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WO2017010224A1 - Curable adhesive composition for polarizing film, polarizing film, manufacturing method for said polarizing film, optical film, and image display device - Google Patents

Curable adhesive composition for polarizing film, polarizing film, manufacturing method for said polarizing film, optical film, and image display device Download PDF

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Publication number
WO2017010224A1
WO2017010224A1 PCT/JP2016/067977 JP2016067977W WO2017010224A1 WO 2017010224 A1 WO2017010224 A1 WO 2017010224A1 JP 2016067977 W JP2016067977 W JP 2016067977W WO 2017010224 A1 WO2017010224 A1 WO 2017010224A1
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WO
WIPO (PCT)
Prior art keywords
polarizing film
adhesive composition
meth
curable adhesive
acrylate
Prior art date
Application number
PCT/JP2016/067977
Other languages
French (fr)
Japanese (ja)
Inventor
昌之 岡本
武士 斉藤
池田　哲朗
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2017010224A1 publication Critical patent/WO2017010224A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to a polarizing film curable adhesive composition 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 is used in which a transparent protective film is bonded to both surfaces of a polarizer with a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water (Patent Document 1 below).
  • the transparent protective film triacetyl cellulose having a high moisture permeability is used.
  • 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.
  • a radical polymerization type active energy ray-curable adhesive composition using an N-substituted amide monomer as a curable component has been proposed (Patent Document 2 below).
  • Such an adhesive composition exhibits excellent durability under harsh environments under high humidity and high temperature.
  • the adhesive composition can further improve adhesion and / or water resistance. It was the actual situation that is being demanded.
  • the present invention has been developed in view of the above circumstances, and has an excellent adhesive property between a polarizer and a transparent protective film, and is excellent in water resistance even under severe conditions such as in a dew condensation environment. It aims at providing the curable adhesive composition for polarizing films which comprises a layer.
  • 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 composition for polarizing films, Furthermore, the said polarizing film is provided. It is an object of the present invention to provide an optical film used, and 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 composition for polarizing film, and have solved the present invention.
  • the present invention is a polarizing film curable adhesive composition for adhering a transparent protective film to at least one surface of a polarizer, the compound having an acid anhydride group and an alkoxysilane group, and an active
  • the present invention relates to a curable adhesive composition for polarizing film, which contains an energy ray curable component.
  • the polarizing film curable adhesive composition preferably further contains a compound having an epoxy group.
  • the polarizing film curable adhesive composition preferably further contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates.
  • the metal of the organometallic compound is preferably titanium.
  • the metal alkoxide is preferably contained as the organometallic compound, and the organic alkoxide has an organic group having 4 or more carbon atoms, and the organometallic compound is preferably the metal. It is preferable that the organic chelate containing the chelate has 4 or more carbon atoms.
  • the ratio of the organometallic compound is preferably 0.05 to 9 parts by weight.
  • the active energy ray-curable component preferably contains a radical polymerizable compound, and 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 curable adhesive composition for polarizing film preferably further contains a photopolymerization initiator, further preferably contains a compound having a vinyl ether group, and further contains a photoacid generator. preferable.
  • the storage modulus at 25 ° C. of a cured product obtained by curing the curable adhesive composition is preferably 1 ⁇ 10 7 Pa or more.
  • the present invention also provides a polarizing film in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer, and the adhesive layer is any one of claims 1 to 11. It is formed with the cured
  • the adhesive layer preferably has a thickness of 0.1 to 3 ⁇ m. Furthermore, when the adhesive layer is immersed in pure water at 23 ° C.
  • the present invention is the above-described method for producing a polarizing film, wherein the polarizing film and the transparent protective film are coated with the polarizing film curable adhesive composition on at least one surface. And a bonding step of bonding the polarizer and the transparent protective film, and irradiating active energy rays from the polarizer surface side or the transparent protective film surface side, and the active energy ray-curable adhesive composition.
  • the manufacturing method of a polarizing film characterized by including the adhesion process which adheres the above-mentioned light polarizer and the above-mentioned transparent protective film through the above-mentioned adhesive layer obtained by making it harden.
  • the present invention is characterized in that at least one polarizing film described above is laminated, and the polarizing film described above or the optical film described above is used.
  • the present invention relates to an image display device.
  • the mechanism that causes adhesive peeling between the adhesive layer and the polarizer is as follows. Can be estimated. First, moisture that has passed through the protective film diffuses into the adhesive layer, and the moisture diffuses to the polarizer interface side.
  • the contribution of hydrogen bonds and / or ionic bonds is large with respect to the adhesive force between the adhesive layer and the polarizer, but at the interface due to moisture diffused to the polarizer interface side.
  • the hydrogen bond and the ionic bond are dissociated, and as a result, the adhesive force between the adhesive layer and the polarizer decreases. Thereby, adhesive debonding between the adhesive layer and the polarizer may occur in a dew condensation environment.
  • the curable adhesive composition for a polarizing film according to the present invention contains a compound having an acid anhydride group and an alkoxysilane group. Therefore, even when moisture permeates the protective film and moisture diffuses into the adhesive layer, the alkoxysilane group of the compound becomes a silanol group due to the presence of moisture, and a strong interaction is formed on the polarizer surface. At the same time, the acid anhydride group of the compound becomes an acid group due to the presence of moisture, so that the surface of the polarizer is more activated, whereby only hydrogen bonds and / or ionic bonds are formed at the interface between the polarizer and the adhesive layer.
  • the curable adhesive composition for a polarizing film according to the present invention contains a compound having an epoxy group, a stronger interaction occurs particularly between the acid group present on the surface of the polarizer and the adhesive layer. Interlayer adhesion that is not easily peeled off even in the presence is exhibited.
  • the curable adhesive composition for polarizing films according to the present invention contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates, it is between the polarizer and the adhesive layer.
  • the water resistance of the adhesive is greatly improved.
  • the reason can be estimated as follows.
  • the adhesive composition that constitutes the adhesive layer contains an organometallic compound, and moisture diffuses into the adhesive layer, the organometallic compound becomes an active metal species due to the presence of moisture, and as a result
  • the organometallic compound strongly interacts with both the polarizer and the active energy ray-curable component constituting the adhesive layer.
  • the adhesive water resistance between the polarizer and the adhesive layer There is a dramatic improvement.
  • the bulk water absorption of a cured product obtained by curing the curable adhesive composition is preferably 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 by using the curable adhesive composition for polarizing film of the present invention can be used in a severe humid environment (for example, 85 ° C. ⁇ 85% RH).
  • a severe humid environment for example, 85 ° C. ⁇ 85% RH.
  • Optical durability humidity durability test
  • 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.
  • 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 the polarizer and the transparent protective film even under conditions where the contact environment with water is severe It is possible to suppress a decrease in the adhesive strength between the layers (the polarizer and the adhesive layer).
  • the curable adhesive composition for a polarizing film according to the present invention contains a compound having an acid anhydride group and an alkoxysilane group, and an active energy ray-curable component.
  • Examples of the acid anhydride group in the present invention include anhydrides of succinic acid, anhydrides of ethylenically unsaturated dicarboxylic acids (for example, maleic acid, itaconic acid, citraconic acid, phthalic acid, etc.), or monocarboxylic acids Anhydrous type, and the like.
  • the linking group that can be interposed between the acid anhydride and the alkoxysilane group is not particularly limited, and examples thereof include an alkyl group having 1 to 14 carbon atoms and an alkylene glycol skeleton such as ethylene glycol and propylene glycol.
  • Examples of the alkoxysilane group include alkoxy groups such as methoxy, ethoxy, and propoxy. Specific examples of the compound include 3-trimethoxysilylpropyl succinic anhydride.
  • the content ratio of the compound having an acid anhydride group and an alkoxysilane group is preferably in the range of 0.5 to 40 parts by weight with respect to 100 parts by weight of the total amount of the active energy ray-curable component, 0.7%
  • the amount is preferably 35 parts by weight, more preferably 1-30 parts by weight.
  • the amount exceeds 40 parts by weight, the storage stability of the adhesive composition may be deteriorated, or the ratio of components for adhering to a polarizer or a protective film may be relatively insufficient, resulting in a decrease in adhesiveness. .
  • the amount is less than 0.5 parts by weight, the effect of adhesion and water resistance is not sufficiently exhibited.
  • the curable adhesive composition for polarizing film according to the present invention contains a compound having an epoxy group, a stronger interaction occurs between the acid group present on the surface of the polarizer and the adhesive layer, It is preferable because interlayer adhesion that is difficult to peel easily even in the presence of moisture is exhibited.
  • Examples of the compound having an epoxy group in the present invention include a monofunctional epoxy compound having a radical polymerizable functional group at one end, such as 4-hydroxybutyl acrylate glycidyl ether and glycidyl methacrylate, lauryl alcohol glycidyl ether, and ethylene glycol glycidyl ether.
  • a monofunctional epoxy compound or a diglycidyl ether compound having a radical polymerizable functional group at the end is preferable, and particularly 4-hydroxybutyl.
  • a monofunctional epoxy compound having a radical polymerizable functional group at its terminal such as acrylate glycidyl ether or glycidyl methacrylate, is preferred.
  • the content ratio of the compound having an epoxy group is preferably in the range of 0 to 20 parts by weight, preferably 0.2 to 15 parts by weight with respect to 100 parts by weight of the total amount of the active energy ray-curable component.
  • the amount is preferably 0.5 to 10 parts by weight.
  • the storage stability of the adhesive composition may be deteriorated, or the ratio of components for adhering to a polarizer or a protective film may be relatively insufficient, resulting in a decrease in adhesiveness. .
  • the polarizing film curable adhesive composition according to the present invention preferably further contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates together with an active energy ray-curable component.
  • a metal alkoxide is a compound in which at least one alkoxy group, which is an organic group, is bonded to a metal
  • a metal chelate is a compound in which an organic group is bonded or coordinated to the metal via an oxygen atom.
  • Titanium, aluminum, and zirconium are preferable as the metal. Among these, compared with titanium, aluminum and zirconium are fast in reactivity, the pot life of the adhesive composition is shortened, and the effect of improving the adhesion water resistance may be lowered. Therefore, titanium is more preferable as the metal of the organometallic compound from the viewpoint of improving the adhesive water resistance of the adhesive layer.
  • the curable adhesive composition for a polarizing film according to the present invention contains a metal alkoxide as the organometallic compound, it is preferable to use a metal alkoxide having an organic group having 4 or more carbon atoms, It is more preferable to contain a thing.
  • the carbon number is 3 or less, the pot life of the adhesive composition may be shortened, and the effect of improving the adhesion water resistance may be reduced.
  • the organic group having 6 or more carbon atoms include an octoxy group, which can be suitably used.
  • suitable metal alkoxides include, for example, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary amyl titanate, tetra tertiary butyl titanate, tetrastearyl titanate, zirconium tetraisopropoxide, zirconium Tetranormal butoxide, zirconium tetraoctoxide, zirconium tetratertiary butoxide, zirconium tetrapropoxide, aluminum sec butyrate, aluminum ethylate, aluminum isopropylate, aluminum butyrate, aluminum diisopropylate monosecondary butyrate, monosec butoxyaluminum And diisopropylate. Of these, tetraoctyl titanate is preferable.
  • the organic chelate preferably has an organic group having 4 or more carbon atoms.
  • the carbon number is 3 or less, the pot life of the adhesive composition may be shortened, and the effect of improving the adhesion water resistance may be reduced.
  • the organic group having 4 or more carbon atoms include acetylacetonate group, ethylacetoacetate group, isostearate group, octylene glycolate group and the like. Among these, from the viewpoint of improving the adhesive water resistance of the adhesive layer, an acetylacetonate group or an ethylacetoacetate group is preferable as the organic group.
  • suitable metal chelates include, for example, titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethylacetoacetate, polyhydroxytitanium stearate, dipropoxy-bis (acetylacetonato) titanium, di Butoxytitanium-bis (octylene glycolate), dipropoxytitanium-bis (ethylacetoacetate), titanium lactate, titanium diethanolamate, titanium triethanolamate, dipropoxytitanium-bis (lactate), dipropoxytitanium-bis ( Triethanolaminate), di-n-butoxytitanium-bis (triethanolaminato), tri-n-butoxytitanium monostearate, diisopropoxy bis (ethylacetoacetate) Titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy bis (acetylacetone) titanium, titanium phosphate compound, titanium lactate
  • the organic metal compounds usable in the present invention include organic carboxylic acid metal salts such as zinc octylate, zinc laurate, zinc stearate, tin octylate, acetylacetone zinc chelate, benzoylacetone zinc chelate, dibenzoylmethane zinc
  • the chelate include zinc chelate compounds such as ethyl zinc acetoacetate chelate.
  • the content of the organometallic compound is preferably in the range of 0.05 to 9 parts by weight and preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the total amount of the active energy ray-curable component.
  • the amount is preferably 0.15 to 5 parts by weight.
  • the storage stability of the adhesive composition may be deteriorated, or the ratio of components for adhering to a polarizer or a protective film may be relatively insufficient, resulting in a decrease in adhesiveness. .
  • it is less than 0.05 part by weight the effect of adhesion water resistance is not sufficiently exhibited.
  • the polarizing film curable adhesive composition of the present invention contains an active energy ray-curable component as the curable component.
  • an active energy ray curable type such as an electron beam curable type, an ultraviolet curable type, a visible light curable type, or the like can be suitably used.
  • the ultraviolet curable and visible light curable adhesive compositions can be classified into radical polymerization curable adhesive compositions and cationic polymerization adhesive compositions.
  • an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light
  • an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light.
  • Examples of the curable component include radical polymerizable compounds used in radical polymerization curable adhesive compositions.
  • 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.
  • 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-methoxy N-alkoxy group-containing (meth) acrylamide derivatives such as methyl
  • 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, dicyclopentenyl (meth) ) Polycyclic (meth) acrylates such as acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxy Ethyl (meth) acrylate Alkoxy groups such as 2-methoxymethoxyeth
  • 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 And [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and other hydroxy acids Containing (meth) acrylate; glycidyl (meth) acrylate, epoxy group-containing (meth) acrylate such as 4-hydroxybuty
  • 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-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, 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-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone
  • vinylpyridine vinylpiperidone
  • vinylpyrimidine vinylpiperazine
  • vinylpyrazine 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 N, N′-methylenebis (meth) acrylamide, tripropylene glycol di (meth) acrylate, and tetraethylene glycol diester which are polyfunctional (meth) acrylamide derivatives.
