TWI814940B - Polarizing film, image display panel and image display device with adhesive layer - Google Patents

Abstract

The invention is a polarizing film with an adhesive layer, which has a polarizing film, a conductive layer and an adhesive layer in sequence. The polarizing film has a polarizer and a protective film located on one or both sides of the polarizer; the adhesive is attached The polarizing film of the layer has a special-shaped portion other than a rectangular shape; the adhesive layer is formed of an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B). Even when the polarizing film with an adhesive layer having a special-shaped portion of the present invention is applied to a built-in liquid crystal panel, it can still suppress the occurrence of special-shaped cracks and suppress static electricity unevenness.

Description

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

The present invention relates to a polarizing film having an adhesive layer with a non-rectangular shaped portion. Furthermore, the present invention relates to an image display panel and an image display device using the polarizing film with the adhesive layer.

For image display panels, such as liquid crystal panels used in liquid crystal display devices, polarizing films are usually laminated on both sides of a liquid crystal unit through an adhesive. The liquid crystal unit is composed of a liquid crystal layer arranged between a pair of transparent substrates. form. On the other hand, when manufacturing an image display panel, when the aforementioned polarizing film with an adhesive layer is attached to a liquid crystal cell, the release film will be peeled off from the adhesive layer of the polarizing film with an adhesive layer, and the release film will be peeled off. Static electricity will be generated. The static electricity generated in this way may affect the orientation of the liquid crystal layer inside the liquid crystal display panel, leading to defects. Therefore, for example, by forming an antistatic layer (conductive layer) on the outside of the polarizing film, the generation of static electricity can be suppressed.

For example, Patent Document 1 proposes that in a liquid crystal display device with a touch sensing function, an antistatic layer having a surface resistance of 1.0×10 ⁹ to 1.0×10 ¹¹ Ω/□ be disposed on the viewing side of the liquid crystal layer. Polarizing film to reduce the occurrence of display defects or malfunctions. It is also known that adding an ionic compound as an antistatic agent to the adhesive layer can suppress the generation of static electricity.

On the other hand, in recent years, smartphones and car navigation On the system, special-shaped built-in liquid crystal display devices are increasing, and polarizing films are also used in conjunction with the display devices. Patent Document 2 discloses a method of processing a polarizing film to produce a polarizing film having an irregular shape other than a rectangular shape. In Patent Document 3, the transparent protective film used for the polarizing film contains special-shaped inorganic particles, thereby improving the special-shaped punching properties of the polarizing film and the crack durability of the punched special-shaped polarizing film after a thermal cycle test.

Prior technical literature

patent documents

Patent Document 1: Japanese Patent Application Publication No. 2013-105154

Patent Document 2: Japanese Patent Application Publication No. 2017-151191

Patent Document 3: Japanese Patent Application Publication No. 2017-097111

Summary of the invention

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 provided with an antistatic layer or an adhesive layer containing an ionic compound with an adhesive layer cannot sufficiently suppress static unevenness. As for the polarizing film with an adhesive layer attached to a special shape, a polarizing film with an adhesive layer provided with an antistatic layer or an adhesive layer containing an ionic compound cannot fully suppress special-shaped cracks generated in the special-shaped parts. It is known that, especially when a polarizing film whose adhesive layer contains an ionic compound and has a special-shaped adhesive layer is applied to a built-in liquid crystal panel, a large amount of ionic compounds need to be added to the adhesive layer, resulting in The abnormal cracks produced in the special-shaped parts worsen.

The object of the present invention is to provide an adhesive layer-attached polarizing film with antistatic properties, which is an adhesive layer-attached polarizing film with a special-shaped portion, and can still suppress abnormal shapes even when applied to a built-in liquid crystal panel. Cracks are generated and static unevenness is suppressed.

Moreover, an object of the present invention is to provide an image display panel and an image display device using the polarizing film with the above-mentioned adhesive layer.

The inventors of the present invention actively worked hard to solve the above-mentioned problems and discovered the following polarizing film with an adhesive layer, thereby completing the present invention.

That is to say, the present invention relates to a polarizing film with an adhesive layer, which has a polarizing film, a conductive layer and an adhesive layer in order. The polarizing film has a polarizing element and a protective film located on one or both sides of the polarizing element; The polarizing film with the adhesive layer is characterized in that: the polarizing film with the adhesive layer has a special-shaped portion other than a rectangular shape; the adhesive layer is made of a polymer containing (meth)acrylic polymer (A) and an ionic compound (B). The adhesive composition is formed.

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

The polarizing film with the adhesive layer preferably contains 0.1 to 10 parts by weight of the ionic compound (B) relative to 100 parts by weight of the (meth)acrylic polymer (A).

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

Among the polarizing films with adhesive layers, a single-sided protective polarizing film having a polarizing element and a protective film only on one side of the polarizing element can be used as the polarizing film. In the aforementioned single-sided protective polarizing film, it is preferable that the other side of the aforementioned polarizer has the aforementioned conductive layer.

The single-sided protective polarizing film may have the conductive layer on the other side of the polarizer via a transparent layer. The transparent layer is directly formed on the polarizer and has a thickness of 10 μm or less. 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 polyol, can be used.

In the polarizing film with an adhesive layer, the creep value of the adhesive layer at 85°C is preferably 120 μm or less.

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

The present invention also relates to an image display device, which is characterized in that Yu: having the aforementioned image display panel.

The polarizing film with an adhesive layer of the present invention has a conductive layer between the adhesive layer and the polarizing film, and the adhesive layer contains ionic compounds. The antistatic properties can be improved through the conductive layer and the adhesive layer. Therefore, even if the amount of ionic compounds in the adhesive layer is reduced, the antistatic properties of the two layers can still suppress static unevenness when the polarizing film attached with the adhesive layer is applied to a built-in LCD panel. In addition, although the polarizing film with an adhesive layer of the present invention has irregularly shaped portions other than rectangular shapes, the amount of ionic compounds in the adhesive layer can be reduced as mentioned above, so the occurrence of irregular cracks can be suppressed.

Furthermore, it is known that the smaller the molecular weight of the cationic component in the aforementioned ionic compound, the smaller the adverse effect on irregular cracks. It is known that in particular, when a lithium salt is used as the cation component in an ionic compound, the effect of suppressing irregular cracks is good. It is also known that the effect of suppressing irregular cracks is beneficial when the polarizing film uses a single-sided protective polarizing film with a protective film on only one side of the polarizer. Single-sided protective polarizing films are also advantageous from the viewpoint of thinning and cost reduction. Furthermore, it is known that from the viewpoint of suppressing electrostatic unevenness, the smaller the molecular weight of the cationic component is, the better.

On the other hand, it is also known that when a single-sided protective polarizing film is used as the polarizing film as mentioned above, since the conductive layer is directly formed on the polarizer, the antistatic agent of the conductive layer will invade the interior of the polarizer in a humidified environment. The end of the polarizer will be discolored, and the ionic compounds contained in the adhesive layer will segregate to the polarizer, which may reduce the antistatic performance of the adhesive layer. As mentioned when using a single-sided protective polarizing film, by Providing a conductive layer on the polarizer through the transparent layer prevents the conductive layer from directly affecting the polarizer, thereby inhibiting the end of the polarizer from discoloring in a humidified environment.

As described above, the polarizing film with an adhesive layer according to the present invention can provide a polarizing film with an adhesive layer, which can suppress the deterioration of the optical reliability of the polarizer even when a single-sided protective polarizing film is used. , is thin, has good optical reliability, and has excellent long-term antistatic properties.

1: Polarizing film with adhesive layer

2: Notch part (special-shaped part)

3: Liquid crystal layer

4: The intersection of two straight lines

5:Touch sensor department

6: Driving electrode and sensor part

7: Driving electrode

11: (No. 1) Polarizing film, single-sided protective polarizing film

11A: Single-sided protective polarizing film

12:Second polarizing film

21: (1st) Adhesive layer

22: 2nd adhesive layer

41: First transparent substrate

42: Second transparent substrate

A2: Single-sided protective polarizing film

C: Liquid crystal unit

D: The maximum depth of the notch from W1

R1: radius of curvature of curve

W1: Length of the notch

a:Polarizer

b: protective film

c: conductive layer

d:Transparent layer

θ1: The angle formed by 2 straight lines

FIG. 1 is a cross-sectional view showing an example of a polarizing film with an adhesive layer attached thereto according to the present invention.

FIG. 2 is a cross-sectional view showing an example of a polarizing film with an adhesive layer attached thereto according to the present invention.

FIG. 3 is a cross-sectional view showing an example of a polarizing film with an adhesive layer attached thereto according to the present invention.

FIG. 4 is a top view showing an example of a non-rectangular shaped portion of the polarizing film with an adhesive layer according to the present invention.

FIG. 5 is a top view of a polarizing film with an adhesive layer attached with a special-shaped portion according to an embodiment of the present invention.

FIG. 6 is a cross-sectional view showing an example of a liquid crystal panel with a touch sensing function using the polarizing film with an adhesive layer of the present invention.

FIG. 7 is a cross-sectional view showing an example of a liquid crystal panel with a touch sensing function using the polarizing film with an adhesive layer of the present invention.

FIG. 8 is a cross-sectional view showing an example of a liquid crystal panel with a touch sensing function using the polarizing film with an adhesive layer of the present invention.

Form used to implement the invention

An example of a polarizing film with an adhesive layer of the present invention is shown in Figure 1 . As shown in Figure 1, the polarizing film 1 with an adhesive layer has a polarizing film 11, a conductive layer c and an adhesive layer 21 in sequence. Figure 2 is a case where the polarizing film 11 of Figure 1 uses a single-sided protective polarizing film 11A with a protective film b on only one side of the polarizer a. In the single-sided protective polarizing film 11A, the polarizer a is not protected. The other surface on the side having the protective film b has the adhesive layer 21 via the conductive layer c. In addition, although not shown in the figure, a single-sided protective polarizing film A2 having a protective film b on one side of the aforementioned polarizer a can also be used, in which polarizer a/protective film b/conductive layer c/adhesive layer are laminated in this order. The accumulation of 21. Figure 3 shows the case where the single-sided protective polarizing film 11A is used and a transparent layer d is provided on the other side of the polarizer a. In FIG. 3 , the aforementioned single-sided protective polarizing film 11A is provided with a transparent layer d, a conductive layer c, and an adhesive layer 21 in this order. From the viewpoint of suppressing an increase in the moisture content of the polarizer in a high-temperature and high-humidity environment, the transparent layer d is preferably provided directly on the polarizer a.

<Abnormal Department>

In addition, the polarizing film with an adhesive layer of the present invention has a special-shaped portion other than a rectangular shape. Fig. 4 is a top view of an example of a device having a special-shaped portion other than a rectangular shape. There are no special restrictions on the special shape, and any shape can be adopted according to the use, function and design of the polarizing film with the adhesive layer. Examples of unusual shapes other than a rectangular shape include a rectangular shape having a notch or a through hole.

