TW201700684A - Adhesive composition, adhesive layer for transparent conductive layers, polarizing film with adhesive layer, and image display device - Google Patents

Abstract

The purpose of the present invention is to provide an adhesive composition for forming an adhesive layer that, even when pasted to a transparent conductive base material having a transparent conductive layer upon a transparent base material, has high durability, and, in particular, has excellent durability in a humidified environment and is capable of maintaining high durability even after being left for a long period. In addition, the purpose of the present invention is to provide: an adhesive layer for transparent conductive layers, formed from said adhesive composition; a polarizing film with adhesive layer, having said adhesive layer; and an image display device including said polarizing film with adhesive layer. The adhesive composition: is for forming an adhesive layer that is used pasted on to a transparent conductive layer of a transparent conductive base material having the transparent conductive layer upon a transparent base material; and is characterized by including a (meth) acrylic polymer and a oligomer epoxy group-containing silane coupling agent.

Description

Adhesive composition, adhesive layer for transparent conductive layer, polarizing film with adhesive layer, and image display device

The present invention relates to an adhesive composition for forming an adhesive layer and an adhesive layer for a transparent conductive layer formed of the adhesive composition, the adhesive layer being adhered to a transparent substrate The transparent conductive layer of the transparent conductive substrate of the conductive layer is used. Further, the present invention relates to an image display device comprising a polarizing film with an adhesive layer of the above-mentioned adhesive layer and a polarizing film comprising the above-mentioned adhesive layer.

A liquid crystal panel used in a liquid crystal display device or the like generally has a polarizing film laminated 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. Such an adhesive layer is required to have high durability. For example, in an endurance test using heating and humidification, which is usually performed as an environmental promotion test, it is required that defects such as peeling or bulging of the adhesive layer are not caused.

Various studies have been conducted on the above-mentioned adhesive composition for optical use, for example, an adhesive composition which does not cause peeling or foaming after being placed under high heat and humidity conditions after bonding an optical film (for example, Refer to Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-242767

A transparent conductive film such as an indium tin oxide (ITO) film is formed on the transparent substrate on one side of the liquid crystal cell constituting the liquid crystal panel, and the adhesive layer that is in contact with the transparent conductive film is likely to be peeled off or swelled, and the durability is changed. Low tendency. Moreover, the durability is particularly degraded particularly in a humidified environment. The adhesive layer formed of the adhesive composition of Patent Document 1 is inferior in 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.

Further, the adhesive layer may be attached to the transparent conductive film after being stored for a long period of time of 6 months or longer, and excellent durability is required even after the long-term storage.

Accordingly, it is an object of the present invention to provide an adhesive composition for forming an adhesive layer which adheres even to a transparent conductive substrate having a transparent conductive layer on a transparent substrate. It has high durability, especially in a humidified environment, and it maintains high durability even after standing for a long time. Moreover, an object of the present invention is to provide an adhesive layer for a transparent conductive layer formed of the above adhesive composition, a polarizing film having an adhesive layer of the above adhesive layer, and a polarizing film comprising the above adhesive layer. Image display device.

The inventors of the present invention have conducted intensive studies in order to solve the above problems, and as a result, have found the following adhesive compositions to achieve the present invention.

That is, the present invention relates to an adhesive composition characterized in that it is used for forming an adhesive layer which is bonded to a transparent conductive substrate having a transparent conductive layer on a transparent substrate. The transparent conductive layer is used, and comprises a (meth)acrylic polymer and an oligomeric epoxy group-containing decane coupling agent.

The oligomer-containing epoxy group-containing decane coupling agent preferably has two or more alkoxyalkyl groups in the molecule.

The above oligomer type is used in an amount of 100 parts by weight based on the above (meth)acrylic polymer. The compounding amount of the epoxy group-containing decane coupling agent is preferably 0.01 to 3 parts by weight.

The epoxy group-containing decane coupling agent of the above oligomer type preferably has an epoxy equivalent of 300 g/mol or less.

Further, the present invention relates to an adhesive layer for a transparent conductive layer characterized by being formed of the above-described adhesive composition.

Further, the present invention relates to a polarizing film with an adhesive layer attached to a transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and having a polarizing film and the above Adhesive layer.

Furthermore, the present invention relates to an image display device comprising: the polarizing film with the adhesive layer attached thereto; and a liquid crystal cell including a transparent conductive substrate having a transparent conductive layer on a transparent substrate. Further, the adhesive layer of the polarizing film with the adhesive layer is bonded to the transparent conductive layer of the liquid crystal cell.

The adhesive composition of the present invention comprises an oligomer-type epoxy group-containing decane coupling agent, so that even when the adhesive layer formed of the adhesive composition is attached to the transparent conductive layer, High durability, especially in a humidified environment, maintains high durability even after long-term placement. Further, the present invention can provide an adhesive layer formed of the above-described adhesive composition having higher durability, a polarizing film having an adhesive layer having the adhesive layer, and a polarizing film having the adhesive layer Image display device.

1‧‧‧LCD panel

2‧‧‧Visual side transparent protective film

3‧‧‧Polarized components

4‧‧‧ Liquid crystal side transparent protective film

5‧‧‧Adhesive layer

6‧‧‧Transparent conductive layer

7‧‧‧Transparent substrate

8‧‧‧Liquid layer

9‧‧‧Transparent substrate

10‧‧‧Adhesive layer

11‧‧‧ Liquid crystal side transparent protective film

12‧‧‧Polarized elements

13‧‧‧Light source side transparent protective film

Fig. 1 is a cross-sectional view schematically showing an embodiment of a liquid crystal panel which can be used in the present invention.

Adhesive composition

The adhesive composition of the present invention is characterized in that it is used for forming an adhesive layer which is adhered to the above transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate. Further, a (meth)acrylic polymer and an oligomeric epoxy group-containing decane coupling agent are used. Hereinafter, the composition of the adhesive composition of the present invention will be described.

(1) (meth)acrylic polymer

The adhesive composition of the present invention contains a (meth)acrylic polymer and an oligomeric epoxy group-containing decane coupling agent, and preferably contains a (meth)acrylic polymer as a main component. Here, the term "main component" means a component having the highest ratio among all the solid components contained in the adhesive composition, and for example, more than 50% by weight of all the solid components contained in the adhesive composition. The ingredients, in turn, comprise more than 70% by weight of the ingredients.

