TWI784930B - Built-in liquid crystal panel and liquid crystal display device - Google Patents

Abstract

[Problem] The present invention provides a built-in liquid crystal panel that has good antistatic performance and satisfies touch sensor sensitivity, conduction reliability and durability in a humidified environment. [Solution] A built-in liquid crystal panel, characterized by having: a built-in liquid crystal unit having a liquid crystal layer, a first transparent substrate and a second transparent substrate, a touch sensor unit, and a drive electrode and sensor unit, The liquid crystal layer contains liquid crystal molecules aligned in parallel in the absence of an electric field, the first transparent substrate and the second transparent substrate sandwich the liquid crystal layer from both sides, and the touch sensor unit is provided between the liquid crystal layer and the second transparent substrate. 1 Between the transparent substrates, the aforementioned driving electrodes and sensor parts are arranged between the aforementioned liquid crystal layer and the second transparent substrate; and the polarizing film with the adhesive layer is not sandwiched between the conductive layer and is arranged through the first adhesive layer. The first transparent substrate side of the viewing side of the aforementioned built-in liquid crystal unit; wherein, the aforementioned polarizing film with an adhesive layer has a surface treatment layer, a first polarizing film, and a first adhesive layer in sequence, or has a surface in sequence Treatment layer, first polarizing film, anchor layer, first adhesive layer; at least one layer selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer contains an antistatic agent.

Description

Built-in liquid crystal panel and liquid crystal display device

Field of the Invention The present invention relates to a built-in liquid crystal unit incorporating a touch sensing function inside the liquid crystal unit, and a built-in liquid crystal panel having a polarizing film with an adhesive layer on the viewing side of the built-in liquid crystal unit. In addition, the present invention relates to a liquid crystal display device using the liquid crystal panel. The liquid crystal display device with touch sensing function using the built-in liquid crystal panel of the present invention can be used as various input display devices such as mobile devices.

Background of the Invention In liquid crystal display devices, a polarizing film is generally bonded on both sides of the liquid crystal unit through an adhesive layer according to its image forming method. In addition, products equipped with a touch panel on the display screen of a liquid crystal display device have already been put into practical use. As far as touch panels are concerned, there are various formats such as capacitive, resistive film, optical, ultrasonic, or electromagnetic induction. Recently, capacitive is mostly used. In recent years, a liquid crystal display device with a touch sensing function embedded with a capacitive sensor as a touch sensor portion has been widely used.

In terms of manufacturing liquid crystal display devices, 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 peeling of the release film will cause static electricity. The resulting static electricity will affect the alignment of the liquid crystal layer inside the liquid crystal display device, leading to adverse consequences. Therefore, for example, by forming an antistatic layer on the outside of the polarizing film, generation of static electricity can be suppressed.

On the other hand, the capacitance sensor of the liquid crystal display device with touch sensing function is used to detect the weak capacitance formed by the transparent electrode pattern and the finger when the user's finger approaches the surface. If there is a conductive layer such as an antistatic layer between the above-mentioned transparent electrode pattern and the user's finger, the electric field between the drive electrode and the sensor electrode will be disturbed, resulting in unstable capacitance of the sensor electrode and reducing the sensitivity of the touch panel. cause of failure. For liquid crystal display devices with touch sensing functions, it is necessary to suppress the generation of static electricity and failure of capacitive sensors. For example, in response to the above-mentioned problems, there are documents suggesting that in a liquid crystal display device with touch sensing function, a polarizing film is arranged on the viewing side of the liquid crystal layer to reduce the occurrence of display defects or failures. The polarizing film has a surface resistance value of 1.0× 10 ⁹ ~1.0×10 ¹¹ Ω/□ antistatic layer (Patent Document 1). Prior Art Documents Patent Documents

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

Summary of the Invention Problems to be Solved by the Invention The polarizing film with an antistatic layer described in Patent Document 1 can suppress the generation of static electricity to a certain extent. However, in Patent Document 1, the arrangement location of the antistatic layer deviates from the fundamental location where static electricity is generated, so the effect is not as good as that of imparting antistatic function to the adhesive layer. It is also known that in a liquid crystal display device with touch sensing function, by providing a conductive structure on the side of the polarizing film, conductivity from the side can be given, but when the antistatic layer is very thin, the contact area between the side and the conductive structure If the temperature is too small, sufficient conductivity cannot be obtained and poor conduction occurs. On the other hand, once the antistatic layer becomes thicker, the sensitivity of the touch sensor will decrease. In addition, the antistatic layer provided on the outside of the polarizing film cannot obtain sufficient conductivity due to poor adhesion to the conductive structure provided on the side under a humidified or heated environment (after the humidified or heated reliability test), causing Poor conduction.

In addition, the adhesive layer endowed with antistatic function can suppress the generation of static electricity better than the antistatic layer provided on the aforementioned polarizing film, and can effectively prevent uneven static electricity. However, it is known that once the conductive function of the adhesive layer is increased due to the emphasis on the antistatic function of the adhesive layer, the sensitivity of the touch sensor will be reduced. Especially in a liquid crystal display device with a touch sensing function, the sensitivity of the touch sensor will decrease. In addition, it is known that the antistatic agent mixed in the adhesive layer to improve the conductivity will segregate at the interface with the polarizing film or move to the viewing side of the liquid crystal cell in a humidified environment (after the humidification reliability test) Interface, lack of durability.

