WO2020188871A1

WO2020188871A1 - Polarizing film with adhesive layer, image display panel, and image display device

Info

Publication number: WO2020188871A1
Application number: PCT/JP2019/042603
Authority: WO
Inventors: 智之木村; 寛大小野; 悟士山本; 雄祐外山
Original assignee: 日東電工株式会社
Priority date: 2019-03-20
Filing date: 2019-10-30
Publication date: 2020-09-24
Also published as: JP2024098982A

Abstract

This invention is a polarizing film with adhesive layer having, in the following order, a polarizing film having a polarizer and a protective film on one or both sides of the polarizer, an electro-conductive layer and an adhesive layer, the polarizing film with adhesive layer having a deformed portion of a shape other than a rectangle, and the adhesive layer being formed of an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound(B). With this polarizing film with adhesive layer having a deformed portion it is possible to curb the occurrence of deformation cracks and curb electrostatic unevenness, even if applied to in-cell LCD panels.

Description

Polarizing film with adhesive layer, image display panel and image display device

The present invention relates to a polarizing film with an adhesive layer having a deformed portion other than a rectangle. The present invention also relates to an image display panel and an image display device to which the polarizing film with an adhesive layer is applied.

In an image display panel, for example, a liquid crystal panel used for a liquid crystal display device or the like, a polarizing film is usually laminated on both sides of a liquid crystal cell formed of liquid crystal layers arranged between a pair of transparent substrates via an adhesive layer. Has been done. On the other hand, at the time of manufacturing the image display panel, when the polarizing film with the pressure-sensitive adhesive layer is attached to the liquid crystal cell, the release film is peeled off from the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer. Electrostatic force is generated by peeling. The static electricity generated in this way affects, for example, the orientation of the liquid crystal layer inside the liquid crystal display panel, and causes defects. The generation of static electricity can be suppressed, for example, by forming an antistatic layer (conductive layer) on the outer surface of the polarizing film.

For example, in Patent Document 1, in a liquid crystal display device with a touch sensing function, a surface resistance value of 1.0 × 10 ⁹ to 1.0 × 10 ¹¹ Ω / □ is provided in order to reduce the occurrence of display defects and malfunctions. It has been proposed to arrange a polarizing film having an antistatic layer on the visible side of the liquid crystal layer. It is also known that the generation of static electricity can be suppressed by adding an ionic compound as an antistatic agent to the pressure-sensitive adhesive layer.

On the other hand, in recent years, in smartphones and car navigation systems, the number of irregularly shaped in-cell liquid crystal display devices has increased, and polarizing films having irregular shapes are also used according to the display devices. Patent Document 2 discloses a method of processing a polarizing film to produce a polarizing film having a deformed shape other than a rectangle. Patent Document 3 describes the deformed punching property of the polarizing film and the crack durability after the heat cycle test of the deformed polarizing film after punching by incorporating inorganic particles having deformability into the transparent protective film used for the polarizing film. It has been proposed to improve.

Japanese Unexamined Patent Publication No. 2013-105154 Japanese Unexamined Patent Publication No. 2017-15191 Japanese Unexamined Patent Publication No. 2017-097111

According to the polarizing film having an antistatic layer described in Patent Document 1, the generation of static electricity can be suppressed. However, even a polarizing film with an adhesive layer provided with an antistatic layer or an adhesive layer containing an ionic compound has not been able to sufficiently suppress static electricity unevenness. Further, in the case of the polarizing film with a deformed pressure-sensitive adhesive layer, the polarizing film with a pressure-sensitive adhesive layer provided with an antistatic layer or a pressure-sensitive adhesive layer containing an ionic compound sufficiently suppresses the deformed cracks generated in the deformed portion. It wasn't something I could do. In particular, when an ionic compound is contained in the pressure-sensitive adhesive layer and a polarizing film with a pressure-sensitive adhesive layer having a deformed portion is applied to an in-cell liquid crystal panel, it is necessary to add a large amount of the ionic compound to the pressure-sensitive adhesive layer. As a result, it was found that the deformed cracks generated in the deformed portion were exacerbated.

The present invention is a polarizing film with an adhesive layer having a deformed portion, and has an antistatic function capable of suppressing the occurrence of deformed cracks and suppressing static electricity unevenness even when applied to an in-cell liquid crystal panel. It is an object of the present invention to provide a polarizing film with an adhesive layer.

Another object of the present invention is to provide an image display panel and an image display device to which the polarizing film with an adhesive layer is applied.

As a result of diligent studies to solve the above problems, the present inventors have found the following polarizing film with an adhesive layer, and have completed the present invention.

That is, the present invention
A polarizing film and a polarizing film having a protective film on one or both sides of the polarizing element, and a polarizing film with an adhesive layer having a conductive layer and an adhesive layer in this order.
The polarizing film with an adhesive layer has a deformed portion other than a rectangle and has a deformed portion.
The present invention relates to a polarizing film with a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B).

In the polarizing film with an adhesive layer, it is preferable that the conductive layer contains a conductive polymer.

In the polarizing film with an adhesive layer, the thickness of the conductive layer is preferably 1 μm or less.

In the polarizing film with an adhesive layer, the ionic compound (B) preferably has a molecular weight of a cationic component of 210 or less. Furthermore, the cation component is preferably lithium ion.

In the polarizing film with an adhesive layer, the ionic compound (B) is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (A).

In the polarizing film with an adhesive layer, it is suitable when the protective film is any one selected from a cellulose resin film and a (meth) acrylic resin film. Further, the thickness of the polarizer in the polarizing film is preferably 10 μm or less.

In the polarizing film with an adhesive layer, as the polarizing film, a single protective polarizing film having a protector and a protective film on only one side of the polarizer can be used. The one-sided protective polarizing film preferably has the conductive layer on the other side of the polarizer.

The one-sided protective polarizing film can have the conductive layer via a transparent layer having a thickness of 10 μm or less directly formed on the polarizing element on the other side of the polarizing element. As the transparent layer, a cured product of a forming material containing a urethane prepolymer which is a reaction product of an isocyanate compound and a polyhydric alcohol can be used.

In the polarizing film with the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer preferably has a creep value of 120 μm or less at 85 ° C.

The present invention also relates to an image display panel characterized by having the polarizing film with an adhesive layer. The image display panel can be applied to a liquid crystal cell having a built-in touch sensing function having a liquid crystal layer and a touch sensor unit, to which an adhesive layer of a polarizing film with an adhesive layer is bonded.

The present invention also relates to an image display device, which comprises the image display panel.

The polarizing film with a pressure-sensitive adhesive layer of the present invention has a conductive layer between the pressure-sensitive adhesive layer and the polarizing film, and the pressure-sensitive adhesive layer contains an ionic compound, and both the conductive layer and the pressure-sensitive adhesive layer are formed. Therefore, the antistatic performance can be improved. Therefore, even if the amount of the ionic compound in the pressure-sensitive adhesive layer is reduced, the antistatic function of both layers can suppress static electricity unevenness even when the polarizing film with the pressure-sensitive adhesive layer is applied to the in-cell liquid crystal panel. .. Further, the polarizing film with the pressure-sensitive adhesive layer of the present invention has a deformed portion other than a rectangle, but as described above, the amount of the ionic compound in the pressure-sensitive adhesive layer can be reduced, so that the deformed crack Can be suppressed.

It was also found that the smaller the molecular weight of the cation component of the ionic compound, the smaller the adverse effect on the deformed crack. In particular, it was found that when a lithium salt was used as the cationic component of the ionic compound, the effect of suppressing deformed cracks was excellent. Furthermore, it was also found that the effect of suppressing irregularly shaped cracks is advantageous when a single protective polarizing film having a protective film on only one side of the polarizer is used as the polarizing film. The single-protective polarizing film is also advantageous from the viewpoint of thinning and cost reduction. It was also found that the smaller the molecular weight of the cation component, the more preferable it is from the viewpoint of suppressing static electricity unevenness.

On the other hand, when a single protective polarizing film is used as the polarizing film as described above, the conductive layer is directly formed on the polarizing element, so that the antistatic agent of the conductive layer is inside the polarizing element in a humid environment. It was also found that the intrusion decolorizes the end portion of the polarizing element, and the segregation of the ionic compound contained in the pressure-sensitive adhesive layer into the polarizer may reduce the antistatic function of the pressure-sensitive adhesive layer. .. When a single-protective polarizing film is used in this way, a conductive layer is provided on the polarizing element via a transparent layer so that the conductive layer does not directly affect the polarizer under a humid environment. It is possible to suppress the decolorization of the end portion of the polarizer in the above.

As described above, according to the polarizing film with an adhesive layer of the present invention, even when a single protective polarizing film is used, deterioration of the optical reliability of the polarizer can be suppressed, and the polarizing film is thin and has good optical reliability. Moreover, it is possible to provide a polarizing film with an adhesive layer having excellent antistatic properties for a long period of time.

It is sectional drawing which shows an example of the polarizing film with an adhesive layer of this invention. It is sectional drawing which shows an example of the polarizing film with an adhesive layer of this invention. It is sectional drawing which shows an example of the polarizing film with an adhesive layer of this invention. It is a top view which shows an example of the deformed part other than a rectangle of the polarizing film with an adhesive layer of this invention. It is a top view which shows the polarizing film with an adhesive layer which has the deformed part which concerns on Example of this invention. It is sectional drawing which shows an example of the liquid crystal panel with a touch sensing function using the polarizing film with an adhesive layer of this invention. It is sectional drawing which shows an example of the liquid crystal panel with a touch sensing function using the polarizing film with an adhesive layer of this invention. It is sectional drawing which shows an example of the liquid crystal panel with a touch sensing function using the polarizing film with an adhesive layer of this invention.

The polarizing film with an adhesive layer of the present invention is shown in FIG. 1, for example. As shown in FIG. 1, the polarizing film 1 with an adhesive layer has a polarizing film 11, a conductive layer c, and an adhesive layer 21 in this order. FIG. 2 shows a case where a single protective polarizing film 11A having a protective film b on only one side of the polarizing element a is used as the polarizing film 11 of FIG. 1, and in the single protective polarizing film 11A, the polarizing element a is used. On the other hand, the pressure-sensitive adhesive layer 21 is provided on the other side of the side that does not have the protective film b via the conductive layer c. Although not shown, the polarizing element a / protective film b / conductive layer c / adhesive layer 21 are laminated in this order as the single protective polarizing film A2 having the protective film b on only one side of the polarizer a. You can also use things. FIG. 3 shows a case where the one-sided protective polarizing film 11A is used and the transparent layer d is further provided on the other side of the polarizing element a. In FIG. 3, the one-sided protective polarizing film 11A is provided with a transparent layer d, a conductive layer c, and an adhesive layer 21 in this order. It is preferable that the transparent layer d is provided directly on the polarizer a because it is possible to suppress an increase in the water content of the polarizer in a high temperature and high humidity environment.