The aforementioned notch can be provided on the outer edge of the polarizing film attached to the adhesive layer. When multiple aforementioned notches are to be provided, they may have the same shape, Also available in different shapes. Two or more of the notches may be provided on one side, or more than one notch may be provided on each of the two sides. In addition, the notch portion may be provided at one of the four outer edge corners of the rectangle, or may be provided at two or more places. In addition, the outer edge corners where the aforementioned notches are not provided may be square corners or rounded corners. The aforementioned notch portion may be composed of a straight line, a curve, or a combination thereof. Figure 4 is an example of a polarizing film 1 with a special-shaped adhesive layer, and notches 2 of different shapes are respectively provided on the two short sides of the rectangle.

The length of the side W1 of the notch can be appropriately adjusted according to the use of the polarizing film. For example, W1 should be adjusted within the range of about 2~100mm. In addition, the maximum depth D of the aforementioned notch 2 from the side W1 should be adjusted to approximately 2 to 100 mm.

4 shows a case where the angle θ1 formed by the two straight lines constituting the shape of the notch 2 is 90°. The angle θ1 is 90° or more and less than 180°, and is preferably 90° or more and 135° or less. When the angle θ1 falls outside the aforementioned range, under the harsh environment of thermal shock, the stress caused by expansion and contraction will be concentrated on the part 4 where the two straight lines intersect, making this part 4 prone to cracks.

In addition, Figure 4 shows a curve constituting the shape of the notch 2. The curvature radius R1 of the curve is 0.2 mm or more, preferably 1 mm or more, more preferably 2 mm or more, more preferably 3 mm or more, and more preferably 5 mm or more. . When the radius of curvature R1 is less than 0.2mm, in the harsh environment of thermal shock, the stress caused by expansion and contraction will be concentrated on the curved portion, making the curved portion prone to cracks.

The aforementioned through holes can be provided in the polarizing film attached to the adhesive layer inside the plane. When a plurality of the aforementioned through holes are to be provided inside the plane of the polarizing film attached to the adhesive layer, they may have the same shape or different shapes. The aforementioned through holes are composed of straight lines, curves, or a combination thereof. Examples of the shape of the through hole include a circle, an ellipse (one with one symmetry axis, two symmetry axes), a rounded rectangle, a quadrangle (square, rectangle), a polygon with more than five corners, and the like.

Examples of methods for forming the special-shaped portion include punching, end milling, and laser processing. The above-described special-shaped portion is generally formed by the above-mentioned processing after laminating each layer.

<Polarizing film with adhesive layer>

First, each component constituting the polarizing film with an adhesive layer of the present invention will be described. As the polarizing film, a polarizing element and a polarizing element having a protective film on one or both sides thereof can be used.

The polarizer is not particularly limited, and various polarizers can be used. Examples of polarizers include hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films that adsorb iodine or dichroic dyes. Polyene-based oriented films such as polyvinyl alcohol dehydrated products or polyvinyl chloride dehydrochloric acid-treated products that are uniaxially stretched. Among these, a polarizer composed of a polyvinyl alcohol-based film and a dichroic material such as iodine is more suitable. The thickness of these polarizers is not particularly limited, but is generally below about 80 μm.

In addition, a thin polarizer having a thickness of 10 μm or less can be used as the polarizer. From the perspective of thinning, the thickness is preferably 1 to 7 μm. This thin polarizer is durable due to its small thickness variation, good visibility, and small size changes. It is ideal from the viewpoint of excellent performance and the ability to reduce the thickness of the polarizing film.

As a material constituting the protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, and the like can be used. Specific examples of the thermoplastic resin include cellulose resins such as cellulose triacetate, polyester resin, polyether resin, polyurethane resin, polycarbonate resin, polyamide resin, polyimide resin, polyamide resin, etc. Olefin resin, (meth)acrylic resin, cyclic polyolefin resin (norbornene-based resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof. In addition, on one side of the polarizer, the protective film is usually bonded with an adhesive layer, while on the other side, the protective film can be made of (meth)acrylic, urethane, or acrylic urethane. thermosetting resin such as thermosetting resin, epoxy type, polysilicone type, or ultraviolet curing resin.

The material of the protective film (transparent protective film) is preferably cellulose resin or (meth)acrylic resin because it can control the change in the surface resistance value of the adhesive layer to a small level. In addition, it is preferable to use a (meth)acrylic resin having a lactone ring structure as the (meth)acrylic resin. Examples of the (meth)acrylic resin having a lactone ring structure include Japanese Patent Application Publication No. 2000-230016, Japanese Patent Application Publication No. 2001-151814, Japanese Patent Application Publication No. 2002-120326, and Japanese Patent Application Publication No. 2002-254544. , a (meth)acrylic resin having a lactone ring structure described in Japanese Patent Application Laid-Open No. 2005-146084, etc. In particular, cellulose resin is more effective than (meth)acrylic resin in preventing irregular cracks and cracks in polarizers, which is the problem of single-sided protection of polarizing films. From this point of view, it is better.

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

The surface of the aforementioned protective film that is not connected to the polarizer can be provided with functional layers such as a hard coating layer, an anti-reflection layer, an anti-adhesion layer, a diffusion layer and even an anti-glare layer.

The protective film and the polarizing element are laminated via an intermediary layer such as an adhesive layer, an adhesive layer, and a primer layer. At this time, it is expected that the two can be laminated without air gaps through an interposer layer. It is preferable that the protective film and the polarizer are laminated with an adhesive interposed therebetween. As long as the adhesive used for bonding the polarizer and the protective film is optically transparent, various forms including water-based, solvent-based, hot-melt adhesive-based, radical curing type, and cation curing type can be used without any particular restrictions. Of the adhesives, water-based adhesives or free radical hardening adhesives are more suitable.

<Conductive layer>

From the viewpoint of the stability of the surface resistance value and the adhesion to the adhesive layer 21, the thickness of the aforementioned conductive layer c is preferably less than 1 μm, and preferably 0.01~0.5 μm, preferably 0.01~0.2 μm, and 0.01~ 0.1μm is better. In addition, from the perspective of antistatic performance, the surface resistance value of the aforementioned conductive layer c is preferably 1×10 ⁷ ~1×10 ¹² Ω/□, and preferably 1×10 ⁷ ~1×10 ¹¹ Ω/□ , 1×10 ⁷ ~1×10 ¹⁰ Ω/□ is better.

The conductive layer can be formed from various antistatic agent compositions. As the antistatic agent forming the conductive layer, ionic surfactant systems, conductive polymers, conductive fine particles, carbon nanotubes, etc. can be used.

From the viewpoints of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, it is appropriate to use conductive polymers and carbon nanotubes as these antistatic agents. In particular, conductive polymers such as polyaniline and polythiophene are suitable. Conductive polymers that are organic solvent-soluble, water-soluble, or water-dispersible can be appropriately used, but water-soluble conductive polymers or water-dispersible conductive polymers are preferably used. Because the water-soluble conductive polymer or water-dispersible conductive polymer can prepare the coating liquid when forming the antistatic layer into an aqueous solution or a water dispersion, the coating liquid can suppress optical films without using a non-aqueous organic solvent. The base material is deteriorated by the organic solvent. Moreover, the aqueous solution or aqueous dispersion may contain an aqueous solvent other than water. Examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-amyl alcohol, isoamyl alcohol, secondary amyl alcohol, and tertiary amyl alcohol. , 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols.

In addition, the water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline and polythiophene preferably has a hydrophilic functional group in the molecule. Examples of hydrophilic functional groups include sulfonic acid group, amine group, amide group, imine group, quaternary ammonium salt group, hydroxyl group, mercapto group, hydrazine group, carboxyl group, sulfate group, phosphate group or salts thereof, etc. . Because it has hydrophilic functional groups in the molecule, it can be easily dissolved in water or can be easily dispersed in water in the form of fine particles, and the aforementioned water-soluble conductive polymer or 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 in terms of polystyrene: 150,000). Examples of commercially available water-dispersed conductive polymers include polythiophene-based conductive polymers (manufactured by Nagase ChemteX Co., trade name: Denatron series).

唑啉基聚合物、聚胺甲酸酯系樹脂、聚酯系樹脂、丙烯酸系樹脂、聚醚系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、環氧樹脂、聚乙烯基吡咯啶酮、聚苯乙烯系樹脂、聚乙二醇、新戊四醇等。尤其以聚胺甲酸酯系樹脂、聚酯系樹脂、丙烯酸系樹脂為宜。該等黏結劑可依其用途適當使用1種或2種以上。 In addition, regarding the material for forming the conductive layer, a binder component may be added together with the antistatic agent for the purpose of improving film formation properties of the antistatic agent and improving adhesion to the optical film. When the antistatic agent is a water-based material of a water-soluble conductive polymer or a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of binders include

Oxazoline-based polymer, polyurethane resin, polyester resin, acrylic resin, polyether resin, cellulose resin, polyvinyl alcohol resin, epoxy resin, polyvinylpyrrolidone, Polystyrene resin, polyethylene glycol, neopentyl erythritol, etc. In particular, polyurethane resin, polyester resin, and acrylic resin are suitable. One or more types of these binders may be used appropriately depending on the purpose.

The amount of antistatic agent and adhesive used depends on their types, but should be controlled so that the surface resistance of the resulting conductive layer becomes 1×10 ⁷ ~1×10 ¹² Ω/□.

<Adhesive layer>

The adhesive layer is formed from an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B).

The (meth)acrylic polymer (A) contains alkyl (meth)acrylate as a main component as a monomer unit. In addition, (meth)acrylic acid Esters refer to acrylic acid esters and/or methacrylic acid esters, and (methyl) in the present invention is also synonymous.

Examples of the alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms. For example, the aforementioned alkyl group may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, and nonyl. , decyl, isodecyl, dodecyl, isomyristyl, lauryl, thirteenth, fifteenth, sixteenth, seventeenth, eighteenth, etc. These may be used alone or in combination. The average carbon number of the alkyl groups is preferably 3 to 9.

The weight ratio of the alkyl (meth)acrylate is preferably 70% by weight or more as a monomer unit in the weight ratio of the total monomers (100% by weight) constituting the (meth)acrylic polymer (A). . The aforementioned weight ratio of alkyl (meth)acrylate can be considered as the remaining portion of other comonomers. If the weight ratio of the alkyl (meth)acrylate is within the above range, it is preferable to ensure adhesion.

In order to improve the adhesion and heat resistance, in addition to the monomer unit of the alkyl (meth)acrylate, one or more types of compounds having specific properties may be introduced into the (meth)acrylic polymer (A) through copolymerization. Comonomer of polymerizable functional groups of unsaturated double bonds such as (meth)acryl group or vinyl group.

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

Carboxyl-containing monosystem is a compound that contains carboxyl groups in its structure and contains polymerizable unsaturated double bonds such as (meth)acrylyl groups and vinyl groups. 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. From the viewpoint of copolymerizability, price and adhesive properties, acrylic acid is preferred among the aforementioned carboxyl group-containing monomers.

