unit.
　本発明の粘着剤層付き偏光フィルムは、紫外線吸収機能を有する粘着剤層が偏光フィルムの視認側に予め積層されている構成であるため、工程削除、歩留まり低下の課題を解決することができ、かつ、偏光フィルムが薄型の場合であっても、より高い紫外線カット機能を付与することができ、カール発生を抑制することができる。また、本発明の画像表示装置は、前記粘着剤層付き偏光フィルムを用いているため、画像表示装置に用いられる液晶パネル、有機ＥＬ素子等をはじめとする各種光学部材の紫外線による劣化を抑制することができる。 Since the polarizing film with the pressure-sensitive adhesive layer of the present invention has a configuration in which the pressure-sensitive adhesive layer having an ultraviolet absorbing function is laminated in advance on the viewing side of the polarizing film, the problem of process deletion and yield reduction can be solved. And even if it is a case where a polarizing film is thin, a higher ultraviolet cut function can be provided and curling generation | occurrence | production can be suppressed. Moreover, since the image display apparatus of this invention uses the said polarizing film with an adhesive layer, it suppresses the deterioration by ultraviolet rays of various optical members used for an image display apparatus, such as a liquid crystal panel and an organic EL element. be able to.
本発明の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。It is sectional drawing which shows typically one Embodiment of the polarizing film with an adhesive layer of this invention. 本発明の画像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 sectional drawing which shows typically one Embodiment of the image display apparatus of this invention. 本発明の画像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 sectional drawing which shows typically one Embodiment of the image display apparatus of this invention. 本発明の画像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 sectional drawing which shows typically one Embodiment of the image display apparatus of this invention.
　１．粘着剤層付き偏光フィルム
　本発明の粘着剤層付き偏光フィルムは、画像表示装置において画像表示部より視認側に用いられ、
　前記粘着剤層付き偏光フィルムは、偏光フィルムと当該偏光フィルムの両面に粘着剤層を有し、
　前記偏光フィルムは、偏光子と当該偏光子の両面に透明保護フィルムを有し、
　前記偏光子の視認側の透明保護フィルムの波長３８０ｎｍにおける透過率が６％未満であり、かつ
　前記偏光フィルムの視認側の粘着剤層が紫外線吸収機能を有することを特徴とする。 1. The polarizing film with the pressure-sensitive adhesive layer The polarizing film with the pressure-sensitive adhesive layer of the present invention is used on the viewing side from the image display unit in the image display device,
The polarizing film with the pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer on both sides of the polarizing film and the polarizing film,
The polarizing film has a transparent protective film on both sides of the polarizer and the polarizer,
The transmittance of the transparent protective film on the viewing side of the polarizer at a wavelength of 380 nm is less than 6%, and the adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function.
　図１に示すように、本発明の粘着剤層付き偏光フィルム１は、視認側粘着剤層２ａ／視認側透明保護フィルム３ａ／偏光子４／画像表示部側透明保護フィルム３ｂ／画像表示部側粘着剤層２ｂを含む構成であればよく、さらに位相差フィルム等を含む構成であってもよい。具体的には、視認側粘着剤層２ａ／視認側透明保護フィルム３ａ／偏光子４／画像表示部側透明保護フィルム３ｂ／画像表示部側粘着剤層２ｂ／位相差フィルム（不図示）／画像表示部側粘着剤層（不図示）等の構成であってもよい。偏光フィルム５は、視認側透明保護フィルム３ａ／偏光子４／画像表示部側透明保護フィルム３ｂから構成される。各層について、以下に詳細に説明する。 As shown in FIG. 1, the polarizing film 1 with the pressure-sensitive adhesive layer of the present invention has a viewing-side pressure-sensitive adhesive layer 2 a / viewing-side transparent protective film 3 a / polarizer 4 / image display unit side transparent protective film 3 b / image display unit side. Any structure including the pressure-sensitive adhesive layer 2b may be used, and a structure including a retardation film or the like may be used. Specifically, viewing side adhesive layer 2a / viewing side transparent protective film 3a / polarizer 4 / image display unit side transparent protective film 3b / image display unit side adhesive layer 2b / retardation film (not shown) / image A structure such as a display unit side pressure-sensitive adhesive layer (not shown) may be used. The polarizing film 5 includes a viewing-side transparent protective film 3a / a polarizer 4 / an image display unit-side transparent protective film 3b. Each layer will be described in detail below.
　（１）視認側粘着剤層
　本発明において、前記偏光フィルムの視認側の粘着剤層（視認側粘着剤層）が紫外線吸収機能を有することを特徴とする。前記視認側粘着剤層は、紫外線吸収機能を有すればよく、その組成は特に限定されない。 (1) Viewing-side pressure-sensitive adhesive layer In the present invention, the viewing-side pressure-sensitive adhesive layer (viewing-side pressure-sensitive adhesive layer) of the polarizing film has an ultraviolet absorbing function. The visible-side pressure-sensitive adhesive layer only needs to have an ultraviolet absorbing function, and the composition thereof is not particularly limited.
　前記視認側粘着剤層の形成には、適宜な粘着剤を用いることができ、その種類について特に制限はない。粘着剤としては、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が挙げられる。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。前記アクリル系粘着剤（組成物）は、アクリル系ポリマーをベースポリマーとして含有する。 For the formation of the viewing-side pressure-sensitive adhesive layer, an appropriate pressure-sensitive adhesive can be used, and the type thereof is not particularly limited. Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate adhesiveness, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like. . The acrylic pressure-sensitive adhesive (composition) contains an acrylic polymer as a base polymer.
　前記アクリル系粘着剤組成物は、例えば、アルキル（メタ）アクリレートを含有するモノマー成分の部分重合物及び／又は前記モノマー成分から得られる（メタ）アクリル系ポリマーと、紫外線吸収剤を含むことが好ましい。 The acrylic pressure-sensitive adhesive composition preferably contains, for example, a partial polymer of a monomer component containing an alkyl (meth) acrylate and / or a (meth) acrylic polymer obtained from the monomer component and an ultraviolet absorber. .
　（１－１）モノマー成分の部分重合物、及び（メタ）アクリル系ポリマー
　前記アクリル系粘着剤組成物は、アルキル（メタ）アクリレートを含有するモノマー成分の部分重合物及び／又は前記モノマー成分から得られる（メタ）アクリル系ポリマーを含む。 (1-1) Partially polymerized monomer component and (meth) acrylic polymer The acrylic pressure-sensitive adhesive composition is obtained from a partially polymerized monomer component containing alkyl (meth) acrylate and / or the monomer component. (Meth) acrylic polymer.
　前記アルキル（メタ）アクリレートとしては、直鎖状又は分岐鎖状の炭素数１～２４のアルキル基をエステル末端に有するものを例示できる。アルキル（メタ）アクリレートは１種を単独で又は２種以上を組み合わせて用いることができる。なお、アルキル（メタ）アクリレートはアルキルアクリレート及び／又はアルキル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。 Examples of the alkyl (meth) acrylate include those having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester end. Alkyl (meth) acrylate can be used individually by 1 type or in combination of 2 or more types. Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
　前記アルキル（メタ）アクリレートとしては、例えば、前記炭素数１～９の分岐を有するアルキル（メタ）アクリレートを好ましく例示することができる。当該アルキル（メタ）アクリレートは、粘着特性のバランスがとりやすい点で好ましい。具体的には、ｎ－ブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、イソヘキシル（メタ）アクリレート、イソヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート等が挙げられ、これらを１種単独で又は２種以上を組み合わせて使用することができる。 As the alkyl (meth) acrylate, for example, the alkyl (meth) acrylate having 1 to 9 carbon atoms can be preferably exemplified. The alkyl (meth) acrylate is preferable in terms of easily balancing the adhesive properties. Specifically, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isohexyl (Meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and the like are used, and these are used alone or in combination of two or more. be able to.
　本発明において、前記炭素数１～２４のアルキル基をエステル末端に有するアルキル（メタ）アクリレートは、（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の全量に対して４０重量％以上であることが好ましく、５０重量％以上がより好ましく、６０重量％以上がさらに好ましい。 In the present invention, the alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms at the ester terminal is 40% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. It is preferably 50% by weight or more, more preferably 60% by weight or more.
　前記モノマー成分には、単官能性モノマー成分として、前記アルキル（メタ）アクリレート以外の共重合モノマーを含有することができる。共重合モノマーは、モノマー成分における前記アルキル（メタ）アクリレートの残部として用いることができる。 The monomer component may contain a copolymerization monomer other than the alkyl (meth) acrylate as a monofunctional monomer component. A copolymerization monomer can be used as the remainder of the said alkyl (meth) acrylate in a monomer component.
　共重合モノマーとしては、例えば、環状窒素含有モノマーを含むことができる。上記環状窒素含有モノマーとしては、（メタ）アクリロイル基又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し、かつ環状窒素構造を有するものを特に制限なく用いることができる。環状窒素構造は、環状構造内に窒素原子を有するものが好ましい。環状窒素含有モノマーとしては、例えば、Ｎ－ビニルピロリドン、Ｎ－ビニル－ε－カプロラクタム、メチルビニルピロリドン等のラクタム系ビニルモノマー；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、ビニルモルホリン等の窒素含有複素環を有するビニル系モノマー等が挙げられる。また、モルホリン環、ピペリジン環、ピロリジン環、ピペラジン環等の複素環を含有する（メタ）アクリルモノマーが挙げられる。具体的には、Ｎ－アクリロイルモルホリン、Ｎ－アクリロイルピペリジン、Ｎ－メタクリロイルピペリジン、Ｎ－アクリロイルピロリジン等が挙げられる。前記環状窒素含有モノマーの中でも、ラクタム系ビニルモノマーが好ましい。 As the copolymerization monomer, for example, a cyclic nitrogen-containing monomer can be included. As said cyclic nitrogen containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a cyclic nitrogen structure can be especially used without a restriction | limiting. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. Examples of cyclic nitrogen-containing monomers include lactam vinyl monomers such as N-vinyl pyrrolidone, N-vinyl-ε-caprolactam, and methyl vinyl pyrrolidone; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as imidazole, vinyl oxazole and vinyl morpholine. Moreover, the (meth) acryl monomer containing heterocyclic rings, such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, is mentioned. Specific examples include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like. Among the cyclic nitrogen-containing monomers, lactam vinyl monomers are preferable.
　本発明において、環状窒素含有モノマーは、（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の全量に対して、０．５～５０重量％であるのが好ましく、０．５～４０重量％がより好ましく、０．５～３０重量％がさらに好ましい。 In the present invention, the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by weight, and preferably 0.5 to 40% by weight, based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable, and 0.5 to 30% by weight is even more preferable.
　本発明で用いるモノマー成分には、単官能性モノマー成分として、ヒドロキシル基含有モノマーを含むことができる。ヒドロキシル基含有モノマーとしては、（メタ）アクリロイル基又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し、かつヒドロキシル基を有するものを特に制限なく用いることができる。ヒドロキシル基含有モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、１２－ヒドロキシラウリル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等のヒドロキシアルキルシクロアルカン（メタ）アクリレートが挙げられる。その他、ヒドロキシエチル（メタ）アクリルアミド、アリルアルコール、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、ジエチレングリコールモノビニルエーテル等が挙げられる。これらは単独で又は組み合わせて使用できる。これらの中でもヒドロキシアルキル（メタ）アクリレートが好適である。 The monomer component used in the present invention can contain a hydroxyl group-containing monomer as a monofunctional monomer component. As the hydroxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; -Hydroxyalkylcycloalkane (meth) acrylates such as -hydroxymethylcyclohexyl) methyl (meth) acrylate. Other examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. These can be used alone or in combination. Of these, hydroxyalkyl (meth) acrylate is preferred.
　本発明において、前記ヒドロキシル基含有モノマーは、（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の全量に対して、接着力、凝集力を高める点から１重量％以上であるのが好ましく、２重量％以上であるがより好ましく、３重量％以上であるのがさらに好ましい。一方、前記ヒドロキシル基含有モノマーが多くなりすぎると、粘着剤層が固くなり、接着力が低下する場合があり、また、粘着剤の粘度が高くなりすぎたり、ゲル化したりする場合があることから、前記ヒドロキシル基含有モノマーは、（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の全量に対して、３０重量％以下であるのが好ましく、２７重量％以下がより好ましく、２５重量％以下がさらに好ましい。 In the present invention, the hydroxyl group-containing monomer is preferably 1% by weight or more from the viewpoint of enhancing adhesive force and cohesive force with respect to the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, It is more preferably 2% by weight or more, and further preferably 3% by weight or more. On the other hand, if the amount of the hydroxyl group-containing monomer is too large, the pressure-sensitive adhesive layer becomes hard and the adhesive strength may decrease, and the viscosity of the pressure-sensitive adhesive may become too high or gel. The hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 27% by weight or less, and more preferably 25% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable.
　また、（メタ）アクリル系ポリマーを形成するモノマー成分には、単官能性モノマーとして、その他の官能基含有モノマーを含有することができ、例えば、カルボキシル基含有モノマー、環状エーテル基を有するモノマーが挙げられる。 In addition, the monomer component that forms the (meth) acrylic polymer can contain other functional group-containing monomers as monofunctional monomers, such as carboxyl group-containing monomers and monomers having a cyclic ether group. It is done.
　カルボキシル基含有モノマーとしては、（メタ）アクリロイル基又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し、かつカルボキシル基を有するものを特に制限なく用いることができる。カルボキシル基含有モノマーとしては、例えば、（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、イソクロトン酸等が挙げられ、これらは単独で又は組み合わせて使用できる。イタコン酸、マレイン酸はこれらの無水物を用いることができる。これらの中でも、アクリル酸、メタクリル酸が好ましく、特にアクリル酸が好ましい。なお、本発明の（メタ）アクリル系ポリマーの製造に用いるモノマー成分にはカルボキシル基含有モノマーを任意に用いることができ、一方では、カルボキシル基含有モノマーを用いなくともよい。 As the carboxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Can be used alone or in combination. These anhydrides can be used for itaconic acid and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. In addition, a carboxyl group-containing monomer can be arbitrarily used for the monomer component used for manufacture of the (meth) acrylic-type polymer of this invention, On the other hand, it is not necessary to use a carboxyl group-containing monomer.