  • 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 described later are preferable.
  • the curable adhesive composition 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 be measured (flask immersion method described in JIS-Z-7260), but can also be calculated. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft is used. Further, the logPow value of the adhesive composition can be calculated by the following formula.
  • LogPow of adhesive composition ⁇ (logPow ⁇ Wi) logPowi: logPow value of each component of composition Wi: (number of moles of i component) / (total number of moles of adhesive composition)
  • the logPow value of the curable adhesive composition of the present invention is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more.
  • Radical polymerizable compounds should be used in combination with monofunctional radical polymerizable compounds and polyfunctional radical polymerizable compounds from the viewpoint of achieving both adhesion to polarizers and various transparent protective films and optical durability in harsh environments. Is preferred. 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 adhesive composition for polarizing film of the present invention can be used as an active energy ray curable adhesive composition when a curable component is used as the active energy ray curable component.
  • the active energy ray-curable adhesive composition uses an electron beam or the like for the active energy ray
  • the active energy ray-curable adhesive composition need not contain a photopolymerization initiator, When ultraviolet rays or visible rays are used for the active energy rays, it is preferable to contain a photopolymerization initiator.
  • the photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray.
  • 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
  • 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.
  • the curable adhesive composition for polarizing film of the present invention when used in a visible light curable type containing a radical polymerizable compound as a curable component, photopolymerization that is particularly sensitive to light of 380 nm or more is initiated. It is preferable to use an agent. 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 composition is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component, 0.5 to The amount is more preferably 4 parts by weight, still more preferably 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% by weight
  • the radically polymerizable compound (a1) having an active methylene group is 1 to 50% by weight
  • the radical polymerization initiator (a2) is 0% by weight based on 100 parts by weight of the total amount of the curable component. It is preferable to contain 1 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 for the hydrogen abstraction reaction to proceed sufficiently, 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 composition.
  • the cationic polymerizable compound used in the cationic polymerization curable resin composition includes a monofunctional cationic polymerizable compound having one cationic polymerizable functional group in the molecule and two or more cationic polymerizable functional groups in the molecule. And having a polyfunctional cationically polymerizable compound. Since the monofunctional cation polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be reduced by containing it in the resin composition.
  • monofunctional cationically polymerizable compounds often have functional groups that develop various functions, and by incorporating them into the resin composition, various functions are exhibited in the resin composition and / or the cured product of the resin composition. Can be made.
  • the polyfunctional cation polymerizable compound is preferably contained in the resin composition because the cured product of the resin composition can be three-dimensionally crosslinked.
  • the ratio of the monofunctional cation polymerizable compound to the polyfunctional cation polymerizable compound is such that the polyfunctional cation polymerizable compound is mixed in the range of 10 to 1000 parts by weight with respect to 100 parts by weight of the monofunctional cation polymerizable compound. Is preferred.
  • Examples of the cationic polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group.
  • Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound, and the cationic polymerization curable resin composition of the present invention is excellent in curability and adhesiveness. It is particularly preferable to contain an alicyclic epoxy compound.
  • Examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate caprolactone-modified products and trimethylcaprolactone-modified products.
  • the compound having an oxetanyl group is a cationic polymerization compound of the present invention.
  • the compound having an oxetanyl group is preferably contained because it has the effect of improving the curability of the curable resin composition or lowering the liquid viscosity of the composition, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl -3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, and the like, including Aron Oxetane OXT-101, Aron Oxetane OXT-121, Aron Oxetane OXT-211, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (Above, manufactured
  • 2-hydroxyethyl vinyl ether diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl ether of diethylene glycol, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxy Examples thereof include ethyl vinyl ether, ethoxyethyl vinyl ether, and pentaerythritol type tetravinyl ether.
  • the cationic polymerization curable resin composition contains at least one compound selected from a compound having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group as described above as a curable component. Therefore, a cationic photopolymerization initiator is blended. 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 photocationic polymerization initiator a photoacid generator described later is preferably used.
  • a photocationic polymerization initiator that is highly sensitive to light of 380 nm or more. Is generally a compound that exhibits maximum absorption in the vicinity of 300 nm or shorter, and therefore, a photosensitizer that exhibits maximum absorption in light having a wavelength longer than that, specifically, longer than 380 nm should be blended. Thus, it is possible to respond to light having a wavelength in the vicinity and promote generation of cationic species or acid from the photocationic polymerization initiator.
  • the photosensitizer examples include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, and the like. Two or more types may be mixed and used.
  • anthracene compounds are preferable because of their excellent photosensitization effect, and specific examples include anthracure UVS-1331 and anthracure UVS-1221 (manufactured by Kawasaki Kasei Co., Ltd.).
  • the content of the photosensitizer is preferably 0.1% by weight to 5% by weight, and more preferably 0.5% by weight to 3% by weight.
  • the curable adhesive composition according to the present invention preferably contains the following components.
  • the active energy ray-curable adhesive composition according to the present invention may contain an acrylic oligomer (A) formed by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound. it can.
  • an acrylic oligomer (A) formed by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound. it can.
  • 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. If the content of the acrylic oligomer (A) in the adhesive composition is too large, the reaction rate when the active energy ray is irradiated onto the composition is so severe that poor curing may occur. 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.
  • the active energy ray-curable adhesive composition preferably has a low viscosity in consideration of workability and uniformity during coating. Therefore, an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer. It is also preferable that the viscosity is low.
  • 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
  • the (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.
  • the acrylic oligomers (A) obtained by polymerizing (meth) acrylic monomers those having a high logPow value are preferable.
  • 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 said active energy ray hardening-type adhesive composition can contain a photo-acid generator (B).
  • the active energy ray-curable resin composition 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).
  • 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.
  • preferred onium salts constituting the photoacid generator (B) of the present invention include “Syracure UVI-6922” and “Syracure UVI-6974” (above, manufactured by Dow Chemical Japan Co., Ltd.).
  • 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 active energy ray-curable adhesive composition can be used in combination with a photoacid generator (B) and a compound (C) containing either an alkoxy group or an epoxy group. .
  • Compound having epoxy group and polymer When using 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, two functional groups having reactivity with the epoxy group are contained in the molecule. Two or more compounds 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, and a primary or secondary aromatic amino group. 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 , Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc.
  • epoxy resins may be halogenated and hydrogenated It 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 Co., Ltd., Epolide series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resins (polysynthesized from bisphenols and epichlorohydrin) Mud carboxymethyl at both ends with polyether having an epoxy group; and YP series), Nagase Chel Chel Che
  • Epo light series are exemplified but not limited thereto. Two or more of these epoxy resins may be used in combination.
  • Tg of the adhesive layer the compound having an epoxy group and the polymer (C) are not included in the calculation.
  • the compound having an alkoxyl 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. Representative examples of such compounds include melamine compounds, amino resins, and silane coupling agents. In calculating the glass transition temperature Tg of the adhesive layer, the compound having an alkoxyl group and the polymer (C) are not included in the calculation.
  • 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, and the content of the compound (C) in the composition When there is too much, adhesiveness falls and the impact resistance with respect to a drop test may deteriorate.
  • the content of the compound (C) in the composition is more preferably 20 parts by weight or less.
  • the composition preferably contains 2 parts by weight or more of the compound (C), more preferably 5 parts by weight or more.
  • the silane coupling agent (D) is preferably an active energy ray curable compound. Even if it is not energy ray curable, the same water resistance can be imparted.
  • silane coupling agent (D) examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and the like as active energy ray-curable compounds.
  • a silane coupling agent (D1) having an amino group is preferable.
  • the silane coupling agent (D1) 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 (D1) having an amino group may be used alone or in combination of two or more.
  • the amount of the silane coupling agent (D) is preferably 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 if the amount exceeds 20 parts by weight, the storage stability of the adhesive composition deteriorates, and if it is less than 0.1 parts by weight, the effect of adhesion water resistance is not sufficiently exhibited. When calculating the glass transition temperature Tg of the adhesive layer, the silane coupling agent (D) 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 curable adhesive composition for polarizing films of the present invention contains a compound (E) having a vinyl ether group, it is preferable because adhesion water resistance between the polarizer and the adhesive layer is improved.
  • the compound (E) is preferably a radical polymerizable compound having a vinyl ether group.
  • the content of the compound (E) is preferably 0.1 to 19 parts by weight with respect to 100 parts by weight of the total amount of the curable component.
  • the curable adhesive composition for polarizing film of the present invention may contain a compound that causes keto-enol tautomerism.
  • a compound that causes keto-enol tautomerism for example, in an adhesive composition containing a cross-linking agent or an adhesive composition that can be used by blending a cross-linking agent, an embodiment containing a compound that produces the keto-enol tautomerism can be preferably employed.
  • an adhesive composition containing a cross-linking agent or an adhesive composition that can be used by blending a cross-linking agent an embodiment containing a compound that produces the keto-enol tautomerism can be preferably employed.
  • the excessive viscosity rise and gelation of the adhesive composition after the compounding of the organometallic compound and the formation of a microgel product can be suppressed, and the effect of extending the pot life of the composition can be realized.
  • various ⁇ -dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane- ⁇ -diketones such as 3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate propionyl acetates such as tert-butyl; ethyl isobutyryl acetate, ethyl iso
  • the amount of the compound that generates keto-enol tautomerism is, for example, 0.05 to 10 parts by weight, preferably 0.2 to 3 parts by weight (for example, 0.3 parts by weight) per 1 part by weight of the organometallic compound. Parts by weight to 2 parts by weight). If the amount of the compound used is less than 0.05 parts by weight relative to 1 part by weight of the organometallic compound, it may be difficult to achieve a sufficient use effect. On the other hand, when the amount of the compound used exceeds 10 parts by weight with respect to 1 part by weight of the organometallic compound, it may be difficult to express the desired water resistance due to excessive interaction with the organometallic compound.
  • additives can be mix
  • additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Plasticizers; UV absorbers; inorganic fillers; pigments; dyes and the like.
  • those having a high logPow value are preferable.
  • 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 viscosity of the adhesive composition is preferably 100 cp or less at 25 ° C. from the viewpoint of coatability.
  • the temperature of the adhesive composition 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 curable adhesive composition for polarizing film 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.
  • the curable adhesive composition for polarizing film of the present invention is the above-described bulk water absorption measured when a cured product obtained by curing the curable adhesive composition is immersed in pure water at 23 ° C. for 24 hours.
  • the rate is preferably 10% by weight or less.
  • 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. Most preferably, it is 1% by weight or less.
  • the polarizer retains a certain amount of moisture, and when the curable adhesive composition and moisture contained in the polarizer come into contact with each other, Such as appearance defects may occur.
  • the curable adhesive composition 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 composition for polarizing films of the present invention has a curable component, curing shrinkage usually occurs when the curable adhesive composition is cured.
  • the cure shrinkage rate is an index indicating the rate of cure shrinkage when an adhesive layer is formed from the curable adhesive composition for polarizing film.
  • the curing shrinkage rate of the cured product obtained by curing the curable adhesive composition 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, specifically, measured by a method using a cure shrinkage sensor manufactured by Centec.
  • 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 curable adhesive composition for polarizing film.
  • the adhesive layer that is the cured product layer preferably has a bulk water absorption of 10% by weight or less.
  • the thickness of the adhesive layer formed from the curable adhesive composition 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 composition 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. As described above, 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.
  • the storage elastic modulus of the adhesive layer formed thereby is preferably 1.0 ⁇ 10 7 Pa or more at 25 ° C., and 1.0 ⁇ 10 8 Pa or more. It is more preferable.
  • the storage elastic modulus of the pressure-sensitive adhesive layer is 1.0 ⁇ 10 3 Pa to 1.0 ⁇ 10 6 Pa, which is different from the storage elastic modulus of the adhesive layer.
  • 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.). If the storage elastic modulus is low, defects in the polarizer cracks occur. Cheap.
  • the temperature region having a high storage elastic modulus is more preferably 80 ° C.
  • 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 the storage elastic modulus (E ′) was adopted.
  • the polarizing film according to the present invention comprises the following production method: A coating step of applying the curable adhesive composition for polarizing film to at least one surface of the polarizer and the transparent protective film, a bonding step of bonding the polarizer and the transparent protective film, and the polarizer surface side or An adhesion step of adhering the polarizer and the transparent protective film via the adhesive layer obtained by irradiating the active energy ray from the transparent protective film surface side and curing the active energy ray-curable adhesive composition; Can be manufactured by a manufacturing method including: In such a production method, the moisture content of the polarizer in the bonding step is preferably 8 to 19%.
  • the polarizer and the transparent protective film may be subjected to a surface modification treatment before applying the curable adhesive composition.
  • Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
  • the coating method of the curable adhesive composition is appropriately selected depending on the viscosity of the composition 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 composition applied as described above. Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.
  • the curable adhesive composition for polarizing films according to the present invention is used as an active energy ray-curable adhesive composition.
  • the active energy ray curable adhesive composition can be used in an electron beam curable type, an ultraviolet ray curable type, or a visible ray curable type.
  • the embodiment of the curable adhesive composition is preferably a visible light curable adhesive composition from the viewpoint of productivity.
  • the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated to obtain the active energy ray-curable adhesive composition. Cure 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.).
  • the acceleration voltage is preferably 5 kV to 300 kV, and 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 composition 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 bulb, 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 active energy ray curable adhesive composition pre-irradiation warming
  • the active energy ray-curable adhesive composition according to the present invention can be suitably used particularly when forming an adhesive layer that bonds a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. It is.
  • the active energy ray-curable adhesive composition 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 cured and formed. 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 composition 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.).
  • the line speed depends on the curing time of the adhesive composition, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m / 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. If the line speed is too high, the adhesive composition may not be sufficiently cured, and the target adhesiveness may not be obtained.
  • a polarizer and a transparent protective film are bonded together via an adhesive layer formed by a cured product layer of the active energy ray-curable adhesive composition.
  • An easily adhesive layer can be provided between the adhesive layer and the adhesive layer.
  • 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 composition of the present invention exhibits the effect (satisfying optical durability in a harsh environment under high temperature and high humidity) when a thin polarizer having a thickness of 10 ⁇ m or less is used as the polarizer. It can be remarkably 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 contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates.
