TW201841028A - Liquid crystal panel and image display device - Google Patents

Abstract

The purpose of the present invention is to provide a liquid crystal panel that includes a liquid crystal cell having a transparent conductive layer on one surface, enables improvement in the durability of the entire liquid crystal pane, and further enables suppression of panel warpage and light leakage. Another purpose of the present invention is to provide an image display device that uses the liquid crystal panel. A liquid crystal panel in which a transparent conductive layer is formed on one surface of a liquid crystal cell, a first polarizing film is bonded onto the transparent conductive layer with a first adhesive layer formed from an adhesive composition (A1) therebetween, and a second polarizing film is bonded to the other surface of the liquid crystal cell with a second adhesive layer formed from an adhesive composition (A2) therebetween, the liquid crystal panel being characterized in that the adhesive composition (A1) contains a (meth)acrylic polymer (a1) and a silane coupling agent containing an epoxy group, the adhesive composition (A2) contains a (meth)acrylic polymer (a2) and a silane coupling agent containing a thiol group, and the gel fractions of the first adhesive layer and the second adhesive layer are 65-90% inclusive, and satisfy the following formula (1).

Description

Liquid crystal panel and image display device

The invention relates to a liquid crystal panel and an image display device using the liquid crystal panel.

A liquid crystal panel used in a liquid crystal display device or the like is usually laminated with a polarizing film on both sides of a liquid crystal cell formed by a liquid crystal layer disposed between a pair of transparent substrates via an adhesive layer. The adhesive layer is required to have high durability. For example, in the durability test using heating and humidification, which is usually performed as an environmental acceleration test, it is required that no defects such as peeling or bulging caused by the adhesive layer occur. . The industry has conducted various studies on such adhesive compositions for optical applications. For example, it is proposed that the adhesive composition does not produce peeling or foaming even when it is placed under high humidity and heat conditions after being bonded to an optical film (for example, refer to a patent). Reference 1). [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2009-242767

[Problems to be Solved by the Invention] It is known that a transparent conductive film such as an indium tin oxide (ITO) film is formed on a transparent substrate constituting one side of a liquid crystal cell of a liquid crystal panel, and an adhesive agent is connected to the transparent conductive film. Compared with an adhesive layer which is in contact with a transparent substrate such as a glass substrate, the layer tends to be easily peeled off or raised, and tends to have lower durability. The adhesive layer formed by the adhesive composition of Patent Document 1 has poor adhesion to an indium tin oxide (ITO) layer, and is not sufficient as an adhesive composition for a liquid crystal panel having a transparent conductive layer. As described above, in most cases, a transparent conductive film such as an ITO film is formed on a transparent substrate on one side of the liquid crystal cell, and a transparent substrate such as a glass substrate is on the other side. The properties of the two sides of the liquid crystal cell are different. On both sides of such a liquid crystal cell, there is a problem that it is difficult to maintain the durability without foaming or peeling, and it is difficult to maintain the durability of the entire liquid crystal panel. Patent Document 1 does not specify any relationship with an adherend such as a liquid crystal cell, and is insufficient from the viewpoint of durability of the entire liquid crystal panel. In recent years, the thickness of a liquid crystal panel has been required. However, if the thickness of a liquid crystal panel is reduced, the panel may be warped. If the warpage of the panel becomes large, the display image becomes uneven due to the contact between the liquid crystal panel and the housing of the display, or the defects such as peeling of the double-sided adhesive tape that fixes the liquid crystal panel and the backlight device occur. Furthermore, the technology of making the area around the peripheral portion of the liquid crystal display device narrower and increasing the area ratio (narrow edge) of the display area in the display device has been continuously developed. However, due to the width of the light-shielded peripheral portion outside the display area, It is relatively narrow, so that the end of the polarizing film may enter the display area due to the shrinkage of the polarizing film, and light leakage may occur in the peripheral portion of the display area. In this way, in recent years, the thinner and narrower edge of the liquid crystal panel has been continuously developed, and the requirements for the warpage prevention or light leakage of the panel have been continuously improved. Therefore, an object of the present invention is to provide a liquid crystal panel which is included in a liquid crystal cell having a transparent conductive layer on one side, and which can improve the durability of the entire liquid crystal panel, and can further suppress panel warpage or light leakage. Another object of the present invention is to provide an image display device using the liquid crystal panel. [Technical Means for Solving the Problem] The inventors of the present invention made intensive studies in order to solve the above-mentioned problems, and as a result, discovered the following liquid crystal panel, and completed the present invention. That is, the present invention relates to a liquid crystal panel, which is characterized in that a transparent conductive layer is formed on one surface of a liquid crystal cell, and a first adhesive layer formed of the adhesive composition (A1) is formed on the transparent conductive layer. A first polarizing film is bonded, and a second polarizing film is bonded to the other side of the liquid crystal cell via a second adhesive layer formed of an adhesive composition (A2), and the adhesive composition (A1) contains (Meth) acrylic polymer (a1) and epoxy-containing silane coupling agent, and the adhesive composition (A2) contains (meth) acrylic polymer (a2) and thiol group-containing silane coupling agent The gel fraction of the first adhesive layer and the second adhesive layer is 65% or more and 90% or less, and further satisfies the following formula (1). [Number 1] (1) The epoxy group-containing silane coupling agent is preferably an oligomer-type epoxy group-containing silane coupling agent having two or more alkoxysilane groups in the molecule. The thiol group-containing silane coupling agent is preferably an oligomeric thiol group-containing silane coupling agent having two or more alkoxysilyl groups in the molecule. The blending amount of the epoxy group-containing silane coupling agent is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (a1). The blending amount of the thiol group-containing silane coupling agent is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (a2). The (meth) acrylic polymer (a1) and / or (a2) preferably contains a carboxyl group-containing monomer as a monomer unit in an amount of 0.01 to 2% by weight. It is preferable that the said (meth) acrylic-type polymer (a1) and / or (a2) contains the amine group containing monomer as a monomer unit from 0.1 to 8 weight%. The (meth) acrylic polymer (a1) and / or (a2) preferably contain a hydroxyl group-containing monomer as a monomer unit in an amount of 0.01 to 7% by weight. The adhesive composition (A1) and / or (A2) preferably contains at least one type of crosslinking agent selected from the group consisting of an isocyanate-based crosslinking agent and a peroxide-based crosslinking agent. The present invention also relates to an image display device using the liquid crystal panel. [Effects of the Invention] In the present invention, a first polarizing film is arranged on a transparent conductive layer on one surface of a liquid crystal cell via a first adhesive layer formed of a specific adhesive composition (A1), and is placed on the other side of the liquid crystal cell. The second polarizing film is arranged on one side through the second adhesive layer formed of the specific adhesive composition (A2), and the gel fraction of the first adhesive layer and the second adhesive layer is controlled, thereby improving the quality of the film. The durability of the entire liquid crystal panel can further suppress panel warpage or light leakage.