　環状エーテル基を有するモノマーとしては、（メタ）アクリロイル基又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し、かつエポキシ基又はオキセタン基等の環状エーテル基を有するものを特に制限なく用いることができる。エポキシ基含有モノマーとしては、例えば、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等が挙げられる。オキセタン基含有モノマーとしては、例えば、３－オキセタニルメチル（メタ）アクリレート、３－メチル－オキセタニルメチル（メタ）アクリレート、３－エチル－オキセタニルメチル（メタ）アクリレート、３－ブチル－オキセタニルメチル（メタ）アクリレート、３－ヘキシル－オキセタニルメチル（メタ）アクリレート等が挙げられる。これらは単独で又は組み合わせて使用できる。 As a monomer having a cyclic ether group, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group. It can be used without particular limitation. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl-oxetanylmethyl (meth) acrylate and the like. These can be used alone or in combination.
　本発明において、前記カルボキシル基含有モノマー、環状エーテル基を有するモノマーは、（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の全量に対して、３０重量％以下であるのが好ましく、２７重量％以下がより好ましく、２５重量％以下がさらに好ましい。 In the present invention, the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, and 27% by weight. % Or less is more preferable, and 25% by weight or less is more preferable.
　本発明の（メタ）アクリル系ポリマーを形成するモノマー成分には、共重合モノマーとしては、例えば、ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２（前記Ｒ１は水素又はメチル基、Ｒ２は炭素数１～３の置換されたアルキル基、環状のシクロアルキル基を表す。）で表されるアルキル（メタ）アクリレートが挙げられる。 The monomer component forming the (meth) acrylic polymer of the present invention includes, for example, CH 2 ═C (R 1 ) COOR 2 (wherein R 1 is hydrogen or a methyl group, and R 2 is the number of carbon atoms). And an alkyl (meth) acrylate represented by 1 to 3 substituted alkyl groups and cyclic cycloalkyl groups.
　ここで、Ｒ２としての、炭素数１～３の置換されたアルキル基の置換基としては、炭素数３～８個のアリール基又は炭素数３～８個のアリールオキシ基であることが好ましい。アリール基としては、限定はされないが、フェニル基が好ましい。 Here, the substituent of the substituted alkyl group having 1 to 3 carbon atoms as R 2 is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms. . The aryl group is not limited, but is preferably a phenyl group.
　このようなＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２で表されるモノマーの例としては、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、シクロヘキシル（メタ）アクリレート、３，３，５－トリメチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等が挙げられる。これらは単独で又は組み合わせて使用できる。 Examples of such a monomer represented by CH 2 ═C (R 1 ) COOR 2 include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl. (Meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned. These can be used alone or in combination.
　本発明において、前記ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２で表される（メタ）アクリレートは、（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の全量に対して、５０重量％以下で用いることができ、４５重量％以下が好ましく、４０重量％以下がより好ましく、３５重量％以下がさらに好ましい。 In the present invention, the (meth) acrylate represented by CH 2 ═C (R 1 ) COOR 2 is 50% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. 45% by weight or less is preferable, 40% by weight or less is more preferable, and 35% by weight or less is more preferable.
　他の共重合モノマーとしては、酢酸ビニル、プロピオン酸ビニル、スチレン、α－メチルスチレン；（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；アミド基含有モノマー、アミノ基含有モノマー、イミド基含有モノマー、Ｎ－アクリロイルモルホリン、ビニルエーテルモノマー等も使用することができる。また、共重合モノマーとしては、テルペン（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の環状構造を有するモノマーを用いることができる。 Other copolymerization monomers include vinyl acetate, vinyl propionate, styrene, α-methylstyrene; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; Monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers and the like can also be used. Moreover, as a copolymerization monomer, the monomer which has cyclic structures, such as terpene (meth) acrylate and dicyclopentanyl (meth) acrylate, can be used.
　さらに、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。 Further examples include silane monomers containing silicon atoms. Examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane. , 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.
　本発明の（メタ）アクリル系ポリマーを形成するモノマー成分には、前記例示の単官能性モノマーの他に、粘着剤の凝集力を調整するために、必要に応じて多官能性モノマーを含有することができる。 The monomer component that forms the (meth) acrylic polymer of the present invention contains a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive, in addition to the monofunctional monomer exemplified above. be able to.
　多官能性モノマーは、（メタ）アクリロイル基又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少なくとも２つ有するモノマーであり、例えば、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，２－エチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート等の多価アルコールと（メタ）アクリル酸とのエステル化合物；アリル（メタ）アクリレート、ビニル（メタ）アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ブチルジ（メタ）アクリレート、ヘキシルジ（メタ）アクリレート等が挙げられる。これらの中でも、トリメチロールプロパントリ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートを好適に使用することができる。多官能性モノマーは、１種を単独で又は２種以上を組み合わせて使用することができる。 The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as (poly) ethylene glycol di (meth) acrylate, (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) acrylate Ester compounds of polyhydric alcohols such as carbonate and (meth) acrylic acid; allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di (meth) acrylate, hexyl di ( And (meth) acrylate. Among these, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
　多官能性モノマーの使用量は、その分子量や官能基数等により異なるが、単官能性モノマーの合計１００重量部に対して、３重量部以下で用いることが好ましく、２重量部以下がより好ましく、１重量部以下がさらに好ましい。また、下限値としては特に限定されないが、０重量部以上であることが好ましく、０．００１重量部以上であることがより好ましい。多官能性モノマーの使用量が前記範囲内であることにより、接着力を向上することができる。 The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but it is preferably used at 3 parts by weight or less, more preferably 2 parts by weight or less, with respect to a total of 100 parts by weight of the monofunctional monomer. 1 part by weight or less is more preferable. Moreover, it does not specifically limit as a lower limit, However It is preferable that it is 0 weight part or more, and it is more preferable that it is 0.001 weight part or more. Adhesive force can be improved when the usage-amount of a polyfunctional monomer exists in the said range.
　前記（メタ）アクリル系ポリマーの製造は、溶液重合、紫外線（ＵＶ）重合等の放射線重合、塊状重合、乳化重合等の各種ラジカル重合等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、グラフト共重合体等のいずれでもよい。 The production of the (meth) acrylic polymer can be appropriately selected from known production methods such as radiation polymerization such as solution polymerization and ultraviolet (UV) polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
　また、本発明においては、前記モノマー成分の部分重合物も好適に用いることができる。 In the present invention, a partial polymer of the monomer component can also be suitably used.
　前記（メタ）アクリル系ポリマーをラジカル重合により製造する場合には、前記モノマー成分に、ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等を適宜添加して、重合を行うことができる。前記ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等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その使用量が調整される。 When the (meth) acrylic polymer is produced by radical polymerization, polymerization can be carried out by appropriately adding a polymerization initiator, a chain transfer agent, an emulsifier and the like used for radical polymerization to the monomer component. The polymerization initiator, chain transfer agent, emulsifier and the like used for the radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, and the usage-amount is suitably adjusted according to these kinds.
　例えば、溶液重合等においては、重合溶媒として、例えば、酢酸エチル、トルエン等が用いられる。具体的な溶液重合例としては、反応は窒素等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。 For example, in solution polymerization or the like, 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 in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
　溶液重合等に用いられる、熱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－メチルブチロニトリル、２，２’－アゾビス（２－メチルプロピオン酸）ジメチル、４，４’－アゾビス－４－シアノバレリアン酸、アゾビスイソバレロニトリル、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（ＶＡ－０５７、和光純薬工業（株）製）等のアゾ系開始剤；過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、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、過酸化水素等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等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等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。 Examples of thermal polymerization initiators used for solution polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (2 -Methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 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′-dimethyleneisobutyl) Amidine), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, Wako Pure Chemical Industries, Ltd.) Azo initiators such as potassium persulfate, ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di- sec-butyl peroxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t- Hexylperoxy) cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, etc. Examples include oxide initiators, redox initiators that combine a peroxide and a reducing agent, such as a combination of persulfate and sodium bisulfite, and a combination of peroxide and sodium ascorbate. It is not limited to.
　前記重合開始剤は、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、モノマー成分の全量１００重量部に対して、１重量部以下程度であることが好ましく、０．００５～１重量部程度であることがより好ましく、０．０２～０．５重量部程度であることがさらに好ましい。 The polymerization initiator may be used alone or in combination of two or more, but is preferably about 1 part by weight or less with respect to 100 parts by weight of the total amount of monomer components. The amount is more preferably about 0.005 to 1 part by weight, and further preferably about 0.02 to 0.5 part by weight.
　なお、重合開始剤として、２，２’－アゾビスイソブチロニトリルを用いる場合、重合開始剤の使用量は、モノマー成分の全量１００重量部に対して、０．２重量部以下程度であることが好ましく、０．０６～０．２重量部程度とするのがより好ましい。 When 2,2′-azobisisobutyronitrile is used as the polymerization initiator, the amount of the polymerization initiator used is about 0.2 parts by weight or less with respect to 100 parts by weight of the total amount of monomer components. The amount is preferably about 0.06 to 0.2 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－プロパノール等が挙げられる。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、０．３重量部程度以下である。 Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.3 parts by weight relative 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等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等のノニオン系乳化剤等が挙げられる。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。 Examples of the emulsifier used in emulsion polymerization include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer and the like can be 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、アリルエーテル基等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（株）製）、アデカリアソープＳＥ１０Ｎ（ＡＤＥＫＡ社製）等がある。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、５重量部以下であることが好ましい。 Further, as reactive emulsifiers, as emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SE10N (manufactured by ADEKA), and the like. The amount of the emulsifier used is preferably 5 parts by weight or less with respect to 100 parts by weight of the total amount of the monomer components.
　また、前記（メタ）アクリル系ポリマーを放射線重合により製造する場合には、前記モノマー成分に、電子線、紫外線（ＵＶ）等の放射線を照射することにより重合して製造することができる。これらの中でも、紫外線重合が好ましい。以下、放射線重合の中で好ましい態様である紫外線重合について説明する。 Further, when the (meth) acrylic polymer is produced by radiation polymerization, it can be produced by polymerizing the monomer component by irradiating the monomer component with radiation such as an electron beam or ultraviolet (UV). Among these, ultraviolet polymerization is preferable. Hereinafter, ultraviolet polymerization which is a preferable embodiment in radiation polymerization will be described.
　紫外線重合を行う際には、重合時間を短くすることができる利点等から、モノマー成分に光重合開始剤を含有させることが好ましい。従って、紫外線重合を行う場合、例えば、前記アルキル（メタ）アクリレートを含有するモノマー成分及び／又は前記モノマー成分の部分重合物、紫外線吸収剤、及び光重合開始剤を含む紫外線硬化型アクリル系粘着剤組成物を紫外線重合することにより形成されることが好ましい。前記紫外線硬化型アクリル系粘着剤組成物を紫外線重合することにより形成された粘着剤層は、１５０μｍ以上の厚手のものも形成が可能になり、幅広い厚みの粘着剤層を形成することができるため好ましい。 When performing ultraviolet polymerization, it is preferable to contain a photopolymerization initiator in the monomer component from the advantage that the polymerization time can be shortened. Therefore, when performing ultraviolet polymerization, for example, an ultraviolet curable acrylic pressure-sensitive adhesive containing a monomer component containing the alkyl (meth) acrylate and / or a partial polymer of the monomer component, an ultraviolet absorber, and a photopolymerization initiator. It is preferably formed by ultraviolet polymerization of the composition. Since the pressure-sensitive adhesive layer formed by ultraviolet polymerization of the ultraviolet curable acrylic pressure-sensitive adhesive composition can be formed to have a thickness of 150 μm or more, and a pressure-sensitive adhesive layer having a wide thickness can be formed. preferable.
　前記光重合開始剤としては、波長４００ｎｍ以上に吸収帯を有する光重合開始剤（Ａ）を含むものであることが好ましい。粘着剤組成物に紫外線吸収剤を含む場合、紫外線重合を行うと、前記紫外線吸収剤により紫外線が吸収されてしまい十分に重合できないものであった。しかしながら、波長４００ｎｍ以上に吸収帯を有する光重合開始剤（Ａ）であれば、紫外線吸収剤を含むにもかかわらず十分に重合することができるため、好ましい。 It is preferable that the photopolymerization initiator includes a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more. When the ultraviolet light absorber was included in the pressure-sensitive adhesive composition, the ultraviolet light was absorbed by the ultraviolet light absorber and was not sufficiently polymerized. However, the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is preferable because it can be sufficiently polymerized even though it contains an ultraviolet absorber.
　波長４００ｎｍ以上に吸収帯を有する光重合開始剤（Ａ）としては、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（Ｉｒｇａｃｕｒｅ８１９、ＢＡＳＦ製）、２,４,６－トリメチルベンゾイル－ジフェニル-フォスフィンオキサイド（ＬＵＣＩＲＩＮ　ＴＰＯ、ＢＡＳＦ製）等を挙げることができる。 As a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF), 2,4,6-trimethylbenzoyl- And diphenyl-phosphine oxide (LUCIRIN TPO, manufactured by BASF).
　前記波長４００ｎｍ以上に吸収帯を有する光重合開始剤（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。 The photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more may be used alone or in combination of two or more.
　また、前記波長４００ｎｍ以上に吸収帯を有する光重合開始剤（Ａ）の添加量は、特に限定されるものではないが、後述する紫外線吸収剤の添加量よりも少ないことが好ましく、（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、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。光重合開始剤（Ａ）の添加量が前記範囲であることで、紫外線重合を十分に進行することができるため好ましい。 Further, the addition amount of the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is not particularly limited, but is preferably smaller than the addition amount of an ultraviolet absorber described later, (meta) The amount is preferably about 0.005 to 1 part by weight and more preferably about 0.02 to 0.5 part by weight with respect to 100 parts by weight of the monofunctional monomer component forming the acrylic polymer. It is preferable that the amount of the photopolymerization initiator (A) added is in the above range because ultraviolet polymerization can sufficiently proceed.
　また、前記光重合開始剤には、波長４００ｎｍ未満に吸収帯を有する光重合開始剤（Ｂ）を含有することができる。また、光重合開始剤（Ｂ）は、波長４００ｎｍ以上に吸収帯を有さないことが好ましい。当該光重合開始剤（Ｂ）としては、紫外線によりラジカルを発生し、光重合を開始するものであって、波長４００ｎｍ未満に吸収帯を有するものであれば特に制限されず、通常用いられる光重合開始剤をいずれも好適に用いることができる。例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α－ケトール系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤等を用いることができる。 The photopolymerization initiator can contain a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm. Moreover, it is preferable that a photoinitiator (B) does not have an absorption band in wavelength 400nm or more. The photopolymerization initiator (B) is not particularly limited as long as it generates radicals by ultraviolet rays and starts photopolymerization and has an absorption band at a wavelength of less than 400 nm. Any initiator can be suitably used. For example, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, α-ketol photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone A photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or the like can be used.
