WO2015030203A1 - Curable adhesive for polarizing films, polarizing film, optical film and image display device - Google Patents

Curable adhesive for polarizing films, polarizing film, optical film and image display device Download PDF

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Publication number
WO2015030203A1
WO2015030203A1 PCT/JP2014/072816 JP2014072816W WO2015030203A1 WO 2015030203 A1 WO2015030203 A1 WO 2015030203A1 JP 2014072816 W JP2014072816 W JP 2014072816W WO 2015030203 A1 WO2015030203 A1 WO 2015030203A1
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Prior art keywords
meth
curable adhesive
adhesive
polarizing film
curable
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PCT/JP2014/072816
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French (fr)
Japanese (ja)
Inventor
武士 斉藤
美紀 岡本
山崎　達也
池田　哲朗
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020167006693A priority Critical patent/KR20160048105A/en
Priority to KR1020207035422A priority patent/KR102278125B1/en
Priority to CN201480047627.0A priority patent/CN105492564B/en
Publication of WO2015030203A1 publication Critical patent/WO2015030203A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a polarizing film curable adhesive for forming an adhesive layer in a polarizing film in which a polarizer and a transparent protective film are laminated via an adhesive layer.
  • the present invention also relates to a polarizing film using the adhesive layer.
  • the polarizing film can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP alone or as an optical film obtained by laminating the polarizing film.
  • Liquid crystal display devices are rapidly expanding in the market for watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, etc.
  • the liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle.
  • polarizing films are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.
  • an iodine-based polarizer having a stretched structure by adsorbing iodine to polyvinyl alcohol (hereinafter also simply referred to as “PVA”) is most widely used. in use.
  • PVA polyvinyl alcohol
  • a polarizing film in which a transparent protective film is bonded to both surfaces of a polarizer by a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water is used (Patent Document 1 and Patent Document 2 below).
  • the transparent protective film triacetyl cellulose having a high moisture permeability is used. When the water-based adhesive is used (so-called wet lamination), a drying process is required after the polarizer and the transparent protective film are bonded together.
  • an active energy ray-curable adhesive has been proposed.
  • an active energy ray-curable adhesive has been proposed.
  • an active energy ray-curable adhesive has been proposed.
  • radical polymerization type active energy ray-curable adhesives using an N-substituted amide monomer as a curable component have been proposed (Patent Documents 3 and 4 below).
  • Such an adhesive exhibits excellent durability under harsh environments under high humidity and high temperature.
  • an adhesive there is a demand for an adhesive that can further improve adhesiveness and / or water resistance. There was a real situation.
  • JP 2006-220732 A JP 2001-296427 A JP 2008-287207 A JP 2010-078700 A JP 2012-144690 A
  • the active energy ray-curable adhesive described in Patent Document 5 durability and water resistance can be satisfied with respect to various transparent protective films used in the production of a polarizing film.
  • the polarizing film obtained using the active energy ray-curable adhesive described in Patent Document 5 can satisfy water resistance (hot water immersion test) when immersed in hot water at 60 ° C. for 6 hours. In the market, optical durability under a severe environment under further high temperature and high humidity is required. Furthermore, the polarizing film is required to have sufficient adhesive strength even when immersed in water for a long time.
  • the present invention has good adhesion between the polarizer and the transparent protective film, and can satisfy optical durability in a severe environment under high temperature and high humidity, and also when immersed in water for a long time. It aims at providing the curable adhesive for polarizing films which has sufficient adhesive force.
  • this invention provides the polarizing film by which the transparent protective film is provided in the polarizer by the adhesive bond layer formed using the curable adhesive for polarizing films, Furthermore, the said polarizing film was used.
  • An object is to provide an optical film, and further to provide an image display device using the polarizing film or the optical film.
  • the present inventors have found that the above object can be achieved by the following curable adhesive for polarizing film, and have solved the present invention.
  • the present invention is a polarizing film curable adhesive containing a curable component
  • M1 represents the weight of the cured product before dipping
  • M2 represents the weight of the cured product after dipping ⁇
  • the bulk water absorption is 10% by weight or less.
  • the present invention relates to a curable adhesive.
  • the polarizing film curable adhesive preferably has an octanol / water partition coefficient (logPow value) of 1 or more.
  • the polarizing film curable adhesive can be used as an active energy ray curable adhesive when the curable component is an active energy ray curable component.
  • a radical polymerizable compound can be contained.
  • the radical polymerizable compound preferably contains a (meth) acrylamide derivative.
  • the radical polymerizable compound preferably contains a polyfunctional compound having at least two functional groups having radical polymerizable properties.
  • the said active energy ray hardening-type adhesive agent can contain a photoinitiator further.
  • the polarizing film curable adhesive may further contain an acrylic oligomer (A).
  • the polarizing film curable adhesive may further contain a photoacid generator (B).
  • the polarizing film curable adhesive may further contain a compound (C) containing either an alkoxy group or an epoxy group.
  • the compound (C) containing either an alkoxy group or an epoxy group is preferably a compound (C1) containing an alkoxy group.
  • the compound (C1) containing an alkoxy group is preferably a melamine compound containing an alkoxy group.
  • the said curable adhesive for polarizing films can contain an isocyanate compound (D) further.
  • the polarizing film curable adhesive can be used as a thermosetting adhesive by further containing a thermal polymerization initiator.
  • the present invention is a polarizing film, wherein a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer,
  • the said adhesive layer is formed with the hardened
  • the cured adhesive layer preferably has a thickness of 0.1 to 3 ⁇ m.
  • the present invention relates to an optical film characterized in that at least one polarizing film is laminated.
  • the present invention relates to an image display device using the polarizing film or the optical film.
  • the bulk water absorption of a cured product obtained by curing the curable adhesive is 10% by weight or less.
  • the said bulk water absorption has shown that the water absorption at the time of forming an adhesive bond layer by the hardened
  • a polarizing film having a cured product layer (adhesive layer) formed using the curable adhesive for polarizing film of the present invention has optical durability even in a severe humidified environment (85 ° C. ⁇ 85% RH). (Humidification durability test) is good. Therefore, the polarizing film of the present invention can suppress a decrease (change) in the transmittance and the degree of polarization of the polarizing film even when the polarizing film is placed in the severe humidified environment. Further, the polarizing film of the present invention can suppress a decrease in adhesive force even under a harsh environment such as being immersed in water, and a polarizing film having sufficient adhesive force even when immersed in water for a long time. Can be provided.
  • the curable adhesive for polarizing film of the present invention has a bulk water absorption of 10 wt% measured when a cured product obtained by curing the curable adhesive is immersed in pure water at 23 ° C. for 24 hours. % Or less.
  • a polarizing film is placed in a severe environment of high temperature and high humidity (85 ° C / 85% RH, etc.)
  • moisture that has passed through the transparent protective film and the adhesive layer enters the polarizer and the crosslinked structure is hydrolyzed.
  • the orientation of the dichroic dye is disturbed, and optical durability such as an increase in transmittance and a decrease in polarization degree occurs.
  • the bulk water absorption of the adhesive layer 10% by weight or less, the movement of water to the polarizer when the polarizing film is placed in a severe high temperature and high humidity environment is suppressed, and the transmittance of the polarizer is increased. A decrease in the degree of polarization can be suppressed.
  • the bulk water absorption is preferably 5% by weight or less, more preferably 3% by weight or less from the viewpoint of making the optical durability in a harsh environment at a high temperature more favorable for the adhesive layer of the polarizing film. It is preferably 1.5% by weight or less, and most preferably 1% by weight or less.
  • the polarizer and the transparent protective film are bonded together, the polarizer retains a certain amount of moisture.
  • the curable adhesive When the curable adhesive comes into contact with moisture contained in the polarizer, repelling, bubbles, etc. Appearance defects may occur. In order to suppress poor appearance, it is preferable that the curable adhesive can absorb a certain amount of moisture. More specifically, the bulk water absorption is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more. Specifically, the bulk water absorption rate is measured by a water absorption rate test method described in JISK 7209.
  • the curable adhesive for polarizing film of the present invention preferably has a high octanol / water partition coefficient (hereinafter referred to as logPow value).
  • the logPow value is an index representing the lipophilicity of a substance and means the logarithmic value of the octanol / water partition coefficient.
  • High logPow means that it is lipophilic, that is, low water absorption.
  • the logPow value can also be measured (flask immersion method described in JIS-Z-7260), but calculated based on the structure of each compound that is a component (such as a curable component) of a curable adhesive for polarizing films. Can also be calculated.
  • the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft is used. Based on the calculated value, the logPow value of the polarizing film curable adhesive in the present invention can be calculated by the following formula.
  • LogPow of curable adhesive ⁇ (logPow ⁇ Wi) logPowi: logPow value of each component of curable adhesive Wi: (number of moles of i component) / (total number of moles of each component of curable adhesive)
  • the logPow value of the curable adhesive for polarizing film of the present invention is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. Thereby, water resistance and humidification durability can be improved.
  • the logPow value of the curable adhesive for polarizing film of the present invention is usually about 8 or less, preferably 5 or less, and more preferably 4 or less. If the logPow value is too high, appearance defects such as repelling and bubbles are likely to occur as described above, which is not preferable.
  • the means for setting the bulk water absorption to 10% by weight or less in the present invention is not particularly limited, but in the case where the curable adhesive for polarizing film is a composition containing a plurality of components, each component is added.
  • the polarizing film curable adhesive is an adhesive composition containing a plurality of components
  • the adhesive composition is prepared so that the proportion of components having a logPow value of 1 or less in the adhesive composition is reduced.
  • the bulk water absorption can be controlled within the above range.
  • the bulk water absorption in the present invention can be adjusted to 10% by weight or less, for example, by controlling the logPow value of the polarizing film curable adhesive to 1 or more.
  • the curable adhesive for polarizing films of the present invention has a curable component, curing shrinkage usually occurs when the curable adhesive is cured.
  • the cure shrinkage rate is an index indicating the rate of cure shrinkage when an adhesive layer is formed from a curable adhesive for polarizing film.
  • the curing shrinkage rate of the cured product obtained by curing the curable adhesive for polarizing film of the present invention is 10% or less.
  • the curing shrinkage rate is preferably small, and the curing shrinkage rate is preferably 8% or less, more preferably 5% or less.
  • the cure shrinkage rate is measured by the method described in JP2013-104869A, and specifically, measured by the method using a cure shrinkage sensor manufactured by Centec Co., Ltd. described in the examples.
  • the polarizing film curable adhesive of the present invention contains a curable component.
  • the curable component is appropriately selected so that the cured product satisfies the bulk water absorption rate.
  • the curable component can be roughly classified into an active energy ray curable type such as an electron beam curable type, an ultraviolet curable type, a visible light curable type, and a thermosetting type. Furthermore, ultraviolet curable and visible light curable adhesives can be classified into radical polymerization curable adhesives and cationic polymerization adhesives. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light.
  • the curable component of the radical polymerization curable adhesive can be used as a curable component of a thermosetting adhesive.
  • the curable component examples include radical polymerizable compounds used in radical polymerization curable adhesives.
  • the radical polymerizable compound include compounds having a radical polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group.
  • these curable components either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used.
  • these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types.
  • compounds having a (meth) acryloyl group are suitable.
  • (meth) acryloyl means an acryloyl group and / or methacryloyl group, and “(meth)” has the same meaning hereinafter.
  • Examples of the monofunctional radical polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group.
  • a (meth) acrylamide derivative is preferable in terms of securing adhesiveness with a polarizer and various transparent protective films, and having a high polymerization rate and excellent productivity.
  • (meth) acrylamide derivatives include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N— N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as
  • heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocyclic ring examples include, for example, N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine. Etc.
  • N-hydroxyalkyl group-containing (meth) acrylamide derivatives are preferable from the viewpoint of adhesion to polarizers and various transparent protective films, and in particular, N-hydroxyethyl (meth) acrylamide. Is preferred.
  • examples of the monofunctional radical polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-
  • Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; Aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclo Polycyclic (meth) acrylates such as pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (
  • Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc.
  • hydroxyl groups such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.
  • Meth) acrylate Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) ) Halogen-containing (meth) acrylates such as acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate; Alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 3-Oxetanylmethyl (meth) acrylate
  • examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • Examples of the monofunctional radical polymerizable compound 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, Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
  • 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 examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
  • a radically polymerizable compound having an active methylene group can be used as the monofunctional radically polymerizable compound.
  • the radical polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group at the terminal or in the molecule.
  • the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group.
  • the active methylene group is preferably an acetoacetyl group.
  • radical polymerizable compound having an active methylene group examples include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate, and the like.
  • Examples include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, and N- (2-acetoacetylaminoethyl) acrylamide.
  • the radical polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
  • Examples of the bifunctional or higher polyfunctional radical polymerizable compound include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) ) Acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) Acryte, cyclic trimethylol
  • Aronix M-220, M-306 manufactured by Toagosei Co., Ltd.
  • light acrylate 1,9ND-A manufactured by Kyoeisha Chemical Co., Ltd.
  • light acrylate DGE-4A manufactured by Kyoeisha Chemical Co., Ltd.
  • light acrylate DCP- A manufactured by Kyoeisha Chemical Co., Ltd.
  • SR-531 manufactured by Sartomer
  • CD-536 manufactured by Sartomer
  • various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary.
  • the radical polymerizable compound contains the polyfunctional radical polymerizable compound in order to control the water absorption rate of the cured product and to satisfy the optical durability of the polarizing film in a severely humidified environment.
  • the polyfunctional radical polymerizable compounds those having a high logPow value are preferable.
  • the logPow value of the radical polymerizable compound is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
  • a radically polymerizable compound uses a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound together from the viewpoint of achieving both adhesiveness with a polarizer and various transparent protective films and optical durability under harsh environments. It is preferable. Usually, it is preferable to use a combination of 3 to 80% by weight of the monofunctional radical polymerizable compound and 20 to 97% by weight of the polyfunctional radical polymerizable compound with respect to 100% by weight of the radical polymerizable compound.
  • the curable component is used as an active energy ray curable component
  • the polarizing film curable adhesive of the present invention is used as an active energy ray curable adhesive
  • the curable component is used as a thermosetting component.
  • the active energy ray-curable adhesive uses an electron beam or the like as the active energy ray
  • the active energy ray-curable adhesive does not need to contain a photopolymerization initiator.
  • ultraviolet rays or visible rays it is preferable to contain a photopolymerization initiator.
  • the curable component of the adhesive is used as a thermosetting component
  • the adhesive preferably contains a thermal polymerization initiator.
  • the photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray. In the case of curing with ultraviolet light or visible light, a photopolymerization initiator for ultraviolet light or visible light cleavage is used.
  • photopolymerization initiator examples include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2 -Propyl) ketone, aromatic ketone compounds such as ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, ⁇ -hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether; Benzoin ethyl ether, benzoin Benzoin ether compounds such as isopropyl ether, benzoin butyl ether and ani
  • photopolymerization initiators those having a high logPow value are preferred.
  • the photopolymerization initiator is not included in the component for calculating the logPow value of the curable adhesive for polarizing film, but the logPow value of the photopolymerization initiator is preferably 1 or more, more preferably 2 or more, most preferably 3 or more.
  • the blending amount of the photopolymerization initiator is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound).
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.
  • a photopolymerization initiator that is particularly sensitive to light of 380 nm or more is used. It is preferable to use it.
  • a photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.
  • the compound represented by following General formula (1) (Wherein R 1 and R 2 represent —H, —CH 2 CH 3 , —iPr or Cl, and R 1 and R 2 may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later.
  • the adhesiveness is excellent as compared with a case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone.
  • diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable.
  • the composition ratio of the compound represented by the general formula (1) in the adhesive is preferably 0.1 to 5 parts by weight, and preferably 0.5 to 4 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferably, it is 0.9 to 3 parts by weight.
  • polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable.
  • a polymerization initiation assistant When a polymerization initiation assistant is used, its addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component. is there.
  • a known photopolymerization initiator can be used in combination as necessary. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator.
  • 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.
  • a photopolymerization initiator in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2); Wherein R 3 , R 4 and R 5 represent —H, —CH 3 , —CH 2 CH 3 , —iPr or Cl, and R 3 , R 4 and R 5 may be the same or different. It is preferable to use it.
  • the compound represented by the general formula (2) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercial product is suitable. Can be used.
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF)
  • 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferred because of its high sensitivity.
  • the radically polymerizable compound (a1) having an active methylene group is taken into the main chain and / or the side chain of the base polymer in the adhesive layer while being polymerized together with other radically polymerizable compounds constituting the adhesive layer.
  • Forming an adhesive layer when a radical polymerization initiator (a2) having a hydrogen abstracting action is present, the base polymer constituting the adhesive layer is formed, and hydrogen is generated from the radical polymerizable compound (a2) having an active methylene group. It is extracted and a radical is generated in the methylene group.
  • examples of the radical polymerization initiator (a2) having a hydrogen abstracting action include thioxanthone radical polymerization initiators and benzophenone radical polymerization initiators.
  • the radical polymerization initiator (a2) is preferably a thioxanthone radical polymerization initiator.
  • examples of the thioxanthone radical polymerization initiator include compounds represented by the above general formula (1).
  • Specific examples of the compound represented by the general formula (1) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone.
  • diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable.
  • the total amount of the curable component is 100.
  • the weight percent the radically polymerizable compound (a1) having an active methylene group is 1 to 50% by weight, and the radical polymerization initiator (a2) is 0.1% with respect to 100 parts by weight of the total amount of the curable component.
  • the content is preferably 10 to 10 parts by weight.
  • a radical is generated in the methylene group of the radical polymerizable compound (a1) having an active methylene group in the presence of the radical polymerization initiator (a2) having a hydrogen abstracting action, and the methylene group And a hydroxyl group of a polarizer such as PVA react to form a covalent bond.
  • the active methylene group it is preferable to contain 1 to 50% by weight of the radically polymerizable compound (a1) having a more preferable content of 3 to 30% by weight.
  • the radical polymerizable compound (a1) having an active methylene group is preferably 1% by weight or more. On the other hand, if it exceeds 50% by weight, the adhesive layer may be poorly cured.
  • the radical polymerization initiator (a2) having a hydrogen abstracting action is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total amount of the curable component. More preferably. In order to sufficiently advance the hydrogen abstraction reaction, it is preferable to use 0.1 parts by weight or more of the radical polymerization initiator (a2). On the other hand, if it exceeds 10 parts by weight, it may not completely dissolve in the adhesive.
  • thermal polymerization initiator those in which polymerization does not start by thermal cleavage when the adhesive layer is formed are preferable.
  • thermal polymerization initiator those having a 10-hour half-life temperature of 65 ° C. or higher, more preferably 75 to 90 ° C. are preferable.
  • the half-life is an index representing the decomposition rate of the polymerization initiator, and means the time until the remaining amount of the polymerization initiator is halved.
  • the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic peroxide catalog 9th edition by Nippon Oil & Fats Co., Ltd.” (May 2003) ".
  • thermal polymerization initiator examples include lauroyl peroxide (10 hour half-life temperature: 64 ° C.), benzoyl peroxide (10 hour half-life temperature: 73 ° C.), 1,1-bis (t-butylperoxy) -3.
  • thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile (10 hour half-life temperature: 67 ° C.), 2,2′-azobis (2-methylbutyronitrile) (10 hours). And azo compounds such as 1,1-azobis-cyclohexane-1-carbonitrile (10 hour half-life temperature: 87 ° C.).
  • the blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound).
  • the blending amount of the thermal polymerization initiator is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight.
  • Cationic polymerization curable adhesive examples include compounds having an epoxy group or an oxetanyl group.
  • the compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used.
  • a preferable epoxy compound a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or at least two epoxy groups in the molecule, at least one of them. Examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
  • the cationic polymerization curable adhesive contains the epoxy compound and the oxetane compound described above as curable components, and these are cured by cationic polymerization, and therefore, a photocationic polymerization initiator is blended therein.
  • This cationic photopolymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and starts a polymerization reaction of an epoxy group or an oxetanyl group.
  • the curable adhesive according to the present invention preferably contains the following components.
  • the active energy ray-curable adhesive according to the present invention can contain an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound.
  • an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound.
  • the content of the acrylic oligomer (A) is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component. Is preferable, and it is more preferably 15 parts by weight or less.
  • the acrylic oligomer (A) is preferably contained in an amount of 3 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the total amount of the curable component.
  • the active energy ray-curable adhesive preferably has a low viscosity in consideration of workability and uniformity during coating, and therefore, an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer is also low. Viscosity is preferred.
  • the acrylic oligomer having a low viscosity and capable of preventing curing shrinkage of the adhesive layer preferably has a weight average molecular weight (Mw) of 15000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. preferable.
  • the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, and more preferably 1000 or more. More preferably, it is particularly preferably 1500 or more.
  • the (meth) acrylic monomer constituting the acrylic oligomer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2 -Methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2 -Ethy
  • acrylic oligomer (A) examples include “ARUFON” manufactured by Toagosei Co., Ltd., “Act Flow” manufactured by Soken Chemical Co., Ltd., “JONCRYL” manufactured by BASF Japan.
  • acrylic oligomers (A) obtained by polymerizing (meth) acrylic monomers those having a high logPow value are preferable.
  • the acrylic oligomer (A) is included as a component in the calculation of the logPow value of the curable adhesive for polarizing films.
  • the number of moles of the component relating to the acrylic oligomer (A) is the number of moles converted to the (meth) acrylic monomer constituting the acrylic oligomer (A).
  • the logPow value of the acrylic oligomer (A) obtained by polymerizing the (meth) acrylic monomer is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
  • the photoacid generator (B) can be contained.
  • the active energy ray-curable adhesive contains a photoacid generator, the water resistance and durability of the adhesive layer can be dramatically improved as compared with the case where no photoacid generator is contained.
  • the photoacid generator (B) can be represented by the following general formula (3).
  • Preferred examples of the onium cation structure as the onium cation L + constituting the general formula (3) include onium cations selected from the following general formulas (4) to (12).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyl group, R 4 represents a group selected from a substituted or unsubstituted carbonyloxy group, a substituted or unsubstituted oxycarbonyl group, or a halogen atom, and R 4 represents a group similar to the groups described in R 1 , R 2 and R 3.
  • .R 5 is a substituted or unsubstituted alkyl group
  • R 6 and R 7 represents a substituted or unsubstituted alkylthio group, independently, be substituted
  • Alkyl group substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, substituted or .Ar 4 represent either a non-substituted oxycarbonyl group, Ar Is a substituted or unsubstituted aryl group, .X represent either a substituted or unsubstituted heterocyclic group, .j is .i representing an oxygen or sulfur atom represents
  • Adjacent Rs, Ar 4 and Ar 5 , R 2 and R 3 , R 2 and R 4 , R 3 and R 4 , R 1 and R 2 , R 1 and R 3 , R 1 and R 4 , R 1 and R, or R 1 and R 5 may be a cyclic structure bonded to each other.
  • Onium cation (sulfonium cation) corresponding to general formula (4): Dimethylphenylsulfonium, dimethyl (o-fluorophenyl) sulfonium, dimethyl (m-chlorophenyl) sulfonium, dimethyl (p-bromophenyl) sulfonium, dimethyl (p-cyanophenyl) sulfonium, dimethyl (m-nitrophenyl) sulfonium, dimethyl ( 2,4,6-tribromophenyl) sulfonium, dimethyl (pentafluorophenyl) sulfonium, dimethyl (p- (trifluoromethyl) phenyl) sulfonium, dimethyl (p-hydroxyphenyl) sulfonium, dimethyl (p-mercaptophenyl) sulfonium , Dimethyl (p-methylsulfinylphenyl) sulfonium, dimethyl
  • Onium cation corresponding to general formula (5) (sulfoxonium cation): Dimethylphenylsulfoxonium, dimethyl (o-fluorophenyl) sulfoxonium, dimethyl (m-chlorophenyl) sulfoxonium, dimethyl (p-bromophenyl) sulfoxonium, dimethyl (p-cyanophenyl) sulfoxonium, dimethyl (M-nitrophenyl) sulfoxonium, dimethyl (2,4,6-tribromophenyl) sulfoxonium, dimethyl (pentafluorophenyl) sulfoxonium, dimethyl (p- (trifluoromethyl) phenyl) sulfoxonium Dimethyl (p-hydroxyphenyl) sulfoxonium, dimethyl (p-mercaptophenyl) sulfoxonium, dimethyl (p-methylsulfinylphenyl) sulfoxonium, dimethyl (p
  • Onium cation (phosphonium cation) corresponding to the general formula (6): Examples of phosphonium cations: Trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl (p-fluorophenyl) phosphonium, triphenyl (o-chlorophenyl) phosphonium, triphenyl (m-bromophenyl) phosphonium, triphenyl (p-cyanophenyl) phosphonium , Triphenyl (m-nitrophenyl) phosphonium, triphenyl (p-phenylsulfanylphenyl) phosphonium, (7-methoxy-2-oxo-2H-chromen-4-yl) triphenylphosphonium, triphenyl (o-hydroxyphenyl) ) Phosphonium, triphenyl (o-acetylphenyl) phosphonium, triphenyl (m
  • Onium cation corresponding to general formula (7) (pyridinium cation): Examples of pyridinium cations: N-phenylpyridinium, N- (o-chlorophenyl) pyridinium, N- (m-chlorophenyl) pyridinium, N- (p-cyanophenyl) pyridinium, N- (o-nitrophenyl) pyridinium, N- (p-acetylphenyl) ) Pyridinium, N- (p-isopropylphenyl) pyridinium, N- (p-octadecyloxyphenyl) pyridinium, N- (p-methoxycarbonylphenyl) pyridinium, N- (9-anthryl) pyridinium, 2-chloro-1- Phenylpyridinium, 2-cyano-1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-viny
  • Onium cation (quinolinium cation) corresponding to general formula (8): Examples of quinolinium cations: N-methylquinolinium, N-ethylquinolinium, N-phenylquinolinium, N-naphthylquinolinium, N- (o-chlorophenyl) quinolinium, N- (m-chlorophenyl) quinolinium, N- (p -Cyanophenyl) quinolinium, N- (o-nitrophenyl) quinolinium, N- (p-acetylphenyl) quinolinium, N- (p-isopropylphenyl) quinolinium, N- (p-octadecyloxyphenyl) quinolinium, N- ( p-methoxycarbonylphenyl) quinolinium, N- (9-anthryl) quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquino
  • Onium cation (isoquinolinium cation) corresponding to the general formula (9):
  • isoquinolinium cations N-phenylisoquinolinium, N-methylisoquinolinium, N-ethylisoquinolinium, N- (o-chlorophenyl) isoquinolinium, N- (m-chlorophenyl) isoquinolinium, N- (p-cyanophenyl) Isoquinolinium, N- (o-nitrophenyl) isoquinolinium, N- (p-acetylphenyl) isoquinolinium, N- (p-isopropylphenyl) isoquinolinium, N- (p-octadecyloxyphenyl) isoquinolinium, N- (p-methoxycarbonyl) Phenyl) isoquinolinium, N- (9-anthryl) isoquinolinium, 1,2-diphenylisoquinolinium, N- (2-fury
  • Onium cation corresponding to general formula (10) (benzoxazolium cation, benzothiazolium cation): Examples of benzoxazolium cations: N-methylbenzoxazolium, N-ethylbenzoxazolium, N-naphthylbenzoxazolium, N-phenylbenzoxazolium, N- (p-fluorophenyl) benzoxazolium, N- (p- Chlorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (o-methoxycarbonylphenyl) benzoxazolium, N- (2-furyl) benzoxazolium, N- (o -Fluorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (m-nitrophenyl) benzoxazolium, N- (p-iso
  • benzothiazolium cations N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N- (1-naphthyl) benzothiazolium, N- (p-fluorophenyl) benzothiazolium, N -(P-chlorophenyl) benzothiazolium, N- (p-cyanophenyl) benzothiazolium, N- (o-methoxycarbonylphenyl) benzothiazolium, N- (p-tolyl) benzothiazolium, N- (o-fluorophenyl) benzothiazolium, N- (m-nitrophenyl) benzothiazolium, N- (p-isopropoxycarbonylphenyl) benzothiazolium, N- (2-furyl) benzothia Zorium, N- (4-methylthiophenyl) benzothiazolium, N-
  • Onium cation corresponding to general formula (11) (furyl or thienyl iodonium cation): Difuryliodonium, dithienyliodonium, bis (4,5-dimethyl-2-furyl) iodonium, bis (5-chloro-2-thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis (5- Nitro-2-thienyl) iodonium, bis (5-acetyl-2-furyl) iodonium, bis (5-carboxy-2-thienyl) iodonium, bis (5-methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl) -2-furyl) iodonium, bis (5- (p-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium, bis (5-ethyn
  • Onium cation corresponding to general formula (12) (diaryliodonium cation): Diphenyliodonium, bis (p-tolyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (P-octadecyloxyphenyl) iodonium, 4-isopropyl-4′-methyldiphenyliodonium, (4-isobutylphenyl) -p-tolyliodonium, bis (1-naphthyl) iodonium, bis (4-phenylsulfanylphenyl) iodonium, Phenyl (6-benzoyl-9-ethy
  • counter anion X in - are but are not theoretically limited to, non-nucleophilic anion is preferred.
  • the counter anion X ⁇ is a non-nucleophilic anion, a nucleophilic reaction is unlikely to occur in the cation coexisting in the molecule and various materials used in combination, and as a result, the photoacid generator itself represented by the general formula (2) It is possible to improve the temporal stability of an adhesive using the same.
  • the non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction.
  • Examples of such anions include PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SbCl 6 ⁇ , BiCl 5 ⁇ , SnCl 6 ⁇ , ClO 4 ⁇ , dithiocarbamate anion, SCN ⁇ and the like.
  • the counter anion X ⁇ in the general formula (3) particularly preferred as the counter anion X ⁇ in the general formula (3) include PF 6 ⁇ , SbF 6 ⁇ and AsF 6 ⁇ , and particularly preferably PF 6 ⁇ and SbF. 6 - and the like.
  • preferable onium salts constituting the photoacid generator (B) include specific examples of the structure of the onium cation represented by the above general formulas (3) to (12) and PF 6 ⁇ . , SbF 6 ⁇ , AsF 6 ⁇ , SbCl 6 ⁇ , BiCl 5 ⁇ , SnCl 6 ⁇ , ClO 4 ⁇ , dithiocarbamate anion, and an anion selected from SCN ⁇ .
  • the content of the photoacid generator (B) is 10 parts by weight or less, preferably 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferably, the amount is 0.1 to 3 parts by weight.
  • the compound (C) containing either an alkoxy group or an epoxy group can be contained.
  • the compound (C1) containing an alkoxy group the condensation reaction of the alkoxy group and the hydroxyl group proceeds, and in the compound (C2) containing an epoxy group, the addition of the epoxy group and the hydroxyl group. The reaction proceeds, and a stronger adhesiveness can be imparted to the active energy ray-curable adhesive.
  • the compound (C2) containing an epoxy group When the compound (C2) containing an epoxy group is used, a secondary hydroxyl group is generated after the reaction due to an addition reaction between the epoxy group and the hydroxyl group, which may increase the bulk water absorption rate of the present invention. It is more preferable to use the compound (C1) having a group. That is, a polarizer and a transparent protective film are laminated through an active energy ray-curable adhesive containing a photoacid generator (B) and an alkoxy group-containing compound (C1), and active energy rays are irradiated.
  • the alkoxy group of the compound (C1) having an alkoxy group and the hydroxyl group of the polarizer undergo a condensation reaction with the acid generated from the photoacid generator (B), and good adhesion between the polarizer and the transparent protective film is exhibited.
  • an adhesive layer having a lower water absorption rate can be formed by a condensation reaction between the alkoxy group-containing compounds (C1), and optical durability under a severe environment under high temperature and high humidity can be satisfied.
  • the compound (C) containing either an alkoxy group or an epoxy group may be used alone or in combination. Moreover, the compound (C) containing either an alkoxy group or an epoxy group can also be used in combination with the compound (C1) containing an alkoxy group and the compound (C2) containing an epoxy group.
  • the compound (C) containing either an alkoxy group or an epoxy group can be used in combination with or without using the photoacid generator (B), but the hydroxyl group and alkoxy group of the PVA polarizer can be used. From the viewpoint of promoting the reaction with the epoxy group, the compound (C) containing either an alkoxy group or an epoxy group is preferably used in combination with the photoacid generator (B).
  • the compound (C1) having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxyl groups in the molecule, and known compounds can be used.
  • a substituent the general formula: — (CH 2 ) n —O—R (wherein n is an integer of 1 to 3 and R represents an alkyl group having 1 to 4 carbon atoms or H.
  • R is preferably a methyl group.
  • alkoxy group-containing radical polymerizable compound include Wasmer 2MA, Wasmer 3MA, Wasmer IBM, N-isobutoxymethylacrylamide, Wasmer EMA, N-MAM-PC, MM90, Wasmer A, etc. manufactured by Kasano Kosan Co., Ltd. It is done.
  • the melamine compound examples include M-3, MK, M-6, M-100, MC, etc. of Sumitex Resin series manufactured by Sumitomo Chemical Co., Ltd. and Nikarac MW-30, MW- manufactured by Sanwa Chemical Co., Ltd. Examples thereof include 100LM, MX-750LM, MX-280, MX-270 and the like. Among these, from the viewpoint of reactivity, it is preferable to use Wasmer 2MA, N-MAM-PC, MX-750LM and the like. In calculating the glass transition temperature Tg of the adhesive layer, the compound having an alkoxyl group and the polymer (C1) are not included in the calculation.
  • Compound having epoxy group (C2) As the compound (C2) having an epoxy group, a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule can be used.
  • a polymer (epoxy resin) When a polymer (epoxy resin) is used, a compound having two or more functional groups having reactivity with an epoxy group in the molecule may be used in combination.
  • the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.
  • Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin.
  • Resin bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Multifunctional epoxy resin such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin There are glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins, etc.
  • epoxy resins may be halogenated and hydrogenated. May be.
  • resin products for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron manufactured by DIC Corporation 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Industries, Ltd., Eporide series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyethylene synthesized from bisphenols and epichlorohydrin) B carboxymethyl having an epoxy group at both ends with polyether; YP series, etc.), Nagase Chemt
  • the compounding amount of the compound (C) containing either an alkoxy group or an epoxy group is usually 30 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component, When there is too much content of a compound (C), adhesiveness will fall and the impact resistance with respect to a drop test may deteriorate.
  • the content of the compound (C) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less.
  • the active energy ray-curable adhesive preferably contains 2 parts by weight or more of the compound (C), more preferably 5 parts by weight or more.
  • the active energy ray-curable adhesive of the present invention can contain an isocyanate compound (D).
  • the isocyanate compound (D) is a compound having at least one isocyanate group in the molecule.
  • the active energy ray curable adhesive contains an isocyanate compound (D)
  • the hydroxyl group and the isocyanate group on the surface of the polarizer interact to impart stronger adhesion and water resistance to the polarizing film. it can.
  • the active energy ray-curable adhesive contains an N-hydroxyalkyl group-containing (meth) acrylamide derivative as a radical polymerizable compound
  • the content of the N-hydroxyalkyl group-containing (meth) acrylamide derivative increases, Since the hydroxyl group is contained in the adhesive layer, the bulk water absorption rate tends to be high, and as a result, the optical durability tends to be lowered in a severe humidified environment.
  • a N-hydroxyalkyl group-containing (meth) acrylamide derivative and a compound having an isocyanate group in combination, a hydroxyl group that does not contribute to adhesion to the polarizer and an isocyanate group form a urethane bond, while maintaining adhesiveness. Bulk water absorption can be reduced.
  • Examples of the isocyanate compound (D) include polyfunctional isocyanate compounds and active energy ray-curable isocyanate compounds.
  • Examples of the polyfunctional isocyanate compound include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate.
  • Cycloaliphatic polyisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylene diisocyanate; aromatics such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate Group polyisocyanates and the like.
  • Examples of the isocyanate compound (D) include trimethylolpropane / tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”], trimethylolpropane / hexamethylene diisocyanate adduct [Japan Polyurethane Industry Co., Ltd. Product name “Coronate HL”], product name “Coronate HX” (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / xylylene diisocyanate adduct [Mitsui Chemicals, product name “Takenate 110N”], etc. A commercial item is also mentioned.
  • Examples of the active energy ray-curable isocyanate compound (D) include isocyanates having a (meth) acryloyl group, such as Karenz AOI (manufactured by Showa Denko KK), Karenz BEI (manufactured by Showa Denko KK), Laromer LR9000. Commercial products such as (manufactured by BASF) are listed.
  • the compounding amount of the isocyanate compound (D) is usually 30 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component, and the content of the compound (D) in the active energy ray-curable adhesive group is When the amount is too large, the adhesiveness is lowered, and the impact resistance against the drop test may be deteriorated.
  • the content of the compound (D) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less.
  • the active energy ray-curable adhesive preferably contains 0.1 part by weight or more of the compound (D), more preferably 1 part by weight or more.
  • Silane coupling agent (E) When the curable adhesive for polarizing film of the present invention is an active energy ray curable type, it is preferable to use an active energy ray curable compound as the silane coupling agent (E). Even if it is not curable, the same water resistance can be provided.
  • silane coupling agent (E) examples include, as active energy ray-curable compounds, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.
  • a silane coupling agent (E1) having an amino group is preferable.
  • Specific examples of the silane coupling agent (E1) having an amino group include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxysilane ⁇ - (2-aminoethyl) aminopropylmethyldiethoxysilane, ⁇ - (2-aminoeth
  • the silane coupling agent (E1) having an amino group may be used alone or in combination of two or more.
