WO2016152564A1 - Composition adhésive durcissable pour films polarisants, film polarisant et procédé de production associé, film optique, et dispositif d'affichage d'image - Google Patents

Composition adhésive durcissable pour films polarisants, film polarisant et procédé de production associé, film optique, et dispositif d'affichage d'image Download PDF

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Publication number
WO2016152564A1
WO2016152564A1 PCT/JP2016/057650 JP2016057650W WO2016152564A1 WO 2016152564 A1 WO2016152564 A1 WO 2016152564A1 JP 2016057650 W JP2016057650 W JP 2016057650W WO 2016152564 A1 WO2016152564 A1 WO 2016152564A1
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Prior art keywords
polarizing film
meth
adhesive composition
curable adhesive
acrylate
Prior art date
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PCT/JP2016/057650
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English (en)
Japanese (ja)
Inventor
昌之 岡本
武士 斉藤
康彰 岡田
美紀 岡本
池田　哲朗
菅野　亮
Original Assignee
日東電工株式会社
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Priority claimed from JP2015196948A external-priority patent/JP6712846B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201680018238.4A priority Critical patent/CN107430237B/zh
Priority to KR1020177029378A priority patent/KR102425611B1/ko
Publication of WO2016152564A1 publication Critical patent/WO2016152564A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a polarizing film curable adhesive 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 present invention relates to a curable adhesive composition for a polarizing film comprising an active energy ray-curable component and 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 contained as the organometallic compound, and the organic alkoxide has preferably 6 or more carbon atoms, and the organometallic compound includes 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 is reduced. 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 at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates.
  • 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 Will improve dramatically.
  • 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 polarizing film curable adhesive composition according to the present invention 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 composition may contain a polymerizable compound having a polymerizable functional group and a carboxyl group together with the organometallic compound.
  • the polymerizable compound having a polymerizable functional group and a carboxyl group has a polymerizable functional group and a carboxyl group.
  • the polymerizable functional group and the carboxyl group contained may be either one or two or more.
  • the polymerizable functional group is not particularly limited, and examples thereof include a carbon-carbon double bond-containing group, an epoxy group, an oxetanyl group, and a vinyl ether group.
  • the polymerizable functional group in particular, the following general formula (I): H 2 C ⁇ C (R 1 ) —COO— (I) (Wherein R 1 represents hydrogen or an organic group having 1 to 20 carbon atoms), or the following formula (II): H 2 C ⁇ C (R 2 ) —R 3 — (II) Wherein R 1 represents hydrogen or an organic group having 1 to 20 carbon atoms, and R 3 represents a direct bond or an organic group having 1 to 20 carbon atoms.
  • a radically polymerizable functional group in which 1 or R 2 is hydrogen or a methyl group is particularly preferable.
  • the bonding position of the carboxyl group in the polymerizable compound having a polymerizable functional group and a carboxyl group is not particularly limited, but from the viewpoint of improving the liquid stability of the organometallic compound in the composition, the radical polymerizable functional group and A radical polymerizable compound in which a radical polymerizable functional group is bonded to a carboxyl group via an organic group having 1 to 20 carbon atoms which may contain oxygen is preferable to (meth) acrylic acid to which a carboxyl group is directly bonded.
  • the molecular weight of the polymerizable compound having a polymerizable functional group and a carboxyl group is large, and when bonded and / or coordinated to the organometallic compound, the bulk is high. It is preferable that it is sterically hindered when other ligands are coordinated. Therefore, the molecular weight of the polymerizable compound having a polymerizable functional group and a carboxyl group is preferably 100 (g / mol) or more, more preferably 125 (g / mol) or more, and 150 (g / mol). The above is particularly preferable.
  • the upper limit of the molecular weight of the polymerizable compound having a polymerizable functional group and a carboxyl group is not particularly limited, but about 300 (g / mol) can be exemplified.
  • the polymerizable compound having a polymerizable functional group and a carboxyl group is bonded via an organic group having 1 to 20 carbon atoms which may contain oxygen.
  • a polymerizable compound having a polymerizable functional group and a carboxyl group is preferred.
  • organic groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, alicyclic groups, unsaturated alicyclic groups, alkyl ester groups, aromatic ester groups, acyl groups, hydroxyalkyl groups, alkylene oxides.