  • the adhesive layer is further laminated with an adhesive layer having a bulk water absorption of 10% by weight or less, the movement of water to the polarizer is suppressed in a severe environment of high temperature and high humidity. Deterioration of optical durability such as increase in transmittance and decrease in polarization degree 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
  • 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, and the like 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
  • polyethylene polypropylene Polyolefin polymers such as ethylene / propylene copolymers, cyclic olefin resins having a cyclo or norbornene structure, (meth) acrylic resins, or a mixture thereof
  • 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, and 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 Using subjected to corona treatment having a lactone ring structure having a thickness of 40 [mu] m (meth) acrylic resin (moisture permeability 96g / m 2 / 24h) (in Table 1, referred to as acrylic).
  • Transparent protective film 2 a cycloolefin polymer film with a thickness of 52 .mu.m (moisture permeability 11g / m 2 / 24h), was used performs corona treatment (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.
  • ⁇ Storage modulus> The storage elastic modulus was measured using TA Instruments dynamic viscoelasticity measuring device RSAIII under the following measurement conditions. 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 the storage elastic modulus was measured at 25 ° C.
  • active energy rays As the active energy ray, visible light (gallium sealed metal halide lamp) irradiation apparatus: Fusion UV Systems, Inc, Inc. Light HAMMER10 Valve: V Valve peak irradiance: 1600 mW / cm @ 2, integrated dose 1000 / mJ / cm 2 (wavelength 380 ⁇ 440 nm )It was used. The illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
  • Examples 1 to 5 and Comparative Example 1 Preparation of active energy ray-curable adhesive
  • each component was mixed, and further KAYACURE-DETX-S (2,4-diethylthioxanthone; manufactured by Nippon Kayaku Co., Ltd.) and Irgacure 907 (2-methyl-1- (4-methylthio) 1.5 g and 3 g of phenyl) -2-morpholinopropan-1-one (manufactured by BASF) were added to 100 g of the radical polymerizable compound, respectively, and stirred.
  • KAYACURE-DETX-S 2,4-diethylthioxanthone
  • Irgacure 907 2-methyl-1- (4-methylthio) 1.5 g and 3 g of phenyl) -2-morpholinopropan-1-one
  • the active energy ray-curable adhesive according to Examples 1 to 5 or Comparative Example 1 is coated with an MCD coater (manufactured by Fuji Machine) (cell shape: honeycomb, number of gravure roll wires: 1000 / inch). , Rotation speed 140% / vs. Line speed) was applied so as to have a thickness of 0.7 ⁇ m, and was bonded to both sides of the polarizer X by a roll machine. Thereafter, from the bonded transparent protective film side (both sides), the active energy ray curable adhesive according to Example 1 and Comparative Example 1 is cured by irradiating the visible light on both sides with an active energy ray irradiation device. And dried 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.
  • ⁇ Adhesive strength after water immersion (water resistance evaluation)> The polarizing film is cut into a size of 200 mm parallel to the stretching direction of the polarizer and 15 mm in the orthogonal direction.
  • the polarizing film is immersed in water at 23 ° C. for 18 hours, and then taken out within 30 minutes (in a non-dried state) )
  • a polarizing film was bonded to a glass plate.
  • a slit is cut between the transparent protective film (acrylic or COP) and the polarizer with a cutter knife, and the protective film and the polarizer are peeled off at a peeling rate of 1000 mm / min with a tensilon in a 90-degree direction. N / 15 mm).
  • a case where the peel strength was 0.5 N / 15 mm or more was evaluated as ⁇ , and a case where the peel strength was less than 0.5 N / 15 mm was evaluated as x.
  • the radical polymerizable monomer is HEAA: hydroxyethyl acrylamide, manufactured by Kojinsha; 4HBA; 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemicals; ACMO: acryloylmorpholine, manufactured by Kojinsha; TPGDA: Tripropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.
  • the compound having an acid anhydride group and an alkoxysilane group is X-12-967C: 3-trimethoxysilylpropyl succinic anhydride, manufactured by Shin-Etsu Silicone;
  • the epoxy group-containing compound is 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether, manufactured by Shin-Etsu Silicone;
  • Indicate Metal alkoxide is D-20: Titanium butoxide (carbon number of organic group: 4), manufactured by Shin-Etsu Silicone;
  • the photoacid generator is CPI-100P, manufactured by Sun Apro Corporation; Indicates.

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Abstract

Provided is a curable adhesive composition for a polarizing film that is for adhering a transparent protective film to at least one surface of a polarizer, said curable adhesive composition for a polarizing film being characterized by containing: a compound having an acid anhydride group and an alkoxysilane group; and an active energy ray curable component.

Description

偏光フィルム用硬化型接着剤組成物、偏光フィルムおよびその製造方法、光学フィルムならびに画像表示装置Curable adhesive composition for polarizing film, polarizing film and method for producing the same, 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組成物に関する。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 composition 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）。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 is used in which a transparent protective film is bonded to both surfaces of a polarizer with a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water (Patent Document 1 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組成物が提案されている（下記特許文献２）。かかる接着剤組成物は、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組成物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, a radical polymerization type active energy ray-curable adhesive composition using an N-substituted amide monomer as a curable component has been proposed (Patent Document 2 below). Such an adhesive composition exhibits excellent durability under harsh environments under high humidity and high temperature. However, in the market, the adhesive composition can further improve adhesion and / or water resistance. It was the actual situation that is being demanded.
特開２００６－２２０７３２号公報JP 2006-220732 A 特開２００８－２８７２０７号公報JP 2008-287207 A
　本発明は上記実情に鑑みて開発されたものであり、偏光子と透明保護フィルムとの接着性が良好であり、かつ結露環境下などの過酷な条件であっても耐水性に優れた接着剤層を構成する偏光フィルム用硬化型接着剤組成物を提供することを目的とする。 The present invention has been developed in view of the above circumstances, and has an excellent adhesive property between a polarizer and a transparent protective film, and is excellent in water resistance even under severe conditions such as in a dew condensation environment. It aims at providing the curable adhesive composition for polarizing films which comprises a layer.
　また本発明は、偏光フィルム用硬化型接着剤組成物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 composition for polarizing films, Furthermore, the said polarizing film is provided. It is an object of the present invention to provide an optical film used, and 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組成物により、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 composition for polarizing film, and have solved the present invention.
　即ち、本発明は、偏光子の少なくとも一方の面に、透明保護フィルムを接着させるための偏光フィルム用硬化型接着剤組成物であって、酸無水物基およびアルコキシシラン基を有する化合物、ならびに活性エネルギー線硬化性成分を含有することを特徴とする偏光フィルム用硬化型接着剤組成物、に関する。 That is, the present invention is a polarizing film curable adhesive composition for adhering a transparent protective film to at least one surface of a polarizer, the compound having an acid anhydride group and an alkoxysilane group, and an active The present invention relates to a curable adhesive composition for polarizing film, which contains an energy ray curable component.
　前記偏光フィルム用硬化型接着剤組成物において、さらに、エポキシ基を有する化合物を含有することが好ましい。 The polarizing film curable adhesive composition preferably further contains a compound having an epoxy group.
　前記偏光フィルム用硬化型接着剤組成物において、さらに、金属アルコキシドおよび金属キレートからなる群より選択される少なくとも１種の有機金属化合物を含有することが好ましい。 The polarizing film curable adhesive composition preferably further contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates.
　前記偏光フィルム用硬化型接着剤組成物において、前記有機金属化合物の金属がチタンであることが好ましい。 In the curable adhesive composition for a polarizing film, the metal of the organometallic compound is preferably titanium.
　前記偏光フィルム用硬化型接着剤組成物において、前記有機金属化合物として前記金属アルコキシドを含有し、前記金属アルコキシドが有する有機基の炭素数が４以上であることが好ましく、前記有機金属化合物として前記金属キレートを含有し、前記金属キレートが有する有機基の炭素数が４以上であることが好ましい。 In the curable adhesive composition for a polarizing film, the metal alkoxide is preferably contained as the organometallic compound, and the organic alkoxide has an organic group having 4 or more carbon atoms, and the organometallic compound is preferably the metal. It is preferable that the organic chelate containing the chelate has 4 or more carbon atoms.
　前記偏光フィルム用硬化型接着剤組成物において、前記活性エネルギー線硬化性成分の全量を１００重量部としたとき、前記有機金属化合物の割合が０．０５～９重量部であることが好ましい。 In the polarizing film curable adhesive composition, when the total amount of the active energy ray-curable component is 100 parts by weight, the ratio of the organometallic compound is preferably 0.05 to 9 parts by weight.
　前記偏光フィルム用硬化型接着剤組成物において、硬化型接着剤組成物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、
　式：｛（Ｍ２－Ｍ１）／Ｍ１｝×１００（％）、
　但し、Ｍ１：浸漬前の硬化物の重量、Ｍ２：浸漬後の硬化物の重量、
　で表わされるバルク吸水率が１０重量％以下であることが好ましい。 In the curable adhesive composition for polarizing film, when a cured product obtained by curing the curable adhesive composition is immersed in pure water at 23 ° C. for 24 hours,
Formula: {(M2-M1) / M1} × 100 (%),
However, M1: Weight of cured product before immersion, M2: Weight of cured product after immersion,
It is preferable that the bulk water absorption represented by these is 10 weight% or less.
　前記偏光フィルム用硬化型接着剤組成物において、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が好ましく、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が好ましく、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が好ましい。 In the curable adhesive composition for polarizing film, the active energy ray-curable component preferably contains a radical polymerizable compound, and 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.
　前記偏光フィルム用硬化型接着剤組成物において、さらに、光重合開始剤を含有することが好ましく、さらに、ビニルエーテル基を有する化合物を含有することが好ましく、さらに、光酸発生剤を含有することが好ましい。 The curable adhesive composition for polarizing film preferably further contains a photopolymerization initiator, further preferably contains a compound having a vinyl ether group, and further contains a photoacid generator. preferable.
　前記偏光フィルム用硬化型接着剤組成物において、硬化型接着剤組成物を硬化させて得られる硬化物の、２５℃における貯蔵弾性率が１×１０７Ｐａ以上であることが好ましい。 In the curable adhesive composition for a polarizing film, the storage modulus at 25 ° C. of a cured product obtained by curing the curable adhesive composition is preferably 1 × 10 7 Pa or more.
　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、請求項１～１１のいずれかに記載の偏光フィルム用硬化型接着剤組成物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。前記接着剤層の厚みが０．１～３μｍであることが好ましい。さらに、前記接着剤層は、２３℃の純水に２４時間浸漬した場合に、
　式：｛（Ｍ２－Ｍ１）／Ｍ１｝×１００（％）、
　但し、Ｍ１：浸漬前の硬化物の重量、Ｍ２：浸漬後の硬化物の重量、
　で表わされるバルク吸水率が１０重量％以下であることが好ましく、前記接着剤層は、２５℃における貯蔵弾性率が１．０×１０７Ｐａ以上であることが好ましい。 The present invention also provides a polarizing film in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer, and the adhesive layer is any one of claims 1 to 11. It is formed with the cured | curing material layer of the curable adhesive composition for polarizing films of this invention, It is related with the polarizing film characterized by the above-mentioned. The adhesive layer preferably has a thickness of 0.1 to 3 μm. Furthermore, when the adhesive layer is immersed in pure water at 23 ° C. for 24 hours,
Formula: {(M2-M1) / M1} × 100 (%),
However, M1: Weight of cured product before immersion, M2: Weight of cured product after immersion,
Is preferably 10% by weight or less, and the adhesive layer preferably has a storage elastic modulus at 25 ° C. of 1.0 × 10 7 Pa or more.
　また、本発明は、前記記載の偏光フィルムの製造方法であって、前記偏光子および前記透明保護フィルムの少なくとも一方の面に、前記偏光フィルム用硬化型接着剤組成物を塗工する塗工工程と、前記偏光子および前記透明保護フィルムを貼り合わせる貼合工程と、前記偏光子面側または前記透明保護フィルム面側から活性エネルギー線を照射して、前記活性エネルギー線硬化型接着剤組成物を硬化させることにより得られた前記接着剤層を介して、前記偏光子および前記透明保護フィルムを接着させる接着工程とを含むことを特徴とする偏光フィルムの製造方法、に関する。 Further, the present invention is the above-described method for producing a polarizing film, wherein the polarizing film and the transparent protective film are coated with the polarizing film curable adhesive composition on at least one surface. And a bonding step of bonding the polarizer and the transparent protective film, and irradiating active energy rays from the polarizer surface side or the transparent protective film surface side, and the active energy ray-curable adhesive composition. The manufacturing method of a polarizing film characterized by including the adhesion process which adheres the above-mentioned light polarizer and the above-mentioned transparent protective film through the above-mentioned adhesive layer obtained by making it harden.
　さらに本発明は、前記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、および前記記載の偏光フィルム、または前記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、に関する。 Furthermore, the present invention is characterized in that at least one polarizing film described above is laminated, and the polarizing film described above or the optical film described above is used. The present invention relates to an image display device.
　接着剤層を介して偏光子に透明保護フィルムが積層された偏光フィルムが結露環境下に曝された場合に、特に接着剤層と偏光子との間の接着剥離が発生するメカニズムは以下のように推定可能である。まず、保護フィルムを透過した水分が接着剤層中に拡散し、偏光子界面側に該水分が拡散する。ここで、従来の偏光フィルムでは、接着剤層と偏光子との間の接着力に対し、水素結合および／またはイオン結合の寄与度が大きいが、偏光子界面側に拡散した水分により、界面での水素結合およびイオン結合が解離し、その結果、接着剤層と偏光子との接着力が低下する。これにより、結露環境下では接着剤層と偏光子との間の接着剥離が発生する場合があった。 When a polarizing film in which a transparent protective film is laminated on a polarizer via an adhesive layer is exposed to a dew condensation environment, the mechanism that causes adhesive peeling between the adhesive layer and the polarizer is as follows. Can be estimated. First, moisture that has passed through the protective film diffuses into the adhesive layer, and the moisture diffuses to the polarizer interface side. Here, in the conventional polarizing film, the contribution of hydrogen bonds and / or ionic bonds is large with respect to the adhesive force between the adhesive layer and the polarizer, but at the interface due to moisture diffused to the polarizer interface side. The hydrogen bond and the ionic bond are dissociated, and as a result, the adhesive force between the adhesive layer and the polarizer decreases. Thereby, adhesive debonding between the adhesive layer and the polarizer may occur in a dew condensation environment.