Hydroxyl-containing monosystem is a compound that contains hydroxyl groups in its structure and polymerizable unsaturated double bonds such as (meth)acrylyl groups and vinyl groups. Specific examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-(meth)acrylate. Hydroxyalkyl (meth)acrylate or (4- Hydroxymethylcyclohexyl)-methacrylate, etc. From the viewpoint of durability, among the aforementioned hydroxyl-containing monomers, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred, and 4-hydroxybutyl (meth)acrylate is particularly preferred. .

Carboxyl-containing monomers and hydroxyl-containing monomers will become reaction points with the cross-linking agent when the adhesive composition contains a cross-linking agent. Carboxyl-containing monomers and hydroxyl-containing monomers have good intermolecular reactivity with cross-linking agents, so they are suitable for improving the cohesion and heat resistance of the resulting adhesive layer. Furthermore, from the viewpoint of both durability and heavy workability, a carboxyl group-containing monomer is preferable, and from the viewpoint of heavy workability, a hydroxyl group-containing monomer is preferable.

The aforementioned weight ratio of the carboxyl group-containing monomer is preferably 10% by weight or less, and preferably 0.01~8% by weight, more preferably 0.05~6% by weight, and even more preferably 0.1~5% by weight. The weight ratio of the carboxyl group-containing monomer is preferably 0.01% by weight or more from the viewpoint of durability. On the other hand, when it exceeds 10% by weight, it is unfavorable from the viewpoint of heavy workability.

The aforementioned weight ratio of the hydroxyl-containing monomer is preferably 3% by weight or less, and preferably 0.01~3% by weight, more preferably 0.1~2% by weight, and more preferably 0.2~2% by weight. From the viewpoint of the crosslinked adhesive layer, durability or adhesive properties, the weight ratio of the hydroxyl-containing monomer is preferably 0.01% by weight or more. On the other hand, when it exceeds 3% by weight, it is unfavorable from the viewpoint of durability.

The amide group-containing monosystem is a compound that contains a amide group in its structure and contains polymerizable unsaturated double bonds such as (meth)acrylyl group and 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, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-hydroxymethyl(methyl)acrylamide base) acrylamide, N-hydroxymethyl-N-propane(meth)acrylamide, aminomethyl(meth)acrylamide, amineethyl(meth)acrylamide, mercaptomethyl(meth)acrylamide acrylamide monomers such as mercaptoethyl(meth)acrylamide; N-(meth)acrylamide, N-(meth)acrylylpiperidine, N-(meth)acrylamide - N-acrylyl heterocyclic monomers such as (meth)acrylylpyrrolidine; N-vinyllactam-containing monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, etc. Monomer etc. The amide group-containing monomer is preferable because it can suppress the increase in surface resistance value over time (especially in a humidified environment) and satisfy durability, and it is also preferable because it can suppress irregular cracks. Especially among the amide group-containing monomers, N-vinyl lactam-containing monomers can suppress the increase in surface resistance value over time (especially in humidified environments) and meet the requirements for transparent conductive layers (contacts). It is especially good in terms of durability and suppression of abnormal cracks (controlling sensor layer).

The above-mentioned weight ratio of the amide group-containing monomer is large, which has good effects on light. Since the anchoring property of the film tends to decrease, the aforementioned weight ratio is preferably 10% by weight or less, and more preferably 5% by weight or less. From the viewpoint of suppressing an increase in the surface resistance value over time (especially in a humidified environment), the weight ratio of the amide group-containing monomer is preferably 0.1% by weight or more. The aforementioned 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 view of its relationship with the ionic compound (B) contained in the adhesive layer of the present invention.

In the adhesive composition used to form the adhesive layer, when there is a amide group introduced into the side chain of the (meth)acrylic polymer (A) of the base polymer, the presence of the amide group Even in a humidified environment, the surface resistance value of the adhesive layer adjusted by blending the ionic compound (B) can be suppressed from changing and increasing, and can be maintained within the desired value range. This seems better. We believe that the presence of the amide group in the side chain introduced into the (meth)acrylic polymer (A) as a functional group of the comonomer can improve the performance of the (meth)acrylic polymer (A). Compatibility with ionic compound (B).

In addition, when the amide group of the side chain introduced into the (meth)acrylic polymer (A) of the base polymer is present in the adhesive layer, the durability of the glass and the transparent conductive layer (ITO layer, etc.) All are good and can prevent peeling or embossing when attached to the LCD panel. Moreover, the durability is still satisfactory in a humidified environment (after humidification reliability test).

In addition, as the comonomer, for example, aromatic ring-containing (meth)acrylate can be used. Aromatic ring-containing (meth)acrylate is a compound that contains an aromatic ring structure and a (meth)acrylyl group in its structure. As an aromatic ring, Examples include benzene ring, naphthalene ring or biphenyl ring.

Specific examples of aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, and phenoxy (meth)acrylate. , Phenoxyethyl (meth)acrylate, Phenoxypropyl (meth)acrylate, Phenoxydiethylene glycol (meth)acrylate, Ethylene oxide modified nonylphenol (meth)acrylate, Ethylene oxide modified cresol (meth)acrylate, phenol ethylene oxide modified (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, methoxybenzyl hydroxyethylated β-naphthalene Phenol acrylate, 2-naphthol ethyl (meth)acrylate, 2-naphthoxyethyl acrylate, 2-(4-methoxy-1-naphthyloxy)ethyl (meth)acrylate, etc. have naphthalene Ring substances; those with biphenyl rings such as (meth)acrylic acid biphenyl ester.

From the viewpoint of adhesive properties and durability, the aforementioned aromatic ring-containing (meth)acrylate is preferably benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and especially phenoxyethyl (meth)acrylate .

The aforementioned weight ratio of the aromatic ring-containing (meth)acrylate is preferably 25% by weight or less, and preferably 3% to 25% by weight, preferably 10% to 22% by weight, and more preferably 14% to 20% by weight. When the weight ratio of the aromatic ring-containing (meth)acrylate is 3% by weight or more, it is preferable from the viewpoint of suppressing display unevenness. On the other hand, if it exceeds 25% by weight, the suppression of display unevenness is insufficient, and the durability tends to decrease.

Specific examples of comonomers other than the above include acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone addition of acrylic acid Chemicals; allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl(meth)acrylate, etc. Sulfonic acid group monomers; 2-hydroxyethylacrylyl phosphate and other phosphate group-containing monomers, etc.

Examples of monomers intended for modification include amine ethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tertiary butylamine ethyl (meth)acrylate. Alkylaminoalkyl (meth)acrylate and other acrylic esters; Alkoxyalkyl (meth)acrylate such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate Esters; N-(meth)acryloxymethylenesuccinimide or N-(meth)acryl-6-oxyhexamethylenesuccinimide, N-(meth)propylene Succinimide-based monomers such as acyl-8-oxyoctamethylenesuccinimide; N-cyclohexylmaleimide or N-isopropylmaleimide, N-laurylmaline Maleimide-based monomers such as leimide or N-phenylmaleimide; N-methylyconimide, N-ethylyconimide, and N-butyliconide Ikonimide, N-octylicotrimide, N-2-ethylhexylicotrimide, N-cyclohexylicotrimide, N-laurylicotrimide, etc. Imine monomers, etc.

In addition, vinyl-based monomers such as vinyl acetate and vinyl propionate; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; glycidyl (meth)acrylate, etc. can also be used as the modifying monomer. Containing epoxy (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methyl (meth)acrylate Diol-based (meth)acrylates such as oxypolypropylene glycol ester; tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, polysiloxy (meth)acrylate or 2-methoxyethyl (meth)acrylate monomers such as acrylic acid esters, etc. Also listed isoprene Alkene, butadiene, isobutylene, vinyl ether, etc.

Examples of copolymerizable monomers other than the above include silane-based monomers containing silicon atoms. Examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4- Vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-propylene Cyloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, etc.

Furthermore, as comonomers, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and bisphenol A can also be used. Diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, Neopenterythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, caprolactone modified dineopenterythritol hexa(meth)acrylate Polyfunctional monomers with two or more unsaturated double bonds such as (meth)acryl groups and vinyl groups, such as esterification products of (meth)acrylic acid and polyols, such as meth)acrylates, or in polyester, Polyester (meth)acrylate, cyclic polyester (meth)acrylate, etc., which have 2 or more unsaturated double bonds such as (meth)acrylic groups or vinyl groups added to the skeleton of epoxy, urethane, etc. as the same functional groups as the monomer components. Oxygen (meth)acrylate, urethane (meth)acrylate, etc.

In the weight ratio of the total monomers (100% by weight) of the (meth)acrylic polymer (A), the (meth)acrylic polymer The ratio of the aforementioned other comonomers in (A) is preferably about 0 to 10% by weight, more preferably about 0 to 7% by weight, and more preferably about 0 to 5% by weight.

The (meth)acrylic polymer (A) of the present invention usually has a weight average molecular weight of 1 million to 2.5 million. Considering durability, especially heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. From the viewpoint of heat resistance, it is appropriate if the weight average molecular weight is 1 million or more. In addition, if the weight average molecular weight exceeds 2.5 million, the adhesive tends to harden easily and peel off easily. In addition, the weight average molecular weight (Mw)/number average molecular weight (Mn) showing the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, more preferably 1.8 to 5. If the molecular weight distribution (Mw/Mn) exceeds 10, it is unfavorable from the viewpoint of durability. In addition, the weight average molecular weight and the molecular weight distribution (Mw/Mn) were measured in accordance with GPC (gel permeation chromatography) and calculated in terms of polystyrene.

The (meth)acrylic polymer (A) can be produced by appropriately selecting a known production method such as solution polymerization, block polymerization, emulsion polymerization, and various radical polymerizations. Moreover, the obtained (meth)acrylic polymer (A) may be any of a random copolymer, a block copolymer, a graft copolymer, etc.

In addition, in solution polymerization, a polymerization solvent such as ethyl acetate, toluene, etc. can be used. As a specific example of solution polymerization, a polymerization initiator can be added under a flow of inert gas such as nitrogen, and is generally carried out under reaction conditions of about 50 to 70°C for 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. In addition, the weight average molecular weight of the (meth)acrylic polymer (A) can be determined by polymerization initiation The usage amount and reaction conditions of the agent and chain transfer agent can be controlled, and the usage amount can be appropriately adjusted according to their types.

<Ionic compound (B)>

As the ionic compound (B) contained in the adhesive composition forming the adhesive layer of the present invention, alkali metal salts and/or organic cation-anion salts can be suitably used. As the alkali metal salt, organic salts and inorganic salts of alkali metal can be used. In addition, the "organic cation anion salt" 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. "Organic cation-anion salts" are also called ionic liquids and ionic solids. By making the adhesive layer contain the ionic compound (B), the surface resistance value of the adhesive layer can be reduced and the generation of static electricity can be suppressed. This can suppress the static electricity from disrupting the orientation of the liquid crystal layer and causing light leakage (uneven charging).

<Alkali metal salt>

Examples of alkali metal ions constituting the cation component of the alkali metal salt include ions of lithium, sodium, and potassium. Among the alkali metal ions, lithium ions are preferred.

The anionic component of the alkali metal salt can be composed of organic matter or inorganic matter. Examples of the anionic component 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 Those shown in (4): (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (but, n is an integer from 0 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (but, m is an integer from 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (but, l is an integer from 1 to 10), (4): (C _p F _2p+1 SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (However, p and q are integers from 1 to 10).