  • the amount of the silane coupling agent (E) is preferably in the range of 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the total amount of the curable component. More preferably, it is 1 to 10 parts by weight. This is because when the blending amount exceeds 20 parts by weight, the storage stability of the adhesive deteriorates, and when the blending amount is less than 0.1 part by weight, the water-resistant adhesive effect is not sufficiently exhibited. In calculating the glass transition temperature Tg of the adhesive layer, the silane coupling agent (E) is not included in the calculation.
  • silane coupling agents that are not active energy ray-curable other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy.
  • Examples include silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and imidazolesilane.
  • the logPow value of each component is preferably 1 or more. More preferably, it is 2 or more.
  • a photo-acid generator (B) and a silane coupling agent (E) are not contained in the component in calculation of the logPow value of the curable adhesive for polarizing films.
  • the compound (C) containing either an alkoxy group or an epoxy group and the isocyanate compound (D) are included in the components for calculating the logPow value of the curable adhesive for polarizing films.
  • additives can be mix
  • additives include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone-based oligomer.
  • Polymers or oligomers such as polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; UV absorbers; inorganic fillers; pigments; dyes and the like.
  • various additives those having a high logPow value are preferable.
  • the logPow value of various additives is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more. In addition, these additives are not contained in the component in calculation of the logPow value of the curable adhesive for polarizing films.
  • the above additives are usually 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and most preferably 0 to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable component.
  • the curable adhesive for polarizing films of this invention contains the said sclerosing
  • the temperature of the adhesive can be controlled at the time of coating and adjusted to 100 cp or less.
  • a more preferable range of the viscosity is 1 to 80 cp, and most preferably 10 to 50 cp.
  • the viscosity can be measured using an E-type viscometer TVE22LT manufactured by Toki Sangyo Co., Ltd.
  • the polarizing film curable adhesive of the present invention preferably uses a material having low skin irritation as the curable component from the viewpoint of safety.
  • Skin irritation is P.I. I.
  • Judgment can be made with the index I.
  • P. I. I is widely used to indicate the degree of skin injury and is measured by the Draise method. The measured value is displayed in the range of 0 to 8, and it is determined that the irritation is lower as the value is smaller. However, since the error of the measured value is large, it should be taken as a reference value.
  • P. I. I is preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.
  • a transparent protective film is bonded to at least one surface of a polarizer via an adhesive layer formed of a cured product layer of the polarizing film curable adhesive.
  • the adhesive layer that is the cured product layer has a bulk water absorption of 10% by weight or less.
  • the thickness of the adhesive layer formed by the curable adhesive is preferably controlled to be 0.1 to 3 ⁇ m.
  • the thickness of the adhesive layer is more preferably 0.3 to 2 ⁇ m, and further preferably 0.5 to 1.5 ⁇ m. Setting the thickness of the adhesive layer to 0.1 ⁇ m or more is preferable in order to suppress the occurrence of poor adhesion due to the cohesive force of the adhesive layer and the occurrence of poor appearance (bubbles) during lamination.
  • the adhesive layer is thicker than 3 ⁇ m, the polarizing film may not be able to satisfy the durability.
  • the curable adhesive is preferably selected so that the Tg of the adhesive layer formed thereby is 60 ° C. or higher, more preferably 70 ° C. or higher, and further 75 ° C. or higher, Further, it is preferably 100 ° C. or higher, more preferably 120 ° C. or higher.
  • the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower.
  • Tg ⁇ glass transition temperature> is measured under the following measurement conditions using a TA Instruments dynamic viscoelasticity measuring apparatus RSAIII.
  • the curable adhesive preferably has a storage elastic modulus of an adhesive layer formed thereby of 1.0 ⁇ 10 6 Pa or more in a region of 70 ° C. or less. Further, it is more preferably 1.0 ⁇ 10 7 Pa or more.
  • the storage elastic modulus of the adhesive layer affects the polarizer cracks when the polarizing film is subjected to a heat cycle ( ⁇ 40 ° C. to 80 ° C., etc.). Cheap.
  • the temperature region having a high storage elastic modulus is more preferably 80 ° C. or less, and most preferably 90 ° C. or less.
  • the storage elastic modulus is measured under the same measurement conditions using a dynamic viscoelasticity measuring device RSAIII manufactured by TA Instruments simultaneously with Tg ⁇ glass transition temperature>. The dynamic viscoelasticity was measured and the value of storage elastic modulus (E ′ ′) was adopted.
  • the polarizer and the transparent protective film are coated with a curable adhesive on the surface of the polarizer forming the adhesive layer and / or the surface of the transparent protective film forming the adhesive layer. And then a step of curing the curable adhesive to form an adhesive layer.
  • the polarizer and the transparent protective film may be subjected to surface modification treatment before applying the curable adhesive.
  • Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
  • the coating method of the curable adhesive is appropriately selected depending on the viscosity of the curable adhesive and the target thickness.
  • coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like.
  • a method such as a dapping method can be appropriately used.
  • the polarizer and the transparent protective film are bonded together through the curable adhesive applied as described above. Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.
  • the polarizing film curable adhesive according to the present invention is used as an active energy ray curable adhesive or a thermosetting adhesive.
  • the active energy ray curable adhesive can be used in an electron beam curable type, an ultraviolet ray curable type, or a visible light curable type.
  • the embodiment of the curable adhesive is preferably an active energy ray curable adhesive rather than a thermosetting adhesive from the viewpoint of productivity, and moreover, the active energy ray curable adhesive is a visible light curable adhesive. It is preferable from the viewpoint of productivity.
  • the active energy ray curable adhesive After bonding the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated and the active energy ray curable adhesive is cured and bonded. An agent layer is formed.
  • the irradiation direction of active energy rays can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side.
  • the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet ray, visible light, etc.).
  • the acceleration voltage is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong and damages the transparent protective film and the polarizer. There is a risk of giving.
  • the irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy.
  • the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.
  • the electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, the transparent protective film surface where the electron beam first hits can be obstructed to prevent oxygen damage and prevent damage to the transparent protective film. An electron beam can be irradiated efficiently.
  • active energy rays containing visible light having a wavelength range of 380 nm to 450 nm particularly active energy rays having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm are used as active energy rays. It is preferable.
  • a transparent protective film ultraviolet non-transparent transparent protective film
  • ultraviolet absorbing ability in the ultraviolet curable type and visible light curable type, light having a wavelength shorter than about 380 nm is absorbed.
  • Light does not reach the active energy ray-curable adhesive and does not contribute to the polymerization reaction. Furthermore, light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curling and wrinkling of the polarizing film. Therefore, when the ultraviolet curable type or the visible light curable type is adopted in the present invention, it is preferable to use a device that does not emit light having a wavelength shorter than 380 nm as the active energy ray generating device, and more specifically, the wavelength range 380.
  • the ratio of the integrated illuminance of ⁇ 440 nm to the integrated illuminance of the wavelength range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40.
  • a gallium-encapsulated metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable.
  • low pressure mercury lamp medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight
  • a light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter.
  • a gallium-encapsulated metal halide lamp can be used and light with a wavelength shorter than 380 nm can be blocked. It is preferable to use an active energy ray obtained through a band pass filter or an active energy ray having a wavelength of 405 nm obtained using an LED light source.
  • the temperature should be increased to 40 ° C. or higher. Is preferable, and heating to 50 ° C. or higher is more preferable. It is also preferable to heat the active energy ray-curable adhesive after irradiation with ultraviolet rays or visible light (heating after irradiation), in which case it is preferable to heat to 40 ° C. or higher, and warm to 50 ° C. or higher. It is more preferable.
  • the active energy ray-curable adhesive according to the present invention can be suitably used particularly when forming an adhesive layer that adheres a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm.
  • the active energy ray-curable adhesive according to the present invention irradiates ultraviolet rays through the transparent protective film having UV absorption ability by containing the photopolymerization initiator of the general formula (1) described above,
  • the adhesive layer can be hardened. Therefore, an adhesive bond layer can be hardened also in a polarizing film which laminated a transparent protective film which has UV absorption ability on both sides of a polarizer.
  • the adhesive layer can also be cured in a polarizing film in which a transparent protective film having no UV absorbing ability is laminated.
  • the transparent protective film which has UV absorption ability means the transparent protective film whose transmittance
  • Examples of the method for imparting UV absorbing ability to the transparent protective film include a method of containing an ultraviolet absorber in the transparent protective film and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.
  • ultraviolet absorber examples include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like.
  • the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated to cure the active energy ray-curable adhesive to form an adhesive layer.
  • the irradiation direction of active energy rays can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side.
  • the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet ray, visible light, etc.).
  • thermosetting adhesive after laminating a polarizer and a transparent protective film, by heating, polymerization is started by a thermal polymerization initiator to form a cured product layer.
  • the heating temperature is set according to the thermal polymerization initiator, but is about 60 to 200 ° C., preferably 80 to 150 ° C.
  • the line speed depends on the curing time of the adhesive, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m / min. min.
  • the line speed is too low, the productivity is poor, or the damage to the transparent protective film is too great, and a polarizing film that can withstand the durability test cannot be produced.
  • the line speed is too high, the adhesive is not sufficiently cured, and the target adhesiveness may not be obtained.
  • the polarizer and the transparent protective film are bonded together via an adhesive layer formed by the cured layer of the active energy ray-curable adhesive.
  • An easy-adhesion layer can be provided between the agent layers.
  • the easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.
  • the easy-adhesion layer is usually provided in advance on a transparent protective film, and the easy-adhesion layer side of the transparent protective film and the polarizer are bonded together with an adhesive layer.
  • the easy-adhesion layer is formed by coating and drying the material for forming the easy-adhesion layer on the transparent protective film by a known technique.
  • the material for forming the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating.
  • the thickness of the easy-adhesion layer after drying is preferably 0.01 to 5 ⁇ m, more preferably 0.02 to 2 ⁇ m, and still more preferably 0.05 to 1 ⁇ m. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.
  • the polarizer is not particularly limited, and various types can be used.
  • the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye.
  • polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
  • a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
  • the thickness of these polarizers is not particularly limited, but is generally about 80 ⁇ m or less.
  • 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 boric acid or potassium iodide. 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 dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. 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 in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • the curable adhesive of the present invention is remarkably effective when a thin polarizer having a thickness of 10 ⁇ m or less is used as the polarizer (satisfying optical durability in a severe environment under high temperature and high humidity). Can be expressed.
  • the polarizer having a thickness of 10 ⁇ m or less is relatively more affected by moisture than a polarizer having a thickness exceeding 10 ⁇ m, and has insufficient optical durability in a high-temperature and high-humidity environment, resulting in increased transmittance and degree of polarization. Decline is likely to occur.
  • the polarizer of 10 ⁇ m or less when the polarizer of 10 ⁇ m or less is laminated with the adhesive layer having a bulk water absorption of 10% by weight or less according to the present invention, the movement of water to the polarizer is suppressed in a severe high temperature and high humidity environment. Thus, deterioration of optical durability such as an increase in transmittance of the polarizing film and a decrease in the degree of polarization can be remarkably suppressed.
  • the thickness of the polarizer is preferably 1 to 7 ⁇ m from the viewpoint of thinning. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, and the thickness of the polarizing film can be reduced.
  • the thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- And a thin polarizing film described in Japanese Patent Application No. 269002 and Japanese Patent Application No. 2010-263692.
  • These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing 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
  • the thin polarizing film among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, the one obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending
  • the thin high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 ⁇ m or less made of a PVA-based resin oriented with a dichroic material, which is integrally formed on a resin base material. It is a high-functional polarizing film, and has optical properties such as a single transmittance of 42.0% or more and a polarization degree of 99.95% or more.
  • the thin high-performance polarizing film generates a PVA-based resin layer by applying and drying a PVA-based resin on a resin substrate having a thickness of at least 20 ⁇ m, and the generated PVA-based resin layer is used as a dichroic dyeing solution. So that the dichroic substance is adsorbed on the PVA resin layer, and the PVA resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the boric acid aqueous solution so that the total draw ratio is the original length. It can manufacture by extending
  • a method for producing a laminate film including a thin high-performance polarizing film in which a dichroic substance is oriented and includes a resin base material having a thickness of at least 20 ⁇ m and a PVA resin on one side of the resin base material.
  • surface of the resin base material A step of adsorbing the dichroic substance to the PVA resin layer contained in the laminate film by immersing the film in a dye solution containing the dichroic substance, and a PVA resin adsorbing the dichroic substance
  • the thin polarizing films in the above-mentioned Japanese Patent Application Nos. 2010-269002 and 2010-263692 are continuous web polarizing films made of a PVA-based resin in which a dichroic material is oriented, and are amorphous.
  • the laminate including the PVA-based resin layer formed on the ester-based thermoplastic resin base material was stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching, so that the thickness was 10 ⁇ m or less. Is.
  • Such thin polarizing film a single transmittance T, hours the polarization was P, P> - (10 0.929T -42.4-1) ⁇ 100 ( however, T ⁇ 42.3), and P ⁇ It is preferable that the optical properties satisfy 99.9 (where T ⁇ 42.3).
  • the thin polarizing film is a stretch intermediate formed of an oriented PVA resin layer by high-temperature stretching in the air with respect to the PVA resin layer formed on the amorphous ester thermoplastic resin substrate of the continuous web.
  • a colored intermediate product comprising a PVA-based resin layer in which a dichroic material (preferably iodine or a mixture of iodine and an organic dye) is oriented by adsorption of the dichroic material to the stretched intermediate product and a step of generating the product.
  • a thin polarizing film comprising a step of forming a product, and a step of generating a polarizing film having a thickness of 10 ⁇ m or less comprising a PVA-based resin layer in which a dichroic material is oriented by stretching in a boric acid solution with respect to a colored intermediate product It can be manufactured by a manufacturing method.
  • the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable.
  • stretching can be 60 degreeC or more.
  • the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping.
  • the amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed.
  • the draw ratio of high-temperature drawing in the air is preferably 3.5 times or less, and the drawing temperature of high-temperature drawing in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C.
  • the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times .
  • the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred. More specifically, a thin polarizing film can be produced by the following method.
  • a base material for a continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared.
  • the glass transition temperature of amorphous PET is 75 ° C.
  • a laminate comprising a continuous web of amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.
  • a 200 ⁇ m-thick amorphous PET base material and a 4-5% PVA aqueous solution in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more are dissolved in water are prepared.
  • an aqueous PVA solution is applied to a 200 ⁇ m thick amorphous PET substrate and dried at a temperature of 50 to 60 ° C. to obtain a laminate in which a 7 ⁇ m thick PVA layer is formed on the amorphous PET substrate. .
  • a thin and highly functional polarizing film having a thickness of 3 ⁇ m is manufactured from the laminate including the PVA layer having a thickness of 7 ⁇ m through the following steps including a two-stage stretching process of air-assisted stretching and boric acid water stretching.
  • the laminate including the 7 ⁇ m-thick PVA layer is integrally stretched with the amorphous PET substrate to produce a stretched laminate including the 5 ⁇ m-thick PVA layer.
  • a laminate including a 7 ⁇ m-thick PVA layer is subjected to a stretching apparatus disposed in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio is 1.8 times. Are stretched uniaxially at the free end.
  • the PVA layer contained in the stretched laminate is changed to a 5 ⁇ m thick PVA layer in which PVA molecules are oriented.
  • this colored laminate has a single layer transmittance of the PVA layer constituting the high-functional polarizing film that is finally produced by using the stretched laminate in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C.
  • Iodine is adsorbed to the PVA layer contained in the stretched laminate by dipping for an arbitrary period of time so as to be 40 to 44%.
  • the staining solution uses water as a solvent, and an iodine concentration within the range of 0.12 to 0.30% by weight and a potassium iodide concentration within the range of 0.7 to 2.1% by weight.
  • concentration ratio of iodine and potassium iodide is 1 to 7.
  • potassium iodide is required to dissolve iodine in water.
  • the stretched laminate is immersed for 60 seconds in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight. A colored laminate is adsorbed on the substrate.
  • the colored laminated body is further stretched integrally with the amorphous PET base material by the second stage boric acid underwater stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 ⁇ m.
  • the optical film laminate is subjected to stretching by applying the colored laminate to a stretching apparatus provided in a treatment apparatus set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C. containing boric acid and potassium iodide. It is stretched uniaxially at the free end so that the magnification is 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C.
  • the colored laminate having an adjusted iodine adsorption amount is first immersed in an aqueous boric acid solution for 5 to 10 seconds. After that, the colored laminate is passed as it is between a plurality of sets of rolls with different peripheral speeds, which is a stretching apparatus installed in the processing apparatus, and the stretching ratio can be freely increased to 3.3 times over 30 to 90 seconds. Stretch uniaxially.
  • the PVA layer contained in the colored laminate is changed into a PVA layer having a thickness of 3 ⁇ m in which the adsorbed iodine is oriented higher in one direction as a polyiodine ion complex.
  • This PVA layer constitutes a highly functional polarizing film of the optical film laminate.
  • the optical film laminate was removed from the boric acid aqueous solution and adhered to the surface of the 3 ⁇ m-thick PVA layer formed on the amorphous PET substrate by the washing step. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process using hot air at 60 ° C.
  • the cleaning process is a process for eliminating appearance defects such as boric acid precipitation.
  • an adhesive is applied to the surface of a 3 ⁇ m-thick PVA layer formed on an amorphous PET substrate by a bonding and / or transfer process.
  • the amorphous PET substrate can be peeled off, and the 3 ⁇ m thick PVA layer can be transferred to the 80 ⁇ m thick triacetyl cellulose film.
  • the manufacturing method of said thin-shaped polarizing film may include another process other than the said process.
  • Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step.
  • the other steps can be performed at any appropriate timing.
  • the insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer.
  • the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
  • the liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C.
  • the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
  • the crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
  • the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
  • blend iodide it is preferable to mix
  • the blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above.
  • the liquid temperature of the crosslinking bath is preferably 20 ° C. to 50 ° C.
  • the crosslinking step is performed before the second boric acid aqueous drawing step.
  • the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.
  • Transparent protective film As a material for forming the transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable.
  • 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 the above
  • the polymer that forms the transparent protective film include polymer blends. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film.
  • the additive examples include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
  • the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
  • content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
  • the transparent protective film examples include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, B) Resin compositions containing a thermoplastic resin having substituted and / or unsubstituted phenyl and nitrile groups in the side chain.
  • Specific examples include a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer.
  • As the film a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing film can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.
  • moisture permeability of the transparent protective film is not more than 150g / m 2 / 24h. According to such a configuration, it is difficult for moisture in the air to enter the polarizing film, and a change in the moisture content of the polarizing film itself can be suppressed. As a result, the curling and dimensional change of the polarizing film caused by the storage environment can be suppressed.
  • a material for forming a transparent protective film provided on one or both sides of the polarizer a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is preferable.
  • / m more preferably not more 2 / 24h or less, particularly preferably those following 140 g / m 2 / 24h, more preferably the following 120 g / m 2 / 24h.
  • the moisture permeability is determined by the method described in the examples.
  • polyester resins such as polyethylene terephthalate and polyethylene naphthalate
  • polycarbonate resins arylate resins
  • amide resins such as nylon and aromatic polyamide
  • Polyolefin polymers such as ethylene / propylene copolymers, cyclic olefin resins having a cyclo or norbornene structure, (meth) acrylic resins, or a mixture thereof can be used.
  • the resins polycarbonate resins, cyclic polyolefin resins, and (meth) acrylic resins are preferable, and cyclic polyolefin resins and (meth) acrylic resins are particularly preferable.
  • the thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 100 ⁇ m from the viewpoints of workability such as strength and handleability and thin layer properties. 1 to 80 ⁇ m is particularly preferable, and 3 to 60 ⁇ m is more preferable.
  • the transparent protective film which consists of the same polymer material may be used by the front and back, and the transparent protective film which consists of a different polymer material etc. may be used.
  • Functional surfaces such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered.
  • the functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer and antiglare layer can be provided on the transparent protective film itself, and separately provided separately from the transparent protective film. You can also
  • the polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use.
  • the optical layer is not particularly limited.
  • a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film.
  • One or more optical layers that may be used can be used.
  • a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film.
  • a wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.
  • An optical film obtained by laminating the above optical layer on a polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like.
  • Appropriate bonding means such as an adhesive layer can be used for lamination.
  • the pressure-sensitive adhesive layer for adhering to other members such as a liquid crystal cell can be provided on the polarizing film described above or an optical film in which at least one polarizing film is laminated.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
  • an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected.
  • those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.
  • the adhesive layer can be provided on one side or both sides of a polarizing film or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing film or an optical film.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 ⁇ m, preferably 1 to 200 ⁇ m, and particularly preferably 1 to 100 ⁇ m.
  • the exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state.
  • a separator for example, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, or a laminate thereof, or a silicone-based or long sheet as necessary.
  • an appropriate release agent such as a chain alkyl type, fluorine type or molybdenum sulfide, can be used.
  • the polarizing film or the optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device.
  • the liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing film or optical film by invention, and it can apply according to the former.
  • the liquid crystal cell any type such as a TN type, an STN type, or a ⁇ type can be used.
  • liquid crystal display devices such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed.
  • the polarizing film or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell.
  • polarizing film or an optical film on both sides they may be the same or different.
  • liquid crystal display device for example, a single layer or a suitable layer such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.
  • Transparent protective film 1 triacetyl cellulose film having a thickness of 60 ⁇ m (the moisture permeability 530g / m 2 / 24h), was used without saponification, corona treatment or the like (in Table 1, referred to as TAC).
  • Transparent protective film 2 Using subjected to corona treatment having a lactone ring structure having a thickness of 40 [mu] m (meth) acrylic resin (moisture permeability 96 g / m 2 / 24h) (in Table 1, referred to as acrylic).
  • Transparent protective film 3 cyclic polyolefin film having a thickness of 55 .mu.m: using subjected to corona treatment (manufactured by Zeon Corporation ZEONOR, moisture permeability 11g / m 2 / 24h) (in Table 1, referred to as COP).
  • the moisture permeability was measured according to a moisture permeability test (cup method) of JIS Z0208.
  • a sample cut to a diameter of 60 mm was set in a moisture permeable cup containing about 15 g of calcium chloride, and the temperature was 40 ° C. and the humidity was 90% R.D. H.
  • active energy rays As an active energy ray, visible light (gallium filled metal halide lamp) Irradiation device: Fusion UV Systems, Inc. Light HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm 2 , integrated irradiation amount 1000 / mJ / cm 2 (wavelength 380 ⁇ 440 nm) was used. The illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
  • Examples 1 to 4 and Comparative Examples 1 to 5 Preparation of active energy ray-curable adhesive
  • the components were mixed and stirred at 50 ° C. for 1 hour to obtain active energy ray-curable adhesives according to Example 1 and Comparative Example 1.
  • the viscosity of the active energy ray-curable adhesive according to Example 1 was 95 cp (25 ° C.)
  • the viscosity of the active energy ray-curable adhesive according to Comparative Example 1 was 45 cp (25 ° C.).
  • the active energy ray-curable adhesive according to the above examples or comparative examples is coated with an MCD coater (manufactured by Fuji Machine Co., Ltd.) (cell shape: honeycomb, number of gravure roll wires: 1000 / inch, rotation speed). 140% / vs. Line speed) was applied to a thickness of 0.7 ⁇ m, and both surfaces of the polarizer X were bonded together by a roll machine.
  • MCD coater manufactured by Fuji Machine Co., Ltd.
  • the production of the polarizing film was performed for each of the three types of transparent protective films 1 to 3 described above.
  • ⁇ Curing shrinkage> This was measured by a curing shrinkage sensor “resin curing shrinkage stress measuring device EU201C” manufactured by Sentec. Specifically, the cure shrinkage rate is calculated by the method described in JP2013-104869A.
  • the cure shrinkage of the cured product formed from the active energy ray-curable adhesive according to Example 1 was 8.9%, and the cured product formed from the active energy ray-curable adhesive according to Comparative Example 1 was cured.
  • the shrinkage percentage was 11.9%.
  • ⁇ Adhesive strength> The polarizing film obtained in each example was cut into a size of 200 mm in parallel with the stretching direction of the polarizer and 20 mm in the orthogonal direction, and a slit was cut between the transparent protective film and the polarizer with a cutter knife. Laminated to the board. Using Tensilon, the transparent protective film and the polarizer were peeled in the 90-degree direction at a peeling speed of 500 mm / min, and the peel strength was measured. Moreover, the infrared absorption spectrum of the peeling surface after peeling was measured by ATR method, and the peeling interface was evaluated based on the following reference
  • A Cohesive failure of transparent protective film
  • B Interfacial peeling between transparent protective film / adhesive layer
  • C Interfacial peeling between adhesive layer / polarizer
  • D Cohesive failure of polarizer
  • a and D are adhesive strengths Is greater than the cohesive strength of the film, meaning that the adhesive strength is very excellent.
  • B and C mean that the adhesive force at the transparent protective film / adhesive layer (adhesive layer / polarizer) interface is insufficient (adhesive strength is poor).
  • the adhesive strength in the case of A or D is ⁇
  • a ⁇ B cohesive failure of transparent protective film” and “interfacial peeling between transparent protective film / adhesive layer” occur simultaneously
  • a -Adhesive strength in the case of C cohesive failure of transparent protective film” and “interfacial peeling between adhesive layer / polarizer” occur simultaneously
  • adhesive strength in the case of B or C as x To do is ⁇
  • the degree of polarization P is the transmittance when two identical polarizing films are overlapped so that their transmission axes are parallel (parallel transmittance: Tp), and overlapped so that their transmission axes are orthogonal to each other. It is calculated
  • Polarization degree P (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • Each transmittance is represented by a Y value obtained by correcting visibility with a two-degree field of view (C light source) of JIS Z8701, with 100% of the completely polarized light obtained through the Granteller prism polarizer.
  • a polarizing film in which the transparent protective films 1 and 3 were laminated on the both sides of the polarizer as a transparent protective film was prepared as a sample by the same method as in the examples and comparative examples.
  • the polarizing film (sample) was cut into a rectangle of 50 mm in the stretching direction of the polarizer and 25 mm in the vertical direction. This polarizing film was immersed in warm water at 60 ° C. for 6 hours, and then the peeled length was visually measured with a magnifier. The measurement was taken as the maximum value of the vertical distance from the cross section of the part where peeling occurred (mm).
  • a polarizing film in which the transparent protective films 1 and 3 were laminated on the both sides of the polarizer as a transparent protective film was prepared as a sample by the same method as in the examples and comparative examples.
  • the polarizing film (sample) was cut into a size of 200 mm in parallel with the stretching direction of the polarizer and 20 mm in the orthogonal direction.
  • a slit is cut between the transparent protective film and the polarizer with a cutter knife. Laminated to the board. The evaluation was carried out within 1 minute after taking out from the pure water. Thereafter, the same evaluation as in the above ⁇ Adhesive strength> was performed.
  • LogPow of curable adhesive ⁇ (logPow ⁇ Wi) logPowi: logPow value of each component of curable adhesive Wi: (number of moles of i component) / (total number of moles of each component of curable adhesive)
  • Compound containing an alkoxy group: Nicalac MX-750LM, logPow 0.8 is manufactured by Nippon Carbide Industries, Ltd.
  • Compound containing epoxy group: JER828, logPow 4.76 is manufactured by Japan Epoxy Resin Co., Ltd.
  • Isocyanate compound: Karenz AOI, logPow 1.6 is manufactured by Showa Denko KK).
  • CPI-100P a propylene carbonate solution containing 50% active ingredient mainly composed of triarylsulfonium hexafluorophosphate), manufactured by San Apro, is shown.

Abstract

This curable adhesive for polarizing films, which contains a curable component, has a bulk water absorption of 10% by weight or less in cases where a cured product of this curable adhesive for polarizing films is immersed in pure water at 23°C for 24 hours, said bulk water absorption being represented by the following formula. Bulk water absorption (%) = {(M2 - M1)/M1} × 100 (%) (In this formula, M1 represents the weight of the cured product before immersion, and M2 represents the weight of the cured product after immersion.) This curable adhesive for polarizing films provides excellent adhesion between a polarizer and a transparent protective film, and is able to have satisfactory optical durability in a harsh environment at high temperature and high humidity. In addition, this curable adhesive for polarizing films exhibits sufficient adhesive power even if immersed in water for a long period of time.

Description

偏光フィルム用硬化型接着剤、偏光フィルム、光学フィルムおよび画像表示装置Curable adhesive for polarizing film, polarizing film, optical film and image display device
　本発明は、偏光子と透明保護フィルムとを接着剤層を介して積層している偏光フィルムにおいて、前記接着剤層を形成する偏光フィルム用硬化型接着剤に関する。また本発明は、前記接着剤層を用いた偏光フィルムに関する。当該偏光フィルムはこれ単独で、またはこれを積層した光学フィルムとして液晶表示装置（ＬＣＤ）、有機ＥＬ表示装置、ＣＲＴ、ＰＤＰなどの画像表示装置を形成しうる。 The present invention relates to a polarizing film curable adhesive for forming an adhesive layer in a polarizing film in which a polarizer and a transparent protective film are laminated via an adhesive layer. The present invention also relates to a polarizing film using the adhesive layer. The polarizing film can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP alone or as an optical film obtained by laminating the polarizing film.
　時計、携帯電話、ＰＤＡ、ノートパソコン、パソコン用モニタ、ＤＶＤプレーヤー、ＴＶなどでは液晶表示装置が急激に市場展開している。液晶表示装置は、液晶のスイッチングによる偏光状態を可視化させたものであり、その表示原理から、偏光子が用いられる。特に、ＴＶなどの用途では、ますます高輝度、高コントラスト、広い視野角が求められ、偏光フィルムにおいてもますます高透過率、高偏光度、高い色再現性などが求められている。 Liquid crystal display devices are rapidly expanding in the market for watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, etc. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle. In particular, in applications such as TV, higher brightness, higher contrast, and wider viewing angle are required, and polarizing films are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.
　偏光子としては、高透過率、高偏光度を有することから、例えばポリビニルアルコール（以下、単に「ＰＶＡ」ともいう）にヨウ素を吸着させ、延伸した構造のヨウ素系偏光子が最も一般的に広く使用されている。一般的に偏光フィルムは、ポリビニルアルコール系の材料を水に溶かしたいわゆる水系接着剤によって、偏光子の両面に透明保護フィルムを貼り合わせたものが用いられている（下記特許文献１および特許文献２）。透明保護フィルムとしては、透湿度の高いトリアセチルセルロースなどが用いられる。前記水系接着剤を用いた場合（いわゆるウェットラミネーション）には、偏光子と透明保護フィルムとを貼り合わせた後に、乾燥工程が必要となる。 As the polarizer, since it has a high transmittance and a high degree of polarization, for example, an iodine-based polarizer having a stretched structure by adsorbing iodine to polyvinyl alcohol (hereinafter also simply referred to as “PVA”) is most widely used. in use. In general, a polarizing film in which a transparent protective film is bonded to both surfaces of a polarizer by a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water is used (Patent Document 1 and Patent Document 2 below). ). As the transparent protective film, triacetyl cellulose having a high moisture permeability is used. When the water-based adhesive is used (so-called wet lamination), a drying process is required after the polarizer and the transparent protective film are bonded together.
　一方、前記水系接着剤の代わりに、活性エネルギー線硬化型接着剤が提案されている。活性エネルギー線硬化型接着剤を用いて偏光フィルムを製造する場合には、乾燥工程を必要としないため、偏光フィルムの生産性を向上させることができる。例えば、Ｎ－置換アミド系モノマーを硬化性成分として使用した、ラジカル重合型の活性エネルギー線硬化型接着剤が提案されている（下記特許文献３および特許文献４）。かかる接着剤は、高湿度下および高温下の過酷な環境下において優れた耐久性を発揮するものであるが、市場においては、さらなる接着性および／または耐水性を向上できる接着剤が要求されつつあるのが実情であった。 On the other hand, instead of the water-based adhesive, an active energy ray-curable adhesive has been proposed. When manufacturing a polarizing film using an active energy ray hardening-type adhesive, since a drying process is not required, productivity of a polarizing film can be improved. For example, radical polymerization type active energy ray-curable adhesives using an N-substituted amide monomer as a curable component have been proposed (Patent Documents 3 and 4 below). Such an adhesive exhibits excellent durability under harsh environments under high humidity and high temperature. However, in the market, there is a demand for an adhesive that can further improve adhesiveness and / or water resistance. There was a real situation.
　また、硬化性成分のＳＰ値（溶解性パラメータ）に着目して、少なくとも３種類のＳＰ値の異なるラジカル重合性化合物を所定の組成比率で用いることで、耐久性および耐水性を向上した接着剤層を形成できる活性エネルギー線硬化型接着剤が提案されている（下記特許文献５）。 Further, by paying attention to the SP value (solubility parameter) of the curable component, an adhesive having improved durability and water resistance by using at least three kinds of radical polymerizable compounds having different SP values in a predetermined composition ratio. An active energy ray-curable adhesive capable of forming a layer has been proposed (Patent Document 5 below).
特開２００６－２２０７３２号公報JP 2006-220732 A 特開２００１－２９６４２７号公報JP 2001-296427 A 特開２００８－２８７２０７号公報JP 2008-287207 A 特開２０１０－０７８７００号公報JP 2010-078700 A 特開２０１２－１４４６９０号公報JP 2012-144690 A
　上記特許文献５に記載の活性エネルギー線硬化型接着剤によれば、偏光フィルムの製造に際して用いる各種の透明保護フィルムに対して、耐久性および耐水性を満足することができる。しかし、特許文献５に記載の活性エネルギー線硬化型接着剤を用いて得られた偏光フィルムは、６０℃の温水に６時間浸漬した場合の耐水性（温水浸漬試験）を満足することができるものの、市場においては、さらなる高温高湿下の過酷な環境下における光学耐久性が求められている。さらには、前記偏光フィルムには、水中に長時間浸漬した場合にも十分な接着力を有することが求められている。 According to the active energy ray-curable adhesive described in Patent Document 5, durability and water resistance can be satisfied with respect to various transparent protective films used in the production of a polarizing film. However, although the polarizing film obtained using the active energy ray-curable adhesive described in Patent Document 5 can satisfy water resistance (hot water immersion test) when immersed in hot water at 60 ° C. for 6 hours. In the market, optical durability under a severe environment under further high temperature and high humidity is required. Furthermore, the polarizing film is required to have sufficient adhesive strength even when immersed in water for a long time.
　本発明は、偏光子と透明保護フィルムとの接着性が良好であり、かつ高温高湿下の過酷な環境下における光学耐久性を満足することができるとともに、水中に長時間浸漬した場合にも十分な接着力を有する偏光フィルム用硬化型接着剤を提供することを目的とする。 The present invention has good adhesion between the polarizer and the transparent protective film, and can satisfy optical durability in a severe environment under high temperature and high humidity, and also when immersed in water for a long time. It aims at providing the curable adhesive for polarizing films which has sufficient adhesive force.
　また本発明は、偏光フィルム用硬化型接着剤を用いて形成された接着剤層により、偏光子に透明保護フィルムが設けられている偏光フィルムを提供すること、さらには、前記偏光フィルムを用いた光学フィルムを提供すること、さらには前記偏光フィルムまたは光学フィルムを用いた画像表示装置を提供することを目的とする。 Moreover, this invention provides the polarizing film by which the transparent protective film is provided in the polarizer by the adhesive bond layer formed using the curable adhesive for polarizing films, Furthermore, the said polarizing film was used. An object is to provide an optical film, and further to provide an image display device using the polarizing film or the optical film.
　本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、下記の偏光フィルム用硬化型接着剤により、上記目的を達成できることを見出し、本発明を解決するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above object can be achieved by the following curable adhesive for polarizing film, and have solved the present invention.
　即ち、本発明は、硬化性成分を含有する偏光フィルム用硬化型接着剤であって、
　当該偏光フィルム用硬化型接着剤は、当該硬化型接着剤を硬化させて得られる硬化物を２３℃の純水に２４時間浸漬した場合に、下記式：
　バルク吸水率（％）＝｛（Ｍ２－Ｍ１）／Ｍ１｝×１００、
　｛但し、前記式中、Ｍ１は浸漬前の硬化物の重量、Ｍ２は浸漬後の硬化物の重量を示す｝で表わされるバルク吸水率が１０重量％以下であることを特徴とする偏光フィルム用硬化型接着剤、に関する。 That is, the present invention is a polarizing film curable adhesive containing a curable component,
When the cured product obtained by curing the curable adhesive is immersed in pure water at 23 ° C. for 24 hours, the curable adhesive for polarizing film has the following formula:
Bulk water absorption (%) = {(M2-M1) / M1} × 100,
{Wherein, in the above formula, M1 represents the weight of the cured product before dipping, and M2 represents the weight of the cured product after dipping}, and the bulk water absorption is 10% by weight or less. The present invention relates to a curable adhesive.
　前記偏光フィルム用硬化型接着剤は、オクタノール／水分配係数（ｌｏｇＰｏｗ値）が１以上であることが好ましい。 The polarizing film curable adhesive preferably has an octanol / water partition coefficient (logPow value) of 1 or more.
　前記偏光フィルム用硬化型接着剤は、前記硬化性成分が、活性エネルギー線硬化性成分の場合は、活性エネルギー線硬化型接着剤として用いることができる。前記硬化性成分として、ラジカル重合性化合物を含有することできる。前記ラジカル重合性化合物としては、（メタ）アクリルアミド誘導体を含有することが好ましい。また、前記ラジカル重合性化合物としては、ラジカル重合性を有する官能基を少なくとも２つ有する多官能性化合物を含有することが好ましい。また、前記活性エネルギー線硬化型接着剤は、さらに、光重合開始剤を含有することができる。 The polarizing film curable adhesive can be used as an active energy ray curable adhesive when the curable component is an active energy ray curable component. As the curable component, a radical polymerizable compound can be contained. The radical polymerizable compound preferably contains a (meth) acrylamide derivative. The radical polymerizable compound preferably contains a polyfunctional compound having at least two functional groups having radical polymerizable properties. Moreover, the said active energy ray hardening-type adhesive agent can contain a photoinitiator further.