The purpose of the present invention is to provide a built-in liquid crystal panel, which has a built-in liquid crystal unit and a polarizing film with an adhesive layer applied on its viewing side. The built-in liquid crystal panel has good antistatic performance and can satisfy the touch feeling. Sensor sensitivity and conduction reliability and durability in humidified environment.

Furthermore, the object of the present invention is to provide a built-in liquid crystal panel using the aforementioned built-in liquid crystal panel, and further provide a liquid crystal display device using the liquid crystal panel. means to solve problems

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

That is, the present invention relates to a built-in liquid crystal panel, characterized by comprising: a built-in liquid crystal cell having a liquid crystal layer, a first transparent substrate and a second transparent substrate, a touch sensor unit, and a drive electrode and sensor unit The liquid crystal layer contains liquid crystal molecules in a homogenious alignment in the absence of an electric field, the first transparent substrate and the second transparent substrate sandwich the liquid crystal layer from both sides, and the touch sensor part is disposed on Between the aforementioned liquid crystal layer and the first transparent substrate, the aforementioned driving electrode and sensor part is arranged between the aforementioned liquid crystal layer and the second transparent substrate; The adhesive layer is disposed on the first transparent substrate side of the viewing side of the built-in liquid crystal unit; wherein, the polarizing film attached to the adhesive layer has a surface treatment layer, a first polarizing film, and a first adhesive layer in sequence, or It has a surface treatment layer, a first polarizing film, an anchor layer, and a first adhesive layer in sequence; at least one layer selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer contains an antistatic agent.

In the aforementioned built-in type liquid crystal panel, a conduction structure may be provided on the side of the surface treatment layer, the anchor layer, and the layer containing the antistatic agent in the first adhesive layer of the polarizing film attached to the adhesive layer.

In the aforementioned built-in liquid crystal panel, at least one layer selected from the aforementioned surface treatment layer, the anchor layer, and the first adhesive layer should satisfy the following surface resistance value: The surface resistance value of the aforementioned surface treatment layer is 1×10 ⁷ ~1×10 ¹¹ Ω/□, the surface resistance value of the anchor layer is 1×10 ⁸ ~1×10 ¹¹ Ω/□, the surface resistance value of the first adhesive layer is 1×10 ⁸ ~1×10 ^11Ω /□.

In the built-in liquid crystal panel, the first adhesive layer may contain an antistatic agent. As antistatic agents, alkali metal salts and/or organic cation-anion salts are preferred.

In the aforementioned built-in liquid crystal panel, any two or more layers selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer preferably contain an antistatic agent.

In the aforementioned built-in liquid crystal panel, a second polarizing film disposed through the second adhesive layer may be provided on the side of the second transparent substrate of the aforementioned built-in liquid crystal cell.

Furthermore, the present invention relates to a liquid crystal display device having the aforementioned built-in liquid crystal panel. Invention effect

The polarizing film attached to the adhesive layer on the viewing side of the built-in liquid crystal panel of the present invention has an antistatic function on at least one layer selected from the surface treatment layer, the anchor layer and the adhesive layer, so the built-in liquid crystal panel The side can be in contact with the conduction structure, and the contact area can be sufficiently ensured. Therefore, conduction can be ensured on at least one side of the polarizing film with an adhesive layer, thereby suppressing static unevenness due to poor conduction, and satisfying conduction reliability in a humidified environment. When at least two layers selected from the surface treatment layer, the anchor layer and the adhesive layer are endowed with an antistatic function, the conduction can be ensured more effectively, and the uneven static electricity caused by poor conduction can be suppressed, and it can also meet the humidification environment Under the conduction reliability.

In addition, the polarizing film with an adhesive layer of the present invention can control the surface resistance value of at least one layer selected from the surface treatment layer, the anchor layer, and the adhesive layer within a predetermined range. In this way, the polarizing film with an adhesive layer of the present invention can control the sensitivity of the touch sensor from being reduced, and the durability in a humid environment is not deteriorated, and can also reduce at least The surface resistance value of the first layer is given a predetermined antistatic function. Therefore, the polarizing film with the adhesive layer of the present invention has good antistatic performance, and can satisfy the sensitivity of the touch sensor and the durability under humidified environment.

Modes for Carrying Out the Invention The present invention will be described below with reference to the drawings. The polarizing film A attached to the adhesive layer used on the viewing side of the built-in liquid crystal panel of the present invention has a surface treatment layer 4, a first polarizing film 1, and a first adhesive layer 2 in sequence, or has a surface treatment in sequence Layer 4, the first polarizing film 1, the anchor layer 3, and the first adhesive layer 2. FIG. 1 is a case where a surface treatment layer 4 , a first polarizing film 1 , an anchor layer 3 , and a first adhesive layer 2 are provided in sequence. As shown in FIG. 2 , the polarizing film A with an adhesive layer of the present invention can be disposed on the transparent substrate 41 side of the viewing side of the built-in liquid crystal cell B through the aforementioned adhesive layer 2 . Also, although not described in FIG. 1 , the polarizing film A with an adhesive layer of the present invention can be provided with a separator on the first adhesive layer 2 and can be provided with a surface protection film on the surface treatment layer 4 . In addition, the above-mentioned polarizing film with an adhesive layer for a liquid crystal cell embedded with a touch sensor function is controlled to impart conductivity with at least one layer selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer. the surface resistance value. The aforementioned at least one layer can be controlled by the surface resistance value, but from the viewpoint of ensuring the adhesion and contact area with the conduction structure provided on the side under a humidified or heated environment, at least two layers, especially the anchor layer 3 And the first adhesive layer 2 is preferably controlled by the surface resistance value.