In particular, anionic components containing fluorine atoms are suitable for use because an ionic compound with excellent ion dissociation properties can be obtained. As the anionic component constituting the inorganic salt, 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 ^- , etc. The anion component is preferably (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^-, etc. (perfluoroalkylsulfonyl)imide represented by the aforementioned general formula (1), especially ( CF ₃ SO ₂ ) ₂ N ^- (trifluoromethanesulfonyl) acyl imine is suitable.

Specific examples of organic salts of alkali metals include sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, 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, etc., among which 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, etc. are preferred, Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ Fluorine-containing lithium imide salts such as N and other bis(fluorosulfonyl)imide lithium salts are preferred, and (perfluoroalkylsulfonyl)imide lithium salts are particularly preferred. Others include 4,4,5,5-tetrafluoro-1,3,2-ditetrahydrothiazole-1,1,3,3-lithium tetraoxide salt and the like.

Examples of 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 aforementioned cation component is composed of organic matter. Specific examples of the cation component include pyridine cation, piperidine cation, pyrrolidine cation, cation having a dihydropyrrole skeleton, cation having a pyrrole skeleton, imidazole cation, ectoine cation, dihydropyrimidine cation, pyrazole cation, pyrazoline cation, tetraalkyl ammonium cation, trialkyl sulfonium cation, tetraalkyl phosphonium cation, etc.

Examples of the anionic component include 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) Indicates: (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (but, n is an integer from 0 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (However, m is an integer from 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (However, l is an integer from 1 to 10), (4): (C _p F _{2p+ 1} SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (However, p and q are integers from 1 to 10).

Among them, anionic components containing fluorine atoms are particularly suitable for use because an ionic compound with good ion dissociation properties can be obtained.

The organic cation-anion salt can be used by appropriately selecting a compound composed of a combination of the above-mentioned cation component and anion component. Preferred specific examples of organic cation-anion salts include methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonate) acyl) acyl imine, ethylmethylimidazolium bis(fluorosulfonyl acyl imine). Among them, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide and ethylmethylimidazolium bis(fluorosulfonyl)imide are more preferred.

In addition to the aforementioned alkali metal salts and organic cation-anion salts, examples of the ionic compound (B) include ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, etc. of inorganic salts.

From the viewpoint of suppressing the occurrence of irregular cracks, the ionic compound (B) preferably has a cationic component with a molecular weight of 210 or less. The molecular weight of the cationic component is more preferably 150 or less, more preferably 110 or less, more preferably 50 or less, more preferably 10 or less. The larger the molecular weight of the cationic component is, the more it will hinder the entanglement of the (meth)acrylic acid polymers in the adhesive layer, thereby tending to soften the physical properties of the adhesive layer. Therefore, the smaller the aforementioned molecular weight, the less likely the physical properties of the adhesive layer will become soft, thereby inhibiting the occurrence of irregular cracks. In addition, the smaller the molecular weight of the cationic component is, the easier it is to reduce the surface resistance value of the adhesive layer and suppress electrostatic unevenness, which is also preferable from this point of view.

When the ionic compound (B) is an alkali metal salt, alkali metal ions such as lithium, sodium, and potassium are cationic components with a molecular weight of 210 or less. Therefore, alkali metal salts containing these alkali metal ions as cationic components can be suitably used. In particular, from the viewpoint of compatibility with the 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 preferred. Furthermore, the alkali metal ions are preferably lithium ions with the smallest molecular weight. The aforementioned ionic compound (B) is preferably a lithium salt, and an organic salt of lithium is particularly preferred. On the other hand, when the ionic compound (B) is an organic cation-anion salt, it is preferable to start from the above examples. Among the cationic components, select a molecular weight of 210 or less. Especially from the viewpoint of compatibility with the adhesive layer, it is preferable to use an organic cation-anion salt in which the anionic component is composed of an organic substance.

The ratio of the ionic compound (B) in the adhesive composition of the present invention should be appropriately adjusted to satisfy the antistatic properties of the adhesive layer and the sensitivity of the touch panel. For example, in order to make the surface resistance value of the adhesive layer fall into the range of 1.0×10 ⁸ ~1.0×10 ¹² Ω/□, it is advisable to consider the type of protective film of the polarizing film, etc., while also considering the LCD with built-in touch sensing function. Adjust the ratio of ionic compound (B) according to the type of panel. For example, in the LCD panel with built-in touch sensing function shown in Figure 6, the initial surface resistance value of the adhesive layer should be controlled in the range of 1×10 ⁸ ~1×10 ¹² Ω/□, and controlled within The range of 1×10 ⁸ ~1×10 ¹⁰ Ω/□ is better. In addition, in the semi-built-in type as shown in Figure 7 or the over-mounted type LCD panel with built-in touch sensing function as shown in Figure 8, the initial surface resistance value of the adhesive layer should be controlled at 1×10 ¹⁰ ~1×10 ¹² Ω/□ range.

If the amount of the ionic compound (B) increases, the ionic compound (B) may precipitate, which may cause humidification peeling. Moreover, if the amount of the aforementioned ionic compound (B) increases, the surface resistance value may become too low, resulting in a baseline shift (a malfunction during touch due to the low surface resistance value), which may reduce the sensitivity of the touch panel. The ratio of the ionic compound (B), for example, relative to 100 parts by weight of the (meth)acrylic polymer (A), is generally preferably 40 parts by weight or less, more preferably 20 parts by weight or less, and 10 parts by weight or less. Preferably, it is 6 parts by weight or less. If it is too little, there is a risk of poor antistatic properties; if it is too much, it may cause reduced touch sensitivity, precipitation of ionic compounds, and humidification peeling of the adhesive. The risk of deterioration. On the other hand, in order to improve the antistatic performance, it is preferable to use 0.01 parts by weight or more of the aforementioned ionic compound (B). From this viewpoint, the aforementioned ionic compound (B) is preferably 0.1 parts by weight or more, and more preferably 0.5 parts by weight or more.

The adhesive composition of the present invention may contain a cross-linking agent (C). As the cross-linking agent (C), an organic cross-linking agent or a polyfunctional metal chelate compound can be used. Examples of organic cross-linking agents include isocyanate cross-linking agents, peroxide cross-linking agents, epoxy cross-linking agents, imine cross-linking agents, and the like. Multifunctional metal chelates are covalent or coordination bonds between multivalent metals and organic compounds. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. Examples of atoms in organic compounds that can be covalently or coordinately bonded include oxygen atoms, and examples of organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, etc.

The cross-linking agent (C) is preferably an isocyanate-based cross-linking agent and/or a peroxide-based cross-linking agent.

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

Peroxides can be used appropriately as long as they generate free radical active species when heated or irradiated with light to cross-link the base polymer of the adhesive composition. However, considering workability and stability, it is advisable to use a half-life temperature of 1 minute. Peroxide at 80℃~160℃, and preferably used at 90℃ Peroxide at ~140℃.

Peroxides that can be used include bis(2-ethylhexyl)peroxydicarbonate (1-minute half-life temperature: 90.6°C), bis(4-tertiary butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1°C), di-secondary butyl peroxydicarbonate (1-minute half-life temperature: 92.4°C), tertiary butyl peroxyneodecanoate (1-minute half-life temperature: 103.5°C), tertiary butyl peroxide Tertiary hexyl methylacetate (half-life temperature in 1 minute: 109.1°C), butyl trimethylacetate peroxide (half-life temperature in 1 minute: 110.3°C), dilauryl peroxide (half-life temperature in 1 minute: 116.4℃), di-n-octyl peroxide (half-life temperature in 1 minute: 117.4℃), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (half-life temperature in 1 minute: 124.3°C), bis(4-methylbenzoyl) peroxide (1-minute half-life temperature: 128.2°C), dibenzoyl peroxide (1-minute half-life temperature: 130.0°C), perisobutyric acid Tertiary butyl ester (half-life temperature in 1 minute: 136.1°C), 1,1-di(tertiary hexylperoxy)cyclohexane (half-life temperature in 1 minute: 149.2°C), etc. Among them, especially from the viewpoint of good cross-linking reaction efficiency, bis(4-tertiary butylcyclohexyl)peroxydicarbonate (half-life temperature of 1 minute: 92.1°C), dilauryl peroxide (1 minute Half-life temperature: 116.4°C), benzyl peroxide (half-life temperature in 1 minute: 130.0°C), etc. are suitable for use.

The usage amount of the cross-linking agent (C) is preferably 3 parts by weight or less relative to 100 parts by weight of the (meth)acrylic polymer (A), and is more preferably 0.01 to 3 parts by weight, and more preferably 0.02 to 2 parts by weight. parts, and more preferably 0.03~1 parts by weight. In addition, when the cross-linking agent (C) is less than 0.01 parts by weight, the adhesive layer may not be cross-linked enough to meet the durability or adhesive properties; on the other hand, if it exceeds 3 The adhesive layer will become too hard and the durability will tend to decrease.

The adhesive composition of the present invention may contain a silane coupling agent (D). Durability can be improved by using silane coupling agent (D). Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyl Diethoxysilane, 2-(3-4-epoxycyclohexyl)ethyltrimethoxysilane and other silane coupling agents containing epoxy groups; 3-aminopropyltrimethoxysilane, N-2-(amine Ethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-γ-aminepropylamine Silane coupling agents containing amine groups such as trimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. containing (meth)acrylyl groups Silane coupling agents; silane coupling agents containing isocyanate groups such as 3-isocyanate propyltriethoxysilane, etc. The silane coupling agent exemplified above is preferably a silane coupling agent containing an epoxy group.

In addition, the silane coupling agent (D) can also be used if it has a plurality of alkoxysilyl groups in the molecule. Specifically, X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, and wait. The silane coupling agent having multiple alkoxysilyl groups in the molecule is ideal because it is not volatile and has multiple alkoxysilyl groups, so it can effectively improve the durability. Especially when the adherend of the optical film with adhesive is a transparent conductive layer (such as ITO, etc.) that is less likely to react with silicon alkoxide than glass, the durability is still good. In addition, the silane coupling agent having a plurality of alkoxysilyl groups in the molecule is preferably one having an epoxy group in the molecule, and it is more preferable that the epoxy group has a plurality of epoxy groups in the molecule. Has multiple alkoxysilyl groups in the molecule and Silane coupling agents with epoxy groups still tend to have good durability when the adherend is a transparent conductive layer (such as ITO, etc.). Specific examples of silane coupling agents having multiple alkoxysilyl groups and epoxy groups in the molecule include X-41-1053, X-41-1059A, and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd., especially epoxy X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd., which has a large base content, is preferred.

The aforementioned silane coupling agent (D) can be used alone or in mixture of two or more kinds, but the total content is preferably 5 parts by weight or less based on 100 parts by weight of the aforementioned (meth)acrylic polymer (A), and It is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, more preferably 0.02 to 1 part by weight, and preferably 0.05 to 0.6 parts by weight. Is the amount that increases durability.