　一方、本発明に係る偏光フィルム用硬化型接着剤組成物は、酸無水物基およびアルコキシシラン基を有する化合物を含有する。したがって、保護フィルムを水分が透過し、接着剤層中に水分が拡散する場合であっても、化合物が有するアルコキシシラン基が水分の介在によりシラノール基となり偏光子表面における強い相互作用が形成されるとともに、化合物が有する酸無水物基が水分の介在により酸基となることで、偏光子表面がより活性化され、これにより偏光子と接着剤層との界面において水素結合および／またはイオン結合だけでなく、共有結合が形成されることとなり、偏光子と接着剤層との間の接着耐水性が飛躍的に向上する。さらに、本発明に係る偏光フィルム用硬化型接着剤組成物がエポキシ基を有する化合物を含有する場合、特に偏光子表面に存在する酸基と接着剤層との間により強い相互作用が生じ、水分存在下でも簡単に剥離し難い層間接着性が発現する。 On the other hand, the curable adhesive composition for a polarizing film according to the present invention contains a compound having an acid anhydride group and an alkoxysilane group. Therefore, even when moisture permeates the protective film and moisture diffuses into the adhesive layer, the alkoxysilane group of the compound becomes a silanol group due to the presence of moisture, and a strong interaction is formed on the polarizer surface. At the same time, the acid anhydride group of the compound becomes an acid group due to the presence of moisture, so that the surface of the polarizer is more activated, whereby only hydrogen bonds and / or ionic bonds are formed at the interface between the polarizer and the adhesive layer. Instead, a covalent bond is formed, and the water resistance of adhesion between the polarizer and the adhesive layer is dramatically improved. Furthermore, when the curable adhesive composition for a polarizing film according to the present invention contains a compound having an epoxy group, a stronger interaction occurs particularly between the acid group present on the surface of the polarizer and the adhesive layer. Interlayer adhesion that is not easily peeled off even in the presence is exhibited.
　さらに、本発明に係る偏光フィルム用硬化型接着剤組成物は、金属アルコキシドおよび金属キレートからなる群より選択される少なくとも１種の有機金属化合物を含有する場合、偏光子と接着剤層との間の接着耐水性が特に飛躍的に向上する。この理由は以下の如く推定可能である。接着剤層を構成する接着剤組成物が有機金属化合物を含有する場合であって、接着剤層中に水分が拡散した場合、有機金属化合物は、水分の介在により活性な金属種となり、その結果、有機金属化合物が偏光子、および接着剤層を構成する活性エネルギー線硬化性成分の両方と強固に相互作用する。これにより、偏光子と接着剤層との界面に水分が存在しても、これらが有機金属化合物を介して強固に相互作用しているため、偏光子と接着剤層との間の接着耐水性が特に飛躍的に向上する。 Furthermore, when the curable adhesive composition for polarizing films according to the present invention contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates, it is between the polarizer and the adhesive layer. In particular, the water resistance of the adhesive is greatly improved. The reason can be estimated as follows. When the adhesive composition that constitutes the adhesive layer contains an organometallic compound, and moisture diffuses into the adhesive layer, the organometallic compound becomes an active metal species due to the presence of moisture, and as a result The organometallic compound strongly interacts with both the polarizer and the active energy ray-curable component constituting the adhesive layer. As a result, even if moisture is present at the interface between the polarizer and the adhesive layer, since they interact strongly through the organometallic compound, the adhesive water resistance between the polarizer and the adhesive layer There is a dramatic improvement.
　本発明の偏光フィルム用硬化型接着剤組成物としては、当該硬化型接着剤組成物を硬化させて得られる硬化物のバルク吸水率が１０重量％以下であることが好ましい。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組成物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さらに高いレベルで満足することができる。 As the curable adhesive composition for a polarizing film of the present invention, the bulk water absorption of a cured product obtained by curing the curable adhesive composition is preferably 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 composition 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 at a higher level.
　例えば、本発明の偏光フィルム用硬化型接着剤組成物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（例えば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、水との接触環境が厳しい条件下においても、偏光子と透明保護フィルム間（偏光子と接着剤層間）の接着力の低下を小さく抑えることができる。 For example, a polarizing film having a cured product layer (adhesive layer) formed by using the curable adhesive composition for polarizing film of the present invention can be used in a severe humid environment (for example, 85 ° C. × 85% RH). Optical durability (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. In addition, 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 the polarizer and the transparent protective film even under conditions where the contact environment with water is severe It is possible to suppress a decrease in the adhesive strength between the layers (the polarizer and the adhesive layer).
　本発明に係る偏光フィルム用硬化型接着剤組成物は、酸無水物基およびアルコキシシラン基を有する化合物、ならびに活性エネルギー線硬化性成分を含有する。 The curable adhesive composition for a polarizing film according to the present invention contains a compound having an acid anhydride group and an alkoxysilane group, and an active energy ray-curable component.
　＜酸無水物基およびアルコキシシラン基を有する化合物＞
　本発明における酸無水物基としては、コハク酸の無水物の他、たとえばエチレン性不飽和ジカルボン酸（例えば、マレイン酸、イタコン酸、シトラコン酸、フタル酸など）の無水物、あるいは、モノカルボン酸の無水物タイプ、などが挙げられる。酸無水物とアルコキシシラン基との間に介在可能な連結基は、特に制限はないが、たとえば炭素数１～１４のアルキル基や、エチレングリコール、プロピレングリコールなどのアルキレングリコール骨格等が挙げられる。また、アルコキシシラン基については、メトキシ、エトキシ、プロポキシなどのアルコキシ基が挙げられる。具体的な化合物としては、例えば、３－トリメトキシシリルプロピルコハク酸無水物などが挙げられる。 <Compound having acid anhydride group and alkoxysilane group>
Examples of the acid anhydride group in the present invention include anhydrides of succinic acid, anhydrides of ethylenically unsaturated dicarboxylic acids (for example, maleic acid, itaconic acid, citraconic acid, phthalic acid, etc.), or monocarboxylic acids Anhydrous type, and the like. The linking group that can be interposed between the acid anhydride and the alkoxysilane group is not particularly limited, and examples thereof include an alkyl group having 1 to 14 carbon atoms and an alkylene glycol skeleton such as ethylene glycol and propylene glycol. Examples of the alkoxysilane group include alkoxy groups such as methoxy, ethoxy, and propoxy. Specific examples of the compound include 3-trimethoxysilylpropyl succinic anhydride.
　本発明において、酸無水物基およびアルコキシシラン基を有する化合物の含有割合は、活性エネルギー線硬化性成分の全量１００重量部に対して、０．５～４０重量部の範囲が好ましく、０．７～３５重量部であることが好ましく、１～３０重量部であることがさらに好ましい。４０重量部を超える配合量の場合、接着剤組成物の保存安定性が悪化したり、偏光子や保護フィルムに接着するための成分の比率が相対的に不足し接着性が低下するおそれがある。また０．５重量部未満の場合は接着耐水性の効果が十分発揮されないためである。 In the present invention, the content ratio of the compound having an acid anhydride group and an alkoxysilane group is preferably in the range of 0.5 to 40 parts by weight with respect to 100 parts by weight of the total amount of the active energy ray-curable component, 0.7% The amount is preferably 35 parts by weight, more preferably 1-30 parts by weight. When the amount exceeds 40 parts by weight, the storage stability of the adhesive composition may be deteriorated, or the ratio of components for adhering to a polarizer or a protective film may be relatively insufficient, resulting in a decrease in adhesiveness. . Further, when the amount is less than 0.5 parts by weight, the effect of adhesion and water resistance is not sufficiently exhibited.
　また、本発明に係る偏光フィルム用硬化型接着剤組成物は、エポキシ基を有する化合物を含有する場合、特に偏光子表面に存在する酸基と接着剤層との間により強い相互作用が生じ、水分存在下でも簡単に剥離し難い層間接着性が発現するため好ましい。 Moreover, when the curable adhesive composition for polarizing film according to the present invention contains a compound having an epoxy group, a stronger interaction occurs between the acid group present on the surface of the polarizer and the adhesive layer, It is preferable because interlayer adhesion that is difficult to peel easily even in the presence of moisture is exhibited.
　＜エポキシ基を有する化合物＞
　本発明におけるエポキシ基を有する化合物としては、４ヒドロキシブチルアクリレートグリシジルエーテルやグリシジルメタクリレートなどの片末端にラジカル重合性官能基を有する単官能エポキシ化合物や、ラウリルアルコールグリシジルエーテル、エチレングリコールグリシジルエーテルのようなアルキルアルコールグリシジルエーテルに代表される単官能エポキシ化合物、またエチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６―ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ビスフェノールＡジグリシジルエーテルなどのジグリシジルエーテル化合物などが挙げられる。中でも、偏光子側の官能基と接着剤層が強固に結合された構造を得る上では、方末端にラジカル重合性官能基を有する単官能エポキシ化合物あるいはジグリシジルエーテル化合物が好ましく、特に４ヒドロキシブチルアクリレートグリシジルエーテルやグリシジルメタクリレートなどの方末端にラジカル重合性官能基を有する単官能エポキシ化合物が好ましい。 <Compound having an epoxy group>
Examples of the compound having an epoxy group in the present invention include a monofunctional epoxy compound having a radical polymerizable functional group at one end, such as 4-hydroxybutyl acrylate glycidyl ether and glycidyl methacrylate, lauryl alcohol glycidyl ether, and ethylene glycol glycidyl ether. Monofunctional epoxy compounds represented by alkyl alcohol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanedi Lumpur diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl ether compounds such as bisphenol A diglycidyl ether. Among them, in order to obtain a structure in which the functional group on the polarizer side and the adhesive layer are firmly bonded, a monofunctional epoxy compound or a diglycidyl ether compound having a radical polymerizable functional group at the end is preferable, and particularly 4-hydroxybutyl. A monofunctional epoxy compound having a radical polymerizable functional group at its terminal, such as acrylate glycidyl ether or glycidyl methacrylate, is preferred.
　本発明において、エポキシ基を有する化合物の含有割合は、活性エネルギー線硬化性成分の全量１００重量部に対して、０～２０重量部の範囲が好ましく、０．２～１５重量部であることが好ましく、０．５～１０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、接着剤組成物の保存安定性が悪化したり、偏光子や保護フィルムに接着するための成分の比率が相対的に不足し接着性が低下するおそれがある。 In the present invention, the content ratio of the compound having an epoxy group is preferably in the range of 0 to 20 parts by weight, preferably 0.2 to 15 parts by weight with respect to 100 parts by weight of the total amount of the active energy ray-curable component. The amount is preferably 0.5 to 10 parts by weight. In the case of a blending amount exceeding 20 parts by weight, the storage stability of the adhesive composition may be deteriorated, or the ratio of components for adhering to a polarizer or a protective film may be relatively insufficient, resulting in a decrease in adhesiveness. .
　本発明に係る偏光フィルム用硬化型接着剤組成物は、さらに、活性エネルギー線硬化性成分とともに金属アルコキシドおよび金属キレートからなる群より選択される少なくとも１種の有機金属化合物を含有することが好ましい。 The polarizing film curable adhesive composition according to the present invention preferably further contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates together with an active energy ray-curable component.
　＜金属アルコキシドおよび金属キレートからなる群より選択される少なくとも１種の有機金属化合物＞
　金属アルコキシドは、金属に有機基であるアルコキシ基が少なくとも一つ以上結合した化合物であり、金属キレートは、金属に酸素原子を介して有機基が結合または配位した化合物である。金属としてはチタン、アルミニウム、ジルコニウムが好ましい。この中でも、チタンに比べてアルミニウムおよびジルコニウムは反応性が速く、接着剤組成物のポットライフが短くなるとともに、接着耐水性の向上効果が低くなる場合がある。したがって、接着剤層の接着耐水性向上の観点から、有機金属化合物の金属としてチタンがより好ましい。 <At least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates>
A metal alkoxide is a compound in which at least one alkoxy group, which is an organic group, is bonded to a metal, and a metal chelate is a compound in which an organic group is bonded or coordinated to the metal via an oxygen atom. Titanium, aluminum, and zirconium are preferable as the metal. Among these, compared with titanium, aluminum and zirconium are fast in reactivity, the pot life of the adhesive composition is shortened, and the effect of improving the adhesion water resistance may be lowered. Therefore, titanium is more preferable as the metal of the organometallic compound from the viewpoint of improving the adhesive water resistance of the adhesive layer.
　本発明に係る偏光フィルム用硬化型接着剤組成物が、有機金属化合物として金属アルコキシドを含有する場合、金属アルコキシドが有する有機基の炭素数が４以上のものを使用することが好ましく、６以上のものを含有することがより好ましい。炭素数が３以下であると、接着剤組成物のポットライフが短くなるとともに、接着耐水性の向上効果が低くなる場合がある。炭素数が６以上の有機基としては例えば、オクトキシ基が挙げられ、好適に使用可能である。好適な金属アルコキシドの例としては、例えば、テトライソプロピルチタネート、テトラノルマルブチルチタネート、ブチルチタネートダイマー、テトラオクチルチタネート、ターシャリーアミルチタネート、テトラターシャリーブチルチタネート、テトラステアリルチタネート、ジルコニウムテトライソプロポキシド、ジルコニウムテトラノルマルブトキシド、ジルコニウムテトラオクトキシド、ジルコニウムテトラターシャリーブトキシド、ジルコニウムテトラプロポキシド、アルミニウムｓｅｃブチレート、アルミニウムエチレート、アルミニウムイソプレピレート、アルミニウムブチレート、アルミニウムジイソプロピレートモノセカンダリブチレート、モノｓｅｃブトキシアルミニウムジイソプロピレート、などが挙げられる。なかでも、テトラオクチルチタネートが好ましい。 When the curable adhesive composition for a polarizing film according to the present invention contains a metal alkoxide as the organometallic compound, it is preferable to use a metal alkoxide having an organic group having 4 or more carbon atoms, It is more preferable to contain a thing. When the carbon number is 3 or less, the pot life of the adhesive composition may be shortened, and the effect of improving the adhesion water resistance may be reduced. Examples of the organic group having 6 or more carbon atoms include an octoxy group, which can be suitably used. Examples of suitable metal alkoxides include, for example, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary amyl titanate, tetra tertiary butyl titanate, tetrastearyl titanate, zirconium tetraisopropoxide, zirconium Tetranormal butoxide, zirconium tetraoctoxide, zirconium tetratertiary butoxide, zirconium tetrapropoxide, aluminum sec butyrate, aluminum ethylate, aluminum isopropylate, aluminum butyrate, aluminum diisopropylate monosecondary butyrate, monosec butoxyaluminum And diisopropylate. Of these, tetraoctyl titanate is preferable.