1. Liquid crystal panel The liquid crystal panel of the present invention is characterized in that: a transparent conductive layer is formed on one side of a liquid crystal cell, and the transparent conductive layer is pasted through a first adhesive layer formed from an adhesive composition (A1). A first polarizing film is combined, and a second polarizing film is bonded to the other side of the liquid crystal cell via a second adhesive layer formed of an adhesive composition (A2), and the adhesive composition (A1) contains ( (Meth) acrylic polymer (a1) and epoxy-containing silane coupling agent, the adhesive composition (A2) contains (meth) acrylic polymer (a2) and thiol group-containing silane coupling agent, The gel fraction of the first adhesive layer and the second adhesive layer is 65% to 90%, and further satisfies the following formula (1). [Number 2] (1) (1) Adhesive composition (A1) The adhesive composition (A1) used in the present invention contains a (meth) acrylic polymer (a1) and an epoxy-containing silane coupling agent, It is preferable to contain a (meth) acrylic-type polymer (a1) as a main component. Here, the main component refers to a component having the largest ratio of the total solid content components contained in the adhesive composition (A1), and for example, means that the total solid component contained in the adhesive composition (A1) occupies more than A component of 50% by weight, further refers to a component occupying more than 70% by weight. The (meth) acrylic polymer (a1) usually contains, as a main component, an alkyl (meth) acrylate as a monomer unit. In addition, (meth) acrylate means an acrylate and / or a methacrylate, and (meth) in this invention has the same meaning. Examples of the (meth) acrylic acid alkyl ester constituting the main skeleton of the (meth) acrylic polymer (a1) include a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, and isooctyl. , Nonyl, decyl, isodecyl, dodecyl, isomyristoyl, lauryl, tridecyl, pentadecyl, cetyl, heptadecyl, octadecyl and the like. These can be used individually or in combination. The average carbon number of these alkyl groups is preferably 3 to 9. As the monomer constituting the (meth) acrylic polymer (a1), in addition to the above-mentioned (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and a sulfonylamino group-containing monomer may be mentioned. Monomer, aromatic ring-containing (meth) acrylate, and the like. A carboxyl-containing monosystem is a compound containing a carboxyl group in its structure and a polymerizable unsaturated double bond such as a (meth) acrylfluorenyl group, a vinyl group, or the like. Specific examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, and butane Oxalic acid, butenoic acid, etc. Among the carboxyl group-containing monomers, acrylic acid is preferred from the viewpoints of copolymerizability, price, and adhesive properties. A compound containing a hydroxyl-containing single system containing a hydroxyl group in its structure and a polymerizable unsaturated double bond such as a (meth) acrylfluorenyl group, a vinyl group, or the like. Specific examples of the hydroxyl-containing monomer include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (methyl) ) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and other hydroxyalkyl (meth) acrylates Or (4-hydroxymethylcyclohexyl) methyl acrylate and the like. Among the above-mentioned hydroxyl-containing monomers, in terms of durability, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred, and 4-methacrylate (meth) acrylate is particularly preferred. Hydroxybutyl ester. Monoamine-containing monosystems are compounds in which the amine group is contained in the structure and the polymerizable unsaturated double bond such as a (meth) acrylic fluorene group or a vinyl group is contained. Specific examples of the sulfonylamino group-containing monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acryl Ammonium, N-isopropylacrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-hydroxyl Methyl (meth) acrylamide, N-hydroxymethyl-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide Acrylamide-based monomers such as mercaptomethyl (meth) acrylamide, mercaptoethyl (meth) acrylamide; N- (meth) acrylamine N-acrylic fluorenyl heterocyclic monomers such as phthaloline, N- (meth) acrylic piperidine, N- (meth) acrylic acyl pyrrolidine; N-vinyl pyrrolidone, N-vinyl-ε-hexane N-vinyl-containing lactamamine-based monomers such as lactam and the like. From the standpoint of satisfying durability, a monomer containing a fluorenylamine group is preferred, and among monomers containing a fluorenylamine group, in terms of satisfying durability to a transparent conductive layer, N-containing Vinyl lactamamine monomer. The aromatic ring-containing (meth) acrylate is a compound having an aromatic ring structure in its structure and containing a (meth) acrylfluorenyl group. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring. The aromatic ring-containing (meth) acrylate can satisfy durability (especially durability to a transparent conductive layer). Specific examples of the aromatic ring-containing (meth) acrylate include, for example, benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate, and (meth) Phenoxyethyl acrylate, phenoxypropyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, ethylene oxide modified (meth) acrylate nonylphenol, epoxy Ethane-modified (meth) acrylate cresol, phenol ethylene oxide-modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylate Benzyl rings such as oxybenzyl ester, chlorobenzyl (meth) acrylate, and styrene (meth) acrylate; hydroxyethylated β-naphthol acrylate, 2-naphthyl ethyl (meth) acrylate, Those with a naphthalene ring, such as 2-naphthyloxyethyl acrylate and 2- (4-methoxy-1-naphthyloxy) ethyl (meth) acrylate; biphenyl rings, such as biphenyl (meth) acrylate By. As the aromatic ring-containing (meth) acrylate, in terms of adhesive properties or durability, benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are more preferred, and (meth) ) Phenoxyethyl acrylate. When the above-mentioned carboxyl group-containing monomer, hydroxyl group-containing monomer, fluorenamine-group-containing monomer, and aromatic ring-containing (meth) acrylate are contained in the adhesive composition (A1), a crosslinking agent is used. Reaction point of the combination agent. In particular, carboxyl-containing monomers and hydroxyl-containing monomers are rich in reactivity with intermolecular cross-linking agents, and are therefore preferably used to improve the cohesiveness or heat resistance of the obtained adhesive layer. The (meth) acrylic polymer (a1) used in the present invention preferably contains each of the above-mentioned monomers as a monomer unit in the weight ratio of the total constituent monomers (100% by weight). The weight ratio of the said (meth) acrylic acid alkyl ester can be set as the remainder of monomers other than an (meth) acrylic acid alkyl ester, Specifically, it is preferable that it is 70 weight% or more. In terms of ensuring the adhesiveness, it is preferable to set the weight ratio of the alkyl (meth) acrylate within the above range. The weight ratio of the carboxyl group-containing monomer is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, still more preferably 0.05 to 1.5% by weight, and even more preferably 0.05 to 1% by weight. If the weight ratio of the carboxyl group-containing monomer is less than 0.01% by weight, there is a tendency that the durability cannot be satisfied. On the other hand, when it exceeds 2% by weight, the transparent conductive layer may be corroded, and the durability tends to be unsatisfactory, which is not preferable. The weight ratio of the hydroxyl-containing monomer is preferably 0.01 to 7% by weight, more preferably 0.01 to 5% by weight, still more preferably 0.1 to 3% by weight, and even more preferably 0.2 to 2% by weight. If the weight ratio of the hydroxyl-containing monomer is less than 0.01% by weight, there is a tendency that the crosslinking of the adhesive layer is insufficient, and durability or adhesion characteristics cannot be satisfied. On the other hand, when it exceeds 5 weight%, there exists a tendency which cannot satisfy durability. The weight ratio of the amine group-containing monomer is preferably 8% by weight or less, more preferably 0.1 to 8% by weight, still more preferably 0.3 to 5% by weight, still more preferably 0.3 to 4% by weight, and particularly preferably 0.7 to 2.5% by weight. If the weight ratio of the sulfonylamine group-containing monomer is less than 0.1% by weight, it tends to fail to satisfy the durability especially for the transparent conductive layer. On the other hand, if it exceeds 8% by weight, the durability tends to decrease, which is not preferable. The weight ratio of the aromatic ring-containing (meth) acrylate is preferably 25% by weight or less, more preferably 0 to 22% by weight, and still more preferably 0 to 18% by weight. When the weight ratio of the aromatic ring-containing (meth) acrylate exceeds 25% by weight, the durability tends to decrease. In the (meth) acrylic polymer (a1), it is not necessary to include other monomer units in addition to the above-mentioned monomer units, but in order to improve adhesion or heat resistance, it is possible to introduce a (meth) group by copolymerization. One or more comonomers of an unsaturated double bond-containing polymerizable functional group, such as an acrylic fluorenyl group or a vinyl group. Specific examples of such monomers include monomers containing anhydride groups such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; allylsulfonic acid, 2- (methyl) Sulfonyl group-containing monomers, such as acrylamine-2-methylpropanesulfonic acid, (meth) acrylamine propanesulfonic acid, and sulfopropyl (meth) acrylate; 2-hydroxyethylpropenylphosphonate And other phosphate-containing monomers. Moreover, as examples of monomers for the purpose of modification, amino (meth) acrylate aminoethyl, (meth) acrylate N, N-dimethylaminoethyl ester, and (meth) acrylic acid Alkyl alkyl (meth) acrylates such as tributylamino ethyl ester; alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Alkyl esters; N- (meth) acryloxymethylene succinimide or N- (meth) acrylfluorenyl-6-oxyhexamethylene succinimide, N- (methyl Group) Succinimide-based monomers such as propenyl-8-oxyoctamethylene succinimide; N-cyclohexylcis-butenedifluorenimide or N-isopropylcis-butenedifluorenimide Amines, N-lauryl cis-butene diamidine or N-phenylcis-butene diamidine, and other cis-butene diimide-based monomers; N-methyl Ikonimide, N-ethyl Ikonimide, N-butyl Ikonimide, N-octyl