　具体的には、ベンゾインエーテル系光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、アニソールメチルエーテル等が挙げられる。 Specifically, examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- Examples thereof include 1-one and anisole methyl ether.
　アセトフェノン系光重合開始剤としては、例えば、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、４－フェノキシジクロロアセトフェノン、４－ｔ－ブチルジクロロアセトフェノン等が挙げられる。 Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4-t-butyldichloroacetophenone. Etc.
　α－ケトール系光重合開始剤としては例えば、２－メチル－２－ヒドロキシプロピオフェノン、１－［４－（２－ヒドロキシエチル）フェニル］－２－ヒドロキシ－２－メチルプロパン－１－オン等が挙げられる。 Examples of α-ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy-2-methylpropan-1-one, and the like. Is mentioned.
　光活性オキシム系光重合開始剤としては例えば、１－フェニル－１，２－プロパンジオン－２－（Ｏ－エトキシカルボニル）－オキシム等が挙げられる。 Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.
　ベンゾイン系光重合開始剤としては、例えば、ベンゾイン等が挙げられる。 Examples of the benzoin photopolymerization initiator include benzoin.
　ベンジル系光重合開始剤としては、例えば、ベンジル等が含まれる。 Examples of the benzyl photopolymerization initiator include benzyl and the like.
　ベンゾフェノン系光重合開始剤には、例えば、ベンゾフェノン、ベンゾイル安息香酸、３，３’－ジメチル－４－メトキシベンゾフェノン、ポリビニルベンゾフェノン、α－ヒドロキシシクロヘキシルフェニルケトン等が含まれる。 Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like.
　ケタール系光重合開始剤には、ベンジルジメチルケタール等が含まれる。 Ketal photopolymerization initiators include benzyl dimethyl ketal and the like.
　チオキサントン系光重合開始剤には、例えば、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントン等が含まれる。 Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthioxanthone, dodecylthioxanthone and the like are included.
　アシルフォスフィンオキサイド系光重合開始剤には、例えば、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等が含まれる。 Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
　前記波長４００ｎｍ未満に吸収帯を有する光重合開始剤（Ｂ）は、単独で又は２種以上を組み合わせて使用することができる。前記波長４００ｎｍ未満に吸収帯を有する光重合開始剤（Ｂ）は、本発明の効果を損なわない範囲で添加することができるが、添加量としては、（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、０．００５～０．５重量部程度であることが好ましく、０．０２～０．１重量部程度であることがより好ましい。 The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be used alone or in combination of two or more. The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be added within a range that does not impair the effects of the present invention, and the addition amount is a monofunctional that forms a (meth) acrylic polymer. The amount is preferably about 0.005 to 0.5 part by weight, more preferably about 0.02 to 0.1 part by weight based on 100 parts by weight of the monomeric monomer component.
　本発明においては、前記モノマー成分を紫外線重合する場合は、前記モノマー成分に波長４００ｎｍ未満に吸収帯を有する光重合開始剤（Ｂ）を先に添加して、紫外線を照射して一部重合したモノマー成分の部分重合物（プレポリマー組成物）に、前記波長４００ｎｍ以上に吸収帯を有する光重合開始剤（Ａ）及び紫外線吸収剤を添加して紫外線重合することが好ましい。紫外線照射をして一部重合したモノマー成分の部分重合物（プレポリマー組成物）に、前記波長４００ｎｍ以上に吸収帯を有する光重合開始剤（Ａ）を添加する際には、前記光重合開始剤をモノマーに溶解した後添加することが好ましい。 In the present invention, when the monomer component is subjected to ultraviolet polymerization, a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm is first added to the monomer component, and ultraviolet rays are irradiated to partially polymerize. It is preferable to perform ultraviolet polymerization by adding a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more and an ultraviolet absorber to a partial polymerization product (prepolymer composition) of a monomer component. When the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is added to the partial polymerization product (prepolymer composition) of the monomer component partially polymerized by ultraviolet irradiation, the photopolymerization is started. It is preferable to add the agent after dissolving it in the monomer.
　（１－２）紫外線吸収剤
　前記アクリル系粘着剤組成物に含まれる紫外線吸収剤としては、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種単独で又は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、及び、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。 (1-2) Ultraviolet Absorber The ultraviolet absorber contained in the acrylic pressure-sensitive adhesive composition is not particularly limited. For example, a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, An oxybenzophenone type ultraviolet absorber, a salicylic acid ester type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types. Among these, triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable, triazine-based UV absorbers having 2 or less hydroxyl groups in one molecule, and benzones having one benzotriazole skeleton in one molecule. It is at least one ultraviolet absorber selected from the group consisting of triazole-based ultraviolet absorbers, has good solubility in monomers used for forming an acrylic pressure-sensitive adhesive composition, and has a wavelength of around 380 nm This is preferable because of its high ultraviolet absorption ability.
　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 ultraviolet absorbers having 2 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), 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl And [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane reaction product (TINUVIN400, 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 (TINUVIN405, 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-hydroxy-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製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－クレゾール（ＴＩＮＵＶＩＮ　Ｐ、ＢＡＳＦ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。 As a benzotriazole ultraviolet absorber having one benzotriazole skeleton in one molecule, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF), 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (TINUVIN PS, manufactured by BASF), benzene Propanoic acid and ester compounds of 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) (TINUVIN 384-2, BASF 2-, (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-) Enylethyl) phenol (TINUVIN900, 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), methyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (TINUVIN 1130, BASF), 2- (2H-benzotriazol-2-yl) -p-cresol (TINUVIN P, manufactured by BASF), 2 (2H-benzotriazol-2-yl) -4-6-bis (1-methyl- 1-phenylethyl) phenol (TINUVIN234, manufactured by BASF), 2- 5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (TINUVIN 326, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6 -Di-tert-pentylphenol (TINUVIN 328, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 329, manufactured by BASF), Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 (TINUVIN213, manufactured by BASF), 2- (2H- Benzotriazol-2-yl) -6-dodecyl-4-methylpheno (TINUVIN571, manufactured by BASF), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole (Sumisorb250, manufactured by Sumitomo Chemical Co., Ltd.) Etc.
　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、２，４－ジヒドロ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、２－ヒドロキシ－４－メトキシベンゾフェノン－５－スルホン酸（無水及び三水塩）、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´，４，４´－テトラ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。 Examples of the benzophenone ultraviolet absorber (benzophenone compound) and oxybenzophenone ultraviolet absorber (oxybenzophenone compound) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy. -4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 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、フェニル－２－アクリロイルオキシベンゾエ－ト、フェニル－２－アクロリイルオキシ－３－メチルベンゾエ－ト、フェニル－２－アクリロイルオキシ－４－メチルベンゾエ－ト、フェニル－２－アクリロイルオキシ－５－メチルベンゾエ－ト、フェニル－２－アクリロイルオキシ－３－メトキシベンゾエ－ト、フェニル－２－ヒドロキシベンゾエ－ト、フェニル－２－ヒドロキシ－３－メチルベンゾエ－ト、フェニル－２－ヒドロキシ－４メチルベンゾエ－ト、フェニル－２－ヒドロキシ－５－メチルベンゾエ－ト、フェニル２－ヒドロキシ－３－メトキシベンゾエ－ト、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製）等を挙げることができる。 Examples of the salicylic acid ester ultraviolet absorber (salicylic acid ester compound) include, for example, phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, and phenyl-2-acryloyloxy. -4-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl-2-hydroxy -3-methyl benzoate, phenyl-2-hydroxy-4 methyl benzoate, phenyl-2-hydroxy-5-methyl benzoate, phenyl 2-hydroxy-3-methoxy benzoate, 2,4-di-tert -Butylphenyl-3,5-di-tert- Chill-4-hydroxybenzoate (TINUVIN120, manufactured by BASF), and the like.
　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 ultraviolet absorber (cyanoacrylate compound) include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl- Examples include 2-cyanoacrylate.
　また、紫外線吸収剤として、例えば、商品名「ＦＤＢ－００１」（山田化学工業（株）製）、商品名「ＳＭＰ－１２２」（林原（株）製）、アゾメチン化合物（商品名：ＢＯＮＡＳＯＲＢ　ＵＡ－３９１１、オリエント化学工業（株）製）、インドール化学物（商品名：ＢＯＮＡＳＯＲＢ　ＵＡ－３７０１、オリエント化学工業（株）製）、Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ５４（商品名：ＫＡＹＡＳＥＴ　ＹＥＬＬＯＷ　ＡＧ、日本化薬（株）製）、キノフタロン化合物（商品名：ＭＳ　ＹＥＬＬＯＷ　ＨＤ－１３７、山田化学工業（株）製）、Ｓｏｌｖｅｎｔ　Ｙeｌｌoｗ９３（ＰＬＡＳＴＹＥＬＬＯＷ　８０００、有本化学工業（株）製）、Ｓｏｌｖｅｎｔ　Ｙeｌｌoｗ１６３（ＫＰ　Ｐｌａｓｔ　Ｙｅｌｌｏｗ　ＭＫ、紀和化学工業（株）製）等の染料を用いることもできる。 Examples of the ultraviolet absorber include, for example, trade name “FDB-001” (manufactured by Yamada Chemical Co., Ltd.), trade name “SMP-122” (manufactured by Hayashibara), azomethine compound (trade name: BONASORB UA 3911, manufactured by Orient Chemical Industry Co., Ltd.), indole chemicals (trade name: BONASORB UA-3701, manufactured by Orient Chemical Industry Co., Ltd.), Disperse Yellow 54 (trade name: KAYASET YELLOW AG, manufactured by Nippon Kayaku Co., Ltd.) , Quinophthalone compound (trade name: MS YELLOW HD-137, manufactured by Yamada Chemical Co., Ltd.), Solvent Yellow91 (PLASTYELLOW 8000, manufactured by Arimoto Chemical Industry Co., Ltd.), Solvent Yellow 163 (KP Plastic Yellow MK, Kiwa Chemical Industries) Dye etc. made by Co., Ltd. can also be used.
　前記紫外線吸収剤は、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、（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、０．１～５重量部程度であることが好ましく、０．５～３重量部程度であることがより好ましい。紫外線吸収剤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 absorber may be used alone or in combination of two or more, but the total content is a monofunctional monomer component that forms a (meth) acrylic polymer. The amount is preferably about 0.1 to 5 parts by weight, more preferably about 0.5 to 3 parts by weight with respect to 100 parts by weight. By making the addition amount of the ultraviolet absorber within the above range, it is preferable that the ultraviolet ray absorbing function of the pressure-sensitive adhesive layer can be sufficiently exhibited, and when the ultraviolet polymerization is performed, the polymerization is not hindered.
　（１－３）シランカップリング剤
　さらに、本発明で用いるアクリル系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。 (1-3) Silane Coupling Agent Furthermore, the acrylic pressure-sensitive adhesive composition used in 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 based on 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 epoxy cyclohexyl). Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, (3-dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane ( (Meth) acrylic group-containing sila Coupling agents, such as isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like.
　（１－４）架橋剤
　本発明で用いるアクリル系粘着剤組成物は、架橋剤を含有することができる。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、過酸化物等の架橋剤が含まれる。架橋剤は１種を単独で又は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。 (1-4) Crosslinking agent The acrylic pressure-sensitive adhesive composition used in the present invention may contain a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Crosslinkers such as oxides are included. A crosslinking agent 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、（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、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重量部が得に好ましい。 The crosslinking agent may be used alone or in combination of two or more, but the total content is a monofunctional monomer that forms a (meth) acrylic polymer. 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 0.02 to 3 parts by weight with respect to 100 parts by weight of the component. It is preferable to obtain.
　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又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。 The isocyanate-based cross-linking agent refers to a compound having two or more isocyanate groups (including an isocyanate-regenerating functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification) in one molecule. Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
　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, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, 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.), hexamethyle Isocyanurate of diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like, 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); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols, isocyanurate bond, burette bond, Examples thereof include polyisocyanates polyfunctionalized with allophanate bonds.
　（１－５）その他添加剤
　本発明で用いるアクリル系粘着剤組成物には、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；酸化防止剤等が挙げられる。 (1-5) Other additives The acrylic pressure-sensitive adhesive composition used in the present invention may contain appropriate additives in addition to the components described above, depending on the application. For example, tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc., solid, semi-solid, or liquid at room temperature); fillers such as hollow glass balloons; plasticizers; aging Inhibitors; antioxidants and the like.
　（１－６）視認側粘着剤層の形成方法
　本発明において、前記アクリル系粘着剤組成物は、基材上に塗布等する作業に適した粘度に調整するのが好ましい。アクリル系粘着剤組成物の粘度の調整は、例えば、増粘性添加剤等の各種ポリマーや多官能性モノマー等の添加や、アクリル系粘着剤組成物中のモノマー成分を部分重合させることにより行う。なお、当該部分重合は、増粘性添加剤等の各種ポリマーや多官能性モノマー等を添加する前に行っても良く、その後に行っても良い。上記アクリル系粘着剤組成物の粘度は添加剤の量等によって変わるため、アクリル系粘着剤組成物中のモノマー成分を部分重合させる場合の重合率は、一意に決めることはできないが、目安としては２０％以下程度であることが好ましく、３～２０％程度がより好ましく、５～１５％程度がさらに好ましい。２０％を超えると粘度が高くなりすぎるため、基材へ塗布が難しくなる。 (1-6) Method for Forming Visualizing Pressure-Sensitive Adhesive Layer In the present invention, the acrylic pressure-sensitive adhesive composition is preferably adjusted to have a viscosity suitable for work such as coating on a substrate. Adjustment of the viscosity of the acrylic pressure-sensitive adhesive composition is performed, for example, by adding various polymers such as thickening additives, polyfunctional monomers, or the like, or by partially polymerizing monomer components in the acrylic pressure-sensitive adhesive composition. The partial polymerization may be performed before or after adding various polymers such as thickening additives, polyfunctional monomers, and the like. Since the viscosity of the acrylic pressure-sensitive adhesive composition varies depending on the amount of the additive and the like, the polymerization rate when the monomer component in the acrylic pressure-sensitive adhesive composition is partially polymerized cannot be uniquely determined. It is preferably about 20% or less, more preferably about 3 to 20%, still more preferably about 5 to 15%. If it exceeds 20%, the viscosity becomes too high, so that it is difficult to apply to the substrate.