　本発明に係る偏光フィルム用硬化型接着剤組成物が、有機金属化合物として金属キレートを含有する場合、金属キレートが有する有機基の炭素数が４以上のものを含有することが好ましい。炭素数が３以下であると、接着剤組成物のポットライフが短くなるとともに、接着耐水性の向上効果が低くなる場合がある。炭素数が４以上の有機基としては例えば、アセチルアセトナート基、エチルアセトアセテート基、イソステアレート基、オクチレングリコレート基などが挙げられる。これらの中でも、接着剤層の接着耐水性向上の観点から、有機基としてアセチルアセトナート基またはエチルアセトアセテート基が好ましい。好適な金属キレートの例としては、例えば、チタンアセチルアセトナート、チタンオクチレングリコレート、チタンテトラアセチルアセトナート、チタンエチルアセトアセテート、ポリヒドロキシチタンステアレート、ジプロポキシ－ビス（アセチルアセトナト）チタン、ジブトキシチタン－ビス（オクチレングリコレート）、ジプロポキシチタン－ビス（エチルアセトアセテート）、チタンラクテート、チタンジエタノールアミネート、チタントリエタノールアミネート、ジプロポキシチタン－ビス（ラクテート）、ジプロポキシチタン－ビス（トリエタノールアミナート）、ジ－ｎ－ブトキシチタン－ビス（トリエタノールアミナート）、トリ－ｎ－ブトキシチタンモノステアレート、ジイソプロポキシ・ビス（エチルアセトアセテート）チタニウム、ジイソプロポキシ・ビス（アセチルアセテート）チタニウム、ジイソプロポキシ・ビス（アセチルアセトン）チタニウム、りん酸チタン化合物、チタンラクテートアンモニウム塩、チタン－１，３－プロパンジオキシビス（エチルアセトアセテート）、ドデシルベンゼンスルホン酸チタン化合物、チタンアミノエチルアミノエタノレート、ジルコニウムテトラアセチルアセトナート、ジルコニウムモノアセチルアセトナート、ジルコニウムビスアセチルアセトナート、ジルコニウムアセチルアセトナートビスエチルアセトアセテート、ジルコニウムアセテート、トリ－ｎ－ブトキシエチルアセトアセテートジルコニウム、ジ－ｎ－ブトキシビス（エチルアセトアセテート）ジルコニウム、ｎ－ブトキシトリス（エチルアセトアセテート）ジルコニウム、テトラキス（ｎ－プロピルアセトアセテート）ジルコニウム、テトラキス（アセチルアセトアセテート）ジルコニウム、テトラキス（エチルアセトアセテート）ジルコニウム、アルミニウムエチルアセトアセテート、アルミニウムアセチルアセトネート、アルミニウムアセチルアセトネートビスエチルアセトアセテート、ジイソプロポキシエチルアセトアセテートアルミニウム、ジイソプロポキシアセチルアセトナートアルミニウム、イソプロポキシビス（エチルアセトアセテート）アルミニウム、イソプロポキシビス（アセチルアセトナート）アルミニウム、トリス（エチルアセトアセテート）アルミニウム、トリス（アセチルアセトナート）アルミニウム、モノアセチルアセトナート・ビス（エチルアセトアセテート）アルミニウムが挙げられる。なかでも、チタンアセチルアセトナート、チタンエチルアセトアセテートが好ましい。 When the curable adhesive composition for a polarizing film according to the present invention contains a metal chelate as the organometallic compound, the organic chelate preferably has an organic group having 4 or more carbon atoms. When the carbon number is 3 or less, the pot life of the adhesive composition may be shortened, and the effect of improving the adhesion water resistance may be reduced. Examples of the organic group having 4 or more carbon atoms include acetylacetonate group, ethylacetoacetate group, isostearate group, octylene glycolate group and the like. Among these, from the viewpoint of improving the adhesive water resistance of the adhesive layer, an acetylacetonate group or an ethylacetoacetate group is preferable as the organic group. Examples of suitable metal chelates include, for example, titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethylacetoacetate, polyhydroxytitanium stearate, dipropoxy-bis (acetylacetonato) titanium, di Butoxytitanium-bis (octylene glycolate), dipropoxytitanium-bis (ethylacetoacetate), titanium lactate, titanium diethanolamate, titanium triethanolamate, dipropoxytitanium-bis (lactate), dipropoxytitanium-bis ( Triethanolaminate), di-n-butoxytitanium-bis (triethanolaminato), tri-n-butoxytitanium monostearate, diisopropoxy bis (ethylacetoacetate) Titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy bis (acetylacetone) titanium, titanium phosphate compound, titanium lactate ammonium salt, titanium-1,3-propanedioxybis (ethylacetoacetate), dodecyl Benzenesulfonic acid titanium compound, titanium aminoethylamino ethanolate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate, zirconium acetate, tri-n-butoxyethylacetate Acetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) Tate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis (acetyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, aluminum ethyl acetoacetate, aluminum acetylacetonate, aluminum acetylacetonate bisethylacetoacetate, di Isopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum Monoacetylacetonate bis (ethylacetoacetate And aluminum). Of these, titanium acetylacetonate and titanium ethylacetoacetate are preferable.
　本発明で使用可能な有機金属化合物として、上記以外にオクチル酸亜鉛、ラウリン酸亜鉛、ステアリン酸亜鉛、オクチル酸錫などの有機カルボン酸金属塩、アセチルアセトン亜鉛キレート、ベンゾイルアセトン亜鉛キレート、ジベンゾイルメタン亜鉛キレート、アセト酢酸エチル亜鉛キレートなどの亜鉛キレート化合物などが挙げられる。 In addition to the above, the organic metal compounds usable in the present invention include organic carboxylic acid metal salts such as zinc octylate, zinc laurate, zinc stearate, tin octylate, acetylacetone zinc chelate, benzoylacetone zinc chelate, dibenzoylmethane zinc Examples of the chelate include zinc chelate compounds such as ethyl zinc acetoacetate chelate.
　本発明において、有機金属化合物の含有割合は、活性エネルギー線硬化性成分の全量１００重量部に対して、０．０５～９重量部の範囲が好ましく、０．１～８重量部であることが好ましく、０．１５～５重量部であることがさらに好ましい。９重量部を超える配合量の場合、接着剤組成物の保存安定性が悪化したり、偏光子や保護フィルムに接着するための成分の比率が相対的に不足し接着性が低下するおそれがある。また０．０５重量部未満の場合は接着耐水性の効果が十分発揮されないためである。 In the present invention, the content of the organometallic compound is preferably in the range of 0.05 to 9 parts by weight and preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the total amount of the active energy ray-curable component. The amount is preferably 0.15 to 5 parts by weight. When the amount exceeds 9 parts by weight, the storage stability of the adhesive composition may be deteriorated, or the ratio of components for adhering to a polarizer or a protective film may be relatively insufficient, resulting in a decrease in adhesiveness. . Moreover, when it is less than 0.05 part by weight, the effect of adhesion water resistance is not sufficiently exhibited.
　＜硬化性成分＞
　本発明の偏光フィルム用硬化型接着剤組成物は、硬化性成分として、活性エネルギー線硬化性成分を含有する。 <Curable component>
The polarizing film curable adhesive composition of the present invention contains an active energy ray-curable component as the curable component.
　硬化性成分としては、電子線硬化型、紫外線硬化型、可視光線硬化型などの活性エネルギー線硬化型が好適に使用可能である。さらには、紫外線硬化型、可視光線硬化型接着剤組成物は、ラジカル重合硬化型接着剤組成物とカチオン重合型接着剤組成物に区分できる。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。 As the curable component, an active energy ray curable type such as an electron beam curable type, an ultraviolet curable type, a visible light curable type, or the like can be suitably used. Further, the ultraviolet curable and visible light curable adhesive compositions can be classified into radical polymerization curable adhesive compositions and cationic polymerization adhesive compositions. 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.
　＜１：ラジカル重合硬化型接着剤組成物＞
　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組成物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、ビニル基などの炭素－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 composition>
Examples of the curable component include radical polymerizable compounds used in radical polymerization curable adhesive compositions. 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）アクリルアミドなどの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）アクリルアミドなどの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）アクリルアミドなどの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などの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）アクリルアミドなどの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などがあげられる。 ≪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-methoxy N-alkoxy group-containing (meth) acrylamide derivatives such as methylacrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide; Can be mentioned. 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）アクリレートなどのシクロアルキル（メタ）アクリレート；ベンジル（メタ）アクリレートなどのアラルキル（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、などの多環式（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）アクリレートなど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；などが挙げられる。 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, dicyclopentenyl (meth) ) Polycyclic (meth) acrylates such as acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxy Ethyl (meth) acrylate Alkoxy groups such as 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, or phenoxy Group-containing (meth) acrylates; and the like.
　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）アクリレートなど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）アクリレートなどの水酸基含有（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などのエポキシ基含有（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）アクリレートなどのハロゲン含有（メタ）アクリレート；ジメチルアミノエチル（メタ）アクリレートなど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）アクリレートなど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）アクリレートなどが挙げられる。 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 And [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and other hydroxy acids Containing (meth) acrylate; glycidyl (meth) acrylate, epoxy group-containing (meth) acrylate such as 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) acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2- Halogen-containing (meth) acrylates such as hydroxypropyl (meth) acrylate; alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 3-oxetanylmethyl (meth) acrylate Contains oxetane groups such as acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate, 3-hexyloxoxanylmethyl (meth) acrylate (Meth) acrylate; (meth) acrylate having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and butyrolactone (meth) acrylate, neopentyl glycol (meth) acrylic acid adduct of hydroxypivalate, p-phenylphenol ( And (meth) acrylate.
　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など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、ビニルモルホリンなどの窒素含有複素環を有するビニル系モノマーなどが挙げられる。 Examples of the monofunctional radical polymerizable compound include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, 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、多官能（メタ）アクリルアミド誘導体であるＮ，Ｎ‘－メチレンビス（メタ）アクリルアミド、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）アクリレートなどの（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（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）などが好ましい。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などが挙げられる。なお、多官能（メタ）アクリルアミド誘導体は、重合速度が速く生産性に優れる上、樹脂組成物を硬化物とした場合の架橋性に優れるため、硬化性樹脂組成物に含有させることが好ましい。 ≪Polyfunctional radical polymerizable compound≫
Examples of the bifunctional or higher polyfunctional radical polymerizable compound include N, N′-methylenebis (meth) acrylamide, tripropylene glycol di (meth) acrylate, and tetraethylene glycol diester which are polyfunctional (meth) acrylamide derivatives. (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) acrylate, cyclic trimethylolpropane formal (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate (Meth) acrylic such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate An esterified product of an acid and a polyhydric alcohol, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene. Specific examples include Aronix M-220 (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 (Kyoeisha Chemical Co., Ltd.) SR-531 (Sartomer), CD-536 (Sartomer) and the like are preferable. Moreover, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary. The polyfunctional (meth) acrylamide derivative is preferably contained in the curable resin composition because the polymerization rate is high and the productivity is excellent, and the crosslinkability when the resin composition is a cured product is excellent.
　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、後述するｌｏｇＰｏｗ値が高いものが好ましい。 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 described later are preferable.
　本発明の偏光フィルム用硬化型接着剤組成物は、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、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。また、接着剤組成物のｌｏｇＰｏｗ値は、下記式によって計算することができる。
　　接着剤組成物のｌｏｇＰｏｗ＝Σ（ｌｏｇＰｏｗｉ×Ｗｉ）
　ｌｏｇＰｏｗｉ：組成物各成分のｌｏｇＰｏｗ値
　Ｗｉ：（ｉ成分のモル数）／（接着剤組成物の総モル数）
　本発明の硬化型接着剤組成物の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。 The curable adhesive composition 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 be measured (flask immersion method described in JIS-Z-7260), but can also be calculated. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft is used. Further, the logPow value of the adhesive composition can be calculated by the following formula.
LogPow of adhesive composition = Σ (logPow × Wi)
logPowi: logPow value of each component of composition Wi: (number of moles of i component) / (total number of moles of adhesive composition)
The logPow value of the curable adhesive composition of the present invention is preferably 1 or more, more preferably 2 or more, and most preferably 3 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・BR>W（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) acrylate such as 1,9-nonanediol di (meth) acrylate (logPow = 3.68), 1,10-decanediol diacrylate (logPow = 4.10); hydroxypivalic acid Multi-branched (meth) acrylates such as 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, BR> W (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), and (meth) acrylates containing aromatic rings such as p-phenylphenol (meth) acrylate (logPow = 3.98).
　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、過酷な環境下にお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。 Radical polymerizable compounds should be used in combination with monofunctional radical polymerizable compounds and polyfunctional radical polymerizable compounds from the viewpoint of achieving both adhesion to polarizers and various transparent protective films and optical durability in harsh environments. Is preferred. 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組成物の態様＞
　本発明の偏光フィルム用硬化型接着剤組成物は、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組成物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組成物は、活性エネルギー線に電子線などを用いる場合には、当該活性エネルギー線硬化型接着剤組成物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。 <Aspect of radical polymerization curable adhesive composition>
The curable adhesive composition for polarizing film of the present invention can be used as an active energy ray curable adhesive composition when a curable component is used as the active energy ray curable component. In the case where the active energy ray-curable adhesive composition uses an electron beam or the like for the active energy ray, the active energy ray-curable adhesive composition need not contain a photopolymerization initiator, When ultraviolet rays or visible rays are used for the active energy rays, it is preferable to contain a photopolymerization 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；チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントンなどのチオキサントン系化合物；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。 ≪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 by 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, photoactive oxime compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichloro Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; camphorquinone; halogenated ketone; acylphosphine Inokishido; and acyl phospholipase diisocyanate, and the like. Among photopolymerization initiators, those having a high logPow value are preferred. The logPow value of the photopolymerization initiator is preferably 2 or more, more preferably 3 or more, and most preferably 4 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組成物を、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。 In addition, when the curable adhesive composition for polarizing film of the present invention is used in a visible light curable type containing a radical polymerizable compound as a curable component, photopolymerization that is particularly sensitive to light of 380 nm or more is initiated. It is preferable to use an agent. 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。接着剤組成物中の一般式（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 composition is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component, 0.5 to The amount is more preferably 4 parts by weight, still more preferably 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組成物において、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 composition, when the radical polymerizable compound (a1) having an active methylene group is used as the radical polymerizable compound, it is combined with the radical polymerization initiator (a2) having a hydrogen abstraction function. Are preferably used. 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組成物において、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 above active energy ray-curable adhesive composition, 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% by weight, the radically polymerizable compound (a1) having an active methylene group is 1 to 50% by weight, and the radical polymerization initiator (a2) is 0% by weight based on 100 parts by weight of the total amount of the curable component. It is preferable to contain 1 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。水素引き抜き反応が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。一方場合があり、１０重量部を超えると、組成物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 for the hydrogen abstraction reaction to proceed sufficiently, 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 composition.