Ikonimide, N-2-ethylhexyl Ikonimide, N-Cyclohexyl Ikonimide, N-Lauryl Ikonimide and other Ikonimide-based monomers. Further, as the modified monomer, vinyl monomers such as vinyl acetate and vinyl propionate; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; glycidyl (meth) acrylate and the like (Meth) acrylates containing epoxy groups; polyethylene glycol (meth) acrylates, polypropylene glycol (meth) acrylates, methoxyethylene glycol (meth) acrylates, methoxy polypropylene glycols Glycol (meth) acrylates such as (meth) acrylates; tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, polysiloxane (meth) acrylate, or 2-methyl acrylate (Meth) acrylate monomers, such as oxyethyl ester. Further examples include isoprene, butadiene, isobutylene, vinyl ether, and the like. Furthermore, examples of copolymerizable monomers other than the above include silicon atom-containing silane-based monomers and the like. Examples of the silane-based monomer include 3-propenyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-propenyloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-propenyloxydecyltriethoxysilane, and the like. As comonomers, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and bisphenol can also be used. A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylic acid esters, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Polyfunctional monomers having two or more unsaturated double bonds of (meth) acrylfluorene and vinyl groups, such as esters; or backbone addition to polyester, epoxy resin, urethane, etc. Polyester (meth) acrylate, epoxy (meth) acrylate, etc., in which two or more unsaturated double bonds of (meth) acrylfluorenyl, vinyl, etc. are used as the functional group having the same monomer component, (Meth) acrylate urethane and the like. The ratio of the comonomer in the (meth) acrylic polymer (a1) is preferably the weight ratio of the total constituent monomers (100% by weight) of the (meth) acrylic polymer (a1). About 0 to 10% by weight, more preferably about 0 to 7% by weight, and even more preferably about 0 to 5% by weight. The (meth) acrylic polymer (a1) of the present invention is generally one having a weight average molecular weight of 1 to 2.5 million. Considering durability, especially heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. When the weight average molecular weight is less than 1 million, it is inferior in heat resistance. In addition, when the weight average molecular weight is more than 2.5 million, the adhesive tends to be hardened and peeling tends to occur. The weight average molecular weight (Mw) / number average molecular weight (Mn) representing the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, and even more preferably 1.8 to 5. When the molecular weight distribution (Mw / Mn) exceeds 10, it is not good in terms of durability. The weight average molecular weight and molecular weight distribution (Mw / Mn) were measured by GPC (gel permeation chromatography), and were obtained from values calculated by polystyrene conversion. The production of such a (meth) acrylic polymer (a1) can be appropriately selected from known production methods such as solution polymerization, block polymerization, emulsion polymerization, and various radical polymerizations. The obtained (meth) acrylic polymer (a1) may be any of a random copolymer, a block copolymer, and a graft copolymer. In the solution polymerization, as the polymerization solvent, for example, ethyl acetate, toluene, or the like can be used. As a specific example of solution polymerization, the reaction is performed by adding a polymerization initiator under an inert gas flow such as nitrogen, and the reaction is usually performed under reaction conditions of about 50 to 70 ° C. and about 5 to 30 hours. The polymerization initiator, chain transfer agent, emulsifier, and the like used for radical polymerization are not particularly limited, and may be appropriately selected and used. In addition, the weight average molecular weight of the (meth) acrylic polymer (a1) can be controlled by the amount of polymerization initiator, chain transfer agent used, and reaction conditions, and the appropriate amount of use can be adjusted according to the type of these . Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-fluorenylpropane) dihydrochloride, and 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'- Azobis (N, N'-dimethylmethylene isobutylamidine), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropaneamidine] hydrate (trade name : VA-057, azo-based initiators such as Wako Pure Chemical Industries, Ltd .; persulfates such as potassium persulfate and ammonium persulfate; bis (2-ethylhexyl) peroxydicarbonate, peroxidation Di (4-tert-butylcyclohexyl) dicarbonate, di-second butyl peroxydicarbonate, tertiary butyl peroxydecanoate, tertiary hexyl pivalate, terpentyl peroxide Tert-butyl acid, dilauryl peroxide, di-n-octyl peroxide, di (2-ethylhexanoic acid) 1,1,3,3-tetramethylbutyl ester, di (4-methyl peroxide) Benzamidine), benzophenazine peroxide, tert-butyl isobutyrate, 1,1-bis (third hexylperoxy) cyclohexane, tert-butyl hydrogen peroxide, peroxidation Peroxide-based initiators such as hydrogen; persulfates and Combination of sodium hydrogen sulphate, sodium peroxide composition of ascorbate so that a peroxide with a reducing agent a combination of the redox initiator and so forth; is not limited to these examples. The above polymerization initiators may be used alone or in combination of two or more, but the content as a whole is 100 parts by weight relative to the total amount of the monomer components, preferably about 0.005 to 1 part by weight, more preferably 0.02 ~ 0.5 parts by weight. Furthermore, in order to produce the (meth) acrylic polymer (a1) having the above-mentioned weight average molecular weight, for example, using 2,2'-azobisisobutyronitrile as a polymerization initiator, the amount of the polymerization initiator used is relative to The total amount of the monomer components is preferably about 0.06 to 0.2 parts by weight, and more preferably about 0.08 to 0.175 parts by weight. Moreover, a chain transfer agent, an emulsifier, etc. can use a conventionally well-known thing suitably. The amount of these additions may be appropriately determined within a range that does not impair the effects of the present invention. One of the features of the present invention is that the adhesive composition (A1) contains an epoxy group-containing silane coupling agent. By containing the epoxy group-containing silane coupling agent in the adhesive composition (A1), the durability of the entire liquid crystal panel can be improved, and further, panel warpage or light leakage can be suppressed. Examples of the epoxy-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyl Methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. In the present invention, it is preferred to use an oligomeric epoxy group-containing silane coupling agent having two or more alkoxysilane groups in the molecule as the epoxy group-containing silane coupling agent. Specific examples include X-41-1053, X-41-1059A, X-41-1056, etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd. These coupling agents are preferred because they are not easily volatile and have a plurality of alkoxysilyl groups. Here, the oligomer type refers to a polymer having a dimer or more of monomers and less than 100 mers. The weight average molecular weight of the oligomer type silane coupling agent is preferably about 300 to 30,000. . The number of alkoxysilyl groups in the oligomer-type epoxy-containing silane coupling agent may be two or more in the molecule, and the number is not limited. The amount of the alkoxy group of the oligomeric epoxy-containing silane coupling agent in the silane coupling agent is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and still more preferably 15 ~ 40% by weight. The type of the alkoxy group is not limited, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexyloxy group. Among these, methoxy and ethoxy are preferred, and methoxy is more preferred. It is also preferable that both methoxy and ethoxy are contained in one molecule. The epoxy equivalent of the epoxy group-containing silane coupling agent is preferably 1,000 g / mol or less, more preferably 500 g / mol or less, and even more preferably 300 g / mol or less. The lower limit of the epoxy equivalent is not particularly limited, and is preferably 200 g / mol or more, for example. The above-mentioned epoxy group-containing silane coupling agent may be used singly or in combination of two or more kinds, but the content as a whole is preferably 0.001 with respect to 100 parts by weight of the (meth) acrylic polymer (a1). 5 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.02 to 2 parts by weight, and even more preferably 0.05 to 1 part by weight. By containing the epoxy group-containing silane coupling agent in the above range, the durability of the entire liquid crystal panel can be improved, and further, the panel can be prevented from warping or light leakage. Further, a silane coupling agent other than the epoxy group-containing silane coupling agent may be added to the adhesive composition (A1) used in the present invention. Examples of other coupling agents include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxy Silane-N- (1,3-dimethylbutylene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane, and other amine-containing silane coupling agents; 3-propenyloxy (Meth) acrylfluorenyl-containing silane coupling agents such as propyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; isocyanates containing 3-isocyanatepropyltriethoxysilane Based silane coupling agents and the like. A thiol group-containing silane coupling agent may be added to the adhesive composition (A2), but it is preferably not included. The silane coupling agent other than the epoxy group-containing silane coupling agent may be added within a range that does not impair the effect of the present invention, and the amount of addition is not particularly limited. The adhesive composition (A1) used in the present invention preferably contains a crosslinking agent. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate can be used. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent. The polyfunctional metal chelate is a covalent bond or a coordinate bond between a polyvalent metal and an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti Wait. Examples of the atom in an organic compound that is covalently bonded or coordinated include an oxygen atom. Examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. The crosslinking agent is preferably an isocyanate-based crosslinking agent and / or a peroxide-based crosslinking agent. As the isocyanate-based crosslinking agent, a compound having at least two isocyanate groups can be used. For example, a well-known aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, etc. which are generally used for a urethane reaction are used. Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 1,3 -Butyl diisocyanate, dodecyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. Examples of the alicyclic isocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, and hydrogenated diphenyl. Methyl methane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and the like. Examples of the aromatic diisocyanate include phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-diisocyanate. Phenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene dimethionate Isocyanate, etc. Examples of the isocyanate-based cross-linking agent include polymers of the above-mentioned diisocyanates (dimers, trimers, pentamers, etc.), and aminocarboxylic acids reacted with polyols such as trimethylolpropane. Ester-modified, urea-modified, biuret-modified, urethane-modified, isocyanurate-modified, carbodiimide-modified, and the like. Examples of commercially available isocyanate-based cross-linking agents include the trade names “Millionate MT”, “Millionate MTL”, “Millionate MR-200”, “Millionate MR-400”, and “Millionate MT” manufactured by Nippon Polyurethane Industry (stock). Coronate L ｣,｢ Coronate HL ｣,｢ Coronate HX ｣; trade names manufactured by Mitsui Chemicals Co., Ltd.-Takenate D-110N｣, DTakenate D-120N ｣,｢ Takenate D-140N ｣,｢ Takenate D-160N ｣ , ｢Takenate D-165N｣, ｢Takenate D-170HN｣, ｢Takenate D-178N｣, ｢Takenate 500｣, ｢Takenate 600｣, etc. These compounds may be used singly or in combination of two or more kinds. As the isocyanate-based crosslinking agent, an aliphatic polyisocyanate and an aliphatic polyisocyanate-based compound as a modification thereof are preferred. Compared with other isocyanate-based crosslinking agents, aliphatic polyisocyanate-based compounds have a softer cross-linked structure, which is easier to mitigate the stress caused by the expansion / contraction of the optical film, and is less prone to peeling in durability tests. As the aliphatic polyisocyanate-based compound, hexamethylene diisocyanate and a modified product thereof are particularly preferred. As the peroxide, any radical active material generated by heating or light irradiation, and a base polymer ((meth) acrylic polymer) of the adhesive composition can be crosslinked, and it can be suitably used. In consideration of workability or stability, it is preferable to use a peroxide having a half-life temperature of 80 ° C to 160 ° C for 1 minute, and more preferably to use a peroxide having a half-life temperature of 90 ° C to 140 ° C for 1 minute. Examples of usable peroxides include bis (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), and bis (4-tert-butylcyclohexyl) peroxydicarbonate. Ester (1 minute half-life temperature: 92.1 ° C), di-second butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C), third butyl peroxy neodecanoate (1 minute half-life temperature: 103.5 ° C), Tert-hexyl pervalerate (1 minute half-life temperature: 109.1 ° C), tert-butyl pervalerate (1-minute half-life temperature: 110.3 ° C), dilaurate peroxide (1-minute half-life temperature: 116.4 ℃), di-n-octyl peroxide (1 minute half-life temperature: 117.4 ℃), peroxo (2-ethylhexanoic acid) 1,1,3,3-tetramethylbutyl ester (1 minute half-life temperature: 124.3 ℃ ), Bis (4-methylbenzidine) peroxide (1 minute half-life temperature: 128.2 ° C), benzophenazine peroxide (1 minute half-life temperature: 130.0 ° C), tert-butyl isobutyrate peroxide ( 1 minute half-life temperature: 136.1 ° C), 1,1-bis (third hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2 ° C), and the like. Among them, especially in terms of excellent cross-linking reaction efficiency, bis (4-tert-butylcyclohexyl) dicarbonate (1 minute half-life temperature: 92.1 ° C), dilaurin peroxide can be preferably used. (1 minute half-life temperature: 116.4 ° C), benzophenone peroxide (1 minute half-life temperature: 130.0 ° C), and the like. The term "half-life of peroxide" refers to an index indicating the decomposition rate of peroxide, and refers to the time until the residual amount of peroxide becomes half. The decomposition temperature used to obtain the half-life at any time, or the half-life time at any temperature, is described in the manufacturer's catalogue, etc., for example, in the 9th edition of the catalog of organic peroxides in Japan Oils and Fats (stock) May)) waited. The use amount of the crosslinking agent is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 1 part by weight, and still more preferably 0.03 to 0.5 part by weight based on 100 parts by weight of the (meth) acrylic polymer (a1). . Furthermore, if the cross-linking agent is less than 0.01 parts by weight, the adhesive layer may not be sufficiently cross-linked to meet the durability or adhesion characteristics. On the other hand, if it is more than 2 parts by weight, the adhesive layer may change. It tends to be too hard and the durability decreases. The isocyanate-based crosslinking agent may be used singly or as a mixture of two or more kinds. However, the content of the isocyanate-based crosslinking agent is preferably 0.01 based on 100 parts by weight of the (meth) acrylic polymer (a1). It is composed of ˜2 parts by weight, more preferably 0.02 to 1 part by weight, and still more preferably 0.03 to 0.5 part by weight. The isocyanate-based crosslinking agent may be appropriately contained in consideration of cohesive strength, peeling prevention in a durability test, and the like. The above-mentioned peroxides may be used singly or in combination of two or more kinds, but the total content is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (a1). It is more preferably 0.04 to 1.5 parts by weight, and more preferably 0.05 to 1 part by weight. In order to adjust the processability, secondary processability, cross-linking stability, peelability, etc., it is appropriately selected within this range. The adhesive composition (A1) used in the present invention may further contain an ionic compound. As the ionic compound, those generally available in the art can be suitably used, and the amount of addition can be appropriately determined within a range that does not impair the effect of the present invention. A polyether compound having a reactive silane group can be formulated in the adhesive composition (A1) used in the present invention. A polyether compound is preferable from the point which can improve secondary processability. As the polyether compound, those disclosed in Japanese Patent Laid-Open No. 2010-275522 can be used, for example. Furthermore, the adhesive composition (A1) used in the present invention may contain other well-known additives. For example, the following additives may be appropriately added according to the application to be used: polyether compounds of polyalkylene glycols such as polypropylene glycol, Powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization Inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. Further, a redox system with a reducing agent added may be used within a controllable range. These additives are preferably used within a range of 5 parts by weight or less, more preferably 3 parts by weight or less, and still more than 1 part by weight based on 100 parts by weight of the (meth) acrylic polymer (a1). (2) Adhesive composition (A2) The adhesive composition (A2) used in the present invention is preferably one containing a (meth) acrylic polymer (a2) and a thiol group-containing silane coupling agent. The (meth) acrylic polymer (a2) is a main component. Here, the so-called main component is as described above. One of the features of the present invention is that a thiol group-containing silane coupling agent is contained in the adhesive composition (A2). Since the thiol group-containing silane coupling agent is contained in the adhesive composition (A2), the durability of the entire liquid crystal panel can be improved, and further, warping or light leakage of the panel can be suppressed. Examples of the thiol group-containing silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyltriethoxysilane. Mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, 10-mercaptodecyltrimethoxy Compounds having a mercapto group such as silane. The thiol group-containing silane coupling agent is preferably an oligomeric thiol group-containing silane coupling agent having two or more alkoxysilyl groups in the molecule. Specific examples include X-41-1805, X-41-1818, X-41-1810, etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd. These thiol group-containing silane coupling agents are not easily volatile and have a plurality of alkoxysilyl groups, which is effective in improving durability and is therefore preferred. Here, the oligomer type refers to a polymer having a dimer or more of monomers and less than 100 mers. The weight average molecular weight of the oligomer type silane coupling agent is preferably about 300 to 30,000. . The number of alkoxysilyl groups in the oligomeric thiol group-containing silane coupling agent may be two or more in the molecule, and the number is not limited. The alkoxy group content of the oligomeric thiol group-containing silane coupling agent in the silane coupling agent is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and still more preferably 20 to 40. weight%. The type of the alkoxy group is not limited, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexyloxy group. Among these, methoxy and ethoxy are preferred, and methoxy is more preferred. It is also preferable that both methoxy and ethoxy are contained in one molecule. Regarding the thiol group content of the thiol group-containing silane coupling agent, for example, in the case of a thiol group, the thiol equivalent is preferably 1,000 g / mol or less, more preferably 800 g / mol or less, and even more preferably 500 g / mol. mol or less. The lower limit of the mercapto equivalent is not particularly limited, and it is preferably 200 g / mol or more, for example. The thiol group-containing silane coupling agent may be used singly or in combination of two or more kinds, but the content as a whole is preferably 0.001 with respect to 100 parts by weight of the (meth) acrylic polymer (a2). 