　視認側粘着剤層は、前記アクリル系粘着剤組成物を基材の少なくとも片面に塗工し、当該アクリル系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、又は、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。 The viewing-side pressure-sensitive adhesive layer is formed by coating the acrylic pressure-sensitive adhesive composition on at least one side of the substrate and drying the coating film formed from the acrylic pressure-sensitive adhesive composition, or by ultraviolet rays or the like It can be formed by irradiation with active energy rays.
　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。視認側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、当該視認側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。 The substrate is not particularly limited, and for example, various substrates such as a release film and a transparent resin film substrate, and a polarizing film described later can also be suitably used as the substrate. When the viewing-side pressure-sensitive adhesive layer is formed on a substrate other than the polarizing film, the viewing-side pressure-sensitive adhesive layer can be attached to the polarizing film and transferred.
　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、及びこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点から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 films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Suitable thin leaf bodies and the like can be mentioned, but a resin film is suitably used from the viewpoint of excellent 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。 Examples of the resin film include 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, and ethylene. -Vinyl acetate copolymer film and the like.
　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及び防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理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. For the release film, if necessary, release agent and antifouling treatment with silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment 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、ポリイミド系樹脂及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, and various resin films having transparency are used. The resin film is formed of a single layer film. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of 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.
　上記アクリル系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 acrylic pressure-sensitive adhesive composition onto the substrate is roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat. Any known appropriate method such as curtain coating, lip coating, or die coater can be used without particular limitation.
　視認側粘着剤層は、前記アクリル系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。 When the visible-side pressure-sensitive adhesive layer is formed by drying a coating film formed from the acrylic pressure-sensitive adhesive composition, the drying conditions (temperature, time) are not particularly limited, and the pressure-sensitive adhesive composition The temperature can be appropriately set depending on the composition, concentration, etc., but is, for example, about 60 to 170 ° C., preferably 60 to 150 ° C. for 1 to 60 minutes, preferably 2 to 30 minutes.
　前記アクリル系粘着剤組成物が紫外線硬化型アクリル系粘着剤組成物であって、当該紫外線硬化型アクリル系粘着剤組成物から形成される塗布膜に紫外線を照射して形成する場合、照射する紫外線の照度は、５ｍＷ／ｃｍ２以上が好ましい。当該紫外線の照度が５ｍＷ／ｃｍ２未満であると、重合反応時間が長くなり、生産性に劣ることがある。なお、当該紫外線の照度は２００ｍＷ／ｃｍ２以下が好ましい。当該紫外線の照度が２００ｍＷ／ｃｍ２を超えると、光重合開始剤が急激に消費されるため、重合体の低分子量化が起こり、特に高温での保持力が低下することがある。また、紫外線の積算光量は、１００ｍＪ／ｃｍ２～５０００ｍＪ／ｃｍ２であることが好ましい。 When the acrylic pressure-sensitive adhesive composition is an ultraviolet curable acrylic pressure-sensitive adhesive composition and is formed by irradiating a coating film formed from the ultraviolet-curable acrylic pressure-sensitive adhesive composition with ultraviolet rays, the ultraviolet rays to be irradiated The illuminance is preferably 5 mW / cm 2 or more. When the illuminance of the ultraviolet light is less than 5 mW / cm 2 , the polymerization reaction time becomes long and the productivity may be inferior. The illuminance of the ultraviolet light is preferably 200 mW / cm 2 or less. When the illuminance of the ultraviolet rays exceeds 200 mW / cm 2 , the photopolymerization initiator is consumed rapidly, so that the polymer has a low molecular weight, and the holding power particularly at high temperatures may be reduced. Further, the integrated quantity of ultraviolet light is preferably 100mJ / cm 2 ~ 5000mJ / cm 2.
　本発明に用いられる紫外線ランプは、特に限定されるものではないが、ＬＥＤランプが好ましい。ＬＥＤランプは他の紫外線ランプに比べて放出熱が低いランプであるため、粘着剤層の重合中の温度を抑えることができる。そのため、重合体の低分子量化を防ぐことができ、粘着剤層の凝集力の低下を防ぐとともに粘着シートとした場合の高温における保持力を高めることができる。また、複数の紫外線ランプを組み合わせることも可能である。また、紫外線を間欠的に照射し、紫外線を照射する明期と紫外線を照射しない暗期とを設けることもできる。 The ultraviolet lamp used in the present invention is not particularly limited, but an LED lamp is preferable. Since the LED lamp has a lower emission heat than other ultraviolet lamps, the temperature during polymerization of the pressure-sensitive adhesive layer can be suppressed. Therefore, the molecular weight reduction of the polymer can be prevented, the cohesive strength of the pressure-sensitive adhesive layer can be prevented from being lowered, and the holding power at a high temperature when the pressure-sensitive adhesive sheet is used can be increased. It is also possible to combine a plurality of ultraviolet lamps. Further, it is possible to intermittently irradiate ultraviolet rays, and to provide a light period in which ultraviolet rays are irradiated and a dark period in which ultraviolet rays are not irradiated.
　本発明において、紫外線硬化型アクリル系粘着剤組成物中のモノマー成分の最終的な重合率は９０％以上が好ましく、９５％以上がより好ましく、９８％以上が更に好ましい。 In the present invention, the final polymerization rate of the monomer component in the ultraviolet curable acrylic pressure-sensitive adhesive composition is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.
　本発明において、上記紫外線硬化型アクリル系粘着剤組成物に照射する紫外線のピーク波長は、２００～５００ｎｍの範囲内にあることが好ましく、３００～４５０ｎｍの範囲内にあることがより好ましい。紫外線のピーク波長が５００ｎｍを超えると、光重合開始剤が分解せず、重合反応が開始しないことがある。また、紫外線のピーク波長が２００ｎｍ未満であると、ポリマー鎖が切断され、接着特性が低下することがある。 In the present invention, the peak wavelength of ultraviolet rays irradiated to the ultraviolet curable acrylic pressure-sensitive adhesive composition is preferably in the range of 200 to 500 nm, and more preferably in the range of 300 to 450 nm. When the peak wavelength of ultraviolet rays exceeds 500 nm, the photopolymerization initiator may not be decomposed and the polymerization reaction may not start. On the other hand, if the peak wavelength of the ultraviolet light is less than 200 nm, the polymer chain may be cut and the adhesive properties may be deteriorated.
　反応は空気中の酸素に阻害されるため、酸素を遮断するために、紫外線硬化型アクリル系粘着剤組成物から形成される塗布膜上に離型フィルム等を形成したり、光重合反応を窒素雰囲気下で行ったりすることが好ましい。離型フィルムとしては、前述のものを挙げることができる。なお、離型フィルムを用いた場合、当該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る。 Since the reaction is inhibited by oxygen in the air, a release film or the like is formed on the coating film formed from the ultraviolet curable acrylic pressure-sensitive adhesive composition to block oxygen, or the photopolymerization reaction is performed by nitrogen. It is preferable to carry out in an atmosphere. The above-mentioned thing can be mentioned as a release film. In addition, when a release film is used, the said release film can be used as a separator of a polarizing film with an adhesive layer as it is.
　また、本発明で用いる紫外線硬化型アクリル系粘着剤組成物が、光重合開始剤（Ｂ）を含有する場合は、アルキル（メタ）アクリレートを含有するモノマー成分と前記光重合開始剤（Ｂ）（「前添加重合開始剤」ということもある）を含む組成物に紫外線を照射して、前記モノマー成分の部分重合物を形成し、前記モノマー成分の部分重合物に、紫外線吸収剤、並びに波長４００ｎｍ以上に吸収帯を有する光重合開始剤（Ａ）（「後添加重合開始剤」ということもある）を添加して、紫外線硬化型アクリル系粘着剤組成物を作製することが好ましい。部分重合物の重合率は、２０％以下程度であることが好ましく、３～２０％程度がより好ましく、５～１５％程度がさらに好ましい。紫外線の照射条件は前述の通りである。 Moreover, when the ultraviolet curable acrylic adhesive composition used by this invention contains a photoinitiator (B), the monomer component containing an alkyl (meth) acrylate and the said photoinitiator (B) ( The composition containing the “pre-added polymerization initiator” is irradiated with ultraviolet rays to form a partial polymer of the monomer component, and the partial polymerization product of the monomer component contains an ultraviolet absorber and a wavelength of 400 nm. It is preferable to prepare a UV-curable acrylic pressure-sensitive adhesive composition by adding the photopolymerization initiator (A) having an absorption band (sometimes referred to as “post-addition polymerization initiator”). The polymerization rate of the partially polymerized product is preferably about 20% or less, more preferably about 3 to 20%, and further preferably about 5 to 15%. The ultraviolet irradiation conditions are as described above.
　前述の通り、光重合開始剤（Ｂ）を含有する紫外線硬化型アクリル系粘着剤組成物から粘着剤層を形成する場合、前述のような２段階で重合することにより、モノマー成分の重合率を上げることができ、かつ、最終的に作製された粘着剤層の紫外線吸収機能を向上することができる。 As described above, when the pressure-sensitive adhesive layer is formed from the ultraviolet curable acrylic pressure-sensitive adhesive composition containing the photopolymerization initiator (B), the polymerization rate of the monomer component is increased by performing polymerization in the two steps as described above. In addition, the ultraviolet absorbing function of the finally produced pressure-sensitive adhesive layer can be improved.
　前記視認側粘着剤層の厚さは、紫外線吸収機能を確保する観点から、後述する偏光フィルムの画像表示部側の粘着剤層（画像表示部側粘着剤層）の厚さの２倍以上であることが好ましく、５倍以上であることがより好ましく、１０倍以上であることがさらに好ましい。具体的には、前記視認側粘着剤層の厚さは、５０μｍ以上であることが好ましく、１００μｍ以上であることがより好ましく、１５０μｍ以上であることがさらに好ましい。視認側粘着剤層の厚さの上限値は特に限定されないが、１０ｍｍ以下であることが好ましい。粘着剤層の厚さが１０ｍｍ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り、生産性が劣る場合があるため、好ましくない。 The thickness of the visual recognition side pressure-sensitive adhesive layer is at least twice the thickness of the pressure-sensitive adhesive layer (image display part-side pressure-sensitive adhesive layer) on the image display part side of the polarizing film described later from the viewpoint of ensuring the ultraviolet absorption function. Preferably, it is 5 times or more, more preferably 10 times or more. Specifically, the thickness of the viewing-side pressure-sensitive adhesive layer is preferably 50 μm or more, more preferably 100 μm or more, and further preferably 150 μm or more. Although the upper limit of the thickness of a visual recognition side adhesive layer is not specifically limited, It is preferable that it is 10 mm or less. If the thickness of the pressure-sensitive adhesive layer exceeds 10 mm, it is difficult to transmit ultraviolet rays, and it takes time to polymerize the monomer component, which may be inferior in productivity.
　本発明の視認側粘着剤層のゲル分率は、特に限定されるものではないが、３５％以上であることが好ましく、５０％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。視認側粘着剤層のゲル分率が小さい場合には凝集力に劣り、大きすぎると接着力に劣る場合がある。 Although the gel fraction of the visual recognition side adhesive layer of this invention is not specifically limited, It is preferable that it is 35% or more, It is more preferable that it is 50% or more, It is further that it is 75% or more It is preferably 85% or more. When the gel fraction of the visible-side pressure-sensitive adhesive layer is small, the cohesive force is inferior, and when it is too large, the adhesive force may be inferior.
　前記視認側粘着剤層の透過ｂ＊値は、特に限定されないが、３.０以下であることが好ましく、１．５以下であることがより好ましく、０．５以下であることがさらに好ましい。上記ｂ*値とは、ＪＩＳ　Ｚ８７２９に準拠したＬ＊ａ＊ｂ＊表色系におけるｂ＊値（色度）を指し、例えば、分光光度計（製品名：Ｕ４１００、（株）日立ハイテクノロジーズ製）を用いて測定することができる。 The permeation b * value of the viewing side pressure-sensitive adhesive layer is not particularly limited, but is preferably 3.0 or less, more preferably 1.5 or less, and even more preferably 0.5 or less. The b * value refers to the b * value (chromaticity) in the L * a * b * color system conforming to JIS Z8729. For example, a spectrophotometer (product name: U4100, manufactured by Hitachi High-Technologies Corporation) ).
　前記視認側粘着剤層の波長３８０ｎｍにおける透過率が、９％以下であることが好ましく、７％以下であることがより好ましく、５％以下であることがさらに好ましく、３％以下であることが特に好ましい。波長３８０ｎｍにおける透過率が前記範囲であることにより、入射する紫外線をより高度に遮断することができるため、液晶パネル、有機ＥＬ素子、偏光子等をはじめとする光学部材の劣化を著しく抑制することができる。 The transmittance of the viewing side pressure-sensitive adhesive layer at a wavelength of 380 nm is preferably 9% or less, more preferably 7% or less, further preferably 5% or less, and more preferably 3% or less. Particularly preferred. Since the transmittance at a wavelength of 380 nm is within the above range, incident ultraviolet rays can be blocked to a higher degree, so that deterioration of optical members such as liquid crystal panels, organic EL elements, polarizers, etc. is remarkably suppressed. Can do.
　前記視認側粘着剤層の波長４００ｎｍにおける透過率が、６０％以上であることが好ましく、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い。波長４００ｎｍにおける透過率が前記範囲であることにより、入射する可視光を十分の透過することができ、画像表示装置において十分な視認性を確保できるため好ましい。 The transmittance of the viewing-side pressure-sensitive adhesive layer at a wavelength of 400 nm is preferably 60% or more, preferably 70% or more, and more preferably 75% or more. When the transmittance at a wavelength of 400 nm is within the above range, it is preferable because the incident visible light can be sufficiently transmitted and sufficient visibility can be secured in the image display device.
　また、本発明の粘着剤層付偏光フィルムを有機ＥＬ表示装置（ＯＬＥＤ）に用いる場合、前記視認側粘着剤層の波長４２０ｎｍにおける透過率が、７５％以下であることが好ましく、５０％以下であることがより好ましく、４０％以下であることがさらに好ましい。波長４２０ｎｍにおける透過率が前記範囲であることにより、ＯＬＥＤの発光素子保護の観点から好ましい。 Moreover, when using the polarizing film with an adhesive layer of this invention for an organic electroluminescence display (OLED), it is preferable that the transmittance | permeability in wavelength 420nm of the said visual recognition side adhesive layer is 75% or less, and is 50% or less. More preferably, it is more preferably 40% or less. The transmittance at a wavelength of 420 nm is in the above range, which is preferable from the viewpoint of protecting the light emitting element of the OLED.
