JP2017068022A - In-cell liquid crystal panel and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an in-cell type liquid crystal panel that has good antistatic function, and can satisfy the sensitivity of a touch sensor and durability in a humidification environment.SOLUTION: There is provided an in-cell type liquid crystal panel, comprising: an in-cell type liquid crystal cell including a liquid crystal layer having liquid crystal molecules homogeneously aligned in the absence of an electric field, a first transparent substrate and a second transparent substrate each sandwiching the liquid crystal layer from both sides, a touch sensor part provided between the liquid crystal layer and first transparent substrate, and a sensor part also serving as a drive electrode provided between the liquid crystal layer and second transparent substrate; and a polarization film with an adhesive layer arranged on a visible side of the first transparent substrate of the in-cell type liquid crystal cell with a first adhesive layer therebetween without a conductive layer. The polarization film with an adhesive layer includes a first polarization film, an anchor layer, and the first adhesive layer in this order; the anchor layer contains a conductive polymer; the first adhesive layer contains an antistatic agent.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an in-cell type liquid crystal cell in which a touch sensing function is incorporated inside the liquid crystal cell and an in-cell liquid crystal panel having a polarizing film with an adhesive layer on the viewing side of the in-cell type liquid crystal cell. Further, the present invention relates to a liquid crystal display device using the liquid crystal panel. The liquid crystal display device with a touch sensing function using the in-cell type liquid crystal panel of the present invention can be used as various input display devices such as mobile devices.

  In a liquid crystal display device, generally, a polarizing film is bonded to both sides of a liquid crystal cell via an adhesive layer from the image forming method. In addition, a liquid crystal display device in which a touch panel is mounted on a display screen has been put into practical use. There are various types of touch panels such as a capacitance type, a resistance film type, an optical method, an ultrasonic method, and an electromagnetic induction type, but the capacitance type is increasingly adopted. In recent years, a liquid crystal display device with a touch sensing function that incorporates a capacitance sensor as a touch sensor unit has been used.

  On the other hand, at the time of manufacturing the liquid crystal display device, when the polarizing film with the pressure-sensitive adhesive layer is attached to the liquid crystal cell, the release film is peeled off from the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer. Static electricity is generated by peeling. The static electricity generated in this way affects the alignment of the liquid crystal layer inside the liquid crystal display device, leading to defects. Generation of static electricity can be suppressed, for example, by forming an antistatic layer on the outer surface of the polarizing film.

On the other hand, the capacitance sensor in the liquid crystal display device with a touch sensing function detects a weak capacitance formed by the transparent electrode pattern and the finger when the finger of the user approaches the surface. When a conductive layer such as an antistatic layer is provided between the transparent electrode pattern and the user's finger, the electric field between the drive electrode and the sensor electrode is disturbed, the sensor electrode capacitance becomes unstable, and the touch panel sensitivity Lowers, causing malfunction. In the liquid crystal display device with a touch sensing function, it is required to suppress the generation of static electricity and to suppress malfunction of the capacitance sensor. For example, in the liquid crystal display device with a touch sensing function, the surface resistance value is 1.0 × 10 ^{9 to} 1.0 × 10 ¹¹ Ω / □ in order to reduce the occurrence of display defects and malfunctions. It has been proposed to dispose a polarizing film having an antistatic layer on the viewing side of the liquid crystal layer (Patent Document 1).

JP2013-105154A

  According to the polarizing film having the antistatic layer described in Patent Document 1, it is possible to suppress the generation of static electricity to some extent. However, in Patent Document 1, since the place where the antistatic layer is disposed is farther from the fundamental position where static electricity is generated, it is not as effective as when an antistatic function is imparted to the adhesive layer. Also, in a liquid crystal display device with a touch sensing function using an in-cell type liquid crystal cell, it is possible to provide conductivity from the side surface by providing a conductive structure on the side surface of the polarizing film, but when the antistatic layer is thin Since the contact area with the conductive structure on the side surface is small, it has been found that sufficient conductivity cannot be obtained and poor conduction occurs. On the other hand, it was found that when the antistatic layer becomes thicker, the touch sensor sensitivity decreases.

  On the other hand, the pressure-sensitive adhesive layer provided with an antistatic function is more effective in preventing static electricity unevenness by suppressing the generation of static electricity than the antistatic layer provided on the polarizing film. However, the importance of the antistatic function of the pressure-sensitive adhesive layer has been emphasized, and it has been found that the touch sensor sensitivity decreases when the conductive function of the pressure-sensitive adhesive layer is increased. In particular, it has been found that the touch sensor sensitivity decreases in a liquid crystal display device with a touch sensing function using an in-cell type liquid crystal cell. In addition, the antistatic agent blended in the pressure-sensitive adhesive layer in order to enhance the conductive function is segregated at the interface with the polarizing film in the humidified environment (after the humidification reliability test) or at the interface on the viewing side of the liquid crystal cell. It turned out that durability was not enough.

  The present invention is an in-cell type liquid crystal panel having an in-cell type liquid crystal cell and a polarizing film with a pressure-sensitive adhesive layer applied to the viewing side thereof, having a good antistatic function, and touch sensor sensitivity in a humidified environment. It is an object of the present invention to provide an in-cell type liquid crystal panel that can satisfy the above durability.

  Another object of the present invention is to provide a liquid crystal display device using the in-cell liquid crystal panel.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following in-cell liquid crystal panel, and have completed the present invention.

That is, the present invention provides a liquid crystal layer containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field, a first transparent substrate and a second transparent substrate that sandwich the liquid crystal layer on both sides, and the liquid crystal layer and the first transparent substrate. An in-cell type liquid crystal cell having a touch sensor part provided between the liquid crystal layer and the second transparent substrate, and an in-cell type liquid crystal cell provided between the liquid crystal layer and the second transparent substrate;
An in-cell type liquid crystal panel having a pressure-sensitive adhesive layer-attached polarizing film disposed on the first transparent substrate side on the viewing side of the in-cell type liquid crystal cell via the first pressure-sensitive adhesive layer without a conductive layer,
The polarizing film with the pressure-sensitive adhesive layer has a first polarizing film, an anchor layer, and a first pressure-sensitive adhesive layer in this order,
The anchor layer contains a conductive polymer, and the first pressure-sensitive adhesive layer contains an antistatic agent.