From the viewpoint of the stability of the surface resistance value and the adhesion to the adhesive layer, the thickness of the aforementioned anchor layer 3 is preferably 0.01-0.5 μm, more preferably 0.01-0.2 μm, more preferably 0.01-0.1 μm. Also, from the viewpoint of antistatic performance and touch sensor sensitivity, the surface resistance value of the aforementioned anchor layer 3 is preferably 1×10 ⁸ ~1×10 ¹² Ω/□, 1×10 ⁸ ~1×10 ¹¹ Ω/□ is better, and 1×10 ⁸ ~1×10 ¹⁰ Ω/□ is more preferable.

From the viewpoint of ensuring durability and ensuring a contact area with the side conduction structure, the thickness of the first adhesive layer 2 is preferably 5-100 μm, preferably 5-50 μm, more preferably 10-35 μm. In addition, when controlling the conductivity of the first adhesive layer 2, the surface resistance value of the first adhesive layer 2 is preferably 1×10 ⁸ to 1 from the viewpoint of antistatic performance and touch sensor sensitivity. ×10 ¹² Ω/□, preferably 1×10 ⁸ to 1×10 ¹¹ Ω/□, more preferably 1×10 ⁸ to 1×10 ¹⁰ Ω/□.

In addition, when controlling the conductivity of the surface treatment layer 4, from the viewpoint of antistatic function and touch sensor sensitivity, the surface resistance value of the surface treatment layer 4 is preferably 1×10 ⁷ ~1×10 ¹¹ Ω /□, preferably 1×10 ⁷ to 1×10 ¹⁰ Ω/□, more preferably 1×10 ⁷ to 1×10 ⁹ Ω/□.

In addition, the surface resistance of the adhesive layer 2 side of the aforementioned polarizing film A attached to the adhesive layer should be controlled within 1×10 ⁸ ~1×10 ¹¹ Ω/□, so as to meet the antistatic function and not reduce the touch sensing Sensitivity or durability in humidified environments. The aforementioned surface resistance value can be adjusted by individually controlling the surface resistance value of at least one of the aforementioned surface treatment layer 4 , anchor layer 3 and first adhesive layer 2 . The aforementioned surface resistance value is preferably 1×10 ⁸ ~6×10 ¹⁰ Ω/□, more preferably 1×10 ⁸ ~4×10 ¹⁰ Ω/□.

The polarizing film A with an adhesive layer will be described below. As mentioned above, the polarizing film A with an adhesive layer of the present invention has the surface treatment layer 4, the first polarizing film 1, and the first adhesive layer 2 in sequence, or has the surface treatment layer 4 and the first polarizing film 1 in sequence. , an anchor layer 3 , and a first adhesive layer 2 .

<First Polarizing Film> As the first polarizing film, one with a transparent protective film on one or both sides of the polarizer is generally used. The polarizer is not particularly limited, and various substances can be used. Polarizers can be dichroic substances that adsorb iodine or dichroic dyes to hydrophilic polymer films such as polyvinyl alcohol films, partially formaldehyde polyvinyl alcohol films, and ethylene-vinyl acetate copolymer-based partially saponified films. And uniaxially stretched, and polyene-based oriented films such as dehydrated polyvinyl alcohol or polyvinyl chloride dehydrochloridized. Among them, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, and is generally below about 80 μm.

Also, 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. This kind of thin polarizer has little thickness unevenness, good visibility, and little dimensional change, so it has good durability, and it is also suitable for thinning the thickness of the polarizing film.

As a material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, heat stability, water barrier property, isotropy, etc. can be used. Specific examples of such thermoplastic resins include cellulose resins such as cellulose triacetate, polyester resins, polyether resins, polyresins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, etc. Resins, (meth)acrylic resins, cyclic polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. In addition, the transparent protective film can be attached to one side of the polarizer through the adhesive layer, and the other side can use (meth)acrylic, urethane, acrylic urethane, epoxy, A thermosetting resin such as polysiloxane or an ultraviolet curable resin is used as a transparent protective film. The transparent protective film may contain one or more arbitrary and appropriate additives.

The adhesive layer used to bond the above-mentioned polarizer and transparent protective film is not particularly limited as long as it is optically transparent, and various forms such as water-based, solvent-based, hot-melt, radical-curable, and cation-curable can be used. , it is advisable to use water-based adhesives or free-radical hardening adhesives.

<Antistatic agent> As mentioned above, an antistatic agent can be used in order to impart conductivity to at least one layer of the surface treatment layer, the anchor layer, and the first adhesive layer. Examples of the antistatic agent include materials capable of imparting antistatic properties, such as ionic surfactants, conductive polymers, and conductive fine particles. Also, an ionic compound can be used as an antistatic agent.