The (meth)acrylic polymer usually contains, as a main component, an alkyl (meth)acrylate as a monomer unit. Further, (meth) acrylate means acrylate and/or methacrylate, and the (meth) group of the present invention has the same meaning.

The alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic polymer may, for example, be a linear or branched alkyl group having 1 to 18 carbon atoms. For example, as the above alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, and the like can be exemplified. Anthracenyl, fluorenyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like. These may be used singly or in combination. The average carbon number of the alkyl groups is preferably from 3 to 9.

Examples of the monomer having a (meth)acrylic polymer include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and a mercapto group-containing monomer, in addition to the above (meth)acrylic acid alkyl ester. An aromatic ring-containing (meth) acrylate or the like.

A single system containing a carboxyl group having a carboxyl group in its structure and containing a (meth) acrylonitrile group, B A compound of a polymerizable unsaturated double bond such as an alkenyl group. Specific examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and fumaric acid. Butenoic acid, etc. Among the above carboxyl group-containing monomers, acrylic acid is preferred from the viewpoint of copolymerizability, price, and adhesion characteristics.

A compound containing a hydroxyl group and having a hydroxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group. Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (methyl). Ethyl 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, etc. Ester or (4-hydroxymethylcyclohexyl) methacrylate or the like. Among the above hydroxyl group-containing monomers, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 4 are preferable in terms of durability. - Hydroxybutyl ester.

A compound containing a mercaptoamine group, which contains a mercaptoamine group in its structure and contains a polymerizable unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group. Specific examples of the mercapto group-containing monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)propene. Indoleamine, N-isopropyl acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-hydroxy Methyl (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide , acrylamide amine monomer such as mercaptomethyl (meth) acrylamide, mercaptoethyl (meth) acrylamide; N-(methyl) propylene fluorenyl N-propylene hydrazino ruthenium ring monomer such as porphyrin, N-(methyl) propylene hydrazinopiperidine or N-(methyl) propylene decyl pyrrolidine; N-vinylpyrrolidone, N-vinyl-ε An N-vinyl-containing decylamine-based monomer such as caprolactam. In terms of satisfying durability, a monomer containing a guanamine group is preferable, and in the monomer containing a guanamine group, it is preferable to contain N- in terms of durability against a transparent conductive layer. A guanamine monomer in a vinyl group.

The above-mentioned aromatic ring-containing (meth) acrylate is a compound containing an aromatic ring structure and containing a (meth) acryl fluorenyl group in its structure. The aromatic ring may, for example, be a benzene ring, a naphthalene ring or a biphenyl ring. The (meth) acrylate containing an aromatic ring can satisfy durability (especially for the durability of the transparent conductive layer).

Specific examples of the (meth) acrylate-containing (meth) acrylate include benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate, and (methyl). Phenyl acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxy diethylene glycol (meth) acrylate, modified with ethylene oxide Nonylphenol (meth) acrylate, ethylene oxide modified cresol (meth) acrylate, phenol oxirane modified (meth) acrylate, (meth) acrylate 2 Hydroxy-3-phenoxypropyl ester, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, tolyl (meth)acrylate, polystyrene (meth)acrylate, etc. Benzene ring; hydroxyethylated β-naphthol acrylate, 2-naphthylethyl (meth)acrylate, 2-naphthyloxyethyl acrylate, 2-(4-methoxy)(meth)acrylate -1-naphthyloxy)ethyl ester or the like having a naphthalene ring; (meth)acrylic acid biphenyl ester having a biphenyl ring.

The carboxyl group-containing monomer, the hydroxyl group-containing monomer, the guanamine group-containing monomer, and the aromatic ring-containing (meth) acrylate are reacted with the crosslinking agent when the adhesive composition contains a crosslinking agent. point. In particular, the carboxyl group-containing monomer, the hydroxyl group-containing monomer and the intermolecular crosslinking agent are highly reactive, and thus can be preferably used for improving the agglomeration or heat resistance of the obtained adhesive layer.

The (meth)acrylic polymer used in the present invention preferably contains the above monomers as a monomer unit in the following amounts in a weight ratio of all constituent monomers (100% by weight).

The weight ratio of the alkyl (meth)acrylate may be the remainder of the monomer other than the alkyl (meth)acrylate, and specifically, it is preferably 70% by weight or more. In terms of ensuring adhesion, it is preferred to set the weight ratio of the alkyl (meth)acrylate to 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, still more preferably 0.05 to 1% by weight, still more preferably 0.05. ~0.5% by weight. If the weight ratio of the carboxyl group-containing monomer is less than 0.01% by weight, the durability may not be satisfied. On the other hand, in the case of more than 2% by weight, there is a case where the transparent conductive layer is etched, and there is a tendency that durability cannot be satisfied, which is not preferable.

The weight ratio of the hydroxyl group-containing monomer is preferably 3% by weight or less, more preferably 0.01 to 3% by weight, still more preferably 0.1 to 2% by weight, still more preferably 0.2 to 2% by weight. When the weight ratio of the hydroxyl group-containing monomer is less than 0.01% by weight, the adhesive layer becomes insufficiently crosslinked, and the durability or adhesive properties are not satisfied. On the other hand, when it exceeds 3% by weight, there is a tendency that durability cannot be satisfied.

The weight ratio of the amidino 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, particularly preferably 0.7 to 2.5% by weight. If the weight ratio of the mercapto group-containing monomer is less than 0.1% by weight, there is a tendency that the durability to the transparent conductive layer is not particularly satisfied. On the other hand, when it exceeds 8% by weight, the durability tends to decrease, which is not preferable.

The weight ratio of the (meth) acrylate containing an aromatic ring is preferably 25% by weight or less, more preferably 0 to 22% by weight, still more preferably 0 to 18% by weight. When the weight ratio of the (meth) acrylate containing an aromatic ring exceeds 25% by weight, the durability tends to decrease.