Furthermore, the adhesive composition of the present invention may also contain other well-known additives. For example, polyether compounds with reactive silicon groups, polyalkylene glycol polyether compounds such as polypropylene glycol, colorants, and pigments may be appropriately added depending on the intended use. Such as powders, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or Organic fillers, metal powders, particles, foils, etc. Alternatively, a redox system in which a reducing agent is added can be used within a controllable range. These additives are preferably used in a range of 5 parts by weight or less, more preferably 3 parts by weight or less, and more preferably 1 part by weight or less based on 100 parts by weight of the (meth)acrylic polymer (A).

The method of forming the adhesive layer can be produced by, for example, the following method: applying the aforementioned adhesive composition to a release-treated separation member, etc., drying and removing the polymerization solvent, etc. to form an adhesive layer and then transferring it to an optical film ( polarizing film); or apply the aforementioned adhesive composition on A method of drying an optical film (polarizing film) to remove the polymerization solvent to form an adhesive layer on the optical film. In addition, when applying the adhesive, one or more solvents other than the polymerization solvent may be appropriately added.

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

From the perspective of application to special-shaped polarizing films, the creep value of the adhesive layer applied to the polarizing film with the adhesive layer of the present invention should be below 120 μm at 85°C, preferably below 100 μm, and preferably below 85 μm. Below 60μm is especially preferred. The lower limit of the aforementioned creep value is preferably 15 μm or more, more preferably 30 μm or more. If the creep value is greater than 120 μm, there is a risk of cracks occurring in the special-shaped polarizing film as described in the examples. If the creep value is less than 15 μm, the stress relaxation of the adhesive layer will become low, so there is a risk that the adhesive layer will easily peel off during 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, preferably 5 μm or less, more preferably 3 μm or less, more preferably 1.5 μm or less, and still more preferably 1 μm or less. When the transparent layer is too thick, the thickness of the polarizing film will become thicker, which may reduce the optical reliability of the polarizer. On the other hand, from the viewpoint of suppressing the change in the surface resistance value of the adhesive layer to be smaller, the thickness of the transparent layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

The material forming the aforementioned transparent layer can use a transparent And it can suppress the influence of the conductive layer on the polarizer. Examples of the material include a forming material containing a urethane prepolymer (a) which is a reaction product of an isocyanate compound and a polyol.

The isocyanate compound is preferably a polyfunctional isocyanate compound, for example, and specific examples thereof include polyfunctional aromatic isocyanate compounds, alicyclic isocyanate compounds, aliphatic isocyanate compounds or dimers thereof.

Examples of polyfunctional aromatic isocyanate compounds include phenylene diisocyanate, 2,4-tolyl isocyanate, 2,6-tolyl diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate Isocyanate, styrene diisocyanate, methylene bis-4-phenyl isocyanate, p-phenylene diisocyanate, etc.

Examples of polyfunctional alicyclic isocyanate compounds include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and 1,3-diisocyanate. Methylcyclohexane, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated stubble diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl stubble diisocyanate, etc.

Examples of polyfunctional aliphatic isocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 1,3 -Butyl diisocyanate, dodecyl methylene diisocyanate, 2,4,4-tris Methyl hexamethylene diisocyanate, etc.

Examples of the polyfunctional isocyanate compound include those having three or more isocyanate groups, such as ginseng(6-isocyanatohexyl)tripolyisocyanate.

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-butanediol. -2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol , 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, neopentylerythritol, hexanediol Triol, polypropylene glycol, etc.

As the aforementioned urethane prepolymer (a), it is preferable to use the molecular structure in the present invention, and the proportion of the cyclic structure (benzene ring, cyanurate ring, isocyanate ring, etc.) in the structure Large rigid structure. For example, one type of the polyfunctional isocyanate compound may be used alone or two or more types may be used in combination. However, from the viewpoint of suppressing the incorporation of moisture into the polarizer, aromatic isocyanate compounds are preferred. An aromatic isocyanate compound may be used in combination with other polyfunctional isocyanate compounds. Among the aromatic isocyanate compounds, it is particularly preferable to use at least one selected from toluene diisocyanate and diphenylmethane diisocyanate as the isocyanate compound.

As the urethane prepolymer (a), it is preferable to use trimethylolpropane-tris-toluene isocyanate or trimethylolpropane-tris-diphenylmethane diisocyanate. In addition, the urethane prepolymer (a) is a compound having a terminal isocyanate group, and can be obtained, for example, by mixing an isocyanate compound and a polyol and then stirring and reacting the mixture. It is generally preferred to mix the isocyanate compound with the polyol in such a manner that the isocyanate groups are in excess relative to the hydroxyl groups of the polyol.

In addition, the aforementioned urethane prepolymer (a) may be one in which a terminal isocyanate group has been given a protecting group. Protective groups include oxime and lactam. When the isocyanate group is protected, the protecting group is dissociated from the isocyanate group by heating, thereby causing the isocyanate group to react.

In addition to the aforementioned urethane prepolymer (a), the forming material for forming the transparent layer may also contain a compound (b), which compound (b) has at least two functional groups having active hydrogen reactive with an isocyanate group. . Examples of functional groups having active hydrogen reactive with isocyanate groups include hydroxyl groups, amine groups, and the like. The greater the number of functional groups with active hydrogen that the aforementioned compound (b) has, the more reaction points it will have with the isocyanate group of the urethane prepolymer (a), making it easier to form a hardened product. The number of the aforementioned functional groups is preferably 3 or more.

In addition, the value obtained by dividing the molecular weight of the compound (b) by the number of the above-mentioned functional groups is preferably 350 or less. By defining the relationship between the molecular weight and the number of functional groups as described above, the reactivity of the compound (b) with the isocyanate group of the urethane prepolymer (a) can be ensured.

Furthermore, the molecular weight of the compound (b) is preferably 1,000 or less. The molecular weight of the compound (b) is preferably in the range of 1000 or less from the viewpoint of compatibility when the compound (b) is prepared in a solution form with the urethane prepolymer (a) to form a material.

Examples of the compound (b) include polyols, polyamines, and compounds having a hydroxyl group and an amine group in the molecule.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2- Butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol Alcohol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecane Difunctional alcohols such as diol and polypropylene glycol; trifunctional alcohols such as glycerin and trimethylolpropane; tetrafunctional alcohols such as neopentylerythritol, hexanetriol, sorbitol, etc.; others include polyoxypropylglyceryl ether, Polyoxypropylene trimethylolpropane ether, polyoxypropylene sorbitol ether, etc. add alkylene oxide (for example, propylene oxide) adduct to the said polyol, etc.

Examples of the polyamine include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and dicyclohexylmethane-4,4'- Diamine, dimer diamine, etc.

In addition, examples of compounds having a hydroxyl group and an amino group in the molecule include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, and di-2-hydroxyethylpropylenediamine. Propylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine are diamines with hydroxyl groups in the molecule; alkanolamines such as ethanolamine, diethanolamine, and triethanolamine are included.

It is preferable to use a polyol as the aforementioned compound (b) from the viewpoint of preventing deterioration of the optical reliability of the polarizer, especially trimethylolpropane from the viewpoint of reactivity with the urethane prepolymer (a). good.

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 amount of the compound (b) blended with the urethane prepolymer (a) is 100% by weight (solid content ratio) of the total of the urethane prepolymer (a) and the compound (b). The mixing ratio is preferably 5% by weight or more. From the viewpoint of improving film strength, the blending ratio of the aforementioned compound (b) is preferably 10% by weight or more. On the other hand, if the blending ratio of the aforementioned compound (b) is increased, the optical reliability of the polarizer may be deteriorated. Therefore, the blending ratio of the aforementioned compound (b) is preferably 80% by weight or less and 50% by weight. The following is better.

The aforementioned forming material may further use a reaction catalyst in order to increase the reactivity of the isocyanate group. The reaction catalyst is not particularly limited, but a tin-based catalyst or an amine-based catalyst is ideal. One type or two or more types of reaction catalysts may be used. The reaction catalyst is usually used in an amount of 5 parts by weight or less based on 100 parts by weight of the urethane prepolymer (a). Once the amount of reaction catalyst is large, the cross-linking reaction speed will become faster and the forming material will foam. However, sufficient adhesion cannot be obtained by using foamed forming materials. Generally, when using a reaction catalyst, it is preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 4 parts by weight.

Furthermore, a reaction catalyst can be used to increase the reactivity of the isocyanate group. The reaction catalyst is not particularly limited, but a tin-based catalyst or an amine-based catalyst is ideal. One type or two or more types of reaction catalysts may be used. The reaction catalyst is usually used in an amount of 5 parts by weight or less based on 100 parts by weight of the urethane prepolymer. Once the amount of reaction catalyst is large, the cross-linking reaction speed will become faster and the forming material will foam. However, sufficient adhesion cannot be obtained by using foamed forming materials. Generally, when using a reaction catalyst, it is preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 4 parts by weight.

The tin-based catalyst can be either inorganic or organic, but the organic system is preferred. Examples of the inorganic tin-based catalyst include stannous chloride, tin chloride, and the like. The organic tin-based catalyst preferably has at least one of the following organic groups: an aliphatic group, an alicyclic group, etc. having a skeleton such as a methyl group, an ethyl group, an ether group, an ester group, etc. Examples thereof include tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, and dibutyltin dilaurate.

啶、脒類、二氮雜雙環十一烯等脂環族基等有機基者。除此以外，胺系觸媒還可舉三乙胺等。另外，前述以外之反應觸媒可例示環烷酸鈷、氫氧化苄基三甲銨等。 In addition, the amine catalyst is not particularly limited. It is advisable, for example, to have at least 1

Organic radicals such as alicyclic radicals such as pyridines, amidines, diazabicycloundecene, etc. In addition, examples of the amine catalyst include triethylamine and the like. Examples of reaction catalysts other than those mentioned above include cobalt naphthenate, benzyltrimethylammonium hydroxide, and the like.

The aforementioned forming material can generally be used in the form of a solution containing the aforementioned urethane prepolymer (a) and the aforementioned compound (b). The solution can be a solvent system or a water system 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 an active hydrogen reactive with an isocyanate group and can uniformly dissolve the urethane prepolymer (a) and the compound (b) constituting the forming material. The organic solvent can be used alone or in combination of two or more types. Moreover, as the said organic solvent, different solvents may be used for the said urethane prepolymer (a) and the said compound (b) respectively. In this case, the forming material can be prepared by mixing each solution after preparing each solution. An organic solvent can be added to the prepared forming material to adjust the viscosity of the forming material. In the case of a solvent-based solution dissolved in an organic solvent, alcohols, water, etc. as exemplified below may also be contained as a solvent.

Examples of 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 , halogens such as 2-dichloroethane; ethers such as methyl tertiary butyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, acetoacetone and other wait.

In addition, when preparing an aqueous solution, alcohols such as n-butanol and isopropanol, and ketones such as acetone may be blended. When preparing an aqueous solution, this can be done by using a dispersant, or by introducing into the urethane prepolymer functional groups that have low reactivity with isocyanate groups, such as carboxylates, sulfonates, and quaternary ammonium salts. , or water-dispersible ingredients such as polyethylene glycol.