Ionic surfactants include cationic (for example, quaternary ammonium salt type, phosphonium salt type, permeic acid type, etc.), anionic (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphorous acid type, etc.) salt type, etc.), zwitterionic (sulfobetaine type, alkyl betaine type, alkylimidazolinium betaine type, etc.) or nonionic (polyol derivatives, β-cyclodextrin inclusion complex, Sorbitan fatty acid monoesters and diesters, polyalkylene oxide derivatives, amine oxides, etc.) various surfactants.

啉系等之聚合物，該等中又宜使用容易成為水溶性導電性聚合物或水分散性導電性聚合物之聚苯胺、聚噻吩等。尤以聚噻吩為宜。Examples of conductive polymers include polyaniline, polythiophene, polypyrrole, and polyquinone

Polymers such as phyllolines, and polyaniline, polythiophene, etc., which tend to become water-soluble conductive polymers or water-dispersible conductive polymers, are preferably used among them. Polythiophene is especially preferred.

Moreover, metal oxides, such as a tin oxide system, an antimony oxide system, an indium oxide system, and a zinc oxide system, are mentioned as electroconductive fine particle. Among them, the tin oxide system is preferable. For the tin oxide series, for example, 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 The composite body, the composite body of titanium oxide-tin oxide, etc. The average particle size of the microparticles is about 1-100 nm, preferably 2-50 nm.

In addition, antistatic agents other than the aforementioned can be cited: acetylene black, Ketjen black (Ketjen black), natural graphite, artificial graphite, titanium black or cationic (4-grade ammonium salt, etc.), zwitterionic (beet Alkali compounds, etc.), anionic (sulfonate, etc.) or non-ionic (glycerin, etc.) ion-conductive monomer homopolymers or copolymers of such monomers and other monomers, with 4-level ammonium base Ionically conductive polymers such as polymers derived from acrylate or methacrylate moieties; alloying of hydrophilic polymers such as polyethylene methacrylate copolymers to permanent antistatic properties such as acrylic resins agent.

≪Ionic compound≫ In addition, as an ionic compound, an alkali metal salt and/or an organic cation-anion salt can be used suitably. As the alkali metal salt, organic salts and inorganic salts of alkali metals can be used. In addition, the so-called "organic cation-anion salt" in the present invention is an organic salt, which means that the cationic part is composed of organic matter, and the anion part can be organic or inorganic. "Organic cation-anion salts" are also called ionic liquids and ionic solids.

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

The anion portion of the alkali metal salt may be composed of an organic substance or an inorganic substance. As the anion part constituting the organic salt, for example, 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- and the following general formulas (1) to (4) as shown; (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (however, n is an integer from 1 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (but, m is an integer of 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (but, l is an integer of 1 to 10), (4): (C _p F _2p+1 SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (provided that p and q are integers from 1 to 10). In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , AsF ₆ ^- , SbF ₆ ^- can be used for the anion part of the inorganic salt , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , etc. As for the anion part, (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , etc. are preferably (perfluoroalkylsulfonyl)imides represented by the aforementioned general formula (1). , especially (CF ₃ SO ₂ ) ₂ N ^- (trifluoromethanesulfonyl)imide.

The organic salt of alkali metal is preferably 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 them, 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 suitable, Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) are more suitable ₂ N and other fluorine-containing lithium imide salts, especially lithium (perfluoroalkylsulfonyl) imide salts.

Moreover, 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 above-mentioned cation component is composed of an organic substance. The cation component specifically includes: pyridinium cation, piperidinium (piperidinium) cation, pyrrolidinium (pyrrolidinium) cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium (imidazolium) cation, tetrahydrogen Pyrimidinium (tetrahydropyrimidinium) cation, dihydropyrimidinium cation, pyrazolium (pyrazolium) cation, pyrazolinium (pyrazolinium) cation, tetraalkylammonium cation, trialkylconium cation, tetraalkylphosphonium cation, etc.

As anion components, for example, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , C ₃ F ₇ COO ^- , ((CF ₃ SO ₂ )(CF ₃ CO)N ^- , ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- and the following general formulas (1) to (4) (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (provided that n is an integer from 1 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (Only, m is an integer of 1~10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (Only, l is an integer of 1~10), (4): (C _p F _{2p+ 1} SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (provided that p and q are integers ranging from 1 to 10). Among them, especially the anionic components containing fluorine atoms can obtain ionic compounds with good ion dissociation properties, Therefore, it should be used.

Moreover, examples of ionic compounds include inorganic salts such as ammonium chloride, aluminum chloride, cupric chloride, ferrous chloride, ferric chloride, and ammonium sulfate in addition to the aforementioned alkali metal salts and organic cation-anion salts. These ionic compounds may be used alone or in combination.

<Anchor layer> When imparting conductivity to the 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 conductive anchor layer can be formed from various antistatic agent compositions. As for the antistatic agent for forming the anchor layer, ionic surfactants, conductive polymers, conductive fine particles, etc. are suitable in the aforementioned examples.