5 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.02 to 2 parts by weight, and even more preferably 0.05 to 1 part by weight. By containing the thiol group-containing silane coupling agent in the above range, the durability of the entire liquid crystal panel can be improved, and further, the panel can be warped or light leaked. A silane coupling agent other than the thiol group-containing silane coupling agent may be added to the adhesive composition (A2) used in the present invention. Examples of other coupling agents include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxy Silane-N- (1,3-dimethylbutylene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane, and other amine-containing silane coupling agents; 3-propenyloxy (Meth) acrylfluorenyl-containing silane coupling agents such as propyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; isocyanates containing 3-isocyanatepropyltriethoxysilane Based silane coupling agents and the like. The silane coupling agent other than the thiol group-containing silane coupling agent may be added within a range that does not impair the effect of the present invention, and the amount of addition is not particularly limited. As the (meth) acrylic polymer (a2), (meth) of any composition exemplified in the (meth) acrylic polymer (a1) used in the adhesive composition (A1) may be suitably used. Acrylic polymer. In addition, in the adhesive composition (A2), a cross-linking agent, a polyether compound, and other additives can be added in the same manner as the adhesive composition (A1), and the composition and the addition amount are the same as those of the adhesive composition (A1). . However, in the adhesive composition (A1) and the adhesive composition (A2), the composition or addition amount of the (meth) acrylic polymer may be the same or different, and the crosslinking agent, polyether compound, and other additives may be different. The types or addition amounts may be the same or different. (3) Adhesive layer The first and second adhesive layers are formed from the adhesive compositions (A1) and (A2). The gel fraction of the first adhesive layer formed from the adhesive composition (A1) is 65 to 90%, preferably 70 to 85%. In order to suppress light leakage in a display device requiring a narrow edge, it is necessary to suppress the shrinkage of the polarizing film, and a harder adhesive layer is better. However, on the other hand, if the adhesive layer is too hard, it is not good from the viewpoint of durability when bonded to a display unit. In the present invention, by making the gel fraction of the first adhesive layer 65% or more, light leakage can be suppressed, and by making the gel fraction 90% or less, the durability to the transparent conductive layer is excellent. Therefore, it is better. The gel fraction of the second adhesive layer formed from the adhesive composition (A2) is also 65 to 90%, preferably 70 to 85%, based on the same reason as the first adhesive layer. By setting the gel fraction of the second adhesive layer to 65% or more, light leakage can be suppressed. Moreover, since the gel fraction is 90% or less, durability to glass is excellent, so it is preferable. In the present invention, the gel fraction of the first adhesive layer and the second adhesive layer satisfies the following formula (1): [Eq. 3] (1) person. When the hardness of the first adhesive layer formed on the transparent conductive layer on one side of the liquid crystal cell and the second adhesive layer formed on the other side of the liquid crystal cell are close, the warpage of the panel can be suppressed and the gel fraction can be reduced. When the above range is satisfied, the warpage of the panel can be suppressed. The above range is preferably 0.1 or less, and more preferably 0.05 or less. In the formation of the first and second adhesive layers, it is preferable to adjust the total amount of the crosslinking agent, and fully consider the influence of the crosslinking treatment temperature or the crosslinking treatment time. The crosslinking treatment temperature or crosslinking treatment time can be adjusted according to the crosslinking agent used. The crosslinking treatment temperature is preferably 170 ° C or lower. The crosslinking treatment may be performed at a temperature during the drying step of the adhesive layer, or a crosslinking treatment step may be separately performed after the drying step. The crosslinking treatment time can be set in consideration of productivity or workability, and is usually about 0.2 to 20 minutes, and preferably about 0.5 to 10 minutes. The method for forming the above-mentioned adhesive layer is not particularly limited, and may be a method in which the above-mentioned adhesive composition is coated on various substrates and dried by a dryer such as a hot oven to disperse solvents and the like. If necessary, the above-mentioned cross-linking treatment is performed to form an adhesive layer, and the adhesive layer is transferred on the substrate of the polarizing film or liquid crystal cell described below; the adhesive composition can also be directly coated on the polarizing film or liquid crystal cell. An adhesive layer is formed. In the present invention, it is preferable to prepare a polarizing film with an adhesive layer and an adhesive layer formed on the polarizing film in advance, and attach the polarizing film with the adhesive layer to a liquid crystal cell. The substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate. As a method of applying the adhesive composition to the substrate or the polarizing film, various methods can be used. Specifically, for example, a spray coater, a roll coating method, a contact roll coating method, a gravure coating method, a reverse coating method, a roll brush coating method, a spray coating method, and a dip roll Coating method, bar coating method, doctor blade coating method, air knife coating method, curtain coating method, die lip coating method, extrusion coating method using a nozzle coating machine, etc. method. The drying conditions (temperature, time) are not particularly limited, and can be appropriately set according to the composition and concentration of the adhesive composition, for example, about 80 to 170 ° C, preferably 90 to 200 ° C, and 1 to 60 minutes. It is preferably 2 to 30 minutes. After drying, a cross-linking treatment may be performed as necessary, and the conditions are as described above. The thickness (after drying) of the adhesive layer is, for example, preferably 5 to 100 μm, more preferably 7 to 70 μm, and even more preferably 10 to 50 μm. If the thickness of the adhesive layer is less than 5 μm, there is a tendency that the adhesion to the adherend is insufficient, and the durability under high temperature, high temperature and humidity is insufficient. On the other hand, when the thickness of the adhesive layer exceeds 100 μm, there are some cases where the adhesive composition is applied when the adhesive layer is formed and cannot be sufficiently dried during drying to leave air bubbles, or the thickness of the surface of the adhesive layer is not uniform. In all cases, the appearance problem tends to become more obvious. Examples of the constituent materials of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films; porous materials such as paper, cloth, and non-woven fabrics; Suitable sheets such as blister sheets, metal foils, and laminates thereof are suitably used in terms of excellent surface smoothness. Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, and polyterephthalic acid. Ethylene film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc. The thickness of the release film is usually 5 to 200 μm, and preferably about 5 to 100 μm. For the above-mentioned release film, release and antifouling treatments using a polysiloxane, fluorine-based, long-chain alkyl-based or fatty ammonium-based release agent, silicon oxide powder, etc. may be performed as needed; or coating may be performed; Type, mixed type, evaporation type and other antistatic treatment. In particular, by appropriately performing a peeling treatment such as a polysiloxane treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the release film, the peelability from the adhesive layer can be further improved. The transparent resin film substrate is not particularly limited, and various resin films having transparency can be used. This resin film is formed of a single film. Examples of the material include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; acetate resins, polyether fluorene resins, polycarbonate resins, and polyethylene resins. Fluorene resin, polyimide resin, polyolefin resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin , Polyarylate resin, polyphenylene sulfide resin, etc. Among these, polyester resin, polyimide resin, and polyether amidine resin are particularly preferred. The thickness of the film substrate is preferably 15 to 200 μm. Further, an anchor layer may be provided between the polarizing film and the adhesive layer. The material for forming the thickening layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols. Among these, polymers are particularly preferably used. The polymer may be used in any of a solvent-soluble type, a water-dispersible type, and a water-soluble type. Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone, Polystyrene resin and the like. Among these, a polyurethane resin, a polyester resin, and an acrylic resin are particularly preferable. Crosslinking agents can be appropriately blended in these resins. These other adhesive ingredients can be used singly or in combination of two or more kinds depending on the application. The thickness of the tackifier layer is not particularly limited, but is preferably 5 to 300 nm. The formation method of the said thickening layer is not specifically limited, Usually, it can carry out by a well-known method. In addition, during the formation of the thickening layer, the iodine-based polarizing film may be subjected to an activation treatment. Various methods can be used for the activation treatment, for example, corona treatment, low-pressure UV (ultraviolet) treatment, and plasma treatment can be used. The method for forming an adhesive layer on the thickening layer on the polarizing film is as described above. When the adhesive layer of the polarizing film with an adhesive layer and the adhesive layer on the liquid crystal cell are exposed, the adhesive layer may be protected by a release film (separator) until it is put to practical use. Examples of the release film include the above. When a release film is used as a base material in the production of the above-mentioned adhesive layer, the release film can be used as an adhesive agent by bonding the adhesive layer on the release film to a polarizing film or a liquid crystal cell. Layer of a polarizing film or a release film of an adhesive layer of a liquid crystal cell with an adhesive layer, so that steps can be simplified. In addition, the first polarizing film and the second polarizing film are not particularly limited, and are generally used for those having a transparent protective film on one or both sides of a polarizing element. The polarizing element is not particularly limited, and various polarizing elements can be used. Examples of polarizing elements include those that adsorb iodine or dichroic dyes to hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based saponified films. A dichroic material that is uniaxially stretched; a polyolefin-based alignment film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among these, a polarizing element containing a dichroic substance such as a polyvinyl alcohol-based film and iodine is preferred, and an iodine-based polarizing element containing iodine and / or iodine ions is more preferred. In addition, the thickness of these polarizing elements is not particularly limited, but is generally about 5 to 80 μm. A polarizing element obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching it, for example, can be dyed by immersing polyvinyl alcohol in an aqueous solution of iodine, and extended to 3 to 7 times its original length. Production. If necessary, it may be immersed in an aqueous solution which may contain boric acid, potassium sulfate, zinc chloride, or the like. Furthermore, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, in addition to cleaning the dirt or anti-blocking agent on the surface of the polyvinyl alcohol-based film, it also has the effect of preventing uneven dyeing and unevenness by swelling the polyvinyl alcohol-based film. The stretching may be performed after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution or a water bath such as boric acid or potassium iodide. As a material for forming a single-sided or double-sided transparent protective film provided on the above-mentioned polarizing element, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture blocking property, and isotropic property can be used. Specific examples of such thermoplastic resins include cellulose resins such as triethyl cellulose, polyester resins, polyether resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyimide resins. , Polyolefin resin, (meth) acrylic resin, cyclic polyolefin resin (lower Olefinic resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. In addition, a transparent protective film is laminated on one side of the polarizer with an adhesive layer, and a (meth) acrylic, urethane, acrylic urethane, or cyclic As a transparent protective film, a thermosetting resin such as an oxygen-based resin or a polysilicone-based resin or an ultraviolet curing resin is used. The transparent protective film may contain one or more of any appropriate additives. Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, anti-colorants, flame retardants, nucleating agents, antistatic agents, pigments, and colorants. 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 even more preferably 70 to 97% by weight. When the content of the above-mentioned thermoplastic resin in the transparent protective film is 50% by weight or less, there is a possibility that the high transparency and the like originally possessed by the thermoplastic resin may not be sufficiently exhibited. The thickness of the protective film can be appropriately determined, and is generally about 1 to 500 μm in terms of workability such as strength, workability, and film properties. The polarizing element and the protective film are usually closely adhered via an aqueous adhesive or the like. Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, ethylene-based latexes, water-based polyurethanes, and water-based polyesters. In addition to the above, examples of the adhesive for the polarizing element and the transparent protective film include an ultraviolet curing adhesive, an electron beam curing adhesive, and the like. The adhesive for an electron beam-curable polarizing film exhibits suitable adhesion to the above-mentioned various transparent protective films. The adhesive used in the present invention may contain a metal compound filler. In the present invention, a transparent protective film, such as a retardation film, may be formed on the polarizing element instead of the polarizing film. Further, another transparent protective film, a retardation film, or the like may be further provided on the transparent protective film. The surface of the transparent protective film that is not next to the side opposite to the liquid crystal cell (viewable side) may be subjected to a hard coat or anti-reflection treatment, or a treatment for the purpose of anti-adhesion, or diffusion or anti-glare. (4) Structure of liquid crystal panel The structure of the liquid crystal panel of the present invention is characterized in that a transparent conductive layer is formed on one surface of the liquid crystal cell, and an adhesive layer formed from the adhesive composition (A1) is formed on the transparent conductive layer. A first polarizing film is bonded, and a second polarizing film is bonded to the other side of the liquid crystal cell via an adhesive layer formed from an adhesive composition (A2). The adhesive composition (A1) contains (methyl) The acrylic polymer (a1) and an epoxy-containing silane coupling agent, and the adhesive composition (B2) contains a (meth) acrylic polymer (a2) and a thiol group-containing silane coupling agent. The gel fractions of the 1st adhesive layer and the 2nd adhesive layer are not particularly limited with respect to other configurations. One aspect of the specific structure of the liquid crystal panel of the present invention will be described based on FIG. 1, but the present invention is not limited thereto. The aspect of the liquid crystal panel 11 of the present invention shown in FIG. 1 is as follows. The liquid crystal cell 10 includes a liquid crystal layer 8, a first transparent substrate 7 (viewable side) disposed on one side of the liquid crystal layer 8, and a second transparent substrate 9 (light source side) disposed on the other side of the liquid crystal layer, and A transparent conductive layer 6 is formed on the first transparent substrate 7. A first polarizing film 4a is laminated on the transparent conductive layer side of the liquid crystal cell via a first adhesive layer 5a formed of an adhesive composition (A1). The first polarizing film 4a includes a polarizing element 2a between the viewing-side transparent protective film 1a and the liquid crystal cell-side transparent protective film 3a. A second polarizing film 4b is laminated on the opposite side of the liquid crystal cell from the transparent conductive layer via a second adhesive layer 5b formed of the adhesive composition (A2). The second polarizing film 4b includes a polarizing element 2b between the light source-side transparent protective film 3b and the liquid crystal cell-side transparent protective film 1b. In the liquid crystal panel 11 of FIG. 1, the first polarizing film 4 a and the second polarizing film 4 b are both used as a double-sided protective polarizing film having a transparent protective film on both sides of the polarizing element, but it can also be used only on one side of the polarizing element. A single-sided protective polarizing film with a transparent protective film replaces the double-sided protective polarizing film. Alternatively, a retardation layer may be used in place of the liquid crystal cell-side transparent protective films (3a, 1b) of the polarizing films 4a, 4b, or may be formed on the liquid crystal cell-side transparent protective films (3a, 1b) through an adhesive layer. Phase difference layer. Furthermore, in addition to the above-mentioned configuration, an optical film such as a retardation film, a viewing angle compensation film, and a brightness enhancement film may be appropriately provided on the liquid crystal panel 11. The liquid crystal layer 8 is not particularly limited. For example, a TN (Twisted Nematic) type or an STN (Super Twisted Nematic) type, a π type, a VA (Vertical Aligned) type, or the like can be used. Any type such as IPS (In-plane Switching). The first transparent substrate 7 (viewable side) constituting the liquid crystal cell 10 and the second transparent substrate 9 (light source side) disposed on the other side of the liquid crystal layer may be transparent substrates, and the raw materials are not particularly limited. The limitation includes, for example, glass and a transparent resin film substrate. Examples of the transparent resin film substrate include the above. The first polarizing film 4a, the second polarizing film 4b, and the first and second adhesive layers formed of the adhesive composition (A1) or (A2) are as described above. The constituent material of the transparent conductive layer 6 is not particularly limited, and may be selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. A metal oxide of at least one metal in the group. The metal oxide may further contain a metal atom represented by the aforementioned group, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like is preferably used, and ITO is particularly preferably used. The ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide. Examples of the ITO include crystalline ITO and amorphous (amorphous) ITO, and any of them can be used as appropriate. The thickness of the transparent conductive layer 6 is not particularly limited, but it is preferably set to 10 nm or more, more preferably 15 to 40 nm, and still more preferably 20 to 30 nm. The method for forming the transparent conductive layer 6 is not particularly limited, and a conventionally known method can be adopted. Specific examples include a vacuum deposition method, a sputtering method, and an ion plating method. Further, an appropriate method may be adopted depending on the required film thickness. Further, between the transparent conductive layer 6 and the first transparent substrate 7, an undercoat layer, an oligomer prevention layer, and the like may be provided as necessary. In the liquid crystal panel of the present invention, the first polarizing film is arranged on the other side of the liquid crystal cell (the light source side by a transparent conductive layer on the first surface of the liquid crystal cell via a first adhesive layer formed of a specific adhesive composition) Surface, glass surface) The second polarizing film is disposed through the second adhesive layer formed of the specific adhesive composition, which can improve the durability of the entire liquid crystal panel, and can further suppress panel warping or light leakage. 