　前記偏光フィルム用硬化型接着剤は、さらに、アクリル系オリゴマー（Ａ）を含有することができる。 The polarizing film curable adhesive may further contain an acrylic oligomer (A).
　前記偏光フィルム用硬化型接着剤は、さらに、光酸発生剤（Ｂ）を含有することができる。 The polarizing film curable adhesive may further contain a photoacid generator (B).
　前記偏光フィルム用硬化型接着剤は、さらに、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）を含有することができる。前記アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）としては、アルコキシ基を含む化合物（Ｃ１）が好ましい。さらには、前記アルコキシ基を含む化合物（Ｃ１）は、アルコキシ基を含むメラミン化合物であることが好ましい。 The polarizing film curable adhesive may further contain a compound (C) containing either an alkoxy group or an epoxy group. The compound (C) containing either an alkoxy group or an epoxy group is preferably a compound (C1) containing an alkoxy group. Furthermore, the compound (C1) containing an alkoxy group is preferably a melamine compound containing an alkoxy group.
　また、前記偏光フィルム用硬化型接着剤は、さらに、イソシアネート化合物（Ｄ）を含有することができる。 Moreover, the said curable adhesive for polarizing films can contain an isocyanate compound (D) further.
　前記偏光フィルム用硬化型接着剤は、前記硬化性成分が熱硬化性成分の場合は、さらに熱重合開始剤を含有することで、熱硬化型接着剤として用いることができる。 When the curable component is a thermosetting component, the polarizing film curable adhesive can be used as a thermosetting adhesive by further containing a thermal polymerization initiator.
　また本発明は、偏光子の少なくとも一方の面に、接着剤層を介して透明保護フィルムが設けられている偏光フィルムであって、
　前記接着剤層が、上記偏光フィルム用硬化型接着剤の硬化物層により形成されたものであることを特徴とする偏光フィルム、に関する。 Further, the present invention is a polarizing film, wherein a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer,
The said adhesive layer is formed with the hardened | cured material layer of the said curable adhesive for polarizing films, It is related with the polarizing film characterized by the above-mentioned.
　前記偏光フィルムにおいて、前記接着剤硬化物層の厚みが０．１～３μｍであることが好ましい。 In the polarizing film, the cured adhesive layer preferably has a thickness of 0.1 to 3 μm.
　さらに本発明は、前記偏光フィルムが、少なくとも１枚積層されていることを特徴とする光学フィルム、に関する。 Furthermore, the present invention relates to an optical film characterized in that at least one polarizing film is laminated.
　さらに本発明は、前記偏光フィルム、または前記光学フィルムが用いられていることを特徴とする画像表示装置、に関する。 Furthermore, the present invention relates to an image display device using the polarizing film or the optical film.
　本発明の偏光フィルム用硬化型接着剤は、当該硬化型接着剤を硬化させて得られる硬化物のバルク吸水率が１０重量％以下である。当該バルク吸水率は、本発明の偏光フィルム用硬化型接着剤から得られる硬化物層により接着剤層を形成した際の吸水性が非常に低いこと示している。従って、偏光子に、前記硬化物層からなる接着剤層を介して透明保護フィルムが設けられた偏光フィルムは、偏光子と透明保護フィルム層との接着性が良好であり、かつ高温高湿下の過酷な環境下における光学耐久性を満足することができる。 In the curable adhesive for polarizing film of the present invention, the bulk water absorption of a cured product obtained by curing the curable adhesive is 10% by weight or less. The said bulk water absorption has shown that the water absorption at the time of forming an adhesive bond layer by the hardened | cured material layer obtained from the curable adhesive for polarizing films of this invention is very low. Therefore, the polarizing film in which the transparent protective film is provided on the polarizer via the adhesive layer composed of the cured product layer has good adhesiveness between the polarizer and the transparent protective film layer, and also under high temperature and high humidity. The optical durability under the severe environment can be satisfied.
　例えば、本発明の偏光フィルム用硬化型接着剤を用いて形成された硬化物層（接着剤層）を有する偏光フィルムは、過酷な加湿環境下（８５℃×８５％ＲＨ）においても光学耐久性（加湿耐久性試験）が良好である。そのため、本発明の偏光フィルムは、前記過酷な加湿環境下におかれた場合においても、偏光フィルムの透過率、偏光度の低下（変化）を小さく抑えることができる。また、本発明の偏光フィルムは、水に浸漬させるような過酷な環境下においても接着力の低下を抑制することができ、水中に長時間浸漬した場合にも十分な接着力を有する偏光フィルムを提供することができる。 For example, a polarizing film having a cured product layer (adhesive layer) formed using the curable adhesive for polarizing film of the present invention has optical durability even in a severe humidified environment (85 ° C. × 85% RH). (Humidification durability test) is good. Therefore, the polarizing film of the present invention can suppress a decrease (change) in the transmittance and the degree of polarization of the polarizing film even when the polarizing film is placed in the severe humidified environment. Further, the polarizing film of the present invention can suppress a decrease in adhesive force even under a harsh environment such as being immersed in water, and a polarizing film having sufficient adhesive force even when immersed in water for a long time. Can be provided.
　＜バルク吸水率＞
　本発明の偏光フィルム用硬化型接着剤は、当該硬化型接着剤を硬化させて得られる硬化物を２３℃の純水に２４時間浸漬した場合に測定した、上記記載のバルク吸水率が１０重量％以下である。偏光フィルムを過酷な高温高湿（８５℃／８５％ＲＨなど）の環境下においた際、透明保護フィルムと接着剤層とを透過した水分が偏光子へ侵入し、架橋構造が加水分解することによって２色性色素の配向が乱れ、透過率上昇、偏光度低下などの光学耐久性の悪化が起こる。接着剤層のバルク吸水率を１０重量％以下にすることにより、偏光フィルムを過酷な高温高湿の環境下においた時の偏光子への水の移動が抑制され、偏光子の透過率上昇、偏光度低下を抑制することができる。前記バルク吸水率は、偏光フィルムの接着剤層について、高温下の過酷な環境下における光学耐久性をより良好にする観点から、５重量％以下であるのが好ましく、さらには３重量％以下が好ましく、さらには１．５重量％以下が好ましく、最も好ましくは１重量％以下である。一方、偏光子と透明保護フィルムとを貼り合わせる際、偏光子は一定量の水分を保持しており、当該硬化型接着剤と偏光子に含まれる水分とが接触した際にハジキ、気泡などの外観不良が発生することがある。外観不良を抑制するためには、当該硬化型接着剤は一定量の水分を吸収できることが好ましい。より具体的には、バルク吸水率は０．０１重量％以上であるのが好ましく、さらには、０．０５重量％以上であるのが好ましい。前記バルク吸水率は、具体的にはＪＩＳＫ ７２０９に記載の吸水率試験方法によって測定される。 <Bulk water absorption>
The curable adhesive for polarizing film of the present invention has a bulk water absorption of 10 wt% measured when a cured product obtained by curing the curable adhesive is immersed in pure water at 23 ° C. for 24 hours. % Or less. When a polarizing film is placed in a severe environment of high temperature and high humidity (85 ° C / 85% RH, etc.), moisture that has passed through the transparent protective film and the adhesive layer enters the polarizer and the crosslinked structure is hydrolyzed. As a result, the orientation of the dichroic dye is disturbed, and optical durability such as an increase in transmittance and a decrease in polarization degree occurs. By making the bulk water absorption of the adhesive layer 10% by weight or less, the movement of water to the polarizer when the polarizing film is placed in a severe high temperature and high humidity environment is suppressed, and the transmittance of the polarizer is increased. A decrease in the degree of polarization can be suppressed. The bulk water absorption is preferably 5% by weight or less, more preferably 3% by weight or less from the viewpoint of making the optical durability in a harsh environment at a high temperature more favorable for the adhesive layer of the polarizing film. It is preferably 1.5% by weight or less, and most preferably 1% by weight or less. On the other hand, when the polarizer and the transparent protective film are bonded together, the polarizer retains a certain amount of moisture. When the curable adhesive comes into contact with moisture contained in the polarizer, repelling, bubbles, etc. Appearance defects may occur. In order to suppress poor appearance, it is preferable that the curable adhesive can absorb a certain amount of moisture. More specifically, the bulk water absorption is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more. Specifically, the bulk water absorption rate is measured by a water absorption rate test method described in JISK 7209.
　本発明の偏光フィルム用硬化型接着剤は、オクタノール／水分配係数（以下，ｌｏｇＰｏｗ値，という）が高いものが好ましい。ｌｏｇＰｏｗ値とは物質の親油性を表す指標であり、オクタノール／水の分配係数の対数値を意味する。ｌｏｇＰｏｗが高いということは親油性であることを意味し、即ち、吸水率が低いことを意味する。ｌｏｇＰｏｗ値は測定することも可能（ＪＩＳ－Ｚ－７２６０記載のフラスコ浸とう法）だが、偏光フィルム用硬化型接着剤の構成成分（硬化性成分等）である各化合物の構造をもとに計算によって算出することもできる。本明細書では、ケンブリッジソフト社製ＣｈｅｍＤｒａｗ Ｕｌｔｒａで計算されたｌｏｇＰｏｗ値を用いる。
　上記計算値を基に、本発明における偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値は、下記式によって計算することができる。
　　硬化型接着剤のｌｏｇＰｏｗ＝Σ（ｌｏｇＰｏｗｉ×Ｗｉ）
　ｌｏｇＰｏｗｉ：硬化型接着剤の各成分のｌｏｇＰｏｗ値
　Ｗｉ：（ｉ成分のモル数）／（硬化型接着剤の各成分の総モル数）
　上記の計算にあたっては、硬化型接着剤の各成分のなかで、重合開始剤や光酸発生剤などの硬化物（接着剤層）の骨格を形成しない成分は、上記計算における成分から除かれる。本発明の偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値は好ましくは１以上、より好ましくは１．５以上、最も好ましくは２以上である。これにより接着耐水性や加湿耐久性を高めることができる。一方、本発明の偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値は通常８以下程度であって、５以下が好ましく、４以下がより好ましい。このｌｏｇＰｏｗ値が高すぎると、前述の通りハジキや気泡などの外観不良が発生しやすくなるため好ましくない。 The curable adhesive for polarizing film of the present invention preferably has a high octanol / water partition coefficient (hereinafter referred to as logPow value). The logPow value is an index representing the lipophilicity of a substance and means the logarithmic value of the octanol / water partition coefficient. High logPow means that it is lipophilic, that is, low water absorption. The logPow value can also be measured (flask immersion method described in JIS-Z-7260), but calculated based on the structure of each compound that is a component (such as a curable component) of a curable adhesive for polarizing films. Can also be calculated. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft is used.
Based on the calculated value, the logPow value of the polarizing film curable adhesive in the present invention can be calculated by the following formula.
LogPow of curable adhesive = Σ (logPow × Wi)
logPowi: logPow value of each component of curable adhesive Wi: (number of moles of i component) / (total number of moles of each component of curable adhesive)
In the above calculation, among the components of the curable adhesive, components that do not form a skeleton of a cured product (adhesive layer) such as a polymerization initiator and a photoacid generator are excluded from the components in the above calculation. The logPow value of the curable adhesive for polarizing film of the present invention is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. Thereby, water resistance and humidification durability can be improved. On the other hand, the logPow value of the curable adhesive for polarizing film of the present invention is usually about 8 or less, preferably 5 or less, and more preferably 4 or less. If the logPow value is too high, appearance defects such as repelling and bubbles are likely to occur as described above, which is not preferable.
　また、本発明における前記バルク吸水率を１０重量％以下とする手段は特に限定されるものではないが、偏光フィルム用硬化型接着剤が複数の成分を含有する組成物の場合には各成分を選択することにより、前記範囲にバルク吸水率を制御することが可能である。例えば、偏光フィルム用硬化型接着剤が、複数の成分を含有する接着剤組成物の場合には、当該接着剤組成物中のｌｏｇＰｏｗ値が１以下となる成分の割合が少なくなるように調製することなどの方法で、前記範囲にバルク吸水率を制御することができる。本発明における前記バルク吸水率を１０重量％以下に調整するには、例えば、偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値を１以上に制御することにより行うことができる。 In addition, the means for setting the bulk water absorption to 10% by weight or less in the present invention is not particularly limited, but in the case where the curable adhesive for polarizing film is a composition containing a plurality of components, each component is added. By selecting, it is possible to control the bulk water absorption within the above range. For example, in the case where the polarizing film curable adhesive is an adhesive composition containing a plurality of components, the adhesive composition is prepared so that the proportion of components having a logPow value of 1 or less in the adhesive composition is reduced. The bulk water absorption can be controlled within the above range. The bulk water absorption in the present invention can be adjusted to 10% by weight or less, for example, by controlling the logPow value of the polarizing film curable adhesive to 1 or more.
　＜硬化収縮率＞
　また、本発明の偏光フィルム用硬化型接着剤は、硬化性成分を有することから、当該硬化型接着剤を硬化させた場合には、通常、硬化収縮が生じる。硬化収縮率は、偏光フィルム用硬化型接着剤から接着剤層を形成する時における硬化収縮の割合を示す指標である。接着剤層の硬化収縮率が大きくなると、偏光フィルム用硬化型接着剤を硬化させて接着剤層を形成する時に界面ひずみが生じて、接着不良が生じることを抑制するうえで好ましい。上記観点から、本発明の偏光フィルム用硬化型接着剤を硬化させて得られる硬化物に係る上記硬化収縮率は１０％以下であるのが好ましい。前記硬化収縮率は小さいことが好ましく、前記硬化収縮率は８％以下が好ましく、さらには５％以下が好ましい。前記硬化収縮率は、特開２０１３－１０４８６９号に記載の方法によって測定され、具体的には実施例に記載のセンテック社製硬化収縮センサーによる方法により測定される。 <Curing shrinkage>
Moreover, since the curable adhesive for polarizing films of the present invention has a curable component, curing shrinkage usually occurs when the curable adhesive is cured. The cure shrinkage rate is an index indicating the rate of cure shrinkage when an adhesive layer is formed from a curable adhesive for polarizing film. When the cure shrinkage rate of the adhesive layer is increased, it is preferable for suppressing the occurrence of poor adhesion due to interface distortion when the adhesive layer is formed by curing the curable adhesive for polarizing film. From the above viewpoint, it is preferable that the curing shrinkage rate of the cured product obtained by curing the curable adhesive for polarizing film of the present invention is 10% or less. The curing shrinkage rate is preferably small, and the curing shrinkage rate is preferably 8% or less, more preferably 5% or less. The cure shrinkage rate is measured by the method described in JP2013-104869A, and specifically, measured by the method using a cure shrinkage sensor manufactured by Centec Co., Ltd. described in the examples.
　＜硬化性成分＞
　本発明の偏光フィルム用硬化型接着剤は、硬化性成分を含有する。当該硬化性成分は硬化物が上記バルク吸水率を満足するように適宜に選択される。 <Curable component>
The polarizing film curable adhesive of the present invention contains a curable component. The curable component is appropriately selected so that the cured product satisfies the bulk water absorption rate.
　硬化性成分としては、電子線硬化型、紫外線硬化型、可視光線硬化型等の活性エネルギー線硬化型と熱硬化型に大別することができる。さらには、紫外線硬化型、可視光線硬化型接着剤は、ラジカル重合硬化型接着剤とカチオン重合型接着剤に区分出来る。本発明において、波長範囲１０ｎｍ～３８０ｎｍ未満の活性エネルギー線を紫外線、波長範囲３８０ｎｍ～８００ｎｍの活性エネルギー線を可視光線として表記する。前記ラジカル重合硬化型接着剤の硬化性成分は、熱硬化型接着剤の硬化性成分として用いることができる。 The curable component can be roughly classified into an active energy ray curable type such as an electron beam curable type, an ultraviolet curable type, a visible light curable type, and a thermosetting type. Furthermore, ultraviolet curable and visible light curable adhesives can be classified into radical polymerization curable adhesives and cationic polymerization adhesives. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light. The curable component of the radical polymerization curable adhesive can be used as a curable component of a thermosetting adhesive.
　＜１：ラジカル重合硬化型接着剤＞
　前記硬化性成分としては、例えば、ラジカル重合硬化型接着剤に用いられるラジカル重合性化合物が挙げられる。ラジカル重合性化合物は、（メタ）アクリロイル基、ビニル基等の炭素－炭素二重結合のラジカル重合性の官能基を有する化合物が挙げられる。これら硬化性成分は、単官能ラジカル重合性化合物または二官能以上の多官能ラジカル重合性化合物のいずれも用いることができる。また、これらラジカル重合性化合物は、１種を単独で、または２種以上を組み合わせて用いることができる。これらラジカル重合性化合物としては、例えば、（メタ）アクリロイル基を有する化合物が好適である。なお、本発明において、（メタ）アクリロイルとは、アクリロイル基および／またはメタクリロイル基を意味し、「（メタ）」は以下同様の意味である。 <1: Radical polymerization curable adhesive>
Examples of the curable component include radical polymerizable compounds used in radical polymerization curable adhesives. Examples of the radical polymerizable compound include compounds having a radical polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. As these curable components, either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. As these radically polymerizable compounds, for example, compounds having a (meth) acryloyl group are suitable. In the present invention, (meth) acryloyl means an acryloyl group and / or methacryloyl group, and “(meth)” has the same meaning hereinafter.
　≪単官能ラジカル重合性化合物≫
　単官能ラジカル重合性化合物としては、例えば、（メタ）アクリルアミド基を有する（メタ）アクリルアミド誘導体が挙げられる。（メタ）アクリルアミド誘導体は、偏光子や各種の透明保護フィルムとの接着性を確保するうえで、また、重合速度が速く生産性に優れる点で好ましい。（メタ）アクリルアミド誘導体の具体例としては、例えば、Ｎ－メチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド等のＮ－アルキル基含有（メタ）アクリルアミド誘導体；Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド、Ｎ－メチロール－Ｎ－プロパン（メタ）アクリルアミド等のＮ－ヒドロキシアルキル基含有（メタ）アクリルアミド誘導体；アミノメチル（メタ）アクリルアミド、アミノエチル（メタ）アクリルアミド等のＮ－アミノアルキル基含有（メタ）アクリルアミド誘導体；Ｎ－メトキシメチルアクリルアミド、Ｎ－エトキシメチルアクリルアミド等のＮ－アルコキシ基含有（メタ）アクリルアミド誘導体；メルカプトメチル（メタ）アクリルアミド、メルカプトエチル（メタ）アクリルアミド等のＮ－メルカプトアルキル基含有（メタ）アクリルアミド誘導体；などが挙げられる。また、（メタ）アクリルアミド基の窒素原子が複素環を形成している複素環含有（メタ）アクリルアミド誘導体としては、例えば、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あげられる。 ≪Monofunctional radical polymerizable compound≫
Examples of the monofunctional radical polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group. A (meth) acrylamide derivative is preferable in terms of securing adhesiveness with a polarizer and various transparent protective films, and having a high polymerization rate and excellent productivity. Specific examples of (meth) acrylamide derivatives include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N— N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxymethyl N-alkoxy group-containing (meth) acrylamide derivatives such as acrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide; It is done. Examples of the heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocyclic ring include, for example, N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine. Etc.
　前記（メタ）アクリルアミド誘導体のなかでも、偏光子や各種の透明保護フィルムとの接着性の点から、Ｎ－ヒドロキシアルキル基含有（メタ）アクリルアミド誘導体が好ましく、特に、Ｎ－ヒドロキシエチル（メタ）アクリルアミドが好ましい。 Among the (meth) acrylamide derivatives, N-hydroxyalkyl group-containing (meth) acrylamide derivatives are preferable from the viewpoint of adhesion to polarizers and various transparent protective films, and in particular, N-hydroxyethyl (meth) acrylamide. Is preferred.
　また、単官能ラジカル重合性化合物としては、例えば、（メタ）アクリロイルオキシ基を有する各種の（メタ）アクリル酸誘導体が挙げられる。具体的には、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、２－メチル－２－ニトロプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（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、ｎ－ペンチル（メタ）アクリレート、ｔ－ペンチル（メタ）アクリレート、３－ペンチル（メタ）アクリレート、２，２－ジメチルブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、セチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、４－メチル－２－プロピルペンチル（メタ）アクリレート、ｎ－オクタデシル（メタ）アクリレートなどの（メタ）アクリル酸（炭素数１－２０）アルキルエステル類が挙げられる。 In addition, examples of the monofunctional radical polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl ( (Meth) acrylate, n-o Tadeshiru (meth) (meth) acrylic acid (1-20 carbon atoms) such as acrylates alkyl esters.
　また、前記（メタ）アクリル酸誘導体としては、例えば、シクロヘキシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート等のシクロアルキル（メタ）アクリレート；
　ベンジル（メタ）アクリレート等のアラルキル（メタ）アクリレート；
　２－イソボルニル（メタ）アクリレート、２－ノルボルニルメチル（メタ）アクリレート、５－ノルボルネン－２－イル－メチル（メタ）アクリレート、３－メチル－２－ノルボルニルメチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレ－ト、ジシクロペンテニルオキシエチル（メタ）アクリレ－ト、ジシクロペンタニル（メタ）アクリレ－ト、等の多環式（メタ）アクリレート；
　２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－メトキシメトキシエチル（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、アルキルフェノキシポリエチレングリコール（メタ）アクリレート等のアルコキシ基またはフェノキシ基含有（メタ）アクリレート；等が挙げられる。 Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate;
Aralkyl (meth) acrylates such as benzyl (meth) acrylate;
2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclo Polycyclic (meth) acrylates such as pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) Examples thereof include alkoxy groups such as acrylates and alkylphenoxypolyethylene glycol (meth) acrylates or phenoxy group-containing (meth) acrylates.
　また、前記（メタ）アクリル酸誘導体としては、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、３－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、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）アクリレートや、［４－（ヒドロキシメチル）シクロヘキシル］メチルアクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；
　グリシジル（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のエポキシ基含有（メタ）アクリレート；
　２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，２－トリフルオロエチルエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、ヘキサフルオロプロピル（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート、ヘプタデカフルオロデシル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート等のハロゲン含有（メタ）アクリレート；
　ジメチルアミノエチル（メタ）アクリレート等のアルキルアミノアルキル（メタ）アクリレート；
　３－オキセタニルメチル（メタ）アクリレート、３－メチルーオキセタニルメチル（メタ）アクリレート、３－エチルーオキセタニルメチル（メタ）アクリレート、３－ブチルーオキセタニルメチル（メタ）アクリレート、３－ヘキシルーオキセタニルメチル（メタ）アクリレート等のオキセタン基含有（メタ）アクリレート；
　テトラヒドロフルフリル（メタ）アクリレート、ブチロラクトン（メタ）アクリレート、などの複素環を有する（メタ）アクリレートや、ヒドロキシピバリン酸ネオペンチルグリコール（メタ）アクリル酸付加物、ｐ－フェニルフェノール（メタ）アクリレート等が挙げられる。 Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc. And hydroxyl groups such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Meth) acrylate;
Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether;
2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) ) Halogen-containing (meth) acrylates such as acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate;
Alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate;
3-Oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate, 3-hexyloxetanylmethyl (meta) ) Oxetane group-containing (meth) acrylates such as acrylates;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate, butyrolactone (meth) acrylate, neopentyl glycol (meth) acrylic acid adducts such as hydroxypivalate, p-phenylphenol (meth) acrylate, etc. Can be mentioned.
　また、単官能ラジカル重合性化合物としては、（メタ）アクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸などのカルボキシル基含有モノマーが挙げられる。 Also, examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
　また、単官能ラジカル重合性化合物としては、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。 Examples of the monofunctional radical polymerizable compound 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, Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole and vinyl morpholine.
　また、単官能ラジカル重合性化合物としては、活性メチレン基を有するラジカル重合性化合物を用いることができる。活性メチレン基を有するラジカル重合性化合物は、末端または分子中に（メタ）アクリル基などの活性二重結合基を有し、かつ活性メチレン基を有する化合物である。活性メチレン基としては、例えばアセトアセチル基、アルコキシマロニル基、またはシアノアセチル基などが挙げられる。前記活性メチレン基がアセトアセチル基であることが好ましい。活性メチレン基を有するラジカル重合性化合物の具体例としては、例えば２－アセトアセトキシエチル（メタ）アクリレート、２－アセトアセトキシプロピル（メタ）アクリレート、２－アセトアセトキシ－１－メチルエチル（メタ）アクリレートなどのアセトアセトキシアルキル（メタ）アクリレート；２－エトキシマロニルオキシエチル（メタ）アクリレート、２－シアノアセトキシエチル（メタ）アクリレート、Ｎ－（２－シアノアセトキシエチル）アクリルアミド、Ｎ－（２－プロピオニルアセトキシブチル）アクリルアミド、Ｎ－（４－アセトアセトキシメチルベンジル）アクリルアミド、Ｎ－（２－アセトアセチルアミノエチル）アクリルアミドなどが挙げられる。活性メチレン基を有するラジカル重合性化合物は、アセトアセトキシアルキル（メタ）アクリレートであることが好ましい。 Also, as the monofunctional radically polymerizable compound, a radically polymerizable compound having an active methylene group can be used. The radical polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group at the terminal or in the molecule. Examples of the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group. The active methylene group is preferably an acetoacetyl group. Specific examples of the radical polymerizable compound having an active methylene group include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate, and the like. Acetoacetoxyalkyl (meth) acrylate; 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) Examples include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, and N- (2-acetoacetylaminoethyl) acrylamide. The radical polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
　≪多官能ラジカル重合性化合物≫
　また、二官能以上の多官能ラジカル重合性化合物としては、例えば、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジアクリレート、２－エチル－２－ブチルプロパンジオールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡプロピレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、ネオぺンチルグリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリート、環状トリメチロールプロパンフォルマル（メタ）アクリレート、ジオキサングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ＥＯ変性ジグリセリンテトラ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステル化物、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレンがあげられる。具体例としては、アロニックスＭ－２２０、Ｍ－３０６（東亞合成社製）、ライトアクリレート１，９ＮＤ－Ａ（共栄社化学社製）、ライトアクリレートＤＧＥ－４Ａ（共栄社化学社製）、ライトアクリレートＤＣＰ－Ａ（共栄社化学社製）、ＳＲ－５３１（Ｓａｒｔｏｍｅｒ社製）、ＣＤ－５３６（Ｓａｒｔｏｍｅｒ社製）等が挙げられる。また必要に応じて、各種のエポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレートや、各種の（メタ）アクリレート系モノマー等が挙げられる。 ≪Polyfunctional radical polymerizable compound≫
Examples of the bifunctional or higher polyfunctional radical polymerizable compound include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) ) Acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) Acryte, cyclic trimethylolpropane formal (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta Esterified products of (meth) acrylic acid and polyhydric alcohols such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate, 9,9-bis [4- (2- (Meth) acryloyloxyethoxy) phenyl] fluorene. Specific examples include Aronix M-220, M-306 (manufactured by Toagosei Co., Ltd.), light acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DCP- A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sartomer), CD-536 (manufactured by Sartomer) and the like. Moreover, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary.
　ラジカル重合性化合物は、前記多官能ラジカル重合性化合物を含有することが、上記硬化物の吸水率を制御するうえ、また、偏光フィルムの過酷な加湿環境下での光学耐久性を満足させるうえで好ましい。前記多官能ラジカル重合性化合物のなかでも、ｌｏｇＰｏｗ値が高いものが好ましい。ラジカル重合性化合物のｌｏｇＰｏｗ値は、好ましくは２以上、より好ましくは３以上、最も好ましくは４以上である。 The radical polymerizable compound contains the polyfunctional radical polymerizable compound in order to control the water absorption rate of the cured product and to satisfy the optical durability of the polarizing film in a severely humidified environment. preferable. Among the polyfunctional radical polymerizable compounds, those having a high logPow value are preferable. The logPow value of the radical polymerizable compound is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
　ｌｏｇＰｏｗ値が高いラジカル重合性化合物としては、例えば、トリシクロデカンジメタノールジ（メタ）アクリート（ｌｏｇＰｏｗ＝３．０５）、イソボルニル（メタ）アクリレート（ｌｏｇＰｏｗ＝３．２７）などの脂環（メタ）アクリレート；
　１，９－ノナンジオールジ（メタ）アクリレート（ｌｏｇＰｏｗ＝３．６８）、１，１０－デカンジオールジアクリレート（ｌｏｇＰｏｗ＝４．１０）などの長鎖脂肪族（メタ）アクリレート；
　ヒドロキシピバリン酸ネオペンチルグリコール（メタ）アクリル酸付加物（ｌｏｇＰｏｗ＝３．３５）、２－エチル－２－ブチルプロパンジオールジ（メタ）アクリレート（ｌｏｇＰｏｗ＝３．９２）などの多分岐（メタ）アクリレート；
　ビスフェノールＡジ（メタ）アクリレート（ｌｏｇＰｏｗ＝５．４６）、ビスフェノールＡエチレンオキサイド４モル付加物ジ（メタ）アクリレート（ｌｏｇＰｏｗ＝５．１５）、ビスフェノールＡプロピレンオキサイド２モル付加物ジ（メタ）アクリレート（ｌｏｇＰｏｗ＝６．１０）、ビスフェノールＡプロピレンオキサイド４モル付加物ジ（メタ）アクリレート（ｌｏｇＰｏｗ＝６．４３）、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン（ｌｏｇＰｏｗ＝７．４８）、ｐ－フェニルフェノール（メタ）アクリレート（ｌｏｇＰｏｗ＝３．９８）などの芳香環を含有する（メタ）アクリレート；
などが挙げられる。 Examples of the radical polymerizable compound having a high log Pow value include alicyclic (meth) such as tricyclodecane dimethanol di (meth) acrylate (logPow = 3.05) and isobornyl (meth) acrylate (logPow = 3.27). Acrylate;
Long chain aliphatic (meth) acrylates such as 1,9-nonanediol di (meth) acrylate (logPow = 3.68), 1,10-decanediol diacrylate (logPow = 4.10);
Multi-branched (meth) acrylates such as hydroxypivalate neopentyl glycol (meth) acrylic acid adduct (logPow = 3.35), 2-ethyl-2-butylpropanediol di (meth) acrylate (logPow = 3.92) ;
Bisphenol A di (meth) acrylate (logPow = 5.46), bisphenol A ethylene oxide 4 mol adduct di (meth) acrylate (logPow = 5.15), bisphenol A propylene oxide 2 mol adduct di (meth) acrylate ( logPow = 6.10), bisphenol A propylene oxide 4 mol adduct di (meth) acrylate (logPow = 6.43), 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene ( logPow = 7.48), (meth) acrylates containing aromatic rings such as p-phenylphenol (meth) acrylate (logPow = 3.98);
Etc.
　ラジカル重合性化合物は、偏光子や各種透明保護フィルムとの接着性と、過酷な環境下にける光学耐久性を両立させる観点から、単官能ラジカル重合性化合物と多官能ラジカル重合性化合物を併用することが好ましい。通常は、ラジカル重合性化合物１００重量％に対して、単官能ラジカル重合性化合物３～８０重量％と多官能ラジカル重合性化合物２０～９７重量％の割合で併用することが好ましい。 A radically polymerizable compound uses a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound together from the viewpoint of achieving both adhesiveness with a polarizer and various transparent protective films and optical durability under harsh environments. It is preferable. Usually, it is preferable to use a combination of 3 to 80% by weight of the monofunctional radical polymerizable compound and 20 to 97% by weight of the polyfunctional radical polymerizable compound with respect to 100% by weight of the radical polymerizable compound.
　＜ラジカル重合硬化型接着剤の態様＞
　本発明の偏光フィルム用硬化型接着剤は、硬化性成分を活性エネルギー線硬化性成分として用いる場合には活性エネルギー線硬化型接着剤として、また、硬化性成分を熱硬化性成分として用いる場合には熱硬化型接着剤として用いることができる。前記活性エネルギー線硬化型接着剤は、活性エネルギー線に電子線等を用いる場合には、当該活性エネルギー線硬化型接着剤は光重合開始剤を含有することは必要ではないが、活性エネルギー線に紫外線または可視光線を用いる場合には、光重合開始剤を含有するのが好ましい。一方、前記接着剤の硬化性成分を熱硬化性成分として用いる場合には、当該接着剤は熱重合開始剤を含有するのが好ましい。 <Aspect of radical polymerization curable adhesive>
When the curable component is used as an active energy ray curable component, the polarizing film curable adhesive of the present invention is used as an active energy ray curable adhesive, and when the curable component is used as a thermosetting component. Can be used as a thermosetting adhesive. When the active energy ray-curable adhesive uses an electron beam or the like as the active energy ray, the active energy ray-curable adhesive does not need to contain a photopolymerization initiator. When ultraviolet rays or visible rays are used, it is preferable to contain a photopolymerization initiator. On the other hand, when the curable component of the adhesive is used as a thermosetting component, the adhesive preferably contains a thermal polymerization initiator.
　≪光重合開始剤≫
　ラジカル重合性化合物を用いる場合の光重合開始剤は、活性エネルギー線によって適宜に選択される。紫外線または可視光線により硬化させる場合には紫外線または可視光線開裂の光重合開始剤が用いられる。前記光重合開始剤としては、例えば、ベンジル、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などのベンゾフェノン系化合物；４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン、α－ヒドロキシ－α，α´－ジメチルアセトフェノン、２－メチル－２－ヒドロキシプロピオフェノン、α－ヒドロキシシクロヘキシルフェニルケトンなどの芳香族ケトン化合物；メトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフエノン、２，２－ジエトキシアセトフェノン、２－メチル－１－［４－（メチルチオ）－フェニル］－２－モルホリノプロパン－１などのアセトフェノン系化合物；べンゾインメチルエーテル、べンゾインエチルエーテル、ベンゾインイソプロピルエーテル、べンゾインブチルエーテル、アニソインメチルエーテルなどのベンゾインエーテル系化合物；ベンジルジメチルケタールなどの芳香族ケタール系化合物；２－ナフタレンスルホニルクロリドなどの芳香族スルホニルクロリド系化合物；１－フェノン－１，１―プロパンジオン－２－（ｏ－エトキシカルボニル）オキシムなどの光活性オキシム系化合物；チオキサンソン、２－クロロチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、２，４－ジクロロチオキサンソン、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソン、ドデシルチオキサントンなどのチオキサンソン系化合物；カンファーキノン；ハロゲン化ケトン；アシルホスフィノキシド；アシルホスフォナートなどがあげられる。光重合開始剤のなかでも、ｌｏｇＰｏｗ値が高いものが好ましい。光重合開始剤は、偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値の計算における成分には含まれないが、光重合開始剤のｌｏｇＰｏｗ値は、好ましくは１以上、より好ましくは２以上、最も好ましくは３以上である。 ≪Photopolymerization initiator≫
The photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray. In the case of curing with ultraviolet light or visible light, a photopolymerization initiator for ultraviolet light or visible light cleavage is used. Examples of the photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2 -Propyl) ketone, aromatic ketone compounds such as α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether; Benzoin ethyl ether, benzoin Benzoin ether compounds such as isopropyl ether, benzoin butyl ether and anisoin methyl ether; aromatic ketal compounds such as benzyldimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenone-1 , 1-propanedione-2- (o-ethoxycarbonyl) oxime, etc .; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone Thioxanthone compounds such as Son, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; camphorquinone; halogenated ketone; Inokishido; and acyl phospholipase diisocyanate, and the like. Among photopolymerization initiators, those having a high logPow value are preferred. The photopolymerization initiator is not included in the component for calculating the logPow value of the curable adhesive for polarizing film, but the logPow value of the photopolymerization initiator is preferably 1 or more, more preferably 2 or more, most preferably 3 or more.
　前記光重合開始剤の配合量は、硬化性成分（ラジカル重合性化合物）の全量１００重量部に対して、２０重量部以下である。光重合開始剤の配合量は、０．０１～２０重量部であるのが好ましく、さらには、０．０５～１０重量部、さらには０．１～５重量部であるのが好ましい。 The blending amount of the photopolymerization initiator is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.
　また本発明の偏光フィルム用硬化型接着剤を、硬化性成分としてラジカル重合性化合物を含有する可視光線硬化型で用いる場合には、特に３８０ｎｍ以上の光に対して高感度な光重合開始剤を用いることが好ましい。３８０ｎｍ以上の光に対して高感度な光重合開始剤については後述する。 Moreover, when using the curable adhesive for polarizing films of the present invention in a visible light curable type containing a radical polymerizable compound as a curable component, a photopolymerization initiator that is particularly sensitive to light of 380 nm or more is used. It is preferable to use it. A photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.
　前記光重合開始剤としては、下記一般式（１）で表される化合物；
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ１およびＲ２は－Ｈ、－ＣＨ２ＣＨ３、－ｉＰｒまたはＣｌを示し、Ｒ１およびＲ２は同一または異なっても良い）を単独で使用するか、あるいは一般式（１）で表される化合物と後述する３８０ｎｍ以上の光に対して高感度な光重合開始剤とを併用することが好ましい。一般式（１）で表される化合物を使用した場合、３８０ｎｍ以上の光に対して高感度な光重合開始剤を単独で使用した場合に比べて接着性に優れる。一般式（１）で表される化合物の中でも、Ｒ１およびＲ２が－ＣＨ２ＣＨ３であるジエチルチオキサントンが特に好ましい。接着剤中の一般式（１）で表される化合物の組成比率は、硬化性成分の全量１００重量部に対して、０．１～５重量部であることが好ましく、０．５～４重量部であることがより好ましく、０．９～３重量部であることがさらに好ましい。 As said photoinitiator, the compound represented by following General formula (1);
Figure JPOXMLDOC01-appb-C000001
 (Wherein R 1 and R 2 represent —H, —CH 2 CH 3 , —iPr or Cl, and R 1 and R 2 may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later. When the compound represented by the general formula (1) is used, the adhesiveness is excellent as compared with a case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (1), diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable. The composition ratio of the compound represented by the general formula (1) in the adhesive is preferably 0.1 to 5 parts by weight, and preferably 0.5 to 4 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferably, it is 0.9 to 3 parts by weight.