　＜２：カチオン重合硬化型接着剤組成物＞
　カチオン重合硬化性樹脂組成物に使用されるカチオン重合性化合物としては、分子内にカチオン重合性官能基を１つ有する単官能カチオン重合性化合物と、分子内にカチオン重合性官能基を２つ以上有する多官能カチオン重合性化合物とに分類される。単官能カチオン重合性化合物は比較的液粘度が低いため、樹脂組成物に含有させることで樹脂組成物の液粘度を低下させることができる。また、単官能カチオン重合性化合物は各種機能を発現させる官能基を有している場合が多く、樹脂組成物に含有させることで樹脂組成物及び／又は樹脂組成物の硬化物に各種機能を発現させることができる。多官能カチオン重合性化合物は、樹脂組成物の硬化物を３次元架橋させることができるため樹脂組成物に含有させることが好ましい。単官能カチオン重合性化合物と多官能カチオン重合性化合物の比は、単官能カチオン重合性化合物１００重量部に対して、多官能カチオン重合性化合物を１０重量部から１０００重量部の範囲で混合することが好ましい。カチオン重合性官能基としては、エポキシ基やオキセタニル基、ビニルエーテル基が挙げられる。エポキシ基を有する化合物としては、脂肪族エポキシ化合物、脂環式エポキシ化合物、芳香族エポキシ化合物が挙げられ、本発明のカチオン重合硬化性樹脂組成物としては、硬化性や接着性に優れることから、脂環式エポキシ化合物を含有することが特に好ましい。脂環式エポキシ化合物としては、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレートのカプロラクトン変性物やトリメチルカプロラクトン変性物やバレロラクトン変性物等が挙げられ、具体的には、セロキサイド２０２１、セロキサイド２０２１Ａ、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０８３、セロキサイド２０８５（以上、ダイセル化学工業（株製）、サイラキュアＵＶＲ－６１０５、サイラキュアＵＶＲ－６１０７、サイラキュア３０、Ｒ－６１１０（以上、ダウ・ケミカル日本（株）製）等が挙げられる。オキセタニル基を有する化合物は、本発明のカチオン重合硬化性樹脂組成物の硬化性を改善したり、該組成物の液粘度を低下させる効果があるため、含有させることが好ましい。オキセタニル基を有する化合物としては、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス［（３－エチル－３－オキセタニル）メトキシメチル］ベンゼン、３－エチル－３－（フェノキシメチル）オキセタン、ジ［（３－エチル－３－オキセタニル）メチル］エーテル、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、フェノールノボラックオキセタンなどが挙げられ、アロンオキセタンＯＸＴ－１０１、アロンオキセタンＯＸＴ－１２１、アロンオキセタンＯＸＴ－２１１、アロンオキセタンＯＸＴ－２２１、アロンオキセタンＯＸＴ－２１２（以上、東亞合成社製）等が市販されている。ビニルエーテル基を有する化合物は、本発明のカチオン重合硬化性樹脂組成物の硬化性を改善したり、該組成物の液粘度を低下させる効果があるため、含有させることが好ましい。ビニルエーテル基を有する化合物としては、２－ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、４－ヒドロキシブチルビニルエーテル、ジエチレングリコールものビニルエーテル、トリエチレングリコールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、トリシクロデカンビニルエーテル、シクロヘキシルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、ペンタエリスリトール型テトラビニルエーテル等が挙げられる。 <2: Cationic polymerization curable adhesive composition>
The cationic polymerizable compound used in the cationic polymerization curable resin composition includes a monofunctional cationic polymerizable compound having one cationic polymerizable functional group in the molecule and two or more cationic polymerizable functional groups in the molecule. And having a polyfunctional cationically polymerizable compound. Since the monofunctional cation polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be reduced by containing it in the resin composition. In addition, monofunctional cationically polymerizable compounds often have functional groups that develop various functions, and by incorporating them into the resin composition, various functions are exhibited in the resin composition and / or the cured product of the resin composition. Can be made. The polyfunctional cation polymerizable compound is preferably contained in the resin composition because the cured product of the resin composition can be three-dimensionally crosslinked. The ratio of the monofunctional cation polymerizable compound to the polyfunctional cation polymerizable compound is such that the polyfunctional cation polymerizable compound is mixed in the range of 10 to 1000 parts by weight with respect to 100 parts by weight of the monofunctional cation polymerizable compound. Is preferred. Examples of the cationic polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound, and the cationic polymerization curable resin composition of the present invention is excellent in curability and adhesiveness. It is particularly preferable to contain an alicyclic epoxy compound. Examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate caprolactone-modified products and trimethylcaprolactone-modified products. And valerolactone modified products, and specifically, Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085 (above, Daicel Chemical Industries, Ltd., Cyracure UVR-6105, Cyracure UVR) -6107, Cyracure 30, R-6110 (above, manufactured by Dow Chemical Japan Co., Ltd.), etc. The compound having an oxetanyl group is a cationic polymerization compound of the present invention. The compound having an oxetanyl group is preferably contained because it has the effect of improving the curability of the curable resin composition or lowering the liquid viscosity of the composition, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl -3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, and the like, including Aron Oxetane OXT-101, Aron Oxetane OXT-121, Aron Oxetane OXT-211, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (Above, manufactured by Toagosei Co., Ltd.) The compound having a vinyl ether group is preferably contained because it has the effect of improving the curability of the cationic polymerization curable resin composition of the present invention or lowering the liquid viscosity of the composition. As 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl ether of diethylene glycol, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxy Examples thereof include ethyl vinyl ether, ethoxyethyl vinyl ether, and pentaerythritol type tetravinyl ether.
　＜光カチオン重合開始剤＞
　カチオン重合硬化性樹脂組成物は、硬化性成分として以上説明したエポキシ基を有する化合物、オキセタニル基を有する化合物、ビニルエーテル基を有する化合物から選ばれる少なくとも１つの化合物を含有し、　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、電子線など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。光カチオン重合開始剤としては、後述の光酸発生剤が好適に使用される。また本発明で使用する硬化性樹脂組成物を可視光線硬化性で用いる場合には、特に３８０ｎｍ以上の光に対して高感度な光カチオン重合開始剤を用いることが好ましいが、光カチオン重合開始剤は一般に、３００ｎｍ付近またはそれより短い波長域に極大吸収を示す化合物であるため、それより長い波長域、具体的には３８０ｎｍより長い波長の光に極大吸収を示す光増感剤を配合することで、この付近の波長の光に感応し、光カチオン重合開始剤からのカチオン種または酸の発生を促進させることができる。光増感剤としては、例えば、アントラセン化合物、ピレン化合物、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾおよびジアゾ化合物、ハロゲン化合物、光還元性色素等が挙げられ、これらは、２種類以上を混合して使用してもよい。特にアントラセン化合物は、光増感効果に優れるため好ましく、具体的にはアントラキュアＵＶＳ－１３３１、アントラキュアＵＶＳ－１２２１（川崎化成社製）が挙げられる。光増感剤の含有量は、０．１重量％～５重量％であることが好ましく、０．５重量％～３重量％であることがより好ましい。 <Photocationic polymerization initiator>
The cationic polymerization curable resin composition contains at least one compound selected from a compound having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group as described above as a curable component. Therefore, a cationic photopolymerization initiator is blended. 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. As the photocationic polymerization initiator, a photoacid generator described later is preferably used. In addition, when the curable resin composition used in the present invention is used with visible light curability, it is particularly preferable to use a photocationic polymerization initiator that is highly sensitive to light of 380 nm or more. Is generally a compound that exhibits maximum absorption in the vicinity of 300 nm or shorter, and therefore, a photosensitizer that exhibits maximum absorption in light having a wavelength longer than that, specifically, longer than 380 nm should be blended. Thus, it is possible to respond to light having a wavelength in the vicinity and promote generation of cationic species or acid from the photocationic polymerization initiator. Examples of the photosensitizer include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, and the like. Two or more types may be mixed and used. In particular, anthracene compounds are preferable because of their excellent photosensitization effect, and specific examples include anthracure UVS-1331 and anthracure UVS-1221 (manufactured by Kawasaki Kasei Co., Ltd.). The content of the photosensitizer is preferably 0.1% by weight to 5% by weight, and more preferably 0.5% by weight to 3% by weight.
　＜その他の成分＞
　本発明に係る硬化型接着剤組成物は、下記成分を含有することが好ましい。 <Other ingredients>
The curable adhesive composition 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組成物は、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組成物中に（Ａ）成分を含有することで、該組成物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。接着剤組成物中のアクリル系オリゴマー（Ａ）の含有量が多すぎると、該組成物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 composition according to the present invention may contain an acrylic oligomer (A) formed by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound. it can. By containing the component (A) in the active energy ray-curable adhesive composition, curing shrinkage when the active energy ray is irradiated and cured on the composition is reduced, and the adhesive, polarizer and transparent protection are reduced. 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. If the content of the acrylic oligomer (A) in the adhesive composition is too large, the reaction rate when the active energy ray is irradiated onto the composition is so severe that poor curing may occur. 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組成物は、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。（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 composition preferably has a low viscosity in consideration of workability and uniformity during coating. Therefore, an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer. It is also preferable that the viscosity is low. 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 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組成物において、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樹脂組成物に、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)>
The said active energy ray hardening-type adhesive composition can contain a photo-acid generator (B). When the active energy ray-curable resin composition 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
 (However, L + represents any onium cation. 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-)
　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、本発明の光酸発生剤（Ｂ）を構成する好ましいオニウム塩の具体例としては、「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）が本発明の光酸発生剤（Ｂ）の好ましい具体例として挙げられる。 Accordingly, specific examples of preferred onium salts constituting the photoacid generator (B) of the present invention include “Syracure UVI-6922” and “Syracure UVI-6974” (above, 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 "(Sanshin Chemical Co., Ltd.)," CPI-100P " "CPI-100A" (manufactured by San Apro Co., Ltd.), "WPI-069", "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.) are preferable specific examples of the photoacid generator (B) of the present invention. It is done.
　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組成物において、活性エネルギー線硬化型接着剤組成物中に光酸発生剤（Ｂ）とアルコキシ基、エポキシ基いずれかを含む化合物（Ｃ）を併用することができる。 <Compound (C) containing either an alkoxy group or an epoxy group>
In the active energy ray-curable adhesive composition, the active energy ray-curable adhesive composition can be used in combination with a photoacid generator (B) and a compound (C) containing either an alkoxy group or an epoxy group. .
　（エポキシ基を有する化合物及び高分子）（Ｃ）
　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などが挙げられる。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 and polymer) (C)
When using 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, two functional groups having reactivity with the epoxy group are contained in the molecule. Two or more compounds 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, and a primary or secondary aromatic amino group. 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など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などがあり、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など）、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シリーズなど）、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など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及び高分子（Ｃ）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 , Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. These epoxy resins may be halogenated and hydrogenated It 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 Co., Ltd., Epolide series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resins (polysynthesized from bisphenols and epichlorohydrin) Mud carboxymethyl at both ends with polyether having an epoxy group; and YP series), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha although chemical Co. Epo light series are exemplified but 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 having an epoxy group and the polymer (C) are not included in the calculation.
　（アルコキシル基を有する化合物及び高分子）（Ｃ）分子内にアルコキシル基を有する化合物としては、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。このような化合物としては、メラミン化合物、アミノ樹脂、シランカップリング剤などが代表として挙げられる。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（Ｃ）を計算には入れないこととする。 (Alkoxyl group-containing compound and polymer) (C) The compound having an alkoxyl 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. Representative examples of such compounds include melamine compounds, amino resins, and silane coupling agents. In calculating the glass transition temperature Tg of the adhesive layer, the compound having an alkoxyl group and the polymer (C) are not included in the calculation.
　アルコキシ基、エポキシ基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、組成物中の化合物（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。組成物中の化合物（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、組成物中、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, and the content of the compound (C) in the composition When there is too much, adhesiveness falls and the impact resistance with respect to a drop test may deteriorate. The content of the compound (C) in the composition is more preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the composition preferably contains 2 parts by weight or more of the compound (C), more preferably 5 parts by weight or more.
　＜シランカップリング剤（Ｄ）＞
　本発明の偏光フィルム用硬化型接着剤組成物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（Ｄ）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 (D)>
In the case where the curable adhesive composition for polarizing film of the present invention is an active energy ray curable curable composition, the silane coupling agent (D) is preferably an active energy ray curable compound. Even if it is not energy ray curable, the same water resistance can be imparted.
　シランカップリング剤（Ｄ）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 (D) include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and the like as active energy ray-curable compounds. -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（Ｄ１）が好ましい。アミノ基を有するシランカップリング剤（Ｄ１）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］エチレンジアミンなど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－プロパンアミンなど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 (D1) having an amino group is preferable. Specific examples of the silane coupling agent (D1) 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) 3 may be mentioned ketimines type silanes such as (triethoxysilyl) -1-propanamine.
　アミノ基を有するシランカップリング剤（Ｄ１）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 (D1) 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（Ｄ）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、接着剤組成物の保存安定性が悪化し、また０．１重量部未満の場合は接着耐水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（Ｄ）を計算には入れないこととする。 The amount of the silane coupling agent (D) is preferably 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 if the amount exceeds 20 parts by weight, the storage stability of the adhesive composition deteriorates, and if it is less than 0.1 parts by weight, the effect of adhesion water resistance is not sufficiently exhibited. When calculating the glass transition temperature Tg of the adhesive layer, the silane coupling agent (D) 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.