<Deformed part>
Further, the polarizing film with an adhesive layer of the present invention has a deformed portion other than a rectangle. FIG. 4 is a top view of an example having a deformed portion other than a rectangle. The irregular shape is not particularly limited, and any shape can be taken depending on the application, function, design, etc. of the polarizing film with the adhesive layer. The irregular shape other than the rectangle may be, for example, a case where the rectangle has a chipped portion or a through hole.

The chipped portion is provided on the outer edge of the polarizing film with an adhesive layer. When a plurality of the chipped portions are provided, they may have the same shape or different shapes. Two or more of the chipped portions may be provided on one side, or one or more may be provided on each of the two sides. Further, the chipped portion may be provided at one of the four corners of the outer edge of the rectangle, or may be provided at two or more locations. The corners of the outer edge not provided with the chipped portion may be angular or rounded. The chipped portion can be formed of a straight line, a curved line, or a combination thereof. FIG. 4 is an example of a polarizing film 1 with an adhesive layer having a deformed shape, and chipped portions 2 having different shapes are provided on both short sides of the rectangle.

The length of the side W1 of the chipped portion is appropriately adjusted according to the use of the polarizing film. For example, W1 is preferably adjusted in the range of about 2 to 100 mm. Further, it is preferable that the chipped portion 2 is adjusted so that the maximum depth D from the side W1 is about 2 to 100 mm.

FIG. 4 shows a case where the angle θ1 formed by the two straight lines forming the shape of the chipped portion 2 is 90 °, but the angle θ1 is 90 ° or more and less than 180 °, preferably 90 ° or more. It is 135 ° or less. When the angle θ1 is out of the above range, the stress based on expansion and contraction is concentrated on the portion 4 where the two straight lines intersect in a harsh environment of thermal impact, and cracks are likely to occur in the portion 4.

Further, in FIG. 4, a curve forming the shape of the chipped portion 2 can be described, but the radius of curvature R1 of the curve is 0.2 mm or more, preferably 1 mm or more, more preferably 2 mm or more, still more preferable. Is 3 mm or more, more preferably 5 mm or more. When the radius of curvature R1 is less than 0.2 mm, stress based on expansion and contraction is concentrated on the curved portion in a harsh environment of thermal shock, and cracks are likely to occur in the curved portion.

The through hole is provided inside the plane of the polarizing film with an adhesive layer. When a plurality of the through holes are provided inside the plane of the polarizing film with the pressure-sensitive adhesive layer, they may have the same shape or different shapes. The through hole is composed of a straight line, a curved line, or a combination thereof. Examples of the shape of the through hole include a circle, an ellipse (one axis of symmetry, two axes of symmetry), a rectangle with rounded corners, a quadrangle (square, rectangle), and a polygon having five or more angles. Be done.

Examples of the method for forming the deformed portion include punching, end milling, and laser processing. The deformed portion is usually formed by the processing after laminating each layer.

<Polarizing film with adhesive layer>
First, each member constituting the polarizing film with an adhesive layer of the present invention will be described. As the polarizing film, a polarizing element and one having a protective film on one side or both sides of the polarizing element is used.

The polarizer is not particularly limited, and various types of polarizers can be used. Examples of the polarizer include a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and an ethylene / vinyl acetate copolymer system partially saponified film, and a bicolor property of iodine or a bicolor dye. Examples thereof include a uniaxially stretched film by adsorbing a substance, a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol and a dehydrogenated product of polyvinyl chloride. Among these, a polarizer made of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

Further, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. It is preferable that such a thin polarizing element has less unevenness in thickness, is excellent in visibility, is excellent in durability because there is little dimensional change, and can be made thinner as a polarizing film.

As a material constituting the protective film, for example, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture blocking property, isotropic property, etc. is used. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, and cyclic resins. Examples thereof include polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. A protective film is usually bonded to one side of the polarizer by an adhesive layer, but as a protective film on the other side, (meth) acrylic, urethane, acrylic urethane, epoxy, etc. A thermosetting resin such as silicone or an ultraviolet curable resin can be used.

As the material of the protective film (transparent protective film), a cellulose resin and a (meth) acrylic resin are preferable because the fluctuation of the surface resistance value of the pressure-sensitive adhesive layer can be controlled to be small. As the (meth) acrylic resin, it is preferable to use a (meth) acrylic resin having a lactone ring structure. Examples of the (meth) acrylic resin having a lactone ring structure include JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, JP-A-2002-254544, JP-A-2005 Examples thereof include (meth) acrylic resins having a lactone ring structure described in Japanese Patent Application Laid-Open No. 146084. In particular, the cellulose resin is preferable to the (meth) acrylic resin in that it is effective in suppressing irregularly shaped cracks and polarizer cracks, which are problems in the single-protective polarizing film.

As the protective film, a retardation film, a brightness improving film, a diffusion film and the like can also be used. Examples of the retardation film include those having a frontal retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more. The front phase difference is usually controlled in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 300 nm. When a retardation film is used as the protective film, the retardation film also functions as a polarizer protective film, so that the thickness can be reduced.

A functional layer such as a hard coat layer, an antireflection layer, a sticking prevention layer, a diffusion layer or an antiglare layer can be provided on the surface of the protective film to which the polarizer is not adhered.

The protective film and the polarizer are laminated via an intervening layer such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer). At this time, it is desirable that both are laminated without an air gap by an intervening layer. The protective film and the polarizer are preferably laminated via an adhesive layer. The adhesive used for bonding the polarizer and the protective film is not particularly limited as long as it is optically transparent, and various forms such as water-based, solvent-based, hot-melt-based, radical-curing type, and cation-curing type are used. However, water-based adhesives or radical curable adhesives are suitable.

<Conductive layer>
The thickness of the conductive layer c is preferably 1 μm or less, preferably 0.01 to 0.5 μm, from the viewpoint of stability of the surface resistance value and adhesion to the pressure-sensitive adhesive layer 21, and 0. It is preferably 01 to 0.2 μm, and more preferably 0.01 to 0.1 μm. Further, the surface resistance value of the conductive layer c is preferably 1 × 10 ⁷ to 1 × 10 ¹² Ω / □ from the viewpoint of the antistatic function, and is preferably 1 × 10 ⁷ to 1 × 10 ¹¹ Ω / □. It is preferable that the value is 1 × 10 ⁷ to 1 × 10 ¹⁰ Ω / □.

The conductive layer can be formed from various antistatic agent compositions. As the antistatic agent forming the conductive layer, an ionic surfactant system, a conductive polymer, conductive fine particles, carbon nanotubes and the like can be used.

Among these antistatic agents, conductive polymers and carbon nanotubes are preferably used from the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heat and humidification. In particular, conductive polymers such as polyaniline and polythiophene are preferably used. As the conductive polymer, an organic solvent-soluble, water-soluble, or water-dispersible polymer can be appropriately used, but a water-soluble conductive polymer or a water-dispersible conductive polymer is preferably used. The water-soluble conductive polymer and the water-dispersible conductive polymer can be prepared as an aqueous solution or an aqueous dispersion as a coating liquid for forming an antistatic layer, and the coating liquid does not need to use a non-aqueous organic solvent and is organic. This is because the deterioration of the optical film base material due to the solvent can be suppressed. The aqueous solution or the aqueous dispersion can contain an aqueous solvent in addition to water. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1. -Alcohols such as propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and the like can be mentioned.

Further, the water-soluble conductive polymer such as polyaniline and polythiophene or the water-dispersible conductive polymer preferably has a hydrophilic functional group in the molecule. Examples of the hydrophilic functional group include a sulfon group, an amino group, an amide group, an imino group, a quaternary ammonium base, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate ester group, a phosphoric acid ester group, or a salt thereof. And so on. By having a hydrophilic functional group in the molecule, it becomes easy to be dissolved in water or dispersed in water in the form of fine particles, and the water-soluble conductive polymer or the water-dispersible conductive polymer can be easily prepared.

Examples of commercially available water-soluble conductive polymers include polyaniline sulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight of 150,000 in terms of polystyrene). Examples of commercially available water-dispersible conductive polymers include polythiophene-based conductive polymers (manufactured by Nagase Chemtech, trade name, Denatron series).

Further, as a material for forming the conductive layer, a binder component can be added together with the antistatic agent for the purpose of improving the film-forming property of the antistatic agent and the adhesion to the optical film. When the antistatic agent is a water-soluble conductive polymer or a water-based material of the water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of binders include oxazoline group-containing polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone, polystyrene resins, polyethylene glycol, etc. Examples include pentaerythritol. In particular, polyurethane-based resins, polyester-based resins, and acrylic-based resins are preferable. One or two or more of these binders can be appropriately used according to the intended use.

The amount of the antistatic agent and the binder used depends on their types, but it is preferable to control the surface resistance value of the obtained conductive layer to be 1 × 10 ⁷ to 1 × 10 ¹² Ω / □.

<Adhesive layer>
The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B).

The (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component as a monomer unit. In addition, (meth) acrylate means 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 (A) include those having a linear or branched alkyl group having 1 to 18 carbon atoms. For example, the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group and decyl. Examples thereof include a group, an isodecyl group, a dodecyl group, an isomyristyl group, a lauryl group, a tridecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group and the like. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3 to 9.

The weight ratio of the alkyl (meth) acrylate is preferably 70% by weight or more in terms of the weight ratio of all the constituent monomers (100% by weight) constituting the (meth) acrylic polymer (A) as a monomer unit. The weight ratio of the alkyl (meth) acrylate can be considered as the balance of the other copolymerized monomers. It is preferable to set the weight ratio of the alkyl (meth) acrylate in the above range in order to ensure adhesiveness.

In the (meth) acrylic polymer (A), in addition to the above-mentioned alkyl (meth) acrylate monomer unit, unsaturated (meth) acryloyl group, vinyl group, etc. are used for the purpose of improving adhesiveness and heat resistance. One or more types of copolymerizable monomers having a polymerizable functional group having a double bond can be introduced by copolymerization.

Examples of the copolymerization monomer include functional group-containing monomers such as a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and an amide group-containing monomer.

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 and a vinyl group. Specific examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. Among the carboxyl group-containing monomers, acrylic acid is preferable from the viewpoint of copolymerizability, price, and adhesive properties.

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 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyhexyl (meth) acrylate. Examples thereof include hydroxyalkyl (meth) acrylates such as hydroxyoctyl (meth) acrylates, 10-hydroxydecyl (meth) acrylates and 12-hydroxylauryl (meth) acrylates, and (4-hydroxymethylcyclohexyl) -methyl acrylates. Among the hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, and 4-hydroxybutyl (meth) acrylate is particularly preferable, from the viewpoint of durability.

