KR20180135432A - Polarizing film with adhesive layer and image display device - Google Patents

Abstract

The present invention relates to an adhesive layer used by being bonded to a transparent conductive layer of the transparent conductive base material having a transparent conductive layer on a transparent base material and a polarizing film with the adhesive layer. An adhesive composition for forming the adhesive layer includes a (meth) acrylic-based polymer and a silane coupling agent containing a thiol group. The polarizing film of the present invention in which the adhesive layer is formed has high durability, particularly excellent durability under a humidifying environment, and excellent rework property even when the polarizing film is bonded to the transparent conductive base material having the transparent conductive layer on the transparent base material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polarizing film and an image display device,

The present invention relates to a polarizing film on which a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer and a polarizing film is formed by using a transparent conductive base material having a transparent conductive layer on a transparent base. The present invention also relates to an image display panel comprising a transparent conductive base to which a polarizing film having the pressure-sensitive adhesive layer formed thereon is applied. Further, the present invention relates to an image display apparatus including the image display panel.

In a liquid crystal panel used in an image display panel, for example, a liquid crystal display device or the like, a polarizing film is laminated on both sides of a liquid crystal cell formed of a liquid crystal layer disposed between a pair of transparent substrates with an adhesive layer interposed therebetween . Such a pressure-sensitive adhesive layer is required to have high durability. For example, in the durability test such as heating and humidification, which is normally conducted as an environmental promotion test, it is required that no problems such as peeling or lifting due to the pressure- .

Such a pressure-sensitive adhesive composition for optical use has been studied variously, and for example, there has been proposed a pressure-sensitive adhesive composition that does not cause peeling or foaming even when the optical film is adhered (adhered) under high humidity and heat conditions See, for example, Patent Document 1).

Japanese Laid-Open Patent Publication No. 2009-242767

A transparent conductive film such as an indium tin oxide (ITO) thin film or an organic conductive film using an electroconductive polymer is formed on one of the transparent substrates of the liquid crystal cell constituting the liquid crystal panel. The adhesive layer, which is in contact with the transparent conductive film, It is easy to remove or peel off, and the durability tends to be lowered. In addition, especially in a humidifying environment, the durability deteriorated remarkably. The pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of Patent Document 1 is poor in adhesion to the indium tin oxide (ITO) layer, and the pressure-sensitive adhesive composition for a liquid crystal panel having a transparent conductive layer is not sufficient.

In addition, the pressure-sensitive adhesive layer designed to secure the heat resistance has high adhesion with the transparent conductive layer, and the pressure-sensitive adhesive residue or the polarizing film sometimes breaks during reworking. The pressure-sensitive adhesive layer is also required to have a workability without such problems.

Accordingly, the present invention relates to a polarizing film, which is excellent in durability under a humidified environment and has excellent workability even when it is applied to a transparent conductive substrate having a transparent conductive layer on a transparent substrate, It is also an object of the present invention to provide a polarizing film on which a pressure-sensitive adhesive layer is formed.

Another object of the present invention is to provide an image display panel comprising a transparent conductive base material to which a polarizing film on which the pressure-sensitive adhesive layer is formed is applied. Further, it is another object of the present invention to provide an image display apparatus including the image display panel.

As a result of intensive investigations to solve the above problems, the present inventors have found a polarizing film on which a pressure-sensitive adhesive layer is formed, and have completed the present invention.

That is, the present invention relates to a polarizing film on which a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer and a polarizing film to be used in combination with the transparent conductive layer of a transparent conductive base having a transparent conductive layer on a transparent base is formed,

Wherein the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises a (meth) acryl-based polymer and a silane coupling agent containing a thiol group.

It is preferable that the thiol group-containing silane coupling agent is an oligomer-type thiol group-containing silane coupling agent.

It is preferable that the thiol group-containing silane coupling agent has two or more alkoxysilyl groups in the molecule.

It is preferable that the blending amount of the thiol group-containing silane coupling agent is 0.01 to 3 parts by weight based on 100 parts by weight of the (meth) acryl-based polymer.

The thiol equivalent of the thiol group-containing silane coupling agent is preferably 700 g / mol or less.

The present invention also provides an image display panel comprising a polarizing film on which the pressure-sensitive adhesive layer is formed and a transparent conductive base material having a transparent conductive layer on the transparent base,

Wherein the pressure sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is bonded to the transparent conductive layer of the image display panel.

The present invention also relates to an image display device having the image display panel.

The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer in the polarizing film in which the pressure-sensitive adhesive layer of the present invention is formed contains a thiol group-containing silane coupling agent. Therefore, even when the pressure-sensitive adhesive layer is adhered to the transparent conductive layer, Especially, it has excellent durability under humidified environment. In addition, the pressure-sensitive adhesive layer has good reworkability, and can suppress breakage of adhesive residue and polarizing film during rework. As described above, the polarizing film in which the pressure-sensitive adhesive layer of the present invention is formed can have both durability and reworkability with respect to the transparent conductive layer. Further, according to the present invention, it is possible to provide an image display panel having a polarizing film on which the pressure-sensitive adhesive layer is formed, and further, an image display apparatus having the image display panel.

1 is a cross-sectional view schematically showing an embodiment of a liquid crystal panel which is one of image display panels usable in the present invention.

1. Adhesive composition

The pressure-sensitive adhesive composition of the present invention is used for forming a pressure-sensitive adhesive layer to be used by being attached to the transparent conductive layer of a transparent conductive base material having a transparent conductive layer on a transparent base material. And a control unit. Hereinafter, the composition of the pressure-sensitive adhesive composition of the present invention will be described.

(1) (meth) acrylic polymer

The pressure-sensitive adhesive composition of the present invention comprises a silane coupling agent containing a (meth) acryl-based polymer and a thiol group, and preferably contains a (meth) acryl-based polymer as a main component. Here, the main component means a component having the highest content ratio among all the solid components contained in the pressure-sensitive adhesive composition, and is, for example, more than 50% by weight of all the solid components contained in the pressure-sensitive adhesive composition, and more preferably more than 70% Represents the component occupying.

The (meth) acryl-based polymer usually contains alkyl (meth) acrylate as a main component as a monomer unit. Further, (meth) acrylate refers to acrylate and / or methacrylate and has the same meaning as (meth) of the present invention.

Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer include linear or branched alkyl groups having 1 to 18 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an amyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, A heptyl group, a heptyl group, a heptyl group, a heptyl group, a heptyl group, a heptyl group, a heptyl group, a heptyl group, a heptyl group, a heptyl group, These can be used alone or in combination. The average number of carbon atoms of these alkyl groups is preferably from 3 to 9.