2. Image display device The image display device of the present invention includes the liquid crystal panel of the present invention. Hereinafter, as an example, a liquid crystal display device will be described. The present invention can be applied to all display devices that require a liquid crystal panel. Specific examples of the image display device to which the liquid crystal panel of the present invention can be applied include a liquid crystal display device, an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED: Field Emission Display). . The image display device of the present invention may be any one including the liquid crystal panel of the present invention, and other configurations are the same as those of the conventional image display device. [Examples] The present invention will be specifically described below by examples, but the present invention is not limited by these examples. In addition, all room temperature storage conditions without special regulations are 23 ° C and 65% RH. <Measurement of weight average molecular weight of (meth) acrylic polymer> The weight average molecular weight (Mw) of the (meth) acrylic polymer is measured by GPC (gel permeation chromatography). Mw / Mn was measured in the same manner. · Analytical device: HLC-8120GPC, manufactured by Tosoh Corporation · Pipe: G7000H _XL + GMH _XL + GMH _XL , Tosoh (stock) manufacturing · Pipe size: 7.8 mm each × 30 cm total 90 cm · column temperature: 40 ° C · flow rate: 0.8 mL / min · injection volume: 100 μL · eluent: tetrahydrofuran · detector: differential refractometer (RI) · standard sample: made of polystyrene Example 1 (production of a polarizing film) A polyvinyl alcohol film with a thickness of 80 μm was placed between rollers with different speed ratios, and one side was dyed in an iodine solution at a concentration of 0.3% by weight at 30 ° C for one minute, and extended three times. Thereafter, it was immersed in an aqueous solution containing boric acid at a concentration of 4% by weight and potassium iodide at a concentration of 10% by weight for 0.5 minutes while extending at 60 ° C until the comprehensive extension ratio was 6 times. Then, it was washed by immersion in an aqueous solution containing potassium iodide at a concentration of 1.5% by weight at 30 ° C for 10 seconds, and then dried at 50 ° C for 4 minutes to obtain a polarizing element having a thickness of 30 µm. A triethylammonium cellulose film having a thickness of 80 μm after saponification treatment was bonded to both sides of the polarizing element with a polyvinyl alcohol-based adhesive to prepare a polarizing film. Production Example 2 (Adjustment of Solution of Acrylic Polymer (a-1)) A four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler was charged with 99 parts by weight of butyl acrylate and 4-hydroxy acrylate 1 part by weight of a butyl ester monomer mixture. Furthermore, 0.1 part by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was added together with 100 parts by weight of ethyl acetate with respect to 100 parts by weight of the above-mentioned monomer mixture (solid content component). After stirring slowly, while introducing nitrogen for nitrogen substitution, the temperature of the liquid in the flask was maintained at around 55 ° C, and polymerization was performed for 8 hours to prepare an acrylic polymerization having a weight average molecular weight (Mw) of 1.56 million and Mw / Mn of 3.2 Of a substance (a-1). Production Examples 3 and 4 In Production Example 2, as shown in Table 1, the types of monomers used in the preparation of the acrylic polymer and the use ratios thereof were changed, and were produced by the same method as in Production Example 2. Solutions of acrylic polymers (a-2) and (a-3). [Table 1] The abbreviations in Table 1 are as follows. BA: Butyl acrylate NVP: N-vinyl-2-pyrrolidone AA: Acrylic acid HBA: 4-hydroxybutyl acrylate Example 1 (Adjustment of the acrylic adhesive composition (A1)) Compared to that in Production Example 2 100 parts by weight of the solid content of the obtained solution of the acrylic polymer (a-1), and an isocyanate crosslinking agent (trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, Mitsui Chemicals Co., Ltd.) )) 0.1 parts, benzamidine peroxide (Nyper BMT 40SV, manufactured by Nippon Oil & Fats Co., Ltd.) 0.3 parts, and γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, Shin-Etsu Chemical Industry (Production: 0.3 parts) to prepare a solution of the acrylic pressure-sensitive adhesive composition (A1). (Adjustment of the acrylic adhesive composition (A2)) An isocyanate cross-linking agent (trade name: Takenate D160N) was prepared based on 100 parts by weight of the solid content of the solution of the acrylic polymer (a1) obtained in Production Example 2. , Trimethylolpropane hexamethylene diisocyanate, 0.1 part of Mitsui Chemicals (stock), 0.3 part of benzamidine peroxide (Nyper BMT 40SV, manufactured by Nippon Oil & Fats Co., Ltd.), and 3-mercaptopropyl trimethyl 0.3 parts of oxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) to prepare a solution of an acrylic adhesive composition (A2). (Production of Polarizing Film with Adhesive Layer) A solution of the acrylic adhesive composition (A1) was applied so that the thickness of the dried adhesive layer became 23 μm on a polysiloxane-based release agent. One side of the treated polyethylene terephthalate film (release film, trade name: MRF38, manufactured by Mitsubishi Chemical Polyester Film (stock)), dried at 155 ° C for 1 minute, and formed on the surface of the release film Adhesive layer. Then, the polarizing film produced in Manufacturing Example 1 was transferred to an adhesive layer formed on the release film, and a polarizing film (A1) with an adhesive layer was produced. Further, a polarizing film (A2) with an adhesive layer was produced by the same method using a solution of the acrylic adhesive composition (A2). Examples 2 to 12 and Comparative Examples 1 to 10 In Example 1, as shown in Table 2, the types of the acrylic polymers (a1) and (a2), the types of the silane coupling agents, and their addition amounts were changed, except that Other than that, solutions of the acrylic adhesive compositions (A1) and (A2) were prepared in the same manner as in Example 1. Using the solution of the obtained acrylic adhesive composition, a polarizing film with an adhesive layer was produced by the same method as in Example 1. [Table 2] The abbreviations in Table 2 are as follows. Isocyanate series: Trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd. Peroxide system: trade name: Nyper BMT 40SV, benzamidine peroxide, Japanese oil and fat (stock) Manufactured KBM403: γ-glycidoxypropyltrimethoxysilane, trade name: KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBM803: 3-mercaptopropyltrimethoxysilane, trade name: KBM-803, Shin-Etsu X-41-1056 manufactured by Chemical Industry Co., Ltd .: oligomer-type epoxy group-containing silane coupling agent, alkoxy group amount: 17% by weight, epoxy equivalent weight: 280 g / mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd. X-41-1810: oligomeric type mercapto-containing silane coupling agent, alkoxy group amount: 30% by weight, mercapto group equivalent weight: 450 g / mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBM-5103: 3-propenyloxy Propyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBE-9007: 3-isocyanatepropyltriethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd. The polarizing film with an adhesive layer was evaluated as follows. The evaluation results are shown in Table 3. <Production of liquid crystal panel> The polarizing films (A1) and (A2) with an adhesive layer obtained in Examples and Comparative Examples were cut to a size of 109 mm × 59 mm. For the polarizing film (A1) with an adhesive layer, cut it so that the absorption axis of the polarizing plate is parallel to the short side, and for the polarizing film (A2) with an adhesive layer, use the absorption axis and length of the polarizing plate Cut in parallel. Use a laminator to attach the polarizing film (A1) with an adhesive layer to the ITO surface of a 110 mm × 60 mm LCD panel with a thickness of 0.32 mm, and attach the polarizing film (A2) with an adhesive layer to Glass surface. Then, the autoclave process was performed at 50 degreeC and 0.5 MPa for 15 minutes, and the polarizing film was fully adhered to the liquid crystal panel, and the liquid crystal panel for evaluation was produced. Furthermore, the polarizing films (A1) and (A2) with an adhesive layer attached to the ITO surface and the glass surface of the liquid crystal panel are polarizing films with an adhesive layer (as in the examples and comparative examples). A1), (A2). <Panel Warpage> The produced liquid crystal panel for evaluation was exposed to an environment of 80 ° C. for 24 hours. After the exposed liquid crystal panel was left at room temperature for 1 hour, it was placed on a flat table in the form of a four-corner bulge according to the warped direction. A laser displacement meter (product name: LK-G35, Keyence) was used. (Manufacturing) to measure the height of the four corners. The average value of the measured values of the four corners was used as the amount of warpage, and the determination was performed according to the following evaluation criteria. ○: The amount of warpage is less than 0.2 mm △: The amount of warpage is 0.2 mm or more and less than 0.5 mm ×: The amount of warpage is 0.5 mm or more <Durability test> The produced liquid crystal panel for evaluation is charged to 85 ° C. After 500 hours in the environment (heating test) and 500 hours in the environment of 60 ° C and 95% RH (humidification test), the foaming or peeling of the adhesive layer was visually observed, and evaluation was performed according to the following evaluation criteria. (Evaluation criteria) ◎: No change in appearance such as foaming or peeling. ○: Slight peeling or foaming at the end, but practically no problem. △: There is peeling or foaming at the end, but as long as it is not used for a special purpose, there is no practical problem. ×: There is obvious peeling at the end, which is a problem in practical use. <Light leakage> The liquid crystal panel after the durability test at 85 ° C was placed in a dark room under transmitted light from a backlight device, and the presence or absence of light leakage from the end of the polarizing plate was observed, and evaluated according to the following evaluation criteria. ○: There is no light leakage. ×: There is light leakage. [table 3]