The carboxyl group-containing monomer and the hydroxyl group-containing monomer serve as reaction points with the cross-linking agent when the pressure-sensitive adhesive composition contains the cross-linking agent. Since the carboxyl group-containing monomer and the hydroxyl group-containing monomer are highly reactive with the intermolecular cross-linking agent, they are preferably used for improving the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer. Further, the carboxyl group-containing monomer is preferable in terms of achieving both durability and reworkability, and the hydroxyl group-containing monomer is preferable in terms of reworkability.

The weight ratio of the carboxyl group-containing monomer is preferably 10% by weight or less, more preferably 0.01 to 8% by weight, further preferably 0.05 to 6% by weight, and further preferably 0.1 to 0.1% by weight. 5% by weight is preferable. It is preferable that the weight ratio of the carboxyl group-containing monomer is 0.01% by weight or more from the viewpoint of durability. On the other hand, if it exceeds 10% by weight, it is not preferable from the viewpoint of reworkability.

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, and further 0.2 to 0.2 to 2% by weight. 2% by weight is preferable. It is preferable that the weight ratio of the hydroxyl group-containing monomer is 0.01% by weight or more from the viewpoint of cross-linking the pressure-sensitive adhesive layer, durability and adhesive properties. On the other hand, if it exceeds 3% by weight, it is not preferable from the viewpoint of durability.

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 and 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-methyl (meth) acrylamide, and N-. Butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl Acrylamide-based monomers such as (meth) acrylamide and mercaptoethyl (meth) acrylamide; N-acrylloyl heterocyclic monomers such as N- (meth) acryloylmorpholin, N- (meth) acryloyl piperidine, N- (meth) acryloylpyrrolidin; Examples thereof include N-vinyl group-containing lactam-based monomers such as -vinylpyrrolidone and N-vinyl-ε-caprolactam. The amide group-containing monomer is preferable in suppressing an increase in surface resistance value over time (particularly in a humid environment), satisfying durability, and further suppressing deformed cracks. In particular, among the amide group-containing monomers, the N-vinyl group-containing lactam-based monomer suppresses an increase in the surface resistance value over time (particularly in a humid environment), and is a transparent conductive layer (touch sensor layer). It is preferable for satisfying the durability against and suppressing irregular cracks.

As the weight ratio of the amide group-containing monomer increases, the anchoring property with respect to the optical film tends to decrease. Therefore, the weight ratio is preferably 10% by weight or less, more preferably 5% by weight or less. Especially preferable. The weight ratio of the amide group-containing monomer is preferably 0.1% by weight or more from the viewpoint of suppressing an increase in the surface resistance value over time (particularly in a humid environment). The weight ratio is preferably 0.3% by weight or more, more preferably 0.5% by weight or more. The amide group-containing monomer is suitable in relation to the ionic compound (B) contained in the pressure-sensitive adhesive layer of the present invention.

In the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer, if an amide group introduced into the side chain of the (meth) acrylic polymer (A) as the base polymer is present, the amide group is present. Due to the presence of, the surface resistance value of the pressure-sensitive adhesive layer adjusted by blending the ionic compound (B) is suppressed from fluctuating and increasing even in a humid environment, and is maintained within the desired value range. It is preferable to do so. The phase of the (meth) acrylic polymer (A) and the ionic compound (B) due to the presence of an amide group introduced as a functional group of the copolymerization monomer in the side chain of the (meth) acrylic polymer (A). It is thought that the solubility will increase.

Further, the pressure-sensitive adhesive layer is made of glass or a transparent conductive layer (ITO layer or the like) when an amide group introduced into the side chain of the (meth) acrylic polymer (A) as the base polymer is present. The durability is good for all of the above, and it is possible to suppress the occurrence of peeling, floating, etc. in the state of being attached to the liquid crystal panel. Further, the durability can be satisfied even in a humidified environment (after the humidification reliability test).

As the copolymerization monomer, for example, an aromatic ring-containing (meth) acrylate can be used. An aromatic ring-containing (meth) acrylate is a compound having an aromatic ring structure in its structure and containing a (meth) acryloyl group. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring.

Specific examples of the aromatic ring-containing (meth) acrylate include, for example, benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxypropyl. (Meta) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, ethylene oxide-modified cresol (meth) acrylate, phenolethylene oxide-modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Those having a benzene ring such as acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, cresyl (meth) acrylate, polystyryl (meth) acrylate; hydroxyethylated β-naphthol acrylate, 2-naphthoethyl (meth) acrylate , 2-naphthoxyethyl acrylate, 2- (4-methoxy-1-naphthoxy) ethyl (meth) acrylate or the like having a naphthalene ring; examples thereof include those having a biphenyl ring such as biphenyl (meth) acrylate.

As the aromatic ring-containing (meth) acrylate, benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable, and phenoxyethyl (meth) acrylate is particularly preferable, from the viewpoint of adhesive properties and durability.

The weight ratio of the aromatic ring-containing (meth) acrylate is preferably 25% by weight or less, more preferably 3 to 25% by weight, further preferably 10 to 22% by weight, and further preferably 14 to 20% by weight. Is preferable. When the weight ratio of the aromatic ring-containing (meth) acrylate is 3% by weight or more, it is preferable in order to suppress display unevenness. On the other hand, if it exceeds 25% by weight, the display unevenness is not sufficiently suppressed, and the durability tends to decrease.

Specific examples of other copolymerization monomers other than the above include; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; allylsulfonic acid, 2- (meth) acrylamide-2. -Sulfonic acid group-containing monomers such as methylpropanesulfonic acid, (meth) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate; and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate.

In addition, alkylaminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl ( Alkoxyalkyl (meth) acrylates such as meta) acrylates; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, etc. Succinimide-based monomers; maleimide-based monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide and N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N- Itaconimide-based monomers such as octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide are also mentioned as examples of monomers for modification purposes.

Further, as the modified monomer, a vinyl-based monomer such as vinyl acetate and vinyl propionate; a cyanoacrylate-based monomer such as acrylonitrile and methacrylonitrile; an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate; and polyethylene glycol (meth). Glycol-based (meth) acrylates such as acrylates, polypropylene glycol (meth) acrylates, methoxyethylene glycol (meth) acrylates, and methoxypolypropylene glycol (meth) acrylates; tetrahydrofurfuryl (meth) acrylates, fluorine (meth) acrylates, silicones (meth). ) (Meta) acrylate monomers such as acrylate and 2-methoxyethyl acrylate can also be used. Further, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.

Further, examples of copolymerizable monomers other than the above include silane-based monomers containing a silicon atom. Examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane. , 8-Vinyloctyloxydecyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane and the like.

Examples of the copolymerization monomer include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and neo. Pentyl glycol di (meth) acrylate, trimethyl propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Caprolactone-modified dipentaerythritol Hexa (meth) Acrylate and other (meth) acrylic acids and polyhydric alcohols such as esterified products such as (meth) acryloyl groups and vinyl groups and other unsaturated double bonds having two or more unsaturated double bonds. Polyester (meth) acrylates and epoxys (meth) acrylates and epoxys in which two or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups are added as functional groups similar to the monomer components to the skeletons of sex monomers, polyesters, epoxys, urethanes, etc. Meta) acrylate, urethane (meth) acrylate and the like can also be used.

The proportion of the other copolymerized monomer in the (meth) acrylic polymer (A) is about 0 to 10% by weight based on the weight ratio of all the constituent monomers (100% by weight) of the (meth) acrylic polymer (A). Further, it is preferably about 0 to 7% by weight, more preferably about 0 to 5% by weight.

The (meth) acrylic polymer (A) of the present invention usually preferably has a weight average molecular weight of 1 million to 2.5 million. Considering durability, particularly heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. When the weight average molecular weight is 1 million or more, it is preferable from the viewpoint of heat resistance. Further, when the weight average molecular weight is larger than 2.5 million, the adhesive tends to be hard and peeling is likely to occur. The weight average molecular weight (Mw) / number average molecular weight (Mn), which indicates the molecular weight distribution, is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, and further 1.8 to. It is preferably 5. When the molecular weight distribution (Mw / Mn) exceeds 10, it is not preferable in terms of durability. The weight average molecular weight and the molecular weight distribution (Mw / Mn) are measured by GPC (gel permeation chromatography) and obtained from the values calculated by polystyrene conversion.

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

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

The polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not particularly limited and can be appropriately selected and used. The weight average molecular weight of the (meth) acrylic polymer (A) can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types. To.

<Ionic compound (B)>
As the ionic compound (B) contained in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer of the present invention, an alkali metal salt and / or an organic cation-anion salt can be preferably used. As the alkali metal salt, organic salts and inorganic salts of alkali metals can be used. The term "organic cation-anionic salt" as used in the present invention refers to an organic salt whose cation component is composed of an organic substance, and the anion component may be an organic substance or an inorganic substance. There may be. The "organic cation-anionic salt" is also referred to as an ionic liquid or an ionic solid. By containing the ionic compound (B) in the pressure-sensitive adhesive layer, the surface resistance value of the pressure-sensitive adhesive layer can be lowered to suppress the generation of static electricity, and the orientation of the liquid crystal layer due to electrification is disturbed and light leakage (light leakage). It is possible to suppress the occurrence of uneven charging).

<Alkali metal salt>
Examples of the alkali metal ions constituting the cationic component of the alkali metal salt include lithium, sodium, and potassium ions. Among these alkali metal ions, lithium ions are preferable.

The anionic component of the alkali metal salt may be composed of an organic substance or an inorganic substance. Examples of the anion components constituting the organic salt include CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ^{_{_{^{-, C 3 F 7 COO -}}}} , (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, PF 6 -, CO 3 2-, or the following general formula ( 1) to (4),
_{_{(1) :( C n F 2n}} + 1 SO 2) 2 N - ( where, n is an integer of 0 to 10),
_{_{_{(2): CF 2 (C}}} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
^{_{_{(3): - O 3 S}}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
(4): (C _p F _{2p + 1} SO ₂ ) N ⁻ (C _q F _{2q + 1} SO ₂ ), (where p and q are integers of 1 to 10), and the like are used. In particular, an anionic component containing a fluorine atom is preferably used because an ionic compound having good ionic dissociation property can be obtained. The anionic component constituting the inorganic ^{^{^{_{^{salts, Cl -, Br -, I}}}}} -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF _{^{_{^{_{^{6 -, NbF 6 -, TaF}}}}}} 6 -, (CN) 2 N -, and the like can be used. Examples of the anionic _{_{_{^{component, (CF 3 SO 2) 2}}}} N -, (C 2 F 5 SO 2) 2 N -, wherein represented by formula (1) etc., (perfluoroalkyl sulfonyl) imide are preferable, especially ( A (trifluoromethanesulfonyl) imide represented by CF ₃ SO ₂ ) ₂ N ⁻ is preferred.