  In the in-cell type liquid crystal panel, a conductive structure may be provided on side surfaces of the anchor layer and the first pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer.

In the in-cell type liquid crystal panel, the anchor layer has a thickness of 0.01 to 0.5 μm and a surface resistance value of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □,
The first pressure-sensitive adhesive layer has a thickness of 5 to 100 μm, a surface resistance value of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □, and
The surface resistance value of the pressure-sensitive adhesive layer-attached polarizing film on the pressure-sensitive adhesive layer side is preferably 1 × 10 ⁸ to 1 × 10 ¹¹ Ω / □.

  The in-cell type liquid crystal panel may have a second polarizing film disposed on the second transparent substrate side of the in-cell type liquid crystal cell via a second pressure-sensitive adhesive layer.

  The in-cell type liquid crystal panel may contain an alkali metal salt and / or an organic cation-anion salt as the antistatic agent.

  The present invention also relates to a liquid crystal display device having the in-cell liquid crystal panel.

  The polarizing film with an adhesive layer on the viewing side in the in-cell type liquid crystal panel of the present invention contains a conductive polymer in the anchor layer and an antistatic agent in the adhesive layer and has an antistatic function. In the in-cell liquid crystal panel, when a conductive structure is provided on each side surface of the anchor layer and the pressure-sensitive adhesive layer, the conductive structure can be contacted and a sufficient contact area can be ensured. Therefore, conduction on the side surfaces of the anchor layer and the pressure-sensitive adhesive layer is ensured, and the occurrence of uneven static electricity due to poor conduction can be suppressed.

  The polarizing film with the pressure-sensitive adhesive layer of the present invention is such that the surface resistance value of each of the anchor layer and the pressure-sensitive adhesive layer is controlled within a predetermined range, and the pressure-sensitive adhesive layer side of the polarizing film with the pressure-sensitive adhesive layer The surface resistance value can be controlled to be within a predetermined range. Thus, the polarizing film with the pressure-sensitive adhesive layer of the present invention is controlled so that the sensitivity of the touch sensor is not lowered or the durability under a humidified environment is not deteriorated, and the surface resistance value of the anchor layer and the pressure-sensitive adhesive layer. And a predetermined antistatic function can be imparted. Therefore, the polarizing film with a pressure-sensitive adhesive layer of the present invention can satisfy touch sensor sensitivity and durability in a humidified environment while having a good antistatic function.

It is sectional drawing which shows an example of the polarizing film with an adhesive layer used for the visual recognition side of the in-cell liquid crystal panel of this invention. It is sectional drawing which shows an example of the in-cell liquid crystal panel of this invention.

  The present invention will be described below with reference to the drawings. As shown in FIG. 1, the polarizing film A with an adhesive layer used on the viewing side of the in-cell liquid crystal panel of the present invention has a first polarizing film 1, an anchor layer 3, and a first adhesive layer 2 in this order. Further, a surface treatment layer 4 can be provided on the side of the first polarizing film 1 where the anchor layer 3 is not provided. In FIG. 1, the case where the polarizing film A with an adhesive layer has the surface treatment layer 4 is illustrated. The polarizing film A with pressure-sensitive adhesive layer of the present invention is disposed on the transparent substrate 41 side on the viewing side of the in-cell type liquid crystal cell B shown in FIG. Although not shown in FIG. 1, a separator can be provided in the first pressure-sensitive adhesive layer 2 of the polarizing film A with the pressure-sensitive adhesive layer of the present invention, and the surface treatment layer 4 (the surface treatment layer 4 is not provided). In some cases, the first polarizing film 1) can be provided with a surface protective film.

The thickness of the anchor layer 3 is preferably 0.01 to 0.5 [mu] m, and preferably 0.01 to 0.2 [mu] m, from the viewpoint of the stability of the surface resistance value and the adhesiveness with the adhesive layer. It is preferably 0.01 to 0.1 μm. Also, the surface resistance of the anchor layer 3 from the viewpoint of antistatic function and the touch sensor ^{sensitivity, 1 × 10 8 ~1 × 10} 12 Ω / □ is preferably ^{from, 1 × 10 8 ~1 × 10} 11 Ω / □ is preferable, and 1 × 10 ⁸ to 1 × 10 ¹⁰ Ω / □ is more preferable.

The thickness of the first pressure-sensitive adhesive layer 2 is preferably 5 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 35 μm from the viewpoint of ensuring durability and ensuring a contact area with the side conductive structure. Is preferred. Also, the terms of the first surface resistance antistatic function and the touch sensor sensitivity of the pressure-sensitive adhesive layer ^{2, 1 × 10 8 ~1 ×} 10 12 Ω / □ is preferably from, 1 × ¹⁰ 8 to 1 × It is preferably 10 ¹¹ Ω / □, and more preferably 1 × 10 ⁸ to 1 × 10 ¹⁰ Ω / □.

Further, the surface resistance value on the pressure-sensitive adhesive layer 2 side of the polarizing film A with the pressure-sensitive adhesive layer satisfies the antistatic function and reduces the sensitivity of the touch sensor so as not to decrease the durability in a humidified environment. In addition, it is preferably controlled to 1 × 10 ⁸ to 1 × 10 ¹¹ Ω / □. The surface resistance value can be adjusted by controlling the surface resistance values of the anchor layer 3 and the first pressure-sensitive adhesive layer 2, respectively. The surface resistance value is preferably 1 × 10 ^{8 to} 6 × 10 ¹⁰ Ω / □, and more preferably 1 × 10 ⁸ to 4 × 10 ¹⁰ Ω / □.