Examples of the monomer constituting the (meth) acryl-based polymer include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer and an aromatic ring-containing (meth) acrylate besides the alkyl (meth) acrylate.

The carboxyl group-containing monomer is a compound containing a carboxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the carboxyl group-containing monomers include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid . Among the above-mentioned carboxyl group-containing monomers, acrylic acid is preferable from the viewpoint of copolymerization, price and adhesive property.

The hydroxyl group-containing monomer is a compound containing a hydroxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the hydroxyl group-containing monomer include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) (Meth) acrylate such as hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate and 12- ) Acrylate and (4-hydroxymethylcyclohexyl) -methylacrylate. Among the hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the standpoint of durability, and 4-hydroxybutyl (meth) desirable.

The amide group-containing monomer is a compound containing an amide group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the amide group-containing monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-propyl (meth) acrylamide, N-methyl (meth) acrylamide, N-methyl Acrylamide monomers such as N- (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl (meth) acrylamide and mercaptoethyl Acryloyl heterocyclic monomers such as (meth) acryloylpiperidine and N- (meth) acryloylpyrrolidine, N-vinylpyrrolidone such as N-vinylpyrrolidone and N-vinyl-epsilon -caprolactam Containing lactam-based monomer, and the like. The amide group-containing monomer is preferable for satisfying the durability, and among the amide group-containing monomers, in particular, the N-vinyl group-containing lactam monomer is preferable in terms of both durability and reworkability to the transparent conductive layer desirable.

The aromatic ring-containing (meth) acrylate is a compound containing an aromatic ring structure in its structure and further containing a (meth) acryloyl 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 the durability (particularly, the durability against the transparent conductive layer).

Specific examples of the aromatic ring-containing (meth) acrylate include benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate, phenoxy (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide modified nonylphenol (Meth) acrylates such as ethylene oxide modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (Meth) acrylate, 2-naphthoyl (meth) acrylate, 2-naphthoxyethyl acrylate, 2- (4-methylphenyl) Lt; / RTI > Naphthoxy) ethyl (meth) acrylate; and those having a biphenyl ring such as biphenyl (meth) acrylate.

The carboxyl group-containing monomer, the hydroxyl group-containing monomer, the amide group-containing monomer and the aromatic ring-containing (meth) acrylate are reaction points with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent. In particular, carboxyl group-containing monomers and hydroxyl group-containing monomers are preferably used because they are rich in reactivity with an intermolecular crosslinking agent, and therefore, improve the cohesiveness and heat resistance of the resulting pressure-sensitive adhesive layer.

The (meth) acryl-based polymer used in the present invention preferably contains the above monomers as monomer units in the following amounts by weight of the total constituent monomers (100% by weight).

The weight ratio of the alkyl (meth) acrylate may be set as the remainder of the monomer other than the alkyl (meth) acrylate, and it is preferably 70 wt% or more. Setting the weight ratio of the alkyl (meth) acrylate to the above range is preferable in securing adhesiveness.

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% 0.5% by weight is particularly preferable. When the weight ratio of the carboxyl group-containing monomer is less than 0.01% by weight, the durability and the workability tends to be incompatible. On the other hand, if it exceeds 2% by weight, the transparent conductive layer may be corroded, which tends to make both durability and reworkability incompatible.

The weight ratio of the hydroxyl group-containing monomer is preferably 3% by weight or less, more preferably 0.01 to 3% by weight, further preferably 0.1 to 2% by weight, particularly 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 pressure-sensitive adhesive layer tends to be inadequate in cross-linking so that both durability and reworkability can not be satisfied and the pressure-sensitive adhesive property can not be satisfied. On the other hand, if it exceeds 3% by weight, durability and reworkability can not be achieved at the same time.

The proportion by weight of the amide group-containing monomer is preferably 8% by weight or less, more preferably 0.1 to 8% by weight, further preferably 0.3 to 5% by weight, further preferably 0.3 to 4% by weight, Particularly preferably 2.5% by weight. When the weight ratio of the amide group-containing monomer is less than 0.1% by weight, the durability and reworkability of the transparent conductive layer tends to be incompatible. On the other hand, if it exceeds 8% by weight, the balance between durability and reworkability can not be satisfied.

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 balance between durability and reworkability tends to be unsatisfactory.

In the (meth) acryl-based polymer, besides the monomer unit, it is not particularly necessary to contain other monomer units, but a (meth) acryloyl group or vinyl (meth) acryloyl group is preferable for the purpose of improving both adhesiveness, heat resistance, One or more kinds of copolymerizable monomers having a polymerizable functional group having an unsaturated double bond such as a group can be introduced by copolymerization.

The proportion of the copolymerizable monomer in the (meth) acrylic polymer is preferably 0 to 10% by weight, more preferably 0 to 7% by weight in the weight ratio of the total constituent monomer (100% by weight) By weight, more preferably about 0 to 5% by weight.

The (meth) acrylic polymer of the present invention is usually one having a weight average molecular weight of 1,000,000 to 2,500,000. In consideration of durability, particularly heat resistance, the weight average molecular weight is preferably 1.2 to 2 million. If the weight average molecular weight is less than 1,000,000, it is not preferable from the viewpoint of heat resistance. On the other hand, if the weight average molecular weight is larger than 2.5 million, the pressure-sensitive adhesive tends to be hardened, and peeling easily occurs. The weight average molecular weight (Mw) / number average molecular weight (Mn) representing the molecular weight distribution is preferably from 1.8 to 10, more preferably from 1.8 to 7, and even more preferably from 1.8 to 5. When the molecular weight distribution (Mw / Mn) exceeds 10, it is not preferable from the viewpoint of durability. The weight average molecular weight and the molecular weight distribution (Mw / Mn) are determined from the value measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.

Such (meth) acryl-based polymers can be suitably selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerization. The (meth) acryl-based polymer to be obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.

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

The polymerization initiator, chain transfer agent and emulsifier used in the radical polymerization are not particularly limited and can be appropriately selected and used. The weight average molecular weight of the (meth) acryl-based polymer can be controlled by the amount of the polymerization initiator, the amount of the chain transfer agent used, and the reaction conditions.

Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- Azobis (N, N ', N'-tetramethyluronium tetrafluoroborate), 2,2'-azobis Azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Kowa Pure Chemical Industries, Ltd.) (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydi Carbonate, t-butyl peroxyneodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauryl peroxide, di-n-octanoyl peroxide, 1,1,3,3 - tetramethylbutyl peroxy-2-ethyl hexanoate, Peroxide such as di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1,1-di (t-hexylperoxy) cyclohexane, A system initiator, a combination of persulfate and sodium hydrogen sulfite, a redox initiator combined with a peroxide such as a combination of peroxide and sodium ascorbate, and a reducing agent, but the present invention is not limited thereto.

The content of the whole is preferably about 0.005 to 1 part by weight, more preferably about 0.02 to 1 part by weight based on 100 parts by weight of the total amount of the monomer components, More preferably about 0.5 part by weight.

In addition, in the case of using, for example, 2,2'-azobisisobutyronitrile as the polymerization initiator and preparing the (meth) acrylic polymer having the weight average molecular weight, the amount of the polymerization initiator to be used is preferably such that the total amount of the monomer components Is preferably about 0.06 to about 0.2 part by weight, more preferably about 0.08 to about 0.175 part by weight, based on 100 parts by weight.

As the chain transfer agent, emulsifier and the like, conventionally known ones can be suitably used. The addition amount thereof can also be appropriately determined within a range that does not impair the effect of the present invention.

(2) Thiol group-containing silane coupling agent

The present invention is characterized in that the pressure-sensitive adhesive composition contains a thiol group-containing silane coupling agent. By including a thiol group-containing silane coupling agent in the pressure-sensitive adhesive composition, it is possible to improve the durability of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition and, in particular, to have excellent durability under a humidified environment and to achieve both reworkability. Among the thiol group-containing silane coupling agents, oligomer-type thiol group-containing silane coupling agents are particularly preferred. Here, the oligomer type indicates a polymer of about 2 or more monomeric units and less than 100 monomeric units of the monomer, and the weight average molecular weight of the oligomeric silane coupling agent is preferably about 300 to 30,000.

As the oligomer-type thiol group-containing silane coupling agent, an oligomer type thiol group-containing silane coupling agent having at least two alkoxysilyl groups in the molecule is preferred. Specific examples thereof include X-41-1805, X-41-1810, and X-41-1818 manufactured by Shin-Etsu Chemical Co., These coupling agents are difficult to volatilize and are preferable because they have a plurality of alkoxysilyl groups and are effective for improving durability and reworkability.

Examples of the thiol group-containing silane coupling agent other than the oligomer type include 3-mercaptopropyltrimethoxysilane and? -Mercaptopropylmethyldimethoxysilane. Concretely, for example, KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned.

The number of alkoxysilyl groups of the thiol group-containing silane coupling agent is not particularly limited, but is preferably two or more in the molecule. The amount of the alkoxy group of the thiol group-containing silane coupling agent is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and even more preferably 20 to 40% by weight in the silane coupling agent Do.

Examples of the alkoxy group include, but are not limited to, alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy. Among them, methoxy and ethoxy are preferable, and methoxy is more preferable. It is also preferable that both of methoxy and ethoxy are contained in one molecule.

The thiol equivalent (mercapto equivalent) of the thiol group-containing silane coupling agent is preferably 1000 g / mol or less, more preferably 800 g / mol or less, even more preferably 700 g / mol or less, more preferably 500 g / mol Or less. The lower limit of the thiol equivalent is not particularly limited. However, when the thiol group-containing silane coupling agent is an oligomer type, it is preferably 200 g / mol or more, for example.

The thiol group-containing silane coupling agent (particularly, oligomer-type thiol group-containing silane coupling agent) may be used singly or in combination of two or more kinds. The total content of the thiol group- Is preferably 0.01 to 6 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.05 to 1 part by weight, based on the weight of the composition. By including the thiol group-containing silane coupling agent in the above range, the durability of the pressure-sensitive adhesive layer can be improved, and particularly, the durability under humidified environment is excellent and the reworkability can be satisfied.

In the pressure-sensitive adhesive composition of the present invention, a silane coupling system other than the thiol group-containing silane coupling agent may be added. Other coupling agents include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3- Amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. ) Acryl group-containing silane coupling agents, and isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane.

The silane coupling agent other than the thiol group-containing silane coupling agent can be added within a range that does not impair the effect of the present invention, and the addition amount thereof is not particularly limited.

(3) Crosslinking agent

The pressure-sensitive 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 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. In the polyfunctional metal chelate, the polyvalent metal is covalently bonded or coordinated with the organic compound. Examples of the multivalent 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 . Examples of the reactive group in the covalent bond or the coordination 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, known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like which are generally used for the urethanization reaction are used.

Examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, Isocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and the like.

Examples of the aromatic diisocyanate include aromatic diisocyanates such as phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'- Isocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.

Examples of the isocyanate crosslinking agent include urethane modified products obtained by reacting the above diisocyanates with polyhydric alcohols such as dimers (dimers, trimesters, pentamers), trimethylolpropane, urea modified products, urea modified products, A modified product thereof, an isocyanurate-modified product, and a carbodiimide-modified product.

Examples of commercial products of isocyanate-based crosslinking agents include trade name "Millionate MT", "Millionate MTL", "Millionate MR-200", "Millionate (trade name)" manufactured by Nippon Polyurethane Industry Co., Takenate D-120N "," Takenate D-120N "," Takenate D-120N "and" Takenate D-120N "manufactured by Mitsui Chemicals, Takenate D-160N "," Takenate D-160N "," Takenate D-165N "," Takenate D-170HN "," Takenate D-178N "," Takenate 500 "," Takenate 600 " . These compounds may be used alone or in combination of two or more.

As the isocyanate crosslinking agent, an aliphatic polyisocyanate and an aliphatic polyisocyanate compound as a modifier thereof are preferable. Compared with other isocyanate-based crosslinking agents, the aliphatic polyisocyanate-based compounds are more flexible in their crosslinked structure, easily relax stress accompanying expansion / shrinkage of the optical film, and do not easily peel off in the durability test. As the aliphatic polyisocyanate compound, hexamethylene diisocyanate and its modified product are particularly preferable.

The peroxide is not particularly limited as far as it is capable of generating radical active species by heating or light irradiation to promote crosslinking of the base polymer ((meth) acrylic polymer) of the pressure-sensitive adhesive composition. However, in consideration of workability and stability, It is preferable to use a peroxide having a temperature of 80 ° C to 160 ° C, and more preferably a peroxide having a temperature of 90 ° C to 140 ° C.