Specific examples of the organic salt of the alkali metal include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, and Li (CF ₃ SO _2). ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, KO ₃ S (CF ₂ ) ₃ SO ₃ K, _{_{_{LiO 3 S (CF 2) 3}}} SO 3 K , and the like, among these _{_{_{_{LiCF 3 SO 3, Li (CF}}}} 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C and the like are preferable, and Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO) ₂₎ bis (fluorosulfonyl) more preferably a fluorine-containing lithium imide salt imide lithium salts such as 2 _N, in particular (perfluoroalkyl sulfonyl) imide lithium salts are preferred. In addition, 4,4,5,5-tetrafluoro-1,3,2-dithiazolidine-1,1,3,3-tetraoxide lithium salt and the like can be mentioned.

Inorganic salts of alkali metals include lithium perchlorate and lithium iodide.

<Organic cation-anion salt>
The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the cation component is composed of an organic substance. Specific examples of the cation component include pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, and dihydropyrimidinium cation. Examples thereof include pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation and the like.

The anionic component, ^{^{^{_{^{e.g., Cl -, Br -, I}}}}} -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO ^{_{_{^{_{-, CH 3 SO 3 -,}}}}} CF 3 SO 3 -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, (CN) 2 N -, C 4 F ₉ SO ₃ ⁻ , C ₃ F ₇ COO ⁻ , ((CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ , ⁻ O ₃ S (CF ₂ ) ₃ SO ₃ ⁻ , and the following general formulas (1) to (4) ),
_{_{(1) :( C n F 2n}} + 1 SO 2) 2 N - ( where, n is an integer of 0 to 10),
_{_{_{(2): CF 2 (C}}} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
^{_{_{(3): - O 3 S}}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
(4): (C _p F _{2p + 1} SO ₂ ) N ⁻ (C _q F _{2q + 1} SO ₂ ), (where p and q are integers of 1 to 10), and the like are used. Among them, an anionic component containing a fluorine atom is particularly preferably used because an ionic compound having good ionic dissociation property can be obtained.

As the organic cation-anion salt, a compound composed of a combination of the above cation component and an anion component is appropriately selected and used. Preferred specific examples of the organic cation-anionic salt include, for example, methyltrioctylammonium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, and ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide. Fluorosulfonylimide). Of these, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide and ethyl methylimidazolium bis (fluorosulfonylimide) are more preferable.

As the ionic compound (B), in addition to the above-mentioned alkali metal salt and organic cation-anionic salt, inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferric chloride, ferric chloride and ammonium sulfate Can be mentioned.

The ionic compound (B) preferably has a cation component with a molecular weight of 210 or less from the viewpoint of suppressing the occurrence of irregular cracks. The molecular weight of the cation component is further preferably 150 or less, further preferably 110 or less, further preferably 50 or less, and further preferably 10 or less. The larger the molecular weight of the cation component, the more the (meth) acrylic polymers in the pressure-sensitive adhesive layer are prevented from being entangled with each other, and the physical properties of the pressure-sensitive adhesive layer tend to be softened. Therefore, the smaller the molecular weight, the less likely the physical properties of the pressure-sensitive adhesive layer are to be softened, and the occurrence of irregularly shaped cracks can be suppressed. Further, the smaller the molecular weight of the cation component, the lower the surface resistance value of the pressure-sensitive adhesive layer, which is preferable from the viewpoint of suppressing static electricity unevenness.

When the ionic compound (B) is an alkali metal salt, alkali metal ions such as lithium, sodium, and potassium are cationic components having a molecular weight of 210 or less. Therefore, alkali metals containing these alkali metal ions as cationic components. Salt can be preferably used. In particular, from the viewpoint of compatibility with the pressure-sensitive adhesive layer, an organic salt of an alkali metal in which the anionic component of the alkali metal salt is composed of an organic substance is preferable. Further, as the alkali metal ion, lithium ion having the smallest molecular weight is preferable. As the ionic compound (B), a lithium salt is preferable, and an organic salt of lithium is particularly preferable. On the other hand, when the ionic compound (B) is an organic cation-anion salt, a molecular weight of 210 or less can be selected and used from the above-exemplified cation components. In particular, from the viewpoint of compatibility with the pressure-sensitive adhesive layer, an organic cation-anion salt in which the anionic component is composed of an organic substance is preferable.

The proportion of the ionic compound (B) in the pressure-sensitive adhesive composition of the present invention can be appropriately adjusted so as to satisfy the antistatic properties of the pressure-sensitive adhesive layer and the sensitivity of the touch panel. For example, a touch sensing function is built in while considering the type of protective film of the polarizing film so that the surface resistance value of the adhesive layer is in the range of 1.0 × 10 ⁸ to 1.0 × 10 ¹² Ω / □. It is preferable to adjust the ratio of the ionic compound (B) according to the type of the liquid crystal panel. For example, in the in-cell type liquid crystal panel with a built-in touch sensing function shown in FIG. 6, the initial surface resistance value of the adhesive layer is preferably controlled in the range of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □. It is more preferable to control in the range of 1 × 10 ⁸ to 1 × 10 ¹⁰ Ω / □. Further, in the semi-in-cell type liquid crystal panel shown in FIG. 7 or the on-cell type liquid crystal panel with a built-in touch sensing function shown in FIG. 8, the initial surface resistance value of the adhesive layer is 1 × 10 ¹⁰ to 1 × 10 ¹² Ω /. It is preferable to control within the range of □.

If the amount of the ionic compound (B) increases, the ionic compound (B) may precipitate, and further, humidification peeling tends to occur. Further, if the amount of the ionic compound (B) increases, the surface resistance value becomes too low, and the sensitivity of the touch panel may decrease due to the baseline fluctuation (malfunction at the time of touch caused by the surface resistance value being too low). There is. The ratio of the ionic compound (B) is, for example, preferably 40 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer (A). Is preferable, more preferably 10 parts by weight or less, and further preferably 6 parts by weight or less. If it is too small, the antistatic property is poor, and if it is too large, the touch sensitivity may be lowered, the precipitation of ionic compounds, and the humidification peeling of the adhesive may be deteriorated. On the other hand, in order to improve the antistatic performance, it is preferable to use 0.01 part by weight or more of the ionic compound (B). From this point of view, the ionic compound (B) is preferably 0.1 part by weight or more, more preferably 0.5 part by weight or more.

The pressure-sensitive adhesive composition of the present invention can contain a cross-linking agent (C). As the cross-linking agent (C), an organic cross-linking agent or a polyfunctional metal chelate can be used. Examples of the organic cross-linking agent include isocyanate-based cross-linking agents, peroxide-based cross-linking agents, epoxy-based cross-linking agents, and imine-based cross-linking agents. A polyfunctional metal chelate is one in which a polyvalent metal is covalently 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, Ti and the like. Can be mentioned. Examples of the atom in the organic compound having a covalent bond or a coordination bond include an oxygen atom and the like, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound and a ketone compound.

As the cross-linking agent (C), an isocyanate-based cross-linking agent and / or a peroxide-based cross-linking agent is preferable.

As the isocyanate-based cross-linking agent (C), a compound having at least two isocyanate groups can be used. For example, known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, etc., which are generally used for urethanization reactions, are used.

As the peroxide, any peroxide that generates radically active species by heating or light irradiation to promote cross-linking of the base polymer of the pressure-sensitive adhesive composition can be appropriately used, but in consideration of workability and stability. It is preferable to use a peroxide having a half-life temperature of 80 ° C. to 160 ° C. for 1 minute, and more preferably to use a peroxide having a half-life temperature of 90 ° C. to 140 ° C.

Examples of the peroxide that can be used include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.) and di (4-t-butylcyclohexyl) peroxydicarbonate (1). Minute half-life temperature: 92.1 ° C., di-sec-butylperoxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butylperoxyneodecanoate (1 minute half-life temperature: 103) .5 ° C), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C), dilauroyl peroxide (1 minute half-life temperature: 110.3 ° C) 1 minute half temperature: 116.4 ° C), di-n-octanoyl peroxide (1 minute half temperature: 117.4 ° C), 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate (1 minute half-life temperature: 124.3 ° C.), di (4-methylbenzoyl) peroxide (1 minute half-life temperature: 128.2 ° C.), dibenzoyl peroxide (1 minute half-life temperature: 130. 0 ° C.), t-Butylperoxyisobutyrate (1 minute half-life temperature: 136.1 ° C.), 1,1-di (t-hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2 ° C.) And so on. Among them, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.) and dilauroyl peroxide (1 minute half-life temperature: 116.) Since the cross-linking reaction efficiency is particularly excellent. 4 ° C.), dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C.) and the like are preferably used.

The amount of the cross-linking agent (C) used is preferably 3 parts by weight or less, more preferably 0.01 to 3 parts by weight, and further 0.02 with respect to 100 parts by weight of the (meth) acrylic polymer (A). It is preferably from 2 parts by weight, more preferably 0.03 to 1 part by weight. If the amount of the cross-linking agent (C) is less than 0.01 parts by weight, the pressure-sensitive adhesive layer may be insufficiently cross-linked and the durability and adhesive properties may not be satisfied. There is a tendency for it to become too hard and its durability to decrease.

The pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent (D). Durability can be improved by using the silane coupling agent (D). Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3, 4-Epylcyclohexyl) Epyl group-containing silane coupling agent such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N- (1,3-dimethylbutylidene) propylamine and N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltri. Examples thereof include (meth) acrylic group-containing silane coupling agents such as ethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanuppropyltriethoxysilane. As the above-exemplified silane coupling agent, an epoxy group-containing silane coupling agent is preferable.

Further, as the silane coupling agent (D), one having a plurality of alkoxysilyl groups in the molecule can also be used. Specifically, for example, X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40 manufactured by Shin-Etsu Chemical Co., Ltd. -2651 and the like. A silane coupling agent having a plurality of alkoxysilyl groups in these molecules is preferable because it is difficult to volatilize and has a plurality of alkoxysilyl groups, which is effective in improving durability. In particular, durability is preferable even when the adherend of the optical film with the pressure-sensitive adhesive layer is a transparent conductive layer (for example, ITO or the like) in which the alkoxysilyl group is less likely to react than glass. Further, the silane coupling agent having a plurality of alkoxysilyl groups in the molecule preferably has an epoxy group in the molecule, and more preferably has a plurality of epoxy groups in the molecule. A silane coupling agent having a plurality of alkoxysilyl groups in the molecule and having an epoxy group tends to have good durability even when the adherend is a transparent conductive layer (for example, ITO). Specific examples of the silane coupling agent having a plurality of alkoxysilyl groups in the molecule and having an epoxy group include X-41-1053, X-41-1059A, and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. In particular, X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd., which has a high epoxy group content, is preferable.

The silane coupling agent (D) may be used alone or in combination of two or more, but the content as a whole is the (meth) acrylic polymer (A) 100. It is preferably 5 parts by weight or less, more preferably 0.001 to 5 parts by weight, further preferably 0.01 to 1 part by weight, still more preferably 0.02 to 1 part by weight, and further. Is preferably 0.05 to 0.6 parts by weight. It is an amount that improves durability.