  Below, the polarizing film A with an adhesive layer is demonstrated. As mentioned above, the polarizing film A with an adhesive layer of this invention has the 1st polarizing film 1, the anchor layer 3, and the 1st adhesive layer 2 in this order. Moreover, the surface treatment layer 4 can be provided.

<First polarizing film>
As the first polarizing film, one having a transparent protective film on one side or both sides of a polarizer is generally used. The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

  As the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.

  As a material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic Examples thereof include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. A transparent protective film is bonded to one side of the polarizer by an adhesive layer. On the other side, as a transparent protective film, (meth) acrylic, urethane-based, acrylurethane-based, epoxy-based, silicone A thermosetting resin such as a system or an ultraviolet curable resin can be used. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film.

  The adhesive used for laminating the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and water-based, solvent-based, hot-melt-based, radical curable, and cationic curable types are used. However, water-based adhesives or radical curable adhesives are suitable.

<Antistatic agent>
Examples of the antistatic agent include materials capable of imparting antistatic properties such as ionic surfactants, conductive polymers, and conductive fine particles. As the antistatic agent, an ionic compound can be used.

  Examples of ionic surfactants include cationic (for example, quaternary ammonium salt type, phosphonium salt type, sulfonium salt type), anionic type (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.) Zwitterionic (sulfobetaine, alkylbetaine, alkylimidazolium betaine, etc.) or nonionic (polyhydric alcohol derivatives, β-cyclodextrin inclusion compounds, sorbitan fatty acid monoesters / diesters, polyalkylene oxide derivatives, amines) Various surfactants such as oxides).

  Examples of the conductive polymer include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers. Among these, polyaniline, polythiophene, which easily becomes a water-soluble conductive polymer or a water-dispersible conductive polymer. Etc. are preferably used. Polythiophene is particularly preferable.

  Examples of the conductive fine particles include metal oxides such as tin oxide, antimony oxide, indium oxide, and zinc oxide. Of these, tin oxide is preferable. Examples of the tin oxide-based material include, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide composite, titanium oxide- Examples thereof include a composite of tin oxide. The average particle diameter of the fine particles is about 1 to 100 nm, preferably 2 to 50 nm.

  Further, as antistatic agents other than the above, acetylene black, ketjen black, natural graphite, artificial graphite, titanium black, cationic type (quaternary ammonium salt etc.), amphoteric ion type (betaine compound etc.), anionic type (sulfonic acid) Salt or the like) or nonionic type (glycerin etc.) monomer-containing homopolymer or copolymer of the monomer and other monomers, quaternary ammonium base acrylate or methacrylate Examples thereof include a polymer having ionic conductivity such as a polymer having a site derived from; a type of permanent antistatic agent in which a hydrophilic polymer such as a polyethylene methacrylate copolymer is alloyed with an acrylic resin or the like.

≪Ionic compounds≫
Moreover, as an ionic compound, an alkali metal salt and / or an organic cation-anion salt can be preferably used. As the alkali metal salt, an organic salt or inorganic salt of an alkali metal can be used. The “organic cation-anion salt” in the present invention refers to an organic salt whose cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. There may be. “Organic cation-anion salt” is also called an ionic liquid or ionic solid.

<Alkali metal salt>
Examples of the alkali metal ions constituting the cation part of the alkali metal salt include lithium, sodium, and potassium ions. Of these alkali metal ions, lithium ions are preferred.

The anion part of the alkali metal salt may be composed of an organic material or an inorganic material. Examples of the anion part 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 ⁻ , and C ₄ F ₉ SO _{3. ^{-, C 3 F 7 COO -}} , (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, PF 6 -, CO 3 2-, or the following general formula ( 1) to (4),
(1): (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ (where n is an integer of 1 to 10),
_{(2): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
^{_{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by those such as are used. In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. The anion part constituting the inorganic salt includes Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , AsF ₆ ⁻ , SbF. ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , (CN) ₂ N ⁻ , and the like are used. As the anion moiety, (perfluoroalkylsulfonyl) imide represented by the general formula (1) such as (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , and the like is preferable. (Trifluoromethanesulfonyl) imide represented by CF ₃ SO ₂ ) ₂ N ⁻ is preferable.

Specific examples of the alkali metal organic salt include sodium acetate, sodium alginate, sodium lignin sulfonate, 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 , and the like, among these _{LiCF 3 SO 3, Li (CF} 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C and the like are preferable, and Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO _{2) 2} Fluorine-containing lithium imide salt is more preferably equal, particularly (perfluoroalkyl sulfonyl) imide lithium salts are preferred.

  Examples of the alkali metal inorganic salt include lithium perchlorate and lithium iodide.

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

Examples of the anion component include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , and 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 -, or the following general formula (1) to (4 ),
(1): (C _n F _{2n + 1} SO ₂ ) ₂ N ⁻ (where n is an integer of 1 to 10),
_{(2): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
_{^{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by those such as are used. Among these, an anion component containing a fluorine atom is particularly preferably used because an ionic compound having good ion dissociation properties can be obtained.

  Examples of the ionic compound include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate in addition to the alkali metal salts and organic cation-anion salts. . These ionic compounds can be used alone or in combination.

<Anchor layer>
As described above, the anchor layer is preferably formed to have a thickness of 0.01 to 0.5 μm and a surface resistance value of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □. The anchor layer can be formed from various antistatic agent compositions. As the antistatic agent for forming the anchor layer, a conductive polymer is used.

  Among these antistatic agents, conductive polymers are preferably used from the viewpoints of optical properties, appearance, antistatic effect and antistatic effect when heated and humidified. In particular, water-soluble conductive polymers such as polyaniline and polythiophene or water-dispersible conductive polymers are preferably used. A water-soluble conductive polymer or a water-dispersible conductive polymer can be prepared as an aqueous solution or aqueous dispersion as the coating solution for forming the antistatic layer, and the coating solution does not need to use a non-aqueous organic solvent. This is because deterioration of the optical film substrate due to the solvent can be suppressed. The aqueous solution or aqueous dispersion may contain an aqueous solvent in addition to water. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1 Examples include alcohols such as -propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol.