　＜ビニルエーテル基を有する化合物（Ｅ）＞
　本発明の偏光フィルム用硬化型接着剤組成物がビニルエーテル基を有する化合物（Ｅ）を含有する場合、偏光子と接着剤層との接着耐水性が向上するため好ましい。かかる効果が得られる理由は明らかではないが、化合物（Ｅ）が有するビニルエーテル基が偏光子と相互作用することにより、偏光子と接着剤層との接着力が高まることが理由の一つであると推測される。偏光子と接着剤層との接着耐水性をさらに高めるためには、化合物（Ｅ）はビニルエーテル基を有するラジカル重合性化合物であることが好ましい。また、化合物（Ｅ）の含有量は、硬化性成分の全量１００重量部に対して０．１～１９重量部含有することが好ましい。 <Compound (E) having a vinyl ether group>
When the curable adhesive composition for polarizing films of the present invention contains a compound (E) having a vinyl ether group, it is preferable because adhesion water resistance between the polarizer and the adhesive layer is improved. The reason why such an effect is obtained is not clear, but one of the reasons is that the adhesive force between the polarizer and the adhesive layer is increased by the interaction of the vinyl ether group of the compound (E) with the polarizer. It is guessed. In order to further increase the water resistance of adhesion between the polarizer and the adhesive layer, the compound (E) is preferably a radical polymerizable compound having a vinyl ether group. The content of the compound (E) is preferably 0.1 to 19 parts by weight with respect to 100 parts by weight of the total amount of the curable component.
　＜ケト－エノール互変異性を生じる化合物（Ｆ）＞
　本発明の偏光フィルム用硬化型接着剤組成物には、ケト－エノール互変異性を生じる化合物を含有させることができる。例えば、架橋剤を含む接着剤組成物または架橋剤を配合して使用され得る接着剤組成物において、上記ケト－エノール互変異性を生じる化合物を含む態様を好ましく採用することができる。これにより、有機金属化合物配合後における接着剤組成物の過剰な粘度上昇やゲル化、ならびにミクロゲル物の生成を抑制し、該組成物のポットライフを延長する効果が実現され得る。 <Compound (F) producing keto-enol tautomerism>
The curable adhesive composition for polarizing film of the present invention may contain a compound that causes keto-enol tautomerism. For example, in an adhesive composition containing a cross-linking agent or an adhesive composition that can be used by blending a cross-linking agent, an embodiment containing a compound that produces the keto-enol tautomerism can be preferably employed. Thereby, the excessive viscosity rise and gelation of the adhesive composition after the compounding of the organometallic compound and the formation of a microgel product can be suppressed, and the effect of extending the pot life of the composition can be realized.
　上記ケト－エノール互変異性を生じる化合物（Ｆ）としては、各種のβ－ジカルボニル化合物を用いることができる。具体例としては、アセチルアセトン、２，４－ヘキサンジオン、３，５―ヘプタンジオン、２－メチルヘキサン－３，５－ジオン、６－メチルヘプタン－２，４－ジオン、２，６－ジメチルヘプタン－３，５－ジオンなどのβ－ジケトン類；アセト酢酸メチル、アセト酢酸エチル、アセト酢酸イソプロピル、アセト酢酸ｔｅｒｔ－ブチルなどのアセト酢酸エステル類；プロピオニル酢酸エチル、プロピオニル酢酸エチル、プロピオニル酢酸イソプロピル、プロピオニル酢酸ｔｅｒｔ－ブチルなどのプロピオニル酢酸エステル類；イソブチリル酢酸エチル、イソブチリル酢酸エチル、イソブチリル酢酸イソプロピル、イソブチリル酢酸ｔｅｒｔ－ブチルなどの・BR>Cソブチリル酢酸エステル類；マロン酸メチル、マロン酸エチルなどのマロン酸エステル類；などが挙げられる。なかでも好適な化合物として、アセチルアセトンおよびアセト酢酸エステル類が挙げられる。かかるケト－エノール互変異性を生じる化合物（Ｆ）は、単独で使用してもよく、２種以上を組み合わせて使用してもよい。 As the compound (F) that produces the keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane- Β-diketones such as 3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate propionyl acetates such as tert-butyl; ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutyryl acetate; and BR> C sobutyryl acetates; malonic acid such as methyl malonate and ethyl malonate Ethers; and the like. Among these, acetylacetone and acetoacetic acid esters are preferable compounds. The compound (F) that produces such keto-enol tautomerism may be used alone or in combination of two or more.
　ケト－エノール互変異性を生じる化合物の使用量は、例えば有機金属化合物１重量部に対して０．０５重量部～１０重量部、好ましくは０．２重量部～３重量部（例えば０．３重量部～２重量部）とすることができる。上記化合物の使用量が有機金属化合物１重量部に対して０．０５重量部未満であると、十分な使用効果が発揮され難くなる場合がある。一方、該化合物の使用量が有機金属化合物１重量部に対して１０重量部を超えると、有機金属化合物に過剰に相互作用しすぎて目的とする耐水性を発現しにくくなる場合がある。 The amount of the compound that generates keto-enol tautomerism is, for example, 0.05 to 10 parts by weight, preferably 0.2 to 3 parts by weight (for example, 0.3 parts by weight) per 1 part by weight of the organometallic compound. Parts by weight to 2 parts by weight). If the amount of the compound used is less than 0.05 parts by weight relative to 1 part by weight of the organometallic compound, it may be difficult to achieve a sufficient use effect. On the other hand, when the amount of the compound used exceeds 10 parts by weight with respect to 1 part by weight of the organometallic compound, it may be difficult to express the desired water resistance due to excessive interaction with the organometallic compound.
　＜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組成物には、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、エポキシ樹脂、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。 <Additives other than the above>
Moreover, various additives can be mix | blended with the curable adhesive composition 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 epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Plasticizers; 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.
　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.
　＜接着剤組成物の粘度＞
　本発明の偏光フィルム用硬化型接着剤組成物は、前記硬化性成分を含有するが、当該接着剤組成物の粘度は、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組成物が２５℃において１００ｃｐを超える場合には、塗工時に接着剤組成物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 composition>
Although the curable adhesive composition for polarizing films of the present invention contains the curable component, the viscosity of the adhesive composition is preferably 100 cp or less at 25 ° C. from the viewpoint of coatability. On the other hand, when the curable adhesive composition for polarizing film of the present invention exceeds 100 cp at 25 ° C., the temperature of the adhesive composition 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組成物は、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。 In addition, the curable adhesive composition for polarizing film 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.
　＜バルク吸水率＞
　本発明の偏光フィルム用硬化型接着剤組成物は、当該硬化型接着剤組成物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％以下であることが好ましい。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、最も好ましくは１重量％以下であるのが好ましい。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、当該硬化型接着剤組成物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、当該硬化型接着剤組成物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 composition for polarizing film of the present invention is the above-described bulk water absorption measured when a cured product obtained by curing the curable adhesive composition is immersed in pure water at 23 ° C. for 24 hours. The rate is preferably 10% by weight 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 the degree of polarization 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. Most preferably, it is 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, and when the curable adhesive composition and moisture contained in the polarizer come into contact with each other, Such as appearance defects may occur. In order to suppress poor appearance, it is preferable that the curable adhesive composition 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.
　＜硬化収縮率＞
　また、本発明の偏光フィルム用硬化型接着剤組成物は、硬化性成分を有することから、当該硬化型接着剤組成物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組成物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組成物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組成物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 composition for polarizing films of the present invention has a curable component, curing shrinkage usually occurs when the curable adhesive composition is cured. The cure shrinkage rate is an index indicating the rate of cure shrinkage when an adhesive layer is formed from the curable adhesive composition for polarizing film. When the cure shrinkage rate of the adhesive layer is increased, it is preferable to suppress the occurrence of poor adhesion due to interface distortion when the polarizing film curable adhesive composition is cured to form the adhesive layer. From the above viewpoint, it is preferable that the curing shrinkage rate of the cured product obtained by curing the curable adhesive composition 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, specifically, measured by a method using a cure shrinkage sensor manufactured by Centec.
　＜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組成物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％以下であることが好ましい。 <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 curable adhesive composition for polarizing film. As described above, the adhesive layer that is the cured product layer preferably has a bulk water absorption of 10% by weight or less.
　＜接着剤層＞
　上記硬化型接着剤組成物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 from the curable adhesive composition 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、硬化型接着剤組成物は、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。 The curable adhesive composition 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. As described above, 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、硬化型接着剤組成物は、これにより形成される接着剤層の貯蔵弾性率が２５℃で１．０×１０７Ｐａ以上であることが好ましく、１．０×１０８Ｐａ以上であることがより好ましい。なお、粘着剤層の貯蔵弾性率は１．０×１０３Ｐａ～１．０×１０６Ｐａであり、接着剤層の貯蔵弾性率とは異なる。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, in the curable adhesive composition, the storage elastic modulus of the adhesive layer formed thereby is preferably 1.0 × 10 7 Pa or more at 25 ° C., and 1.0 × 10 8 Pa or more. It is more preferable. The storage elastic modulus of the pressure-sensitive adhesive layer is 1.0 × 10 3 Pa to 1.0 × 10 6 Pa, which is different from the storage elastic modulus of the adhesive layer. 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.). If the storage elastic modulus is low, defects in the polarizer cracks occur. 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 the storage elastic modulus (E ′) was adopted.
　本発明に係る偏光フィルムは、下記製造方法；
　偏光子および透明保護フィルムの少なくとも一方の面に、偏光フィルム用硬化型接着剤組成物を塗工する塗工工程と、偏光子および透明保護フィルムを貼り合わせる貼合工程と、偏光子面側または透明保護フィルム面側から活性エネルギー線を照射して、活性エネルギー線硬化型接着剤組成物を硬化させることにより得られた接着剤層を介して、偏光子および透明保護フィルムを接着させる接着工程とを含む製造方法、により製造可能である。かかる製造方法において、貼合工程における偏光子の水分率が８～１９％であることが好ましい。 The polarizing film according to the present invention comprises the following production method:
A coating step of applying the curable adhesive composition for polarizing film to at least one surface of the polarizer and the transparent protective film, a bonding step of bonding the polarizer and the transparent protective film, and the polarizer surface side or An adhesion step of adhering the polarizer and the transparent protective film via the adhesive layer obtained by irradiating the active energy ray from the transparent protective film surface side and curing the active energy ray-curable adhesive composition; Can be manufactured by a manufacturing method including: In such a production method, the moisture content of the polarizer in the bonding step is preferably 8 to 19%.
　偏光子、透明保護フィルムは、上記硬化型接着剤組成物を塗工する前に、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 a surface modification treatment before applying the curable adhesive composition. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
　硬化型接着剤組成物の塗工方式は、組成物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 composition is appropriately selected depending on the viscosity of the composition 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組成物を介して、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 composition applied as described above. Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.
　＜接着剤組成物の硬化＞
　本発明に係る偏光フィルム用硬化型接着剤組成物は、活性エネルギー線硬化型接着剤組成物として用いられる。活性エネルギー線硬化型接着剤組成物では、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。前記硬化型接着剤組成物の態様は生産性の観点から、可視光線硬化型接着剤組成物が好ましい。 <Curing of the adhesive composition>
The curable adhesive composition for polarizing films according to the present invention is used as an active energy ray-curable adhesive composition. The active energy ray curable adhesive composition can be used in an electron beam curable type, an ultraviolet ray curable type, or a visible ray curable type. The embodiment of the curable adhesive composition is preferably a visible light curable adhesive composition 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組成物では、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組成物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 composition, after bonding the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated to obtain the active energy ray-curable adhesive composition. Cure 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.).
　≪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組成物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 electron beam irradiation condition as long as the active energy ray curable adhesive composition can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and 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組成物に到達せず、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 composition 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 bulb, 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組成物を加温すること（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組成物を加温すること（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 warm the active energy ray curable adhesive composition (pre-irradiation warming) before irradiating the ultraviolet ray or visible light. It is preferable to heat it to 50 ° C. or higher. It is also preferable to heat the active energy ray-curable adhesive composition 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 to 50 ° C. or higher. It is more preferable to warm.
　本発明に係る活性エネルギー線硬化型接着剤組成物は、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組成物は、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 composition according to the present invention can be suitably used particularly when forming an adhesive layer that bonds a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. It is. Here, the active energy ray-curable adhesive composition 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. Thus, the adhesive layer can be cured and formed. 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組成物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 composition 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.).
　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、接着剤組成物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、接着剤組成物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 composition, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m / 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. If the line speed is too high, the adhesive composition may not be 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組成物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, a polarizer and a transparent protective film are bonded together via an adhesive layer formed by a cured product layer of the active energy ray-curable adhesive composition. An easily adhesive layer can be provided between the adhesive layer and the adhesive layer. 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組成物は、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。したがって、上記１０μｍ以下の偏光子を、金属アルコキシドおよび金属キレートからなる群より選択される少なくとも１種の有機金属化合物を含有する、本発明に係る偏光フィルム用硬化型接着剤組成物の硬化物からなる接着剤層、さらにはバルク吸水率が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 composition of the present invention exhibits the effect (satisfying optical durability in a harsh environment under high temperature and high humidity) when a thin polarizer having a thickness of 10 μm or less is used as the polarizer. It can be remarkably 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. Therefore, from the cured product of the curable adhesive composition for a polarizing film according to the present invention, wherein the polarizer of 10 μm or less contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates. When the adhesive layer is further laminated with an adhesive layer having a bulk water absorption of 10% by weight or less, the movement of water to the polarizer is suppressed in a severe environment of high temperature and high humidity. Deterioration of optical durability such as increase in transmittance and decrease in polarization degree 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.
　＜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, and the like 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など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などのアミド系樹脂；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, 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, and 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２：厚み５２μｍのシクロオレフィンポリマーフィルム（透湿度１１ｇ／ｍ２／２４ｈ）を、コロナ処理を行い用いた（表１中で、ＣＯＰと表記する）。 <Transparent protective film>
Transparent protective film 1: Using subjected to corona treatment having a lactone ring structure having a thickness of 40 [mu] m (meth) acrylic resin (moisture permeability 96g / m 2 / 24h) (in Table 1, referred to as acrylic).