In addition to the aforementioned urethane prepolymer, examples of materials forming the transparent layer include cyanoacrylate-based forming materials, epoxy-based forming materials, urethane acrylate-based forming materials, and the like.

The formation of the transparent layer can be appropriately selected according to the type of the forming material. For example, the forming material can be coated on a polarizer or the like and then cured. The transparent layer can be obtained in the form of a coating layer. Generally speaking, this is carried out by drying at about 30 to 100°C, more preferably 50 to 80°C, for about 0.5 to 15 minutes after the aforementioned coating to form a hardened layer. In addition, when the above-mentioned forming material contains an isocyanate component, in order to promote the reaction, annealing treatment can be performed at about 30 to 100°C, more preferably at 50 to 80°C for about 0.5 to 24 hours.

<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 previous image display devices. The other components of the image display device are the same as those of conventional image display devices. Specific examples of image display devices to which the image display panel can be applied include liquid crystal display devices, electroluminescence (EL) displays, plasma displays (PD), and field emission displays (FED: Field Emission Display).

The surface electricity of the polarizing film attached with the adhesive layer of the present invention The resistance change ratio is small and is suitable for use in LCD panels with built-in touch sensing functions.

Furthermore, in addition to the above-described configuration, optical films such as retardation films, viewing angle compensation films, and brightness enhancement films may be appropriately provided in the liquid crystal panel.

The liquid crystal layer is not particularly limited, and any type such as TN type, STN type, π type, VA type, IPS type, etc. can be used. The transparent substrate 9 (light source side) only needs to be a transparent substrate, and its material is not particularly limited. Examples thereof include glass and a transparent resin film base material. Examples of the transparent resin film base material include those mentioned above.

In addition, on the light source side with respect to the liquid crystal layer, a polarizing film with an adhesive layer conventionally used in this field can be used, and those described in this specification can also be used appropriately.

Specific examples of the above-mentioned liquid crystal panel with built-in touch sensing function are shown in FIGS. 6 to 8 . Figures 6 to 8 illustrate the polarizing film as the adhesive layer of the present invention. The polarizing film 1 with the adhesive layer shown in Figure 1 (but the conductive layer c is omitted) is used on the viewing side of the liquid crystal cell. situation. That is, the single-sided protective polarizing film 11 and adhesive 21 in Figure 1 are shown as the first polarizing film 11 and the first adhesive layer 21 in Figures 6 to 8 .

Figure 6 is a so-called built-in touch sensing function LCD panel, which has a first polarizing film 11/a first adhesive layer 21/a first transparent substrate 41/a touch sensor part 5 from the viewing side. /Structure of liquid crystal layer 3/driving electrode and sensor part 6/second transparent substrate 42/second adhesive layer 22/second polarizing film 12. Figure 6 shows a built-in LCD panel with built-in touch sensing function, for example The liquid crystal cell C has a touch sensor part 5 and a drive electrode-sensor part 6 in the first and second glass substrates 41 and 42 sandwiching the liquid crystal layer 3 (inside the liquid crystal cell).

In addition, FIG. 7 is a modification of the so-called built-in (semi-built-in) liquid crystal panel with a built-in touch sensing function, which has a first polarizing film 11 / first adhesive layer 21 / touch sensor from the viewing side. The structure is composed of detector part 5/first transparent substrate 41/liquid crystal layer 3/driving electrode and sensor part 6/second transparent substrate 42/second adhesive layer 22/second polarizing film 12. In the LCD panel with built-in touch sensing function in Figure 7, for example, the liquid crystal unit C is outside the first transparent substrate 41, the touch sensor part 5 is in direct contact with the first adhesive layer 21, and the liquid crystal unit C has a driving electrode and sensor part 6 on the side of the second transparent substrate 42 in the first and second glass substrates 41 and 42 sandwiching the liquid crystal layer 3 (inside the liquid crystal cell).

In addition, FIG. 8 is a so-called top-mounted liquid crystal panel with built-in touch sensing function. It has a first polarizing film 11 / a first adhesive layer 21 / a touch sensor part 5 / a driving electrode and a sensor from the viewing side. The structure of the detector unit 6/first transparent substrate 41/liquid crystal layer 3/driving electrode 7/second transparent substrate 42/second adhesive layer 22/second polarizing film 12. In the over-mounted liquid crystal panel with built-in touch sensing function as shown in Figure 8, for example, the liquid crystal unit C has a touch sensor part 5 and a driving electrode-sensor part 6 outside the first transparent substrate 41. The detector part 5 is in direct contact with the first adhesive layer 21, and the liquid crystal unit C has a driver on the side of the second transparent substrate 42 in the first and second glass substrates 41 and 42 sandwiching the liquid crystal layer 3 (inside the liquid crystal unit). Electrode 7.

In a liquid crystal panel with built-in touch sensing function, when the touch sensor portion 5 of the liquid crystal unit C is in direct contact with the first adhesive layer 21, the resistance of the first adhesive layer 21 (containing ionic compounds) Static performance is easily reduced Low, especially in humidified environment. Therefore, the liquid crystal panel with built-in touch sensing function of the present invention is suitable for use in the above-mentioned example of the built-in type (modified example) shown in FIG. 7 or the top-mounted type LCD panel with built-in touch sensing function shown in FIG. 8 .

In addition, the first polarizing film 11 disposed on the viewing side of the liquid crystal cell C and the second polarizing film 12 disposed on the opposite side to the viewing side can be laminated with other optical films according to the suitability of each placement position. The aforementioned other optical films can be, for example, reflective plates or anti-transmission plates, phase difference films (including 1/2 or 1/4 wavelength plates), viewing angle compensation films, brightness enhancement films, etc., which can be used to form liquid crystal display devices, etc. Optical layer. These can be used with 1 layer or more than 2 layers. When using other optical films, it is also suitable to use the adhesive layer closest to the liquid crystal layer 3 as the first adhesive layer 21 .

The liquid crystal layer 3 of the liquid crystal cell C can be a liquid crystal layer containing liquid crystal molecules oriented in parallel in the absence of an electric field, which can be applied to a liquid crystal panel with built-in touch sensing function. As the liquid crystal layer 3, it is suitable to use, for example, an IPS liquid crystal layer. In addition, the liquid crystal layer 3 may be any type of liquid crystal layer such as TN type, STN type, π type, VA type, etc. 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 may sandwich the liquid crystal layer 3 to form a liquid crystal cell. A touch sensor part 5, a driving electrode-sensor part 6, a driving electrode 7, etc. are formed inside or outside the liquid crystal unit according to the shape of the liquid crystal panel with built-in touch sensing function. In addition, a color filter substrate may be provided on the liquid crystal cell (first transparent substrate 41).

The material forming the aforementioned transparent substrate may include glass or 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 above-mentioned transparent substrate may have an easy-adhesion layer or a hard coat layer on its surface.

The touch sensor part 5 (capacitive sensor), the driving electrode-sensor part 6, and the driving electrode 7 are formed as a transparent conductive layer. The constituent materials of the aforementioned transparent conductive layer are not particularly limited, and may include metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, tungsten, and alloys of these metals. . In addition, the constituent materials of the transparent conductive layer include metal oxides of indium, tin, zinc, gallium, antimony, zirconium, and cadmium, and specifically include indium oxide, tin oxide, titanium oxide, cadmium oxide, and mixtures thereof. Metal oxides composed of etc. Other metal compounds composed of copper iodide, etc. can be used. The aforementioned metal oxides may further contain oxides of metal atoms shown in the above group if necessary. It is suitable to use, for example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, etc., especially ITO. ITO should contain 80~99% by weight of indium oxide and 1~20% by weight of tin oxide.

The location where the touch sensor layer 5 is formed in the liquid crystal unit C is not limited, and the touch sensor layer 5 can be formed according to the shape of the liquid crystal panel with built-in touch sensing function. For example, FIGS. 6 to 8 illustrate the case where the touch sensor layer 5 is disposed between the first polarizing film 11 and the liquid crystal layer 3 . The touch sensor layer 5 can be formed on the first transparent substrate 41 in a transparent electrode pattern, for example. As for the driving electrode-sensor part 6 and the driving electrode 7, the transparent electrode pattern can be formed according to the general method according to the shape of the liquid crystal panel with built-in touch sensing function. superior The transparent electrode pattern is usually electrically connected to a winding wire (not shown) formed on an end of the transparent substrate, and the winding wire is connected to a controller IC (not shown). In addition to the zigzag shape, the shape of the transparent electrode pattern can be any shape, such as stripe shape or rhombus shape, depending on the application. The height of the transparent electrode pattern is, for example, 10nm~100nm, and the width is 0.1mm~5mm.

In addition, liquid crystal display panels with built-in touch sensing functions can appropriately use components used to form liquid crystal display devices, such as backlights or reflective plates in lighting systems.

Example

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited by these examples. In addition, parts and % in each example are based on weight. Below, the room temperature storage conditions not specified are all 23℃ 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) is measured by GPC (gel permeation chromatography). Mw/Mn was also measured in the same manner.

‧Analysis device: Made by Tosoh Corporation, HLC-8120GPC

‧Pipe string: Made by Tosoh Co., Ltd., G7000H _XL +GMH _XL +GMH _XL

‧Pipe string size: 7.8mmφ×30cm each, totaling 90cm

‧Column temperature: 40℃

‧Flow rate: 0.8mL/min

‧Injection volume: 100μL

‧Eluent: Tetrahydrofuran

‧Detector: Differential Refractometer (RI)

‧Standard sample: polystyrene

<Manufacturing Example 1>

(Production of 40μmTAC film with HC and 25μmTAC film with HC)

A resin solution in which a UV-curable resin monomer or oligomer containing urethane acrylate as the main component is dissolved in butyl acetate (manufactured by DIC Co., Ltd., trade name: UNIDIC 17-806, solid content concentration: 80 %), add 5 parts of photopolymerization initiator (manufactured by BASF Co., Ltd., trade name: IRGACURE 907) and leveling agent (manufactured by DIC Co., Ltd., trade name:) for every 100 parts of the solid content in the solution. GRANDIC PC4100)0.1 part. Furthermore, cyclopentanone and propylene glycol monomethyl ether were added to the aforementioned solution at a ratio of 45:55 so that the solid content concentration in the aforementioned solution became 36%, thereby producing a hard coat forming material. The prepared hard coat layer forming material was applied to TJ40UL (manufactured by Fujifilm, raw material: cellulose triacetate polymer, thickness: 40 μm) so that the thickness of the hard coat layer after hardening became 7 μm. And form a coating film. After that, the coating film was dried at 90°C for 1 minute, and a high-pressure mercury lamp was used to irradiate the coating film with ultraviolet light with a cumulative light intensity of 300 mJ/cm ² to harden the coating film to form a hard coat (HC) to produce a 40 μm TAC film with HC. .

Then, a hard coat layer (HC) with a thickness of 7 μm was formed on TJ25UL (manufactured by Fujifilm, raw material: cellulose triacetate polymer, thickness: 25 μm) in the same manner, and a 25 μm TAC film with HC was produced. membrane.