  The water-soluble conductive polymer such as polyaniline or polythiophene or the water-dispersible conductive polymer preferably has a hydrophilic functional group in the molecule. Examples of hydrophilic functional groups include sulfone groups, amino groups, amide groups, imino groups, quaternary ammonium bases, hydroxyl groups, mercapto groups, hydrazino groups, carboxyl groups, sulfate ester groups, phosphate ester groups, or salts thereof. Etc. By having a hydrophilic functional group in the molecule, it becomes easy to dissolve in water or to be easily dispersed in water as fine particles, and the 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 of 150,000 in terms of polystyrene). Examples of commercially available water-dispersible conductive polymers include polythiophene conductive polymers (manufactured by Nagase Chemtech, trade name, Denatron series).

  As the material for forming the anchor layer, a binder component can be added together with the conductive polymer for the purpose of improving the film-forming property of the conductive polymer and the adhesion to the optical film. When the conductive polymer is a water-soluble conductive polymer or an aqueous material of a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of binders include oxazoline group-containing polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinyl pyrrolidone, polystyrene resins, polyethylene glycols, And pentaerythritol. Particularly preferred are polyurethane resins, polyester resins and acrylic resins. These binders can be used alone or in combination of two or more as appropriate.

The amount of the conductive polymer and binder used depends on the kind of the polymer, but it is preferable to control the surface resistance value of the obtained anchor layer to be 1 × 10 ⁸ to 1 × 10 ¹² Ω / □.

<First adhesive layer>
As described above, the first pressure-sensitive adhesive layer is preferably formed so as to have a thickness of 5 to 100 μm and a surface resistance value of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □. A 1st adhesive layer can be formed from the composition which mix | blended antistatic agent with various adhesives.

  Various pressure-sensitive adhesives can be used as the pressure-sensitive adhesive forming the first pressure-sensitive adhesive layer. For example, rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and vinyl alkyl ether-based pressure-sensitive adhesives. Agents, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, cellulose adhesives, and the like. An adhesive base polymer is selected according to the type of the adhesive. Among the pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like. The

  The acrylic pressure-sensitive adhesive contains a (meth) acrylic polymer as a base polymer. The (meth) acrylic polymer usually contains an alkyl (meth) acrylate as a main component as a monomer unit. (Meth) acrylate refers to acrylate and / or methacrylate, and (meth) of the present invention has the same meaning.

  Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer include linear or branched alkyl groups having 1 to 18 carbon atoms. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3-9.

  Also, alkyl (meth) acrylates containing aromatic rings such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are used from the viewpoints of adhesive properties, durability, retardation adjustment, refractive index adjustment, and the like. be able to.

  In the (meth) acrylic polymer, one or more having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group for the purpose of improving adhesiveness and heat resistance These copolymerizable monomers can be introduced by copolymerization. Specific examples of such copolymerization monomers include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 6 Hydroxyl group-containing monomers such as hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Monomer-containing monomer with acrylic acid caprolactone Products; sulfones such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Acid group-containing monomers: Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate.

  In addition, (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc. Monomer; (meth) acrylic acid aminoethyl, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid alkylaminoalkyl-based monomers such as t-butylaminoethyl; (meth) acrylic (Meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl acid and ethoxyethyl (meth) acrylate; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- ( (Meth) acryloyl-8-o Succinimide monomers such as cyoctamethylene succinimide and N-acryloylmorpholine; Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; N-methylitaconimide, N-ethylitacon Examples of monomers for modification include itaconimide monomers such as imide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide, and the like. .

  Further, as modifying monomers, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N- Vinyl monomers such as vinylcarboxylic amides, styrene, α-methylstyrene, N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; (Meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolyethylene Glycol acrylic ester monomers such as propylene glycol; acrylic acid ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate can also be used. . Furthermore, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.

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

  Moreover, as a copolymerization monomer, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neodymium Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acryloyl such as esterified product of (meth) acrylic acid and polyhydric alcohol such as caprolactone-modified dipentaerythritol hexa (meth) acrylate , Polyfunctional monomers having two or more unsaturated double bonds such as vinyl groups, and unsaturated groups such as (meth) acryloyl groups and vinyl groups as functional groups similar to the monomer components in the backbone of polyester, epoxy, urethane, etc. Polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like to which two or more double bonds are added can also be used.

  The (meth) acrylic polymer has alkyl (meth) acrylate as a main component in the weight ratio of all constituent monomers, and the ratio of the copolymerizable monomer in the (meth) acrylic polymer is not particularly limited, but the copolymer The ratio of the monomer is preferably about 0 to 20%, about 0.1 to 15%, and more preferably about 0.1 to 10% in the weight ratio of all the constituent monomers.

  Among these copolymer monomers, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferably used from the viewpoint of adhesiveness and durability. A hydroxyl group-containing monomer and a carboxyl group-containing monomer can be used in combination. These copolymerization monomers serve as reaction points with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent. Since a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and the like are rich in reactivity with an intermolecular crosslinking agent, they are preferably used for improving the cohesiveness and heat resistance of the resulting pressure-sensitive adhesive layer. A hydroxyl group-containing monomer is preferable from the viewpoint of reworkability, and a carboxyl group-containing monomer is preferable from the viewpoint of achieving both durability and reworkability.

  When the hydroxyl group-containing monomer is contained as a copolymerization monomer, the proportion is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and further preferably 0.05 to 7% by weight. . When a carboxyl group-containing monomer is contained as a copolymerization monomer, the proportion is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and further preferably 0.2 to 6% by weight. .