In the above (meth)acrylic polymer, it is not necessary to contain other monomer units in addition to the above monomer units, but it is also possible to introduce (methyl group) by copolymerization in order to improve adhesion or heat resistance. One or more kinds of copolymerizable monomers having a polymerizable functional group containing an unsaturated double bond such as an acrylonitrile group or a vinyl group.

The ratio of the above-mentioned copolymerized monomer in the (meth)acrylic polymer is in the weight ratio of all the constituent monomers (100% by weight) of the above (meth)acrylic polymer. Preferably, it is about 0 to 10% by weight, more preferably about 0 to 7% by weight, and still more preferably about 0 to 5% by weight.

The (meth)acrylic polymer of the present invention usually has a weight average molecular weight of from 1,000,000 to 2.5 million. In consideration of durability, particularly heat resistance, it is preferred that the weight average molecular weight is from 1.2 million to 2,000,000. If the weight average molecular weight is less than 1,000,000, it is not preferable in terms of heat resistance. Moreover, when the weight average molecular weight is more than 2.5 million, the adhesive tends to be hard, and peeling easily occurs. Further, the weight average molecular weight (Mw) / number average molecular weight (Mn) indicating the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, and still more preferably 1.8 to 5. When the molecular weight distribution (Mw/Mn) exceeds 10, it is not preferable in terms of durability. Further, the weight average molecular weight and the molecular weight distribution (Mw/Mn) were measured by GPC (Gel Permeation Chromatography), and were determined from values calculated in terms of polystyrene.

A known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected for the production of the above (meth)acrylic polymer. Further, the obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like.

Further, in the solution polymerization, as the polymerization solvent, for example, ethyl acetate, toluene or the like is used. As a specific solution polymerization example, the reaction is carried out by adding a polymerization initiator under an inert gas stream such as nitrogen, and is usually carried out at about 50 to 70 ° C for about 5 to 30 hours.

The polymerization initiator, the chain transfer agent, the emulsifier and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. Further, the weight average molecular weight of the (meth)acrylic polymer can be controlled according to the amount of the polymerization initiator, the chain transfer agent used, and the reaction conditions, and the amount of use thereof can be appropriately adjusted depending on the types thereof.

Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, and 2,2'-azodiene. [2-(5-methyl-2-imidazolin-2-yl)propane] II Hydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(N,N'-dimethylisobutylphosphonium), 2,2 An azo initiator such as '-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries Co., Ltd.), Persulfate such as potassium persulfate or ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, and second peroxydicarbonate Butyl ester, tert-butyl peroxy neodecanoate, third hexyl peroxypivalate, tert-butyl peroxypivalate, dilaurin peroxide, di-n-octyl peroxide, peroxidation-2 -1,1,3,3-tetramethylbutyl ethylhexanoate, bis(4-methylbenzhydryl) peroxide, benzhydryl peroxide, tert-butyl peroxyisobutyrate, a peroxide-based initiator such as 1,1-di(dihexyl peroxide)cyclohexane, hydrogen peroxide tert-butyl or hydrogen peroxide, a combination of persulfate and sodium hydrogen sulfite, and a peroxide a combination of a peroxide and a redox initiator of a reducing agent, such as a combination with sodium ascorbate, etc., but is not limited thereto.

The polymerization initiator may be used singly or in combination of two or more kinds, and the total content is preferably from 0.005 to 1 part by weight, more preferably from 0.02 to 0.5 part by weight based on 100 parts by weight of the total amount of the monomer component. About.

Further, as the polymerization initiator, for example, 2,2'-azobisisobutyronitrile is used, and in order to produce the above-mentioned weight average molecular weight (meth)acrylic polymer, 100 parts by weight of the total monomer component is used. The amount of the polymerization initiator to be used is preferably from about 0.06 to 0.2 parts by weight, more preferably from about 0.08 to 0.175 parts by weight.

Further, a chain transfer agent, an emulsifier or the like can be used as previously known. The addition amount of these can also be suitably determined within the range which does not impair the effect of this invention.

(2) oligomeric type epoxy group-containing decane coupling agent

The present invention is characterized in that an oligomer-type epoxy group-containing decane coupling agent is contained in the adhesive composition. By including an oligomer-type epoxy group-containing decane coupling agent in the adhesive composition, the durability of the adhesive layer formed of the adhesive composition can be improved, especially in a humidified environment. Excellent, even after a long time, can maintain High durability. Here, the oligomer type means a polymer having a dimer or more of a monomer and not more than about 100 mer, and the weight average molecular weight of the oligomer decane coupling agent is preferably about 300 to 30,000.

The oligomer-containing epoxy group-containing decane coupling agent is preferably an epoxy group-containing decane coupling agent having an oligomeric type of two or more alkoxyalkylene groups in the molecule. Specific examples thereof include X-41-1053, X-41-1059A, and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. These coupling agents are less volatile and have a plurality of alkoxyalkylene groups, which is preferable because it is effective for improving durability.

The number of the alkoxyalkylene group of the oligomer-containing epoxy group-containing decane coupling agent is not particularly limited, but is preferably two or more in the molecule. Further, in the decane coupling agent, the amount of the alkoxy group of the oligomer-containing epoxy group-containing decane coupling agent is preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, still more preferably 20~40% 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 pentyloxy group and a hexyloxy group. Among these, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. Further, it is also preferred to contain both a methoxy group and an ethoxy group in one molecule.

The epoxy equivalent of the oligomer-containing epoxy group-containing decane coupling agent is preferably 1000 g/mol or less, more preferably 500 g/mol or less, still more preferably 300 g/mol or less. Further, the lower limit of the epoxy equivalent is not particularly limited, and is preferably, for example, 200 g/mol or more.

The epoxy group-containing decane coupling agent of the above oligomer type may be used singly or in combination of two or more kinds thereof, and the total content is preferably 0.01 based on 100 parts by weight of the (meth)acrylic polymer. ~6 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.05 to 1 part by weight. By containing an oligomer-containing epoxy group-containing decane coupling agent in the above range, the durability of the adhesive layer can be improved, and the durability in an humidified environment is excellent, and even after standing for a long period of time, it can be maintained. High durability.