<Manufacturing Example 2>

(Production of 30μm acrylic film)

Into a 30L kettle-type reactor equipped with a stirring device, a temperature sensor, a cooling pipe, and a nitrogen inlet pipe, 8,000g of methyl methacrylate (MMA) and 2,000g of 2-(hydroxymethyl) were fed. Methyl acrylate (MHMA), 10,000g of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK), 5g of n-dodecanethiol, and while passing nitrogen through them, the temperature was raised to 105°C and After refluxing, 5.0 g of tertiary butyl peroxy isopropyl carbonate (Kayakarubon BIC-7, manufactured by KAYAKU AKZO CO., LTD.) was added as a polymerization initiator, and 10.0 g of tertiary butylperoxyisopropyl carbonate was added dropwise over 4 hours. A solution composed of grade butylperoxyisopropyl carbonate and 230g of MIBK was solution polymerized at about 105~120°C under reflux, and then matured for another 4 hours.

30 g of stearyl phosphate/octadecyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the obtained polymer solution, and the process was carried out under reflux at about 90 to 120°C. 5 hours cyclization condensation reaction. Next, the obtained polymer solution was introduced into a vented twin-screw extruder (φ=29.75mm, L/D=30) at a processing speed of 2.0kg/h in terms of resin amount, and placed in the extruder. Further perform cyclization condensation reaction, devolatization and extrusion to obtain transparent pellets of the lactone ring-containing polymer. The vented twin-screw extruder has a sleeve temperature of 260°C and a rotation speed of 100 rpm. The pressure reduction degree is 13.3~400hPa (10~300mmHg), the number of rear vents is 1, and the number of front vents is 4.

After measuring the dynamic TG of the obtained polymer containing a lactone ring, a mass loss of 0.17% by mass was detected. In addition, the weight average molecular weight of the lactone ring-containing polymer was 133,000, the melt flow rate was 6.5 g/10 min, and the glass transition temperature was 131°C.

The obtained pellets and acrylonitrile-styrene (AS) resin (TOYO AS AS20, manufactured by TOYO STYRENE CO., LTD.) were kneaded and extruded using a single-screw extruder (screw 30 mmφ) at a mass ratio of 90/10. This results in transparent pellets. The glass transition temperature of the resulting pellets was 127°C.

Using a 50mmφ single-screw extruder, the pellets are melt-extruded from a 400mm wide coat-hanger T-shaped die to produce a film with a thickness of 120μm. The produced film was stretched longitudinally to 2.0 times and transversely to 2.0 times at a temperature of 150° C. using a biaxial stretching device to obtain a stretched film (30 μm acrylic film) with a thickness of 30 μm. After measuring the optical properties of the stretched film, it was found that the total light transmittance was 93%, the in-plane phase difference Δnd was 0.8nm, and the thickness direction phase difference Rth was 1.5nm.

<Making polarizing film (1)>

A polyvinyl alcohol film with a thickness of 45 μm was dyed in an iodine solution with a concentration of 0.3% at 30°C for 1 minute between rollers with different speed ratios until it was extended 3 times. Thereafter, the film was stretched while being immersed in an aqueous solution containing 4% boric acid and 10% potassium iodide at 60° C. for 0.5 minutes until the total stretching ratio reached 6 times. Next, it was washed by immersing it in an aqueous solution containing 1.5% potassium iodide at 30° C. for 10 seconds, and then dried at 50° C. for 4 minutes to obtain a polarizing element with a thickness of 18 μm. The saponified HC-attached film obtained in Production Example 1 was bonded to one side of the polarizer using a polyvinyl alcohol-based adhesive. 40 μm TAC film (tricellulose acetate film side), and the 30 μm acrylic film obtained in Production Example 2 was bonded to the other side to prepare a polarizing film (1).

<Making polarizing film (2)>

(Production of thin polarizer A)

Corona treatment was performed on one side of the substrate of an amorphous isophthalic acid copolymer polyethylene terephthalate (IPA copolymer PET) film (thickness: 100 μm) with a water absorption rate of 0.75% and a Tg of 75°C. The halo-treated surface was coated with polyvinyl alcohol (degree of polymerization 4200, saponification degree 99.2 mol%) and acetyl-acetyl modified PVA (degree of polymerization 1200, acetate-acetyl modified PVA) at a ratio of 9:1 at 25°C. The aqueous solution with a base modification degree of 4.6% and a saponification degree of 99.0 mol% or more (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gohsefimer Z200") was dried to form a PVA-based resin layer with a thickness of 11 μm, and a laminate was produced.

The obtained laminated body was uniaxially stretched 2.0 times along the longitudinal direction (long side direction) at the free end between rollers with different circumferential speeds in an oven at 120° C. (air-assisted stretching treatment).

Next, the laminated body was immersed in an insolubilization bath (a boric acid aqueous solution in which 4 parts by weight of boric acid was mixed with 100 parts by weight of water) having a liquid temperature of 30°C for 30 seconds (insolubilization treatment).

Next, while immersing it in a dyeing bath with a liquid temperature of 30° C., the iodine concentration and the immersion time were adjusted so that the polarizing plate would have a predetermined transmittance. In this example, the material was immersed in an iodine aqueous solution in which 0.2 parts by weight of iodine and 1.0 parts by weight of potassium iodide were mixed with 100 parts by weight of water for 60 seconds (dyeing treatment).

Next, it was immersed in a crosslinking bath with a liquid temperature of 30° C. (100 g/w of water). 30 seconds (cross-linking treatment) in a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid.

Thereafter, while immersing the laminated body in a boric acid aqueous solution with a liquid temperature of 70°C (an aqueous solution obtained by mixing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide per 100 parts by weight of water), the laminate was rolled on rollers with different peripheral speeds. Uniaxial stretching is performed along the longitudinal direction (long side direction) so that the total stretching magnification reaches 5.5 times (extension in water).

Thereafter, the laminated body was immersed in a cleaning bath (an aqueous solution in which 4 parts by weight of potassium iodide was mixed with 100 parts by weight of water) having a liquid temperature of 30° C. (washing treatment).

In the above manner, an optical film laminated body including a polarizer with a thickness of 5 μm was obtained.

(Making adhesives for transparent protective films)

Acrylic oligomer (ARUFON UP1190, manufactured by Toagosei Co., Ltd.) 10 obtained by polymerizing 45 parts by weight of acrylomorphine, 45 parts by 1,9-nonanediol diacrylate, and (meth)acrylic acid monomer. parts, 3 parts of photopolymerization initiator (IRGACURE 907, manufactured by BASF Corporation), and 1.5 parts of polymerization initiator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) were mixed to prepare an ultraviolet curable adhesive.

<Making polarizing film (2)>

On the surface of the polarizer A of the above-mentioned optical film laminate, the above-mentioned ultraviolet curable adhesive was applied so that the thickness of the adhesive layer after curing became 1 μm, and the HC-attached film obtained in the above-mentioned Production Example 1 was bonded. After the 25 μm TAC film (cellulose triacetate film side) is irradiated, ultraviolet rays are irradiated as active energy rays to harden the adhesive. Ultraviolet irradiation uses a metal halide lamp filled with gallium, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illumination: 1600mW/cm ² , cumulative irradiation dose 1000/mJ/cm ² (wavelength 380~440nm), and the ultraviolet illuminance was measured using the Sola-Check system manufactured by Solatell. Then, the amorphous PET base material is peeled off to produce a polarizing film (2) using a thin polarizer. The optical properties of the obtained polarizing film were a single transmittance of 42.8% and a polarization degree of 99.99%.

<Preparation of polarizing film with transparent layer (2)>

Use a bar coater to coat the following transparent layer-forming material on the surface of the polarizer of the above-mentioned polarizing film (2) (the surface of the polarizer that is not provided with the 25 μm TAC film with HC), and then apply it at 60°C for 12 hours. After heat treatment, a urethane resin layer with a thickness of 3 μm was formed, and a polarizing film (2) with a transparent layer was produced.

≪Transparent layer forming material≫

The solution of the urethane prepolymer (a) was a 75% ethyl acetate solution (Tosoh) of a urethane prepolymer composed of toluene diisocyanate (TDI) and trimethylolpropane (TMP). (Made by Tosoh Corporation, trade name "CORONATE L").

On the other hand, trimethylolpropane was dissolved in cyclopentanone so that the solid content concentration became 10%, and a trimethylolpropane solution was prepared.

The above-mentioned trimethylolpropane solution was added to 100 parts of a 75% ethyl acetate solution of the above-mentioned urethane prepolymer (manufactured by Tosoh Co., Ltd., trade name "Coronate L") to prepolymerize the urethane. Material: Trimethylolpropane The solid content ratio is 90:10, then add 0.1 part of dioctyltin dilaurate catalyst (manufactured by Tokyo Fine Chemical CO., LTD., trade name "EMBILIZER OL-1"), and add methyl as a solvent isobutyl ketone to prepare a forming material (coating liquid) with a solid content concentration of 10%.

<Formation material of modulated conductive layer>

唑啉基之丙烯酸聚合物的溶液(商品名：Epocros WS-700、(股)日本觸媒製)1份及水90.4份混合，調製出固體成分濃度為0.5重量%之導電層形成用塗佈液。所得導電層形成用塗佈液中含有0.04重量%之聚噻吩系聚合物、0.25重量%之含

唑啉基丙烯酸聚合物。 In terms of solid content, 8.6 parts of a solution containing 10 to 50% by weight of a thiophene-based polymer (trade name: Denatron P-580W, manufactured by Nagase ChemteX Co.) containing

Mix 1 part of a solution of an oxazoline-based acrylic polymer (trade name: Epocros WS-700, manufactured by Nippon Shokubai Co., Ltd.) and 90.4 parts of water to prepare a coating for forming a conductive layer with a solid content concentration of 0.5% by weight. liquid. The obtained coating liquid for forming a conductive layer contained 0.04% by weight of polythiophene-based polymer and 0.25% by weight of

Zozolinyl acrylic polymer.

Example 1

(Production of polarizing film with conductive layer)

唑啉基丙烯酸聚合物。 The conductive layer-forming coating liquid was applied to the acrylic film side of the polarizing film (1) so that the thickness after drying became 0.06 μm, and dried at 80° C. for 2 minutes to form a conductive layer. The obtained conductive layer contained 8% by weight of thiophene polymer and 50% by weight of

Zozolinyl acrylic polymer.

(Preparation of acrylic polymer (A))

A monomer containing 78.9 parts of butyl acrylate, 16 parts of phenoxyethyl acrylate, 5 parts of acrylic acid, and 0.1 part of 4-hydroxybutyl acrylate was fed into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet pipe, and a cooler. mixture. and With respect to 100 parts of the aforementioned monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was fed together with 100 parts of ethyl acetate, and nitrogen gas was introduced while stirring slowly. After the substitution, the liquid temperature in the flask was maintained at around 55° C., and a polymerization reaction was performed for 8 hours to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 2.2 million and Mw/Mn = 4.0.