　また、必要に応じて重合開始助剤を添加することが好ましい。重合開始助剤としては、トリエチルアミン、ジエチルアミン、Ｎ－メチルジエタノールアミン、エタノールアミン、４－ジメチルアミノ安息香酸、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸イソアミルなどが挙げられ、４－ジメチルアミノ安息香酸エチルが特に好ましい。重合開始助剤を使用する場合、その添加量は、硬化性成分の全量１００重量部に対して、通常０～５重量部、好ましくは０～４重量部、最も好ましくは０～３重量部である。 Further, it is preferable to add a polymerization initiation assistant as necessary. Examples of polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable. When a polymerization initiation assistant is used, its addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component. is there.
　また、必要に応じて公知の光重合開始剤を併用することができる。ＵＶ吸収能を有する透明保護フィルムは、３８０ｎｍ以下の光を透過しないため、光重合開始剤としては、３８０ｎｍ以上の光に対して高感度な光重合開始剤を使用することが好ましい。具体的には、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、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、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウムなどが挙げられる。 Further, a known photopolymerization initiator can be used in combination as necessary. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.
　特に、光重合開始剤として、一般式（１）の光重合開始剤に加えて、さらに下記一般式（２）で表される化合物；
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ３、Ｒ４およびＲ５は－Ｈ、－ＣＨ３、－ＣＨ２ＣＨ３、－ｉＰｒまたはＣｌを示し、Ｒ３、Ｒ４およびＲ５は同一または異なっても良い）を使用することが好ましい。一般式（２）で表される化合物としては、市販品でもある２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ９０７　メーカー：ＢＡＳＦ）が好適に使用可能である。その他、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（商品名：ＩＲＧＡＣＵＲＥ３６９　メーカー：ＢＡＳＦ）、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン（商品名：ＩＲＧＡＣＵＲＥ３７９　メーカー：ＢＡＳＦ）が感度が高いため好ましい。 In particular, as a photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2);
Figure JPOXMLDOC01-appb-C000002
 Wherein R 3 , R 4 and R 5 represent —H, —CH 3 , —CH 2 CH 3 , —iPr or Cl, and R 3 , R 4 and R 5 may be the same or different. It is preferable to use it. As the compound represented by the general formula (2), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercial product is suitable. Can be used. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF), 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferred because of its high sensitivity.
　＜活性メチレン基を有するラジカル重合性化合物（ａ１）と、水素引き抜き作用のあるラジカル重合開始剤（ａ２）＞
　上記活性エネルギー線硬化型接着剤において、ラジカル重合性化合物として、活性メチレン基を有するラジカル重合性化合物（ａ１）を用いる場合には、水素引き抜き作用のあるラジカル重合開始剤（ａ２）と組み合わせて用いるのが好ましい。かかる構成によれば、特に高湿度環境または水中から取り出した直後（非乾燥状態）であっても、偏光フィルムの有する接着剤層の接着性が著しく向上する。この理由は明らかでは無いが、以下の原因が考えられる。つまり、活性メチレン基を有するラジカル重合性化合物（ａ１）は、接着剤層を構成する他のラジカル重合性化合物とともに重合しつつ、接着剤層中のベースポリマーの主鎖および／または側鎖に取り込まれ、接着剤層を形成する。かかる重合過程において、水素引き抜き作用のあるラジカル重合開始剤（ａ２）が存在すると、接着剤層を構成するベースポリマーが形成されつつ、活性メチレン基を有するラジカル重合性化合物（ａ２）から、水素が引き抜かれ、メチレン基にラジカルが発生する。そして、ラジカルが発生したメチレン基とＰＶＡなどの偏光子の水酸基とが反応し、接着剤層と偏光子との間に共有結合が形成される。その結果、特に非乾燥状態であっても、偏光フィルムの有する接着剤層の接着性が著しく向上するものと推測される。 <Radically polymerizable compound (a1) having an active methylene group and radical polymerization initiator (a2) having a hydrogen abstracting action>
In the active energy ray-curable adhesive, when the radical polymerizable compound (a1) having an active methylene group is used as the radical polymerizable compound, it is used in combination with the radical polymerization initiator (a2) having a hydrogen abstraction function. Is preferred. According to such a configuration, the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a high humidity environment or immediately after being taken out from water (non-dried state). The reason for this is not clear, but the following causes are considered. That is, the radically polymerizable compound (a1) having an active methylene group is taken into the main chain and / or the side chain of the base polymer in the adhesive layer while being polymerized together with other radically polymerizable compounds constituting the adhesive layer. Forming an adhesive layer. In this polymerization process, when a radical polymerization initiator (a2) having a hydrogen abstracting action is present, the base polymer constituting the adhesive layer is formed, and hydrogen is generated from the radical polymerizable compound (a2) having an active methylene group. It is extracted and a radical is generated in the methylene group. And the methylene group which the radical generate | occur | produced, and the hydroxyl group of polarizers, such as PVA, react, and a covalent bond is formed between an adhesive bond layer and a polarizer. As a result, it is speculated that the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a non-dry state.
　本発明においては、水素引き抜き作用のあるラジカル重合開始剤（ａ２）として、例えばチオキサントン系ラジカル重合開始剤、ベンゾフェノン系ラジカル重合開始剤などが挙げられる。前記ラジカル重合開始剤（ａ２）は、チオキサントン系ラジカル重合開始剤であることが好ましい。チオキサントン系ラジカル重合開始剤としては、例えば上記一般式（１）で表される化合物が挙げられる。一般式（１）で表される化合物の具体例としては、例えば、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントンなどが挙げられる。一般式（１）で表される化合物の中でも、Ｒ１およびＲ２が－ＣＨ２ＣＨ３であるジエチルチオキサントンが特に好ましい。 In the present invention, examples of the radical polymerization initiator (a2) having a hydrogen abstracting action include thioxanthone radical polymerization initiators and benzophenone radical polymerization initiators. The radical polymerization initiator (a2) is preferably a thioxanthone radical polymerization initiator. Examples of the thioxanthone radical polymerization initiator include compounds represented by the above general formula (1). Specific examples of the compound represented by the general formula (1) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. Among the compounds represented by the general formula (1), diethylthioxanthone in which R 1 and R 2 are —CH 2 CH 3 is particularly preferable.
　上記活性エネルギー線硬化型接着剤において、活性メチレン基を有するラジカル重合性化合物（ａ１）と、水素引き抜き作用のあるラジカル重合開始剤（ａ２）を含有する場合には、硬化性成分の全量を１００重量％としたとき、前記活性メチレン基を有するラジカル重合性化合物（ａ１）を１～５０重量％、およびラジカル重合開始剤（ａ２）を、硬化性成分の全量１００重量部に対して０．１～１０重量部含有することが好ましい。 In the active energy ray-curable adhesive, when the radical polymerizable compound (a1) having an active methylene group and the radical polymerization initiator (a2) having a hydrogen abstraction function are contained, the total amount of the curable component is 100. When the weight percent, the radically polymerizable compound (a1) having an active methylene group is 1 to 50% by weight, and the radical polymerization initiator (a2) is 0.1% with respect to 100 parts by weight of the total amount of the curable component. The content is preferably 10 to 10 parts by weight.
　上述のとおり、本発明においては、水素引き抜き作用のあるラジカル重合開始剤（ａ２）の存在下で、活性メチレン基を有するラジカル重合性化合物（ａ１）のメチレン基にラジカルを発生させ、かかるメチレン基とＰＶＡなどの偏光子の水酸基とが反応し、共有結合を形成する。したがって、活性メチレン基を有するラジカル重合性化合物（ａ１）のメチレン基にラジカルを発生させ、かかる共有結合を十分に形成するために、硬化性成分の全量を１００重量％としたとき、活性メチレン基を有するラジカル重合性化合物（ａ１）を１～５０重量％含有するのが好ましく、さらには３～３０重量％含有することがより好ましい。耐水性を十分に向上させて非乾燥状態での接着性を向上させるには活性メチレン基を有するラジカル重合性化合物（ａ１）は１重量％以上とするのが好ましい。一方、５０重量％を超えると、接着剤層の硬化不良が発生する場合がある。また、水素引き抜き作用のあるラジカル重合開始剤（ａ２）は、硬化性成分の全量１００重量部に対して０．１～１０重量部含有することが好ましく、さらには０．３～９重量部含有することがより好ましい。水素引き抜き反応を十分に進行させるには、ラジカル重合開始剤（ａ２）を０．１重量部以上用いることが好ましい。一方、１０重量部を超えると、接着剤中で完全に溶解しない場合がある。 As described above, in the present invention, a radical is generated in the methylene group of the radical polymerizable compound (a1) having an active methylene group in the presence of the radical polymerization initiator (a2) having a hydrogen abstracting action, and the methylene group And a hydroxyl group of a polarizer such as PVA react to form a covalent bond. Therefore, in order to generate radicals in the methylene group of the radically polymerizable compound (a1) having an active methylene group and to sufficiently form such a covalent bond, when the total amount of the curable component is 100% by weight, the active methylene group It is preferable to contain 1 to 50% by weight of the radically polymerizable compound (a1) having a more preferable content of 3 to 30% by weight. In order to sufficiently improve the water resistance and improve the adhesion in a non-dry state, the radical polymerizable compound (a1) having an active methylene group is preferably 1% by weight or more. On the other hand, if it exceeds 50% by weight, the adhesive layer may be poorly cured. The radical polymerization initiator (a2) having a hydrogen abstracting action is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total amount of the curable component. More preferably. In order to sufficiently advance the hydrogen abstraction reaction, it is preferable to use 0.1 parts by weight or more of the radical polymerization initiator (a2). On the other hand, if it exceeds 10 parts by weight, it may not completely dissolve in the adhesive.
　≪熱重合開始剤≫
　熱重合開始剤としては、接着剤層の形成の際には熱開裂によって重合が開始しないものが好ましい。例えば、熱重合開始剤としては、１０時間半減期温度が６５℃以上、さらには７５～９０℃であるものが好ましい。なお、の半減期とは、重合開始剤の分解速度を表す指標であり、重合開始剤の残存量が半分になるまでの時間をいう。任意の時間で半減期を得るための分解温度や、任意の温度での半減期時間に関しては、メーカーカタログなどに記載されており、たとえば、日本油脂株式会社の「有機過酸化物カタログ第９版（２００３年５月）」などに記載されている。 ≪Thermal polymerization initiator≫
As the thermal polymerization initiator, those in which polymerization does not start by thermal cleavage when the adhesive layer is formed are preferable. For example, as the thermal polymerization initiator, those having a 10-hour half-life temperature of 65 ° C. or higher, more preferably 75 to 90 ° C. are preferable. The half-life is an index representing the decomposition rate of the polymerization initiator, and means the time until the remaining amount of the polymerization initiator is halved. The decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic peroxide catalog 9th edition by Nippon Oil & Fats Co., Ltd.” (May 2003) ".
　熱重合開始剤としては、例えば、過酸化ラウロイル（１０時間半減期温度：６４℃）、過酸化ベンゾイル（１０時間半減期温度：７３℃）、１，１－ビス（ｔ－ブチルペルオキシ）－３，３，５－トリメチルシクロへキサン（１０時間半減期温度：９０℃）、ジ（２－エチルヘキシル）パーオキシジカーボネート（１０時間半減期温度：４９℃）、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（１０時間半減期温度：５１℃）、ｔ－ブチルパーオキシネオデカノエート（１０時間半減期温度：４８℃）、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（１０時間半減期温度：６４℃）、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（１０時間半減期温度：６６℃）、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（１０時間半減期温度：７３℃）、ｔ－ブチルパーオキシイソブチレート（１０時間半減期温度：８１℃）、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン等の有機系過酸化物があげられる。 Examples of the thermal polymerization initiator include lauroyl peroxide (10 hour half-life temperature: 64 ° C.), benzoyl peroxide (10 hour half-life temperature: 73 ° C.), 1,1-bis (t-butylperoxy) -3. , 3,5-trimethylcyclohexane (10-hour half-life temperature: 90 ° C.), di (2-ethylhexyl) peroxydicarbonate (10-hour half-life temperature: 49 ° C.), di (4-t-butylcyclohexyl) Peroxydicarbonate, di-sec-butylperoxydicarbonate (10-hour half-life temperature: 51 ° C.), t-butyl peroxyneodecanoate (10-hour half-life temperature: 48 ° C.), t-hexyl peroxy Pivalate, t-butylperoxypivalate, dilauroyl peroxide (10 hour half-life temperature: 64 ° C.), di-n-octanoyl peroxide 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (10-hour half-life temperature: 66 ° C.), di (4-methylbenzoyl) peroxide, dibenzoyl peroxide (half-hour 10 hours) Organic peroxide such as t-butyl peroxyisobutyrate (10-hour half-life temperature: 81 ° C.), 1,1-di (t-hexylperoxy) cyclohexane, and the like.
　また、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（１０時間半減期温度：６７℃）、２，２’－アゾビス（２－メチルブチロニトリル）（１０時間半減期温度：６７℃）、１，１－アゾビス－シクロへキサン－１－カルボニトリル（１０時間半減期温度：８７℃）などのアゾ系化合物があげられる。 Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile (10 hour half-life temperature: 67 ° C.), 2,2′-azobis (2-methylbutyronitrile) (10 hours). And azo compounds such as 1,1-azobis-cyclohexane-1-carbonitrile (10 hour half-life temperature: 87 ° C.).
　熱重合開始剤の配合量は、硬化性成分（ラジカル重合性化合物）の全量１００重量部に対して、０．０１～２０重量部である。熱重合開始剤の配合量は、さらには０．０５～１０重量部、さらには０．１～３重量部であるのが好ましい。 The blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the thermal polymerization initiator is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts by weight.
　＜２：カチオン重合硬化型接着剤＞
　カチオン重合硬化型接着剤の硬化性成分としては、エポキシ基やオキセタニル基を有する化合物が挙げられる。エポキシ基を有する化合物は、分子内に少なくとも２個のエポキシ基を有するものであれば特に限定されず、一般に知られている各種の硬化性エポキシ化合物を用いることができる。好ましいエポキシ化合物として、分子内に少なくとも２個のエポキシ基と少なくとも１個の芳香環を有する化合物（芳香族系エポキシ化合物）や、分子内に少なくとも２個のエポキシ基を有し、そのうちの少なくとも１個は脂環式環を構成する隣り合う２個の炭素原子との間で形成されている化合物（脂環式エポキシ化合物）等が例として挙げられる。 <2: Cationic polymerization curable adhesive>
Examples of the curable component of the cationic polymerization curable adhesive include compounds having an epoxy group or an oxetanyl group. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used. As a preferable epoxy compound, a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or at least two epoxy groups in the molecule, at least one of them. Examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
　＜光カチオン重合開始剤＞
　カチオン重合硬化型接着剤は、硬化性成分として以上説明したエポキシ化合物及びオキセタン化合物を含有し、これらはいずれもカチオン重合により硬化するものであることから、光カチオン重合開始剤が配合される。この光カチオン重合開始剤は、可視光線、紫外線、Ｘ線、電子線等の活性エネルギー線の照射によって、カチオン種又はルイス酸を発生し、エポキシ基やオキセタニル基の重合反応を開始する。 <Photocationic polymerization initiator>
The cationic polymerization curable adhesive contains the epoxy compound and the oxetane compound described above as curable components, and these are cured by cationic polymerization, and therefore, a photocationic polymerization initiator is blended therein. This cationic photopolymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and starts a polymerization reaction of an epoxy group or an oxetanyl group.
　＜その他の成分＞
　本発明に係る硬化型接着剤は、下記成分を含有することが好ましい。 <Other ingredients>
The curable adhesive according to the present invention preferably contains the following components.
　＜アクリル系オリゴマー（Ａ）＞
　本発明に係る活性エネルギー線硬化型接着剤は、前記ラジカル重合性化合物に係る硬化性成分に加えて、（メタ）アクリルモノマーを重合してなるアクリル系オリゴマー（Ａ）を含有することができる。活性エネルギー線硬化型接着剤中にアクリル系オリゴマー（Ａ）を含有することで、該接着剤に活性エネルギー線を照射・硬化させる際の硬化収縮を低減し、接着剤と、偏光子および透明保護フィルムなどの被着体との界面応力を低減することができる。その結果、接着剤層と被着体との接着性の低下を抑制することができる。硬化物層（接着剤層）の硬化収縮を十分に抑制するためには、硬化性成分の全量１００重量部に対して、アクリル系オリゴマー（Ａ）の含有量は、２０重量部以下であることが好ましく、１５重量部以下であることがより好ましい。接着剤中のアクリル系オリゴマー（Ａ）の含有量が多すぎると、該接着剤に活性エネルギー線を照射した際の反応速度の低下が激しく、硬化不良となる場合がある。一方、硬化性成分の全量１００重量部に対して、アクリル系オリゴマー（Ａ）を３重量部以上含有することが好ましく、５重量部以上含有することがより好ましい。 <Acrylic oligomer (A)>
The active energy ray-curable adhesive according to the present invention can contain an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound. By containing the acrylic oligomer (A) in the active energy ray-curable adhesive, curing shrinkage when the active energy ray is irradiated and cured to the adhesive is reduced, and the adhesive, the polarizer and the transparent protection Interfacial stress with an adherend such as a film can be reduced. As a result, it is possible to suppress a decrease in adhesiveness between the adhesive layer and the adherend. In order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the content of the acrylic oligomer (A) is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component. Is preferable, and it is more preferably 15 parts by weight or less. When there is too much content of the acrylic oligomer (A) in an adhesive agent, the reaction rate at the time of irradiating an active energy ray to this adhesive agent will fall sharply, and it may become a hardening defect. On the other hand, the acrylic oligomer (A) is preferably contained in an amount of 3 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the total amount of the curable component.
　活性エネルギー線硬化型接着剤は、塗工時の作業性や均一性を考慮した場合、低粘度であることが好ましいため、（メタ）アクリルモノマーを重合してなるアクリル系オリゴマー（Ａ）も低粘度であることが好ましい。低粘度であって、かつ接着剤層の硬化収縮を防止できるアクリル系オリゴマーとしては、重量平均分子量（Ｍｗ）が１５０００以下のものが好ましく、１００００以下のものがより好ましく、５０００以下のものが特に好ましい。一方、硬化物層（接着剤層）の硬化収縮を十分に抑制するためには、アクリル系オリゴマー（Ａ）の重量平均分子量（Ｍｗ）が５００以上であることが好ましく、１０００以上であることがより好ましく、１５００以上であることが特に好ましい。アクリル系オリゴマー（Ａ）を構成する（メタ）アクリルモノマーとしては、具体的には例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、２－メチル－２－ニトロプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（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、ｎ－ペンチル（メタ）アクリレート、ｔ－ペンチル（メタ）アクリレート、３－ペンチル（メタ）アクリレート、２，２－ジメチルブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、セチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、４－メチル－２－プロピルペンチル（メタ）アクリレート、Ｎ－オクタデシル（メタ）アクリレートなどの（メタ）アクリル酸（炭素数１－２０）アルキルエステル類、さらに、例えば、シクロアルキル（メタ）アクリレート（例えば、シクロヘキシル（メタ）アクリレート、シクロペンチル（メタ）アクリレートなど）、アラルキル（メタ）アクリレート（例えば、ベンジル（メタ）アクリレートなど）、多環式（メタ）アクリレート（例えば、２－イソボルニル（メタ）アクリレート、２－ノルボルニルメチル（メタ）アクリレート、５－ノルボルネン－２－イル－メチル（メタ）アクリレート、３－メチル－２－ノルボルニルメチル（メタ）アクリレートなど）、ヒドロキシル基含有（メタ）アクリル酸エステル類（例えば、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、２，３－ジヒドロキシプロピルメチル－ブチル（メタ）メタクリレートなど）、アルコキシ基またはフェノキシ基含有（メタ）アクリル酸エステル類（２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－メトキシメトキシエチル（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、フェノキシエチル（メタ）アクリレートなど）、エポキシ基含有（メタ）アクリル酸エステル類（例えば、グリシジル（メタ）アクリレートなど）、ハロゲン含有（メタ）アクリル酸エステル類（例えば、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，２－トリフルオロエチルエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、ヘキサフルオロプロピル（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート、ヘプタデカフルオロデシル（メタ）アクリレートなど）、アルキルアミノアルキル（メタ）アクリレート（例えば、ジメチルアミノエチル（メタ）アクリレートなど）などが挙げられる。これら（メタ）アクリレートは、単独使用または２種類以上併用することができる。アクリル系オリゴマー（Ａ）の具体例としては、東亞合成社製「ＡＲＵＦＯＮ」、綜研化学社製「アクトフロー」、ＢＡＳＦジャパン社製「ＪＯＮＣＲＹＬ」などが挙げられる。（メタ）アクリルモノマーを重合してなるアクリル系オリゴマー（Ａ）のなかでも、ｌｏｇＰｏｗ値が高いものが好ましい。アクリル系オリゴマー（Ａ）は、偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値の計算における成分に含まれる。ｌｏｇＰｏｗ値の計算において、アクリル系オリゴマー（Ａ）に係る成分のモル数は、アクリル系オリゴマー（Ａ）を構成する（メタ）アクリルモノマーに換算したモル数が採用される。（メタ）アクリルモノマーを重合してなるアクリル系オリゴマー（Ａ）のｌｏｇＰｏｗ値は、好ましくは２以上、より好ましくは３以上、最も好ましくは４以上である。 The active energy ray-curable adhesive preferably has a low viscosity in consideration of workability and uniformity during coating, and therefore, an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer is also low. Viscosity is preferred. The acrylic oligomer having a low viscosity and capable of preventing curing shrinkage of the adhesive layer preferably has a weight average molecular weight (Mw) of 15000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. preferable. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, and more preferably 1000 or more. More preferably, it is particularly preferably 1500 or more. Specific examples of the (meth) acrylic monomer constituting the acrylic oligomer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2 -Methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2 -Ethylhexyl (meth) acryl (Meth) acrylic acid (carbon number 1-20) alkyl esters such as 4-methyl-2-propylpentyl (meth) acrylate and N-octadecyl (meth) acrylate, and further, for example, cycloalkyl (meth) Acrylate (eg, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, etc.), aralkyl (meth) acrylate (eg, benzyl (meth) acrylate, etc.), polycyclic (meth) acrylate (eg, 2-isobornyl (meth) Acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, etc.), hydroxyl group-containing (meth) Acrylic esters (e.g., Droxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (meth) methacrylate, etc.), alkoxy group or phenoxy group-containing (meth) acrylic acid esters (2-methoxyethyl ( (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), epoxy Group-containing (meth) acrylic acid esters (for example, glycidyl (meth) acrylate), halogen-containing (meth) acrylic acid esters (for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2 , 2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc.), alkylaminoalkyl (Meth) acrylate (for example, dimethylaminoethyl (meth) acrylate etc.) etc. are mentioned. These (meth) acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer (A) include “ARUFON” manufactured by Toagosei Co., Ltd., “Act Flow” manufactured by Soken Chemical Co., Ltd., “JONCRYL” manufactured by BASF Japan. Among the acrylic oligomers (A) obtained by polymerizing (meth) acrylic monomers, those having a high logPow value are preferable. The acrylic oligomer (A) is included as a component in the calculation of the logPow value of the curable adhesive for polarizing films. In the calculation of the logPow value, the number of moles of the component relating to the acrylic oligomer (A) is the number of moles converted to the (meth) acrylic monomer constituting the acrylic oligomer (A). The logPow value of the acrylic oligomer (A) obtained by polymerizing the (meth) acrylic monomer is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.
　＜光酸発生剤（Ｂ）＞
　上記活性エネルギー線硬化型接着剤において、光酸発生剤（Ｂ）を含有することができる。上記活性エネルギー線硬化型接着剤に、光酸発生剤を含有する場合、光酸発生剤を含有しない場合に比べて、接着剤層の耐水性および耐久性を飛躍的に向上することができる。光酸発生剤（Ｂ）は、下記一般式（３）で表すことができる。 <Photoacid generator (B)>
In the active energy ray-curable adhesive, the photoacid generator (B) can be contained. When the active energy ray-curable adhesive contains a photoacid generator, the water resistance and durability of the adhesive layer can be dramatically improved as compared with the case where no photoacid generator is contained. The photoacid generator (B) can be represented by the following general formula (3).
　一般式（３）
Figure JPOXMLDOC01-appb-C000003
 　（ただし、Ｌ＋は、任意のオニウムカチオンを表す。また、Ｘ－は、ＰＦ６６ －、ＳｂＦ６ －、ＡｓＦ６ －、ＳｂＣｌ６ －、ＢｉＣｌ５ －、ＳｎＣｌ６ －、ＣｌＯ４ －、ジチオカルバメートアニオン、ＳＣＮ－よりからなる群より選択されるカウンターアニオンを表す。） General formula (3)
Figure JPOXMLDOC01-appb-C000003
 (Wherein L + represents an arbitrary onium cation, and X − represents PF6 6 − , SbF 6 − , AsF 6 − , SbCl 6 − , BiCl 5 − , SnCl 6 − , ClO 4 − , dithiocarbamate) Represents a counter anion selected from the group consisting of an anion and SCN-)
　一般式（３）を構成するオニウムカチオンＬ＋として好ましいオニウムカチオンの構造としては、下記一般式（４）～一般式（１２）から選ばれるオニウムカチオンをあげることができる。 Preferred examples of the onium cation structure as the onium cation L + constituting the general formula (3) include onium cations selected from the following general formulas (4) to (12).
　一般式（４）
Figure JPOXMLDOC01-appb-C000004
 General formula (4)
Figure JPOXMLDOC01-appb-C000004
　一般式（５）
Figure JPOXMLDOC01-appb-C000005
 General formula (5)
Figure JPOXMLDOC01-appb-C000005
　一般式（６）
Figure JPOXMLDOC01-appb-C000006
 General formula (6)
Figure JPOXMLDOC01-appb-C000006
　一般式（７）
Figure JPOXMLDOC01-appb-C000007
 General formula (7)
Figure JPOXMLDOC01-appb-C000007
　一般式（８）
Figure JPOXMLDOC01-appb-C000008
 General formula (8)
Figure JPOXMLDOC01-appb-C000008
　一般式（９）
Figure JPOXMLDOC01-appb-C000009
 General formula (9)
Figure JPOXMLDOC01-appb-C000009
　一般式（１０）
Figure JPOXMLDOC01-appb-C000010
 General formula (10)
Figure JPOXMLDOC01-appb-C000010
　一般式（１１）
Figure JPOXMLDOC01-appb-C000011
 Formula (11)
Figure JPOXMLDOC01-appb-C000011
　一般式（１２）
Figure JPOXMLDOC01-appb-C000012
 　（上記一般式（４）－（１２）中、ただし、Ｒ１、Ｒ２およびＲ３は、それぞれ独立に、水素原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアルケニル基、置換もしくは未置換のアリール基、置換もしくは未置換の複素環基、置換もしくは未置換のアルコキシル基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換の複素環オキシ基、置換もしくは未置換のアシル基、置換もしくは未置換のカルボニルオキシ基、置換もしくは未置換のオキシカルボニル基、またはハロゲン原子より選ばれる基を表す。Ｒ４は、Ｒ１、Ｒ２およびＲ３に記載した基と同様の基を表す。Ｒ５は、置換もしくは未置換のアルキル基、置換もしくは未置換のアルキルチオ基を表す。Ｒ６およびＲ７は、それぞれ独立に、置換もしくは未置換のアルキル基、置換もしくは未置換のアルコキシル基を表す。Ｒは、ハロゲン原子、水酸基、カルボキシル基、メルカプト基、シアノ基、ニトロ基、置換もしくは未置換のカルバモイル基、置換もしくは未置換のアルキル基、置換もしくは未置換のアルケニル基、置換もしくは未置換のアリール基、置換もしくは未置換の複素環基、置換もしくは未置換のアルコキシル基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換の複素環オキシ基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、置換もしくは未置換の複素環チオ基、置換もしくは未置換のアシル基、置換もしくは未置換のカルボニルオキシ基、置換もしくは未置換のオキシカルボニル基のいずれかを表す。Ａｒ４、Ａｒ５は、置換もしくは未置換のアリール基、置換もしくは未置換の複素環基のいずれかを表す。Ｘは、酸素もしくは硫黄原子を表す。ｉは０～５の整数を表す。ｊは０～４の整数を表す。ｋは０～３の整数を表す。また、隣接したＲ同士、Ａｒ４とＡｒ５、Ｒ２とＲ３、Ｒ２とＲ４、Ｒ３とＲ４、Ｒ１とＲ２、Ｒ１とＲ３、Ｒ１とＲ４、Ｒ１とＲ、もしくはＲ１とＲ５は、相互に結合した環状構造であってもよい。） Formula (12)
Figure JPOXMLDOC01-appb-C000012
 (In the above general formulas (4) to (12), R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyl group, R 4 represents a group selected from a substituted or unsubstituted carbonyloxy group, a substituted or unsubstituted oxycarbonyl group, or a halogen atom, and R 4 represents a group similar to the groups described in R 1 , R 2 and R 3. .R 5 is a substituted or unsubstituted alkyl group, is .R 6 and R 7 represents a substituted or unsubstituted alkylthio group, independently, be substituted Represents an unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, and R represents a halogen atom, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted group. Alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, substituted or .Ar 4 represent either a non-substituted oxycarbonyl group, Ar Is a substituted or unsubstituted aryl group, .X represent either a substituted or unsubstituted heterocyclic group, .j is .i representing an oxygen or sulfur atom represents an integer of 0 to 5 0 to 4 K represents an integer of 0 to 3. Adjacent Rs, Ar 4 and Ar 5 , R 2 and R 3 , R 2 and R 4 , R 3 and R 4 , R 1 and R 2 , R 1 and R 3 , R 1 and R 4 , R 1 and R, or R 1 and R 5 may be a cyclic structure bonded to each other.)
　一般式（４）に該当するオニウムカチオン（スルホニウムカチオン）：
ジメチルフェニルスルホニウム、ジメチル（ｏ－フルオロフェニル）スルホニウム、ジメチル（ｍ－クロロフェニル）スルホニウム、ジメチル（ｐ－ブロモフェニル）スルホニウム、ジメチル（ｐ－シアノフェニル）スルホニウム、ジメチル（ｍ－ニトロフェニル）スルホニウム、ジメチル（２，４，６－トリブロモフェニル）スルホニウム、ジメチル（ペンタフルオロフェニル）スルホニウム、ジメチル（ｐ－（トリフルオロメチル）フェニル）スルホニウム、ジメチル（ｐ－ヒドロキシフェニル）スルホニウム、ジメチル（ｐ－メルカプトフェニル）スルホニウム、ジメチル（ｐ－メチルスルフィニルフェニル）スルホニウム、ジメチル（ｐ－メチルスルホニルフェニル）スルホニウム、ジメチル（ｏ－アセチルフェニル）スルホニウム、ジメチル（ｏ－ベンゾイルフェニル）スルホニウム、ジメチル（ｐ－メチルフェニル）スルホニウム、ジメチル（ｐ－イソプロピルフェニル）スルホニウム、ジメチル（ｐ－オクタデシルフェニル）スルホニウム、ジメチル（ｐ－シクロヘキシルフェニル）スルホニウム、ジメチル（ｐ－メトキシフェニル）スルホニウム、ジメチル（ｏ－メトキシカルボニルフェニル）スルホニウム、ジメチル（ｐ－フェニルスルファニルフェニル）スルホニウム、（７－メトキシ－２－オキソ－２Ｈ－クロメン－４－イル）ジメチルスルホニウム、（４－メトキシナフタレン－１－イル）ジメチルスルホニウム、ジメチル（ｐ－イソプロポキシカルボニルフェニル）スルホニウム、ジメチル（２－ナフチル）スルホニウム、ジメチル（９－アンスリル）スルホニウム、ジエチルフェニルスルホニウム、メチルエチルフェニルスルホニウム、メチルジフェニルスルホニウム、トリフェニルスルホニウム、ジイソプロピルフェニルスルホニウム、ジフェニル（４－フェニルスルファニル－フェニル）－スルホニウム、４，４’－ビス（ジフェニルスルホニウム）ジフェニルスルフィド、４，４’－ビス［ジ［（４－（２－ヒドロキシ－エトキシ）－フェニル）］スルホニウム］］ジフェニルスルフィド、４，４’－ビス（ジフェニルスルホニウム）ビフェニレン、ジフェニル（ｏ－フルオロフェニル）スルホニウム、ジフェニル（ｍ－クロロフェニル）スルホニウム、ジフェニル（ｐ－ブロモフェニル）スルホニウム、ジフェニル（ｐ－シアノフェニル）スルホニウム、ジフェニル（ｍ－ニトロフェニル）スルホニウム、ジフェニル（２，４，６－トリブロモフェニル）スルホニウム、ジフェニル（ペンタフルオロフェニル）スルホニウム、ジフェニル（ｐ－（トリフルオロメチル）フェニル）スルホニウム、ジフェニル（ｐ－ヒドロキシフェニル）スルホニウム、ジフェニル（ｐ－メルカプトフェニル）スルホニウム、ジフェニル（ｐ－メチルスルフィニルフェニル）スルホニウム、ジフェニル（ｐ－メチルスルホニルフェニル）スルホニウム、ジフェニル（ｏ－アセチルフェニル）スルホニウム、ジフェニル（ｏ－ベンゾイルフェニル）スルホニウム、ジフェニル（ｐ－メチルフェニル）スルホニウム、ジフェニル（ｐ－イソプロピルフェニル）スルホニウム、ジフェニル（ｐ－オクタデシルフェニル）スルホニウム、ジフェニル（ｐ－シクロヘキシルフェニル）スルホニウム、ジフェニル（ｐ－メトキシフェニル）スルホニウム、ジフェニル（ｏ－メトキシカルボニルフェニル）スルホニウム、ジフェニル（ｐ－フェニルスルファニルフェニル）スルホニウム、（７－メトキシ－２－オキソ－２Ｈ－クロメン－４－イル）ジフェニルスルホニウム、（４－メトキシナフタレン－１－イル）ジフェニルスルホニウム、ジフェニル（ｐ－イソプロポキシカルボニルフェニル）スルホニウム、ジフェニル（２－ナフチル）スルホニウム、ジフェニル（９－アンスリル）スルホニウム、エチルジフェニルスルホニウム、メチルエチル（ｏ－トリル）スルホニウム、メチルジ（ｐ－トリル）スルホニウム、トリ（ｐ－トリル）スルホニウム、ジイソプロピル（４－フェニルスルファニルフェニル）スルホニウム、ジフェニル（２－チエニル）スルホニウム、ジフェニル（２－フリル）スルホニウム、ジフェニル（９－エチル－９Ｈカルバゾール－３－イル）スルホニウム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。 Onium cation (sulfonium cation) corresponding to general formula (4):
Dimethylphenylsulfonium, dimethyl (o-fluorophenyl) sulfonium, dimethyl (m-chlorophenyl) sulfonium, dimethyl (p-bromophenyl) sulfonium, dimethyl (p-cyanophenyl) sulfonium, dimethyl (m-nitrophenyl) sulfonium, dimethyl ( 2,4,6-tribromophenyl) sulfonium, dimethyl (pentafluorophenyl) sulfonium, dimethyl (p- (trifluoromethyl) phenyl) sulfonium, dimethyl (p-hydroxyphenyl) sulfonium, dimethyl (p-mercaptophenyl) sulfonium , Dimethyl (p-methylsulfinylphenyl) sulfonium, dimethyl (p-methylsulfonylphenyl) sulfonium, dimethyl (o-acetylphenyl) sulfonium Dimethyl (o-benzoylphenyl) sulfonium, dimethyl (p-methylphenyl) sulfonium, dimethyl (p-isopropylphenyl) sulfonium, dimethyl (p-octadecylphenyl) sulfonium, dimethyl (p-cyclohexylphenyl) sulfonium, dimethyl (p-methoxy) Phenyl) sulfonium, dimethyl (o-methoxycarbonylphenyl) sulfonium, dimethyl (p-phenylsulfanylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethylsulfonium, (4-methoxynaphthalene- 1-yl) dimethylsulfonium, dimethyl (p-isopropoxycarbonylphenyl) sulfonium, dimethyl (2-naphthyl) sulfonium, dimethyl (9-anthryl) Rufonium, diethylphenylsulfonium, methylethylphenylsulfonium, methyldiphenylsulfonium, triphenylsulfonium, diisopropylphenylsulfonium, diphenyl (4-phenylsulfanyl-phenyl) -sulfonium, 4,4'-bis (diphenylsulfonium) diphenyl sulfide, 4, 4′-bis [di [(4- (2-hydroxy-ethoxy) -phenyl)] sulfonium]] diphenyl sulfide, 4,4′-bis (diphenylsulfonium) biphenylene, diphenyl (o-fluorophenyl) sulfonium, diphenyl ( m-chlorophenyl) sulfonium, diphenyl (p-bromophenyl) sulfonium, diphenyl (p-cyanophenyl) sulfonium, diphenyl (m-nitrophenyl) ) Sulfonium, diphenyl (2,4,6-tribromophenyl) sulfonium, diphenyl (pentafluorophenyl) sulfonium, diphenyl (p- (trifluoromethyl) phenyl) sulfonium, diphenyl (p-hydroxyphenyl) sulfonium, diphenyl (p -Mercaptophenyl) sulfonium, diphenyl (p-methylsulfinylphenyl) sulfonium, diphenyl (p-methylsulfonylphenyl) sulfonium, diphenyl (o-acetylphenyl) sulfonium, diphenyl (o-benzoylphenyl) sulfonium, diphenyl (p-methylphenyl) ) Sulfonium, diphenyl (p-isopropylphenyl) sulfonium, diphenyl (p-octadecylphenyl) sulfonium, diphenyl (p-si (Rohexylphenyl) sulfonium, diphenyl (p-methoxyphenyl) sulfonium, diphenyl (o-methoxycarbonylphenyl) sulfonium, diphenyl (p-phenylsulfanylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromene-4- Yl) diphenylsulfonium, (4-methoxynaphthalen-1-yl) diphenylsulfonium, diphenyl (p-isopropoxycarbonylphenyl) sulfonium, diphenyl (2-naphthyl) sulfonium, diphenyl (9-anthryl) sulfonium, ethyldiphenylsulfonium, methyl Ethyl (o-tolyl) sulfonium, methyldi (p-tolyl) sulfonium, tri (p-tolyl) sulfonium, diisopropyl (4-phenylsulfanyl) Nyl) sulfonium, diphenyl (2-thienyl) sulfonium, diphenyl (2-furyl) sulfonium, diphenyl (9-ethyl-9Hcarbazol-3-yl) sulfonium, and the like, but are not limited thereto. .