Examples of peroxides that can be used include di (2-ethylhexyl) peroxydicarbonate (1 minute half life temperature: 90.6 占 폚), di (4-t- butylcyclohexyl) peroxydicarbonate Butyl peroxyneodecanoate (1 minute half-life temperature: 103.5 占 폚), t-hexyl peroxy pivalate (1 minute), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 109.1 占 폚), t-butyl peroxypivalate (1 minute half life temperature: 110.3 占 폚), dilauroyl peroxide (1 minute half life temperature: 116.4 占 폚), di-n-octanoyl peroxide (Half-life temperature: 117.4 占 폚), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half life temperature: 124.3 占 폚), di (4-methylbenzoyl) peroxide Half-life temperature: 128.2 占 폚), dibenzoyl peroxide (one-minute half life temperature: 130.0 占 폚), t-butyl peroxyisobutyrate Between the half-life temperature: 136.1 ℃), 1,1- di (t--hexylperoxy) cyclohexane (one minute half life temperature: 149.2 ℃, and the like). Among them, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 占 폚), di rauroyl peroxide (1 minute half life temperature: 116.4 占 폚) Benzoyl peroxide (1 minute half-life temperature: 130.0 占 폚) and the like are preferably used.

The half life of the peroxide is an index indicating the rate of decomposition of the peroxide, and refers to the time until the residual amount of the peroxide becomes half. The decomposition temperature for obtaining a half life at an arbitrary time and the half life time at an arbitrary temperature are described in a manufacturer's catalog or the like. For example, the " Organic Peroxide Catalog Ninth Edition " May) ".

The amount of the crosslinking agent to be used is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, and still more preferably 0.03 to 1 part by weight based on 100 parts by weight of the (meth) acryl-based polymer. If the amount of the crosslinking agent is less than 0.01 part by weight, the pressure-sensitive adhesive layer may become insufficient in cross-linking, and durability and adhesion properties may not be satisfied. On the other hand, if the amount is more than 3 parts by weight, have.

The isocyanate-based crosslinking agent may be used alone or in admixture of two or more. The content of the isocyanate-based crosslinking agent is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the (meth) acryl-based polymer, More preferably 0.02 to 2 parts by weight, still more preferably 0.05 to 1.5 parts by weight. Cohesive force, prevention of peeling in the durability test, and the like.

The peroxide may be used alone or in admixture of two or more. The content of the peroxide is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the (meth) acryl-based polymer, More preferably 1.5 to 1 part by weight, still more preferably 0.05 to 1 part by weight. And is appropriately selected within this range for adjustment of workability, crosslinking stability and the like.

(4) Ionic compounds

The pressure-sensitive adhesive composition of the present invention may further contain an ionic compound. The ionic compound is not particularly limited and those used in this field can be preferably used. (Perfluoroalkylsulfonyl) imide lithium salt is preferable, and bis (trifluoromethanesulfonylimide) is preferable. [0050] Lithium is more preferable. 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, the amount of the ionic compound is preferably 10 parts by weight or less based on 100 parts by weight of the (meth) More preferably 5 parts by weight or less, further preferably 3 parts by weight or less, and particularly preferably 1 part by weight or less.

(5) Others

In the pressure-sensitive adhesive composition used in the present invention, a polyether compound having a reactive silyl group can be incorporated. The polyether compound is preferable in that it can improve the workability. As the polyether compound, for example, those disclosed in JP-A-2010-275522 can be used. The addition amount can be appropriately determined within a range that does not impair the effect of the present invention.

The pressure-sensitive adhesive composition used in the present invention may contain other known additives. Examples thereof include polyether compounds of polyalkylene glycols such as polypropylene glycol, powders such as colorants and pigments, dyes, An antioxidant, an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, a metal powder, a granular material, a foil-like material, And the like can be appropriately added depending on the use. Also, a redox system to which a reducing agent is added may be employed within a controllable range. These additives are preferably used in an amount of 5 parts by weight or less, more preferably 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. Pressure-sensitive adhesive layer for transparent conductive layer

The pressure-sensitive adhesive layer for a transparent conductive layer of the present invention is formed from the pressure-sensitive adhesive composition. When the pressure-sensitive adhesive layer is formed, it is preferable to adjust the addition amount of the entire crosslinking agent and fully take into account the effect of the crosslinking treatment temperature and the crosslinking treatment time.

Depending on the crosslinking agent to be used, the crosslinking temperature and the crosslinking time can be adjusted. The crosslinking treatment temperature is preferably 170 占 폚 or less. The crosslinking treatment may be carried out at a temperature in the drying step of the pressure-sensitive adhesive layer, or may be carried out by forming a separate crosslinking step after the drying step. 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 of forming the pressure-sensitive adhesive layer is not particularly limited, but the pressure-sensitive adhesive composition may be applied to various substrates, and the pressure-sensitive adhesive composition may be dried by a dryer such as a heat oven to volatilize the solvent or the like, Or a method of transferring the pressure-sensitive adhesive layer onto a polarizing film or a transparent conductive substrate to be described later. Alternatively, the pressure-sensitive adhesive composition may be directly applied on the polarizing film or the transparent conductive substrate to form a pressure-sensitive adhesive layer. In the present invention, a method of previously preparing a polarizing film on which a pressure-sensitive adhesive layer is formed on a polarizing film, and then attaching the polarizing film on which the pressure-sensitive adhesive layer is formed is affixed 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 base, and a polarizing film described later.

As a method of applying the pressure-sensitive adhesive composition to the substrate or the polarizing film, various methods are used. Specifically, there may be mentioned, for example, fountain coaters, roll coats, kiss roll coats, gravure coats, reverse coats, roll brushes, spray coats, dip roll coats, bar coats, knife coats, air knife coats, curtain coats, An extrusion coating method using a die coater or the like.

The drying conditions (temperature and time) are not particularly limited and can be appropriately set depending on the composition, concentration and the like of the pressure-sensitive adhesive composition. For example, the drying conditions (temperature and time) may be 80 to 200 ° C, preferably 90 to 170 ° C, , Preferably 2 to 30 minutes.

After drying, crosslinking treatment may be carried out if necessary, and the conditions are as described above.

The thickness of the pressure-sensitive adhesive layer (after drying) is preferably, for example, 5 to 100 占 퐉, more preferably 7 to 70 占 퐉, and further preferably 10 to 50 占 퐉. If the thickness of the pressure-sensitive adhesive layer is less than 5 占 퐉, the adhesion to the adherend becomes insufficient, and the durability under humidifying conditions tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer is more than 100 占 퐉, the pressure-sensitive adhesive layer can not be completely dried at the time of application and drying of the pressure-sensitive adhesive composition at the time of forming the pressure-sensitive adhesive layer, and bubbles remain or thickness irregularities Or the like, and the appearance problem tends to become easier to present.

Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate and polyester films, porous materials such as paper, cloth and nonwoven fabric, nets, foamed sheets, metal foils and laminates thereof And the like, but a resin film is preferably used because of its excellent surface smoothness.

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

The thickness of the release film is usually 5 to 200 占 퐉, preferably 5 to 100 占 퐉. The releasing film may be subjected to antistatic treatment such as releasing treatment with a silicone, fluorine, long chain alkyl or fatty acid amide releasing agent, silica powder or the like, a coating type, a kneading type, a deposition type or the like . Particularly, the releasability from the pressure-sensitive adhesive layer can be further improved by suitably carrying out the surface treatment of the release film, such as silicone treatment, long-chain alkyl treatment or fluorine treatment.

The transparent resin film substrate is not particularly limited, but various resin films having transparency are used. The resin film is formed of a single-layer film. For example, as the material thereof, a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, an acetate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, (Meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, and polyphenylene sulfide resins. Of these, particularly preferred are polyester resins, polyimide resins and polyether sulfone resins.

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

3. Polarizing film formed with a pressure-sensitive adhesive layer

The polarizing film having the pressure-sensitive adhesive layer of the present invention has the pressure-sensitive adhesive layer on at least one surface of the polarizing film. The polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed is used in such a manner that the pressure-sensitive adhesive layer of the polarizing film is in contact with the transparent electroconductive layer of the transparent electroconductive substrate having the transparent electroconductive layer on the transparent substrate.

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

The polarizing film is not particularly limited, but it is generally used that a transparent protective film is provided on one side or both sides of the polarizer.

The polarizer is not particularly limited, and various kinds of polarizers can be used. Examples of the polarizer include a hydrophilic polymer film such as a polyvinyl alcohol film, a partially porous polyvinyl alcohol film, and a partially saponified ethylene / vinyl acetate copolymer film, Polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, and the like. Among them, a polyvinyl alcohol film and a polarizer made of a dichroic substance such as iodine are preferable, and an iodine polarizer containing iodine and / or iodine ion is more preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 탆.

The polarizer obtained by dying a polyvinyl alcohol film with iodine and uniaxially stretching can be produced by, for example, dying polyvinyl alcohol in an aqueous solution of iodine and stretching it to 3 to 7 times the original length. If necessary, may be immersed in an aqueous solution such as potassium iodide, which may contain boric acid, zinc sulfate, zinc chloride or the like. If necessary, the polyvinyl alcohol film may be dipped in water and washed with water before dyeing. The polyvinyl alcohol film can be cleaned by rinsing the surface of the polyvinyl alcohol film with water and swelling the polyvinyl alcohol film to prevent unevenness such as uneven dyeing. The stretching may be carried out after dyeing with iodine, followed by stretching while dyeing, or after stretching, followed by dyeing with iodine. It can be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

In the present invention, a thin polarizer having a thickness of 10 mu m or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 mu m. Such a thin polarizer is preferable because it is excellent in durability because thickness irregularity is small, visibility is excellent, and dimensional change is small, and further thickness and thickness of a polarizing film are achieved.

Examples of the thin polarizer include those described in Japanese Laid-Open Patent Publication Nos. 51-069644 and 2000-338329, International Publication No. 2010/100917, Japanese Patent No. 4751481, and Japanese Laid-Open Patent Publication No. 2012-073563 And a thin polarizing film described in JP-A No. H07-336999. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a lead resin base material in a laminate state, and a step of dyeing. With this method, even if the PVA resin layer is thin, it can be stretched without any problem such as breakage due to stretching because it is supported on the resin base material for drawing.

As the thin polarizing film, a pamphlet of International Publication No. 2010/100917, in view of being capable of stretching at a high magnification and improving polarization performance, including a step of stretching in a laminate state and a step of dyeing, or In the aqueous boric acid solution described in the specification of Japanese Patent No. 4751481 or the Japanese Patent Application Laid-Open Publication No. 2012-073563, and in particular, it is preferable to use a method which is disclosed in Japanese Patent No. 4751481 or Japanese Patent Application Laid-Open Publication No. 2012-073563 In a boric acid aqueous solution having a base material, and a step of auxiliary drawing publicly before stretching in an aqueous boric acid solution having a base.

As a material for forming the transparent protective film formed on one side or both sides of the polarizer, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used. Specific examples of such thermoplastic resins include cellulose resins such as triacetylcellulose, polyester resins, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) Acrylic resin, cyclic polyolefin resin (norbornene resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof. The transparent protective film is adhered to the one side of the polarizer by an adhesive layer while the other side of the polarizing film is provided with a thermosetting resin such as a (meth) acrylic, urethane, acrylic urethane, epoxy or silicone resin or a UV- Can be used. The transparent protective film may contain one or more optional additives. Examples of the additive include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, coloring inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, colorants and the like. 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, particularly preferably 70 to 97% by weight, to be. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, there is a possibility that the high transparency and the like inherently possessed by the thermoplastic resin can not be sufficiently exhibited.

The thickness of the transparent protective film can be appropriately determined. Generally, the thickness of the transparent protective film is about 1 to 500 占 퐉 in view of workability such as strength and handleability, and thin film property.

The polarizer and the transparent protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex-based, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive for the polarizer and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for an electron beam curing type polarizing film exhibits favorable adhesiveness to the above various transparent protective films. The adhesive used in the present invention may contain a metal compound filler.

In the present invention, a retardation film or the like may be formed on the polarizer instead of the transparent protective film of the polarizing film. It is also possible to form another transparent protective film or a retardation film on the transparent protective film.

The surface of the transparent protective film on which the polarizer is not adhered may be subjected to treatment for the purpose of hard coat layer, anti-reflection treatment, anti-sticking, diffusion or anti-glare.

Further, an anchor layer may be provided between the polarizing film and the pressure-sensitive adhesive layer. The material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, sols of metal oxides, silica sol, and the like. Of these, polymers are particularly preferably used. The polymer may be used in any of solvent-soluble type, water-dispersible type and water-soluble type.

Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, and polystyrene resins have. As the polymers, a conductive polymer such as polythiophene, which can be used as a material for forming an organic conductive layer to be described later, can be used.

When the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) until it is provided for practical use. Examples of the release film include those described above. When the releasing film is used as the substrate in the production of the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer on the releasing film is stuck to the polarizing film so that the releasing film can be used as a releasing film of the pressure-sensitive adhesive layer of the polarizing film on which the pressure- And it is possible to simplify the process.

The polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed is used by being attached to the transparent conductive layer of the transparent conductive base having the transparent conductive layer on the transparent base.

The constituent material of the transparent conductive layer of the transparent conductive base material 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 At least one kind of metal oxide selected from metals is used. The metal oxide may further contain metal atoms shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony and the like are preferably used, and ITO is particularly preferably used. ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

As the ITO, crystalline ITO and amorphous (ITO) can be used, and all of them can be preferably used.

The transparent conductive layer of the transparent conductive base may be a metal mesh formed by forming a metal thin wire in a lattice-like pattern or formed by coating metal fine particles. As the metal material to be constituted, any appropriate metal (including alloying material) can be used as long as it is a metal having high conductivity. Concretely, for example, at least one metal selected from the group consisting of gold, platinum, silver, aluminum and copper is preferable, and from the viewpoint of conductivity, aluminum, silver, copper or gold is preferable.

The transparent conductive layer of the transparent conductive base can be formed of an organic conductive film. The material for forming the organic conductive film is not particularly limited, and examples thereof include an ion conductive composition comprising an electroconductive polymer, an electrolyte salt and an organopolysiloxane, an ionic compound, various surfactants (cationic, anionic and amphoteric surfactants) . Among them, a conductive polymer is preferably used from the viewpoints of stability in humidification when the optical characteristics, appearance, antistatic effect and antistatic effect are observed. Particularly, conductive polymers such as polyaniline and polythiophene are preferably used. These conductive polymers may be any of water-soluble, water-dispersible, organic solvent-soluble, and organic solvent-dispersible. In the case of the water-soluble conductive polymer and the water-dispersible conductive polymer, the coating liquid for forming the antistatic layer is prepared as an aqueous solution or an aqueous dispersion And it is not necessary to use a non-aqueous organic solvent as the coating liquid, and deterioration of the transparent substrate by the organic solvent can be suppressed. Further, the aqueous solution or aqueous dispersion may contain an aqueous solvent other than water. Butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, l-butyl alcohol, isopropyl alcohol, isopropanol, isopropanol, n- Ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and the like.

The water-soluble electroconductive polymer such as polyaniline or polythiophene or the water-dispersible electroconductive polymer preferably has a hydrophilic functional group in the molecule. Examples of the hydrophilic functional group include a sulfone group, an amino group, an amide group, an imino group, a quaternary ammonium salt group, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfuric acid ester group, And the like. By having a hydrophilic functional group in the molecule, it is easy to dissolve in water or disperse in fine particles in water, so that the water-soluble electroconductive polymer or water-dispersible electroconductive polymer can be easily prepared.

Examples of commercially available water-soluble conductive polymers include polyaniline sulfonic acid (weight average molecular weight of 150000 in terms of polystyrene manufactured by Mitsubishi Rayon Co., Ltd.). Examples of commercially available water-dispersible conductive polymers include polythiophene-based conductive polymers (trade name, Denatron series, manufactured by Nagase ChemteX Co., Ltd.).

The above-mentioned conductive polymer may also contain a binder component for the purpose of improving the film-forming property of the conductive polymer and the adhesion to the transparent substrate. When the conductive polymer is a water-soluble conductive polymer or a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of the binder include an oxazoline group-containing polymer, a polyurethane resin, a polyester resin, an acrylic resin, a polyether resin, a cellulose resin, a polyvinyl alcohol resin, an epoxy resin, a polyvinylpyrrolidone, , Polyethylene glycol, pentaerythritol, and the like. Particularly, a polyurethane resin, a polyester resin and an acrylic resin are preferable. These binders can be suitably used in accordance with their use.

The amount of the conductive polymer and the binder used may vary depending on the kind thereof, but it is preferable to control the surface resistance value of the obtained transparent conductive film to be 1 x 10 ⁸ to 1 x 10 ¹² ? / ?.

The organic conductive layer used in the present invention may contain other known additives such as a colorant, a powder such as a pigment, a dye, a surfactant, a plasticizer, a surface lubricant, a leveling agent, a softening agent, It may be suitably added in accordance with the use of an antioxidant, an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, a metal powder, a particulate or a foil.

The organic conductive film may be formed on the transparent substrate by electrolytic polymerization of the monomer forming the conductive polymer.

The thickness of the transparent conductive layer is not particularly limited, but is preferably 10 nm to 1000 nm, more preferably 50 to 400 nm.

The method of forming the transparent conductive layer is not particularly limited, and conventionally known methods can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. When the coating solution is applied, there may be used, for example, a micro gravure coating method, a roll coating method, a dipping coating method, a float coating method, a spin coating method, a die coating method, a cast transfer method, have. In the case of a metal mesh, for example, a photosensitive composition (a composition for forming a transparent conductive layer) containing silver salt is applied on an adherend such as a release film, and then subjected to an exposure treatment and a development treatment, And forming a thin metal wire in a predetermined pattern. The transparent conductive layer may be obtained by printing a paste containing a fine metal particle (composition for forming a transparent conductive layer) in a predetermined pattern. An appropriate method may be employed depending on the required film thickness.

An overcoat (OC) layer (not shown) may be provided on the transparent conductive layer. As the overcoat layer, those usually used in this field can be used without particular limitation, and examples thereof include layers formed of an alkyd resin, an acrylic resin, an epoxy resin, a urethane resin, an isocyanate resin or the like. The thickness of the overcoat layer is not particularly limited, but is preferably 0.1 to 10 mu m, for example.

The transparent substrate may be a transparent substrate, and the material thereof is not particularly limited, and examples thereof include glass and transparent resin film substrates. Examples of the transparent resin film substrate include those described above.

An undercoat layer, an oligomer-preventing layer, or the like can be formed between the transparent conductive layer and the transparent substrate, if necessary.

4. Image display panel, image display device

The image display panel of the present invention is an image display panel comprising a polarizing film on which the pressure-sensitive adhesive layer is formed and a transparent conductive base material having a transparent conductive layer on the transparent base,

And a pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is bonded to the transparent conductive layer of the image display panel.

The image display device of the present invention is characterized by having the image display panel.

The polarizing film on which the pressure-sensitive adhesive layer is formed and the transparent conductive base material are as described above. The image display panel forms a part of the image display device together with the polarizing film having the transparent conductive base material and the pressure-sensitive adhesive.

A liquid crystal panel which is a representative embodiment of an image display panel to which a polarizing film having a pressure-sensitive adhesive layer of the present invention is applied will be described. The liquid crystal cell used in the liquid crystal panel is provided with a transparent conductive base material having a transparent conductive layer on a transparent base material. The transparent conductive base material is usually provided on the visual surface side of the liquid crystal cell. A liquid crystal panel including a liquid crystal cell usable in the present invention will be described with reference to Fig. However, the present invention is not limited to Fig.