  As the (meth) acrylic polymer of the present invention, those having a weight average molecular weight in the range of 500,000 to 3,000,000 are usually used. In view of durability, particularly heat resistance, it is preferable to use those having a weight average molecular weight of 700,000 to 2,700,000. Furthermore, it is preferable that it is 800,000-2.5 million. A weight average molecular weight of less than 500,000 is not preferable in terms of heat resistance. On the other hand, if the weight average molecular weight is more than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

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

  As the antistatic agent used for forming the first pressure-sensitive adhesive layer, an ionic compound is preferable from the viewpoint of compatibility with the base polymer and transparency of the pressure-sensitive adhesive layer among the above examples. In particular, when an acrylic pressure-sensitive adhesive having a (meth) acrylic polymer as a base polymer is used, it is preferable to use an ionic compound. As the ionic compound, an ionic liquid is preferable from the viewpoint of the antistatic function.

The amount of the pressure-sensitive adhesive and antistatic agent used is controlled so that the surface resistance value of the obtained first pressure-sensitive adhesive layer is 1 × 10 ⁸ to 1 × 10 ¹² Ω / □, although it depends on the type of the adhesive. The For example, the antistatic agent (for example, in the case of an ionic compound) is preferably used in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer) of the pressure-sensitive adhesive. The use of 0.05 parts by weight or more of the antistatic agent is preferable for improving the antistatic performance. Furthermore, the antistatic agent (B) is preferably 0.1 parts by weight or more, and more preferably 0.5 parts by weight or more. In order to satisfy the durability, it is preferably used at 20 parts by weight or less, and more preferably at 10 parts by weight or less.

  Moreover, the adhesive composition which forms a 1st adhesive layer can contain the crosslinking agent according to a base polymer. For example, when a (meth) acrylic polymer is used as the base polymer, an organic crosslinking agent or a polyfunctional metal chelate can be used as the crosslinking agent. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent. A polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinately bonded to an organic compound. 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, and the like. Can be mentioned. Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.

  The amount of the crosslinking agent used is preferably 3 parts by weight or less, more preferably 0.01 to 3 parts by weight, and further preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Furthermore, 0.03 to 1 part by weight is preferable.

  The pressure-sensitive adhesive composition that forms the first pressure-sensitive adhesive layer can contain a silane coupling agent and other additives. For example, polyether compounds of polyalkylene glycol such as polypropylene glycol, powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants Anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils and the like can be added as appropriate according to the intended use. Moreover, you may employ | adopt the redox system which added a reducing agent within the controllable range. These additives are preferably used in an amount of 5 parts by weight or less, further 3 parts by weight or less, and further 1 part by weight or less based on 100 parts by weight of the (meth) acrylic polymer.

<Surface treatment layer>
The surface treatment layer can be provided on the side of the first polarizing film where the anchor layer is not provided. The surface treatment layer can be provided on the transparent protective film used for the first polarizing film, or can be provided separately from the transparent protective film. As the surface treatment layer, a hard coat layer, an antiglare treatment layer, an antireflection layer, an antisticking layer, and the like can be provided.

  The surface treatment layer is preferably a hard coat layer. As a material for forming the hard coat layer, for example, a thermoplastic resin or a material that is cured by heat or radiation can be used. Examples of the material include radiation curable resins such as thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among these, an ultraviolet curable resin that can efficiently form a cured resin layer by a simple processing operation by a curing treatment by ultraviolet irradiation is preferable. Examples of these curable resins include polyesters, acrylics, urethanes, amides, silicones, epoxies, melamines, and the like, and these monomers, oligomers, polymers, and the like are included. Radiation curable resins, particularly ultraviolet curable resins are particularly preferred because of their high processing speed and low thermal damage to the substrate. Examples of the ultraviolet curable resin preferably used include those having an ultraviolet polymerizable functional group, particularly those containing an acrylic monomer or oligomer component having 2 or more, particularly 3 to 6 functional groups. In addition, a photopolymerization initiator is blended in the ultraviolet curable resin.

  Moreover, as the surface treatment layer, an antiglare treatment layer or an antireflection layer for the purpose of improving visibility can be provided. An antiglare treatment layer or an antireflection layer can be provided on the hard coat layer. The constituent material of the antiglare layer is not particularly limited, and for example, a radiation curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used. As the antireflection layer, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, or the like is used. The antireflection layer can be provided with a plurality of layers. In addition, examples of the surface treatment layer include a sticking prevention layer.

  Conductivity can be imparted to the surface treatment layer by containing an antistatic agent. As the antistatic agent, those exemplified above can be used.

<Other layers>
In addition to the above layers, the polarizing film with the pressure-sensitive adhesive layer of the present invention is provided with an easy-adhesion layer on the surface of the first polarizing film on which the anchor layer is provided, or various easy adhesions such as corona treatment and plasma treatment. Can be processed.

  The in-cell type liquid crystal cell B and the in-cell liquid crystal panel C will be described below.

(In-cell type liquid crystal cell B)
As shown in FIG. 2, the in-cell type liquid crystal cell B includes a liquid crystal layer 20 including liquid crystal molecules that are homogeneously aligned in the absence of an electric field, a first transparent substrate 41 and a second transparent substrate that sandwich the liquid crystal layer 20 on both sides. 42. A touch sensor unit 31 is provided between the liquid crystal layer 20 and the first transparent substrate 41, and a drive electrode / sensor unit 32 is provided between the liquid crystal layer 20 and the second transparent substrate 42.

  As the liquid crystal layer 20 used in the in-cell type liquid crystal cell B, a liquid crystal layer containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field is used. For example, an IPS liquid crystal layer is preferably used as the liquid crystal layer 20. In addition, as the liquid crystal layer 20, any type of liquid crystal layer such as a TN type, an STN type, a π type, and a VA type can be used. The thickness of the liquid crystal layer 20 is, for example, about 1.5 μm to 4 μm.