Further, the pressure-sensitive adhesive composition of the present invention may contain other known additives, for example, a polyether compound having a reactive silyl group, a polyether compound of polyalkylene glycol such as polypropylene glycol, and coloring. Powders of agents, pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization prohibited Agents, inorganic or organic fillers, metal powders, particles, foils and the like can be appropriately added depending on the intended use. Further, a redox system to which a reducing agent is added may be adopted within a controllable range. These additives are preferably used in a range of 5 parts by weight or less, further 3 parts by weight or less, and further 1 part by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A).

As a method for forming the pressure-sensitive adhesive layer, for example, the pressure-sensitive adhesive composition is applied to a peeled separator or the like, and a polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer, which is then transferred to an optical film (polarizing film). This is produced by a method of applying the pressure-sensitive adhesive composition to an optical film (polarizing film) and drying and removing a polymerization solvent or the like to form a pressure-sensitive adhesive layer on the optical film. When applying the pressure-sensitive adhesive, one or more solvents other than the polymerization solvent may be newly added as appropriate.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm. It is preferably 2 to 50 μm, more preferably 2 to 40 μm, and even more preferably 5 to 35 μm.

The pressure-sensitive adhesive layer applied to the polarizing film with a pressure-sensitive adhesive layer of the present invention preferably has a creep value of 120 μm or less, more preferably 100 μm or less, at 85 ° C. from the viewpoint of being applied to a deformed polarizing film. It is more preferably 85 μm or less, and particularly preferably 60 μm or less. The lower limit of the creep value is preferably 15 μm or more, more preferably 30 μm or more. If the creep value exceeds 120 μm, cracks that occur in the deformed polarizing film may be exacerbated as described in Examples. If the creep value is less than 15 μm, the stress relaxation property of the pressure-sensitive adhesive layer is lowered, so that the pressure-sensitive adhesive layer may be easily peeled off in the durability test.

<Transparent layer>
The transparent layer will be described in detail below.

From the viewpoint of thinning and optical reliability, the thickness of the transparent layer is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, and further 1. It is preferably 5 μm or less, and more preferably 1 μm or less. If the transparent layer is too thick, the thickness of the polarizing film may increase, and the optical reliability of the polarizer may be reduced. On the other hand, the thickness of the transparent layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, from the viewpoint of suppressing the fluctuation ratio of the surface resistance value of the pressure-sensitive adhesive layer to be small. Is preferable.

As the material for forming the transparent layer, a material having transparency and capable of suppressing the influence of the conductive layer on the polarizer can be used. Examples of such a material include a forming material containing a urethane prepolymer (a) which is a reaction product of an isocyanate compound and a polyhydric alcohol.

As the isocyanate compound, for example, a polyfunctional isocyanate compound is preferable, and specific examples thereof include a polyfunctional aromatic isocyanate compound, an alicyclic isocyanate, an aliphatic isocyanate compound, or a dimer thereof.

Examples of the polyfunctional aromatic isocyanate compound include phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, 4 , 4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediocyanate, xylylene diisocyanate, methylenebis 4-phenylisocyanate, p-phenylenediisocyanate, and the like.

Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, 1,3-bisisocyanatomethylcyclohexane, isophorone diisocyanate, and hydrogen. Examples thereof include added diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.

Examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4. Examples thereof include 4-trimethylhexamethylene diisocyanate.

Examples of the polyfunctional isocyanate compound include those having three or more isocyanate groups such as trisisocyanurate (6-incyanate hexyl).

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-. 1,3-Propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Examples thereof include methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like.

As the urethane prepolymer (a), in the present invention, it is possible to use a urethane prepolymer having a rigid structure in which a cyclic structure (benzene ring, cyanurate ring, isocyanurate ring, etc.) occupies a large proportion in the structure. preferable. For example, the polyfunctional isocyanate compound may be used alone or in combination of two or more, but an aromatic isocyanate compound is preferable from the viewpoint of suppressing water mixing into the polarizer. Other polyfunctional isocyanate compounds can be used in combination with aromatic isocyanate compounds. In particular, among the aromatic isocyanate compounds, it is preferable to use at least one selected from tolylene diisocyanate and diphenylmethane diisocyanate as the isocyanate compound.

As the urethane prepolymer (a), trimethylolpropane-tri-tolylenisocyanate and trimethylolpropane-tri-diphenylmethane diisocyanate are preferably used. The urethane prepolymer (a) is a compound having a terminal isocyanate group, and is obtained, for example, by mixing an isocyanate compound and a polyhydric alcohol, stirring and reacting them. Usually, it is preferable to mix the isocyanate compound and the polyhydric alcohol so that the isocyanate group is excessive with respect to the hydroxyl group of the polyhydric alcohol.

As the urethane prepolymer (a), one having a protective group added to a terminal isocyanate group can also be used. Protecting groups include oxime and lactam. When the isocyanate group is protected, the protecting group is dissociated from the isocyanate group by heating, and the isocyanate group reacts.

The forming material for forming the transparent layer can contain, in addition to the urethane prepolymer (a), a compound (b) having at least two functional groups having active hydrogen reactive with an isocyanate group. Examples of the functional group having an active hydrogen reactive with the isocyanate group include a hydroxyl group and an amino group. As the number of active hydrogen-containing functional groups of the compound (b) increases, the number of reaction points of the urethane prepolymer (a) with the isocyanate groups increases and a cured product is easily formed. Therefore, the number of the functional groups is 3. The above is preferable.

Further, the value of the compound (b) obtained by dividing its molecular weight by the number of the functional groups is preferably 350 or less. By defining the relationship between the molecular weight and the number of functional groups in this way, the reactivity between the compound (b) and the isocyanate group of the urethane prepolymer (a) can be ensured.

Further, the molecular weight of the compound (b) is preferably 1000 or less. A compound (b) having a molecular weight in the range of 1000 or less is preferable in terms of compatibility when preparing a forming material as a solution together with the urethane prepolymer (a).

Examples of the compound (b) include polyhydric alcohols, polyvalent amines, compounds having a hydroxyl group and an amino group in the molecule, and the like.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-. 1,3-Propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Bifunctional alcohols such as methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, polypropylene glycol, etc .; Trifunctional alcohols such as glycerin, trimethylolpropane, etc.; Alcohols and the like; In addition, alkylene oxide (for example, propylene oxide) adducts to the polyhydric alcohols such as polyoxypropylene glyceryl ether, polyoxypropylene trimetyl propane ether and polyoxypropylene sorbitol ether can be mentioned.

Examples of the polyvalent amine include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, dimerdiamine and the like.

Examples of the compound having a hydroxyl group and an amino group in the molecule include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, and 2-hydroxy. Diamines having a hydroxyl group in the molecule such as propylethylenediamine and di-2-hydroxypropylethylenediamine; alkanolamines such as ethanolamine, diethanolamine and triethanolamine can be mentioned.

It is preferable to use a polyhydric alcohol as the compound (b) from the viewpoint of preventing deterioration of the optical reliability of the polarizer, and in particular, trimethylolpropane is preferable from the viewpoint of reactivity with the urethane prepolymer (a). preferable.

The forming material contains the urethane prepolymer (a) as a main component. The urethane prepolymer (a) preferably contains 50% by weight or more of the solid content of the forming material.

The compounding ratio of the compound (b) to the urethane prepolymer (a) is 5% by weight or more with respect to the total 100% by weight (solid content ratio) of the urethane prepolymer (a) and the compound (b). It is preferable to have it. The blending ratio of the compound (b) is preferably 10% by weight or more from the viewpoint of improving the film strength. On the other hand, if the compounding ratio of the compound (b) is large, the optical reliability of the polarizer may deteriorate. Therefore, the compounding ratio of the compound (b) is 80% by weight or less, further 50% by weight or less. Is preferable.

The forming material can use a reaction catalyst in order to further increase the reactivity of the isocyanate group. The reaction catalyst is not particularly limited, but a tin catalyst or an amine catalyst is preferable. One kind or two or more kinds of reaction catalysts can be used. The amount of the reaction catalyst used is usually 5 parts by weight or less with respect to 100 parts by weight of the urethane prepolymer (a). When the amount of the reaction catalyst is large, the crosslinking reaction rate becomes high and the forming material foams. Sufficient adhesiveness cannot be obtained even if the foamed forming material is used. Usually, when a reaction catalyst is used, 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.

A reaction catalyst can be used to further increase the reactivity of the isocyanate group. The reaction catalyst is not particularly limited, but a tin catalyst or an amine catalyst is preferable. One kind or two or more kinds of reaction catalysts can be used. The amount of the reaction catalyst used is usually 5 parts by weight or less with respect to 100 parts by weight of the urethane prepolymer. When the amount of the reaction catalyst is large, the crosslinking reaction rate becomes high and the forming material foams. Sufficient adhesiveness cannot be obtained even if the foamed forming material is used. Usually, when a reaction catalyst is used, 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.

As the tin catalyst, either an inorganic catalyst or an organic catalyst can be used, but an organic catalyst is preferable. Examples of the inorganic tin-based catalyst include stannous chloride and stannic chloride. The organic tin catalyst preferably has at least one organic group such as an aliphatic group having a skeleton such as a methyl group, an ethyl group, an ether group or an ester group, and an alicyclic group. For example, tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate and the like can be mentioned.

The amine-based catalyst is not particularly limited. For example, those having at least one organic group such as an alicyclic group such as quinoclydin, amidine, and diazabicycloundecene are preferable. Other examples of the amine-based catalyst include triethylamine and the like. Examples of reaction catalysts other than the above include cobalt naphthenate, benzyltrimethylammonium hydroxide and the like.

The forming material is usually used as a solution containing the urethane prepolymer (a) and the compound (b). The solution may be solvent-based or aqueous-based such as an emulsion, colloidal dispersion, or aqueous solution.

The organic solvent is not particularly limited as long as it does not have a functional group having active hydrogen reactive with an isocyanate group and uniformly dissolves the urethane prepolymer (a) and the compound (b) constituting the forming material. Absent. The organic solvent may be used alone or in combination of two or more. Further, as the organic solvent, different solvents can be used for the urethane prepolymer (a) and the compound (b). In this case, the forming material can be prepared by mixing each solution after preparing each solution. Further, the viscosity of the forming material can be adjusted by further adding an organic solvent to the prepared forming material. Further, in the case of a solvent-based solution dissolved in an organic solvent, alcohols, water and the like illustrated below can be contained as a solvent.

Organic solvents include aromatic hydrocarbons such as toluene and xylene); esters such as ethyl acetate and butyl acetate; aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane and methylcyclohexane; 1,2-dichloroethane. Alkanes such as halogenated alkanes; ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, acetylacetone; and the like.