In one embodiment of the liquid crystal panel 1 that can be included in the image display panel of the present invention, the visibility side transparent protective film 2 / polarizer 3 / liquid crystal cell side transparent protective film 4 / The transparent protective layer 11 and the polarizer 12 are laminated on the transparent substrate 9 and the liquid crystal cell side, And a transparent protective film 13 on the light source side. 1, the polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed corresponds to the visibility side transparent protective film 2 / polarizer 3 / liquid crystal cell side transparent protective film 4 / pressure-sensitive adhesive layer 5. In Fig. 1, the transparent conductive base material used in the present invention is composed of the transparent conductive layer 6 / the transparent base material 7. 1, a liquid crystal cell having a transparent conductive base material 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.

In addition to the above-described configuration, an optical film such as a retardation film, a time compensation film, and a brightness enhancement film can be appropriately formed on the liquid crystal panel 1. [

The liquid crystal layer 8 is not particularly limited, and for example, an arbitrary type such as a TN type, an STN type, a pi type, a VA type, and an IPS type can be used. The transparent substrate 9 (on the light source side) may be a transparent substrate, and the material thereof is not particularly limited, and examples thereof include glass and transparent resin film substrates. Examples of the transparent resin film substrate include those described above.

As the pressure-sensitive adhesive layer 10 on the light source side, the liquid crystal cell side transparent protective film 11, the polarizer 12 and the light source side transparent protective film 13, those conventionally used in this field can be used, And those described in this specification can be preferably used.

The liquid crystal panel 1 has a polarizing film in which a pressure sensitive adhesive layer of the present invention is formed on a transparent conductive layer 6 formed on the outermost layer on the viewer side of the liquid crystal cell and a transparent conductive layer 6 of a liquid crystal cell and a pressure- And the pressure-sensitive adhesive layer (5) of the formed polarizing film is brought into contact with each other.

The image display device of the present invention is not limited as long as it includes an image display panel including a polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed and a transparent conductive base material having a transparent conductive layer on the transparent base material. Do. Hereinafter, a liquid crystal display device will be described as an example, but the present invention is not limited thereto.

Specific examples of the image display device to which the image display panel can be applied include a liquid crystal display device, an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED) .

The image display device of the present invention may be any image display panel including a polarizing film on which the pressure-sensitive adhesive layer of the present invention is formed and a transparent conductive base material having a transparent conductive layer on the transparent base material. Device.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. In addition, the room temperature without any specifics was 23 ° C, 65% RH. to be.

<Measurement of weight average molecular weight of (meth) acryl-based polymer>

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

· Analytical Apparatus: HLC-8120GPC manufactured by Tosoh Corporation

· Column: G7000HXL + GMHXL + GMHXL, manufactured by Tosoh Corporation

· Column size: Each 7.8 mmφ × 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: Polystyrene

Production Example 1 (Production of polarizing film)

A polyvinyl alcohol film having a thickness of 80 탆 was stretched to 3 times while dyeing in an iodine solution at a concentration of 0.3 wt% at 30 캜 for 1 minute between rolls having different speed ratios. Thereafter, the substrate was immersed in an aqueous solution containing boric acid at a concentration of 4 wt% at a concentration of 4 wt% and potassium iodide at a concentration of 10 wt% for 0.5 min, and the coating film was stretched to a total draw ratio of 6 times. Subsequently, the substrate was washed by immersing it in an aqueous solution containing potassium iodide at a concentration of 1.5% by weight at 30 DEG C for 10 seconds, and then dried at 50 DEG C for 4 minutes to obtain a polarizer having a thickness of 30 mu m. A saponified triacetylcellulose film having a thickness of 80 mu m was laminated on both surfaces of the polarizer using a polyvinyl alcohol adhesive to prepare a polarizing film.

Preparation Example 2 (Preparation 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 injected into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser. Further, 0.1 part by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was added together with 100 parts by weight of ethyl acetate per 100 parts by weight of the monomer mixture (solid content), nitrogen gas was introduced with gentle stirring, After the replacement, the solution temperature in the flask was maintained at about 55 ° C and polymerization reaction was carried out for 8 hours to prepare a solution of the acrylic polymer (a-1) having a weight average molecular weight (Mw) of 156,000 and an Mw / Mn of 3.2.

Production Examples 3 to 5

(A-2) to (a-2) were obtained in the same manner as in Production Example 2, except that the kind of monomers used in preparation of the acrylic polymer and the use ratio thereof were changed as shown in Table 1 in Production Example 2 -4) was prepared.

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

(Preparation of acrylic pressure-sensitive adhesive composition)

0.1 part of an isocyanate crosslinking agent (trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) was added to 100 parts by weight of the solid content of the solution of the acrylic polymer (a-1) obtained in Production Example 2, (Trade name: KBM-803, amount of alkoxy groups: 47% by weight, thiol equivalent: 196 g / mol, manufactured by Shin-Etsu Chemical Co., 0.3 part) were blended to prepare a solution of the acrylic pressure-sensitive adhesive composition.

(Production of a polarizing film having a pressure-sensitive adhesive layer)

The solution of the acrylic pressure-sensitive adhesive composition was coated on one side of a polyethylene terephthalate film (separator film, trade name: MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) treated with a silicone-based releasing agent so that the thickness of the pressure- And dried at 155 占 폚 for 1 minute to form a pressure-sensitive adhesive layer on the surface of the separator film. Subsequently, the pressure-sensitive adhesive layer formed on the separator film was transferred to the polarizing film produced in Production Example 1 to prepare a polarizing film having a pressure-sensitive adhesive layer.

Examples 2 to 13 and Comparative Examples 1 to 5

A solution of an acrylic pressure sensitive adhesive composition was prepared in the same manner as in Example 1, except that the kind of the acrylic polymer, the kind of the silane coupling agent, and the amount thereof were changed as shown in Table 2 in Example 1. In Example 12, ionic compounds were compounded in the ratios shown in Table 2. Using the obtained solution of the acrylic pressure-sensitive adhesive composition, a polarizing film having a pressure-sensitive adhesive layer formed thereon was prepared in the same manner as in Example 1.

The following evaluations were performed on the polarizing films on which the pressure-sensitive adhesive layer was formed, obtained in the above-mentioned Examples and Comparative Examples. The evaluation results are shown in Table 2.