As described above, the in-cell type liquid crystal cell B includes the touch sensor unit 31 and the drive electrode / sensor unit 32 in the liquid crystal cell, and does not include the touch sensor unit outside the liquid crystal cell. That is, the conductive layer (surface resistance value is 1 × 10 ¹³ Ω / □) on the viewing side of the in-cell type liquid crystal cell B from the first transparent substrate 41 (the liquid crystal cell side of the first adhesive layer 2 of the in-cell liquid crystal panel C). The following is not provided. In addition, in the in-cell liquid crystal panel C illustrated in FIG. 2, the order of each configuration is shown, but the in-cell liquid crystal panel C can have other configurations as appropriate. A color filter substrate can be provided on the liquid crystal cell (first transparent substrate 41).

  Examples of the material forming the transparent substrate include glass and polymer films. Examples of the polymer film include polyethylene terephthalate, polycycloolefin, and polycarbonate. When the transparent substrate is made of glass, the thickness is, for example, about 0.1 mm to 1 mm. When the transparent substrate is formed of a polymer film, the thickness is, for example, about 10 μm to 200 μm. The said transparent substrate can have an easily bonding layer and a hard-coat layer on the surface.

  The touch sensor unit 31 (capacitance sensor) and the drive electrode / sensor unit 32 are formed as a transparent conductive layer. The constituent material of the transparent conductive layer is not particularly limited. For example, gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, tungsten, and the like An alloy etc. are mentioned. Examples of the constituent material of the transparent conductive layer include metal oxides of indium, tin, zinc, gallium, antimony, zirconium, and cadmium. Specifically, indium oxide, tin oxide, titanium oxide, cadmium oxide, and these And metal oxides made of a mixture of these. In addition, other metal compounds such as copper iodide are used. The metal oxide may further include an oxide of a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like is preferably used, and ITO is particularly preferably used. As ITO, it is preferable to contain 80 to 99 weight% of indium oxide and 1 to 20 weight% of tin oxide.

  The touch sensor unit 31 is disposed between the first polarizing film 1 and the liquid crystal layer 20, but usually a transparent electrode pattern on the first transparent substrate 41 (the liquid crystal layer 20 side in the in-cell type liquid crystal cell B). Can be formed as For the drive electrode / sensor unit 32, a transparent electrode pattern can be formed according to a conventional method. The transparent electrode pattern is usually electrically connected to a lead line (not shown) formed at the end of the transparent substrate, and the lead line is connected to a controller IC (not shown). As the shape of the transparent electrode pattern, an arbitrary shape such as a stripe shape or a rhombus shape can be adopted in addition to the comb shape. The height of the transparent electrode pattern is, for example, 10 nm to 100 nm, and the width is 0.1 mm to 5 mm.

(In-cell LCD panel C)
As shown in FIG. 2, the in-cell liquid crystal panel C of the present invention can have the polarizing film A with the adhesive layer on the viewing side of the in-cell type liquid crystal cell B and the second polarizing film 11 on the opposite side. . The said polarizing film A with an adhesive layer is arrange | positioned through the said 1st adhesive layer 2 on the 1st transparent substrate 41 side of the said in-cell type liquid crystal cell B without interposing a conductive layer. On the other hand, the second polarizing film 11 is disposed on the second transparent substrate 42 side of the in-cell type liquid crystal cell B with the second pressure-sensitive adhesive layer 12 interposed therebetween. The first polarizing film 1 and the second polarizing film 11 in the polarizing film A with the pressure-sensitive adhesive layer are arranged on both sides of the liquid crystal layer 20 so that the transmission axes (or absorption axes) of the respective polarizers are orthogonal to each other.

  As the 2nd polarizing film 11, what was demonstrated with the 1st polarizing film 1 can be used. The 2nd polarizing film 11 may use the same thing as the 1st polarizing film 1, and may use a different thing.

  For the formation of the second pressure-sensitive adhesive layer 12, the pressure-sensitive adhesive described in the first pressure-sensitive adhesive layer 2 can be used. As an adhesive used for formation of the 2nd adhesive layer 12, the same thing as the 1st adhesive layer 2 may be used, and a different thing may be used. The thickness in particular of the 2nd adhesive layer 12 is not restrict | limited, For example, it is about 1-100 micrometers. Preferably, it is 2-50 micrometers, More preferably, it is 2-40 micrometers, More preferably, it is 5-35 micrometers.

  In the in-cell liquid crystal panel C, a conductive structure 50 can be provided on the side surfaces of the anchor layer 3 and the first pressure-sensitive adhesive layer 2 of the polarizing film A with the pressure-sensitive adhesive layer. The conduction structure 50 may be provided on all of the side surfaces of the anchor layer 3 and the first pressure-sensitive adhesive layer 2 or may be provided on a part thereof. When the conductive structure is provided in part, the conductive structure is provided at a ratio of 1 area% or more, preferably 3 area% or more of the area of the side surface in order to ensure conduction on the side surface. preferable. In addition to the above, a conductive material 51 can be provided on the side surfaces of the first polarizing film 1 and the surface treatment layer 4 as shown in FIG.

  The conductive structure 50 can suppress the generation of static electricity by connecting a potential from the side surfaces of the anchor layer 3 and the first pressure-sensitive adhesive layer 2 to other suitable locations. Examples of the material for forming the conductive structures 50 and 51 include conductive pastes such as silver, gold, and other metal pastes. In addition, a conductive adhesive and any other suitable conductive material can be used. . The conduction structure 50 can also be formed in a linear shape extending from the side surfaces of the anchor layer 3 and the first pressure-sensitive adhesive layer 2. The conductive structure 51 can also be formed in the same line shape.

  In addition, the 1st polarizing film 1 arrange | positioned at the visual recognition side of the liquid crystal layer 20, and the 2nd polarizing film 11 arrange | positioned at the opposite side to the visual recognition side of the liquid crystal layer 20 are other according to the suitability of each arrangement | positioning location. An optical film can be laminated and used. Examples of the other optical films include liquid crystal display devices such as a reflection plate, an anti-transmission plate, a retardation film (including wavelength plates such as 1/2 and 1/4), a visual compensation film, and a brightness enhancement film. And an optical layer that may be used in the above. These can be used as one layer or two or more layers.