　一般式（５）に該当するオニウムカチオン（スルホキソニウムカチオン）：
ジメチルフェニルスルホキソニウム、ジメチル（ｏ－フルオロフェニル）スルホキソニウム、ジメチル（ｍ－クロロフェニル）スルホキソニウム、ジメチル（ｐ－ブロモフェニル）スルホキソニウム、ジメチル（ｐ－シアノフェニル）スルホキソニウム、ジメチル（ｍ－ニトロフェニル）スルホキソニウム、ジメチル（２，４，６－トリブロモフェニル）スルホキソニウム、ジメチル（ペンタフルオロフェニル）スルホキソニウム、ジメチル（ｐ－（トリフルオロメチル）フェニル）スルホキソニウム、ジメチル（ｐ－ヒドロキシフェニル）スルホキソニウム、ジメチル（ｐ－メルカプトフェニル）スルホキソニウム、ジメチル（ｐ－メチルスルフィニルフェニル）スルホキソニウム、ジメチル（ｐ－メチルスルホニルフェニル）スルホキソニウム、ジメチル（ｏ－アセチルフェニル）スルホキソニウム、ジメチル（ｏ－ベンゾイルフェニル）スルホキソニウム、ジメチル（ｐ－メチルフェニル）スルホキソニウム、ジメチル（ｐ－イソプロピルフェニル）スルホキソニウム、ジメチル（ｐ－オクタデシルフェニル）スルホキソニウム、ジメチル（ｐ－シクロヘキシルフェニル）スルホキソニウム、ジメチル（ｐ－メトキシフェニル）スルホキソニウム、ジメチル（ｏ－メトキシカルボニルフェニル）スルホキソニウム、ジメチル（ｐ－フェニルスルファニルフェニル）スルホキソニウム、（７－メトキシ－２－オキソ－２Ｈ－クロメン－４－イル）ジメチルスルホキソニウム、（４－メトキシナフタレン－１－イル）ジメチルスルホキソニウム、ジメチル（ｐ－イソプロポキシカルボニルフェニル）スルホキソニウム、ジメチル（２－ナフチル）スルホキソニウム、ジメチル（９－アンスリル）スルホキソニウム、ジエチルフェニルスルホキソニウム、メチルエチルフェニルスルホキソニウム、メチルジフェニルスルホキソニウム、トリフェニルスルホキソニウム、ジイソプロピルフェニルスルホキソニウム、ジフェニル（４－フェニルスルファニル－フェニル）－スルホキソニウム、４，４’－ビス（ジフェニルスルホキソニウム）ジフェニルスルフィド、４，４’－ビス［ジ［（４－（２－ヒドロキシ－エトキシ）－フェニル）］　スルホキソニウム］ジフェニルスルフィド、４，４’－ビス（ジフェニルスルホキソニウム）ビフェニレン、ジフェニル（ｏ－フルオロフェニル）スルホキソニウム、ジフェニル（ｍ－クロロフェニル）スルホキソニウム、ジフェニル（ｐ－ブロモフェニル）スルホキソニウム、ジフェニル（ｐ－シアノフェニル）スルホキソニウム、ジフェニル（ｍ－ニトロフェニル）スルホキソニウム、ジフェニル（２，４，６－トリブロモフェニル）スルホキソニウム、ジフェニル（ペンタフルオロフェニル）スルホキソニウム、ジフェニル（ｐ－（トリフルオロメチル）フェニル）スルホキソニウム、ジフェニル（ｐ－ヒドロキシフェニル）スルホキソニウム、ジフェニル（ｐ－メルカプトフェニル）スルホキソニウム、ジフェニル（ｐ－メチルスルフィニルフェニル）スルホキソニウム、ジフェニル（ｐ－メチルスルホニルフェニル）スルホキソニウム、ジフェニル（ｏ－アセチルフェニル）スルホキソニウム、ジフェニル（ｏ－ベンゾイルフェニル）スルホキソニウム、ジフェニル（ｐ－メチルフェニル）スルホキソニウム、ジフェニル（ｐ－イソプロピルフェニル）スルホキソニウム、ジフェニル（ｐ－オクタデシルフェニル）スルホキソニウム、ジフェニル（ｐ－シクロヘキシルフェニル）スルホキソニウム、ジフェニル（ｐ－メトキシフェニル）スルホキソニウム、ジフェニル（ｏ－メトキシカルボニルフェニル）スルホキソニウム、ジフェニル（ｐ－フェニルスルファニルフェニル）スルホキソニウム、（７－メトキシ－２－オキソ－２Ｈ－クロメン－４－イル）ジフェニルスルホキソニウム、（４－メトキシナフタレン－１－イル）ジフェニルスルホキソニウム、ジフェニル（ｐ－イソプロポキシカルボニルフェニル）スルホキソニウム、ジフェニル（２－ナフチル）スルホキソニウム、ジフェニル（９－アンスリル）スルホキソニウム、エチルジフェニルスルホキソニウム、メチルエチル（ｏ－トリル）　スルホキソニウム、メチルジ（ｐ－トリル）　スルホキソニウム、トリ（ｐ－トリル）　スルホキソニウム、ジイソプロピル（４－フェニルスルファニルフェニル）　スルホキソニウム、ジフェニル（２－チエニル）　スルホキソニウム、ジフェニル（２－フリル）　スルホキソニウム、ジフェニル（９－エチル－９Ｈカルバゾール－３－イル）　スルホキソニウム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。 Onium cation corresponding to general formula (5) (sulfoxonium cation):
Dimethylphenylsulfoxonium, dimethyl (o-fluorophenyl) sulfoxonium, dimethyl (m-chlorophenyl) sulfoxonium, dimethyl (p-bromophenyl) sulfoxonium, dimethyl (p-cyanophenyl) sulfoxonium, dimethyl (M-nitrophenyl) sulfoxonium, dimethyl (2,4,6-tribromophenyl) sulfoxonium, dimethyl (pentafluorophenyl) sulfoxonium, dimethyl (p- (trifluoromethyl) phenyl) sulfoxonium Dimethyl (p-hydroxyphenyl) sulfoxonium, dimethyl (p-mercaptophenyl) sulfoxonium, dimethyl (p-methylsulfinylphenyl) sulfoxonium, dimethyl (p-methylsulfonylphenyl) sulfoxo Dimethyl (o-acetylphenyl) sulfoxonium, dimethyl (o-benzoylphenyl) sulfoxonium, dimethyl (p-methylphenyl) sulfoxonium, dimethyl (p-isopropylphenyl) sulfoxonium, dimethyl (p- Octadecylphenyl) sulfoxonium, dimethyl (p-cyclohexylphenyl) sulfoxonium, dimethyl (p-methoxyphenyl) sulfoxonium, dimethyl (o-methoxycarbonylphenyl) sulfoxonium, dimethyl (p-phenylsulfanylphenyl) sulfo Xonium, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethylsulfoxonium, (4-methoxynaphthalen-1-yl) dimethylsulfoxonium, dimethyl (p-isopropoxyca) Bonylphenyl) sulfoxonium, dimethyl (2-naphthyl) sulfoxonium, dimethyl (9-anthryl) sulfoxonium, diethylphenylsulfoxonium, methylethylphenylsulfoxonium, methyldiphenylsulfoxonium, triphenylsulfoxo Ni, diisopropylphenylsulfoxonium, diphenyl (4-phenylsulfanyl-phenyl) -sulfoxonium, 4,4′-bis (diphenylsulfoxonium) diphenyl sulfide, 4,4′-bis [di [(4- ( 2-hydroxy-ethoxy) -phenyl)] sulfoxonium] diphenyl sulfide, 4,4′-bis (diphenylsulfoxonium) biphenylene, diphenyl (o-fluorophenyl) sulfoxonium, diphenyl (m-chloro) Phenyl) sulfoxonium, diphenyl (p-bromophenyl) sulfoxonium, diphenyl (p-cyanophenyl) sulfoxonium, diphenyl (m-nitrophenyl) sulfoxonium, diphenyl (2,4,6-tribromophenyl) ) Sulfoxonium, diphenyl (pentafluorophenyl) sulfoxonium, diphenyl (p- (trifluoromethyl) phenyl) sulfoxonium, diphenyl (p-hydroxyphenyl) sulfoxonium, diphenyl (p-mercaptophenyl) sulfoxo Ni, diphenyl (p-methylsulfinylphenyl) sulfoxonium, diphenyl (p-methylsulfonylphenyl) sulfoxonium, diphenyl (o-acetylphenyl) sulfoxonium, diphenyl (o-benzoy) Ruphenyl) sulfoxonium, diphenyl (p-methylphenyl) sulfoxonium, diphenyl (p-isopropylphenyl) sulfoxonium, diphenyl (p-octadecylphenyl) sulfoxonium, diphenyl (p-cyclohexylphenyl) sulfoxonium, Diphenyl (p-methoxyphenyl) sulfoxonium, diphenyl (o-methoxycarbonylphenyl) sulfoxonium, diphenyl (p-phenylsulfanylphenyl) sulfoxonium, (7-methoxy-2-oxo-2H-chromene-4- Yl) diphenylsulfoxonium, (4-methoxynaphthalen-1-yl) diphenylsulfoxonium, diphenyl (p-isopropoxycarbonylphenyl) sulfoxonium, diphenyl (2-naphthyl) Sulfoxonium, diphenyl (9-anthryl) sulfoxonium, ethyldiphenylsulfoxonium, methylethyl (o-tolyl) sulfoxonium, methyldi (p-tolyl) sulfoxonium, tri (p-tolyl) sulfoxonium , Diisopropyl (4-phenylsulfanylphenyl) sulfoxonium, diphenyl (2-thienyl) sulfoxonium, diphenyl (2-furyl) sulfoxonium, diphenyl (9-ethyl-9Hcarbazol-3-yl) sulfoxonium, etc. However, it is not limited to these.
　一般式（６）に該当するオニウムカチオン（ホスホニウムカチオン）：
ホスホニウムカチオンの例：
トリメチルフェニルホスホニウム、トリエチルフェニルホスホニウム、テトラフェニルホスホニウム、トリフェニル（ｐ－フルオロフェニル）ホスホニウム、トリフェニル（ｏ－クロロフェニル）ホスホニウム、トリフェニル（ｍ－ブロモフェニル）ホスホニウム、トリフェニル（ｐ－シアノフェニル）ホスホニウム、トリフェニル（ｍ－ニトロフェニル）ホスホニウム、トリフェニル（ｐ－フェニルスルファニルフェニル）ホスホニウム、（７－メトキシ－２－オキソ－２Ｈ－クロメン－４－イル）トリフェニルホスホニウム、トリフェニル（ｏ－ヒドロキシフェニル）ホスホニウム、トリフェニル（ｏ－アセチルフェニル）ホスホニウム、トリフェニル（ｍ－ベンゾイルフェニル）ホスホニウム、トリフェニル（ｐ－メチルフェニル）ホスホニウム、トリフェニル（ｐ－イソプロポキシフェニル）ホスホニウム、トリフェニル（ｏ－メトキシカルボニルフェニル）ホスホニウム、トリフェニル（１－ナフチル）ホスホニウム、トリフェニル（９－アンスリル）ホスホニウム、トリフェニル（２－チエニル）　ホスホニウム、トリフェニル（２－フリル）　ホスホニウム、トリフェニル（９－エチル－９Ｈカルバゾール－３－イル）　ホスホニウム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。 Onium cation (phosphonium cation) corresponding to the general formula (6):
Examples of phosphonium cations:
Trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl (p-fluorophenyl) phosphonium, triphenyl (o-chlorophenyl) phosphonium, triphenyl (m-bromophenyl) phosphonium, triphenyl (p-cyanophenyl) phosphonium , Triphenyl (m-nitrophenyl) phosphonium, triphenyl (p-phenylsulfanylphenyl) phosphonium, (7-methoxy-2-oxo-2H-chromen-4-yl) triphenylphosphonium, triphenyl (o-hydroxyphenyl) ) Phosphonium, triphenyl (o-acetylphenyl) phosphonium, triphenyl (m-benzoylphenyl) phosphonium, triphenyl (p-methylphenyl) phospho Phonium, triphenyl (p-isopropoxyphenyl) phosphonium, triphenyl (o-methoxycarbonylphenyl) phosphonium, triphenyl (1-naphthyl) phosphonium, triphenyl (9-anthryl) phosphonium, triphenyl (2-thienyl) phosphonium , Triphenyl (2-furyl) phosphonium, triphenyl (9-ethyl-9Hcarbazol-3-yl) phosphonium, and the like, but are not limited thereto.
　一般式（７）に該当するオニウムカチオン（ピリジニウムカチオン）：
ピリジニウムカチオンの例：
Ｎ－フェニルピリジニウム、Ｎ－（ｏ－クロロフェニル）ピリジニウム、Ｎ－（ｍ－クロロフェニル）ピリジニウム、Ｎ－（ｐ－シアノフェニル）ピリジニウム、Ｎ－（ｏ－ニトロフェニル）ピリジニウム、Ｎ－（ｐ－アセチルフェニル）ピリジニウム、Ｎ－（ｐ－イソプロピルフェニル）ピリジニウム、Ｎ－（ｐ－オクタデシルオキシフェニル）ピリジニウム、Ｎ－（ｐ－メトキシカルボニルフェニル）ピリジニウム、Ｎ－（９－アンスリル）ピリジニウム、２－クロロ－１－フェニルピリジニウム、２－シアノ－１－フェニルピリジニウム、２－メチル－１－フェニルピリジニウム、２－ビニル－１－フェニルピリジニウム、２－フェニル－１－フェニルピリジニウム、１，２－ジフェニルピリジニウム、２－メトキシ－１－フェニルピリジニウム、２－フェノキシ－１－フェニルピリジニウム、２－アセチル－１－（ｐ－トリル）ピリジニウム、２－メトキシカルボニル－１－（ｐ－トリル）ピリジニウム、３－フルオロ－１－ナフチルピリジニウム、４－メチル－１－（２－フリル）ピリジニウム、Ｎ－メチルピリジニウム、Ｎ－エチルピリジニウム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。 Onium cation corresponding to general formula (7) (pyridinium cation):
Examples of pyridinium cations:
N-phenylpyridinium, N- (o-chlorophenyl) pyridinium, N- (m-chlorophenyl) pyridinium, N- (p-cyanophenyl) pyridinium, N- (o-nitrophenyl) pyridinium, N- (p-acetylphenyl) ) Pyridinium, N- (p-isopropylphenyl) pyridinium, N- (p-octadecyloxyphenyl) pyridinium, N- (p-methoxycarbonylphenyl) pyridinium, N- (9-anthryl) pyridinium, 2-chloro-1- Phenylpyridinium, 2-cyano-1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-vinyl-1-phenylpyridinium, 2-phenyl-1-phenylpyridinium, 1,2-diphenylpyridinium, 2-methoxy- 1-phenylpi Dinium, 2-phenoxy-1-phenylpyridinium, 2-acetyl-1- (p-tolyl) pyridinium, 2-methoxycarbonyl-1- (p-tolyl) pyridinium, 3-fluoro-1-naphthylpyridinium, 4-methyl Examples thereof include, but are not limited to, 1- (2-furyl) pyridinium, N-methylpyridinium, N-ethylpyridinium, and the like.
　一般式（８）に該当するオニウムカチオン（キノリニウムカチオン）：
キノリニウムカチオンの例：
Ｎ－メチルキノリニウム、Ｎ－エチルキノリニウム、Ｎ－フェニルキノリニウム、Ｎ－ナフチルキノリニウム、Ｎ－（ｏ－クロロフェニル）キノリニウム、Ｎ－（ｍ－クロロフェニル）キノリニウム、Ｎ－（ｐ－シアノフェニル）キノリニウム、Ｎ－（ｏ－ニトロフェニル）キノリニウム、Ｎ－（ｐ－アセチルフェニル）キノリニウム、Ｎ－（ｐ－イソプロピルフェニル）キノリニウム、Ｎ－（ｐ－オクタデシルオキシフェニル）キノリニウム、Ｎ－（ｐ－メトキシカルボニルフェニル）キノリニウム、Ｎ－（９－アンスリル）キノリニウム、２－クロロ－１－フェニルキノリニウム、２－シアノ－１－フェニルキノリニウム、２－メチル－１－フェニルキノリニウム、２－ビニル－１－フェニルキノリニウム、２－フェニル－１－フェニルキノリニウム、１，２－ジフェニルキノリニウム、２－メトキシ－１－フェニルキノリニウム、２－フェノキシ－１－フェニルキノリニウム、２－アセチル－１－フェニルキノリニウム、２－メトキシカルボニル－１－フェニルキノリニウム、３－フルオロ－１－フェニルキノリニウム、４－メチル－１－フェニルキノリニウム、２－メトキシ－１－（ｐ－トリル）キノリニウム、２－フェノキシ－１－（２－フリル）キノリニウム、２－アセチル－１－（２－チエニル）キノリニウム、２－メトキシカルボニル－１－メチルキノリニウム、３－フルオロ－１－エチルキノリニウム、４－メチル－１－イソプロピルキノリニウム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。 Onium cation (quinolinium cation) corresponding to general formula (8):
Examples of quinolinium cations:
N-methylquinolinium, N-ethylquinolinium, N-phenylquinolinium, N-naphthylquinolinium, N- (o-chlorophenyl) quinolinium, N- (m-chlorophenyl) quinolinium, N- (p -Cyanophenyl) quinolinium, N- (o-nitrophenyl) quinolinium, N- (p-acetylphenyl) quinolinium, N- (p-isopropylphenyl) quinolinium, N- (p-octadecyloxyphenyl) quinolinium, N- ( p-methoxycarbonylphenyl) quinolinium, N- (9-anthryl) quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquinolinium, 2-methyl-1-phenylquinolinium, 2-Vinyl-1-phenylquinolinium, 2-phenyl-1-phenyl Norinium, 1,2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy-1-phenylquinolinium, 2-acetyl-1-phenylquinolinium, 2-methoxycarbonyl-1 -Phenylquinolinium, 3-fluoro-1-phenylquinolinium, 4-methyl-1-phenylquinolinium, 2-methoxy-1- (p-tolyl) quinolinium, 2-phenoxy-1- (2- Furyl) quinolinium, 2-acetyl-1- (2-thienyl) quinolinium, 2-methoxycarbonyl-1-methylquinolinium, 3-fluoro-1-ethylquinolinium, 4-methyl-1-isopropylquinolinium However, it is not limited to these.
　一般式（９）に該当するオニウムカチオン（イソキノリニウムカチオン）：
イソキノリニウムカチオンの例：
Ｎ－フェニルイソキノリニウム、Ｎ－メチルイソキノリニウム、Ｎ－エチルイソキノリニウム、Ｎ－（ｏ－クロロフェニル）イソキノリニウム、Ｎ－（ｍ－クロロフェニル）イソキノリニウム、Ｎ－（ｐ－シアノフェニル）イソキノリニウム、Ｎ－（ｏ－ニトロフェニル）イソキノリニウム、Ｎ－（ｐ－アセチルフェニル）イソキノリニウム、Ｎ－（ｐ－イソプロピルフェニル）イソキノリニウム、Ｎ－（ｐ－オクタデシルオキシフェニル）イソキノリニウム、Ｎ－（ｐ－メトキシカルボニルフェニル）イソキノリニウム、Ｎ－（９－アンスリル）イソキノリニウム、１，２－ジフェニルイソキノリニウム、Ｎ－（２－フリル）イソキノリニウム、Ｎ－（２－チエニル）イソキノリニウム、Ｎ－ナフチルイソキノリニウム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。 Onium cation (isoquinolinium cation) corresponding to the general formula (9):
Examples of isoquinolinium cations:
N-phenylisoquinolinium, N-methylisoquinolinium, N-ethylisoquinolinium, N- (o-chlorophenyl) isoquinolinium, N- (m-chlorophenyl) isoquinolinium, N- (p-cyanophenyl) Isoquinolinium, N- (o-nitrophenyl) isoquinolinium, N- (p-acetylphenyl) isoquinolinium, N- (p-isopropylphenyl) isoquinolinium, N- (p-octadecyloxyphenyl) isoquinolinium, N- (p-methoxycarbonyl) Phenyl) isoquinolinium, N- (9-anthryl) isoquinolinium, 1,2-diphenylisoquinolinium, N- (2-furyl) isoquinolinium, N- (2-thienyl) isoquinolinium, N-naphthylisoquinolinium, etc. To mention That, without being limited thereto.
　一般式（１０）に該当するオニウムカチオン（ベンゾオキサゾリウムカチオン、ベンゾチアゾリウムカチオン）：
ベンゾオキサゾリウムカチオンの例：
Ｎ－メチルベンゾオキサゾリウム、Ｎ－エチルベンゾオキサゾリウム、Ｎ－ナフチルベンゾオキサゾリウム、Ｎ－フェニルベンゾオキサゾリウム、Ｎ－（ｐ－フルオロフェニル）ベンゾオキサゾリウム、Ｎ－（ｐ－クロロフェニル）ベンゾオキサゾリウム、Ｎ－（ｐ－シアノフェニル）ベンゾオキサゾリウム、Ｎ－（ｏ－メトキシカルボニルフェニル）ベンゾオキサゾリウム、Ｎ－（２－フリル）ベンゾオキサゾリウム、Ｎ－（ｏ－フルオロフェニル）ベンゾオキサゾリウム、Ｎ－（ｐ－シアノフェニル）ベンゾオキサゾリウム、Ｎ－（ｍ－ニトロフェニル）ベンゾオキサゾリウム、Ｎ－（ｐ－イソプロポキシカルボニルフェニル）ベンゾオキサゾリウム、Ｎ－（２－チエニル）ベンゾオキサゾリウム、Ｎ－（ｍ－カルボキシフェニル）ベンゾオキサゾリウム、２－メルカプト－３－フェニルベンゾオキサゾリウム、２－メチル－３－フェニルベンゾオキサゾリウム、２－メチルチオ－３－（４－フェニルスルファニルフェニル）ベンゾオキサゾリウム、６－ヒドロキシ－３－（ｐ－トリル）ベンゾオキサゾリウム、７－メルカプト－３－フェニルベンゾオキサゾリウム、４，５－ジフルオロ－３－エチルベンゾオキサゾリウム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。 Onium cation corresponding to general formula (10) (benzoxazolium cation, benzothiazolium cation):
Examples of benzoxazolium cations:
N-methylbenzoxazolium, N-ethylbenzoxazolium, N-naphthylbenzoxazolium, N-phenylbenzoxazolium, N- (p-fluorophenyl) benzoxazolium, N- (p- Chlorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (o-methoxycarbonylphenyl) benzoxazolium, N- (2-furyl) benzoxazolium, N- (o -Fluorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (m-nitrophenyl) benzoxazolium, N- (p-isopropoxycarbonylphenyl) benzoxazolium, N- (2-thienyl) benzoxazolium, N- (m-carboxyphenyl) ben Oxazolium, 2-mercapto-3-phenylbenzoxazolium, 2-methyl-3-phenylbenzoxazolium, 2-methylthio-3- (4-phenylsulfanylphenyl) benzoxazolium, 6-hydroxy-3- (P-tolyl) benzoxazolium, 7-mercapto-3-phenylbenzoxazolium, 4,5-difluoro-3-ethylbenzoxazolium, and the like, but are not limited thereto. Absent.
　ベンゾチアゾリウムカチオンの例：
Ｎ－メチルベンゾチアゾリウム、Ｎ－エチルベンゾチアゾリウム、Ｎ－フェニルベンゾチアゾリウム、Ｎ－（１－ナフチル）ベンゾチアゾリウム、Ｎ－（ｐ－フルオロフェニル）ベンゾチアゾリウム、Ｎ－（ｐ－クロロフェニル）ベンゾチアゾリウム、Ｎ－（ｐ－シアノフェニル）ベンゾチアゾリウム、Ｎ－（ｏ－メトキシカルボニルフェニル）ベンゾチアゾリウム、Ｎ－（ｐ－トリル）ベンゾチアゾリウム、Ｎ－（ｏ－フルオロフェニル）ベンゾチアゾリウム、Ｎ－（ｍ－ニトロフェニル）ベンゾチアゾリウム、Ｎ－（ｐ－イソプロポキシカルボニルフェニル）ベンゾチアゾリウム、Ｎ－（２－フリル）ベンゾチアゾリウム、Ｎ－（４－メチルチオフェニル）ベンゾチアゾリウム、Ｎ－（４－フェニルスルファニルフェニル）ベンゾチアゾリウム、Ｎ－（２－ナフチル）ベンゾチアゾリウム、Ｎ－（ｍ－カルボキシフェニル）ベンゾチアゾリウム、２－メルカプト－３－フェニルベンゾチアゾリウム、２－メチル－３－フェニルベンゾチアゾリウム、２－メチルチオ－３－フェニルベンゾチアゾリウム、６－ヒドロキシ－３－フェニルベンゾチアゾリウム、７－メルカプト－３－フェニルベンゾチアゾリウム、４，５－ジフルオロ－３－フェニルベンゾチアゾリウム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 benzothiazolium cations:
N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N- (1-naphthyl) benzothiazolium, N- (p-fluorophenyl) benzothiazolium, N -(P-chlorophenyl) benzothiazolium, N- (p-cyanophenyl) benzothiazolium, N- (o-methoxycarbonylphenyl) benzothiazolium, N- (p-tolyl) benzothiazolium, N- (o-fluorophenyl) benzothiazolium, N- (m-nitrophenyl) benzothiazolium, N- (p-isopropoxycarbonylphenyl) benzothiazolium, N- (2-furyl) benzothia Zorium, N- (4-methylthiophenyl) benzothiazolium, N- (4-phenylsulfanylphenyl) benzothiazo , N- (2-naphthyl) benzothiazolium, N- (m-carboxyphenyl) benzothiazolium, 2-mercapto-3-phenylbenzothiazolium, 2-methyl-3-phenylbenzothiazolium 2-methylthio-3-phenylbenzothiazolium, 6-hydroxy-3-phenylbenzothiazolium, 7-mercapto-3-phenylbenzothiazolium, 4,5-difluoro-3-phenylbenzothiazolium However, it is not limited to these.
　一般式（１１）に該当するオニウムカチオン（フリルもしくはチエニルヨードニウムカチオン）：
ジフリルヨードニウム、ジチエニルヨードニウム、ビス（４，５－ジメチル－２－フリル）ヨードニウム、ビス（５－クロロ－２－チエニル）ヨードニウム、ビス（５－シアノ－２－フリル）ヨードニウム、ビス（５－ニトロ－２－チエニル）ヨードニウム、ビス（５－アセチル－２－フリル）ヨードニウム、ビス（５－カルボキシ－２－チエニル）ヨードニウム、ビス（５－メトキシカルボニル－２－フリル）ヨードニウム、ビス（５－フェニル－２－フリル）ヨードニウム、ビス（５－（ｐ－メトキシフェニル）－２－チエニル）ヨードニウム、ビス（５－ビニル－２－フリル）ヨードニウム、ビス（５－エチニル－２－チエニル）ヨードニウム、ビス（５－シクロヘキシル－２－フリル）ヨードニウム、ビス（５－ヒドロキシ－２－チエニル）ヨードニウム、ビス（５－フェノキシ－２－フリル）ヨードニウム、ビス（５－メルカプト－２－チエニル）ヨードニウム、ビス（５－ブチルチオ－２－チエニル）ヨードニウム、ビス（５－フェニルチオ－２－チエニル）ヨードニウム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。 Onium cation corresponding to general formula (11) (furyl or thienyl iodonium cation):
Difuryliodonium, dithienyliodonium, bis (4,5-dimethyl-2-furyl) iodonium, bis (5-chloro-2-thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis (5- Nitro-2-thienyl) iodonium, bis (5-acetyl-2-furyl) iodonium, bis (5-carboxy-2-thienyl) iodonium, bis (5-methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl) -2-furyl) iodonium, bis (5- (p-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium, bis (5-ethynyl-2-thienyl) iodonium, bis ( 5-cyclohexyl-2-furyl) iodonium, bis (5-hydroxy-2-thio) Nyl) iodonium, bis (5-phenoxy-2-furyl) iodonium, bis (5-mercapto-2-thienyl) iodonium, bis (5-butylthio-2-thienyl) iodonium, bis (5-phenylthio-2-thienyl) Although iodonium etc. can be mentioned, it is not limited to these.
　一般式（１２）に該当するオニウムカチオン（ジアリールヨードニウムカチオン）：
ジフェニルヨードニウム、ビス（ｐ－トリル）ヨードニウム、ビス（ｐ－オクチルフェニル）ヨードニウム、ビス（ｐ－オクタデシルフェニル）ヨードニウム、ビス（ｐ－オクチルオキシフェニル）ヨードニウム、ビス（ｐ－オクタデシルオキシフェニル）ヨードニウム、フェニル（ｐ－オクタデシルオキシフェニル）ヨードニウム、４－イソプロピル－４’－メチルジフェニルヨードニウム、（４－イソブチルフェニル）－ｐ－トリルヨードニウム、ビス（１－ナフチル）ヨードニウム、ビス（４－フェニルスルファニルフェニル）ヨードニウム、フェニル（６－ベンゾイル－９－エチル－９Ｈ－カルバゾール－３－イル）ヨードニウム、（７－メトキシ－２－オキソ－２Ｈ－クロメン－３－イル）－４’－イソプロピルフェニルヨードニウム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。 Onium cation corresponding to general formula (12) (diaryliodonium cation):
Diphenyliodonium, bis (p-tolyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (P-octadecyloxyphenyl) iodonium, 4-isopropyl-4′-methyldiphenyliodonium, (4-isobutylphenyl) -p-tolyliodonium, bis (1-naphthyl) iodonium, bis (4-phenylsulfanylphenyl) iodonium, Phenyl (6-benzoyl-9-ethyl-9H-carbazol-3-yl) iodonium, (7-methoxy-2-oxo-2H-chromen-3-yl) -4'-isopropylphenyliodonium Although and the like, but is not limited thereto.
　次に、一般式（３）中のカウンターアニオンＸ－について説明する。 Next, the counter anion X − in the general formula (3) will be described.
　一般式（３）中のカウンターアニオンＸ－は原理的に特に限定されるものではないが、非求核性アニオンが好ましい。カウンターアニオンＸ－が非求核性アニオンの場合、分子内に共存するカチオンや併用される各種材料における求核反応が起こりにくいため、結果として一般式（２）で表記される光酸発生剤自身やそれを用いた接着剤の経時安定性を向上させることが可能である。ここでいう非求核性アニオンとは、求核反応を起こす能力が低いアニオンを指す。このようなアニオンとしては、ＰＦ６ －、ＳｂＦ６ －、ＡｓＦ６ －、ＳｂＣｌ６ －、ＢｉＣｌ５ －、ＳｎＣｌ６ －、ＣｌＯ４ －、ジチオカルバメートアニオン、ＳＣＮ－等が挙げられる。 Formula (3) counter anion X in - are but are not theoretically limited to, non-nucleophilic anion is preferred. When the counter anion X − is a non-nucleophilic anion, a nucleophilic reaction is unlikely to occur in the cation coexisting in the molecule and various materials used in combination, and as a result, the photoacid generator itself represented by the general formula (2) It is possible to improve the temporal stability of an adhesive using the same. The non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such anions include PF 6 − , SbF 6 − , AsF 6 − , SbCl 6 − , BiCl 5 − , SnCl 6 − , ClO 4 − , dithiocarbamate anion, SCN − and the like.
　上記した例示アニオンの中で、一般式（３）中のカウンターアニオンＸ－として特に好ましいものとしては、ＰＦ６ －、ＳｂＦ６ －およびＡｓＦ６ －が挙げられ、特に好ましくは、ＰＦ６ －、ＳｂＦ６ －が挙げられる。 Among the above exemplified anions, particularly preferred as the counter anion X − in the general formula (3) include PF 6 − , SbF 6 − and AsF 6 − , and particularly preferably PF 6 − and SbF. 6 - and the like.
　したがって、光酸発生剤（Ｂ）を構成する好ましいオニウム塩の具体例としては、上記例示の一般式（３）～一般式（１２）で表されるオニウムカチオンの構造の具体例とＰＦ６ －、ＳｂＦ６ －、ＡｓＦ６ －、ＳｂＣｌ６ －、ＢｉＣｌ５ －、ＳｎＣｌ６ －、ＣｌＯ４ －、ジチオカルバメートアニオン、ＳＣＮ－より選ばれるアニオンとからなるオニウム塩である。 Therefore, specific examples of preferable onium salts constituting the photoacid generator (B) include specific examples of the structure of the onium cation represented by the above general formulas (3) to (12) and PF 6 −. , SbF 6 − , AsF 6 − , SbCl 6 − , BiCl 5 − , SnCl 6 − , ClO 4 − , dithiocarbamate anion, and an anion selected from SCN − .
　具体的には、「サイラキュアーＵＶＩ－６９９２」、「サイラキュアーＵＶＩ－６９７４」（以上、ダウ・ケミカル日本株式会社製）、「アデカオプトマーＳＰ１５０」、「アデカオプトマーＳＰ１５２」、「アデカオプトマーＳＰ１７０」、「アデカオプトマーＳＰ１７２」（以上、株式会社ＡＤＥＫＡ製）、「ＩＲＧＡＣＵＲＥ２５０」（チバスペシャルティーケミカルズ社製）、「ＣＩ－５１０２」、「ＣＩ－２８５５」（以上、日本曹達社製）、「サンエイドＳＩ－６０Ｌ」、「サンエイドＳＩ－８０Ｌ」、「サンエイドＳＩ－１００Ｌ」、「サンエイドＳＩ－１１０Ｌ」、「サンエイドＳＩ－１８０Ｌ」（以上、三新化学社製）、「ＣＰＩ－１００Ｐ」、「ＣＰＩ－１００Ａ」（以上、サンアプロ株式会社製）、「ＷＰＩ－０６９」、「ＷＰＩ－１１３」、「ＷＰＩ－１１６」、「ＷＰＩ－０４１」、「ＷＰＩ－０４４」、「ＷＰＩ－０５４」、「ＷＰＩ－０５５」、「ＷＰＡＧ－２８１」、「ＷＰＡＧ－５６７」、「ＷＰＡＧ－５９６」（以上、和光純薬社製）が光酸発生剤（Ｂ）の好ましい具体例として挙げられる。 Specifically, “Syracure UVI-6922”, “Syracure UVI-6974” (manufactured by Dow Chemical Japan Co., Ltd.), “Adekaoptomer SP150”, “Adekaoptomer SP152”, “Adekaoptomer” “SP170”, “Adekaoptomer SP172” (manufactured by ADEKA Corporation), “IRGACURE250” (manufactured by Ciba Specialty Chemicals), “CI-5102”, “CI-2855” (manufactured by Nippon Soda Co., Ltd.), “Sun-Aid SI-60L”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-180L” (manufactured by Sanshin Chemical Co., Ltd.), “CPI-100P”, "CPI-100A" (San Apro Co., Ltd.), "WPI-06 "," WPI-113 "," WPI-116 "," WPI-041 "," WPI-044 "," WPI-054 "," WPI-055 "," WPAG-281 "," WPAG-567 " “WPAG-596” (manufactured by Wako Pure Chemical Industries, Ltd.) is a preferred specific example of the photoacid generator (B).
　光酸発生剤（Ｂ）の含有量は、硬化性成分の全量１００重量部に対して、１０重量部以下であり、０．０１～１０重量部であることが好ましく、０．０５～５重量部であることがより好ましく、０．１～３重量部であることが特に好ましい。 The content of the photoacid generator (B) is 10 parts by weight or less, preferably 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferably, the amount is 0.1 to 3 parts by weight.