(Prepare adhesive composition)

With respect to 100 parts of the solid content of the acrylic polymer solution obtained above, 1 part of lithium bis(trifluoromethanesulfonyl)acyl imide, an isocyanate cross-linking agent (Coronate L manufactured by Tosoh Corporation, trimethylolpropane di 0.6 parts of toluyl isocyanate), 0.1 part of benzoyl peroxide (NYPER BMT manufactured by Nippon Oils and Fats Co., Ltd.) and 0.3 parts of epoxy-containing silane coupling agent (X-41-1056 manufactured by Shin-Etsu Chemical Industry Co., Ltd.), And prepare an acrylic adhesive solution.

(Production of polarizing film with adhesive layer)

Next, the solution of the above-mentioned acrylic adhesive composition was applied to a polyethylene terephthalate film (release film) treated with a polysiloxy release agent so that the thickness of the dried adhesive layer became 20 μm. : Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) on one side and dried at 155°C for 1 minute to form an adhesive layer on the surface of the separation film. Next, the adhesive layer formed on the separation film is transferred to the conductive layer of the polarizing film (1) produced above, thereby producing a polarizing film with an adhesive layer.

Examples 2 to 13, Comparative Examples 1 to 2

In Example 1, the types of monomers used to prepare the acrylic polymer (A) and their usage ratios were changed as shown in Table 1, and the production conditions were controlled to prepare the acrylic polymer (A). A solution of the acrylic polymer (A) described in Table 1 was prepared.

And as shown in Table 1, the type of polarizing film, whether a conductive layer is formed, the type of ionic compound (B) used to prepare the adhesive composition or its blending ratio, and the blending amount of the cross-linking agent are changed to as shown in Table 1. As shown in the figure, except for this, a polarizing film with an adhesive layer was produced in the same manner as in Example 1. In addition, when the aforementioned polarizing film (2) is used as the polarizing film, the same conductive layer as described above is formed on the polarizing element surface of the polarizing film (2) (the surface of the polarizing element of the 25 μm TAC film without HC), and When using the polarizing film (2) with a transparent layer as the polarizing film, the same conductive layer as described above is 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 films with adhesive layers obtained in the above examples and comparative examples. The evaluation results are listed in Table 1.

<Surface resistance value (Ω/□): Conductivity>

The surface resistance value of the conductive layer is measured on the side surface of the conductive layer of the polarizing film with the conductive layer attached before forming the adhesive layer. The surface resistance value of the adhesive layer is measured on the surface of the adhesive layer formed on the release film. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical ANALYTECH.

<Measurement of creep value>

The upper end of the polarizing film with adhesive layer (thickness of adhesive layer: 20 μm) cut into a size of 10 mm Conditions and autoclave treatment for 15 minutes. Set the precision heating plate with the heating surface vertical Heat to 85° C., and place the SUS plate with the polarizing film attached with the adhesive layer so that the surface without the adhesive layer is in contact with the heating surface of the heating plate. After starting to heat the SUS plate at 85°C for 5 minutes, load a load of 500g on the lower end of the polarizing film with the adhesive layer and leave it for 1 hour. Measure the difference between the polarizing film with the adhesive layer and the The deflection amplitude of the SUS plate is used as the creep value (μm) at 85°C.

<Evaluation of special-shaped cracks>

The produced polarizing film with the adhesive layer was processed into the shape shown in Figure 5 using a CO ₂ laser processing machine Spirit (manufactured by GCC, 30W) under the conditions of speed 10, laser output 35, 400ppi.

The specially-shaped polarizing film with adhesive layer was bonded to 350mm×250mm×0.7mm thick alkali-free glass (Corning Company, trade name “EG-XG”), and then heated at 50°C and 0.5MPa for 15 minutes. Autoclave treatment to make the adhesive layer adhere closely to the glass. The sample that has been subjected to the above treatment is put into the thermal cycle test tank, and whether there are cracks in the special-shaped part at the time points of 100 cycles and 200 cycles is visually confirmed. Five identical objects were put into the sample under each condition, and the number of samples with cracks was recorded in Table 1.

(Test conditions)

85℃(保持30分鐘)作為1個循環反覆進行且昇溫‧降溫速度：10℃/min Temperature conditions: -40℃ (keep for 30 minutes)

85℃ (maintained for 30 minutes) is repeated as one cycle and the temperature rise and cooling rate: 10℃/min

<ESD test>

After peeling off the separation film from the polarizing film with the adhesive layer, it is attached to the viewing side of the built-in liquid crystal unit to create a liquid crystal with built-in touch sensing function. panel. That is, the obtained polarizing film with the adhesive layer is bonded to the first transparent substrate of the built-in liquid crystal unit shown in FIG. 6 to form the first adhesive layer and the first polarizing film. An ESD (electrostatic discharge) gun (10kV) was used to emit an ESD (electrostatic discharge) gun (10kV) on the polarizing film surface of the liquid crystal panel, and the time it took for the whitened part due to electricity to disappear was measured, and the judgment was made based on the following standards.

(Evaluation Basis)

A: Within 0.5 seconds.

B: greater than 0.5 seconds and within 1 second.

C: greater than 1 second and within 10 seconds.

D: More than 10 seconds.

<Durability Test>

Make the absorption axis of the polarizing film with the adhesive layer attached parallel to the long side, and cut it into a size of 300×220 mm. The polarizing film with the adhesive layer was bonded to 350×250mm×0.7mm thick alkali-free glass (trade name “EG-XG” manufactured by Corning Corporation) using a laminating machine. Next, autoclave processing was performed at 50° C. and 0.5 MPa for 15 minutes to allow the adhesive layer to adhere closely to the glass. After the sample that has been treated as described above is processed for 500 hours in a gas environment of 95°C and 500 hours in a gas environment of 60°C/95%RH, the sample is visually evaluated according to the following standards. its appearance.

(Evaluation Basis)

A: There is no appearance change such as foaming or peeling at all.

B: Although there is very little peeling or foaming at the ends, there is no practical problem.

C: There is peeling or foaming at the end, but it is practical as long as it is not used for special purposes. No problem.

D: There is significant peeling at the end, which poses a practical problem.

<Evaluation of end fading>

The polarizing film with the adhesive layer obtained in the Examples and Comparative Examples was cut into 50 mm × 50 mm, and after peeling off the separation film, it was laminated to 1.2~1.5 mm thick alkali glass (Matsunami Glass Co., Ltd.) through the adhesive layer. (preparation, glass slide), and prepare the specimen. After maintaining the sample in a high temperature and high humidity environment of 60° C. and 90% RH for 500 hours, the amount of edge fading was measured using a differential interference microscope (manufactured by Olympus, product name "MX-61L") under the following conditions. The amount of end fading is measured on the diagonal lines of the four corners of the sample. The straight-line distance between the part closest to the center and the corner connecting the part that becomes lighter in color than the center is determined as the amount of end fading (μm). , and the average value of the four corners is determined as the end fading amount of the sample.

Device: Made by Olympus Corporation, MX-61L

Measurement conditions

Lens magnification: 5 times

ISO:200

Shutter speed: 1/100

Amount of reflected light: scale 0

White balance: automatic

Transmitted light controller: LG-PS2

Amount of transmitted light: scale 5

Transmitted light polarization direction: the direction of polarization orthogonal to the transmission axis of the polarizing film

In Table 1: BA represents butyl acrylate, PEA: phenoxyethyl acrylate, AA represents acrylic acid, NVP represents N-vinyl-2-pyrrolidone, HBA: 4-hydroxybutyl acrylate, and isocyanate represents isocyanate cross-linking. agent (CORONATE L, produced by Tosoh Co., Ltd., toluene trimethylolpropane diisocyanate), BPO represents benzoyl oxide (NYPER BMT produced by Nippon Oils and Fats Co., Ltd.), Li-TFSI represents bis(trifluoromethanesulfonyl) Lithium acyl imide, K-bis(trifluoromethanesulfonyl) acyl imide potassium

TMPA-TFSI stands for trimethylpropylammonium bis(trifluorosulfonyl imide), EMP-TFSI stands for ethylmethylpyrrolidinium bis(trifluorosulfonyl imide), and TBMA-TFSI stands for trifluorosulfonyl imide. Butylmethylammonium bis(fluorosulfonylcarboxylimide) and MTOA-TFSI represent methyltrioctylammonium bis(trifluorosulfonylcarboxylic acid imide).

1: Polarizing film with adhesive layer

11:Polarizing film

21: Adhesive layer

c: conductive layer

Claims (17)

A polarizing film with an adhesive layer, which has a polarizing film, a conductive layer and an adhesive layer in sequence. The polarizing film has a polarizing element and a protective film located on one or both sides of the polarizing element; the polarizing film with an adhesive layer It is characterized in that: the polarizing film attached to the adhesive layer has a special-shaped portion other than a rectangular shape; the adhesive layer is formed from an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B). . The polarizing film with an adhesive layer attached as claimed in Claim 1 has a through hole, or a notch portion provided on the outer edge of the polarizing film with an adhesive layer as the aforementioned special-shaped portion. The polarizing film with an adhesive layer as claimed in claim 1, wherein the conductive layer contains a conductive polymer. The polarizing film with an adhesive layer as claimed in claim 1, wherein the thickness of the conductive layer is less than 1 μm. The polarizing film with an adhesive layer according to claim 1, wherein the molecular weight of the cationic component of the ionic compound (B) is 210 or less. The polarizing film with an adhesive layer as claimed in claim 5, wherein the cationic component is lithium ion. The polarizing film with an adhesive layer according to claim 1 contains 0.1 to 10 parts by weight of the aforementioned ionic compound (B) relative to 100 parts by weight of the aforementioned (meth)acrylic polymer (A). For example, the polarizing film with an adhesive layer as claimed in claim 1, The aforementioned protective film is selected from the group consisting of cellulose resin films and (meth)acrylic resin films. The polarizing film with an adhesive layer as claimed in claim 1, wherein the thickness of the polarizing element is less than 10 μm. A polarizing film with an adhesive layer as claimed in claim 1, wherein the polarizing film is a single-sided protective polarizing film having a polarizing element and a protective film only on one side of the polarizing element. The polarizing film with an adhesive layer as claimed in claim 10, wherein the single-sided protective polarizing film has the conductive layer on the other side of the polarizer. The polarizing film with an adhesive layer as claimed in claim 11, wherein in the single-sided protective polarizing film, the other side of the polarizer has the conductive layer through a transparent layer, and the transparent layer is directly formed on the polarizer. The thickness is 10 μm or less. The polarizing film with an adhesive layer as claimed in claim 12, wherein the transparent layer is a hardened product of a forming material containing a urethane prepolymer, and the urethane prepolymer is a reaction between an isocyanate compound and a polyol. things. The polarizing film with an adhesive layer as claimed in any one of claims 1 to 13, wherein the creep value of the adhesive layer at 85°C is less than 120 μm. An image display panel, characterized by: a polarizing film having an adhesive layer according to any one of claims 1 to 14. The image display panel of claim 15, wherein it has The liquid crystal layer and the touch sensor part are embedded with a liquid crystal unit with a touch sensing function, and are bonded with an adhesive layer of the polarizing film attached to the adhesive layer. An image display device, characterized by having an image display panel as claimed in claim 15 or 16.