Further, in the adhesive composition of the present invention, it is also possible to add an oligomer type other than the above. A decane coupling agent other than the epoxy group-containing decane coupling agent. As other coupling agents, 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-triethoxy Amino-containing decane coupling agent such as decyl-N-(1,3-dimethylbutylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxydecane, 3-propenyloxypropyl group Isocyanate group-containing decane such as (meth)acrylic acid-based decane coupling agent such as trimethoxy decane or 3-methacryloxypropyltriethoxy decane; 3-isocyanate propyl triethoxy decane; Coupling agents, etc.

The decane coupling agent other than the epoxy group-containing decane coupling agent of the above oligomer type can be added within a range not impairing the effects of the present invention, and the amount thereof is not particularly limited.

(3) Crosslinker

The adhesive composition used in the present invention preferably contains a crosslinking agent. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imide crosslinking agent. Polyfunctional metal chelates are those in which a polyvalent metal is covalently bonded or coordinated to 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, and Ti. Wait. Examples of the atom in the organic compound which is a covalent bond or a coordinate bond include an oxygen atom and the like. 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 crosslinking agent and/or a peroxide crosslinking agent, and more preferably an isocyanate crosslinking agent and a peroxide crosslinking agent are used in combination.

As the isocyanate crosslinking agent, a compound having at least two isocyanate groups can be used. For example, a known aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate or the like which is used in the ethyl carbamate reaction is usually used.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate. 1,2-propylidene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Examples of the alicyclic isocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, and hydrogenated diphenyl. Methane diisocyanate, hydrogenated dimethyl dimethyl diisocyanate, hydrogenated toluene diisocyanate hydrogenated tetramethyl dimethyl diisocyanate, and the like.

Examples of the aromatic diisocyanate include phenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-di. Phenyl methane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, phthalic acid Diisocyanate and the like.

Further, examples of the isocyanate crosslinking agent include an aminocarboxylic acid obtained by reacting a polyhydric alcohol (dimer, trimer, pentamer, etc.) of the above diisocyanate or a polyhydric alcohol such as trimethylolpropane. Ethyl ester modified body, urea modified body, biuret modified product, allophanate modified product, isocyanurate modified product, carbodiimide modified product, or the like.

As a commercial product of the isocyanate-based crosslinking agent, for example, the product name "Millionate MT", "Millionate MTL", "Millionate MR-200", "Millionate MR-400", and "Coronate" manufactured by Nippon Polyurethane Industry Co., Ltd. L", "Coronate HL", "Coronate HX", trade names "Takenate D-110N", "Takenate D-120N", "Takenate D-140N", "Takenate D-160N" manufactured by Mitsui Chemicals, Inc. "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.

The isocyanate crosslinking agent is preferably an aliphatic polyisocyanate and an aliphatic polyisocyanate compound as a modified product thereof. Compared with other isocyanate-based crosslinking agents, the aliphatic polyisocyanate-based compound has a crosslinked structure which is soft and easy to relax. The stress of expansion/contraction of the optical film is less likely to cause peeling in the durability test. As the aliphatic polyisocyanate compound, hexamethylene diisocyanate and a modified body thereof are particularly preferable.

The peroxide is a cross-linker of a base polymer ((meth)acrylic polymer) of the adhesive composition as long as it generates a radical active species by heating or light irradiation, and can be suitably used. To the workability or stability, it is preferred to use a peroxide having a one-minute half-life temperature of from 80 ° C to 160 ° C, more preferably a peroxide of from 90 ° C to 140 ° C.

Examples of the peroxide which can be used include di(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), and di(4-tert-butylcyclohexyl)peroxydicarbonate. Ester (1 minute half-life temperature: 92.1 ° C), dibutyl phthalate dihydrate (1 minute half-life temperature: 92.4 ° C), peroxy neodecanoic acid tert-butyl ester (1 minute half-life temperature: 103.5 ° C), Oxidation of third hexyl pivalate (1 minute half-life temperature: 109.1 ° C), third butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C), dilaurin peroxide (1 minute half-life temperature: 116.4 ° C ), di-n-octyl peroxide (1 minute half-life temperature: 117.4 ° C), 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), Bis(4-methylbenzhydryl) peroxide (1 minute half-life temperature: 128.2 ° C), benzoic acid peroxide (1 minute half-life temperature: 130.0 ° C), isobutyl peroxybutyrate (1) Minute half-life temperature: 136.1 ° C), 1,1-di(trihexyl peroxide) cyclohexane (1 minute half-life temperature: 149.2 ° C), and the like. Among them, since the crosslinking reaction efficiency is particularly excellent, it is preferred to use bis(4-tert-butylcyclohexyl)peroxycarbonate (1 minute half-life temperature: 92.1 ° C), dilaurin peroxide (1 minute half-life) Temperature: 116.4 ° C), benzoquinone peroxide (1 minute half-life temperature: 130.0 ° C), and the like.

In addition, the half-life of a peroxide means the time which shows the decomposition rate of a peroxide, and the residual amount of a peroxide becomes half. The decomposition temperature for obtaining the half-life at any time and the half-life time at an arbitrary temperature are described in the manufacturer's catalog, etc., for example, "Oil peroxides" described in Nippon Oil & Fat Co., Ltd. The 9th edition of the catalogue (May 2003) and so on.

The amount of the crosslinking agent used is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 part by weight, based on 100 parts by weight of the (meth)acrylic polymer. In addition, when the crosslinking agent is less than 0.01 parts by weight, the adhesive layer becomes insufficiently crosslinked, and the durability or the adhesive property cannot be satisfied. On the other hand, if it is more than 3 parts by weight, the adhesive layer is provided. It tends to be too hard and the durability is lowered.

The isocyanate-based crosslinking agent may be used singly or in combination of two or more kinds thereof, and the total content is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the (meth)acryl-based polymer. It is preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight. It can be appropriately contained in consideration of the cohesive force, the prevention of peeling in the durability test, and the like.

The peroxide may be used singly or in combination of two or more kinds, and the total content is preferably 0.01 to 2 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the (meth)acrylic polymer. It is 0.04 to 1.5 parts by weight, and more preferably 0.05 to 1 part by weight. In order to adjust workability, crosslinking stability, etc., it is suitably selected within this range.