Transparent protective film 2: a cycloolefin polymer film with a thickness of 52 .mu.m (moisture permeability 11g / m 2 / 24h), was used performs corona treatment (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) .
＜貯蔵弾性率＞
　貯蔵弾性率は、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した。
　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、貯蔵弾性率の２５℃での測定値とした。 <Storage modulus>
The storage elastic modulus was measured using TA Instruments dynamic viscoelasticity measuring device RSAIII under the following measurement conditions.
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 the storage elastic modulus was measured at 25 ° C.
　＜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（Ｍ１）ｇ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（Ｍ２）ｇ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 100 μm spacer, cured under the same active energy conditions as in the examples, and a 100 μm thick adhesive layer (cured) Prepared). This was used as a sample. The weight of the sample was (M1) g. Sample M1g was immersed in pure water at 23 ° C. for 24 hours. Thereafter, the weight (M2) g 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.
　＜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 the active energy ray, visible light (gallium sealed metal halide lamp) irradiation apparatus: Fusion UV Systems, Inc, Inc. Light HAMMER10 Valve: V Valve peak irradiance: 1600 mW / cm @ 2, integrated dose 1000 / mJ / cm 2 (wavelength 380 ~ 440 nm )It was used. The illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
　実施例１～５および比較例１
　（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、さらにＫＡＹＡＣＵＲＥ－ＤＥＴＸ－Ｓ（２，４－ジエチルチオキサントン；日本化薬社製）、およびイルガキュア９０７（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；ＢＡＳＦ社製）をラジカル重合性化合物の合計１００ｇに対してそれぞれ１．５ｇおよび３ｇ添加して撹拌し、実施例１～５および比較例１に係る活性エネルギー線硬化型接着剤組成物を得た。 Examples 1 to 5 and Comparative Example 1
(Preparation of active energy ray-curable adhesive)
According to the recipe shown in Table 1, each component was mixed, and further KAYACURE-DETX-S (2,4-diethylthioxanthone; manufactured by Nippon Kayaku Co., Ltd.) and Irgacure 907 (2-methyl-1- (4-methylthio) 1.5 g and 3 g of phenyl) -2-morpholinopropan-1-one (manufactured by BASF) were added to 100 g of the radical polymerizable compound, respectively, and stirred. In Examples 1 to 5 and Comparative Example 1, Such an active energy ray-curable adhesive composition was obtained.
　（偏光フィルムの作製）
　上記透明保護フィルム上に、実施例１～５または比較例１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、活性エネルギー線照射装置により上記可視光線を両面に照射して実施例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 Examples 1 to 5 or Comparative Example 1 is coated with an MCD coater (manufactured by Fuji Machine) (cell shape: honeycomb, number of gravure roll wires: 1000 / inch). , Rotation speed 140% / vs. Line speed) was applied so as to have a thickness of 0.7 μm, and was bonded to both sides of the polarizer X by a roll machine. Thereafter, from the bonded transparent protective film side (both sides), the active energy ray curable adhesive according to Example 1 and Comparative Example 1 is cured by irradiating the visible light on both sides with an active energy ray irradiation device. And dried 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.
　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。 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.
＜水浸漬後の接着力（耐水性評価）＞
　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１５ｍｍの大きさに切り出し、かかる偏光フィルムを２３℃の水に１８時間浸漬させた後、取り出して３０分以内に（非乾燥状態で）偏光フィルムをガラス板に貼り合わせた。そして透明保護フィルム（アクリルまたはＣＯＰ）と偏光子との間にカッターナイフで切り込みを入れ、テンシロンにより、９０度方向に保護フィルムと偏光子とを剥離速度１０００ｍｍ／ｍｉｎで剥離し、その剥離強度（Ｎ／１５ｍｍ）を測定した。剥離強度が０．５Ｎ／１５ｍｍ以上である場合を○、０．５Ｎ／１５ｍｍ未満である場合を×とした。 <Adhesive strength after water immersion (water resistance evaluation)>
The polarizing film is cut into a size of 200 mm parallel to the stretching direction of the polarizer and 15 mm in the orthogonal direction. The polarizing film is immersed in water at 23 ° C. for 18 hours, and then taken out within 30 minutes (in a non-dried state) ) A polarizing film was bonded to a glass plate. Then, a slit is cut between the transparent protective film (acrylic or COP) and the polarizer with a cutter knife, and the protective film and the polarizer are peeled off at a peeling rate of 1000 mm / min with a tensilon in a 90-degree direction. N / 15 mm). A case where the peel strength was 0.5 N / 15 mm or more was evaluated as ◯, and a case where the peel strength was less than 0.5 N / 15 mm was evaluated as x.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１中、ラジカル重合性単量体は、
　ＨＥＡＡ：ヒドロキシエチルアクリルアミド、興人社製；
　４ＨＢＡ；４－ヒドロキシブチルアクリレート、大阪有機化学社製；
　ＡＣＭＯ：アクリロイルモルホリン、興人社製；
　ＴＰＧＤＡ：トリプロピレングリコールジアクリレート、東亞合成社製（アロニックスＭ－２２０）、
　１、９－ＮＤＡ：１、９ノナジアクリレート、共栄社化学社製；
を示し、
　酸無水物基およびアルコキシシラン基を有する化合物は、
　Ｘ－１２－９６７Ｃ：３－トリメトキシシリルプロピルコハク酸無水物、信越シリコーン社製；
　エポキシ基含有化合物は、
　４ＨＢＡＧＥ：４ヒドロキシブチルアクリレートグリシジルエーテル、信越シリコーン社製；
を示し、
　金属アルコキシドは、
　Ｄ－２０：チタンブトキシド（有機基の炭素数４）、信越シリコーン社製；
を示し、
　ビニルエーテル化合物は、
　ＶＥＥＡ：アクリル酸２－（２－ビニロキシエトキシ）エチル、日本触媒社製、を示し、
　光酸発生剤は、
　ＣＰＩ－１００Ｐ、サンアプロ社製；
を示す。 In Table 1, the radical polymerizable monomer is
HEAA: hydroxyethyl acrylamide, manufactured by Kojinsha;
4HBA; 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemicals;
ACMO: acryloylmorpholine, manufactured by Kojinsha;
TPGDA: Tripropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. (Aronix M-220),
1,9-NDA: 1,9 nonadiacrylate, manufactured by Kyoeisha Chemical;
Indicate
The compound having an acid anhydride group and an alkoxysilane group is
X-12-967C: 3-trimethoxysilylpropyl succinic anhydride, manufactured by Shin-Etsu Silicone;
The epoxy group-containing compound is
4HBAGE: 4-hydroxybutyl acrylate glycidyl ether, manufactured by Shin-Etsu Silicone;
Indicate
Metal alkoxide is
D-20: Titanium butoxide (carbon number of organic group: 4), manufactured by Shin-Etsu Silicone;
Indicate
Vinyl ether compounds
VEEA: 2- (2-vinyloxyethoxy) ethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.
The photoacid generator is
CPI-100P, manufactured by Sun Apro Corporation;
Indicates.

Claims (22)

  1. 　偏光子の少なくとも一方の面に、透明保護フィルムを接着させるための偏光フィルム用硬化型接着剤組成物であって、
    　酸無水物基およびアルコキシシラン基を有する化合物、ならびに活性エネルギー線硬化性成分を含有することを特徴とする偏光フィルム用硬化型接着剤組成物。     A polarizing film curable adhesive composition for adhering a transparent protective film to at least one surface of a polarizer,
    A curable adhesive composition for a polarizing film, comprising a compound having an acid anhydride group and an alkoxysilane group, and an active energy ray-curable component.
  2. 　さらに、エポキシ基を有する化合物を含有する請求項１記載の偏光フィルム用硬化型接着剤組成物。 Furthermore, the curable adhesive composition for polarizing films according to claim 1, further comprising a compound having an epoxy group.
  3. 　さらに、金属アルコキシドおよび金属キレートからなる群より選択される少なくとも１種の有機金属化合物を含有する請求項１または２記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to claim 1 or 2, further comprising at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates.
  4. 　前記有機金属化合物の金属がチタンである請求項３記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to claim 3, wherein the metal of the organometallic compound is titanium.
  5. 　前記有機金属化合物として前記金属アルコキシドを含有し、前記金属アルコキシドが有する有機基の炭素数が４以上である請求項３または４記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to claim 3 or 4, wherein the metal alkoxide is contained as the organometallic compound, and the organic group of the metal alkoxide has 4 or more carbon atoms.
  6. 　前記有機金属化合物として前記金属キレートを含有し、前記金属キレートが有する有機基の炭素数が４以上である請求項３または４記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to claim 3 or 4, wherein the metal chelate is contained as the organometallic compound, and the organic group of the metal chelate has 4 or more carbon atoms.
  7. 　前記活性エネルギー線硬化性成分の全量を１００重量部としたとき、前記有機金属化合物の割合が０．０５～９重量部である請求項３～６のいずれか記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive for a polarizing film according to any one of claims 3 to 6, wherein the ratio of the organometallic compound is 0.05 to 9 parts by weight when the total amount of the active energy ray-curable component is 100 parts by weight. Composition.
  8. 　硬化型接着剤組成物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、
    　式：｛（Ｍ２－Ｍ１）／Ｍ１｝×１００（％）、
    　但し、Ｍ１：浸漬前の硬化物の重量、Ｍ２：浸漬後の硬化物の重量、
    　で表わされるバルク吸水率が１０重量％以下である請求項１～７のいずれか記載の偏光フィルム用硬化型接着剤組成物。     When the cured product obtained by curing the curable adhesive composition is immersed in pure water at 23 ° C. for 24 hours,
    Formula: {(M2-M1) / M1} × 100 (%),
    However, M1: Weight of cured product before immersion, M2: Weight of cured product after immersion,
    The curable adhesive composition for a polarizing film according to any one of claims 1 to 7, wherein the bulk water absorption represented by the formula is 10 wt% or less.
  9. 　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請求項１～８のいずれか記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to any one of claims 1 to 8, wherein the active energy ray-curable component contains a radical polymerizable compound.
  10. 　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請求項９記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to claim 9, wherein the radical polymerizable compound contains a (meth) acrylamide derivative.
  11. 　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請求項９または１０記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to claim 9 or 10, wherein the radical polymerizable compound contains a polyfunctional compound having at least two functional groups having radical polymerizable properties.
  12. 　さらに、光重合開始剤を含有する請求項１～１１のいずれかに記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to any one of claims 1 to 11, further comprising a photopolymerization initiator.
  13. 　さらに、ビニルエーテル基を有する化合物を含有する請求項１～１２いずれかに記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to any one of claims 1 to 12, further comprising a compound having a vinyl ether group.
  14. 　さらに、光酸発生剤を含有する請求項１～１３のいずれかに記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive composition for a polarizing film according to any one of claims 1 to 13, further comprising a photoacid generator.
  15. 　硬化型接着剤組成物を硬化させて得られる硬化物の、２５℃における貯蔵弾性率が１．０×１０７Ｐａ以上である請求項１～１４のいずれか記載の偏光フィルム用硬化型接着剤組成物。 The curable adhesive for polarizing films according to any one of claims 1 to 14, wherein a cured product obtained by curing the curable adhesive composition has a storage elastic modulus at 25 ° C of 1.0 × 10 7 Pa or more. Composition.
  16. 　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１～１５のいずれかに記載の偏光フィルム用硬化型接着剤組成物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 the curable adhesive composition for a polarizing film according to any one of claims 1 to 15.
  17. 　前記接着剤層の厚みが０．１～３μｍであることを特徴とする請求項１６記載の偏光フィルム。 The polarizing film according to claim 16, wherein the adhesive layer has a thickness of 0.1 to 3 µm.
  18. 　前記接着剤層は、２３℃の純水に２４時間浸漬した場合に、
    　式：｛（Ｍ２－Ｍ１）／Ｍ１｝×１００（％）、
    　但し、Ｍ１：浸漬前の硬化物の重量、Ｍ２：浸漬後の硬化物の重量、
    　で表わされるバルク吸水率が１０重量％以下である請求項１６または１７記載の偏光フィルム。     When the adhesive layer is immersed in pure water at 23 ° C. for 24 hours,
    Formula: {(M2-M1) / M1} × 100 (%),
    However, M1: Weight of cured product before immersion, M2: Weight of cured product after immersion,
    The polarizing film of Claim 16 or 17 whose bulk water absorption represented by these is 10 weight% or less.
  19. 　前記接着剤層は、２５℃における貯蔵弾性率が１．０×１０７Ｐａ以上である請求項１６～１８のいずれかに記載の偏光フィルム。 The polarizing film according to claim 16, wherein the adhesive layer has a storage elastic modulus at 25 ° C. of 1.0 × 10 7 Pa or more.
  20. 　請求項１６～１９いずれかに記載の偏光フィルムの製造方法であって、
    　前記偏光子および前記透明保護フィルムの少なくとも一方の面に、前記偏光フィルム用硬化型接着剤組成物を塗工する塗工工程と、
    　前記偏光子および前記透明保護フィルムを貼り合わせる貼合工程と、
    　前記偏光子面側または前記透明保護フィルム面側から活性エネルギー線を照射して、前記活性エネルギー線硬化型接着剤組成物を硬化させることにより得られた前記接着剤層を介して、前記偏光子および前記透明保護フィルムを接着させる接着工程とを含むことを特徴とする偏光フィルムの製造方法。     A method for producing a polarizing film according to any one of claims 16 to 19,
    A coating step of coating the polarizing film curable adhesive composition on at least one surface of the polarizer and the transparent protective film;
    A bonding step of bonding the polarizer and the transparent protective film;
    The polarizer is obtained via the adhesive layer obtained by irradiating active energy rays from the polarizer surface side or the transparent protective film surface side to cure the active energy ray-curable adhesive composition. And a bonding step for bonding the transparent protective film.
  21. 　請求項１６～１９いずれかに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。 20. An optical film, wherein at least one polarizing film according to claim 16 is laminated.
  22. 　請求項１６～１９いずれかに記載の偏光フィルム、または請求項２１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 comprising the polarizing film according to any one of claims 16 to 19 or the optical film according to claim 21.
PCT/JP2016/067977 2015-07-13 2016-06-16 Curable adhesive composition for polarizing film, polarizing film, manufacturing method for said polarizing film, optical film, and image display device WO2017010224A1 (en)

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