　＜アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）＞
　上記活性エネルギー線硬化型接着剤において、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）を含有することができる。例えば、ＰＶＡ系偏光子の水酸基との関係において、アルコキシ基を含む化合物（Ｃ１）ではアルコキシ基と水酸基との縮合反応が進行し、エポキシ基を含む化合物（Ｃ２）ではエポキシ基と水酸基との付加反応が進行し、活性エネルギー線硬化型接着剤に、より強固な接着性を付与することができる。エポキシ基を含む化合物（Ｃ２）を用いた場合には、エポキシ基と水酸基との付加反応により、反応後に２級水酸基が生成し、本発明のバルク吸水率を上昇させる可能性があるため、アルコキシ基を有する化合物（Ｃ１）を使用するのがより好ましい。すなわち、光酸発生剤（Ｂ）とアルコキシ基を有する化合物（Ｃ１）とを含有する活性エネルギー線硬化型接着剤を介して偏光子と透明保護フィルムとを積層し、活性エネルギー線を照射することで、光酸発生剤（Ｂ）から発生する酸によってアルコキシ基を有する化合物（Ｃ１）のアルコキシ基と偏光子の水酸基とが縮合反応し、偏光子と透明保護フィルムとの良好な接着性が発現する。また、アルコキシ基を有する化合物（Ｃ１）同士の縮合反応によってより吸水率の低い接着剤層を形成し、高温高湿下の過酷な環境下における光学耐久性を満足することができる。 <Compound (C) containing either alkoxy group or epoxy group>
In the active energy ray-curable adhesive, the compound (C) containing either an alkoxy group or an epoxy group can be contained. For example, in the relationship with the hydroxyl group of the PVA polarizer, in the compound (C1) containing an alkoxy group, the condensation reaction of the alkoxy group and the hydroxyl group proceeds, and in the compound (C2) containing an epoxy group, the addition of the epoxy group and the hydroxyl group. The reaction proceeds, and a stronger adhesiveness can be imparted to the active energy ray-curable adhesive. When the compound (C2) containing an epoxy group is used, a secondary hydroxyl group is generated after the reaction due to an addition reaction between the epoxy group and the hydroxyl group, which may increase the bulk water absorption rate of the present invention. It is more preferable to use the compound (C1) having a group. That is, a polarizer and a transparent protective film are laminated through an active energy ray-curable adhesive containing a photoacid generator (B) and an alkoxy group-containing compound (C1), and active energy rays are irradiated. Then, the alkoxy group of the compound (C1) having an alkoxy group and the hydroxyl group of the polarizer undergo a condensation reaction with the acid generated from the photoacid generator (B), and good adhesion between the polarizer and the transparent protective film is exhibited. To do. Further, an adhesive layer having a lower water absorption rate can be formed by a condensation reaction between the alkoxy group-containing compounds (C1), and optical durability under a severe environment under high temperature and high humidity can be satisfied.
　上記活性エネルギー線硬化型接着剤において、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）は、１種を単独で用いて良いし、複数を組み合わせて使用しても良い。また、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）は、アルコキシ基を含む化合物（Ｃ１）とエポキシ基を含む化合物（Ｃ２）を併用して用いることもできる。また、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）は、光酸発生剤（Ｂ）と併用して、または併用することなく用いることができるが、ＰＶＡ系偏光子の水酸基とアルコキシ基、エポキシ基との反応を促進する観点からは、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）は、光酸発生剤（Ｂ）と併用することが好ましい。 In the active energy ray-curable adhesive, the compound (C) containing either an alkoxy group or an epoxy group may be used alone or in combination. Moreover, the compound (C) containing either an alkoxy group or an epoxy group can also be used in combination with the compound (C1) containing an alkoxy group and the compound (C2) containing an epoxy group. The compound (C) containing either an alkoxy group or an epoxy group can be used in combination with or without using the photoacid generator (B), but the hydroxyl group and alkoxy group of the PVA polarizer can be used. From the viewpoint of promoting the reaction with the epoxy group, the compound (C) containing either an alkoxy group or an epoxy group is preferably used in combination with the photoacid generator (B).
　（アルコキシ基を有する化合物（Ｃ１））
　分子内にアルコキシ基を有する化合物（Ｃ１）としては、分子内に１個以上のアルコキシル基を有するものであれば特に制限なく、公知のものを使用できる。例えば、置換基として、一般式：－（ＣＨ２）ｎ－Ｏ－Ｒ（式中、ｎは１～３の整数であり、Ｒは炭素数１～４のアルキル基又はＨを示す。前記式中のＲはメチル基であることが好ましい。）で表されるアルコキシ基を有する化合物が挙げられる。具体的には、例えば、アルコキシアルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリルアミドなどのアルコキシ基含有ラジカル重合性化合物、メチロールメラミン、アルコキシメチル化メラミンなどのメラミン化合物、アミノ樹脂及びシランカップリング剤が挙げられる。アルコキシ基含有ラジカル重合性化合物の具体例としては、笠野興産社製のワスマー２ＭＡ、ワスマー３ＭＡ、ワスマーＩＢＭ、Ｎ－イソブトキシメチルアクリルアミド、ワスマーＥＭＡ、Ｎ－ＭＡＭ－ＰＣ、ＭＭ９０、ワスマーＡなどが挙げられる。メラミン化合物の具体例としては、住友化学社製のスミテックスレジンシリーズのＭ－３、ＭＫ、Ｍ－６、Ｍ－１００、ＭＣ等や株式会社三和ケミカル社製のニカラックＭＷ－３０、ＭＷ－１００ＬＭ、ＭＸ－７５０ＬＭ、ＭＸ－２８０、ＭＸ－２７０等が例示できる。これらの中でも反応性の観点から、ワスマー２ＭＡ、Ｎ－ＭＡＭ－ＰＣ、ＭＸ－７５０ＬＭなどを使用するのが好ましい。なお、接着剤層のガラス転移温度Ｔｇを計算する際には、アルコキシル基を有する化合物及び高分子（Ｃ１）を計算には入れないこととする。 (Compound having an alkoxy group (C1))
The compound (C1) having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxyl groups in the molecule, and known compounds can be used. For example, as a substituent, the general formula: — (CH 2 ) n —O—R (wherein n is an integer of 1 to 3 and R represents an alkyl group having 1 to 4 carbon atoms or H. R is preferably a methyl group.) And a compound having an alkoxy group represented by: Specifically, for example, alkoxy group-containing radical polymerizable compounds such as alkoxyalkyl (meth) acrylate and alkoxyalkyl (meth) acrylamide, melamine compounds such as methylol melamine and alkoxymethylated melamine, amino resins and silane coupling agents Can be mentioned. Specific examples of the alkoxy group-containing radical polymerizable compound include Wasmer 2MA, Wasmer 3MA, Wasmer IBM, N-isobutoxymethylacrylamide, Wasmer EMA, N-MAM-PC, MM90, Wasmer A, etc. manufactured by Kasano Kosan Co., Ltd. It is done. Specific examples of the melamine compound include M-3, MK, M-6, M-100, MC, etc. of Sumitex Resin series manufactured by Sumitomo Chemical Co., Ltd. and Nikarac MW-30, MW- manufactured by Sanwa Chemical Co., Ltd. Examples thereof include 100LM, MX-750LM, MX-280, MX-270 and the like. Among these, from the viewpoint of reactivity, it is preferable to use Wasmer 2MA, N-MAM-PC, MX-750LM and the like. In calculating the glass transition temperature Tg of the adhesive layer, the compound having an alkoxyl group and the polymer (C1) are not included in the calculation.
　（エポキシ基を有する化合物（Ｃ２））
　エポキシ基を有する化合物（Ｃ２）としては、分子内に１個以上のエポキシ基を有する化合物又は分子内に２個以上のエポキシ基を有する高分子（エポキシ樹脂）を用いることができる。高分子（エポキシ樹脂）を用いる場合は、エポキシ基との反応性を有する官能基を分子内に二つ以上有する化合物を併用してもよい。ここでエポキシ基との反応性を有する官能基とは、例えば、カルボキシル基、フェノール性水酸基、メルカプト基、１級又は２級の芳香族アミノ基等が挙げられる。これらの官能基は、３次元硬化性を考慮して、一分子中に２つ以上有することが特に好ましい。 (Compound having epoxy group (C2))
As the compound (C2) having an epoxy group, a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule can be used. When a polymer (epoxy resin) is used, a compound having two or more functional groups having reactivity with an epoxy group in the molecule may be used in combination. Here, examples of the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.
　分子内に１個以上のエポキシ基を有する高分子としては、例えば、エポキシ樹脂が挙げられ、ビスフェノールＡとエピクロルヒドリンから誘導されるビスフェノールＡ型エポキシ樹脂、ビスフェノールＦとエピクロルヒドリンから誘導されるビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、３官能型エポキシ樹脂や４官能型エポキシ樹脂等の多官能型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、脂肪族鎖状エポキシ樹脂等があり、これらのエポキシ樹脂はハロゲン化されていてもよく、水素添加されていてもよい。市販されているエポキシ樹脂製品としては、例えばジャパンエポキシレジン株式会社製のＪＥＲコート８２８、１００１、８０１Ｎ、８０６、８０７、１５２、６０４、６３０、８７１、ＹＸ８０００、ＹＸ８０３４、ＹＸ４０００、ＤＩＣ株式会社製のエピクロン８３０、ＥＸＡ８３５ＬＶ、ＨＰ４０３２Ｄ、ＨＰ８２０、株式会社ＡＤＥＫＡ製のＥＰ４１００シリーズ、ＥＰ４０００シリーズ、ＥＰＵシリーズ、ダイセル化学株式会社製のセロキサイドシリーズ（２０２１、２０２１Ｐ、２０８３、２０８５、３０００等）、エポリードシリーズ、ＥＨＰＥシリーズ、新日鐵化学社製のＹＤシリーズ、ＹＤＦシリーズ、ＹＤＣＮシリーズ、ＹＤＢシリーズ、フェノキシ樹脂（ビスフェノール類とエピクロルヒドリンより合成されるポリヒドロキシポリエーテルで両末端にエポキシ基を有する；ＹＰシリーズ等）、ナガセケムテックス社製のデナコールシリーズ、共栄社化学社製のエポライトシリーズ等が挙げられるがこれらに限定されるものではない。これらのエポキシ樹脂は、２種以上を併用してもよい。なお、接着剤層のガラス転移温度Ｔｇを計算する際には、エポキシ基を有する化合物（Ｃ２）を計算には入れないこととする。 Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Multifunctional epoxy resin such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin There are glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins, etc. These epoxy resins may be halogenated and hydrogenated. May be. As commercially available epoxy resin products, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron manufactured by DIC Corporation 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Industries, Ltd., Eporide series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyethylene synthesized from bisphenols and epichlorohydrin) B carboxymethyl having an epoxy group at both ends with polyether; YP series, etc.), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha but Chemical Co. Epo light series, and the like are not limited thereto. Two or more of these epoxy resins may be used in combination. When calculating the glass transition temperature Tg of the adhesive layer, the compound (C2) having an epoxy group is not included in the calculation.
　アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）の配合量は、硬化性成分の全量１００重量部に対して、通常、３０重量部以下であり、活性エネルギー線硬化型接着剤中の前記化合物（Ｃ）の含有量が多すぎると、接着性が低下し、落下試験に対する耐衝撃性が悪化する場合がある。活性エネルギー線硬化型接着剤中の前記化合物（Ｃ）の含有量は、２０重量部以下であることがより好ましい。一方、耐水性の点から、活性エネルギー線硬化型接着剤中、前記化合物（Ｃ）を２重量部以上含有することが好ましく、５重量部以上含有することがより好ましい。 The compounding amount of the compound (C) containing either an alkoxy group or an epoxy group is usually 30 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component, When there is too much content of a compound (C), adhesiveness will fall and the impact resistance with respect to a drop test may deteriorate. The content of the compound (C) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the active energy ray-curable adhesive preferably contains 2 parts by weight or more of the compound (C), more preferably 5 parts by weight or more.
　＜イソシアネート化合物（Ｄ）＞
　本発明の活性エネルギー線硬化型接着剤はイソシアネート化合物（Ｄ）を含有することができる。イソシアネート化合物（Ｄ）は、分子中に少なくとも１つのイソシアネート基を有する化合物である。活性エネルギー線硬化型接着剤が、イソシアネート化合物（Ｄ）を含有する場合、偏光子表面の水酸基とイソシアネート基とが相互作用することによって、偏光フィルムにより強固な接着性、耐水性を付与することができる。また、活性エネルギー線硬化型接着剤が、ラジカル重合性化合物として、Ｎ－ヒドロキシアルキル基含有（メタ）アクリルアミド誘導体を含む場合、Ｎ－ヒドロキシアルキル基含有（メタ）アクリルアミド誘導体の含有量が多くなると、ヒドロキシル基が接着剤層中に含まれるためバルク吸水率が高くなる傾向があり、結果として過酷な加湿環境下における光学耐久性が低下する傾向がある。Ｎ－ヒドロキシアルキル基含有（メタ）アクリルアミド誘導体とイソシアネート基を有する化合物とを併用することで偏光子との接着に寄与しないヒドロキシル基とイソシアネート基とがウレタン結合を形成し、接着性を保持しながらバルク吸水率を低下させることができる。 <Isocyanate compound (D)>
The active energy ray-curable adhesive of the present invention can contain an isocyanate compound (D). The isocyanate compound (D) is a compound having at least one isocyanate group in the molecule. When the active energy ray curable adhesive contains an isocyanate compound (D), the hydroxyl group and the isocyanate group on the surface of the polarizer interact to impart stronger adhesion and water resistance to the polarizing film. it can. Further, when the active energy ray-curable adhesive contains an N-hydroxyalkyl group-containing (meth) acrylamide derivative as a radical polymerizable compound, if the content of the N-hydroxyalkyl group-containing (meth) acrylamide derivative increases, Since the hydroxyl group is contained in the adhesive layer, the bulk water absorption rate tends to be high, and as a result, the optical durability tends to be lowered in a severe humidified environment. While using a N-hydroxyalkyl group-containing (meth) acrylamide derivative and a compound having an isocyanate group in combination, a hydroxyl group that does not contribute to adhesion to the polarizer and an isocyanate group form a urethane bond, while maintaining adhesiveness. Bulk water absorption can be reduced.
　イソシアネート化合物（Ｄ）としては、多官能イソシアネート化合物、活性エネルギー線硬化型イソシアネート化合物などが挙げられる。多官能イソシアネート化合物としては、例えば、１，２－エチレンジイソシアネート、１，４－ブチレンジイソシアネート、１，６－ヘキサメチレンジイソシアネートなど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、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネートなどの脂環族ポリイソシアネート類；２，４－トリレンジイソシアネート、２，６－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などの芳香族ポリイソシアネート類などが挙げられる。上記イソシアネート化合物（Ｄ）としては、例えば、トリメチロールプロパン／トリレンジイソシアネート付加物［日本ポリウレタン工業株式会社製、商品名「コロネートＬ」］、トリメチロールプロパン／ヘキサメチレンジイソシアネート付加物［日本ポリウレタン工業株式会社製、商品名「コロネートＨＬ」］、商品名「コロネート ＨＸ」（日本ポリウレタン工業株式会社）、トリメチロールプロパン／キシリレンジイソシアネート付加物［三井化学株式会社製、商品名「タケネート１１０Ｎ」］などの市販品も挙げられる。活性エネルギー線硬化型イソシアネート化合物（Ｄ）としては、（メタ）アクリロイル基を有するイソシアネート類が挙げられ、例えば、カレンズＡＯＩ（昭和電工株式会社製）、カレンズＢＥI（昭和電工株式会社製）、Laromer LR9000（ＢＡＳＦ社製）などの市販品が挙げられる。 Examples of the isocyanate compound (D) include polyfunctional isocyanate compounds and active energy ray-curable isocyanate compounds. Examples of the polyfunctional isocyanate compound include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. , Cycloaliphatic polyisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylene diisocyanate; aromatics such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate Group polyisocyanates and the like. Examples of the isocyanate compound (D) include trimethylolpropane / tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”], trimethylolpropane / hexamethylene diisocyanate adduct [Japan Polyurethane Industry Co., Ltd. Product name “Coronate HL”], product name “Coronate HX” (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / xylylene diisocyanate adduct [Mitsui Chemicals, product name “Takenate 110N”], etc. A commercial item is also mentioned. Examples of the active energy ray-curable isocyanate compound (D) include isocyanates having a (meth) acryloyl group, such as Karenz AOI (manufactured by Showa Denko KK), Karenz BEI (manufactured by Showa Denko KK), Laromer LR9000. Commercial products such as (manufactured by BASF) are listed.
　イソシアネート化合物（Ｄ）の配合量は、硬化性成分の全量１００重量部に対して、通常、３０重量部以下であり、活性エネルギー線硬化型接着剤組中の前記化合物（Ｄ）の含有量が多すぎると、接着性が低下し、落下試験に対する耐衝撃性が悪化する場合がある。活性エネルギー線硬化型接着剤中の前記化合物（Ｄ）の含有量は、２０重量部以下であることがより好ましい。一方、耐水性の点から、活性エネルギー線硬化型接着剤中、前記化合物（Ｄ）を０．１重量部以上含有することが好ましく、１重量部以上含有することがより好ましい。 The compounding amount of the isocyanate compound (D) is usually 30 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component, and the content of the compound (D) in the active energy ray-curable adhesive group is When the amount is too large, the adhesiveness is lowered, and the impact resistance against the drop test may be deteriorated. The content of the compound (D) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the active energy ray-curable adhesive preferably contains 0.1 part by weight or more of the compound (D), more preferably 1 part by weight or more.
　＜シランカップリング剤（Ｅ）＞
　本発明の偏光フィルム用硬化型接着剤が活性エネルギー線硬化性硬化型の場合には、シランカップリング剤（Ｅ）は、活性エネルギー線硬化性の化合物を使用することが好ましいが、活性エネルギー線硬化性でなくても同様の耐水性を付与することができる。 <Silane coupling agent (E)>
When the curable adhesive for polarizing film of the present invention is an active energy ray curable type, it is preferable to use an active energy ray curable compound as the silane coupling agent (E). Even if it is not curable, the same water resistance can be provided.
　シランカップリング剤（Ｅ）の具体例としては、活性エネルギー線硬化性の化合物としてビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、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、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メチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタ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メチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシランなどが挙げられる。 Specific examples of the silane coupling agent (E) include, as active energy ray-curable compounds, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.
　好ましくは、３－メタクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリメトキシシランである。 Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.
　活性エネルギー線硬化性ではないシランカップリング剤の具体例としては、アミノ基を有するシランカップリング剤（Ｅ１）が好ましい。アミノ基を有するシランカップリング剤（Ｅ１）の具体例としては、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルトリイソプロポキシシラン、γ－アミノプロピルメチルジメトキシシラン、γ－アミノプロピルメチルジエトキシシラン、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルメチルジメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリエトキシシラン、γ－（２－アミノエチル）アミノプロピルメチルジエトキシシラン、γ－（２－アミノエチル）アミノプロピルトリイソプロポキシシラン、γ－（２－（２－アミノエチル）アミノエチル）アミノプロピルトリメトキシシラン、γ－（６－アミノヘキシル）アミノプロピルトリメトキシシラン、３－（Ｎ－エチルアミノ）－２－メチルプロピルトリメトキシシラン、γ－ウレイドプロピルトリメトキシシラン、γ－ウレイドプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、Ｎ－ベンジル－γ－アミノプロピルトリメトキシシラン、Ｎ－ビニルベンジル－γ－アミノプロピルトリエトキシシラン、Ｎ－シクロヘキシルアミノメチルトリエトキシシラン、Ｎ－シクロヘキシルアミノメチルジエトキシメチルシラン、Ｎ－フェニルアミノメチルトリメトキシシラン、（２－アミノエチル）アミノメチルトリメトキシシラン、Ｎ，Ｎ’－ビス［３－（トリメトキシシリル）プロピル］エチレンジアミン等のアミノ基含有シラン類；Ｎ－（１，３－ジメチルブチリデン）－３－（トリエトキシシリル）－１－プロパンアミン等のケチミン型シラン類を挙げることができる。 As a specific example of the silane coupling agent that is not active energy ray-curable, a silane coupling agent (E1) having an amino group is preferable. Specific examples of the silane coupling agent (E1) having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane Γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane , Γ- (6-Aminohexyl) Minopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutyrate) Reden)- - it can be exemplified (triethoxysilyl) -1-propane ketimines type silanes such as amines.
　アミノ基を有するシランカップリング剤（Ｅ１）は、１種のみを用いてもよく、複数種を組み合わせて用いても良い。これらのうち、良好な接着性を確保するためには、γ－アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルメチルジメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリエトキシシラン、γ－（２－アミノエチル）アミノプロピルメチルジエトキシシラン、Ｎ－（１，３－ジメチルブチリデン）－３－（トリエトキシシリル）－１－プロパンアミンが好ましい。 The silane coupling agent (E1) having an amino group may be used alone or in combination of two or more. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- 1-propanamine is preferred.
　シランカップリング剤（Ｅ）の配合量は、硬化性成分の全量１００重量部に対して、０．０１～２０重量部の範囲が好ましく、０．０５～１５重量部であることが好ましく、０．１～１０重量部であることがさらに好ましい。２０重量部を超える配合量の場合、接着剤の保存安定性が悪化し、また０．１重量部未満の場合は耐水接着性の効果が十分発揮されないためである。なお、接着剤層のガラス転移温度Ｔｇを計算する際には、シランカップリング剤（Ｅ）を計算には入れないこととする。 The amount of the silane coupling agent (E) is preferably in the range of 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the total amount of the curable component. More preferably, it is 1 to 10 parts by weight. This is because when the blending amount exceeds 20 parts by weight, the storage stability of the adhesive deteriorates, and when the blending amount is less than 0.1 part by weight, the water-resistant adhesive effect is not sufficiently exhibited. In calculating the glass transition temperature Tg of the adhesive layer, the silane coupling agent (E) is not included in the calculation.
　上記以外の活性エネルギー線硬化性ではないシランカップリング剤の具体例としては、３－ウレイドプロピルトリエトキシシラン、３－クロロプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピルトリエトキシシラン、イミダゾールシランなどが挙げられる。 Specific examples of silane coupling agents that are not active energy ray-curable other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy. Examples include silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and imidazolesilane.
　上記光酸発生剤（Ｂ）、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）、イソシアネート化合物（Ｄ）、シランカップリング剤（Ｅ）についても、各成分のｌｏｇＰｏｗ値は好ましくは１以上、より好ましくは２以上である。なお、光酸発生剤（Ｂ）、シランカップリング剤（Ｅ）は、偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値の計算における成分には含まれない。一方、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）、イソシアネート化合物（Ｄ）は偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値の計算における成分には含まれる。 Regarding the photoacid generator (B), the compound (C) containing any one of an alkoxy group and an epoxy group, the isocyanate compound (D), and the silane coupling agent (E), the logPow value of each component is preferably 1 or more. More preferably, it is 2 or more. In addition, a photo-acid generator (B) and a silane coupling agent (E) are not contained in the component in calculation of the logPow value of the curable adhesive for polarizing films. On the other hand, the compound (C) containing either an alkoxy group or an epoxy group and the isocyanate compound (D) are included in the components for calculating the logPow value of the curable adhesive for polarizing films.
　＜上記以外の添加剤＞
　また、本発明の偏光フィルム用硬化型接着剤には、本発明の目的、効果を損なわない範囲において、その他の任意成分として各種の添加剤を配合することができる。かかる添加剤としては、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン－ブタジエンブロック共重合体、石油樹脂、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコーン系オリゴマー、ポリスルフィド系オリゴマーなどのポリマーあるいはオリゴマー；フェノチアジン、２，６－ジ－ｔ－ブチル－４－メチルフェノールなどの重合禁止剤；重合開始助剤；レベリング剤；濡れ性改良剤；界面活性剤；可塑剤；紫外線吸収剤；無機充填剤；顔料；染料などを挙げることができる。各種の添加剤のなかでも、ｌｏｇＰｏｗ値が高いものが好ましい。各種の添加剤のｌｏｇＰｏｗ値は、好ましくは２以上、より好ましくは３以上、最も好ましくは４以上である。なお、これら添加剤は、偏光フィルム用硬化型接着剤のｌｏｇＰｏｗ値の計算における成分には含まれない。 <Additives other than the above>
Moreover, various additives can be mix | blended with the curable adhesive for polarizing films of this invention as another arbitrary component in the range which does not impair the objective and effect of this invention. Such additives include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone-based oligomer. Polymers or oligomers such as polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; UV absorbers; inorganic fillers; pigments; dyes and the like. Among various additives, those having a high logPow value are preferable. The logPow value of various additives is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more. In addition, these additives are not contained in the component in calculation of the logPow value of the curable adhesive for polarizing films.
　上記の添加剤は、硬化性成分の全量１００重量部に対して、通常０～１０重量部、好ましくは０～５重量部、最も好ましくは０～３重量部である。 The above additives are usually 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and most preferably 0 to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable component.
　＜接着剤の粘度＞
　本発明の偏光フィルム用硬化型接着剤は、前記硬化性成分を含有するが、当該接着剤の粘度は、塗工性の観点から、２５℃において１００ｃｐ以下であるのが好ましい。一方、本発明の偏光フィルム用硬化型接着剤が２５℃において１００ｃｐを超える場合には、塗工時に接着剤の温度をコントロールして、１００ｃｐ以下に調整して用いることもできる。粘度のより好ましい範囲は１～８０ｃｐ、最も好ましくは１０～５０ｃｐである。粘度は東機産業社製のＥ型粘度計ＴＶＥ２２ＬＴを使用して測定することができる。 <Viscosity of adhesive>
Although the curable adhesive for polarizing films of this invention contains the said sclerosing | hardenable component, it is preferable that the viscosity of the said adhesive is 100 cp or less in 25 degreeC from a viewpoint of coating property. On the other hand, when the curable adhesive for polarizing film of the present invention exceeds 100 cp at 25 ° C., the temperature of the adhesive can be controlled at the time of coating and adjusted to 100 cp or less. A more preferable range of the viscosity is 1 to 80 cp, and most preferably 10 to 50 cp. The viscosity can be measured using an E-type viscometer TVE22LT manufactured by Toki Sangyo Co., Ltd.
　また本発明の偏光フィルム用硬化型接着剤は、安全性の観点から、前記硬化性成分として皮膚刺激の低い材料を使用することが好ましい。皮膚刺激性は、Ｐ．Ｉ．Ｉという指標で判断することができる。Ｐ．Ｉ．Ｉは皮膚障害の度合いを示すものとして広く用いられ、ドレーズ法により測定される。測定値は０～８の範囲で表示され、値が小さいほど刺激性は低いと判断されるが、測定値の誤差が大きいため参考値として捉えるのが良い。Ｐ．Ｉ．Ｉは、好ましくは４以下、より好ましくは３以下、最も好ましくは２以下である。 The polarizing film curable adhesive of the present invention preferably uses a material having low skin irritation as the curable component from the viewpoint of safety. Skin irritation is P.I. I. Judgment can be made with the index I. P. I. I is widely used to indicate the degree of skin injury and is measured by the Draise method. The measured value is displayed in the range of 0 to 8, and it is determined that the irritation is lower as the value is smaller. However, since the error of the measured value is large, it should be taken as a reference value. P. I. I is preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.
　＜偏光フィルム＞
　本発明の偏光フィルムは、偏光子の少なくとも片面に、上記偏光フィルム用硬化型接着剤の硬化物層により形成された接着剤層を介して、透明保護フィルムが貼り合わされている。前記硬化物層である接着剤層は、上述のとおり、バルク吸水率が１０重量％以下である。 <Polarizing film>
In the polarizing film of the present invention, a transparent protective film is bonded to at least one surface of a polarizer via an adhesive layer formed of a cured product layer of the polarizing film curable adhesive. As described above, the adhesive layer that is the cured product layer has a bulk water absorption of 10% by weight or less.
　＜接着剤層＞
　上記硬化型接着剤により形成された接着剤層の厚みは、０．１～３μｍになるように制御することが好ましい。接着剤層の厚みは０．３～２μｍであるのがより好ましく、さらには０．５～１．５μｍが好ましい。接着剤層の厚さを０．１μｍ以上とすることは、接着剤層の凝集力により接着不良の発生や、ラミネート時に外観不良（気泡）が生じることを抑えるうえで好ましい。一方、接着剤層が３μｍより厚くなると、偏光フィルムが耐久性を満足できないおそれがある。 <Adhesive layer>
The thickness of the adhesive layer formed by the curable adhesive is preferably controlled to be 0.1 to 3 μm. The thickness of the adhesive layer is more preferably 0.3 to 2 μm, and further preferably 0.5 to 1.5 μm. Setting the thickness of the adhesive layer to 0.1 μm or more is preferable in order to suppress the occurrence of poor adhesion due to the cohesive force of the adhesive layer and the occurrence of poor appearance (bubbles) during lamination. On the other hand, if the adhesive layer is thicker than 3 μm, the polarizing film may not be able to satisfy the durability.
　また、硬化型接着剤は、これにより形成される接着剤層のＴｇが６０℃以上になるように選択されることが好ましく、さらには７０℃以上であることが好ましく、さらには７５℃以上、さらには１００℃以上、さらには１２０℃以上であることが好ましい。一方、接着剤層のＴｇが高くなりすぎると偏光フィルムの屈曲性が低下することから、接着剤層のＴｇは３００℃以下、さらには２４０℃以下、さらには１８０℃以下にすることが好ましい。Ｔｇ＜ガラス転移温度＞は、ＴＡインスツルメンツ製動的粘弾性測定装置ＲＳＡＩＩＩを用い以下の測定条件で測定される。
　サンプルサイズ：幅１０ｍｍ、長さ３０ｍｍ、
　クランプ距離２０ｍｍ、
　測定モード：引っ張り、周波数：１Ｈｚ、昇温速度：５℃／分
動的粘弾性の測定を行い、ｔａｎδのピークトップの温度Ｔｇとして採用した。 Further, the curable adhesive is preferably selected so that the Tg of the adhesive layer formed thereby is 60 ° C. or higher, more preferably 70 ° C. or higher, and further 75 ° C. or higher, Further, it is preferably 100 ° C. or higher, more preferably 120 ° C. or higher. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing film is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower. Tg <glass transition temperature> is measured under the following measurement conditions using a TA Instruments dynamic viscoelasticity measuring apparatus RSAIII.
Sample size: width 10mm, length 30mm,
Clamp distance 20mm,
Measurement mode: Tensile, Frequency: 1 Hz, Temperature rising rate: 5 ° C./min Dynamic viscoelasticity was measured and adopted as the temperature Tg of tan δ peak top.
　また、硬化型接着剤は、これにより形成される接着剤層の貯蔵弾性率が７０℃以下の領域で１．０×１０６Ｐａ以上であることが好ましい。更には１．０×１０７Ｐａ以上であることがより好ましい。接着剤層の貯蔵弾性率は、偏光フィルムにヒートサイクル（－４０℃から８０℃など）をかけた際の偏光子クラックに影響し、貯蔵弾性率が低い場合、偏光子クラックの不具合が発生しやすい。高い貯蔵弾性率を有する温度領域は、８０℃以下がより好ましく、９０℃以下が最も好ましい。貯蔵弾性率はＴｇ＜ガラス転移温度＞と同時に、ＴＡインスツルメンツ製動的粘弾性測定装置ＲＳＡＩＩＩを用い同様の測定条件で測定される。動的粘弾性の測定を行い、貯蔵弾性率（Ｅ´’）の値を採用した。 Further, the curable adhesive preferably has a storage elastic modulus of an adhesive layer formed thereby of 1.0 × 10 6 Pa or more in a region of 70 ° C. or less. Further, it is more preferably 1.0 × 10 7 Pa or more. The storage elastic modulus of the adhesive layer affects the polarizer cracks when the polarizing film is subjected to a heat cycle (−40 ° C. to 80 ° C., etc.). Cheap. The temperature region having a high storage elastic modulus is more preferably 80 ° C. or less, and most preferably 90 ° C. or less. The storage elastic modulus is measured under the same measurement conditions using a dynamic viscoelasticity measuring device RSAIII manufactured by TA Instruments simultaneously with Tg <glass transition temperature>. The dynamic viscoelasticity was measured and the value of storage elastic modulus (E ′ ′) was adopted.
　本発明に係る偏光フィルムは、偏光子の接着剤層を形成する面および／または透明保護フィルムの接着剤層を形成する面に、硬化型接着剤を塗工した後、偏光子と透明保護フィルムを貼り合わせる工程、次いで、硬化型接着剤を硬化して接着剤層を形成する工程、を有する。 In the polarizing film according to the present invention, the polarizer and the transparent protective film are coated with a curable adhesive on the surface of the polarizer forming the adhesive layer and / or the surface of the transparent protective film forming the adhesive layer. And then a step of curing the curable adhesive to form an adhesive layer.
　偏光子、透明保護フィルムは、上記硬化型接着剤を塗工する前に、表面改質処理を行ってもよい。具体的な処理としては、コロナ処理、プラズマ処理、ケン化処理による処理などが挙げられる。 The polarizer and the transparent protective film may be subjected to surface modification treatment before applying the curable adhesive. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
　硬化型接着剤の塗工方式は、当該硬化型接着剤の粘度や目的とする厚みによって適宜に選択される。塗工方式の例として、例えば、リバースコーター、グラビアコーター（ダイレクト，リバースやオフセット）、バーリバースコーター、ロールコーター、ダイコーター、バーコーター、ロッドコーターなどが挙げられる。その他、塗工には、デイッピング方式などの方式を適宜に使用することができる。 The coating method of the curable adhesive is appropriately selected depending on the viscosity of the curable adhesive and the target thickness. Examples of coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like. In addition, for coating, a method such as a dapping method can be appropriately used.
　上記のように塗工した硬化型接着剤を介して、偏光子と透明保護フィルムとを貼り合わせる。偏光子と透明保護フィルムの貼り合わせは、ロールラミネーターなどにより行う事ができる。 The polarizer and the transparent protective film are bonded together through the curable adhesive applied as described above. Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.
　＜接着剤の硬化＞
　本発明に係る偏光フィルム用硬化型接着剤は、活性エネルギー線硬化型接着剤または熱硬化型接着剤として用いられる。活性エネルギー線硬化型接着剤では、電子線硬化型、紫外線硬化型、可視光線硬化型の態様で用いることができる。前記硬化型接着剤の態様は生産性の観点から熱硬化型接着剤よりも、活性エネルギー線硬化型接着剤が好ましく、さらには活性エネルギー線硬化型接着剤としては、可視光線硬化型接着剤が生産性の観点から好ましい。 <Curing the adhesive>
The polarizing film curable adhesive according to the present invention is used as an active energy ray curable adhesive or a thermosetting adhesive. The active energy ray curable adhesive can be used in an electron beam curable type, an ultraviolet ray curable type, or a visible light curable type. The embodiment of the curable adhesive is preferably an active energy ray curable adhesive rather than a thermosetting adhesive from the viewpoint of productivity, and moreover, the active energy ray curable adhesive is a visible light curable adhesive. It is preferable from the viewpoint of productivity.
　≪活性エネルギー線硬化型≫
　活性エネルギー線硬化型接着剤では、偏光子と透明保護フィルムを貼り合わせた後に、活性エネルギー線（電子線、紫外線、可視光線など）を照射し、活性エネルギー線硬化型接着剤を硬化して接着剤層を形成する。活性エネルギー線（電子線、紫外線、可視光線など）の照射方向は、任意の適切な方向から照射することができる。好ましくは、透明保護フィルム側から照射する。偏光子側から照射すると、偏光子が活性エネルギー線（電子線、紫外線、可視光線など）によって劣化するおそれがある。 ≪Active energy ray curing type≫
In the active energy ray curable adhesive, after bonding the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated and the active energy ray curable adhesive is cured and bonded. An agent layer is formed. The irradiation direction of active energy rays (electron beam, ultraviolet ray, visible light, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet ray, visible light, etc.).
　≪電子線硬化型≫
　電子線硬化型において、電子線の照射条件は、上記活性エネルギー線硬化型接着剤を硬化しうる条件であれば、任意の適切な条件を採用できる。例えば、電子線照射は、加速電圧が好ましくは５ｋＶ～３００ｋＶであり、さらに好ましくは１０ｋＶ～２５０ｋＶである。加速電圧が５ｋＶ未満の場合、電子線が接着剤まで届かず硬化不足となるおそれがあり、加速電圧が３００ｋＶを超えると、試料を通る浸透力が強すぎて、透明保護フィルムや偏光子にダメージを与えるおそれがある。照射線量としては、５～１００ｋＧｙ、さらに好ましくは１０～７５ｋＧｙである。照射線量が５ｋＧｙ未満の場合は、接着剤が硬化不足となり、１００ｋＧｙを超えると、透明保護フィルムや偏光子にダメージを与え、機械的強度の低下や黄変を生じ、所定の光学特性を得ることができない。 ≪Electron beam curing type≫
In the electron beam curable type, any appropriate condition can be adopted as the irradiation condition of the electron beam as long as the active energy ray curable adhesive can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong and damages the transparent protective film and the polarizer. There is a risk of giving. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.
　電子線照射は、通常、不活性ガス中で照射を行うが、必要であれば大気中や酸素を少し導入した条件で行ってもよい。透明保護フィルムの材料によるが、酸素を適宜導入することによって、最初に電子線があたる透明保護フィルム面にあえて酸素阻害を生じさせ、透明保護フィルムへのダメージを防ぐことができ、接着剤にのみ効率的に電子線を照射させることができる。 The electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, the transparent protective film surface where the electron beam first hits can be obstructed to prevent oxygen damage and prevent damage to the transparent protective film. An electron beam can be irradiated efficiently.