(4) Ionic compounds

The adhesive composition of the present invention can further contain an ionic compound. The ionic compound is not particularly limited, and those used in the art can be preferably used. For example, it is described in JP-A-2015-4861, and among these, a (perfluoroalkylsulfonyl) quinone imide lithium salt is preferred, and bis(trifluoromethanesulfonate) is more preferred. Lithium imine) lithium. In addition, the ratio of the ionic compound is not particularly limited, and may be within a range that does not impair the effects of the present invention. For example, it is preferably 10 parts by weight or less based on 100 parts by weight of the (meth)acrylic polymer. It is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 1 part by weight or less.

(5) Other

In the adhesive composition used in the present invention, it is possible to formulate a reactive decane a polyether compound. In terms of being able to improve secondary workability, a polyether compound is preferred. The polyether compound can be, for example, those disclosed in Japanese Laid-Open Patent Publication No. 2010-275522. Moreover, the amount of addition can be appropriately determined within a range that does not impair the effects of the present invention.

Further, the adhesive composition used in the present invention may contain other known additives, for example, a polyether compound obtained by using a polypropylene glycol such as polypropylene glycol, a powder, a dye, or the like, a dye, or the like. Surfactant, plasticizer, adhesion imparting agent, surface lubricant, leveling agent, softener, antioxidant, anti-aging agent, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic or organic filler, It is added as appropriate for the use of metal powder, particles, and foil. Further, a redox system to which a reducing agent is added may be used within a range that can be controlled. The additive is preferably used in an amount of 5 parts by weight or less, further 3 parts by weight or less, and further 1 part by weight or less based on 100 parts by weight of the (meth)acryl-based polymer.

2. Adhesive layer for transparent conductive layer

The adhesive layer for a transparent conductive layer of the present invention is characterized by being formed of the above-described adhesive composition. When the adhesive layer is formed, it is preferred to adjust the addition amount of the entire crosslinking agent, and to fully consider the influence of the crosslinking treatment temperature or the crosslinking treatment time.

The crosslinking treatment temperature or the crosslinking treatment time can be adjusted depending on the crosslinking agent to be used. The crosslinking treatment temperature is preferably 170 ° C or lower. Further, the crosslinking treatment may be carried out at a temperature at the drying step of the adhesive layer, or may be carried out by additionally providing a crosslinking treatment step after the drying step. Further, the crosslinking treatment time can be set in consideration of productivity and workability, and is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.

The method for forming the pressure-sensitive adhesive layer is not particularly limited, and the pressure-sensitive adhesive composition may be applied to various base materials, dried by a dryer such as a hot oven, and the solvent may be volatilized, and the crosslinking treatment may be carried out as necessary. The method of forming an adhesive layer and transferring the adhesive layer to the polarizing film or the transparent conductive substrate described below may also be performed on the polarizing film or the above-mentioned polarizing film. The adhesive composition is directly applied onto the conductive substrate to form an adhesive layer. In the present invention, a polarizing film in which an adhesive layer of an adhesive layer is formed on a polarizing film is prepared in advance, and the polarizing film of the adhesive layer is attached to the liquid crystal cell.

The substrate is not particularly limited, and examples thereof include various substrates such as a release film, a transparent resin film substrate, and a polarizing film described below.

As the adhesive composition, various methods can be used for the coating method of the above substrate or the polarizing film. Specific examples thereof include spray coating, roll coating, contact roll coating, gravure coating, reverse coating, roll coating, spray coating, dip roller coating, and bar coating. Cloth, knife coating, air knife coating, curtain coating, lip coating, extrusion coating method using a die coater or the like.

The drying conditions (temperature, time) are not particularly limited, and can be appropriately set depending on the composition, concentration, and the like of the adhesive composition, and are, for example, about 80 to 170 ° C, preferably 90 to 200 ° C, and 1 to 60 minutes. Good for 2~30 minutes.

Further, after drying, a crosslinking treatment may be carried out as needed, and the conditions are as described above.

The thickness of the adhesive layer (after drying) is, for example, preferably from 5 to 100 μm, more preferably from 7 to 70 μm, still more preferably from 10 to 50 μm. When the thickness of the adhesive layer is less than 5 μm, the adhesion to the adherend is insufficient, and the durability under humidification conditions tends to be insufficient. On the other hand, when the thickness of the adhesive layer exceeds 100 μm, there is a tendency that the adhesive composition cannot be sufficiently dried to remain bubbles or adhere to the adhesive when the adhesive composition is formed or dried. The surface of the layer is uneven in thickness, and the appearance problem tends to become apparent.

The constituent material of the release film may, for example, be a resin film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film, or a porous material such as paper, cloth or nonwoven fabric, or a mesh or hair. A resin film can be preferably used in terms of excellent surface smoothness, such as a foam sheet, a metal foil, and a suitable sheet such as the laminate.

Examples of the resin film include a polyethylene film, a polypropylene film, and a polybutene film. Polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane Film, ethylene-vinyl acetate copolymer film, and the like.

The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. The release film can also be subjected to mold release and antifouling treatment using a polyfluorene-based, fluorine-based, long-chain alkyl or fatty acid amide-based release agent, cerium oxide powder, or the like. Antistatic treatment of cloth type, kneading type, vapor deposition type, etc. In particular, by appropriately performing a release treatment such as polyfluorination treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film, the peeling property from the above-mentioned 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 by a single film. For example, examples of the material thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetic acid resins, polyether oxime resins, polycarbonate resins, and polyamines. Resin, polyimide resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyaryl An ester resin, a polyphenylene sulfide resin, or the like. Among these, a polyester resin, a polyamidene resin, and a polyether oxime resin are particularly preferable.

The thickness of the film substrate is preferably 15 to 200 μm.

3. Polarized film with adhesive layer

The polarizing film with an adhesive layer of the present invention is characterized in that the adhesive layer is provided on at least one side surface of the polarizing film. The polarizing film of the adhesive layer of the present invention is used in such a manner that the adhesive layer of the polarizing film is in contact with the transparent conductive layer of the transparent conductive substrate having a transparent conductive layer on the transparent substrate.

The method of forming the adhesive layer is as described above.