(Liquid crystal display device)
The liquid crystal display device with a built-in touch sensing function using the in-cell liquid crystal panel C of the present invention can appropriately use a member for forming a liquid crystal display device such as a backlight using a backlight or a reflector.

  The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight. The room temperature standing conditions not specifically defined below are all 23 ° C. and 65% RH.

<Measurement of weight average molecular weight of (meth) acrylic polymer>
The weight average molecular weight (Mw) of the (meth) acrylic polymer was measured by GPC (gel permeation chromatography). It measured similarly about Mw / Mn.
・ Analyzer: HLC-8120GPC manufactured by Tosoh Corporation
Column: manufactured by Tosoh Corporation, G7000H _XL + GMH _XL + GMH _XL
・ Column size: 7.8mmφ × 30cm each 90cm in total
-Column temperature: 40 ° C
・ Flow rate: 0.8mL / min
・ Injection volume: 100 μL
・ Eluent: Tetrahydrofuran ・ Detector: Differential refractometer (RI)
Standard sample: polystyrene

<Creation of polarizing film>
A polyvinyl alcohol film having a thickness of 80 μm was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 30 μm. A saponified 80 μm thick triacetyl cellulose film was bonded to both surfaces of the polarizer with a polyvinyl alcohol-based adhesive to prepare a polarizing film.

<Formation of surface treatment layer>
100 parts of UV curable acrylic resin (Dainippon Ink & Chemicals, Unidic 17-806), 3 parts of photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 184) and 100 parts of toluene mixed A coating resin composition (coating solution) was prepared. The coating liquid was applied to one side of the polarizing film obtained above with a wire bar, and then heated and dried at 80 ° C. for 1 minute to form a coating film. Next, the coating film was cured by irradiating the coating film with ultraviolet rays of 300 mJ / cm ² with a metal halide lamp to form a hard coat layer having a thickness of 5 μm.

(Preparation of anchor layer forming material)
A solution containing 8.6 parts by weight of a thiophene polymer in a solid content (trade name: Denatron P-580W, manufactured by Nagase ChemteX Corp.), a solution containing an oxazoline group-containing acrylic polymer (trade name: Epocross) WS-700 (manufactured by Nippon Shokubai Co., Ltd.) 1 part and water 90.4 parts were mixed to prepare an anchor layer forming coating solution having a solid content concentration of 0.5% by weight. The obtained coating solution for forming an anchor layer contained 0.04% by weight of a polythiophene polymer and 0.25% by weight of an oxazoline group-containing acrylic polymer.

(Formation of anchor layer)
The anchor layer-forming coating solution is applied to one side of the polarizing film (the side where the hard coat layer is not provided) so that the thickness after drying is as shown in Table 1, and dried at 80 ° C. for 2 minutes. Thus, an anchor layer was formed. The obtained anchor layer contained 8 wt% and 50 wt% of the thiophene polymer and the oxazoline group-containing acrylic polymer, respectively.

(Preparation of acrylic polymer)
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser, 74.8 parts of butyl acrylate, 23 parts of phenoxyethyl acrylate, 0.5 part of N-vinyl-2-pyrrolidone (NVP), A monomer mixture containing 0.3 part of acrylic acid and 0.4 part of 4-hydroxybutyl acrylate was charged. Furthermore, with respect to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged with 100 parts of ethyl acetate, and nitrogen gas was added while gently stirring. After introducing and purging with nitrogen, the temperature in the flask was kept at around 55 ° C., and the polymerization reaction was carried out for 8 hours. A solution of acrylic polymer having a weight average molecular weight (Mw) of 1.6 million and Mw / Mn = 3.7 Was prepared.

(Preparation of adhesive composition)
With respect to 100 parts of the solid content of the acrylic polymer solution obtained as described above, bis (trifluoromethanesulfonyl) imide lithium manufactured by Mitsubishi Materials Corporation is blended as an ionic compound in the amount used shown in Table 1, Isocyanate crosslinking agent (Takenate D160N manufactured by Mitsui Chemicals, trimethylolpropane hexamethylene diisocyanate) 0.1 part, benzoyl peroxide (Nyper BMT manufactured by NOF Corporation) and γ-glycidoxypropylmethoxysilane ( Shin-Etsu Chemical Co., Ltd. product: KBM-403) 0.2 part was mix | blended, and the solution of the acrylic adhesive composition was prepared.

(Formation of adhesive layer)
Next, the solution of the acrylic pressure-sensitive adhesive composition was applied to one side of a polyethylene terephthalate film (separator film: manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) treated with a silicone-based release agent. It was applied so that the thickness was as shown in Table 1, and dried at 155 ° C. for 1 minute to form an adhesive layer on the surface of the separator film. The said adhesive layer was transcribe | transferred to the polarizing film in which the anchor layer was formed, or the polarizing film in which the anchor layer was not formed.

Examples 1-8 and Comparative Examples 1-4
An anchor layer and a pressure-sensitive adhesive layer were sequentially formed on one side of the polarizing film obtained above (side where no hard coat layer was provided) by the combinations shown in Table 1 to produce a polarizing film with a pressure-sensitive adhesive layer. .

In Comparative Example 1, no conductive polymer was added to the anchor layer forming coating solution.
In Comparative Examples 2 and 3, no ionic compound was added to the preparation of the pressure-sensitive adhesive composition.

The anchor layer of Comparative Example 4 was formed according to the following.
100 g of dipentaerythritol hexaacrylate, 10 g of photoinitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals), 100 g of methyl alcohol and 100 g of propylene glycol monomethyl ether (PGM) are sufficiently blended and mixed with a stirrer. Stir for about 1 hour. Next, 40 g of the AZO dispersion liquid was gradually added dropwise to the produced stirring liquid, and the mixture was stirred for about 1 hour so as to be sufficiently mixed to produce a coating liquid. Thereafter, the prepared coating solution was coated on a triacetyl cellulose film using a bar coater so that the thickness after curing was 4 μm, and the coated film was dried in a 60 ° C. oven for 2 minutes. Next, the anchor layer was formed by irradiating the dried film with a medium pressure mercury lamp (UV source, light amount: 1 J / cm ² ) and curing.