　≪紫外線硬化型、可視光線硬化型≫
　本発明に係る偏光フィルムの製造方法では、活性エネルギー線として、波長範囲３８０ｎｍ～４５０ｎｍの可視光線を含むもの、特には波長範囲３８０ｎｍ～４５０ｎｍの可視光線の照射量が最も多い活性エネルギー線を使用することが好ましい。紫外線硬化型、可視光線硬化型において、紫外線吸収能を付与した透明保護フィルム（紫外線不透過型透明保護フィルム）を使用する場合、およそ３８０ｎｍより短波長の光を吸収するため、３８０ｎｍより短波長の光は活性エネルギー線硬化型接着剤に到達せず、その重合反応に寄与しない。さらに、透明保護フィルムによって吸収された３８０ｎｍより短波長の光は熱に変換され、透明保護フィルム自体が発熱し、偏光フィルムのカール・シワなど不良の原因となる。そのため、本発明において紫外線硬化型、可視光線硬化型を採用する場合、活性エネルギー線発生装置として３８０ｎｍより短波長の光を発光しない装置を使用することが好ましく、より具体的には、波長範囲３８０～４４０ｎｍの積算照度と波長範囲２５０～３７０ｎｍの積算照度との比が１００：０～１００：５０であることが好ましく、１００：０～１００：４０であることがより好ましい。本発明に係る活性エネルギー線としては、ガリウム封入メタルハライドランプ、波長範囲３８０～４４０ｎｍを発光するＬＥＤ光源が好ましい。あるいは、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、白熱電球、キセノンランプ、ハロゲンランプ、カーボンアーク灯、メタルハライドランプ、蛍光灯、タングステンランプ、ガリウムランプ、エキシマレーザーまたは太陽光などの紫外線と可視光線を含む光源を使用することができ、バンドパスフィルターを用いて３８０ｎｍより短波長の紫外線を遮断して用いることもできる。偏光子と透明保護フィルムとの間の接着剤層の接着性能を高めつつ、偏光フィルムのカールを防止するためには、ガリウム封入メタルハライドランプを使用し、かつ３８０ｎｍより短波長の光を遮断可能なバンドパスフィルターを介して得られた活性エネルギー線、またはＬＥＤ光源を使用して得られる波長４０５ｎｍの活性エネルギー線を使用することが好ましい。 ≪Ultraviolet curing type, visible light curing type≫
In the method for producing a polarizing film according to the present invention, active energy rays containing visible light having a wavelength range of 380 nm to 450 nm, particularly active energy rays having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm are used as active energy rays. It is preferable. In the case of using a transparent protective film (ultraviolet non-transparent transparent protective film) imparted with ultraviolet absorbing ability in the ultraviolet curable type and visible light curable type, light having a wavelength shorter than about 380 nm is absorbed. Light does not reach the active energy ray-curable adhesive and does not contribute to the polymerization reaction. Furthermore, light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curling and wrinkling of the polarizing film. Therefore, when the ultraviolet curable type or the visible light curable type is adopted in the present invention, it is preferable to use a device that does not emit light having a wavelength shorter than 380 nm as the active energy ray generating device, and more specifically, the wavelength range 380. The ratio of the integrated illuminance of ˜440 nm to the integrated illuminance of the wavelength range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40. As the active energy ray according to the present invention, a gallium-encapsulated metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable. Or low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight A light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter. In order to prevent the polarization film from curling while improving the adhesive performance of the adhesive layer between the polarizer and the transparent protective film, a gallium-encapsulated metal halide lamp can be used and light with a wavelength shorter than 380 nm can be blocked. It is preferable to use an active energy ray obtained through a band pass filter or an active energy ray having a wavelength of 405 nm obtained using an LED light source.
　紫外線硬化型または可視光線硬化型において、紫外線または可視光線を照射する前に活性エネルギー線硬化型接着剤を加温すること（照射前加温）が好ましく、その場合４０℃以上に加温することが好ましく、５０℃以上に加温することがより好ましい。また、紫外線または可視光線を照射後に活性エネルギー線硬化型接着剤を加温すること（照射後加温）も好ましく、その場合４０℃以上に加温することが好ましく、５０℃以上に加温することがより好ましい。 In the ultraviolet curable type or visible light curable type, it is preferable to heat the active energy ray curable adhesive before irradiation with ultraviolet rays or visible light (heating before irradiation), and in this case, the temperature should be increased to 40 ° C. or higher. Is preferable, and heating to 50 ° C. or higher is more preferable. It is also preferable to heat the active energy ray-curable adhesive after irradiation with ultraviolet rays or visible light (heating after irradiation), in which case it is preferable to heat to 40 ° C. or higher, and warm to 50 ° C. or higher. It is more preferable.
　本発明に係る活性エネルギー線硬化型接着剤は、特に偏光子と波長３６５ｎｍの光線透過率が５％未満である透明保護フィルムとを接着する接着剤層を形成する場合に好適に使用可能である。ここで、本発明に係る活性エネルギー線硬化型接着剤は、上述した一般式（１）の光重合開始剤を含有することによって、ＵＶ吸収能を有する透明保護フィルム越しに紫外線を照射して、接着剤層を硬化形成することができる。よって、偏光子の両面にＵＶ吸収能を有する透明保護フィルムを積層した偏光フィルムにおいても、接着剤層を硬化させることができる。ただし、当然ながら、ＵＶ吸収能を有さない透明保護フィルムを積層した偏光フィルムにおいても、接着剤層を硬化させることができる。なお、ＵＶ吸収能を有する透明保護フィルムとは、３８０ｎｍの光に対する透過率が１０％未満である透明保護フィルムを意味する。 The active energy ray-curable adhesive according to the present invention can be suitably used particularly when forming an adhesive layer that adheres a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. . Here, the active energy ray-curable adhesive according to the present invention irradiates ultraviolet rays through the transparent protective film having UV absorption ability by containing the photopolymerization initiator of the general formula (1) described above, The adhesive layer can be hardened. Therefore, an adhesive bond layer can be hardened also in a polarizing film which laminated a transparent protective film which has UV absorption ability on both sides of a polarizer. However, as a matter of course, the adhesive layer can also be cured in a polarizing film in which a transparent protective film having no UV absorbing ability is laminated. In addition, the transparent protective film which has UV absorption ability means the transparent protective film whose transmittance | permeability with respect to light of 380 nm is less than 10%.
　透明保護フィルムへのＵＶ吸収能の付与方法としては、透明保護フィルム中に紫外線吸収剤を含有させる方法や、透明保護フィルム表面に紫外線吸収剤を含有する表面処理層を積層させる方法が挙げられる。 Examples of the method for imparting UV absorbing ability to the transparent protective film include a method of containing an ultraviolet absorber in the transparent protective film and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.
　紫外線吸収剤の具体例としては、例えば、従来公知のオキシベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフェノン系化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物、トリアジン系化合物などが挙げられる。 Specific examples of the ultraviolet absorber include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. .
　偏光子と透明保護フィルムを貼り合わせた後に、活性エネルギー線（電子線、紫外線、可視光線など）を照射し、活性エネルギー線硬化型接着剤を硬化して接着剤層を形成する。活性エネルギー線（電子線、紫外線、可視光線など）の照射方向は、任意の適切な方向から照射することができる。好ましくは、透明保護フィルム側から照射する。偏光子側から照射すると、偏光子が活性エネルギー線（電子線、紫外線、可視光線など）によって劣化するおそれがある。 After laminating the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated to cure the active energy ray-curable adhesive to form an adhesive layer. The irradiation direction of active energy rays (electron beam, ultraviolet ray, visible light, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet ray, visible light, etc.).
　≪熱硬化型≫
　一方、熱硬化型接着剤では、偏光子と透明保護フィルムを貼り合わせた後に、加熱することにより、熱重合開始剤により重合を開始して、硬化物層を形成する。加熱温度は、熱重合開始剤に応じて設定されるが、６０～２００℃程度、好ましくは８０～１５０℃である。 ≪Thermosetting type≫
On the other hand, in a thermosetting adhesive, after laminating a polarizer and a transparent protective film, by heating, polymerization is started by a thermal polymerization initiator to form a cured product layer. The heating temperature is set according to the thermal polymerization initiator, but is about 60 to 200 ° C., preferably 80 to 150 ° C.
　本発明に係る偏光フィルムを連続ラインで製造する場合、ライン速度は、接着剤の硬化時間によるが、好ましくは１～５００ｍ／ｍｉｎ、より好ましくは５～３００ｍ／ｍｉｎ、さらに好ましくは１０～１００ｍ／ｍｉｎである。ライン速度が小さすぎる場合は、生産性が乏しい、または透明保護フィルムへのダメージが大きすぎ、耐久性試験などに耐えうる偏光フィルムが作製できない。ライン速度が大きすぎる場合は、接着剤の硬化が不十分となり、目的とする接着性が得られない場合がある。 When the polarizing film according to the present invention is produced in a continuous line, the line speed depends on the curing time of the adhesive, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m / min. min. When the line speed is too low, the productivity is poor, or the damage to the transparent protective film is too great, and a polarizing film that can withstand the durability test cannot be produced. When the line speed is too high, the adhesive is not sufficiently cured, and the target adhesiveness may not be obtained.
　なお、本発明の偏光フィルムは、偏光子と透明保護フィルムが、上記活性エネルギー線硬化型接着剤の硬化物層により形成された接着剤層を介して貼り合されるが、透明保護フィルムと接着剤層の間には、易接着層を設けることができる。易接着層は、例えば、ポリエステル骨格、ポリエーテル骨格、ポリカーボネート骨格、ポリウレタン骨格、シリコーン系、ポリアミド骨格、ポリイミド骨格、ポリビニルアルコール骨格などを有する各種樹脂により形成することができる。これらポリマー樹脂は１種を単独で、または２種以上を組み合わせて用いることができる。また易接着層の形成には他の添加剤を加えてもよい。具体的にはさらには粘着付与剤、紫外線吸収剤、酸化防止剤、耐熱安定剤などの安定剤などを用いてもよい。 In the polarizing film of the present invention, the polarizer and the transparent protective film are bonded together via an adhesive layer formed by the cured layer of the active energy ray-curable adhesive. An easy-adhesion layer can be provided between the agent layers. The easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.
　易接着層は、通常、透明保護フィルムに予め設けておき、当該透明保護フィルムの易接着層側と偏光子とを接着剤層により貼り合わせる。易接着層の形成は、易接着層の形成材を透明保護フィルム上に、公知の技術により塗工、乾燥することにより行われる。易接着層の形成材は、乾燥後の厚み、塗工の円滑性などを考慮して適当な濃度に希釈した溶液として、通常調整される。易接着層は乾燥後の厚みは、好ましくは０．０１～５μｍ、さらに好ましくは０．０２～２μｍ、さらに好ましくは０．０５～１μｍである。なお、易接着層は複数層設けることができるが、この場合にも、易接着層の総厚みは上記範囲になるようにするのが好ましい。 The easy-adhesion layer is usually provided in advance on a transparent protective film, and the easy-adhesion layer side of the transparent protective film and the polarizer are bonded together with an adhesive layer. The easy-adhesion layer is formed by coating and drying the material for forming the easy-adhesion layer on the transparent protective film by a known technique. The material for forming the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating. The thickness of the easy-adhesion layer after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and still more preferably 0.05 to 1 μm. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.
　＜偏光子＞
　偏光子は、特に制限されず、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などの親水性高分子フィルムに、ヨウ素や二色性染料などの二色性材料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などポリエン系配向フィルムなどが挙げられる。これらのなかでもポリビニルアルコール系フィルムとヨウ素などの二色性物質からなる偏光子が好適である。これら偏光子の厚みは特に制限されないが、一般的に８０μｍ程度以下である。 <Polarizer>
The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. And polyene-based oriented films such as those obtained by adsorbing a functional material 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 material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.
　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ヨウ化カリウムなど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の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など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よし、また延伸してからヨウ素で染色してもよい。ホウ酸やヨウ化カリウムなどの水溶液中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 boric acid or potassium iodide. 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 dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. 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 in an aqueous solution of boric acid or potassium iodide or in a water bath.
　また本発明の硬化型接着剤は、偏光子としては厚みが１０μｍ以下の薄型の偏光子を用いた場合、その効果（高温高湿下の過酷な環境における光学耐久性を満足する）を顕著に発現することができる。上記厚みが１０μｍ以下の偏光子は、厚みが１０μｍを超える偏光子に比べて相対的に水分の影響が大きく、高温高湿下の環境において光学耐久性が十分でなく、透過率上昇や偏光度低下が起こりやすい。即ち、上記１０μｍ以下の偏光子を本発明のバルク吸水率が１０重量％以下の接着剤層で積層した場合、過酷な高温高湿下の環境において偏光子への水の移動が抑制されることによって、偏光フィルムの透過率上昇、偏光度低下などの光学耐久性の悪化を顕著に抑制することができる。偏光子の厚みは薄型化の観点から言えば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く、さらには偏光フィルムとしての厚みも薄型化が図れる点が好ましい。 The curable adhesive of the present invention is remarkably effective when a thin polarizer having a thickness of 10 μm or less is used as the polarizer (satisfying optical durability in a severe environment under high temperature and high humidity). Can be expressed. The polarizer having a thickness of 10 μm or less is relatively more affected by moisture than a polarizer having a thickness exceeding 10 μm, and has insufficient optical durability in a high-temperature and high-humidity environment, resulting in increased transmittance and degree of polarization. Decline is likely to occur. That is, when the polarizer of 10 μm or less is laminated with the adhesive layer having a bulk water absorption of 10% by weight or less according to the present invention, the movement of water to the polarizer is suppressed in a severe high temperature and high humidity environment. Thus, deterioration of optical durability such as an increase in transmittance of the polarizing film and a decrease in the degree of polarization can be remarkably suppressed. The thickness of the polarizer is preferably 1 to 7 μm from the viewpoint of thinning. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, 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、ＷＯ２０１０／１００９１７号パンフレット、ＰＣＴ／ＪＰ２０１０／００１４６０の明細書、または特願２０１０－２６９００２号明細書や特願２０１０－２６３６９２号明細書に記載されている薄型偏光膜を挙げることができる。これら薄型偏光膜は、ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂ともいう）層と延伸用樹脂基材を積層体の状態で延伸する工程と染色する工程を含む製法による得ることができる。この製法であれば、ＰＶＡ系樹脂層が薄くても、延伸用樹脂基材に支持されていることにより延伸による破断などの不具合なく延伸することが可能となる。 As the thin polarizer, typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- And a thin polarizing film described in Japanese Patent Application No. 269002 and Japanese Patent Application No. 2010-263692. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing 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、ＷＯ２０１０／１００９１７号パンフレット、ＰＣＴ／ＪＰ２０１０／００１４６０の明細書、または特願２０１０－２６９００２号明細書や特願２０１０－２６３６９２号明細書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、特に特願２０１０－２６９００２号明細書や特願２０１０－２６３６９２号明細書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, among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, the one obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric acid aqueous solution as described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 is preferable.
　上記のＰＣＴ／ＪＰ２０１０／００１４６０の明細書に記載の薄型高機能偏光膜は、樹脂基材に一体に製膜される、二色性物質を配向させたＰＶＡ系樹脂からなる厚みが７μｍ以下の薄型高機能偏光膜であって、単体透過率が４２．０％以上および偏光度が９９．９５％以上の光学特性を有する。 The thin high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 μm or less made of a PVA-based resin oriented with a dichroic material, which is integrally formed on a resin base material. It is a high-functional polarizing film, and has optical properties such as a single transmittance of 42.0% or more and a polarization degree of 99.95% or more.
　上記薄型高機能偏光膜は、少なくとも２０μｍの厚みを有する樹脂基材に、ＰＶＡ系樹脂の塗布および乾燥によってＰＶＡ系樹脂層を生成し、生成されたＰＶＡ系樹脂層を二色性物質の染色液に浸漬して、ＰＶＡ系樹脂層に二色性物質を吸着させ、二色性物質を吸着させたＰＶＡ系樹脂層を、ホウ酸水溶液中において、樹脂基材と一体に総延伸倍率を元長の５倍以上となるように延伸することによって、製造することができる。 The thin high-performance polarizing film generates a PVA-based resin layer by applying and drying a PVA-based resin on a resin substrate having a thickness of at least 20 μm, and the generated PVA-based resin layer is used as a dichroic dyeing solution. So that the dichroic substance is adsorbed on the PVA resin layer, and the PVA resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the boric acid aqueous solution so that the total draw ratio is the original length. It can manufacture by extending | stretching so that it may become 5 times or more.
　また、二色性物質を配向させた薄型高機能偏光膜を含む積層体フィルムを製造する方法であって、少なくとも２０μｍの厚みを有する樹脂基材と、樹脂基材の片面にＰＶＡ系樹脂を含む水溶液を塗布および乾燥することによって形成されたＰＶＡ系樹脂層とを含む積層体フィルムを生成する工程と、樹脂基材と樹脂基材の片面に形成されたＰＶＡ系樹脂層とを含む前記積層体フィルムを、二色性物質を含む染色液中に浸漬することによって、積層体フィルムに含まれるＰＶＡ系樹脂層に二色性物質を吸着させる工程と、二色性物質を吸着させたＰＶＡ系樹脂層を含む前記積層体フィルムを、ホウ酸水溶液中において、総延伸倍率が元長の５倍以上となるように延伸する工程と、二色性物質を吸着させたＰＶＡ系樹脂層が樹脂基材と一体に延伸されたことにより、樹脂基材の片面に、二色性物質を配向させたＰＶＡ系樹脂層からなる、厚みが７μｍ以下、単体透過率が４２．０％以上かつ偏光度が９９．９５％以上の光学特性を有する薄型高機能偏光膜を製膜させた積層体フィルムを製造する工程を含むことで、上記薄型高機能偏光膜を製造することができる。 Moreover, it is a method for producing a laminate film including a thin high-performance polarizing film in which a dichroic substance is oriented, and includes a resin base material having a thickness of at least 20 μm and a PVA resin on one side of the resin base material. The said laminated body containing the process of producing | generating the laminated body film containing the PVA-type resin layer formed by apply | coating and drying aqueous solution, and the PVA-type resin layer formed in the single side | surface of the resin base material A step of adsorbing the dichroic substance to the PVA resin layer contained in the laminate film by immersing the film in a dye solution containing the dichroic substance, and a PVA resin adsorbing the dichroic substance A step of stretching the laminate film including a layer in a boric acid aqueous solution so that the total stretching ratio is 5 times or more of the original length, and a PVA resin layer on which a dichroic substance is adsorbed Integrated with As a result, a thickness of 7 μm or less, a single transmittance of 42.0% or more, and a degree of polarization of 99.95% or more consisting of a PVA-based resin layer in which a dichroic material is oriented on one surface of a resin base material. The thin high-performance polarizing film can be manufactured by including a step of manufacturing a laminate film on which a thin high-performance polarizing film having the above optical characteristics is formed.
　上記の特願２０１０－２６９００２号明細書や特願２０１０－２６３６９２号明細書の薄型偏光膜は、二色性物質を配向させたＰＶＡ系樹脂からなる連続ウェブの偏光膜であって、非晶性エステル系熱可塑性樹脂基材に製膜されたＰＶＡ系樹脂層を含む積層体が空中補助延伸とホウ酸水中延伸とからなる２段延伸工程で延伸されることにより、１０μｍ以下の厚みにされたものである。かかる薄型偏光膜は、単体透過率をＴ、偏光度をＰとしたとき、Ｐ＞－（１００．９２９Ｔ－４２．４－１）×１００（ただし、Ｔ＜４２．３）、およびＰ≧９９．９（ただし、Ｔ≧４２．３）の条件を満足する光学特性を有するようにされたものであることが好ましい。 The thin polarizing films in the above-mentioned Japanese Patent Application Nos. 2010-269002 and 2010-263692 are continuous web polarizing films made of a PVA-based resin in which a dichroic material is oriented, and are amorphous. The laminate including the PVA-based resin layer formed on the ester-based thermoplastic resin base material was stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching, so that the thickness was 10 μm or less. Is. Such thin polarizing film, a single transmittance T, hours the polarization was P, P> - (10 0.929T -42.4-1) × 100 ( however, T <42.3), and P ≧ It is preferable that the optical properties satisfy 99.9 (where T ≧ 42.3).
　具体的には、前記薄型偏光膜は、連続ウェブの非晶性エステル系熱可塑性樹脂基材に製膜されたＰＶＡ系樹脂層に対する空中高温延伸によって、配向されたＰＶＡ系樹脂層からなる延伸中間生成物を生成する工程と、延伸中間生成物に対する二色性物質の吸着によって、二色性物質（ヨウ素またはヨウ素と有機染料の混合物が好ましい）を配向させたＰＶＡ系樹脂層からなる着色中間生成物を生成する工程と、着色中間生成物に対するホウ酸水中延伸によって、二色性物質を配向させたＰＶＡ系樹脂層からなる厚みが１０μｍ以下の偏光膜を生成する工程とを含む薄型偏光膜の製造方法により製造することができる。 Specifically, the thin polarizing film is a stretch intermediate formed of an oriented PVA resin layer by high-temperature stretching in the air with respect to the PVA resin layer formed on the amorphous ester thermoplastic resin substrate of the continuous web. A colored intermediate product comprising a PVA-based resin layer in which a dichroic material (preferably iodine or a mixture of iodine and an organic dye) is oriented by adsorption of the dichroic material to the stretched intermediate product and a step of generating the product. A thin polarizing film comprising a step of forming a product, and a step of generating a polarizing film having a thickness of 10 μm or less comprising a PVA-based resin layer in which a dichroic material is oriented by stretching in a boric acid solution with respect to a colored intermediate product It can be manufactured by a manufacturing method.
　この製造方法において、空中高温延伸とホウ酸水中延伸とによる非晶性エステル系熱可塑性樹脂基材に製膜されたＰＶＡ系樹脂層の総延伸倍率が、５倍以上になるようにするのが望ましい。ホウ酸水中延伸のためのホウ酸水溶液の液温は、６０℃以上とすることができる。ホウ酸水溶液中で着色中間生成物を延伸する前に、着色中間生成物に対して不溶化処理を施すのが望ましく、その場合、液温が４０℃を超えないホウ酸水溶液に前記着色中間生成物を浸漬することにより行うのが望ましい。上記非晶性エステル系熱可塑性樹脂基材は、イソフタル酸を共重合させた共重合ポリエチレンテレフタレート、シクロヘキサンジメタノールを共重合させた共重合ポリエチレンテレフタレートまたは他の共重合ポリエチレンテレフタレートを含む非晶性ポリエチレンテレフタレートとすることができ、透明樹脂からなるものであることが好ましく、その厚みは、製膜されるＰＶＡ系樹脂層の厚みの７倍以上とすることができる。また、空中高温延伸の延伸倍率は３．５倍以下が好ましく、空中高温延伸の延伸温度はＰＶＡ系樹脂のガラス転移温度以上、具体的には９５℃～１５０℃の範囲であるのが好ましい。空中高温延伸を自由端一軸延伸で行う場合、非晶性エステル系熱可塑性樹脂基材に製膜されたＰＶＡ系樹脂層の総延伸倍率が、５倍以上７．５倍以下であるのが好ましい。また、空中高温延伸を固定端一軸延伸で行う場合、非晶性エステル系熱可塑性樹脂基材に製膜されたＰＶＡ系樹脂層の総延伸倍率が、５倍以上８．５倍以下であるのが好ましい。
　更に具体的には、次のような方法により、薄型偏光膜を製造することができる。 In this production method, the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable. The liquid temperature of the boric acid aqueous solution for boric-acid water extending | stretching can be 60 degreeC or more. Before stretching the colored intermediate product in the aqueous boric acid solution, it is desirable to insolubilize the colored intermediate product. In this case, the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping. The amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed. In addition, the draw ratio of high-temperature drawing in the air is preferably 3.5 times or less, and the drawing temperature of high-temperature drawing in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C. When performing high temperature stretching in the air by free end uniaxial stretching, the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times . In addition, when performing high-temperature stretching in the air by uniaxial stretching at the fixed end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred.
More specifically, a thin polarizing film can be produced by the following method.
　イソフタル酸を６ｍｏｌ％共重合させたイソフタル酸共重合ポリエチレンテレフタレート（非晶性ＰＥＴ）の連続ウェブの基材を作製する。非晶性ＰＥＴのガラス転移温度は７５℃である。連続ウェブの非晶性ＰＥＴ基材とポリビニルアルコール（ＰＶＡ）層からなる積層体を、以下のように作製する。ちなみにＰＶＡのガラス転移温度は８０℃である。 A base material for a continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared. The glass transition temperature of amorphous PET is 75 ° C. A laminate comprising a continuous web of amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.
　２００μｍ厚の非晶性ＰＥＴ基材と、重合度１０００以上、ケン化度９９％以上のＰＶＡ粉末を水に溶解した４～５％濃度のＰＶＡ水溶液とを準備する。次に、２００μｍ厚の非晶性ＰＥＴ基材にＰＶＡ水溶液を塗布し、５０～６０℃の温度で乾燥し、非晶性ＰＥＴ基材に７μｍ厚のＰＶＡ層が製膜された積層体を得る。 A 200 μm-thick amorphous PET base material and a 4-5% PVA aqueous solution in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more are dissolved in water are prepared. Next, an aqueous PVA solution is applied to a 200 μm thick amorphous PET substrate and dried at a temperature of 50 to 60 ° C. to obtain a laminate in which a 7 μm thick PVA layer is formed on the amorphous PET substrate. .
　７μｍ厚のＰＶＡ層を含む積層体を、空中補助延伸およびホウ酸水中延伸の２段延伸工程を含む以下の工程を経て、３μｍ厚の薄型高機能偏光膜を製造する。第１段の空中補助延伸工程によって、７μｍ厚のＰＶＡ層を含む積層体を非晶性ＰＥＴ基材と一体に延伸し、５μｍ厚のＰＶＡ層を含む延伸積層体を生成する。具体的には、この延伸積層体は、７μｍ厚のＰＶＡ層を含む積層体を１３０℃の延伸温度環境に設定されたオーブンに配備された延伸装置にかけ、延伸倍率が１．８倍になるように自由端一軸に延伸したものである。この延伸処理によって、延伸積層体に含まれるＰＶＡ層を、ＰＶＡ分子が配向された５μｍ厚のＰＶＡ層へと変化させる。 A thin and highly functional polarizing film having a thickness of 3 μm is manufactured from the laminate including the PVA layer having a thickness of 7 μm through the following steps including a two-stage stretching process of air-assisted stretching and boric acid water stretching. In the first-stage aerial auxiliary stretching step, the laminate including the 7 μm-thick PVA layer is integrally stretched with the amorphous PET substrate to produce a stretched laminate including the 5 μm-thick PVA layer. Specifically, in this stretched laminate, a laminate including a 7 μm-thick PVA layer is subjected to a stretching apparatus disposed in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio is 1.8 times. Are stretched uniaxially at the free end. By this stretching treatment, the PVA layer contained in the stretched laminate is changed to a 5 μm thick PVA layer in which PVA molecules are oriented.
　次に、染色工程によって、ＰＶＡ分子が配向された５μｍ厚のＰＶＡ層にヨウ素を吸着させた着色積層体を生成する。具体的には、この着色積層体は、延伸積層体を液温３０℃のヨウ素およびヨウ化カリウムを含む染色液に、最終的に生成される高機能偏光膜を構成するＰＶＡ層の単体透過率が４０～４４％になるように任意の時間、浸漬することによって、延伸積層体に含まれるＰＶＡ層にヨウ素を吸着させたものである。本工程において、染色液は、水を溶媒として、ヨウ素濃度を０．１２～０．３０重量％の範囲内とし、ヨウ化カリウム濃度を０．７～２．１重量％の範囲内とする。ヨウ素とヨウ化カリウムの濃度の比は１対７である。ちなみに、ヨウ素を水に溶解するにはヨウ化カリウムを必要とする。より詳細には、ヨウ素濃度０．３０重量％、ヨウ化カリウム濃度２．１重量％の染色液に延伸積層体を６０秒間浸漬することによって、ＰＶＡ分子が配向された５μｍ厚のＰＶＡ層にヨウ素を吸着させた着色積層体を生成する。 Next, a colored laminate in which iodine is adsorbed on a 5 μm-thick PVA layer in which PVA molecules are oriented is generated by a dyeing process. Specifically, this colored laminate has a single layer transmittance of the PVA layer constituting the high-functional polarizing film that is finally produced by using the stretched laminate in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C. Iodine is adsorbed to the PVA layer contained in the stretched laminate by dipping for an arbitrary period of time so as to be 40 to 44%. In this step, the staining solution uses water as a solvent, and an iodine concentration within the range of 0.12 to 0.30% by weight and a potassium iodide concentration within the range of 0.7 to 2.1% by weight. The concentration ratio of iodine and potassium iodide is 1 to 7. Incidentally, potassium iodide is required to dissolve iodine in water. More specifically, the stretched laminate is immersed for 60 seconds in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight. A colored laminate is adsorbed on the substrate.
　さらに、第２段のホウ酸水中延伸工程によって、着色積層体を非晶性ＰＥＴ基材と一体にさらに延伸し、３μｍ厚の高機能偏光膜を構成するＰＶＡ層を含む光学フィルム積層体を生成する。具体的には、この光学フィルム積層体は、着色積層体をホウ酸とヨウ化カリウムを含む液温範囲６０～８５℃のホウ酸水溶液に設定された処理装置に配備された延伸装置にかけ、延伸倍率が３．３倍になるように自由端一軸に延伸したものである。より詳細には、ホウ酸水溶液の液温は６５℃である。それはまた、ホウ酸含有量を水１００重量部に対して４重量部とし、ヨウ化カリウム含有量を水１００重量部に対して５重量部とする。本工程においては、ヨウ素吸着量を調整した着色積層体をまず５～１０秒間ホウ酸水溶液に浸漬する。しかる後に、その着色積層体をそのまま処理装置に配備された延伸装置である周速の異なる複数の組のロール間に通し、３０～９０秒かけて延伸倍率が３．３倍になるように自由端一軸に延伸する。この延伸処理によって、着色積層体に含まれるＰＶＡ層を、吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向した３μｍ厚のＰＶＡ層へと変化させる。このＰＶＡ層が光学フィルム積層体の高機能偏光膜を構成する。 Further, the colored laminated body is further stretched integrally with the amorphous PET base material by the second stage boric acid underwater stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 μm. To do. Specifically, the optical film laminate is subjected to stretching by applying the colored laminate to a stretching apparatus provided in a treatment apparatus set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C. containing boric acid and potassium iodide. It is stretched uniaxially at the free end so that the magnification is 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C. It also has a boric acid content of 4 parts by weight with respect to 100 parts by weight of water and a potassium iodide content of 5 parts by weight with respect to 100 parts by weight of water. In this step, the colored laminate having an adjusted iodine adsorption amount is first immersed in an aqueous boric acid solution for 5 to 10 seconds. After that, the colored laminate is passed as it is between a plurality of sets of rolls with different peripheral speeds, which is a stretching apparatus installed in the processing apparatus, and the stretching ratio can be freely increased to 3.3 times over 30 to 90 seconds. Stretch uniaxially. By this stretching treatment, the PVA layer contained in the colored laminate is changed into a PVA layer having a thickness of 3 μm in which the adsorbed iodine is oriented higher in one direction as a polyiodine ion complex. This PVA layer constitutes a highly functional polarizing film of the optical film laminate.
　光学フィルム積層体の製造に必須の工程ではないが、洗浄工程によって、光学フィルム積層体をホウ酸水溶液から取り出し、非晶性ＰＥＴ基材に製膜された３μｍ厚のＰＶＡ層の表面に付着したホウ酸をヨウ化カリウム水溶液で洗浄するのが好ましい。しかる後に、洗浄された光学フィルム積層体を６０℃の温風による乾燥工程によって乾燥する。なお洗浄工程は、ホウ酸析出などの外観不良を解消するための工程である。 Although not an indispensable step for the production of an optical film laminate, the optical film laminate was removed from the boric acid aqueous solution and adhered to the surface of the 3 μm-thick PVA layer formed on the amorphous PET substrate by the washing step. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process using hot air at 60 ° C. The cleaning process is a process for eliminating appearance defects such as boric acid precipitation.
　同じく光学フィルム積層体の製造に必須の工程というわけではないが、貼合せおよび／または転写工程によって、非晶性ＰＥＴ基材に製膜された３μｍ厚のＰＶＡ層の表面に接着剤を塗布しながら、８０μｍ厚のトリアセチルセルロースフィルムを貼合せたのち、非晶性ＰＥＴ基材を剥離し、３μｍ厚のＰＶＡ層を８０μｍ厚のトリアセチルセルロースフィルムに転写することもできる。 Similarly, it is not an indispensable process for producing an optical film laminate, but an adhesive is applied to the surface of a 3 μm-thick PVA layer formed on an amorphous PET substrate by a bonding and / or transfer process. However, after bonding the 80 μm thick triacetyl cellulose film, the amorphous PET substrate can be peeled off, and the 3 μm thick PVA layer can be transferred to the 80 μm thick triacetyl cellulose film.
［その他の工程］
　上記の薄型偏光膜の製造方法は、上記工程以外に、その他の工程を含み得る。その他の工程としては、例えば、不溶化工程、架橋工程、乾燥（水分率の調節）工程等が挙げられる。その他の工程は、任意の適切なタイミングで行い得る。
　上記不溶化工程は、代表的には、ホウ酸水溶液にＰＶＡ系樹脂層を浸漬させることにより行う。不溶化処理を施すことにより、ＰＶＡ系樹脂層に耐水性を付与することができる。当該ホウ酸水溶液の濃度は、水１００重量部に対して、好ましくは１重量部～４重量部である。不溶化浴（ホウ酸水溶液）の液温は、好ましくは２０℃～５０℃である。好ましくは、不溶化工程は、積層体作製後、染色工程や水中延伸工程の前に行う。
　上記架橋工程は、代表的には、ホウ酸水溶液にＰＶＡ系樹脂層を浸漬させることにより行う。架橋処理を施すことにより、ＰＶＡ系樹脂層に耐水性を付与することができる。当該ホウ酸水溶液の濃度は、水１００重量部に対して、好ましくは１重量部～４重量部である。また、上記染色工程後に架橋工程を行う場合、さらに、ヨウ化物を配合することが好ましい。ヨウ化物を配合することにより、ＰＶＡ系樹脂層に吸着させたヨウ素の溶出を抑制することができる。ヨウ化物の配合量は、水１００重量部に対して、好ましくは１重量部～５重量部である。ヨウ化物の具体例は、上述のとおりである。架橋浴（ホウ酸水溶液）の液温は、好ましくは２０℃～５０℃である。好ましくは、架橋工程は上記第２のホウ酸水中延伸工程の前に行う。好ましい実施形態においては、染色工程、架橋工程および第２のホウ酸水中延伸工程をこの順で行う。 [Other processes]
The manufacturing method of said thin-shaped polarizing film may include another process other than the said process. Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step. The other steps can be performed at any appropriate timing.
The insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C. to 50 ° C. Preferably, the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
The crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. Moreover, when performing a bridge | crosslinking process after the said dyeing | staining process, it is preferable to mix | blend iodide further. By blending iodide, elution of iodine adsorbed on the PVA resin layer can be suppressed. The blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20 ° C. to 50 ° C. Preferably, the crosslinking step is performed before the second boric acid aqueous drawing step. In a preferred embodiment, the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.
　＜透明保護フィルム＞
　上記偏光子の片面または両面に設けられる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、等方性など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など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などのセルロース系ポリマー、ポリメチルメタクリレートなど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）などのスチレン系ポリマー、ポリカーボネート系ポリマーなどが挙げられる。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の如き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などのアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、または上記ポリマーのブレンド物なども上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。透明保護フィルム中には任意の適切な添加剤が１種類以上含まれていてもよい。添加剤としては、例えば、紫外線吸収剤、酸化防止剤、滑剤、可塑剤、離型剤、着色防止剤、難燃剤、核剤、帯電防止剤、顔料、着色剤などが挙げられる。透明保護フィルム中の上記熱可塑性樹脂の含有量は、好ましくは５０～１００重量％、より好ましくは５０～９９重量％、さらに好ましくは６０～９８重量％、特に好ましくは７０～９７重量％である。透明保護フィルム中の上記熱可塑性樹脂の含有量が５０重量％以下の場合、熱可塑性樹脂が本来有する高透明性などが十分に発現できないおそれがある。 <Transparent protective film>
As a material for forming the transparent protective film provided on one side or both sides of the polarizer, 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 the above Examples of the polymer that forms the transparent protective film include polymer blends. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
　また、透明保護フィルムとしては、特開２００１－３４３５２９号公報（ＷＯ０１／３７００７）に記載のポリマーフィルム、例えば、（Ａ）側鎖に置換および／または非置換イミド基を有する熱可塑性樹脂と、（Ｂ）側鎖に置換および／または非置換フェニルならびにニトリル基を有する熱可塑性樹脂を含有する樹脂組成物が挙げられる。具体例としてはイソブチレンとＮ－メチルマレイミドからなる交互共重合体とアクリロニトリル・スチレン共重合体とを含有する樹脂組成物のフィルムが挙げられる。フィルムは樹脂組成物の混合押出品などからなるフィルムを用いることができる。これらのフィルムは位相差が小さく、光弾性係数が小さいため偏光フィルムの歪みによるムラなどの不具合を解消することができ、また透湿度が小さいため、加湿耐久性に優れる。 Examples of the transparent protective film include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, B) Resin compositions containing a thermoplastic resin having substituted and / or unsubstituted phenyl and nitrile groups in the side chain. Specific examples include a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing film can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.
　上記偏光フィルムにおいて、前記透明保護フィルムの透湿度が１５０ｇ／ｍ２／２４ｈ以下であることが好ましい。かかる構成によれば、偏光フィルム中に空気中の水分が入り難く、偏光フィルム自体の水分率変化を抑制することができる。その結果、保存環境により生じる偏光フィルムのカールや寸法変化を抑えることができる。 In the polarizing film, it is preferable moisture permeability of the transparent protective film is not more than 150g / m 2 / 24h. According to such a configuration, it is difficult for moisture in the air to enter the polarizing film, and a change in the moisture content of the polarizing film itself can be suppressed. As a result, the curling and dimensional change of the polarizing film caused by the storage environment can be suppressed.