<Preparation of Evaluation Sample>

The polarizing film on which the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was formed was cut into a 15-inch size sample. This sample was bonded to a glass on which a transparent conductive layer was formed. As the glass on which the transparent conductive layer was formed, a glass in which an ITO layer having an amorphous ITO layer was formed on a non-alkali glass (product name: EG-XG, Corning) having a thickness of 0.7 mm and an organic conductive film having the same alkali- A glass on which the organic conductive film was formed was used. The sample was adhered to a glass ITO layer on which the ITO layer was formed, and an organic conductive film of glass on which the organic conductive film was formed, using a laminator. Subsequently, the sample was autoclaved at 50 DEG C and 0.5 MPa for 15 minutes, and the sample was brought into close contact with the glass on which the ITO layer was completely formed and the glass on which the organic conductive film was formed, respectively.

The ITO layer was formed by sputtering. The composition of ITO was 3 wt% of Sn, and the sample was subjected to a heating step of 140 DEG C for 60 minutes before bonding. The Sn ratio of ITO was calculated from the weight of Sn atom / (weight of Sn atom + weight of In atom). The organic conductive film was formed by spin coating using a coating solution containing a polyethylene dioxythiophene polystyrenesulfonate salt.

&Lt; Durability test immediately after coating &gt;

The sample subjected to such treatment was subjected to a treatment (humidification test) in an atmosphere of 60 DEG C / 95% RH for 500 hours (a humidification test), and then a glass having the polarizing film and the ITO layer formed thereon, Were visually evaluated based on the following criteria.

(Evaluation standard)

&Amp; cir &amp; &amp; cir &amp;: No apparent change such as peeling was found.

O: There is peeling at a slight end, but no problem in practical use.

?: There is peeling at the end, but there is no practical problem unless it is a special use.

X: There is a remarkable peeling at the end portion, and there is a problem in practical use.

<Adhesion>

By the same operation as in the preparation of <evaluation sample> described above, except that the polarizing film on which the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was formed was cut into a width of 25 mm, (The glass on which the ITO layer was formed and the glass on which the organic conductive film was formed), and the polarizing film on which the pressure-sensitive adhesive layer was formed was adhered completely to the glass on which the transparent conductive layer was formed (initial).

Thereafter, heat treatment was performed for 48 hours under drying conditions at 60 캜 (after heating). The adhesion of these samples was measured. The adhesive strength was obtained by measuring the adhesive force (N / 25 mm) at the time of peeling off such samples from a tensile tester (Autograph SHIMAZU AG-1 10KN) at a peeling angle of 90 ° and a peeling speed of 300 mm / min. The measurement was performed at intervals of once / 0.5 s, and the average value was used as a measurement value.

<Workability>

The same processing as that for measuring the adhesive force was performed except that the polarizing film on which the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was formed was cut into 350 mm length x 250 mm length as evaluation samples. With respect to these samples, samples were peeled off from the glass on which the transparent conductive layer was formed by human hands, and the reworkability was evaluated based on the following criteria. The evaluation of the reworkability was carried out by repeating three times and three times in the above order.

◎: All 3 sheets can be peeled off without peeling of adhesive residue or film.

&Amp; cir &amp;: Part of the three films were peeled off by re-peeling, though the film was broken.

?: The film was broken in all three sheets, but peeling was possible by re-peeling.

X: All of the three sheets were peeled off due to peeling of the film even if adhesive residue was generated or peeled several times.

The abbreviations in Table 2 are as follows.

Isocyanate type: trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc .;

Peroxide system: Product name: Nippa BMT 40SV, benzoyl peroxide, manufactured by Nippon Oil and Fats Co., Ltd.

KBM-803: 3-mercaptopropyltrimethoxysilane, amount of alkoxy group: 47% by weight, thiol equivalent: 196 g / mol, manufactured by Shin-Etsu Chemical Co.,

X-41-1805: Oligomer-type thiol group-containing silane coupling agent, amount of alkoxy group: 50% by weight, thiol equivalent: 800 g / mol, manufactured by Shin-Etsu Chemical Co.,

X-41-1818: Oligomer-type thiol group-containing silane coupling agent, amount of alkoxy group: 60% by weight, thiol equivalent: 850 g / mol, manufactured by Shin-Etsu Chemical Co.,

X-41-1810: Oligomer-type thiol group-containing silane coupling agent, amount of alkoxy group: 30% by weight, thiol equivalent: 450 g / mol, manufactured by Shin-Etsu Chemical Co.,

KBM-403:? -Glycidoxypropyltrimethoxysilane, amount of alkoxy group: 39% by weight, manufactured by Shin-Etsu Chemical Co., Ltd.

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

Ionic compound: bis (trifluoromethanesulfonylimide) lithium, manufactured by Mitsubishi Materials Corporation.

1: liquid crystal panel
2: transparent protective film on the poet side
3: Polarizer
4: Transparent protective film of liquid crystal cell side
5: Pressure-sensitive adhesive layer
6: transparent conductive layer
7: transparent substrate
8: liquid crystal layer
9: transparent substrate
10: pressure-sensitive adhesive layer
11: Transparent protective film on the liquid crystal cell side
12: Polarizer
13: transparent protective film on the light source side

Claims (7)

A polarizing film on which a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer and a polarizing film to be used in combination with the transparent conductive layer of a transparent conductive base having a transparent conductive layer on a transparent base is formed,
Wherein the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive layer comprising a (meth) acryl-based polymer, a thiol group-containing silane coupling agent, an isocyanate-based crosslinking agent and a peroxide-based crosslinking agent. The method according to claim 1,
Wherein the thiol group-containing silane coupling agent is an oligomer-type thiol group-containing silane coupling agent. The method according to claim 1,
Wherein the thiol group-containing silane coupling agent has two or more alkoxysilyl groups in the molecule. The method according to claim 1,
Wherein a blending amount of the thiol group-containing silane coupling agent is 0.01 to 3 parts by weight based on 100 parts by weight of the (meth) acryl-based polymer. The method according to claim 1,
Wherein a thiol equivalent of the thiol group-containing silane coupling agent is 700 g / mol or less. An image display panel comprising a polarizing film on which a pressure-sensitive adhesive layer according to any one of claims 1 to 5 is formed and a transparent electroconductive substrate having a transparent electroconductive layer on a transparent substrate,
Wherein the pressure-sensitive adhesive layer of the polarizing film on which the pressure-sensitive adhesive layer is formed is bonded to the transparent conductive layer of the image display panel. An image display apparatus having the image display panel according to claim 6.

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