  • the polymerizable compound (B) include, for example, ⁇ -carboxyethyl acrylate, carboxypentyl acrylate, ⁇ -carboxyethyl methacrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2- Acryloyloxyethylphthalic acid, ⁇ -carboxy-polycaprolactone monoacrylate, 2-acryloyloxyethyltetrahydrophthalic acid, 2-acryloyloxypropyloxyphthalic acid, 2-acryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylhexahydrophthal Acid, methacryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid,
  • the polymerizable functional group and carboxyl group are The content of the polymerizable compound is preferably 0.25 ⁇ (mol) or more, more preferably 0.35 ⁇ (mol) or more, and particularly preferably 0.5 ⁇ (mol) or more.
  • the content of the polymerizable compound having a polymerizable functional group and a carboxyl group is less than 0.25 ⁇ (mol)
  • the stabilization of the organometallic compound becomes insufficient, the hydrolysis reaction and the self-condensation reaction proceed, and the pot life May become shorter.
  • the upper limit of the content of the polymerizable compound having a polymerizable functional group and a carboxyl group with respect to the total amount ⁇ (mol) of the organometallic compound is not particularly limited, but for example, about 4 ⁇ (mol) can be exemplified.
  • Organic metal compound-containing composition In the curable adhesive composition for polarizing film according to the present invention, when the polymerizable compound having a polymerizable functional group and a carboxyl group is used together with the organic metal compound, the active energy ray-curable component, the organic metal compound, and the polymerizable property are used.
  • An organometallic compound and an organometallic compound-containing composition containing a polymerizable compound having a polymerizable functional group and a carboxyl group may be obtained by simultaneously mixing a polymerizable compound having a functional group and a carboxyl group. It may be obtained by preparing a product in advance and mixing it with an active energy ray-curable component.
  • the carboxyl group of the polymerizable compound having a polymerizable functional group and a carboxyl group is strongly bonded to and / or coordinated with the metal of the organometallic compound, whereby an organic metal The compound is stabilized.
  • an organometallic compound and a polymerizable compound having a polymerizable functional group and a carboxyl group are mixed and reacted in the absence of an active energy ray-curable component, the reaction rate and / or coordination rate thereof.
  • the organometallic compound-containing composition obtained contains a reaction product and / or coordination product of an organometallic compound and a polymerizable compound having a polymerizable functional group and a carboxyl group at a high concentration. Become. Therefore, the obtained organometallic compound-containing composition has extremely high stability of the organometallic compound, and the curable adhesive composition for polarizing film including the same also has high stability of organometallic stability.
  • 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
  • Monofunctional radically polymerizable compounds include (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, ⁇ -carboxyethyl acrylate, carboxypentyl acrylate, ⁇ -carboxyethyl methacrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, ⁇ -carboxy-polycaprolactone monoacrylate, 2-acryloyloxyethyltetrahydrophthalic acid 2-acryloyloxypropyloxyphthalic acid, 2-acryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylhexahydrophthalic acid, Tacryloyloxyethyl succinic 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. The 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.
  • valerolactone-modified products 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
  • 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 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; isobutyryl acetates such as ethyl isobutyryl
  • 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) with respect to 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.
  • 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 lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight
  • a light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter.
  • a gallium-encapsulated metal halide lamp can be used and light with a wavelength shorter than 380 nm can be blocked. It is preferable to use an active energy ray obtained through a band pass filter or an active energy ray having a wavelength of 405 nm obtained using an LED light source.
  • the 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.
  • 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.
  • 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 / 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 triacetyl cellulose film having a thickness of 60 ⁇ m (the moisture permeability 530g / m 2 / 24h), used without such saponification, corona treatment (in Table 1, referred to as TAC).