　上記偏光子の片面または両面に設けられる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、等方性などに優れるものが好ましく、特に透湿度が１５０ｇ／ｍ２／２４ｈ以下であるものがより好ましく、１４０ｇ／ｍ２／２４ｈ以下のものが特に好ましく、１２０ｇ／ｍ２／２４ｈ以下のものさらに好ましい。透湿度は、実施例に記載の方法により求められる。 As a material for forming a transparent protective film provided on one or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is preferable. / m, more preferably not more 2 / 24h or less, particularly preferably those following 140 g / m 2 / 24h, more preferably the following 120 g / m 2 / 24h. The moisture permeability is determined by the method described in the examples.
　前記低透湿度を満足する透明保護フィルムの形成材料としては、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樹脂；ポリカーボネート樹脂；アリレート系樹脂；ナイロンや芳香族ポリアミド等のアミド系樹脂；ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、シクロ系ないしはノルボルネン構造を有する環状オレフィン系樹脂、（メタ）アクリル系樹脂、またはこれらの混合体を用いることができる。前記樹脂のなかでも、ポリカーボネート系樹脂、環状ポリオレフィン系樹脂、（メタ）アクリル系樹脂が好ましく、特に、環状ポリオレフィン系樹脂、（メタ）アクリル系樹脂が好ましい。 Examples of the material for forming the transparent protective film satisfying the low moisture permeability include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; arylate resins; amide resins such as nylon and aromatic polyamide; polyethylene and polypropylene Polyolefin polymers such as ethylene / propylene copolymers, cyclic olefin resins having a cyclo or norbornene structure, (meth) acrylic resins, or a mixture thereof can be used. Among the resins, polycarbonate resins, cyclic polyolefin resins, and (meth) acrylic resins are preferable, and cyclic polyolefin resins and (meth) acrylic resins are particularly preferable.
　透明保護フィルムの厚みは、適宜に決定しうるが、一般には強度や取扱性などの作業性、薄層性などの点より１～１００μｍ程度である。特に１～８０μｍが好ましく、３～６０μｍがより好ましい。 The thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 100 μm from the viewpoints of workability such as strength and handleability and thin layer properties. 1 to 80 μm is particularly preferable, and 3 to 60 μm is more preferable.
　なお、偏光子の両面に透明保護フィルムを設ける場合、その表裏で同じポリマー材料からなる透明保護フィルムを用いてもよく、異なるポリマー材料などからなる透明保護フィルムを用いてもよい。 In addition, when providing a transparent protective film on both surfaces of a polarizer, the transparent protective film which consists of the same polymer material may be used by the front and back, and the transparent protective film which consists of a different polymer material etc. may be used.
　上記透明保護フィルムの偏光子を接着させない面には、ハードコート層、反射防止層、スティッキング防止層、拡散層ないしアンチグレア層などの機能層を設けることができる。なお、上記ハードコート層、反射防止層、スティッキング防止層、拡散層やアンチグレア層などの機能層は、透明保護フィルムそのものに設けることができるほか、別途、透明保護フィルムとは別体のものとして設けることもできる。 Functional surfaces such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered. The functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer and antiglare layer can be provided on the transparent protective film itself, and separately provided separately from the transparent protective film. You can also
　＜光学フィルム＞
　本発明の偏光フィルムは、実用に際して他の光学層と積層した光学フィルムとして用いることができる。その光学層については特に限定はないが、例えば反射板や半透過板、位相差板（１／２や１／４などの波長板を含む）、視角補償フィルムなどの液晶表示装置などの形成に用いられることのある光学層を１層または２層以上用いることができる。特に、本発明の偏光フィルムに更に反射板または半透過反射板が積層されてなる反射型偏光フィルムまたは半透過型偏光フィルム、偏光フィルムに更に位相差板が積層されてなる楕円偏光フィルムまたは円偏光フィルム、偏光フィルムに更に視角補償フィルムが積層されてなる広視野角偏光フィルム、あるいは偏光フィルムに更に輝度向上フィルムが積層されてなる偏光フィルムが好ましい。 <Optical film>
The polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or more optical layers that may be used can be used. In particular, a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention, an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film. A wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.
　偏光フィルムに上記光学層を積層した光学フィルムは、液晶表示装置などの製造過程で順次別個に積層する方式にても形成することができるが、予め積層して光学フィルムとしたものは、品質の安定性や組立作業などに優れていて液晶表示装置などの製造工程を向上させうる利点がある。積層には粘着層などの適宜な接着手段を用いうる。上記の偏光フィルムやその他の光学フィルムの接着に際し、それらの光学軸は目的とする位相差特性などに応じて適宜な配置角度とすることができる。 An optical film obtained by laminating the above optical layer on a polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like. Appropriate bonding means such as an adhesive layer can be used for lamination. When adhering the above polarizing film and other optical films, their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.
　前述した偏光フィルムや、偏光フィルムを少なくとも１層積層されている光学フィルムには、液晶セルなどの他部材と接着するための粘着層を設けることもできる。粘着層を形成する粘着剤は特に制限されないが、例えばアクリル系重合体、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系やゴム系などのポリマーをベースポリマーとするものを適宜に選択して用いることができる。特に、アクリル系粘着剤の如く光学的透明性に優れ、適度な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性などに優れるものが好ましく用いうる。 The pressure-sensitive adhesive layer for adhering to other members such as a liquid crystal cell can be provided on the polarizing film described above or an optical film in which at least one polarizing film is laminated. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected. Can be used. In particular, those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.
　粘着層は、異なる組成または種類などのものの重畳層として偏光フィルムや光学フィルムの片面または両面に設けることもできる。また両面に設ける場合に、偏光フィルムや光学フィルムの表裏において異なる組成や種類や厚みなどの粘着層とすることもできる。粘着層の厚みは、使用目的や接着力などに応じて適宜に決定でき、一般には１～５００μｍであり、１～２００μｍが好ましく、特に１～１００μｍが好ましい。 The adhesive layer can be provided on one side or both sides of a polarizing film or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing film or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.
　粘着層の露出面に対しては、実用に供するまでの間、その汚染防止などを目的にセパレータが仮着されてカバーされる。これにより、通例の取扱状態で粘着層に接触することを防止できる。セパレータとしては、上記厚み条件を除き、例えばプラスチックフィルム、ゴムシート、紙、布、不織布、ネット、発泡シートや金属箔、それらのラミネート体などの適宜な薄葉体を、必要に応じシリコーン系や長鎖アルキル系、フッ素系や硫化モリブデンなどの適宜な剥離剤でコート処理したものなどの、従来に準じた適宜なものを用いうる。 The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, or a laminate thereof, or a silicone-based or long sheet as necessary. Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as a chain alkyl type, fluorine type or molybdenum sulfide, can be used.
　＜画像表示装置＞
　本発明の偏光フィルムまたは光学フィルムは液晶表示装置などの各種装置の形成などに好ましく用いることができる。液晶表示装置の形成は、従来に準じて行いうる。すなわち液晶表示装置は一般に、液晶セルと偏光フィルムまたは光学フィルム、および必要に応じての照明システムなどの構成部品を適宜に組立てて駆動回路を組込むことなどにより形成されるが、本発明においては本発明による偏光フィルムまたは光学フィルムを用いる点を除いて特に限定はなく、従来に準じうる。液晶セルについても、例えばＴＮ型やＳＴＮ型、π型などの任意なタイプのものを用いうる。 <Image display device>
The polarizing film or the optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing film or optical film by invention, and it can apply according to the former. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.
　液晶セルの片側または両側に偏光フィルムまたは光学フィルムを配置した液晶表示装置や、照明システムにバックライトあるいは反射板を用いたものなどの適宜な液晶表示装置を形成することができる。その場合、本発明による偏光フィルムまたは光学フィルムは液晶セルの片側または両側に設置することができる。両側に偏光フィルムまたは光学フィルムを設ける場合、それらは同じものであってもよいし、異なるものであってもよい。さらに、液晶表示装置の形成に際しては、例えば拡散板、アンチグレア層、反射防止膜、保護板、プリズムアレイ、レンズアレイシート、光拡散板、バックライトなどの適宜な部品を適宜な位置に１層または２層以上配置することができる。 Appropriate liquid crystal display devices such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the polarizing film or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell. When providing a polarizing film or an optical film on both sides, they may be the same or different. Further, when forming the liquid crystal display device, for example, a single layer or a suitable layer such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.
　以下に、本発明の実施例を記載するが、本発明の実施形態はこれらに限定されない。 Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.
　＜偏光子の作製＞
　平均重合度２４００、ケン化度９９．９モル％の厚み７５μｍのポリビニルアルコールフィルムを、３０℃の温水中に６０秒間浸漬し膨潤させた。次いで、ヨウ素／ヨウ化カリウム（重量比＝０．５／８）の濃度０．３％の水溶液に浸漬し、３．５倍まで延伸させながらフィルムを染色した。その後、６５℃のホウ酸エステル水溶液中で、トータルの延伸倍率が６倍となるように延伸を行った。延伸後に、４０℃のオーブンにて３分間乾燥を行い、ＰＶＡ系偏光子Ｘ（厚み２３μｍ）を得た。 <Production of polarizer>
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 times in 65 degreeC borate ester aqueous solution. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and obtained PVA-type polarizer X (thickness 23 micrometers).
　＜透明保護フィルム＞
　透明保護フィルム１：厚み６０μｍのトリアセチルセルロースフィルム（透湿度５３０ｇ／ｍ２／２４ｈ）を、ケン化・コロナ処理等を行わずに用いた（表１中で、ＴＡＣと表記する）。
　透明保護フィルム２：厚み４０μｍのラクトン環構造を有する（メタ）アクリル樹脂（透湿度９６ｇ／ｍ２／２４ｈ）にコロナ処理を施して用いた（表１中で、アクリルと表記する）。
　透明保護フィルム３：厚み５５μｍの環状ポリオレフィンフィルム（日本ゼオン社製：ＺＥＯＮＯＲ，透湿度１１ｇ／ｍ２／２４ｈ）にコロナ処理を施して用いた（表１中で、ＣＯＰと表記する）。 <Transparent protective film>
Transparent protective film 1: triacetyl cellulose film having a thickness of 60μm (the moisture permeability 530g / m 2 / 24h), was used without saponification, corona treatment or the like (in Table 1, referred to as TAC).
Transparent protective film 2: Using subjected to corona treatment having a lactone ring structure having a thickness of 40 [mu] m (meth) acrylic resin (moisture permeability 96 g / m 2 / 24h) (in Table 1, referred to as acrylic).
Transparent protective film 3: cyclic polyolefin film having a thickness of 55 .mu.m: using subjected to corona treatment (manufactured by Zeon Corporation ZEONOR, moisture permeability 11g / m 2 / 24h) (in Table 1, referred to as COP).
　＜透明保護フィルムの透湿度＞
　透湿度の測定は、ＪＩＳ　Ｚ０２０８の透湿度試験（カップ法）に準じて測定した。直径６０ｍｍに切断したサンプルを約１５ｇの塩化カルシウムを入れた透湿カップにセットし、温度４０℃、湿度９０％Ｒ．Ｈ．の恒温機に入れ、２４時間放置した前後の塩化カルシウムの重量増加を測定することで透湿度（ｇ／ｍ２／２４ｈ）を求めた。 <Water vapor permeability of transparent protective film>
The moisture permeability was measured according to a moisture permeability test (cup method) of JIS Z0208. A sample cut to a diameter of 60 mm was set in a moisture permeable cup containing about 15 g of calcium chloride, and the temperature was 40 ° C. and the humidity was 90% R.D. H. The placed in a constant temperature machine, to determine the moisture permeability by measuring the weight increase of calcium chloride before and after allowing to stand for 24 hours (g / m 2 / 24h) .
　＜活性エネルギー線＞
　活性エネルギー線として、可視光線（ガリウム封入メタルハライドランプ）　照射装置：Ｆｕｓｉｏｎ　ＵＶ　Ｓｙｓｔｅｍｓ，Ｉｎｃ社製Ｌｉｇｈｔ　ＨＡＭＭＥＲ１０　バルブ：Ｖバルブ　ピーク照度：１６００ｍＷ／ｃｍ２、積算照射量１０００／ｍＪ／ｃｍ２（波長３８０～４４０ｎｍ）を使用した。なお、可視光線の照度は、Ｓｏｌａｔｅｌｌ社製Ｓｏｌａ－Ｃｈｅｃｋシステムを使用して測定した。 <Active energy rays>
As an active energy ray, visible light (gallium filled metal halide lamp) Irradiation device: Fusion UV Systems, Inc. Light HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm 2 , integrated irradiation amount 1000 / mJ / cm 2 (wavelength 380˜ 440 nm) was used. The illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
　実施例１～４および比較例１～５
　（活性エネルギー線硬化型接着剤の調製）
　表１に記載の配合表に従い、各成分を混合して５０℃で１時間撹拌し、実施例１および比較例１に係る活性エネルギー線硬化型接着剤を得た。なお、実施例１に係る活性エネルギー線硬化型接着剤の粘度は９５ｃｐ（２５℃）、比較例１に係る活性エネルギー線硬化型接着剤の粘度は４５ｃｐ（２５℃）であった。 Examples 1 to 4 and Comparative Examples 1 to 5
(Preparation of active energy ray-curable adhesive)
According to the recipe shown in Table 1, the components were mixed and stirred at 50 ° C. for 1 hour to obtain active energy ray-curable adhesives according to Example 1 and Comparative Example 1. In addition, the viscosity of the active energy ray-curable adhesive according to Example 1 was 95 cp (25 ° C.), and the viscosity of the active energy ray-curable adhesive according to Comparative Example 1 was 45 cp (25 ° C.).
　（偏光フィルムの作製）
　上記透明保護フィルム上に、上記実施例または比較例に係る活性エネルギー線硬化型接着剤を、ＭＣＤコーター（富士機械社製）（セル形状：ハニカム、グラビアロール線数：１０００本／ｉｎｃｈ、回転速度１４０％／対ライン速）を用いて、厚み０．７μｍになるように塗工し、上記偏光子Ｘの両面にロール機で貼り合わせた。その後、貼り合わせた透明保護フィルム側（両側）から、ＩＲヒーターを用いて５０℃に加温し、上記可視光線を両面に照射して上記実施例または比較例に係る活性エネルギー線硬化型接着剤を硬化させた後、７０℃で３分間熱風乾燥して、偏光子の両側に透明保護フィルムを有する偏光フィルムを得た。貼り合わせのライン速度は２５ｍ／ｍｉｎで行った。 (Preparation of polarizing film)
On the transparent protective film, the active energy ray-curable adhesive according to the above examples or comparative examples is coated with an MCD coater (manufactured by Fuji Machine Co., Ltd.) (cell shape: honeycomb, number of gravure roll wires: 1000 / inch, rotation speed). 140% / vs. Line speed) was applied to a thickness of 0.7 μm, and both surfaces of the polarizer X were bonded together by a roll machine. Then, from the laminated transparent protective film side (both sides), it heated to 50 degreeC using IR heater, and irradiated the said visible light on both surfaces, and the active energy ray hardening-type adhesive which concerns on the said Example or a comparative example Was cured with hot air at 70 ° C. for 3 minutes to obtain a polarizing film having transparent protective films on both sides of the polarizer. The line speed of bonding was 25 m / min.
　偏光フィルムの作製は、上記透明保護フィルム１乃至３の３種類のそれぞれについて行った。 The production of the polarizing film was performed for each of the three types of transparent protective films 1 to 3 described above.
　上記実施例および比較例で得られた、偏光フィルムについて以下の評価を行った。評価結果を表１に示す。なお、加湿耐久性及び接着耐水性の評価にあたっては、別途それぞれ、同様の偏光フィルムを作製した。 The following evaluations were carried out on the polarizing films obtained in the above examples and comparative examples. The evaluation results are shown in Table 1. In addition, in evaluating humidification durability and adhesion water resistance, a similar polarizing film was separately prepared.
　＜バルク吸水率＞
　各例で用いた偏光フィルム用硬化型接着剤を用いて、１００μmのスペーサーを設けた２枚のガラスで挟み、実施例と同様の活性エネルギー条件で硬化して厚さ１００μｍの接着剤層（硬化物）を調製した。これをサンプルとした。サンプルの重量をＭ１ｇとした。サンプルＭ１ｇを、２３℃の純水に２４時間浸漬した。その後、純水から取り出して乾いた布で拭き取った後１分以内に、再度、サンプルの重量（Ｍ２ｇ）を測定した。これらの結果から、
　式：｛（Ｍ２－Ｍ１）／Ｍ１｝×１００（％）、
　により、バルク吸水率を算出した。 <Bulk water absorption>
The polarizing film curable adhesive used in each example was sandwiched between two pieces of glass provided with a spacer of 100 μm, and cured under the same active energy conditions as in the examples to form a 100 μm thick adhesive layer (cured) Prepared). This was used as a sample. The weight of the sample was M1g. Sample M1g was immersed in pure water at 23 ° C. for 24 hours. Thereafter, the weight (M2g) of the sample was measured again within 1 minute after removing from pure water and wiping with a dry cloth. From these results,
Formula: {(M2-M1) / M1} × 100 (%),
Thus, the bulk water absorption was calculated.
　＜硬化収縮率＞
　センテック社製硬化収縮センサー「樹脂硬化収縮応力測定装置ＥＵ２０１Ｃ」によって測定した。具体的には、特開２０１３－１０４８６９記載の方法により硬化収縮率が算出される。なお、実施例１に係る活性エネルギー線硬化型接着剤から形成された硬化物の硬化収縮率は８．９％、比較例１に係る活性エネルギー線硬化型接着剤から形成された硬化物の硬化収縮率は１１．９％であった。 <Curing shrinkage>
This was measured by a curing shrinkage sensor “resin curing shrinkage stress measuring device EU201C” manufactured by Sentec. Specifically, the cure shrinkage rate is calculated by the method described in JP2013-104869A. The cure shrinkage of the cured product formed from the active energy ray-curable adhesive according to Example 1 was 8.9%, and the cured product formed from the active energy ray-curable adhesive according to Comparative Example 1 was cured. The shrinkage percentage was 11.9%.
　＜接着力＞
　各例で得られた偏光フィルムを偏光子の延伸方向と平行に２００ｍｍ、直行方向に２０ｍｍの大きさに切り出し、透明保護フィルムと偏光子との間にカッターナイフで切り込みを入れ、偏光フィルムをガラス板に貼り合わせた。テンシロンにより、９０度方向に透明保護フィルムと偏光子とを剥離速度５００ｍｍ／ｍｉｎで剥離し、その剥離強度を測定した。また、剥離後の剥離面の赤外吸収スペクトルをＡＴＲ法によって測定し、剥離界面を下記の基準に基づき評価した。
　Ａ：透明保護フィルムの凝集破壊
　Ｂ：透明保護フィルム／接着剤層間の界面剥離
　Ｃ：接着剤層／偏光子間の界面剥離
　Ｄ：偏光子の凝集破壊
　上記基準において、ＡおよびＤは、接着力がフィルムの凝集力以上であるため、接着力が非常に優れることを意味する。一方、ＢおよびＣは、透明保護フィルム／接着剤層（接着剤層／偏光子）界面の接着力が不足している（接着力が劣る）ことを意味する。これらを勘案して、ＡまたはＤである場合の接着力を○、Ａ・Ｂ（「透明保護フィルムの凝集破壊」と「透明保護フィルム／接着剤層間の界面剥離」とが同時に発生）あるいはＡ・Ｃ（「透明保護フィルムの凝集破壊」と「接着剤層／偏光子間の界面剥離」とが同時に発生）である場合の接着力を△、ＢまたはＣである場合の接着力を×とする。 <Adhesive strength>
The polarizing film obtained in each example was cut into a size of 200 mm in parallel with the stretching direction of the polarizer and 20 mm in the orthogonal direction, and a slit was cut between the transparent protective film and the polarizer with a cutter knife. Laminated to the board. Using Tensilon, the transparent protective film and the polarizer were peeled in the 90-degree direction at a peeling speed of 500 mm / min, and the peel strength was measured. Moreover, the infrared absorption spectrum of the peeling surface after peeling was measured by ATR method, and the peeling interface was evaluated based on the following reference | standard.
A: Cohesive failure of transparent protective film B: Interfacial peeling between transparent protective film / adhesive layer C: Interfacial peeling between adhesive layer / polarizer D: Cohesive failure of polarizer In the above criteria, A and D are adhesive strengths Is greater than the cohesive strength of the film, meaning that the adhesive strength is very excellent. On the other hand, B and C mean that the adhesive force at the transparent protective film / adhesive layer (adhesive layer / polarizer) interface is insufficient (adhesive strength is poor). Taking these into consideration, the adhesive strength in the case of A or D is ○, A · B ("cohesive failure of transparent protective film" and "interfacial peeling between transparent protective film / adhesive layer" occur simultaneously) or A -Adhesive strength in the case of C ("cohesive failure of transparent protective film" and "interfacial peeling between adhesive layer / polarizer" occur simultaneously) Δ, adhesive strength in the case of B or C as x To do.
　＜加湿耐久性：単体透過率、偏光度変化の測定＞
　透明保護フィルムとして透明保護フィルム２と３を偏光子の両面にそれぞれ１枚ずつ積層した偏光フィルムを実施例および比較例と同様の方法によりサンプルとして作製した。当該偏光フィルム（サンプル）を、８５℃／８５％ＲＨの恒温恒湿機に５００時間投入した。投入前と投入後の偏光フィルムの単体透過率と偏光度を、積分球付き分光透過率測定器（村上色彩技術研究所のＤｏｔ－３ｃ）を用いて測定し、
　単体透過率の変化量（ΔＴ：％）＝（投入後の単体透過率（％））－（投入前の単体透過率（％））、
　偏光度の変化量（ΔＰ：％）＝（投入後の偏光度（％））－（投入前の偏光度（％））、を求めた。
　なお、偏光度Ｐは、２枚の同じ偏光フィルムを両者の透過軸が平行となるように重ね合わせた場合の透過率（平行透過率：Ｔｐ）および、両者の透過軸が直交するように重ね合わせた場合の透過率（直交透過率：Ｔｃ）を以下の式に適用することにより求められるものである。偏光度Ｐ（％）＝｛（Ｔｐ－Ｔｃ）／（Ｔｐ＋Ｔｃ）｝１／２×１００
　各透過率は、グランテラープリズム偏光子を通して得られた完全偏光を１００％として、ＪＩＳ　Ｚ８７０１の２度視野（Ｃ光源）により視感度補整したＹ値で示したものである。 <Humidification durability: Single transmittance, measurement of polarization degree change>
A polarizing film in which the transparent protective films 2 and 3 were laminated on the both sides of the polarizer as a transparent protective film was prepared as a sample by the same method as in the examples and comparative examples. The polarizing film (sample) was put into a constant temperature and humidity machine of 85 ° C./85% RH for 500 hours. Measure the single transmittance and degree of polarization of the polarizing film before and after loading using a spectral transmittance measuring device with an integrating sphere (Dot-3c of Murakami Color Research Laboratory)
Amount of change in single transmittance (ΔT:%) = (single transmittance (%) after loading) − (single transmittance (%) before loading),
The amount of change in the degree of polarization (ΔP:%) = (degree of polarization after introduction (%)) − (degree of polarization before introduction (%)) was determined.
The degree of polarization P is the transmittance when two identical polarizing films are overlapped so that their transmission axes are parallel (parallel transmittance: Tp), and overlapped so that their transmission axes are orthogonal to each other. It is calculated | required by applying the transmittance | permeability (orthogonal transmittance | permeability: Tc) at the time of combining to the following formula | equation. Polarization degree P (%) = {(Tp−Tc) / (Tp + Tc)} 1/2 × 100
Each transmittance is represented by a Y value obtained by correcting visibility with a two-degree field of view (C light source) of JIS Z8701, with 100% of the completely polarized light obtained through the Granteller prism polarizer.
　＜接着耐水性（温水浸漬試験）＞
　透明保護フィルムとして透明保護フィルム１と３を偏光子の両面にそれぞれ１枚ずつ積層した偏光フィルムを実施例および比較例と同様の方法によりサンプルとして作製した。当該偏光フィルム（サンプル）を、偏光子の延伸方向に５０ｍｍ、垂直方向に２５ｍｍの長方形にカットした。かかる偏光フィルムを６０℃の温水に６時間浸漬した後、剥れた長さを拡大鏡にて目視で測定した。測定は剥離が起こった部分の断面からの垂直距離の最大値とした（ｍｍ）。 <Adhesion water resistance (warm water immersion test)>
A polarizing film in which the transparent protective films 1 and 3 were laminated on the both sides of the polarizer as a transparent protective film was prepared as a sample by the same method as in the examples and comparative examples. The polarizing film (sample) was cut into a rectangle of 50 mm in the stretching direction of the polarizer and 25 mm in the vertical direction. This polarizing film was immersed in warm water at 60 ° C. for 6 hours, and then the peeled length was visually measured with a magnifier. The measurement was taken as the maximum value of the vertical distance from the cross section of the part where peeling occurred (mm).
　＜接着耐水性（耐水剥離力）＞
　透明保護フィルムとして透明保護フィルム１と３を偏光子の両面にそれぞれ１枚ずつ積層した偏光フィルムを実施例および比較例と同様の方法によりサンプルとして作製した。当該偏光フィルム（サンプル）を、偏光子の延伸方向と平行に２００ｍｍ、直行方向に２０ｍｍの大きさに切り出した。当該偏光フィルムを２３℃の純水に２４時間浸漬した後に、純水中から取り出し乾いた布で拭き取った後、透明保護フィルムと偏光子との間にカッターナイフで切り込みを入れ、偏光フィルムをガラス板に貼り合わせた。純水中から取り出してから評価までを１分以内に行った。以後は、上記＜接着力＞と同様の評価を行った。 <Adhesion water resistance (water peeling resistance)>
A polarizing film in which the transparent protective films 1 and 3 were laminated on the both sides of the polarizer as a transparent protective film was prepared as a sample by the same method as in the examples and comparative examples. The polarizing film (sample) was cut into a size of 200 mm in parallel with the stretching direction of the polarizer and 20 mm in the orthogonal direction. After immersing the polarizing film in pure water at 23 ° C. for 24 hours, taking it out of pure water and wiping with a dry cloth, a slit is cut between the transparent protective film and the polarizer with a cutter knife. Laminated to the board. The evaluation was carried out within 1 minute after taking out from the pure water. Thereafter, the same evaluation as in the above <Adhesive strength> was performed.
　＜ｌｏｇＰｏｗの計算＞
　Ｃｈｅｍ ＤｒａｗＵｌｔｒａ（ケンブリッジソフト社製）により得られたそれぞれの化合物のｌｏｇＰｏｗ値を用いて、下記式により計算を行った。なお、重合開始剤及び光酸発生剤は計算から除いた。
　硬化型接着剤のｌｏｇＰｏｗ＝Σ（ｌｏｇＰｏｗｉ×Ｗｉ）
　ｌｏｇＰｏｗｉ：硬化型接着剤の各成分のｌｏｇＰｏｗ値
　Ｗｉ：（ｉ成分のモル数）／（硬化型接着剤の各成分の総モル数） <Calculation of logPow>
Using the logPow value of each compound obtained by Chem DrawUltra (manufactured by Cambridge Soft), calculation was performed according to the following formula. The polymerization initiator and photoacid generator were excluded from the calculation.
LogPow of curable adhesive = Σ (logPow × Wi)
logPowi: logPow value of each component of curable adhesive Wi: (number of moles of i component) / (total number of moles of each component of curable adhesive)
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表１中、ラジカル重合性化合物は、
　ＨＥＡＡ：ヒドロキシエチルアクリルアミド、ｌｏｇＰｏｗ＝－０．５６、ホモポリマーのＴｇ＝１２３℃、興人社製；
　ＡＣＭＯ：アクリロイルモルホリン、ｌｏｇＰｏｗ＝－０．２０、ホモポリマーのＴｇ＝１５０℃、興人社製；
　ＦＡ－ＴＨＦＭ：テトラヒドロフルフリル（メタ）アクリレート、ｌｏｇＰｏｗ＝１．１３、ホモポリマーのＴｇ＝４５℃、日立化成社製；
　ライトアクリレートＤＣＰ－Ａ：トリシクロデカンジメタノールジアクリレート、ｌｏｇＰｏｗ＝３．０５、ホモポリマーのＴｇ＝１３４℃、共栄社化学社製；
　ライトアクリレート１，９ＮＤ－Ａ：１，９－ナノンジオールジアクリレート、ｌｏｇＰｏｗ＝３．６８、ホモポリマーのＴｇ＝６８℃、共栄社化学社製；
　アロニックスＭ－２２０：トリプロピレングリコールジアクリレート、ｌｏｇＰｏｗ＝１．６８、ホモポリマーのＴｇ６９℃、東亞合成社製；
　アロニックスＭ－３０６：ペンタエリスリトールトリ／テトラアクリレート、ｌｏｇＰｏｗ＝１．０４、ホモポリマーのＴｇ＝２５０℃以上、東亞合成社製；を示す。
　アクリル系オリゴマー：ＡＲＵＦＯＮ ＵＰ－１１９０、ｌｏｇＰｏｗ＝１．９５は東亞合成社製、
　アルコキシ基を含む化合物：ニカラックＭＸ－７５０ＬＭ、ｌｏｇＰｏｗ＝０．８は日本カーバイト工業社製、
　エポキシ基を含む化合物：ＪＥＲ８２８、ｌｏｇＰｏｗ＝４．７６はジャパンエポキシレジン株式会社製、
　イソシアネート化合物：カレンズＡＯＩ、ｌｏｇＰｏｗ＝１．６は昭和電工株式会社製）、を示す。
　光重合開始剤は、
　ＩＲＧＡＣＵＲＥ９０７（２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン）、ｌｏｇＰｏｗ＝２．０９、ＢＡＳＦ社製
　ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ（ジエチルチオキサントン）、ｌｏｇＰｏｗ＝５．１２、日本化薬社製、を示す。
　光酸発生剤は、ＣＰＩ－１００Ｐ（トリアリールスルホニウムヘキサフルオロホスフェートを主成分とする有効成分５０％のプロピレンカーボネート溶液）、サンアプロ社製、を示す。
 
  In Table 1, the radical polymerizable compound is
HEAA: hydroxyethylacrylamide, logPow = −0.56, homopolymer Tg = 123 ° C., manufactured by Kojin Co .;
ACMO: acryloylmorpholine, logPow = −0.20, Tg of homopolymer = 150 ° C., manufactured by Kojin Co .;
FA-THFM: tetrahydrofurfuryl (meth) acrylate, logPow = 1.13, homopolymer Tg = 45 ° C., manufactured by Hitachi Chemical Co., Ltd .;
Light acrylate DCP-A: tricyclodecane dimethanol diacrylate, logPow = 3.05, homopolymer Tg = 134 ° C., manufactured by Kyoeisha Chemical;
Light acrylate 1,9ND-A: 1,9-nanonediol diacrylate, logPow = 3.68, homopolymer Tg = 68 ° C., manufactured by Kyoeisha Chemical Co., Ltd .;
Aronix M-220: tripropylene glycol diacrylate, logPow = 1.68, homopolymer Tg 69 ° C., manufactured by Toagosei Co., Ltd .;
Aronix M-306: pentaerythritol tri / tetraacrylate, logPow = 1.04, homopolymer Tg = 250 ° C. or higher, manufactured by Toagosei Co., Ltd.
Acrylic oligomer: ARUFON UP-1190, logPow = 1.95 is manufactured by Toagosei Co., Ltd.
Compound containing an alkoxy group: Nicalac MX-750LM, logPow = 0.8 is manufactured by Nippon Carbide Industries, Ltd.
Compound containing epoxy group: JER828, logPow = 4.76 is manufactured by Japan Epoxy Resin Co., Ltd.
Isocyanate compound: Karenz AOI, logPow = 1.6 is manufactured by Showa Denko KK).
The photopolymerization initiator is
IRGACURE907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), logPow = 2.09, KAYACURE DETX-S (diethylthioxanthone), logPow = 5.12, manufactured by BASF Shown by Nippon Kayaku Co., Ltd.
As the photoacid generator, CPI-100P (a propylene carbonate solution containing 50% active ingredient mainly composed of triarylsulfonium hexafluorophosphate), manufactured by San Apro, is shown.

Claims (18)

  1. 　硬化性成分を含有する偏光フィルム用硬化型接着剤であって、
    　当該偏光フィルム用硬化型接着剤は、当該硬化型接着剤を硬化させて得られる硬化物を２３℃の純水に２４時間浸漬した場合に、下記式：
    　バルク吸水率（％）＝｛（Ｍ２－Ｍ１）／Ｍ１｝×１００、
    　｛但し、前記式中、Ｍ１は浸漬前の硬化物の重量、Ｍ２は浸漬後の硬化物の重量を示す｝で表わされるバルク吸水率が１０重量％以下であることを特徴とする偏光フィルム用硬化型接着剤。     A curable adhesive for a polarizing film containing a curable component,
    When the cured product obtained by curing the curable adhesive is immersed in pure water at 23 ° C. for 24 hours, the curable adhesive for polarizing film has the following formula:
    Bulk water absorption (%) = {(M2-M1) / M1} × 100,
    {Wherein, in the above formula, M1 represents the weight of the cured product before dipping, and M2 represents the weight of the cured product after dipping}. Curing adhesive.
  2. 　オクタノール／水分配係数（ｌｏｇＰｏｗ値）が１以上であることを特徴とする請求項１記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to claim 1, wherein the octanol / water partition coefficient (logPow value) is 1 or more.
  3. 　前記硬化性成分が、活性エネルギー線硬化性成分であることを特徴とする請求項１または２記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing film according to claim 1 or 2, wherein the curable component is an active energy ray curable component.
  4. 　前記活性エネルギー線硬化性成分が、ラジカル重合性化合物を含有することを特徴とする請求項３記載の偏光フィルム用硬化型接着剤。 The curable adhesive for a polarizing film according to claim 3, wherein the active energy ray-curable component contains a radical polymerizable compound.
  5. 　前記ラジカル重合性化合物が、（メタ）アクリルアミド誘導体を含有することを特徴とする請求項４記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to claim 4, wherein the radical polymerizable compound contains a (meth) acrylamide derivative.
  6. 　前記ラジカル重合性化合物が、ラジカル重合性を有する官能基を少なくとも２つ有する多官能性化合物を含有することを特徴とする請求項４または５記載の偏光フィルム用硬化型接着剤。 6. The curable adhesive for polarizing films according to claim 4 or 5, wherein the radical polymerizable compound contains a polyfunctional compound having at least two functional groups having radical polymerizability.
  7. 　さらに、光重合開始剤を含有することを特徴とする請求項３～６のいずれかに記載の偏光フィルム用硬化型接着剤。 The polarizing film curable adhesive according to any one of claims 3 to 6, further comprising a photopolymerization initiator.
  8. 　さらに、アクリル系オリゴマー（Ａ）を含有することを特徴とする請求項３～７のいずれかに記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to any one of claims 3 to 7, further comprising an acrylic oligomer (A).
  9. 　さらに、光酸発生剤（Ｂ）を含有することを特徴とする請求項３～８のいずれかに記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to any one of claims 3 to 8, further comprising a photoacid generator (B).
  10. 　さらに、アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）を含有することを特徴とする請求項３～９のいずれかに記載の偏光フィルム用硬化型接着剤。 10. The curable adhesive for polarizing films according to claim 3, further comprising a compound (C) containing either an alkoxy group or an epoxy group.
  11. 　前記アルコキシ基、エポキシ基のいずれかを含む化合物（Ｃ）が、アルコキシ基を含む化合物（Ｃ１）であることを特徴とする、請求項１０記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to claim 10, wherein the compound (C) containing either an alkoxy group or an epoxy group is a compound (C1) containing an alkoxy group.
  12. 　前記アルコキシ基を含む化合物（Ｃ１）が、アルコキシ基を含むメラミン化合物であることを特徴とする、請求項１１記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to claim 11, wherein the compound (C1) containing an alkoxy group is a melamine compound containing an alkoxy group.
  13. 　さらに、イソシアネート化合物（Ｄ）を含有することを特徴とする請求項３～１２のいずれかに記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to any one of claims 3 to 12, further comprising an isocyanate compound (D).
  14. 　前記硬化性成分が、熱硬化性成分であり、さらに熱重合開始剤を含有することを特徴とする請求項１または２記載の偏光フィルム用硬化型接着剤。 The curable adhesive for polarizing films according to claim 1 or 2, wherein the curable component is a thermosetting component and further contains a thermal polymerization initiator.
  15. 　偏光子の少なくとも一方の面に、接着剤層を介して透明保護フィルムが設けられている偏光フィルムであって、
    　前記接着剤層が、請求項１～１４のいずれかに記載の偏光フィルム用硬化型接着剤の硬化物層により形成されたものであることを特徴とする偏光フィルム。     A polarizing film in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer,
    A polarizing film, wherein the adhesive layer is formed by a cured product layer of a curable adhesive for polarizing film according to any one of claims 1 to 14.
  16. 　前記接着剤硬化物層の厚みが０．１～３μｍであることを特徴とする請求項１５記載の偏光フィルム。 The polarizing film according to claim 15, wherein the cured adhesive layer has a thickness of 0.1 to 3 µm.
  17. 　請求項１５または１６記載の偏光フィルムが、少なくとも１枚積層されていることを特徴とする光学フィルム。 An optical film, wherein at least one polarizing film according to claim 15 or 16 is laminated.
  18. 　請求項１５もしくは１６記載の偏光フィルム、または請求項１７に記載の光学フィルムが用いられていることを特徴とする画像表示装置。
          An image display device using the polarizing film according to claim 15 or 16, or the optical film according to claim 17.
PCT/JP2014/072816 2013-08-30 2014-08-29 Curable adhesive for polarizing films, polarizing film, optical film and image display device WO2015030203A1 (en)

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