The polarizing film is not particularly limited, and a transparent protective film is usually used on one surface or both surfaces of the polarizing element.

The polarizing element is not particularly limited, and various polarizing elements can be used. Examples of the polarizing element include adsorption of a dichroic substance of iodine or a dichroic dye to a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer-based partial saponified film. In the hydrophilic polymer film, a uniaxial stretching is carried out, and a polyene-based alignment film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride is used. Among these, a polarizing element comprising a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable, and an iodine-based polarizing element containing iodine and/or iodide ion is more preferable. Further, the thickness of the polarizing elements is not particularly limited, but is usually about 5 to 80 μm.

A polarizing element obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine to carry out dyeing, and extending to the original length of 3 ~7 times. If necessary, it can be immersed in an aqueous solution containing potassium iodide such as boric acid, zinc sulfate or zinc chloride. Further, 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, it is possible to wash the surface of the polyvinyl alcohol-based film or to prevent the adhesion of the anti-adhesion agent. In addition, by swelling the polyvinyl alcohol-based film, it is possible to prevent uneven dyeing. Uneven effect. The extension may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. That is, it is also possible to carry out elongation in an aqueous solution or a water bath such as boric acid or potassium iodide.

Further, in the present invention, a thin polarizing element having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably from 1 to 7 μm. The thin polarizing element is preferable in that the thickness is small and the visibility is excellent, and the dimensional change is small and the durability is excellent, and the thickness of the polarizing film can be made thinner.

The thin-type polarizing element is exemplified by Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, and International Publication No. 2010/100917. The thin type described in the specification, Japanese Patent No. 4751481, or Japanese Patent Laid-Open Publication No. 2012-073563 Polarized film. The thin polarizing film can be obtained by the following production method, which comprises stretching the polyvinyl alcohol resin (hereinafter also referred to as PVA resin) layer and the extending resin substrate in a state of a laminate. Steps and steps of dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be stretched by being supported on the resin substrate for stretching without defects such as breakage due to stretching.

In the method for producing the thin polarizing film, which includes the step of stretching in the state of the laminated body and the step of dyeing, it is preferable to expand the polarizing performance at a high magnification, and it is preferably International Publication No. 2010/ The method disclosed in the specification of No. 100917, the specification of the International Publication No. 2010/100917, the specification of Japanese Patent No. 4751481, or the method of the step of extending in an aqueous boric acid solution, as described in Japanese Laid-Open Patent Publication No. 2012-073563, The method described in the specification of Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563 is obtained by a method comprising the step of assisting in the air extension in an aqueous solution of boric acid before extending.

As a material for forming the transparent protective film provided on one surface or both surfaces of the above-mentioned polarizing element, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, and isotropic property is used. Specific examples of the thermoplastic resin include a cellulose resin such as triethyl fluorene cellulose, a polyester resin, a polyether oxime resin, a polyfluorene resin, a polycarbonate resin, a polyamide resin, and a polyimide resin. Polyolefin resin, (meth)acrylic resin, cyclic polyolefin resin An olefinic resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and a mixture thereof. Further, on one side of the polarizing element, a transparent protective film is bonded by an adhesive layer, and on the other side, (meth)acrylic, urethane, or acrylic can be used as the transparent protective film. A thermosetting resin such as an urethane type, an epoxy type or a polyoxymethylene type, or an ultraviolet curable resin. One or more optional additives may be contained in the transparent protective film. Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color preventive agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the above thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, more preferably from 50 to 99% by weight, still more preferably from 60 to 98% by weight, still more preferably from 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, the high transparency and the like inherent in the thermoplastic resin cannot be sufficiently exhibited.

The thickness of the protective film can be appropriately determined, and is usually about 1 to 500 μm in terms of workability such as strength and workability, and film properties.

The polarizing element and the protective film are usually adhered to each other via a water-based adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, an ethylene-based latex, an aqueous polyurethane, and an aqueous polyester. 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 curing type polarizing film exhibits good adhesion to the above various transparent protective films. Further, in the adhesive used in the present invention, a metal compound filler can be contained.

Further, in the present invention, a retardation film or the like can be formed on the polarizing element instead of the transparent protective film of the polarizing film. Further, another transparent protective film or a retardation film or the like may be further provided on the transparent protective film.

The transparent protective film can be subjected to a treatment for hard coating, anti-reflection treatment, anti-sticking treatment, diffusion or anti-glare without causing the polarizing element to follow the surface.

Further, between the polarizing film and the adhesive layer, an adhesion-promoting layer may be provided. The material for forming the adhesion-promoting layer is not particularly limited, and examples thereof include various polymers, sols of metal oxides, cerium sols, and the like. Among these, a polymer is particularly preferably used. The use form of the above polymer may be any of a solvent-soluble type, a water-dispersible type, and a water-soluble type.

Examples of the polymer include a polyurethane resin, a polyester resin, an acrylic resin, a polyether resin, a cellulose resin, a polyvinyl alcohol resin, and a polyvinylpyrrolidone. Polystyrene resin, etc.

Moreover, when the adhesive layer of the polarizing film with the adhesive layer is exposed, The adhesive layer can be protected by a release film (separator) until it is practical. As a release film, the above is mentioned. When a release film is used as the substrate in the production of the above adhesive layer, the adhesive layer on the release film is bonded to the polarizing film, whereby the release film can be used as a polarizing film with an adhesive layer. The release film of the adhesive layer enables simplification of the steps.

The polarizing film with an adhesive layer of the present invention is used by being bonded to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate.

The constituent material of the transparent conductive layer as the transparent conductive substrate is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, germanium, titanium, cerium, zirconium, magnesium, aluminum, gold, silver, copper, and palladium. a metal oxide of at least one metal of the group consisting of tungsten. Further, in the metal oxide, a metal atom shown in the above group may be further contained as needed. 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.

In addition, as the ITO, crystalline ITO or amorphous (amorphous) ITO can be used, and any of them can be preferably used.

The thickness of the transparent conductive layer is not particularly limited, but is preferably 10 nm or more, more preferably 15 to 40 nm, still more preferably 20 to 30 nm.