In the case of an aqueous system, for example, alcohols such as n-butyl alcohol and isopropyl alcohol, and ketones such as acetone can be blended. When making it aqueous, a dispersant is used, or a functional group that is less reactive with isocyanate groups such as carboxylates, sulfonates, and quaternary ammonium salts, and water dispersibility such as polyethylene glycol are used in urethane prepolymers. This can be done by introducing the ingredients.

Examples of the material for forming the transparent layer other than the urethane prepolymer include a cyanoacrylate-based forming material, an epoxy-based forming material, and a urethane acrylate-based forming material.

The formation of the transparent layer can be appropriately selected according to the type of the forming material. For example, the transparent layer can be formed by applying the forming material to a polarizer or the like and then curing the transparent layer. Can be obtained as a layer. Usually, after the coating, it is dried at about 30 to 100 ° C., preferably 50 to 80 ° C. for about 0.5 to 15 minutes to form a cured layer. Furthermore, when the forming material contains an isocyanate component, annealing treatment is performed at about 30 to 100 ° C., preferably 50 to 80 ° C. for about 0.5 to 24 hours in order to promote the reaction. Can be done.

<Image display panel, image display device>
The polarizing film with an adhesive layer of the present invention can be applied to various image display panels, and the image display panel can be applied to a conventional image display device. Other configurations of the image display device are the same as those of the conventional image display device. 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), and the like. ..

The polarizing film with an adhesive layer of the present invention has a small fluctuation ratio of the surface resistance value, and is suitable for application to a liquid crystal panel with a built-in touch sensing function.

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

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

A polarizing film with an adhesive layer conventionally used in this field can be used on the light source side of the liquid crystal layer, and the one described in the present specification can also be preferably used.

Specific examples of the liquid crystal panel with a built-in touch sensing function are shown in FIGS. 6 to 8, for example. In FIGS. 6 to 8, as the polarizing film with an adhesive layer of the present invention, the polarizing film 1 with an adhesive layer shown in FIG. 1 (however, the description of the conductive layer c is omitted) is used on the visual side of the liquid crystal cell. The case where there was was illustrated. That is, the one-sided protective polarizing film 11 and the pressure-sensitive adhesive layer 21 of FIG. 1 are shown as the first polarizing film 11 and the first pressure-sensitive adhesive layer 21 in FIGS. 6 to 8.

FIG. 6, a so-called in-cell type liquid crystal panel with a built-in touch sensing function. From the visual side, the first polarizing film 11 / first adhesive layer 21 / first transparent substrate 41 / touch sensor unit 5 / liquid crystal layer 3 / drive. It has an electrode / sensor unit 6 / a second transparent substrate 42 / a second pressure-sensitive adhesive layer 22 / a second polarizing film 12. In the in-cell type liquid crystal panel with a built-in touch sensing function of FIG. 6, for example, the liquid crystal cell C has a touch sensor unit 5 and a drive electrode / sensor in the first and second glass substrates 41 and 42 (inside the liquid crystal cell) sandwiching the liquid crystal layer 3. It has a part 6.

Further, FIG. 7 is a modified example of a so-called in-cell type (semi-in-cell type) liquid crystal panel having a built-in touch sensing function. From the visual side, the first polarizing film 11 / first adhesive layer 21 / touch sensor unit 5 / first It has a configuration of 1 transparent substrate 41 / liquid crystal layer 3 / drive electrode / sensor unit 6 / second transparent substrate 42 / second adhesive layer 22 / second polarizing film 12. In the in-cell type liquid crystal panel with a built-in touch sensing function shown in FIG. 7, for example, the liquid crystal cell C is outside the first transparent substrate 41 and the touch sensor unit 5 is in direct contact with the first adhesive layer 21 and sandwiches the liquid crystal layer 3. A drive electrode / sensor unit 6 is provided on the side of the second transparent substrate 42 in the first and second glass substrates 41 and 42 (inside the liquid crystal cell).

Further, FIG. 8 is a so-called on-cell type liquid crystal panel with a built-in touch sensing function, and from the visual side, the first polarizing film 11 / first adhesive layer 21 / touch sensor unit 5 / drive electrode / sensor unit 6 / third. It has a configuration of 1 transparent substrate 41 / liquid crystal layer 3 / drive electrode 7 / second transparent substrate 42 / second adhesive layer 22 / second polarizing film 12. In the on-cell type liquid crystal panel with a built-in touch sensing function shown in FIG. 8, for example, the liquid crystal cell C has a touch sensor unit 5 and a drive electrode / sensor unit 6 outside the first transparent substrate 41, and the touch sensor unit 5 is the first. A drive electrode 7 is provided on the side of the second transparent substrate 42 in the first and second glass substrates 41 and 42 (inside the liquid crystal cell) that are in direct contact with the pressure-sensitive adhesive layer 21 and sandwich the liquid crystal layer 3.

In a liquid crystal panel with a built-in touch sensing function, when the touch sensor unit 5 of the liquid crystal cell C and the first adhesive layer 21 are in direct contact with each other, the antistatic of the first adhesive layer 21 (containing an ionic compound) is prevented. The function tends to deteriorate, especially in a humid environment. Therefore, the liquid crystal panel with a built-in touch sensing function of the present invention is suitably applied to the in-cell type (modified example) shown in FIG. 7 or the on-cell type liquid crystal panel with a built-in touch sensing function shown in FIG. 8 among the above examples.

The first polarizing film 11 arranged on the viewing side of the liquid crystal cell C and the second polarizing film 12 arranged on the opposite side of the viewing side may be different optical films depending on the suitability of the respective arrangement locations. It can be used in layers. Examples of the other optical film include forming a liquid crystal display device such as a reflecting plate, an antitransmissive plate, a retardation film (including a wave plate such as 1/2 or 1/4), a visual compensation film, and a brightness improving film. An optical layer that may be used in the above. These can be used in one layer or two or more layers. Even when these other optical films are used, it is preferable that the pressure-sensitive adhesive layer on the liquid crystal layer 3 side is the first pressure-sensitive adhesive layer 21.

As the liquid crystal layer 3 included in the liquid crystal cell C, a liquid crystal layer containing liquid crystal molecules homogenically oriented in the absence of an electric field, which is applied to a liquid crystal panel with a built-in touch sensing function, is used. As the liquid crystal layer 3, for example, an IPS type liquid crystal layer is preferably used. In addition, as the liquid crystal layer 3, for example, any type of liquid crystal layer such as TN type, STN type, π type, and VA type can be used. The thickness of the liquid crystal layer is, for example, about 1.5 μm to 4 μm.

In the liquid crystal cell C, the first transparent substrate 41 and the second transparent substrate 42 can form a liquid crystal cell with the liquid crystal layer 3 interposed therebetween. A touch sensor unit 5, a drive electrode / sensor unit 6, a drive electrode 7, and the like are formed inside or outside the liquid crystal cell, depending on the form of the liquid crystal panel with a built-in touch sensing function. Further, a color filter substrate can be provided on the liquid crystal cell (first transparent substrate 41).

Examples of the material for forming the transparent substrate include glass or a polymer film. Examples of the polymer film include polyethylene terephthalate, polycycloolefin, polycarbonate and the like. When the transparent substrate is made of glass, its thickness is, for example, about 0.3 mm to 1 mm. When the transparent substrate is formed of a polymer film, its thickness is, for example, about 10 μm to 200 μm. The transparent substrate may have an easy-adhesion layer or a hard coat layer on its surface.

The touch sensor unit 5 (capacitance sensor), the drive electrode / sensor unit 6, and the drive electrode 7 are formed as a transparent conductive layer. The constituent material of the transparent conductive layer is not particularly limited, and for example, metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, and tungsten, and metals such as these metals. Examples include alloys. Examples of the constituent material of the transparent conductive layer include metal oxides of indium, tin, zinc, gallium, antimony, zirconium, and cadmium, and specifically, indium oxide, tin oxide, titanium oxide, cadmium oxide, and these. Examples thereof include metal oxides composed of a mixture of the above. In addition, other metal compounds made of copper iodide or the like are used. The metal oxide may further contain oxides of the 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. The ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

There is no limitation on the location where the touch sensor layer 5 is formed in the liquid crystal cell C, and the touch sensor layer 5 is formed according to the form of the liquid crystal panel with a built-in touch sensing function. For example, in FIGS. 6 to 8, the case where the touch sensor layer 5 is arranged between the first polarizing film 11 and the liquid crystal layer 3 is exemplified. The touch sensor layer 5 can be formed as a transparent electrode pattern on the first transparent substrate 41, for example. With respect to the drive electrode / sensor unit 6 and the drive electrode 7, a transparent electrode pattern can be formed according to a conventional method according to the form of the liquid crystal panel with a built-in touch sensing function. The transparent electrode pattern is usually electrically connected to a routing wire (not shown) formed at the end of the transparent substrate, and the routing wire is connected to a controller IC (not shown). As the shape of the transparent electrode pattern, in addition to the comb shape, any shape such as a stripe shape or a rhombus shape can be adopted depending on the application. The height of the transparent electrode pattern is, for example, 10 nm to 100 nm, and the width is 0.1 mm to 5 mm.

Further, as the liquid crystal panel with a built-in touch sensing function, a member forming a liquid crystal display device such as a lighting system using a backlight or a reflector can be appropriately used.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In addition, each part and% in each example is based on weight. All the conditions for leaving at room temperature, which are not specified below, are 23 ° C. and 65% RH.

<Measurement of weight average molecular weight of (meth) acrylic polymer (A)>
The weight average molecular weight (Mw) of the (meth) acrylic polymer (A) was measured by GPC (gel permeation chromatography). Mw / Mn was also measured in the same manner.
-Analyzer: HLC-8120GPC manufactured by Tosoh Corporation
-Column: Made by Tosoh, G7000H _XL + GMH _XL + GMH _XL
-Column size: 7.8 mm φ x 30 cm each 90 cm in total
-Column temperature: 40 ° C
・ Flow rate: 0.8 mL / min
・ Injection amount: 100 μL
-Eluent: Tetrahydrofuran-Detector: Differential Refractometer (RI)
・ Standard sample: Polystyrene

<Manufacturing example 1>
(Preparation of 40 μm TAC film with HC and 25 μm TAC film with HC)
A solution in a resin solution (manufactured by DIC Co., Ltd., trade name: Unidic 17-806, solid content concentration: 80%) in which an ultraviolet curable resin monomer or oligomer containing urethane acrylate as a main component is dissolved in butyl acetate. Add 5 parts of photopolymerization initiator (BASF Co., Ltd., trade name: IRGACURE907) and 0.1 part of leveling agent (DIC Co., Ltd., trade name: GRANDIC PC4100) per 100 parts of solid content. did. Then, cyclopentanone and propylene glycol monomethyl ether were added to the solution at a ratio of 45:55 so that the solid content concentration in the solution was 36% to prepare a hard coat layer forming material. The produced hard coat layer forming material is applied onto TJ40UL (manufactured by Fujifilm, raw material: triacetyl cellulose-based polymer, thickness: 40 μm) so that the thickness of the hard coat layer after curing is 7 μm to form a coating film. did. Then, the coating film is dried at 90 ° C. for 1 minute, and the coating film is further irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm ^{2 with} a high-pressure mercury lamp to cure the coating film to form a hard coat layer (HC). A 40 μm TAC film with HC was prepared.
Similarly, a hard coat layer (HC) having the same thickness of 7 μm as described above was formed on TJ25UL (manufactured by Fujifilm, raw material: triacetyl cellulose-based polymer, thickness: 25 μm) to prepare a 25 μm TAC film with HC. ..