　前記視認側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。なお、前記離型フィルムは、そのまま粘着剤層付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。 When the viewing-side pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until practical use. In addition, the said release film can be used as a separator of a polarizing film with an adhesive layer as it is, and can simplify in a process surface.
　（２）画像表示部側粘着剤層
　偏光フィルムの画像表示部側表面の粘着剤層（画像表示部側粘着剤層）としては、特に限定されるものではなく、前記視認側粘着剤層で詳述したアクリル系粘着剤組成物と同様のものを用いてもよく、通常用いられる各種粘着剤層を用いることができる。 (2) Image display part side adhesive layer It does not specifically limit as an adhesive layer (image display part side adhesive layer) of the image display part side surface of a polarizing film, It is detailed in the said visual recognition side adhesive layer. The same acrylic adhesive composition as described above may be used, and various adhesive layers that are usually used can be used.
　画像表示部側表面の粘着剤層の形成には、適宜な粘着剤を用いることができ、その種類について特に制限はない。粘着剤としては、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が挙げられる。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。 An appropriate pressure-sensitive adhesive can be used for forming the pressure-sensitive adhesive layer on the image display unit side surface, and the type thereof is not particularly limited. Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate adhesiveness, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like. .
　アクリル系粘着剤は、（メタ）アクリル酸アルキルエステルのモノマーユニットを主骨格とするアクリル系ポリマーをベースポリマーとする。アクリル系ポリマーの主骨格を構成する、（メタ）アクリル酸アルキルエステルとしては、視認側粘着剤層を形成するアクリル系粘着剤組成物に用いるものと同様のものを挙げることができる。また、共重合モノマーやその割合としても、前記アクリル系粘着剤組成物に用いるものと同様のものを挙げることができる。 The acrylic adhesive is based on an acrylic polymer having a monomer unit of (meth) acrylic acid alkyl ester as a main skeleton. Examples of the (meth) acrylic acid alkyl ester constituting the main skeleton of the acrylic polymer may include the same ones as those used for the acrylic pressure-sensitive adhesive composition forming the viewing-side pressure-sensitive adhesive layer. Moreover, the same thing as what is used for the said acrylic adhesive composition can also be mentioned as a copolymerization monomer and its ratio.
　前記アクリル系ポリマーの製造は、各種公知の手法により製造でき、例えば、バルク重合法、溶液重合法、懸濁重合法等のラジカル重合法を適宜選択できる。ラジカル重合開始剤としては、アゾ系、過酸化物系の各種公知のものを使用できる。反応温度は、通常５０～８０℃程度、反応時間は１～８時間とされる。また、前記製造法の中でも溶液重合法が好ましく、アクリル系ポリマーの溶媒としては、一般に酢酸エチル、トルエン等が用いられる。溶液濃度は、通常２０～８０重量％程度とされる。 The acrylic polymer can be produced by various known methods, for example, a radical polymerization method such as a bulk polymerization method, a solution polymerization method, or a suspension polymerization method can be appropriately selected. As the radical polymerization initiator, various known azo and peroxide initiators can be used. The reaction temperature is usually about 50 to 80 ° C., and the reaction time is 1 to 8 hours. Among the above production methods, the solution polymerization method is preferable, and ethyl acetate, toluene and the like are generally used as the solvent for the acrylic polymer. The solution concentration is usually about 20 to 80% by weight.
　また前記粘着剤は、架橋剤を含有する粘着剤組成物とすることができる。架橋剤としても前述のものを挙げることができるが、特に、イソシアネート系架橋剤が好ましい。アクリル系ポリマーと架橋剤の配合割合は特に限定されないが、通常、アクリル系ポリマー（固形分）１００重量部に対して、架橋剤（固形分）０．００１～２０重量部程度であることが好ましく、０．０１～１５重量部程度がより好ましい。 The pressure-sensitive adhesive can be a pressure-sensitive adhesive composition containing a crosslinking agent. Although the above-mentioned thing can also be mentioned as a crosslinking agent, Especially an isocyanate type crosslinking agent is preferable. The blending ratio of the acrylic polymer and the crosslinking agent is not particularly limited, but it is usually preferably about 0.001 to 20 parts by weight of the crosslinking agent (solid content) with respect to 100 parts by weight of the acrylic polymer (solid content). About 0.01 to 15 parts by weight is more preferable.
　さらには、前記粘着剤には、必要に応じて、粘着付与剤、可塑剤、ガラス繊維、ガラスビーズ、金属粉、その他の無機粉末等からなる充填剤、顔料、着色剤、充填剤、酸化防止剤、紫外線吸収剤、シランカップリング剤等を、また本発明の目的を逸脱しない範囲で各種の添加剤を適宜に使用することもできる。また微粒子を含有して光拡散性を示す粘着剤層等としても良い。シランカップリング剤としては、前述のものを挙げることができる。 Furthermore, the pressure-sensitive adhesive may include a tackifier, a plasticizer, glass fiber, glass beads, metal powder, other inorganic powders, a pigment, a colorant, a filler, an antioxidant, if necessary. Various additives may be used as appropriate, such as an agent, an ultraviolet absorber, a silane coupling agent, and the like without departing from the object of the present invention. Moreover, it is good also as an adhesive layer etc. which contain microparticles | fine-particles and show light diffusibility. Examples of the silane coupling agent include those described above.
　画像表示部側粘着剤層は、前記粘着剤組成物を、偏光フィルム又は離型フィルム等の各種基材に塗布し、乾燥することにより形成される。粘着剤層を離型フィルム等の各種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。前記粘着剤の塗布方法、前記各種基材は、前記アクリル系粘着剤組成物の塗布方法、各種基材と同様のものを挙げることができる。 The image display unit side pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition to various substrates such as a polarizing film or a release film and drying. When the pressure-sensitive adhesive layer is formed on various substrates such as a release film, the pressure-sensitive adhesive layer can be attached to a polarizing film and transferred. Examples of the method for applying the pressure-sensitive adhesive and the various base materials include the same methods as those for applying the acrylic pressure-sensitive adhesive composition and various base materials.
　また、前記塗布工程では、形成される粘着剤層が所定の厚み（乾燥後厚み）になるようにその塗布量が制御される。画像表示部側粘着剤層の厚みは、特に限定されるものではないが、視認側粘着剤層の厚さの１／２以下であることが好ましく、１／５以下であることが好ましく、１／１０以下であることが好ましい。画像表示部側粘着剤層の厚さは、具体的には、１～１００μｍ程度であることが好ましく、３～５０μｍ程度がより好ましく、５～３０μｍ程度がさらに好ましい。 In the coating step, the coating amount is controlled so that the formed pressure-sensitive adhesive layer has a predetermined thickness (thickness after drying). The thickness of the image display unit side pressure-sensitive adhesive layer is not particularly limited, but is preferably 1/2 or less, more preferably 1/5 or less of the thickness of the visual recognition side pressure-sensitive adhesive layer. / 10 or less is preferable. Specifically, the thickness of the image display unit side pressure-sensitive adhesive layer is preferably about 1 to 100 μm, more preferably about 3 to 50 μm, and further preferably about 5 to 30 μm.
　画像表示部側粘着剤層の形成にあたっては、塗布された粘着剤に対して乾燥が施される。乾燥温度、乾燥時間は特に限定されるものではなく、適宜設定されるが、例えば、８０～２００℃程度で、０．５～１０分間であることが好ましい。 In the formation of the image display unit side pressure-sensitive adhesive layer, the applied pressure-sensitive adhesive is dried. The drying temperature and drying time are not particularly limited and are set as appropriate. For example, the drying temperature and the drying time are about 80 to 200 ° C. and preferably 0.5 to 10 minutes.
　前記画像表示部側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。なお、前記離型フィルムは、そのまま粘着剤層付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。 When the image display part side pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until practical use. In addition, the said release film can be used as a separator of a polarizing film with an adhesive layer as it is, and can simplify in a process surface.
　（３）偏光フィルム
　本発明で用いる偏光フィルムは、偏光子と当該偏光子の両面に透明保護フィルムを有し、偏光子の視認側の透明保護フィルム（視認側透明保護フィルム）は波長３８０ｎｍにおける透過率は６％未満であることを特徴とする。 (3) Polarizing film The polarizing film used in the present invention has a transparent protective film on both sides of the polarizer and the polarizer, and the transparent protective film on the viewing side of the polarizer (viewing side transparent protective film) transmits at a wavelength of 380 nm. The rate is less than 6%.
　（３－１）視認側透明保護フィルム
　本発明で用いる視認側透明保護フィルムの波長３８０ｎｍにおける透過率は、６％未満であり、３％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く、１％以下であることがさらに好ましい。本発明においては、波長３８０ｎｍにおける透過率が６％未満である視認側透明保護フィルムと、前記視認側粘着剤層（紫外線吸収剤含有）とを組み合わせることによって、より高度な紫外線吸収能力を達成することができるものである。また、視認側透明保護フィルムの波長３８０ｎｍにおける透過率の下限値は特に限定されるものではなく、小さければ小さいほど、紫外線吸収機能の観点から好ましい。 (3-1) Viewing-side transparent protective film The transmittance of the viewing-side transparent protective film used in the present invention at a wavelength of 380 nm is less than 6%, preferably 3% or less, and more preferably 2% or less. Preferably, it is 1% or less. In the present invention, a higher UV absorption capability is achieved by combining a viewing-side transparent protective film having a transmittance of less than 6% at a wavelength of 380 nm and the viewing-side pressure-sensitive adhesive layer (containing an UV absorber). It is something that can be done. Moreover, the lower limit of the transmittance | permeability in wavelength 380nm of the visual recognition side transparent protective film is not specifically limited, The smaller is preferable from a viewpoint of an ultraviolet absorption function.
　視認側透明保護フィルムを形成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れるものが好ましい。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、又は、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。これらの中でも、視認側透明保護フィルムとしては、トリアセチルセルロースフィルム、アクリルフィルム（アクリル系ポリマーを用いたフィルム）、ポリエチレンテレフタレートフィルム、及び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フィルムからなる群から選択される少なくとも１種のフィルムであることが好ましく、トリアセチルセルロースフィルムがより好ましい。 As the material for forming the viewing-side transparent protective film, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone. Among these, the visible-side transparent protective film is selected from the group consisting of a triacetyl cellulose film, an acrylic film (a film using an acrylic polymer), a polyethylene terephthalate film, and a polyolefin film having a cyclo or norbornene structure. At least one film is preferable, and a triacetyl cellulose film is more preferable.
　視認側透明保護フィルムの厚さは、特に限定されないが、４０μｍ以下であることが好ましく、３５μｍ以下であることがより好ましく、３０μｍ以下であることがさらに好ましい。また、視認側透明保護フィルムの厚さの下限値は特に限定されないが、１μｍ以上であることが好ましい。視認側透明保護フィルムの厚さが前記範囲であることで、偏光フィルムの薄型化が十分に達成でき、かつ偏光子の保護機能を損なうことがないため好ましい。 The thickness of the viewing-side transparent protective film is not particularly limited, but is preferably 40 μm or less, more preferably 35 μm or less, and further preferably 30 μm or less. Moreover, the lower limit value of the thickness of the viewing-side transparent protective film is not particularly limited, but is preferably 1 μm or more. It is preferable that the thickness of the viewing-side transparent protective film is in the above range because the polarizing film can be sufficiently thinned and the protective function of the polarizer is not impaired.
　後述する偏光子と視認側保護フィルムとは、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、偏光子と視認側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。 It is preferable that the polarizer and the viewing-side protective film described later are in close contact with each other via an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive between the polarizer and the viewing-side transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesiveness with respect to the various viewing-side transparent protective films. The adhesive used in the present invention can contain a metal compound filler.
　前記視認側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 viewing side transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
　（３－２）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。 (3-2) Polarizer The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed 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 dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even 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. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
　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、又は特許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り得ることができる。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。 As the thin polarizer, typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or a patent. The thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
　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、又は特許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。 As the thin polarizing film, International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing. In particular, those obtained by a production method including a step of stretching in an aqueous boric acid solution as described in International Publication No. 2010/100917 pamphlet or Japanese Patent No. 47514881 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable. Those obtained by a production method including a step of stretching in the air before stretching in a boric acid aqueous solution described in the specification of 4751481 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
　（３－３）画像表示部側透明保護フィルム
　画像表示側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、又は、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。 (3-3) Image Display Side Transparent Protective Film As the image display side transparent protective film, those conventionally used can be appropriately used. Specifically, a transparent protective film formed from a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable. For example, a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate , Cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin), and polycarbonate polymers. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
　画像表示部側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 protective film on the image display portion side can be determined as appropriate, but is generally about 1 to 500 μm from the viewpoint of workability such as strength and handleability and thin film properties.
　前記偏光子と画像表示部側透明保護フィルムも、通常、水系接着剤等を介して密着している。水系接着剤としては、前述のものを挙げることができる。 The polarizer and the image display unit side transparent protective film are also usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include those described above.
　前記画像表示部側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 image display portion side transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
２．画像表示装置
　本発明の画像表示装置は、本発明の粘着剤層付き偏光フィルムを用いたことを特徴とする。 2. Image Display Device The image display device of the present invention is characterized by using the polarizing film with an adhesive layer of the present invention.