1a‧‧‧Transparent protective film

1b‧‧‧Transparent protective film on liquid crystal cell side

2a‧‧‧polarizing element

2b‧‧‧polarizing element

3a‧‧‧Transparent protective film on LCD side

3b‧‧‧Transparent protective film on the light source side

4a‧‧‧The first polarizing film

4b‧‧‧Second polarizing film

5a‧‧‧The first adhesive layer formed from the adhesive composition (A1)

5b‧‧‧ The second adhesive layer formed from the adhesive composition (A2)

6‧‧‧ transparent conductive layer

7‧‧‧The first transparent substrate

8‧‧‧ LCD layer

9‧‧‧ 2nd transparent substrate

10‧‧‧ LCD cell

11‧‧‧ LCD Panel

FIG. 1 is a cross-sectional view schematically showing an embodiment of a liquid crystal panel of the present invention.

Claims (9)

A liquid crystal panel is characterized in that a transparent conductive layer is formed on one side of a liquid crystal cell, and a first polarized light is bonded to the transparent conductive layer via a first adhesive layer formed of an adhesive composition (A1). A film in which a second polarizing film is bonded to the other side of the liquid crystal cell via a second adhesive layer formed from an adhesive composition (A2), and the adhesive composition (A1) contains a (meth) acrylic Polymer (a1) and epoxy-containing silane coupling agent, the adhesive composition (A2) contains (meth) acrylic polymer (a2) and thiol group-containing silane coupling agent, and the first adhesive The gel fraction of the layer and the second adhesive layer is 65% or more and 90% or less, and further satisfies the following formula (1): [Eq. 1] (1). For example, the liquid crystal panel of claim 1, wherein the epoxy group-containing silane coupling agent is an oligomer type epoxy group-containing silane coupling agent having two or more alkoxysilane groups in the molecule. The liquid crystal panel according to claim 1, wherein the thiol group-containing silane coupling agent is an oligomeric thiol group-containing silane coupling agent having two or more alkoxysilyl groups in the molecule. For example, the liquid crystal panel of claim 1, wherein the blending amount of the epoxy group-containing silane coupling agent is 0.001 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (a1). The liquid crystal panel according to claim 1, wherein the blending amount of the thiol group-containing silane coupling agent is 0.001 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (a2). The liquid crystal panel according to claim 1, wherein the (meth) acrylic polymer (a1) and / or (a2) contains 0.01 to 2% by weight of a carboxyl group-containing monomer as a monomer unit. The liquid crystal panel according to claim 1, wherein the (meth) acrylic polymer (a1) and / or (a2) contains 0.1 to 8% by weight of an amine group-containing monomer as a monomer unit. The liquid crystal panel according to claim 1, wherein the (meth) acrylic polymer (a1) and / or (a2) contains 0.01 to 7% by weight of a hydroxyl group-containing monomer as a monomer unit. An image display device characterized by using a liquid crystal panel according to any one of claims 1 to 8.