From the viewpoint of optical characteristics, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, conductive polymers are preferably used among these antistatic agents. In particular, water-soluble conductive polymers such as polyaniline and polythiophene, or water-dispersible conductive polymers are preferably used. Because water-soluble conductive polymers or water-dispersible conductive polymers can prepare the coating solution for forming an antistatic layer into an aqueous solution or a water dispersion, the coating solution does not need to use non-aqueous organic solvents, and can inhibit the formation of optical film substrates. The material is deteriorated by the organic solvent. In addition, the aqueous solution or aqueous dispersion may contain an aqueous solvent other than water. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-amyl alcohol, isoamyl alcohol, secondary amyl alcohol, tertiary pentanol Alcohols such as alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, etc.

In addition, the water-soluble conductive polymer such as polyaniline and polythiophene or the water-dispersible conductive polymer preferably has a hydrophilic functional group in the molecule. Examples of the hydrophilic functional group include phenyl group, amine group, amido group, imine group, quaternary ammonium group, hydroxyl group, mercapto group, hydrazine group, carboxyl group, sulfate group, phosphate group, or salts thereof. Because the molecule has a hydrophilic functional group, it can be easily dissolved in water or easily dispersed in water in the form of particles, so that the aforementioned water-soluble conductive polymer or water-dispersible conductive polymer can be easily prepared.

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

唑啉基聚合物、聚胺甲酸乙酯系樹脂、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。尤以聚胺甲酸乙酯系樹脂、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, as for the forming material of the anchor layer, a binder component may be added together with the above-mentioned antistatic agent for the purpose of film-forming property of the antistatic agent and improvement of 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

Azoline-based polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone, Polystyrene-based resins, polyethylene glycol, neopentylthritol, and the like. In particular, polyurethane-based resins, polyester-based resins, and acrylic-based resins are preferred. One or more types of these binders can be used appropriately depending on the application.

The amount of antistatic agent and binder used depends on the types of these, but should be controlled so that the surface resistance of the obtained anchor layer becomes 1×10 ⁸ ~1×10 ¹² Ω/□.

<First Adhesive Layer> When imparting conductivity to the first adhesive layer, as described above, the first adhesive layer is preferably formed to have a thickness of 5 to 100 μm and a surface resistance of 1×10 ⁸ to 1×10 ¹² Ω/□. The conductive first adhesive layer can be formed of a composition in which an antistatic agent is mixed with various adhesives.

Various adhesives can be used as the adhesive forming the first adhesive layer, for example, rubber-based adhesives, acrylic adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, etc. Adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. The adhesive base polymer can be selected according to the type of the aforementioned adhesive. Among the aforementioned adhesives, an acrylic adhesive is preferably used from the viewpoint of good optical transparency, moderate wettability, cohesiveness, and adhesiveness, and excellent weather resistance and heat resistance.

The aforementioned acrylic adhesive contains a (meth)acrylic polymer as a base polymer. A (meth)acrylic polymer usually contains an alkyl (meth)acrylate as a main component as a monomer unit. In addition, (meth)acrylate means acrylate and/or methacrylate, and (meth) in this invention means the same thing.

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 may be used alone or in combination. The average carbon number of these alkyl groups is preferably 3-9.

In addition, from the viewpoints of adhesive properties, durability, phase difference adjustment, and refractive index adjustment, aromatic ring-containing materials such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate can be used. Alkyl (meth)acrylates.

In the aforementioned (meth)acrylic polymers, for the purpose of improving adhesiveness and heat resistance, one of polymerizable functional groups having unsaturated double bonds such as (meth)acryl groups or vinyl groups can be added The above comonomers are introduced by copolymerization. Specific examples of such comonomers include: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 6-Hydroxyhexyl, 8-Hydroxyoctyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 12-Hydroxylauryl (meth)acrylate and (4-Hydroxymethylcyclohexyl)-methyl Hydroxyl-containing monomers such as acrylate and other hydroxyl groups; (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and other carboxyl-containing monomers Monomers; monomers containing anhydride groups such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; styrenesulfonic acid or allylsulfonic acid, 2-(meth)acrylamide-2-methanol Monomers containing sulfonic acid groups such as propanesulfonic acid, (meth)acrylamide propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid; 2-hydroxyethyl Phosphate-containing monomers such as acryl phosphate, etc.

In addition, the following examples of monomers for the purpose of modification can also be cited: (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide And N-methylol (meth)acrylamide, N-methylolpropane (meth)acrylamide and other (N-substituted) amide monomers; (meth)aminoethyl acrylate, (methyl ) N,N-dimethylaminoethyl acrylate, tertiary butylaminoethyl (meth)acrylate and other alkylaminoalkyl (meth)acrylate monomers; methoxyethyl (meth)acrylate, Alkoxyalkyl (meth)acrylate monomers such as ethoxyethyl (meth)acrylate; N-(meth)acryloxymethylene succinimide and N-(meth)acryl Succinyl-6-oxyhexamethylene succinimide, N-(meth)acryl-8-oxyoctamethylene succinimide, N-acrylylmoephrine and other succinimides Amine monomers; maleimides such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide Amine monomers; N-methyl iconamide, N-ethyl iconamide, N-butyl iconamide, N-octyl iconamide, N-2-ethyl Iconimide-based monomers such as ylhexyl iconimide, N-cyclohexyl iconimide, and N-lauryl iconimide.