The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, or an ion plating method can be exemplified. Further, an appropriate method may be employed depending on the desired film thickness.

The transparent substrate is not particularly limited as long as it is a transparent substrate, and examples thereof include glass and a transparent resin film substrate. The transparent resin film substrate is as described above.

Further, an undercoat layer, an oligomer blocking layer, or the like may be provided between the transparent conductive layer and the transparent substrate as needed.

4. Image display device

An image display device according to the present invention is characterized in that it comprises a polarizing film with an adhesive layer and a liquid crystal cell having a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and the adhesive is attached thereto. The adhesive layer of the polarizing film of the agent layer is bonded to the transparent conductive layer of the liquid crystal cell.

The polarizing film and the transparent conductive substrate with an adhesive layer are as described above.

The liquid crystal cell used in the image display device of the present invention is provided with a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and the transparent conductive substrate is usually located on the surface of the liquid crystal cell on the viewing side. A liquid crystal panel including a liquid crystal cell which can be used in the present invention will be described with reference to Fig. 1 . However, the invention is not limited by FIG.

An embodiment of the liquid crystal panel 1 that can be included in the image display device of the present invention includes a viewing side transparent protective film 2 / a polarizing element 3 / a liquid crystal cell side transparent protective film 4 / an adhesive layer 5 from the viewing side. / Transparent Conductive Layer 6 / Transparent Substrate 7 / Liquid Crystal Layer 8 / Transparent Substrate 9 / Adhesive Layer 10 / Liquid Crystal Cell Side Transparent Protective Film 11 / Polarizing Element 12 / Light Source Side Transparent Protective Film 13. In Fig. 1, the polarizing film of the adhesive layer of the present invention corresponds to the viewing side transparent protective film 2/polarizing element 2/liquid crystal cell side transparent protective film 3/adhesive layer 5. Further, in Fig. 1, the transparent conductive substrate used in the present invention is composed of a transparent conductive layer 6 / a transparent substrate 7. Further, in Fig. 1, the liquid crystal cell including the transparent conductive substrate used in the present invention is composed of a transparent conductive layer 6 / a transparent substrate 7 / a liquid crystal layer 8 / a transparent substrate 9.

Further, in addition to the above configuration, an optical film such as a retardation film, a viewing angle compensation film, or a brightness enhancement film can be appropriately provided in the liquid crystal panel 1.

The liquid crystal layer 8 is not particularly limited, and for example, any type such as a TN type, an STN type, a π type, a VA type, or an IPS type can be used. The transparent substrate 9 (light source side) is not particularly limited as long as it is a transparent substrate, and examples thereof include glass and a transparent resin film substrate. The transparent resin film substrate is as described above.

Further, the adhesive layer 10 on the light source side, the liquid crystal cell side transparent protective film 11, the polarizing element 12, and the light source side transparent protective film 13 can be used in the prior art, and can also preferably be used in the present specification. Recorder.

The liquid crystal panel 1 is characterized in that the polarizing film of the adhesive layer of the present invention is laminated on the liquid crystal cell so that the transparent conductive layer 6 of the liquid crystal cell is in contact with the adhesive layer 5 of the polarizing film with the adhesive layer. It is on the transparent conductive layer 6 of the outermost layer of the viewing side.

The image display device of the present invention may be any one of a polarizing film comprising the adhesive layer of the present invention and a liquid crystal cell having a transparent conductive substrate having a transparent conductive layer on a transparent substrate. LCD panel. Hereinafter, the liquid crystal display device will be described as an example, and the present invention is not limited thereto.

Specific examples of the image display device that can be used in the liquid crystal panel 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 of a polarizing film containing the adhesive layer of the present invention and a transparent conductive substrate having a transparent conductive layer on a transparent substrate. The image display device is the same.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited by the Examples. Further, room temperature conditions which were not particularly specified were 23 ° C and 65% R.H.

<Measurement of Weight Average Molecular Weight of (Meth)Acrylic Polymer>

The weight average molecular weight (Mw) of the (meth)acrylic polymer was measured by GPC (gel permeation chromatography). Mw/Mn was also measured in the same manner.

‧Analytical device: manufactured by HLC-8120GPC, Dongsuo Co., Ltd.

‧Tube: G7000HXL+GMHXL+GMHXL, manufactured by Dongsuo Co., Ltd.

‧ Column size: 7.8mm each ×30cm meter 90cm

‧column temperature: 40 ° C

‧Flow: 0.8mL/min

‧Injection amount: 100μL

‧Dissolved solution: tetrahydrofuran

‧Detector: Differential Refractometer (RI)

‧Standard sample: polystyrene

Production Example 1 (Production of Polarizing Film)

The polyvinyl alcohol film having a thickness of 80 μm was dyed for one minute at 30° C. and a 0.3% by weight iodine solution, and stretched three times between rolls having different speed ratios. Thereafter, it was extended to a comprehensive stretching ratio of 6 times while immersing for 0.5 minute while containing an aqueous solution containing boric acid having a concentration of 4% by weight and a concentration of potassium iodide at a concentration of 4% by weight. Next, it was washed by immersing in an aqueous solution containing potassium iodide at a concentration of 1.5% by weight and a concentration of 1.5% by weight for 10 seconds, and then dried at 50 ° C for 4 minutes to obtain a polarizing element having a thickness of 30 μm. A saponified 80 μm-thick triethylene fluorene cellulose film was bonded to both surfaces of the polarizing element by a polyvinyl alcohol-based adhesive to prepare a polarizing film.

Production Example 2 (Adjustment of Solution of Acrylic Polymer (a-1))

A monomer mixture containing 99 parts by weight of butyl acrylate and 1 part by weight of 4-hydroxybutyl acrylate was added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. Furthermore, 0.1 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator is added to 100 parts by weight of the monomer mixture (solid content), and 100 parts by weight of ethyl acetate is gradually added thereto. After nitrogen gas was introduced while stirring, the temperature of the liquid in the flask was maintained at around 55 ° C, and polymerization was carried out for 8 hours to prepare an acrylic polymer having a weight average molecular weight (Mw) of 1.56 million and Mw/Mn 3.2 (a). -1) solution.