  • Transparent protective film 2 100 parts by weight of the imidized MS resin described in Preparation Example 1 of JP 2010-284840 A and 0.62 parts by weight of a triazine-based ultraviolet absorber (trade name: T-712, manufactured by Adeka) The mixture was mixed at 220 ° C. with a biaxial kneader to produce resin pellets. The obtained resin pellets were dried at 100.5 kPa and 100 ° C.
  • a film for 12 hours, extruded from a T-die at a die temperature of 270 ° C. with a single screw extruder, and formed into a film (thickness: 160 ⁇ m). Further, the film is stretched in the conveyance direction in a 150 ° C. atmosphere (thickness 80 ⁇ m), and after applying an easy-adhesive containing an aqueous urethane resin, the film is stretched in a direction perpendicular to the film conveyance direction in a 150 ° C. atmosphere. to obtain a transparent protective film 2 having a thickness of 40 [mu] m (moisture permeability 58g / m 2 / 24h) (in Table 1, referred to as acrylic).
  • 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: Pull, frequency: 1 Hz, temperature increase rate: 5 ° C./min The dynamic viscoelasticity was measured and the storage elastic modulus was measured at 25 ° C.
  • active energy rays As an active energy ray, visible light (gallium filled metal halide lamp) Irradiation device: Fusion UV Systems, Inc. Light HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm 2, integrated dose 1000 / mJ / cm 2 (wavelength 380 to 440 nm) )It was used. The illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
  • Examples 1 to 12 and Comparative Examples 1 to 3 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 a total of 100 g of radically polymerizable compounds, and the mixture was stirred.
  • KAYACURE-DETX-S 2,4-diethylthioxanthone; manufactured by Nippon Kayaku Co., Ltd.
  • Irgacure 907 2-methyl-1- (4-methylthio) 1.5 g and 3 g of phenyl) -2-morpholinopropan-1-one
  • the active energy ray-curable adhesives according to Examples 1 to 12 or Comparative Examples 1 to 3 were coated with an MCD coater (manufactured by Fuji Machine Co., Ltd.) (cell shape: honeycomb, number of gravure roll wires: 1000). / Inch, rotation speed 140% / vs. Line speed) was applied to a thickness of 0.7 ⁇ m, and was bonded to both sides of the polarizer X with 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 was 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 was immersed in water at 23 ° C. for 3 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 TAC) and the polarizer with a cutter knife, and the protective film and the polarizer are peeled off at a peeling rate of 300 mm / min in a 90-degree direction with Tensilon. N / 15 mm).
  • 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.
  • TC-750 Ethyl acetoacetate chelate (organic group carbon number 6), manufactured by Matsumoto Fine Chemical Co., Ltd .; TC-100: Titanium acetylacetonate (organic group carbon number 5), manufactured by Matsumoto Fine Chemical Co., Ltd .; TA-30: Titanium octoxide (carbon number of organic group: 8), manufactured by Matsumoto Fine Chemicals; D-20: Titanium butoxide (carbon number of organic group: 4), manufactured by Shin-Etsu Silicone; ZA-65: zirconium butoxide (4 carbon atoms of organic group) manufactured by Matsumoto Fine Chemical Co., Ltd .; Aluminum chelate M: alkyl acetoacetate diisopropylate (having 4 or more organic carbon atoms), manufactured by Kawaken Fine Chemicals;
  • Examples 13-15 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), respectively, with respect to a total of 100 g of the radical polymerizable compound and stirred, and the active energy rays according to Examples 13 to 15 A curable adhesive composition was obtained.
  • the active energy ray-curable adhesive according to Examples 13 to 15 was coated with an MCD coater (manufactured by Fuji Machine Co., Ltd.) (cell shape: honeycomb, number of gravure roll wires: 1000 / inch, rotation speed: 140). % / Line speed) was applied to a thickness of 0.7 ⁇ m, and both surfaces of the polarizer X were bonded 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.
  • the radical polymerizable monomer is HEAA: hydroxyethyl acrylamide, manufactured by Kojinsha; ACMO: acryloylmorpholine, manufactured by Kojinsha; 1,9-NDA: 1,9 nonadiacrylate, manufactured by Kyoeisha Chemical; M-5300: ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate (polymerizable compound having a polymerizable functional group and a carboxyl group), manufactured by Toagosei Co., Ltd .; Metal alkoxide and metal chelate are TA-21: Titanium butoxide (4 carbon atoms of organic group), manufactured by Matsumoto Fine Chemical Co., Ltd .; TC-750: Ethyl acetoacetate chelate (organic group carbon number 6), manufactured by Matsumoto Fine Chemical Co., Ltd .; TC-100: Titanium acetylacetonate (organic group carbon number 5), manufactured by Matsumoto Fine Chemical Co.
  • ⁇ Adhesive strength after water immersion (water resistance evaluation)> The polarizing film was 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 was immersed in water at 23 ° C. for 3 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 TAC) and the polarizer with a cutter knife, and the protective film and the polarizer are peeled off at a peeling rate of 300 mm / min in a 90-degree direction with Tensilon. N / 15 mm).