、乙烯吡

、乙烯吡咯、乙烯咪唑、乙烯

唑、乙烯嗎福林、N-乙烯羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯己內醯胺等乙烯基系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體；(甲基)丙烯酸環氧丙酯等含環氧基丙烯酸系單體；(甲基)丙烯酸聚乙二醇、(甲基)丙烯酸聚丙二醇、(甲基)丙烯酸甲氧基乙二醇、(甲基)丙烯酸甲氧基聚丙二醇等二醇系丙烯酸酯單體；(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯及2-甲氧乙基丙烯酸酯等丙烯酸酯系單體等。此外，可列舉異戊二烯、丁二烯、異丁烯、乙烯基醚等。In addition, the following monomers can also be used as modifying monomers: vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, ethylene Piper

, vinylpyridine

, vinyl pyrrole, vinyl imidazole, vinyl

Vinyl monomers such as azoles, vinylmorphine, N-vinylcarboxamides, styrene, α-methylstyrene, N-vinylcaprolactam, etc.; cyanoacrylic acid such as acrylonitrile and methacrylonitrile Ester-based monomers; epoxy-based acrylic monomers such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyl (meth)acrylate Glycol-based acrylate monomers such as ethylene glycol and methoxypolypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, polysiloxane (meth)acrylate And acrylate-based monomers such as 2-methoxyethyl acrylate. In addition, isoprene, butadiene, isobutylene, vinyl ether, etc. are mentioned.

Furthermore, examples of copolymerizable monomers other than those mentioned above include silicon atom-containing silane-based monomers and the like. Silane-based monomers such as 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltrimethoxysilane, Ethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltrimethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane , 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, etc.

In addition, the following monomers can also be used as comonomers: tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bis Phenol A Diglycidyl Ether Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Neopentylthritol Tri(meth)acrylate Ester, neopentylthritol tetra(meth)acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, caprolactone modified dipenteoerythritol Polyfunctional monomers such as hexa(meth)acrylate and other esterified products of (meth)acrylic acid and polyols having two or more unsaturated double bonds such as (meth)acryl and vinyl groups; and in polyester , Polyester (meth)acrylate with two or more unsaturated double bonds such as (meth)acryl and vinyl added to the skeleton of epoxy and urethane as the same functional group as the monomer component, Epoxy (meth)acrylate, urethane (meth)acrylate, etc.

The (meth)acrylic polymer contains alkyl (meth)acrylate as the main component in the weight ratio of the total constituent monomers, and the ratio of the aforementioned comonomers in the (meth)acrylic polymer is not particularly limited. , the ratio of the aforementioned comonomer accounts for about 0-20% in the weight ratio of the total constituent monomers, preferably about 0.1-15%, more preferably about 0.1-10%.

Among these comonomers, hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesiveness and durability. A hydroxyl group-containing monomer and a carboxyl group-containing monomer may be used in combination. When the adhesive composition contains a cross-linking agent, these comonomers will become the reaction sites of the cross-linking agent. Hydroxyl-containing monomers and carboxyl-containing monomers are rich in reactivity with crosslinking agents between molecules, so they are very suitable for improving the cohesion and heat resistance of the obtained adhesive layer. In terms of reworkability, hydroxyl-containing monomers are suitable, and in terms of both durability and reworkability, carboxyl-containing monomers are suitable. In addition, when adding an antistatic agent, it is preferable to use an amide group-containing monomer from the viewpoint that the resistance value can be easily lowered and that it is easy to stabilize in a humidified environment, and it can also be used in combination with the aforementioned hydroxyl-containing monomer and carboxyl-containing monomer. .

When the comonomer contains a hydroxyl-containing monomer, the ratio is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, more preferably 0.05 to 7% by weight. When the comonomer contains a carboxyl group-containing monomer, the ratio is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight. When an amide group-containing monomer is contained, the ratio is preferably 0.1% by weight or more.

The (meth)acrylic polymer of the present invention usually uses a weight average molecular weight in the range of 500,000 to 3,000,000. In consideration of durability, especially heat resistance, it is preferable to use one with a weight average molecular weight of 700,000 to 2,700,000. It is more appropriate to use 800,000 to 2.5 million. If the weight average molecular weight is less than 500,000, it is unfavorable from the viewpoint of heat resistance. Also, if the weight average molecular weight exceeds 3 million, a large amount of diluent solvent is required to increase the cost in order to adjust the viscosity for coating, so it is not suitable. In addition, the weight average molecular weight means the 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. In addition, the obtained (meth)acrylic polymer may be any of random copolymer, block copolymer, graft copolymer, and the like.

Regarding the antistatic agent used to form the first adhesive layer, ionic compounds are preferred in the above examples from the viewpoints of compatibility with the base polymer and transparency of the adhesive layer. Especially in the case of using an acrylic adhesive using a (meth)acrylic polymer as a base polymer, it is preferable to use an ionic compound. The ionic compound is preferably an ionic liquid from the viewpoint that the resistance value can be easily lowered by adding a small amount, and that it is easy to be stable in a humidified environment.