Manufacturing example 3~5

In Production Example 2, the monomer for preparing an acrylic polymer was changed as shown in Table 1. A solution of the acrylic polymer (a-2) to (a-4) was prepared by the same method as in Production Example 2 except for the type and the use ratio.

The abbreviations in Table 1 are as follows.

BA: butyl acrylate

NVP: N-vinyl-2-pyrrolidone

AA: Acrylic

HBA: 4-hydroxybutyl acrylate

Example 1

(Adjustment of Acrylic Adhesive Composition)

The isocyanate crosslinking agent was formulated with respect to 100 parts by weight of the solid solution of the solution of the acrylic polymer (a-1) obtained in Production Example 2 (trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate) , manufactured by Mitsui Chemicals Co., Ltd., 0.1 parts, 0.3 parts of benzoyl peroxide (Nyper BMT40SV, manufactured by Nippon Oil & Fats Co., Ltd.), and an oligomeric type of epoxy group-containing decane coupling agent (trade name: X- A solution of an acrylic pressure-sensitive adhesive composition was prepared by dissolving 0.31 parts of 41-1053, alkoxy group amount: 50% by weight, epoxy equivalent: 830 g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.).

(Production of polarizing film with adhesive layer)

The solution of the acrylic adhesive composition was applied to a polyethylene terephthalate film treated with a polyfluorene-based release agent so that the thickness of the adhesive layer after drying became 23 μm (isolation film, trade name: MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) The surface was dried at 155 ° C for 1 minute to form an adhesive layer on the surface of the separator. Next, the adhesive layer formed on the separator was transferred onto the polarizing film produced in Production Example 1 to prepare a polarizing film with an adhesive layer.

Examples 2 to 12 and Comparative Examples 1 to 4

In the same manner as in Example 1, except that the type of the acrylic polymer, the type of the decane coupling agent, and the addition amount thereof were changed as shown in Table 1, an acrylic adhesive composition was prepared in the same manner as in Example 1. a solution of the substance. Further, in Example 12, the ionic compound was formulated in the ratio shown in Table 2. A polarizing film with an adhesive layer was prepared by the same method as in Example 1 using the obtained solution of the acrylic adhesive composition.

The polarizing film with the adhesive layer obtained in the above Examples and Comparative Examples was evaluated as follows. The evaluation results are shown in Table 2.

< Durability test immediately after coating>

The polarizing film of the adhesive layer obtained in the examples and the comparative examples was cut into 15 inches, and the obtained one was set as a sample. This sample was bonded to an ITO layer of glass having an ITO layer having an amorphous ITO layer on an alkali-free glass (trade name: EG-XG, manufactured by Corning Incorporated) having a thickness of 0.7 mm using a laminator. Next, the autoclave treatment was carried out for 15 minutes at 50 ° C and 0.5 MPa to completely adhere the sample to the glass to which the ITO layer was attached. The sample subjected to the treatment was subjected to a treatment for 500 hours in each of an environment of 60° C./90% RH and 60° C./95% RH (humidification test), and the polarizing film and the ITO layer were visually evaluated according to the following criteria. The appearance between the glass. Further, the ITO layer is formed by sputtering. The composition ratio of ITO was 3% by weight, and a heating step of 140 ° C × 60 minutes was carried out before the sample was bonded. Further, the Sn ratio of ITO is calculated from the weight of Sn atoms / (weight of Sn atoms + weight of In atoms).

(evaluation benchmark)

◎: There was no change in appearance such as peeling at all.

○: The end portion was slightly peeled off, but there was no problem in practical use.

△: The end portion was peeled off, but if it was not used for a special purpose, it was practically free from problems.

×: There is a significant peeling at the end, which is problematic in practical use.

<Endurance test after long-term storage (12 months)>

The polarizing film of the adhesive layer obtained in the examples and the comparative examples was stored under the conditions of 23 ° C / 55% R.H. for 12 months. The durability test after long-term storage was carried out in the same manner as in the above-described "durability test after coating", except that the polarizing film with the adhesive layer for 12 months was stored. Further, the evaluation was carried out in accordance with the evaluation criteria similar to the above-mentioned "durability test immediately after application".

The abbreviations in Table 2 are as follows.

Isocyanate system: trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd.

Peroxide: Trade name: Nyper BMT40SV, benzoyl peroxide, manufactured by Nippon Oil & Fats Co., Ltd.

X-41-1056: Oligomer-containing decane coupling agent of oligomer type, alkoxy group amount: 17% by weight, epoxy equivalent: 280 g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.

X-41-1053: oligomeric type epoxy group-containing decane coupling agent, alkoxy group amount: 50% by weight, epoxy equivalent: 830 g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.

X-41-1059A: oligomeric type epoxy group-containing decane coupling agent, alkoxy group amount: 43% by weight, epoxy equivalent: 350 g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.

Ionic compound: bis(trifluoromethanesulfonyl quinone imide) lithium, manufactured by Mitsubishi Materials Co., Ltd.

KBM-403: γ-glycidoxypropyl methoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd.

Claims (7)

An adhesive composition for forming an adhesive layer which is adhered to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate. A (meth)acrylic polymer and an oligomeric epoxy group-containing decane coupling agent are used. The adhesive composition according to claim 1, wherein the oligomer-containing epoxy group-containing decane coupling agent has two or more alkoxyalkyl groups in the molecule. The adhesive composition according to claim 1 or 2, wherein the oligomer-type epoxy group-containing decane coupling agent is formulated in an amount of 0.01 to 3 by weight based on 100 parts by weight of the above (meth)acrylic polymer. Share. The adhesive composition according to any one of claims 1 to 3, wherein the oligomer-type epoxy group-containing decane coupling agent has an epoxy equivalent of 300 g/mol or less. An adhesive layer for a transparent conductive layer, which is formed by the adhesive composition according to any one of claims 1 to 4. A polarizing film with an adhesive layer, which is bonded to a transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and has a polarizing film and a request item 5 adhesive layer. An image display device comprising: a polarizing film with an adhesive layer as claimed in claim 6; and a liquid crystal cell having a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and The adhesive layer of the polarizing film with the adhesive layer is bonded to the transparent conductive layer of the liquid crystal cell.