  The following evaluation was performed about the polarizing film with an adhesive layer obtained by the said Example and comparative example. The evaluation results are shown in Table 1.

<Surface resistance (Ω / □): conductivity>
The surface resistance value was measured for the anchor layer and the pressure-sensitive adhesive layer.
The surface resistance value of the anchor layer was measured on the anchor layer side surface of the polarizing film with the anchor layer before forming the pressure-sensitive adhesive layer.
The surface resistance value of the pressure-sensitive adhesive layer was measured on the surface of the pressure-sensitive adhesive layer formed on the separator film.
Moreover, after peeling a separator film from the obtained polarizing film with an adhesive layer, the surface resistance value of the adhesive layer surface was measured. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech. The measurement results are listed at the top of the grid where other evaluation items are listed in Table 1.

<ESD test>
After the separator film was peeled off from the polarizing film with the pressure-sensitive adhesive layer, it was bonded to the viewing side of the in-cell type liquid crystal cell as shown in FIG. Next, a silver paste having a width of 5 mm was applied to the side surfaces of the bonded polarizing film so as to cover the side surfaces of the hard coat layer, the polarizing film, the anchor layer, and the adhesive layer, and connected to an external ground electrode. . Further, a lead wiring (not shown) around the transparent electrode pattern inside the in-cell type liquid crystal cell was connected to a controller IC (not shown) to produce a liquid crystal display device with a built-in touch sensing function. In the liquid crystal display device, an electrostatic discharge gun was applied to the polarizing film surface at an applied voltage of 10 kV, and the time until the white spots disappeared due to electricity was measured and judged according to the following criteria. . However, in Example 1, the conductive structure was not formed with silver paste.
(Evaluation criteria)
A: Within 3 seconds.
A: Over 3 seconds to within 5 seconds.
Δ: Over 5 seconds and within 20 seconds.
X: Over 20 seconds.

<TSP sensitivity>
Visual observation was performed in the state where the input display device of the liquid crystal display device with a built-in touch sensing function produced in the ESD test was used, and the presence or absence of malfunction was confirmed.
○: No malfunction.
X: There is a malfunction.

<TSP sensitivity under humidification>
The liquid crystal display device with a built-in touch sensing function produced in the ESD test was put in a humidified atmosphere of 60 ° C./90% RH for 120 hours, and then the TSP sensitivity was confirmed in the humidified atmosphere.

<Humidification durability test>
A sample obtained by cutting a polarizing film with an adhesive layer into a size of 15 inches was used as a sample. The sample was attached to a non-alkali glass having a thickness of 0.7 mm (EG-XG, manufactured by Corning) using a laminator.
Subsequently, the sample was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to completely adhere the sample to the alkali-free glass. The sample subjected to this treatment was treated for 500 hours in an atmosphere of 60 ° C./90% RH, and then the appearance between the polarizing film and the alkali-free glass was visually evaluated according to the following criteria.
(Evaluation criteria)
A: No change in appearance such as foaming or peeling.
○: Slightly peeled off or foamed at the end, but no problem in practical use.
Δ: There is peeling or foaming at the end, but there is no practical problem unless it is a special use.
X: Remarkably peeled off at the end, causing practical problems.

In Table 1, Li-TFSI represents bis (trifluoromethanesulfonyl) imide lithium.

A A polarizing film with an adhesive layer B In-cell type liquid crystal cell C In-cell liquid crystal panel 1, 11 First and second polarizing films 2, 12 First and second adhesive layers 3 Anchor layer 4 Surface treatment layer 20 Liquid crystal layer 31 Touch sensor Part 32 Drive electrode / sensor part 41, 42 First and second transparent substrates

Claims (6)

A liquid crystal layer containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field, a first transparent substrate and a second transparent substrate that sandwich the liquid crystal layer on both sides, and provided between the liquid crystal layer and the first transparent substrate. An in-cell type liquid crystal cell having a touch sensor unit and a drive electrode and sensor unit provided between the liquid crystal layer and the second transparent substrate;
An in-cell type liquid crystal panel having a pressure-sensitive adhesive layer-attached polarizing film disposed on the first transparent substrate side on the viewing side of the in-cell type liquid crystal cell via the first pressure-sensitive adhesive layer without a conductive layer,
The polarizing film with the pressure-sensitive adhesive layer has a first polarizing film, an anchor layer, and a first pressure-sensitive adhesive layer in this order,
The in-cell type liquid crystal panel, wherein the anchor layer contains a conductive polymer, and the first pressure-sensitive adhesive layer contains an antistatic agent.   The in-cell type liquid crystal panel according to claim 1, wherein a conductive structure is provided on a side surface of the anchor layer and the first pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer. The anchor layer has a thickness of 0.01 to 0.5 μm and a surface resistance value of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □,
The first pressure-sensitive adhesive layer has a thickness of 5 to 100 μm, a surface resistance value of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □, and
3. The in-cell type liquid crystal panel according to claim 1, wherein a surface resistance value on the pressure-sensitive adhesive layer side of the polarizing film with the pressure-sensitive adhesive layer is 1 × 10 ⁸ to 1 × 10 ¹¹ Ω / □.   The in-cell type liquid crystal panel according to claim 1, wherein the antistatic agent is an alkali metal salt and / or an organic cation-anion salt.   5. The in-cell type liquid crystal according to claim 1, further comprising a second polarizing film disposed on the second transparent substrate side of the in-cell type liquid crystal cell via a second pressure-sensitive adhesive layer. panel. A liquid crystal display device comprising the in-cell type liquid crystal panel according to claim 5.