The amount of the aforementioned adhesive and antistatic agent used depends on the type, but when controlled so that the surface resistance value of the obtained first adhesive layer becomes 1×10 ⁸ ~1×10 ¹² Ω/□, for example, With respect to 100 parts by weight of the base polymer (such as (meth)acrylic polymer) of the adhesive, it is preferable to use the antistatic agent (such as an ionic compound) within the range of 20 parts by weight. It is quite appropriate to use more than 0.05 parts by weight of antistatic agent to improve antistatic performance. In addition, the antistatic agent (B) is preferably at least 0.1 parts by weight, more preferably at least 0.5 parts by weight. From the viewpoint of satisfying durability, it is preferably used in an amount of not more than 20 parts by weight, more preferably not more than 10 parts by weight.

In addition, a crosslinking agent corresponding to the base polymer may be contained in the adhesive composition forming the first adhesive layer. For example, when a (meth)acrylic polymer is used as the base polymer, an organic crosslinking agent or a polyfunctional metal chelate compound can be used as the crosslinking agent. Examples of the organic crosslinking agent include isocyanate crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, and imine crosslinking agents. Multifunctional metal chelates are those in which polyvalent metals and organic compounds are covalently bonded or coordinately bonded. 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. Atoms that can be covalently bonded or coordinately bonded in organic compounds include oxygen atoms, and organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.

Relative to 100 parts by weight of the (meth)acrylic polymer, the amount of the crosslinking agent used is preferably less than 3 parts by weight, more preferably 0.01~3 parts by weight, more preferably 0.02~2 parts by weight, and 0.03~1 Parts by weight are better.

In addition, a silane coupling agent and other additives may be contained in the adhesive composition forming the first adhesive layer. For example, polyether compounds of polyalkylene glycols such as polypropylene glycol, powders such as coloring agents and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, and leveling agents can be appropriately added according to the application. , softener, antioxidant, anti-aging agent, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic or organic filler, metal powder, granular, foil, etc. In addition, a redox system in which a reducing agent is added can also be used within a controllable range. With respect to 100 parts by weight of the (meth)acrylic polymer, these additives are preferably used in the range of not more than 5 parts by weight, more preferably not more than 3 parts by weight, and more preferably not more than 1 part by weight.

<Surface treatment layer> When imparting conductivity to the surface treatment layer, as described above, the surface treatment layer is preferably formed so that the surface resistance value is 1×10 ⁷ to 1×10 ¹¹ Ω/□. Conductivity can be imparted to the said surface treatment layer by containing an antistatic agent. In addition to the transparent protective film used for the first polarizing film, the surface treatment layer may be provided separately from the transparent protective film. As the aforementioned surface treatment layer, a hard coat layer, an antiglare treatment layer, an antireflection layer, an antisticking layer, and the like may be provided. The antistatic agent for imparting conductivity to the surface treatment layer can use the ones exemplified above, but preferably contains at least one selected from the group consisting of ionic surfactants, conductive fine particles, and conductive polymers. From the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, the antistatic agent used in the surface treatment layer is preferably conductive fine particles.

The aforementioned surface treatment layer is preferably a hard coat layer. As a material for forming the hard coat layer, for example, a thermoplastic resin, a material cured by heat or radiation can be used. Examples of the aforementioned material include radiation curable resins such as thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among them, an ultraviolet curable resin is preferable, and the ultraviolet curable resin can efficiently form a cured resin layer with a simple processing operation by hardening treatment by ultraviolet irradiation. Such curable resins include polyester-based, acrylic-based, urethane-based, amide-based, polysiloxane-based, epoxy-based, and melamine-based resins, and include monomers and oligomers thereof. , polymers, etc. From the standpoint of rapid processing speed and less heat loss to the substrate, radiation-curable resins, especially ultraviolet-curable resins, are preferable. Examples of suitably used ultraviolet curable resins include those having ultraviolet polymerizable functional groups, those containing acrylic monomers or oligomer components having 2 or more, especially 3 to 6 functional groups. In addition, a photopolymerization initiator may be blended in the ultraviolet curable resin.

In addition, an anti-glare treatment layer or an anti-reflection layer for the purpose of improving visibility may be provided for the above-mentioned surface treatment layer. In addition, an antiglare treatment layer or an antireflection layer may be provided on the aforementioned hard coat layer. The constituent material of the antiglare treatment layer is not particularly limited, and for example, radiation curable resin, thermosetting resin, thermoplastic resin, etc. can be used. For the antireflection layer, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, etc. can be used. The antireflection layer may be provided in plural layers. In addition, examples of the surface treatment layer include an antisticking layer and the like.

The thickness of the above-mentioned surface treatment layer can be appropriately set according to the type of surface treatment layer, and generally it is preferably 0.1-100 μm. For example, the thickness of the hard coat layer is preferably 0.5-20 μm. The thickness of the hard coat layer is not particularly limited, but if it is too thin, sufficient hardness cannot be obtained as a hard coat layer, and if it is too thick, cracking or peeling will easily occur. The thickness of the hard coating is preferably 1-10 μm.

The amount of antistatic agent and binder (resin material, etc.) used in the above-mentioned surface treatment layer depends on the type of these, but the surface resistance value of the obtained surface treatment layer is preferably 1×10 ⁷ ~1×10 ¹¹ Ω/ □ way to control. Usually, relative to 100 parts by weight of the antistatic agent, the binder is preferably less than 1000 parts by weight, more preferably 10-200 parts by weight.