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  • Adhesives Or Adhesive Processes (AREA)

Abstract

Une composition adhésive durcissable pour films polarisants, utilisée pour coller un film de protection transparent sur au moins une surface d'un polariseur, est caractérisée en ce qu'elle contient un composant durcissable par rayonnement d'énergie active et au moins un composé métallique organique qui est sélectionné dans le groupe comprenant des alcoxydes métalliques et des chélates métalliques. Il est préférable que le métal du composé métallique organique soit du titane. Il est également préférable qu'un alcoxyde métallique soit contenu en tant que composé métallique organique et que le groupe organique de l'alcoxyde métallique comprenne au moins 6 atomes de carbone. Il est également préférable qu'un chélate métallique soit contenu en tant que composé métallique organique et que le groupe organique du chélate métallique comprenne au moins 4 atomes de carbone.
PCT/JP2016/057650 2015-03-25 2016-03-10 Composition adhésive durcissable pour films polarisants, film polarisant et procédé de production associé, film optique, et dispositif d'affichage d'image WO2016152564A1 (fr)

Priority Applications (2)

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CN201680018238.4A CN107430237B (zh) 2015-03-25 2016-03-10 偏振膜用固化型粘接剂组合物、偏振膜及其制造方法、光学膜以及图像显示装置
KR1020177029378A KR102425611B1 (ko) 2015-03-25 2016-03-10 편광 필름용 경화형 접착제 조성물, 편광 필름 및 그 제조 방법, 광학 필름 그리고 화상 표시 장치

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JP2015-062983 2015-03-25
JP2015062983 2015-03-25
JP2015-196948 2015-10-02
JP2015196948A JP6712846B2 (ja) 2015-03-25 2015-10-02 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

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WO2017057615A1 (fr) * 2015-10-02 2017-04-06 日東電工株式会社 Composition adhésive de type durcissable pour film de polarisation et son procédé de fabrication, film de polarisation et son procédé de fabrication, film optique et dispositif d'affichage d'image

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WO2010047386A1 (fr) * 2008-10-24 2010-04-29 チェイル インダストリーズ インコーポレイテッド Composition adhésive et élément optique
WO2015022825A1 (fr) * 2013-08-12 2015-02-19 日本合成化学工業株式会社 Composition d'agent adhésif, composition d'agent adhésif pour lame polarisante, agent adhésif pour lame polarisante et lame polarisante fabriquée par utilisation dudit agent adhésif
WO2015030203A1 (fr) * 2013-08-30 2015-03-05 日東電工株式会社 Adhésif durcissable pour films polarisants, film polarisant, film optique et dispositif d'affichage d'images
JP2015151425A (ja) * 2014-02-12 2015-08-24 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性樹脂組成物及び積層体
JP2015151424A (ja) * 2014-02-12 2015-08-24 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性樹脂組成物及び積層体
WO2016010031A1 (fr) * 2014-07-16 2016-01-21 日東電工株式会社 Film polarisant et son procédé de fabrication

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WO2010047386A1 (fr) * 2008-10-24 2010-04-29 チェイル インダストリーズ インコーポレイテッド Composition adhésive et élément optique
WO2015022825A1 (fr) * 2013-08-12 2015-02-19 日本合成化学工業株式会社 Composition d'agent adhésif, composition d'agent adhésif pour lame polarisante, agent adhésif pour lame polarisante et lame polarisante fabriquée par utilisation dudit agent adhésif
WO2015030203A1 (fr) * 2013-08-30 2015-03-05 日東電工株式会社 Adhésif durcissable pour films polarisants, film polarisant, film optique et dispositif d'affichage d'images
JP2015151425A (ja) * 2014-02-12 2015-08-24 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性樹脂組成物及び積層体
JP2015151424A (ja) * 2014-02-12 2015-08-24 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性樹脂組成物及び積層体
WO2016010031A1 (fr) * 2014-07-16 2016-01-21 日東電工株式会社 Film polarisant et son procédé de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017057615A1 (fr) * 2015-10-02 2017-04-06 日東電工株式会社 Composition adhésive de type durcissable pour film de polarisation et son procédé de fabrication, film de polarisation et son procédé de fabrication, film optique et dispositif d'affichage d'image

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