<Manufacturing example 2>
(Preparation of 30 μm acrylic film)
8,000 g of methyl methacrylate (MMA) and 2,000 g of methyl 2- (hydroxymethyl) acrylate (MHMA) in a 30 L pot-type reactor equipped with a stirrer, temperature sensor, cooling tube, and nitrogen introduction tube. ), 10,000 g of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK), and 5 g of n-dodecyl mercaptan were charged, and the temperature was raised to 105 ° C. and refluxed while passing nitrogen through the mixture. As a result, 5.0 g of t-butylperoxyisopropyl carbonate (Kayacarboxylic BIC-7, manufactured by Kayaku Akzo Corporation) was added, and at the same time, a solution consisting of 10.0 g of t-butylperoxyisopropyl carbonate and 230 g of MIBK was added. Solution polymerization was carried out at about 105 to 120 ° C. under reflux while dropping over 4 hours, and aging was further carried out over 4 hours.
To the obtained polymer solution, 30 g of a stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added, and cyclization condensation was carried out at about 90 to 120 ° C. for 5 hours under reflux. The reaction was carried out. Next, the obtained polymer solution was subjected to a vent type screw twin-screw extruder having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a reduced pressure of 13.3 to 400 hPa (10 to 300 mmHg), one rear vent, and four fore vents. Introduced into (φ = 29.75 mm, L / D = 30) at a processing speed of 2.0 kg / h in terms of resin amount, and further subjected to cyclization condensation reaction and volatile in this extruder to extrude. To obtain transparent pellets of the lactone ring-containing polymer.
When the dynamic TG of the obtained lactone ring-containing polymer was measured, a mass loss of 0.17% by mass was detected. The lactone ring-containing polymer had a weight average molecular weight of 133,000, a melt flow rate of 6.5 g / 10 min, and a glass transition temperature of 131 ° C.
The obtained pellets and acrylonitrile-styrene (AS) resin (Toyo SAS20, manufactured by Toyo Styrene Co., Ltd.) are kneaded and extruded at a mass ratio of 90/10 using a single-screw extruder (screw 30 mmφ). , Clear pellets were obtained. The glass transition temperature of the obtained pellet was 127 ° C.
This pellet was melt-extruded from a coat hanger type T die having a width of 400 mm using a 50 mmφ single-screw extruder to prepare a film having a thickness of 120 μm. A stretched film (30 μm acrylic film) having a thickness of 30 μm is obtained by stretching the produced film 2.0 times in length and 2.0 times in width under a temperature condition of 150 ° C. using a biaxial stretching device. Obtained. When the optical characteristics of this stretched film were measured, the total light transmittance was 93%, the in-plane retardation Δnd was 0.8 nm, and the thickness direction retardation Rth was 1.5 nm.

<Preparation of polarizing film (1)>
A polyvinyl alcohol film having a thickness of 45 μm was dyed between rolls having different speed ratios in an iodine solution at 30 ° C. and a 0.3% concentration for 1 minute, and stretched up to 3 times. Then, the total stretching ratio was stretched to 6 times while being immersed in an aqueous solution containing boric acid having a concentration of 4% and potassium iodide at a concentration of 10% for 0.5 minutes at 60 ° C. Then, it was washed by immersing it in an aqueous solution containing potassium iodide having a concentration of 1.5% at 30 ° C. for 10 seconds, and then dried at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 18 μm. Polyvinyl alcohol-treated 40 μm TAC film with HC (triacetyl cellulose film side) obtained in Production Example 1 and 30 μm acrylic film obtained in Production Example 2 on the other side of the polarizer. A polarizing film (1) was prepared by laminating with an alcohol-based adhesive.

<Preparation of polarizing film (2)>
(Preparation of thin polarizer A)
Amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 μm) having a water absorption rate of 0.75% and a Tg of 75 ° C. Alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and acetoacetyl-modified PVA (degree of polymerization 1200, degree of acetoacetyl modification 4.6%, degree of saponification 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. , Trade name "Gosefimer Z200") at a ratio of 9: 1 was applied and dried at 25 ° C. to form a PVA-based resin layer having a thickness of 11 μm to prepare a laminate.
The obtained laminate was uniaxially stretched at the free end in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (aerial auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 30 ° C. (an aqueous boric acid solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Next, the polarizing plate was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance. In this example, 0.2 parts by weight of iodine was mixed with 100 parts by weight of water, and 1.0 part by weight of potassium iodide was mixed and immersed in the obtained iodine aqueous solution for 60 seconds (dyeing treatment). ..
Next, it was immersed in a cross-linked bath at a liquid temperature of 30 ° C. (an aqueous boric acid solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds. (Crossing treatment).
Then, the laminate is immersed in an aqueous solution of boric acid having a liquid temperature of 70 ° C. (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water). However, uniaxial stretching was performed between rolls having different peripheral speeds so that the total stretching ratio was 5.5 times in the longitudinal direction (longitudinal direction) (underwater stretching treatment).
Then, the laminate was immersed in a washing bath at a liquid temperature of 30 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) (cleaning treatment).
From the above, an optical film laminate containing a polarizer having a thickness of 5 μm was obtained.

(Preparation of adhesive to be applied to transparent protective film)
45 parts by weight of acryloylmorpholin, 45 parts of 1,9-nonanediol diacrylate, 10 parts of acrylic oligomer (ARUFONUP1190, manufactured by Toa Synthetic Co., Ltd.) obtained by polymerizing (meth) acrylic monomer, photopolymerization initiator (IRGACURE 907, BASF) 3 parts of the polymerization initiator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) were mixed to prepare an ultraviolet curable adhesive.

<Preparation of polarizing film (2)>
25 μm TAC with HC obtained in Production Example 1 while applying the ultraviolet curable adhesive to the surface of the polarizer A of the optical film laminate so that the thickness of the adhesive layer after curing is 1 μm. After the film (triacetyl cellulose film side) was attached, ultraviolet rays were irradiated as active energy rays to cure the adhesive. For ultraviolet irradiation, gallium-filled metal halide lamp, irradiation device: Fusion UV Systems, Light HAMMER10 manufactured by Inc., valve: V valve, peak illuminance: 1600 mW / cm ² , cumulative irradiation amount 1000 / mJ / cm ² (wavelength 380 to 440 nm). ), And the illuminance of ultraviolet rays was measured using a Solar-Check system manufactured by Solartell. Next, the amorphous PET substrate was peeled off to prepare a polarizing film (2) using a thin polarizer. The optical characteristics of the obtained polarizing film were a simple substance transmittance of 42.8% and a degree of polarization of 99.99%.

<Preparation of polarizing film (2) with transparent layer>
The following transparent layer forming material is applied to the polarizing element surface of the polarizing film (2) (the polarizing element surface on which the 25 μm TAC film with HC is not provided) with a bar coater, and then heat-treated at 60 ° C. for 12 hours. As a result, a urethane resin layer having a thickness of 3 μm was formed to prepare a polarizing film (2) with a transparent layer.

≪Forming material for transparent layer≫
As the solution of the urethane prepolymer (a), a 75% ethyl acetate solution of the urethane prepolymer composed of toluene diisocyanate (TDI) and trimethylol propane (TMP) (manufactured by Tosoh Corporation, trade name "Coronate L") was used.
On the other hand, trimethylolpropane was dissolved in cyclopentanone so as to have a solid content concentration of 10% to prepare a trimethylolpropane solution.
The above trimethylolpropane solution was added to 100 parts of the above 75% ethyl acetate solution of urethane prepolymer (manufactured by Tosoh Corporation, trade name "Coronate L"), and the solid content ratio of urethane prepolymer: trimethylolpropane was 90 :. Add 10 parts, add 0.1 part of dioctylstindilaurate catalyst (manufactured by Tokyo Fine Chemicals, trade name "Envirizer OL-1"), and use methyl isobutyl ketone as a solvent to obtain a solid content concentration of 10%. The forming material (coating solution) prepared in 1 was prepared.

<Preparation of conductive layer forming material>
Solution containing 10 to 50% by weight of thiophene polymer (trade name: Denatron P-580W, manufactured by Nagase ChemteX Corporation) 8.6 parts, solution containing oxazoline group-containing acrylic polymer (trade name: Epocross) WS-700, manufactured by Nippon Catalyst Co., Ltd.) and 90.4 parts of water were mixed to prepare a coating solution for forming a conductive layer having a solid content concentration of 0.5% by weight. The obtained coating liquid for forming a conductive layer contained 0.04% by weight of a polythiophene-based polymer and 0.25% by weight of an oxazoline group-containing acrylic polymer.

Example 1
(Manufacturing of polarizing film with conductive layer)
The coating liquid for forming a conductive layer was applied to the acrylic film side of the polarizing film (1) so that the thickness after drying was 0.06 μm, and dried at 80 ° C. for 2 minutes to form a conductive layer. The obtained conductive layer contained 8% by weight and 50% by weight, respectively, of a thiophene-based polymer and an oxazoline group-containing acrylic polymer.

(Preparation of acrylic polymer (A))
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, 78.9 parts of butyl acrylate, 16 parts of phenoxyethyl acrylate, 5 parts of acrylic acid, 0.1 part of 4-hydroxybutyl acrylate, A monomer mixture containing the above was charged. Further, with respect to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator is charged together with 100 parts of ethyl acetate, and nitrogen gas is added while gently stirring. After the introduction and nitrogen substitution, the liquid temperature in the flask was maintained at around 55 ° C. and the polymerization reaction was carried out for 8 hours to carry out a polymerization reaction, and a solution of an acrylic polymer having a weight average molecular weight (Mw) of 2.2 million and Mw / Mn = 4.0. Was prepared.

(Preparation of adhesive composition)
For 100 parts of the solid content of the acrylic polymer solution obtained above, 1 part of bis (trifluoromethanesulfonyl) imide lithium and an isocyanate cross-linking agent (Coronate L manufactured by Toso Co., Ltd., trimethylolpropane tolylene diisocyanate) 0 .6 parts, 0.1 part of benzoyl peroxide (Niper BMT manufactured by Nippon Oil & Fat Co., Ltd.) and 0.3 part of epoxy group-containing silane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd .: X-41-1056) are blended. A solution of the acrylic pressure-sensitive adhesive composition was prepared.