　画像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、カバーガラス又はカバープラスチック６／視認側粘着剤層２ａ／視認側透明保護フィルム３ａ／偏光子４／画像表示部側透明保護フィルム３ｂ／画像表示部側粘着剤層２ｂ／液晶表示装置（ＬＣＤ）又は有機ＥＬ表示装置（ＯＬＥＤ）７（図２）；カバーガラス又はカバープラスチック６／粘着剤層８ａ／センサー層９／視認側粘着剤層２ａ／視認側透明保護フィルム３ａ／偏光子４／画像表示部側透明保護フィルム３ｂ／画像表示部側粘着剤層２ｂ／液晶表示装置（ＬＣＤ）又は有機ＥＬ表示装置（ＯＬＥＤ）７（図３）；カバーガラス又はカバープラスチック６／粘着剤層８ａ／センサー層９／粘着剤層８ｂ／センサー層９／視認側粘着剤層２ａ／視認側透明保護フィルム３ａ／偏光子４／画像表示部側透明保護フィルム３ｂ／画像表示部側粘着剤層２ｂ／液晶表示装置（ＬＣＤ）又は有機ＥＬ表示装置（ＯＬＥＤ）７（図４）；のように、各層がこの順に積層された画像表示装置を挙げることができる。本発明の粘着剤層付き偏光フィルム１は、前述の構成中、「視認側粘着剤層２ａ／視認側透明保護フィルム３ａ／偏光子４／画像表示部側透明保護フィルム３ｂ／画像表示部側粘着剤層２ｂ」の部分をいい、これら以外にも位相差フィルム等を含んでいてもよい。また、位相差フィルムを含む場合、具体的には、前記画像表示部側粘着剤層２ｂと液晶表示装置（ＬＣＤ）又は有機ＥＬ表示装置（ＯＬＥＤ）７との間に粘着剤層を介して積層することができる。また、各層の積層において、適宜粘着剤層及び／又は接着剤層を用いることができる。 As an example of a specific configuration of the image display device, for example, as shown in FIGS. 2 to 4, a cover glass or cover plastic 6 / viewing side pressure-sensitive adhesive layer 2a / viewing side transparent protective film 3a / polarizer 4 / Image display unit side transparent protective film 3b / Image display unit side adhesive layer 2b / Liquid crystal display (LCD) or organic EL display unit (OLED) 7 (FIG. 2); Cover glass or cover plastic 6 / Adhesive layer 8a / Sensor layer 9 / Viewing side adhesive layer 2a / Viewing side transparent protective film 3a / Polarizer 4 / Image display unit side transparent protective film 3b / Image display unit side adhesive layer 2b / Liquid crystal display (LCD) or organic EL display Device (OLED) 7 (FIG. 3); cover glass or cover plastic 6 / adhesive layer 8a / sensor layer 9 / adhesive layer 8b / sensor layer 9 / viewing side adhesive layer 2a / visible Transparent protective film 3a / polarizer 4 / image display part side transparent protective film 3b / image display part side adhesive layer 2b / liquid crystal display device (LCD) or organic EL display device (OLED) 7 (FIG. 4); An image display device in which each layer is laminated in this order can be given. The polarizing film 1 with the pressure-sensitive adhesive layer of the present invention is “viewing-side pressure-sensitive adhesive layer 2a / viewing-side transparent protective film 3a / polarizer 4 / image display unit-side transparent protective film 3b / image display unit-side pressure-sensitive adhesive”. It refers to the portion of the agent layer 2b "and may contain a retardation film or the like other than these. When a retardation film is included, specifically, the image display unit side adhesive layer 2b and a liquid crystal display device (LCD) or an organic EL display device (OLED) 7 are laminated via an adhesive layer. can do. Moreover, in lamination | stacking of each layer, an adhesive layer and / or an adhesive layer can be used suitably.
　画像表示装置としては、液晶表示装置、有機ＥＬ（エレクトロルミネッセンス）表示装置、ＰＤＰ（プラズマディスプレイパネル）、電子ペーパー等が挙げられるが、これらの中でも、前述の構成を有する液晶表示装置、有機ＥＬ（エレクトロルミネッセンス）表示装置等が好ましい。 Examples of the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper. Among these, a liquid crystal display device having the above-described configuration, an organic EL ( An electroluminescence display device or the like is preferable.
　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、各例中の部及び％はいずれも重量基準である。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight.
　製造例１（アクリル系粘着剤組成物（ａ－１）の製造）
　アクリル酸２－エチルヘキシル（２ＥＨＡ）７８重量部、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）１８重量部、及びアクリル酸２－ヒドロキシエチル（ＨＥＡ）４重量部から構成されるモノマー混合物に、光重合開始剤として、１－ヒドロキシシクロヘキシルフェニルケトン（商品名：イルガキュア１８４、波長２００～３７０ｎｍに吸収帯を有する、ＢＡＳＦ社製）０．０３５重量部、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名：イルガキュア６５１、波長２００～３８０ｎｍに吸収帯を有する、ＢＡＳＦ社製）０．０３５重量部を配合した後、粘度（計測条件：ＢＨ粘度計Ｎｏ.５ローター、１０ｒｐｍ、測定温度３０℃）が約２０Ｐａ・ｓになるまで紫外線を照射して、上記モノマー成分の一部が重合したプレポリマー組成物（重合率：８％）を得た。次に、該プレポリマー組成物に、ヘキサンジオールジアクリレート（ＨＤＤＡ）０．１５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）０．３重量部を添加して混合し、アクリル系粘着剤組成物（ａ－１）を得た。 Production Example 1 (Production of acrylic pressure-sensitive adhesive composition (a-1))
Photopolymerization started on a monomer mixture composed of 78 parts by weight of 2-ethylhexyl acrylate (2EHA), 18 parts by weight of N-vinyl-2-pyrrolidone (NVP), and 4 parts by weight of 2-hydroxyethyl acrylate (HEA). As an agent, 0.035 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, having an absorption band at a wavelength of 200 to 370 nm, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane-1 -ON (trade name: Irgacure 651, having an absorption band at a wavelength of 200 to 380 nm, manufactured by BASF) 0.035 parts by weight, and then viscosity (measurement conditions: BH viscometer No. 5 rotor, 10 rpm, measurement temperature) (30 ° C.) is irradiated with ultraviolet rays until it reaches about 20 Pa · s, and a prepolymer in which a part of the monomer component is polymerized. A polymer composition (polymerization rate: 8%) was obtained. Next, 0.15 parts by weight of hexanediol diacrylate (HDDA) and 0.3 parts by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) are added to the prepolymer composition. To obtain an acrylic pressure-sensitive adhesive composition (a-1).
　製造例２　（アクリル系粘着剤組成物（ａ－２）の製造）
　２－エチルヘキシルアクリレート（２ＥＨＡ）７２重量部、メタクリル酸アクリレート（ＭＭＡ）１重量部、Ｎ－ビニルピロリドン（ＮＶＰ）１２重量部、ヒドロキシエチルアクリレート（ＨＥＡ）１５重量部から構成されるモノマー混合物に、重合開始剤として、アゾビスブチルニトリル（ＡＩＢＮ）０．２重量部、及び酢酸エチル２３３重量部を投入した後、窒素雰囲気下、６０℃で７時間反応させることで上記モノマー成分の一部が重合した部分重合物を得た。次に、該部分重合物に、シランカップリング剤（商品名：ＫＢＭ－４０３、信越化学工業（株）製）０．３重量部、架橋剤としてイソシアネート系架橋剤（商品名：タケネートＤ１１０Ｎ、三井化学（株）製）０．２１重量部を添加して、アクリル系粘着剤組成物（ａ－２）を得た。 Production Example 2 (Production of acrylic pressure-sensitive adhesive composition (a-2))
Polymerized into a monomer mixture composed of 72 parts by weight of 2-ethylhexyl acrylate (2EHA), 1 part by weight of methacrylic acid acrylate (MMA), 12 parts by weight of N-vinylpyrrolidone (NVP), and 15 parts by weight of hydroxyethyl acrylate (HEA) As an initiator, 0.2 parts by weight of azobisbutylnitrile (AIBN) and 233 parts by weight of ethyl acetate were added and then reacted at 60 ° C. for 7 hours in a nitrogen atmosphere to partially polymerize the monomer components. A partially polymerized product was obtained. Next, 0.3 parts by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and an isocyanate-based cross-linking agent (trade name: Takenate D110N, Mitsui) as a cross-linking agent were added to the partially polymerized product. Acrylic pressure-sensitive adhesive composition (a-2) was obtained by adding 0.21 part by weight of Chemical Co., Ltd.
　製造例３（画像表示部側粘着剤層（Ｂ－１）の製造）
　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。
　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）上に、得られた粘着剤組成物溶液を、乾燥後の厚さが１２μｍ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、粘着剤層を得た。その後、５０℃で４８時間加熱して架橋処理を行った。以下、この粘着剤層を「画像表示部側粘着剤層（Ｂ－１）」と言う。 Production Example 3 (Production of image display part side adhesive layer (B-1))
In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, 95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 part by weight of azobisisobutyronitrile as a polymerization initiator, and After 233 parts by weight of ethyl acetate was added, nitrogen gas was passed, and nitrogen substitution 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.
To the acrylic polymer solution (with a solid content of 100 parts by weight), 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate crosslinking agent, A pressure-sensitive adhesive composition (solution) was prepared by adding 0.1 part by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
The obtained pressure-sensitive adhesive composition solution was applied onto a 38 μm thick separator (polyethylene terephthalate film whose surface was peeled) so that the thickness after drying was 12 μm, and dried at 100 ° C. for 3 minutes. The solvent was removed by layering to obtain an adhesive layer. Then, the crosslinking process was performed by heating at 50 degreeC for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as “image display portion side pressure-sensitive adhesive layer (B-1)”.
　製造例４（画像表示部側粘着剤層（Ｂ－２）の製造）
　厚さ３８μｍのセパレータ（表面が離型処理されたポリエチレンテレフタレート系フィルム）上に、製造例３で得られた粘着剤組成物溶液を、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、粘着剤層を得た。その後、５０℃で４８時間加熱して架橋処理を行った。以下、この粘着剤層を「画像表示部側粘着剤層（Ｂ－２）」と言う。 Production Example 4 (Production of image display part side adhesive layer (B-2))
The pressure-sensitive adhesive composition solution obtained in Production Example 3 was applied on a 38 μm-thick separator (polyethylene terephthalate film whose surface was release-treated) so that the thickness after drying was 15 μm. The solvent was removed by drying at 3 ° C. for 3 minutes to obtain a pressure-sensitive adhesive layer. Then, the crosslinking process was performed by heating at 50 degreeC for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as “image display portion side pressure-sensitive adhesive layer (B-2)”.
　実施例１
　（紫外線吸収機能付き粘着剤組成物の製造）
　得られたアクリル系粘着剤組成物（ａ－１）に、ブチルアクリレートに固形分１５％となるように溶解させた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、表１、２中の「紫外線吸収剤１」、ＢＡＳＦジャパン社製）１．４重量部と、ビス(２，４，６－トリメチルベンゾイル)－フェニルフォスフィンオキサイド（商品名：イルガキュア８１９、波長２００～４５０ｎｍに吸収耐を有する、ＢＡＳＦジャパン社製）０．２重量部を添加し撹拌することにより紫外線吸収機能付き粘着剤組成物を得た。 Example 1
(Manufacture of pressure-sensitive adhesive composition with ultraviolet absorption function)
2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy dissolved in butyl acrylate to a solid content of 15% in the obtained acrylic pressure-sensitive adhesive composition (a-1) } -Phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, “UV absorber 1” in Tables 1 and 2, manufactured by BASF Japan Ltd.) 1.4 weight And 0.2 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, having absorption resistance at wavelengths of 200 to 450 nm, manufactured by BASF Japan Ltd.) By doing this, an adhesive composition with an ultraviolet absorbing function was obtained.
　前記紫外線吸収機能付き粘着剤組成物を、離型フィルムの剥離処理されたフィルム上に、粘着剤層形成後の厚さが１５０μｍとなるように塗布し、次いで、該粘着剤組成物層の表面に、離型フィルムを貼り合わせた。その後、照度：６．５ｍＷ／ｃｍ２、光量：１５００ｍＪ／ｃｍ２、ピーク波長：３５０ｎｍの条件で紫外線照射を行い、粘着剤組成物層を光硬化させて、視認側粘着剤層（Ａ－１）を形成した。 The pressure-sensitive adhesive composition with an ultraviolet absorbing function is applied on the release-treated film so that the thickness after forming the pressure-sensitive adhesive layer is 150 μm, and then the surface of the pressure-sensitive adhesive composition layer A release film was bonded to the substrate. Thereafter, UV irradiation was performed under the conditions of illuminance: 6.5 mW / cm 2 , light quantity: 1500 mJ / cm 2 , peak wavelength: 350 nm, and the pressure-sensitive adhesive composition layer was photocured, whereby the visible-side pressure-sensitive adhesive layer (A-1 ) Was formed.
　（偏光フィルム（Ｐ－１）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の視認側に、ポリビニルアルコール系接着剤を用いて厚さ２５μｍのシクロオレフィンポリマー（ＣＯＰ）フィルムを貼り合せ、偏光子の画像表示部側表面に、ポリビニルアルコール系接着剤を用いて厚さ２０μｍのアクリルフィルムを積層し、偏光フィルム（Ｐ－１）とした。偏光フィルムの偏光度は９９．９９５であった。 (Manufacture of polarizing film (P-1))
A 25 μm thick cycloolefin polymer (COP) film is bonded to the viewing side of a polarizer composed of a 5 μm thick stretched polyvinyl alcohol film impregnated with iodine using a polyvinyl alcohol-based adhesive to display an image of the polarizer. A polarizing film (P-1) was obtained by laminating an acrylic film with a thickness of 20 μm using a polyvinyl alcohol-based adhesive on the part-side surface. The polarization degree of the polarizing film was 99.995.
　（粘着剤層付き偏光フィルムの製造）
　前記偏光フィルム（Ｐ－１）の視認側（すなわち、厚さ２５μｍのシクロオレフィンポリマー（ＣＯＰ）フィルムの表面）に、視認側粘着剤層（Ａ－１）を積層した。前記偏光フィルム（Ｐ－１）の画像表示部側表面（すなわち、厚さ２０μｍのアクリルフィルムの表面）に、画像表示部側粘着剤層（Ｂ－１）を積層し、さらに、位相差フィルム（厚み：５６μｍ、材料：ポリカーボネート）と画像表示部側粘着剤層（Ｂ－２）を積層し、粘着剤層付き偏光フィルムを形成した。得られた粘着剤層付き偏光フィルムは、視認側粘着剤層（Ａ－１）／偏光フィルム（Ｐ－１）／画像表示部側粘着剤層（Ｂ－１）／位相差フィルム／画像表示部側粘着剤層（Ｂ－２）の構成を有していた。 (Manufacture of polarizing film with adhesive layer)
The viewing-side pressure-sensitive adhesive layer (A-1) was laminated on the viewing side of the polarizing film (P-1) (that is, the surface of a cycloolefin polymer (COP) film having a thickness of 25 μm). An image display unit side pressure-sensitive adhesive layer (B-1) is laminated on the image display unit side surface of the polarizing film (P-1) (that is, the surface of an acrylic film having a thickness of 20 μm), and a retardation film ( Thickness: 56 μm, material: polycarbonate) and an image display part side pressure-sensitive adhesive layer (B-2) were laminated to form a polarizing film with a pressure-sensitive adhesive layer. The obtained polarizing film with the pressure-sensitive adhesive layer is: viewing-side pressure-sensitive adhesive layer (A-1) / polarizing film (P-1) / image-displaying part-side pressure-sensitive adhesive layer (B-1) / retardation film / image-displaying part. It had the structure of a side pressure-sensitive adhesive layer (B-2).