(Preparation of polarizing film with adhesive layer)
Next, the solution of the acrylic pressure-sensitive adhesive composition was applied to one side of a polyethylene terephthalate film (separator film: manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) treated with a silicone-based release agent, and the pressure-sensitive adhesive layer after drying was applied. It was applied so as to have a thickness of 20 μm and dried at 155 ° C. for 1 minute to form an adhesive layer on the surface of the separator film. Next, the pressure-sensitive adhesive layer formed on the separator film was transferred to the conductive layer of the polarizing film (1) prepared above to prepare a polarizing film with a pressure-sensitive adhesive layer.

Examples 2 to 13, Comparative Examples 1 and 2
In Example 1, as shown in Table 1, the type of the monomer used for preparing the acrylic polymer (A) and the ratio of the monomer used thereof were changed, and the production conditions were controlled to control the acrylic polymer (A) shown in Table 1. The solution of A) was prepared.

Further, as shown in Table 1, the types of the polarizing film, the presence or absence of the formation of the conductive layer, the type of the ionic compound (B) used for preparing the pressure-sensitive adhesive composition or its blending ratio, and the blending amount of the cross-linking agent are shown. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that the changes were shown in 1. When the polarizing film (2) is used as the polarizing film, the polarizing element surface of the polarizing film (2) (the polarizing element surface on which the 25 μm TAC film with HC is not provided) is polarized with the transparent layer. When the film (2) was used, the same conductive layer as described above was formed on the transparent layer of the polarizing film (2) with a transparent layer. In Comparative Examples 1 and 2, the conductive layer was not formed.

The following evaluation was performed on the polarizing film with an adhesive layer obtained from the above Examples, Comparative Examples and Referenceability. The evaluation results are shown in Table 1.

<Surface resistance value (Ω / □): Conductivity>
The surface resistance value of the conductive layer was measured on the surface of the polarizing film with the conductive layer on the conductive layer side before the pressure-sensitive adhesive layer was formed. The surface resistance value of the pressure-sensitive adhesive layer was measured on the surface of the pressure-sensitive adhesive layer formed on the separator film. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech.

<Measurement of creep value>
The upper end portion 10 mm × 10 mm of a polarizing film with an adhesive layer (thickness of the adhesive layer: 20 μm) cut into a size of 10 mm × 30 mm was attached to a SUS plate via the adhesive layer, and the temperature was 50 ° C. and 5 atm. It was autoclaved for 15 minutes under the conditions. A precision hot plate installed so that the heating surface is vertical is heated to 85 ° C., and the SUS plate to which the polarizing film with the adhesive layer is attached is the surface of the hot plate to which the adhesive layer is not attached. It was installed so as to be in contact with the heating surface. Five minutes after starting to heat the SUS plate at 85 ° C., the polarizing film with an adhesive layer before and after the load was applied when a load of 500 g was applied to the lower end of the polarizing film with an adhesive layer and left for 1 hour. The deviation width between the SUS plate and the SUS plate was measured, and the deviation width was defined as a creep value (μm) at 85 ° C.

<Evaluation of deformed cracks>
The produced polarizing film with an adhesive layer was processed into the shape shown in FIG. 5 using a CO ₂ laser processing machine Spirit (manufactured by GCC, 30 W) under the conditions of speed 10, laser output 35, and 400 ppi.
A deformed polarizing film with an adhesive layer is attached to a non-alkali glass (manufactured by Corning Inc., trade name "EG-XG") having a thickness of 350 mm × 250 mm × 0.7 mm, and then at 50 ° C. and 0.5 MPa for 15 It was autoclaved for minutes to bring the pressure-sensitive adhesive layer into close contact with the glass. The sample subjected to such treatment was put into a heat cycle test tank, and the presence or absence of cracks generated in the deformed portion at the time of 100 cycles and 200 cycles was visually confirmed. Five samples of the same type were used for each condition, and the number of samples in which cracks occurred is shown in Table 1.
(Test conditions)
Temperature condition: -40 ° C (hold for 30 minutes) ⇒ 85 ° C (hold for 30 minutes) is repeated as one cycle. Temperature rise / fall rate: 10 ° C / min

<ESD test>
After peeling the separator film from the polarizing film with the adhesive layer, it was attached to the visual side of the in-cell type liquid crystal cell to create a liquid crystal panel with a built-in touch sensing function. That is, the obtained polarizing film with the pressure-sensitive adhesive layer was bonded to the first transparent substrate of the in-cell type liquid crystal cell shown in FIG. 6 to form the first pressure-sensitive adhesive layer and the first polarizing film. In the liquid crystal panel, an ESD (electrostatic discharge) gun (10 kV) was fired on the surface of the polarizing film, and the time until the white spot disappeared by electricity was measured and judged according to the following criteria.
(Evaluation criteria)
A: Within 0.5 seconds.
B: Over 0.5 seconds to within 1 second.
C: Over 1 second to within 10 seconds.
D: Exceeds 10 seconds.

<Durability test>
The produced polarizing film with an adhesive layer was cut into a size of 300 × 220 mm so that the absorption axis of the polarizing film was parallel to the long side. The polarizing film with an adhesive layer was attached to a non-alkali glass (manufactured by Corning Inc., trade name "EG-XG") having a thickness of 350 x 250 mm x 0.7 mm with a laminator. Then, it was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to bring the pressure-sensitive adhesive layer into close contact with the glass. After the treated sample is treated in an atmosphere of 95 ° C. for 500 hours and then in an atmosphere of 60 ° C./95% RH for 500 hours, the appearance of the sample is based on the following criteria. Was visually evaluated.
(Evaluation criteria)
A: There is no change in appearance such as foaming and peeling.
B: There is slight peeling or foaming at the edges, but there is no problem in practical use.
C: There is peeling or foaming at the end, but there is no problem in practical use unless it is for special purposes.
D: There is a significant peeling at the end, and there is a problem in practical use.

<Evaluation of color loss at the edges>
The polarizing film with the adhesive layer obtained in Examples and Comparative Examples was cut into 50 mm × 50 mm, the separator film was peeled off, and then an alkaline glass having a thickness of 1.2 to 1.5 mm (manufactured by Matsunami Glass Co., Ltd., microslide glass). ) Was attached via an adhesive layer to prepare a sample. After holding the sample in a high temperature and high humidity environment of 60 ° C. and 90% RH for 500 hours, the amount of color loss at the edges was measured by a differential interference microscope (manufactured by Olympus, product name "MX-61L") under the following conditions. .. The amount of color loss at the edge is the distance of the straight line connecting the corners with the part closest to the center of the part where the color is lighter than the center on the diagonal of the four corners of the sample. μm), and the average value of the four corners was taken as the amount of color loss at the edge of the sample.
Equipment: MX-61L manufactured by Olympus
Measurement conditions Lens magnification: 5x ISO: 200
Shutter speed: 1/100
Amount of reflected light: Scale 0
White balance: Auto transmitted light controller: LG-PS2
Transmitted light amount: Scale 5
Transmitted light Polarization direction: Direction of cross Nicol with respect to the polarizing film transmission axis

In Table 1,
BA is butyl acrylate,
PEA is phenoxyethyl acrylate,
AA is acrylic acid,
NVP is N-vinyl-2-pyrrolidone,
HBA is 4-hydroxybutyl acrylate,
The isocyanate type is an isocyanate cross-linking agent (Coronate L manufactured by Tosoh Corporation, trimethylolpropane tolylene diisocyanate),
BPO is benzoyl peroxide (NOF BMT manufactured by NOF Corporation),
Li-TFSI is bis (trifluoromethanesulfonyl) imide lithium,
K-bis (trifluoromethanesulfonyl) imide potassium TMPA-TFSI is trimethylpropylammonium bis (trifluorosulfonylimide),
EMP-TFSI is ethylmethylpyrrolidinium bis (trifluorosulfonylimide),
TBMA-TFSI is tributylmethylammonium bis (fluorosulfonylimide),
MTOA-TFSI represents methyltrioctylammonium bis (trifluorosulfonylimide).

1 Polarizing film with adhesive layer 11 Single protective polarizing film a Polarizer b Protective film c Conductive layer d Transparent layer 21 Adhesive layer 2 Missing part (deformed part)
W1 Length of chipped portion D Maximum depth of chipped portion from W1 θ1 Angle formed by two straight lines R1 Radius of curvature of

curve

11, 12 First and second

polarizing films

21, 22 First and second adhesive layers 3 Liquid crystal layers 41, 42 1st and 2nd transparent substrates 5 Touch sensor part 6 Drive electrode and sensor part 7 Drive electrode C Liquid crystal cell

Claims

A polarizing film and a polarizing film having a protective film on one or both sides of the polarizing element, and a polarizing film with an adhesive layer having a conductive layer and an adhesive layer in this order.
The polarizing film with an adhesive layer has a deformed portion other than a rectangle and has a deformed portion.
A polarizing film with a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B).
The polarizing film with an adhesive layer according to claim 1, wherein the conductive layer contains a conductive polymer.
The polarizing film with an adhesive layer according to claim 1 or 2, wherein the thickness of the conductive layer is 1 μm or less.
The polarizing film with an adhesive layer according to any one of claims 1 to 3, wherein the ionic compound (B) has a molecular weight of a cationic component of 210 or less.
The polarizing film with an adhesive layer according to claim 4, wherein the cation component is lithium ions.
The invention according to any one of claims 1 to 5, wherein the ionic compound (B) is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (A). Polarizing film with adhesive layer.
The polarizing film with an adhesive layer according to any one of claims 1 to 6, wherein the protective film is any one selected from a cellulose resin film and a (meth) acrylic resin film.
The polarizing film with an adhesive layer according to any one of claims 1 to 7, wherein the thickness of the polarizer is 10 μm or less.
The polarizing film with an adhesive layer according to any one of claims 1 to 8, wherein the polarizing film is a polarizing element and a single protective polarizing film having a protective film on only one side of the polarizing element.
The polarizing film with an adhesive layer according to claim 9, wherein the one-sided protective polarizing film has the conductive layer on the other side of the polarizer.
The method according to any one of claims 10, wherein the conductive layer is provided on the other side of the polarizing element of the one-side protective polarizing film via a transparent layer having a thickness of 10 μm or less directly formed on the polarizing element. Polarizing film with adhesive layer.
The polarizing film with an adhesive layer according to claim 11, wherein the transparent layer is a cured product of a forming material containing a urethane prepolymer which is a reaction product of an isocyanate compound and a polyhydric alcohol.
The polarizing film with an adhesive layer according to any one of claims 1 to 12, wherein the pressure-sensitive adhesive layer has a creep value of 120 μm or less at 85 ° C.
An image display panel comprising the polarizing film with an adhesive layer according to any one of claims 1 to 13.
The image display panel according to claim 14, wherein the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer is bonded to a liquid crystal cell having a touch-sensing function and a liquid crystal layer and a touch sensor unit.
An image display device comprising the image display panel according to claim 14 or 15.