　実施例２～３
　アクリル系粘着剤組成物の種類、紫外線吸収剤１の添加量、及び視認側粘着剤層形成後の厚さを表１に記載のようにした以外は、実施例１と同様にして粘着剤層付き偏光フィルムを形成した。 Examples 2 to 3
The pressure-sensitive adhesive layer was the same as in Example 1 except that the type of the acrylic pressure-sensitive adhesive composition, the addition amount of the ultraviolet absorber 1, and the thickness after forming the visible-side pressure-sensitive adhesive layer were as shown in Table 1. An attached polarizing film was formed.
　実施例４
　視認側の粘着剤層を、視認側粘着剤層（Ａ－１）から下記で得られた視認側粘着剤層（Ａ－２）に変更した以外は、実施例１と同様にして粘着剤付き偏光フィルムを形成した。 Example 4
A pressure-sensitive adhesive layer was attached in the same manner as in Example 1 except that the visual-side pressure-sensitive adhesive layer (A-1) was changed to the visual-side pressure-sensitive adhesive layer (A-2) obtained below. A polarizing film was formed.
（視認側粘着剤層（Ａ－２）の製造）
　製造例２で得られたアクリル系粘着剤組成物（ａ－２）に、酢酸エチルに固形分１５％になるように溶解させた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ジャパン社製）１．４重量部を添加し撹拌することにより紫外線吸収機能付き粘着剤組成物を得た。 (Manufacture of visible side adhesive layer (A-2))
2,4-bis-[{4- (4-ethylhexyloxy) dissolved in ethyl acetate to a solid content of 15% in the acrylic pressure-sensitive adhesive composition (a-2) obtained in Production Example 2 By adding 1.4 parts by weight of -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, manufactured by BASF Japan Ltd.) and stirring, ultraviolet rays An adhesive composition with an absorption function was obtained.
　前記紫外線吸収機能付き粘着剤組成物を、離型フィルムの剥離処理されたフィルム上に、粘着剤層形成後の厚さが１５０μｍとなるように塗布し、６０℃で２分、１２０℃で２分乾燥させた後、剥離処理されたフィルムを貼り合わせることで視認側粘着剤層（Ａ－２）を形成した。 The pressure-sensitive adhesive composition with an ultraviolet absorbing function was applied on the release film of the release film so that the thickness after forming the pressure-sensitive adhesive layer was 150 μm, and 2 minutes at 60 ° C. and 2 minutes at 120 ° C. After partial drying, the peel-side film was bonded to form a viewing side pressure-sensitive adhesive layer (A-2).
　実施例５～６
　視認側粘着剤層形成後の厚さ、画像表示部側粘着剤層を表１に記載のようにした以外は、実施例４と同様にして粘着剤層付き偏光フィルムを形成した。 Examples 5-6
A polarizing film with a pressure-sensitive adhesive layer was formed in the same manner as in Example 4 except that the thickness after forming the viewing-side pressure-sensitive adhesive layer and the image display part-side pressure-sensitive adhesive layer were as shown in Table 1.
　実施例７
　（視認側粘着剤層（Ａ－３）の製造）
　製造例１で得られたアクリル系粘着剤組成物（ａ－１）に、ブチルアクリレートに固形分１５％となるように溶解させた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ジャパン社製）０．７重量部、Ｓｏｌｖｅｎｔ　Ｙeｌｌoｗ１６３（ＫＰ　Ｐｌａｓｔ　Ｙｅｌｌｏｗ　ＭＫ、表２中の「紫外線吸収剤２」、紀和化学工業（株）製）０．２重量部、ビス(２，４，６－トリメチルベンゾイル)－フェニルフォスフィンオキサイド（商品名：イルガキュア８１９、波長２００～４５０ｎｍに吸収耐を有する、ＢＡＳＦジャパン社製）０．２重量部を添加し撹拌することにより紫外線吸収機能付き粘着剤組成物を得た。 Example 7
(Manufacture of viewing side adhesive layer (A-3))
2,4-bis-[{4- (4-ethylhexyloxy) dissolved in butyl acrylate to a solid content of 15% in the acrylic pressure-sensitive adhesive composition (a-1) obtained in Production Example 1 -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, manufactured by BASF Japan Ltd.) 0.7 part by weight, Solvent Yellow 163 (KP Plas Yellow MK) In Table 2, “UV absorber 2”, manufactured by Kiwa Chemical Industry Co., Ltd., 0.2 parts by weight, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, wavelength) A pressure-sensitive adhesive composition with an ultraviolet absorption function is obtained by adding 0.2 parts by weight of BASF Japan, which has an absorption resistance at 200 to 450 nm, and stirring. .
　前記紫外線吸収機能付き粘着剤組成物を、離型フィルムの剥離処理されたフィルム上に、粘着剤層形成後の厚さが１５０μｍとなるように塗布し、次いで、該粘着剤組成物層の表面に、離型フィルムを貼り合わせた。その後、照度：６．５ｍＷ／ｃｍ２、光量：３０００ｍＪ／ｃｍ２、ピーク波長：３５０ｎｍの条件で紫外線照射を行い、粘着剤組成物層を光硬化させて、視認側粘着剤層（Ａ－３）を形成した。 The pressure-sensitive adhesive composition with an ultraviolet absorbing function is applied on the release-treated film so that the thickness after forming the pressure-sensitive adhesive layer is 150 μm, and then the surface of the pressure-sensitive adhesive composition layer A release film was bonded to the substrate. Thereafter, illuminance: 6.5 mW / cm 2, light quantity: 3000 mJ / cm 2, the peak wavelength irradiated with ultraviolet rays under the condition of 350 nm, the pressure-sensitive adhesive composition layer by light-curing, the visible side pressure-sensitive adhesive layer (A-3 ) Was formed.
　視認側の粘着剤層を、視認側粘着剤層（Ａ－１）から上記で得られた視認側粘着剤層（Ａ－３）に変更した以外は、実施例１と同様にして粘着剤付き偏光フィルムを形成した。 A pressure-sensitive adhesive layer was attached in the same manner as in Example 1 except that the visual-side pressure-sensitive adhesive layer (A-1) was changed to the visual-side pressure-sensitive adhesive layer (A-3) obtained above. A polarizing film was formed.
　比較例１
　視認側粘着剤層（Ａ－１）、位相差フィルム、及び画像表示部側粘着剤層（Ｂ－２）を形成しなかった以外は、実施例１と同様にして粘着剤層付き偏光フィルムを形成した。 Comparative Example 1
A polarizing film with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the viewing-side pressure-sensitive adhesive layer (A-1), the retardation film, and the image display unit-side pressure-sensitive adhesive layer (B-2) were not formed. Formed.
　比較例２
　視認側粘着剤層（Ａ－１）を形成しなかった以外は、実施例１と同様にして粘着剤層付き偏光フィルムを形成した。 Comparative Example 2
A polarizing film with a pressure-sensitive adhesive layer was formed in the same manner as in Example 1 except that the viewing-side pressure-sensitive adhesive layer (A-1) was not formed.
　比較例３、４
　視認側粘着剤層（Ａ－１）、（Ａ－２）に、紫外線吸収剤を添加しなかったこと以外は実施例１、４と同様の方法で粘着剤付き偏光フィルムを形成した。 Comparative Examples 3 and 4
A polarizing film with an adhesive was formed in the same manner as in Examples 1 and 4 except that no ultraviolet absorber was added to the viewing-side adhesive layers (A-1) and (A-2).
　比較例５
　（偏光フィルム（Ｐ－２）の製造）
　ヨウ素が含浸された厚さ１２μｍの延伸ポリビニルアルコールフィルムからなる偏光子の視認側に、ポリビニルアルコール系接着剤を用いて厚さ２５μｍのトリアセチルセルロースフィルムを貼り合せ、偏光子の画像表示部側表面に、ポリビニルアルコール系接着剤を用いて厚さ２０μｍのアクリルフィルムを積層し、偏光フィルム（Ｐ－２）とした。偏光フィルムの偏光度は９９．９９５であった。 Comparative Example 5
(Manufacture of polarizing film (P-2))
A 25 μm thick triacetylcellulose film is bonded to the viewing side of a polarizer made of a stretched polyvinyl alcohol film having a thickness of 12 μm impregnated with iodine, using a polyvinyl alcohol-based adhesive, and the image display side surface of the polarizer A polarizing film (P-2) was obtained by laminating an acrylic film having a thickness of 20 μm using a polyvinyl alcohol-based adhesive. The polarization degree of the polarizing film was 99.995.
　実施例２において、偏光フィルム（Ｐ－１）を前記偏光フィルム（Ｐ－２）に変更した以外は、実施例２と同様にして粘着剤付き偏光フィルムを形成した。 In Example 2, a polarizing film with an adhesive was formed in the same manner as in Example 2 except that the polarizing film (P-1) was changed to the polarizing film (P-2).
　得られた粘着剤層、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。 The following evaluation was performed about the obtained adhesive layer and a polarizing film with an adhesive layer.
　＜重合率＞
　実施例及び比較例で得られた視認側粘着剤層の離型フィルムを剥離して、重さを測ったアルミシャーレに視認側粘着剤層のみをのせた。（アルミシャーレ+視認側粘着剤層）の重さを測定し、乾燥前の粘着剤層の重さを求めた。１３０℃、２時間乾燥後、常温で約２０分冷却した後に、再び（アルミシャーレ+粘着剤）の重さを測定し、乾燥後の視認側粘着剤層の重さを求めた。以下の計算式により重合率を求めた。
Figure JPOXMLDOC01-appb-M000001
 <Polymerization rate>
The release film of the viewing-side pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, and only the viewing-side pressure-sensitive adhesive layer was placed on the weighed aluminum petri dish. The weight of (aluminum petri dish + viewing side pressure-sensitive adhesive layer) was measured, and the weight of the pressure-sensitive adhesive layer before drying was determined. After drying at 130 ° C. for 2 hours and cooling at room temperature for about 20 minutes, the weight of (aluminum petri dish + adhesive) was measured again, and the weight of the viewing-side adhesive layer after drying was determined. The polymerization rate was determined by the following calculation formula.
Figure JPOXMLDOC01-appb-M000001
　＜ゲル分率＞
　実施例及び比較例で得られた視認側粘着剤層から約０．１ｇ採取し、平均孔径０．２μｍの多孔質テトラフルオロエチレンシート（商品名：ＮＴＦ１１２２、日東電工（株）製）に包んだ後、凧糸で縛り、その際の重量を測定し（Ｚｇ）、該重量を浸漬前重量とした。なお、該浸漬前重量は、視認側粘着剤層（上記で採取した粘着剤層）と、テトラフルオロエチレンシートと、凧糸との総重量である。また、テトラフルオロエチレンシートと凧糸との合計重量も測定した（Ｙｇ）。次に、視認側粘着剤層をテトラフルオロエチレンシートで包み凧糸で縛ったもの（「サンプル」と称する）を、酢酸エチルで満たした５０ｍＬ容器に入れ、２３℃にて７日間静置した。その後、容器からサンプル（酢酸エチル処理後）を取り出して、アルミニウム製カップに移し、１３０℃で２時間、乾燥機中で乾燥して酢酸エチルを除去した後、重量を測定し（Ｘｇ）、該重量を浸漬後重量とした。下記の式からゲル分率を算出した。
　　ゲル分率（重量％）＝（Ｘ－Ｙ）／（Ｚ－Ｙ）×１００ <Gel fraction>
About 0.1 g was collected from the viewing-side pressure-sensitive adhesive layers obtained in Examples and Comparative Examples, and wrapped in a porous tetrafluoroethylene sheet (trade name: NTF1122, manufactured by Nitto Denko Corporation) having an average pore diameter of 0.2 μm. Then, it tied up with the kite string, the weight in that case was measured (Zg), and this weight was made into the weight before immersion. The weight before immersion is the total weight of the viewing-side pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer collected above), the tetrafluoroethylene sheet, and the kite string. The total weight of the tetrafluoroethylene sheet and the kite string was also measured (Yg). Next, a visible-side pressure-sensitive adhesive layer wrapped with a tetrafluoroethylene sheet and tied with a kite string (referred to as “sample”) was placed in a 50 mL container filled with ethyl acetate and allowed to stand at 23 ° C. for 7 days. Thereafter, a sample (after ethyl acetate treatment) was taken out from the container, transferred to an aluminum cup, dried in a dryer at 130 ° C. for 2 hours to remove ethyl acetate, and then weighed (Xg). The weight was defined as the weight after immersion. The gel fraction was calculated from the following formula.
Gel fraction (% by weight) = (XY) / (ZY) × 100
　＜視認側粘着剤層の透過率、ｂ＊値の測定＞
　実施例及び比較例で得られた視認側粘着剤層の離型フィルムを剥離して、視認側粘着剤層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３８０ｎｍ、４００ｎｍ、４２０ｎｍにおける透過率を測定した（但し、波長４２０ｎｍについては、実施例２、７のみで測定した）。 <Measurement of transmittance and b * value of adhesive layer on viewing side>
The release film of the viewing-side pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, and the viewing-side pressure-sensitive adhesive layer was attached to a measuring jig, and a spectrophotometer (product name: U4100, Hitachi High Co., Ltd.) (Manufactured by Technologies). For the transmittance, the transmittance at wavelengths of 380 nm, 400 nm, and 420 nm was measured (however, the wavelength of 420 nm was measured only in Examples 2 and 7).
　＜残存応力＞
　実施例及び比較例で得られた視認側粘着剤層から、幅３０ｍｍ、長さ５０ｍｍを切り出し、筒状にして試験片を作製した。これをチャック間２０ｍｍで設置し、該試験片を引張速度２００ｍｍ／分で、６０ｍｍ（３００％）引っ張った(引張後のチャック間は８０ｍｍ)。６０ｍｍ引っ張った位置で、３００秒間固定(保持)し、３００秒後の応力値(Ｎ)を測定した。以下の式により、残存応力を求めた。
　　３００秒後残存応力＝３００秒後の応力値(Ｎ)／(４×試験片の厚さ／１０) <Residual stress>
From the viewing-side pressure-sensitive adhesive layers obtained in the examples and comparative examples, a test piece was prepared by cutting out a width of 30 mm and a length of 50 mm and forming a cylinder. This was installed with 20 mm between chucks, and the test piece was pulled 60 mm (300%) at a pulling speed of 200 mm / min (80 mm between the chucks after tension). At a position pulled 60 mm, it was fixed (held) for 300 seconds, and the stress value (N) after 300 seconds was measured. The residual stress was determined by the following formula.
Residual stress after 300 seconds = Stress value after 300 seconds (N) / (4 × thickness of test piece / 10)
　＜光学信頼性＞
　実施例１で用いた偏光フィルム（Ｐ－１）のＣＯＰフィルムに対して実施例１～７及び比較例３～５で得られた視認側粘着剤層を貼り合わせた。さらに、視認側粘着剤層を貼り合わせた偏光フィルムの逆側（アクリルフィルム側）に１５μｍの粘着剤付き５６μｍの位相差フィルム（日東電工（株）製）を貼り合わせた。そのサンプルの両面をガラス（商品名：Ｓ２００２００、厚さ：１．３ｍｍ、サイズ：４５ｍｍ×５０ｍｍ、松浪硝子工業（株）製）で貼り合わせをし、オートクレーブ処理（気圧：０．５ＭＰａ、温度：５０℃）を１５分間実施した。その後、以下の各種信頼性条件下に投入し、分光透過率測定器（製品名：ＤＯＴ－３、（株）村上色彩技術研究所製）で透過率を測定した。初期からの透過率変化量を求めた。以下の評価基準により評価した。
（各種信頼性条件）
（条件１）８５℃×５００ｈ
（条件２）６０℃、９５％×５００ｈ
（条件３）ヒートショック(ＨＳ)（－４０℃～８５℃）×３００サイクル
（条件４）ＵＶ照射下×１００ｈ、照度：５００Ｗ/ｃｍ２(３００～７００ｎｍ)、環境温度：６０～６５℃、環境湿度：５０％
（条件５）Ｘｅｎｏｎ照射下×３００ｈ、照度：２．４０Ｗ/ｃｍ２（４２０ｎｍ）、環境温度：５０℃、環境湿度：３０％
（評価基準）
　○：透過率変化量が２．０％以下である。
　△：透過率変化量が２．０％を超え、３．０％以下である。
　×：透過率変化量が３．０％を超える。 <Optical reliability>
The viewing-side pressure-sensitive adhesive layers obtained in Examples 1 to 7 and Comparative Examples 3 to 5 were bonded to the COP film of the polarizing film (P-1) used in Example 1. Furthermore, a 56 μm phase difference film with a 15 μm adhesive (manufactured by Nitto Denko Corporation) was bonded to the opposite side (acrylic film side) of the polarizing film to which the viewing-side pressure-sensitive adhesive layer was bonded. Both surfaces of the sample were bonded with glass (trade name: S200200, thickness: 1.3 mm, size: 45 mm × 50 mm, manufactured by Matsunami Glass Industry Co., Ltd.), and autoclaved (atmospheric pressure: 0.5 MPa, temperature: 50 ° C.) for 15 minutes. Thereafter, the sample was charged under the following various reliability conditions, and the transmittance was measured with a spectral transmittance meter (product name: DOT-3, manufactured by Murakami Color Research Laboratory Co., Ltd.). The change in transmittance from the initial stage was determined. Evaluation was performed according to the following evaluation criteria.
(Various reliability conditions)
(Condition 1) 85 ° C. × 500 h
(Condition 2) 60 ° C., 95% × 500 h
(Condition 3) Heat shock (HS) (−40 ° C. to 85 ° C.) × 300 cycles (Condition 4) Under UV irradiation × 100 h, Illuminance: 500 W / cm 2 (300 to 700 nm), Environmental temperature: 60 to 65 ° C. Environmental humidity: 50%
(Condition 5) Under Xenon irradiation × 300 h, illuminance: 2.40 W / cm 2 (420 nm), environmental temperature: 50 ° C., environmental humidity: 30%
(Evaluation criteria)
○: The transmittance change amount is 2.0% or less.
(Triangle | delta): The transmittance | permeability change amount exceeds 2.0% and is 3.0% or less.
X: The transmittance change amount exceeds 3.0%.
　＜糊汚れ、寸法精度、端部外観＞
　実施例、比較例で得られた粘着剤層付き偏光フィルムを、スーパーカッターにて、２５ｍｍ×３０ｍｍのサイズに切断した。その後、端面加工機（メガロテクニカ（株）製）により、切断片の側面の四面を０．０５ｍｍ切削し、サンプルとした。糊汚れについてはサンプルの側面を目視で確認し、糊汚れの有無を確認した。寸法精度、端部外観については光学顕微鏡で観測し、以下の評価基準で評価した。
　（寸法精度）
　○：±０．３ｍｍ以内
　×：±０．３ｍｍを超える
　（端部外観）
　○：手で触った際に端部のベトツキが無い場合
　×：手で触った際に端部のベトツキがある場合 <Glue stain, dimensional accuracy, end appearance>
The polarizing film with an adhesive layer obtained in Examples and Comparative Examples was cut into a size of 25 mm × 30 mm with a super cutter. Thereafter, the end surface processing machine (manufactured by Megaro Technica Co., Ltd.) was used to cut the four side surfaces of the cut piece by 0.05 mm to obtain a sample. Regarding the glue stain, the side surface of the sample was visually confirmed to check for the presence or absence of glue stain. The dimensional accuracy and edge appearance were observed with an optical microscope and evaluated according to the following evaluation criteria.
(Dimensional accuracy)
○: Within ± 0.3mm ×: Over ± 0.3mm (External appearance)
○: When there is no stickiness at the end when touched by hand ×: When there is stickiness at the end when touched by hand
　＜カール測定＞
　５０ｍｍ×４０ｍｍに切断したサンプルを平坦な机の上にサンプルを置き、スキマゲージによりカールを測定した。
　(カール)
　○：±１．０ｍｍ以内
　△：±１．０ｍｍより大きく、±２．０ｍｍ以内
　×：±２．０ｍｍより大きい <Curl measurement>
The sample cut into 50 mm × 40 mm was placed on a flat desk, and the curl was measured with a skimmer gauge.
(curl)
○: within ± 1.0 mm Δ: larger than ± 1.0 mm, within ± 2.0 mm ×: larger than ± 2.0 mm
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１中、Ｐ－１は、偏光フィルム（Ｐ－１）を、Ｐ－２は、偏光フィルム（Ｐ－２）を、ａ－１は、製造例１で得られたアクリル系粘着剤組成物（ａ－１）を、ａ－２は、製造例２で得られたアクリル系粘着剤組成物（ａ－２）を、紫外線吸収剤１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ジャパン社製）を、紫外線吸収剤２は、Ｓｏｌｖｅｎｔ　Ｙeｌｌoｗ１６３（ＫＰ　Ｐｌａｓｔ　Ｙｅｌｌｏｗ　ＭＫ、紀和化学工業（株）製）を、Ｂ－１は、製造例３で得られた画像表示部側粘着剤層（Ｂ－１）を、Ｂ－２は、製造例４で得られた画像表示部側粘着剤層（Ｂ－２）を、示す。 In Table 1, P-1 is the polarizing film (P-1), P-2 is the polarizing film (P-2), and a-1 is the acrylic pressure-sensitive adhesive composition obtained in Production Example 1. (A-1), a-2 is the acrylic pressure-sensitive adhesive composition (a-2) obtained in Production Example 2, and the ultraviolet absorber 1 is 2,4-bis-[{4- (4 -Ethylhexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, manufactured by BASF Japan Ltd.), UV absorber 2 is Solvent Yellow 163 (KP Last Yellow MK, manufactured by Kiwa Chemical Industry Co., Ltd.), B-1 is the image display part side adhesive layer (B-1) obtained in Production Example 3, and B-2 is Production Example The image display part side pressure-sensitive adhesive layer (B-2) obtained in 4 is shown.
　　１　　粘着剤層付き偏光フィルム
　　２ａ　視認側粘着剤層
　　２ｂ　画像表示部側粘着剤層
　　３ａ　視認側透明保護フィルム
　　３ｂ　画像表示部側透明保護フィルム
　　４　　偏光子
　　５　　偏光フィルム
　　６　　カバーガラス又はカバープラスチック
　　７　　液晶表示装置（ＬＣＤ）又は有機ＥＬ表示装置（ＯＬＥＤ）
　　８ａ、８ｂ　粘着剤層
　　９　　センサー層 DESCRIPTION OF SYMBOLS 1 Polarizing film with an adhesive layer 2a Viewing side adhesive layer 2b Image display part side adhesive layer 3a Viewing side transparent protective film 3b Image display part side transparent protective film 4 Polarizer 5 Polarizing film 6 Cover glass or cover plastic 7 Liquid crystal display Device (LCD) or organic EL display (OLED)
8a, 8b Adhesive layer 9 Sensor layer

Claims (9)

  1. 　画像表示装置において画像表示部より視認側に用いられる粘着剤層付き偏光フィルムであって、
    　前記粘着剤層付き偏光フィルムは、偏光フィルムと当該偏光フィルムの両面に粘着剤層を有し、
    　前記偏光フィルムは、偏光子と当該偏光子の両面に透明保護フィルムを有し、
    　前記偏光子の視認側の透明保護フィルムの波長３８０ｎｍにおける透過率が６％未満であり、かつ
    　前記偏光フィルムの視認側の粘着剤層が紫外線吸収機能を有することを特徴とする粘着剤層付き偏光フィルム。     In the image display device is a polarizing film with an adhesive layer used on the viewing side from the image display unit,
    The polarizing film with the pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer on both sides of the polarizing film and the polarizing film,
    The polarizing film has a transparent protective film on both sides of the polarizer and the polarizer,
    Polarized light with pressure-sensitive adhesive layer, wherein the transparent protective film on the viewing side of the polarizer has a transmittance at a wavelength of 380 nm of less than 6%, and the pressure-sensitive adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function the film.
  2. 　前記偏光子の視認側の透明保護フィルムが、トリアセチルセルロースフィルム、アクリルフィルム、ポリエチレンテレフタレートフィルム、及び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フィルムからなる群から選択される少なくとも１種のフィルムであり、かつ厚さが４０μｍ以下であることを特徴とする請求項１に記載の粘着剤層付き偏光フィルム。 The transparent protective film on the viewer side of the polarizer is at least one film selected from the group consisting of a triacetyl cellulose film, an acrylic film, a polyethylene terephthalate film, and a polyolefin film having a cyclo or norbornene structure, and The polarizing film with a pressure-sensitive adhesive layer according to claim 1, wherein the thickness is 40 μm or less.
  3. 　前記偏光フィルムの視認側の粘着剤層の厚さが、前記偏光フィルムの画像表示部側の粘着剤層の厚さの２倍以上であることを特徴とする請求項１又は２に記載の粘着剤層付き偏光フィルム。 The pressure-sensitive adhesive layer according to claim 1 or 2, wherein the thickness of the pressure-sensitive adhesive layer on the viewing side of the polarizing film is at least twice the thickness of the pressure-sensitive adhesive layer on the image display unit side of the polarizing film. Polarizing film with an agent layer.
  4. 　前記偏光フィルムの視認側の粘着剤層が、波長３８０ｎｍの透過率が９％以下であり、かつ、波長４００ｎｍの透過率が６０％以上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粘着剤層付き偏光フィルム。 4. The adhesive layer on the viewing side of the polarizing film has a transmittance of 9% or less at a wavelength of 380 nm and a transmittance of 400% or more at a wavelength of 400 nm. The polarizing film with an adhesive layer of description.
  5. 　前記偏光フィルムの視認側の粘着剤層が、波長３８０ｎｍの透過率が９％以下であり、かつ、波長４２０ｎｍの透過率が７５％以下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粘着剤層付き偏光フィルム。 The adhesive layer on the viewing side of the polarizing film has a transmittance of 9% or less at a wavelength of 380 nm and a transmittance of 420% or less at a wavelength of 420 nm. The polarizing film with an adhesive layer of description.
  6. 　前記偏光フィルムの視認側の粘着剤層のｂ＊値が３．０以下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粘着剤層付き偏光フィルム。 5. The polarizing film with a pressure-sensitive adhesive layer according to claim 1, wherein the b * value of the pressure-sensitive adhesive layer on the viewing side of the polarizing film is 3.0 or less.
  7. 　前記偏光フィルムの視認側の粘着剤層が、アクリル系ポリマーをベースポリマーとして含有していることを特徴とする請求項１～６のいずれかに記載の粘着剤層付き偏光フィルム。 The polarizing film with the pressure-sensitive adhesive layer according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive layer on the viewing side of the polarizing film contains an acrylic polymer as a base polymer.
  8. 　液晶表示装置又は有機ＥＬ表示装置に用いることを特徴とする請求項１～７のいずれかに記載の粘着剤層付き偏光フィルム。 The polarizing film with an adhesive layer according to any one of claims 1 to 7, which is used for a liquid crystal display device or an organic EL display device.
  9. 　請求項１～８のいずれかに記載の粘着剤層付き偏光フィルムを画像表示部より視認側に用いたことを特徴とする画像表示装置。 An image display device comprising the polarizing film with an adhesive layer according to any one of claims 1 to 8 on the viewing side from the image display unit.
PCT/JP2016/084344 2015-12-25 2016-11-18 Polarizing film with pressure-sensitive adhesive layer, and image display device WO2017110332A1 (en)

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KR1020187015835A KR20180097535A (en) 2015-12-25 2016-11-18 A polarizing film having a pressure-sensitive adhesive layer and an image display device
SG11201804877QA SG11201804877QA (en) 2015-12-25 2016-11-18 Pressure-sensitive-adhesive layer attached polarizing film, and image display device
CN202011114600.2A CN112433287B (en) 2015-12-25 2016-11-18 Polarizing film with adhesive layer and image display device
KR1020247011112A KR20240050450A (en) 2015-12-25 2016-11-18 Polarizing film with pressure-sensitive adhesive layer, and image display device
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JP2015-254524 2015-12-25
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JP2016095329A JP2017120363A (en) 2015-12-25 2016-05-11 Polarizing film with pressure-sensitive adhesive layer, and image display device
JP2016-095329 2016-05-11

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