<Other layers> For the polarizing film with an adhesive layer of the present invention, in addition to the above-mentioned layers, an easy-adhesive layer may be provided on the side surface of the first polarizing film where the anchor layer is provided, or corona treatment, plasma treatment, etc. may be performed. Various easy-adhesive treatments.

The built-in liquid crystal unit B and the built-in liquid crystal panel C will be described below.

(Built-in liquid crystal cell B) As shown in FIG. 2, the built-in liquid crystal cell B has a liquid crystal layer 20, a first transparent substrate 41 and a second transparent substrate 42 sandwiching the liquid crystal layer 20 from both sides, and the liquid crystal layer 20 contains Liquid crystal molecules aligned in parallel in the absence of an electric field. Furthermore, a touch sensor unit 31 is provided between the liquid crystal layer 20 and the first transparent substrate 41 , and a driving electrode and 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 built-in liquid crystal cell B, a liquid crystal layer containing liquid crystal molecules aligned in parallel in the absence of an electric field can be used. For the liquid crystal layer 20, for example, an IPS type liquid crystal layer is suitably used. In addition, for the liquid crystal layer 20 , for example, any type of liquid crystal layer such as TN type, STN type, π type, or VA type can be used. The thickness of the aforementioned liquid crystal layer 20 is, for example, about 1.5 μm˜4 μm.

As mentioned above, the built-in liquid crystal unit B has the touch sensor unit 31 and the driving electrode and sensor unit 32 inside the liquid crystal unit, and does not have the touch sensor unit outside the liquid crystal unit. That is, no conductive layer is provided on the side of the first transparent substrate 41 of the built-in liquid crystal cell B (the side closer to the liquid crystal cell than the first adhesive layer 2 of the built-in liquid crystal panel C) (surface resistance value 1×10 ¹³ Ω/□ or less). Also, the built-in liquid crystal panel C described in FIG. 2 shows the order of the respective structures, but the built-in liquid crystal panel C may have other structures as appropriate. A color filter substrate may be provided on the liquid crystal cell (the first transparent substrate 41).

The material for forming the aforementioned transparent substrate may be, for example, glass or a polymer film. Examples of the aforementioned polymer film include polyethylene terephthalate, polycycloolefin, and polycarbonate. When the aforementioned transparent substrate is formed of glass, its thickness is, for example, about 0.1 mm to 1 mm. When the aforementioned transparent substrate is formed of a polymer film, its thickness is, for example, about 10 μm˜200 μm. The above-mentioned transparent substrate may have an easy-adhesive layer or a hard coat layer on its surface.

A touch sensor part 31 (capacitive sensor) and a driving electrode and sensor part 32 are formed as transparent conductive layers. The constituent materials of the aforementioned transparent conductive layer are not particularly limited, and examples include metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, tungsten, and alloys of these metals, etc. . In addition, the constituent materials of the aforementioned transparent conductive layer include metal oxides of indium, tin, zinc, potassium, antimony, zirconium, and cadmium, specifically, indium oxide, tin oxide, titanium oxide, cadmium oxide, and mixtures thereof. Metal oxides composed of etc. Other metal compounds composed of copper iodide and the like can be used. The aforementioned metal oxides may further contain oxides of metal atoms of the aforementioned group as required. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, etc. are suitably used, and ITO is particularly preferably used. ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

The touch sensor part 31 is arranged between the first polarizing film 1 and the liquid crystal layer 20 , and can usually be formed on the first transparent substrate 41 (on the side of the liquid crystal layer 20 in the built-in liquid crystal cell B) with a transparent electrode pattern. It is also possible to form a transparent electrode pattern for the driving electrode and sensor unit 32 by a conventional method. The above-mentioned transparent electrode patterns are usually electrically connected to routing wires (not shown) formed on the end of the transparent substrate, and the above-mentioned routing wires are connected to a controller IC (not shown). In addition to the comb shape, the shape of the transparent electrode pattern can be any shape depending on the application, such as a stripe shape or a rhombus shape. The height of the transparent electrode pattern is, for example, 10 nm˜100 nm, and the width is 0.1 mm˜5 mm.

(Built-in liquid crystal panel C) As shown in Figure 2, the built-in liquid crystal panel C of the present invention can have polarizing film A with an adhesive layer on the viewing side of built-in liquid crystal unit B, and has a second polarizing film A on its opposite side. Polarizing film 11. The aforementioned polarizing film A attached to the adhesive layer is not sandwiched by a conductive layer and is arranged on the side of the first transparent substrate 41 of the aforementioned built-in liquid crystal unit B through the aforementioned first adhesive layer 2 . On the other hand, the second polarizing film 11 is disposed on the side of the second transparent substrate 42 of the aforementioned built-in liquid crystal cell B through the second adhesive layer 12 . The first polarizing film 1 and the second polarizing film 11 of the aforementioned polarizing film A with the adhesive layer are arranged on both sides of the liquid crystal layer 20 in such a way that the transmission axes (or absorption axes) of the polarizers are perpendicular to each other.

As the second polarizing film 11, those described in the first polarizing film 1 can be used. As the second polarizing film 11, the same thing as the first polarizing film 1 may be used, or a different thing may be used.

The adhesive described in the first adhesive layer 2 can be used for forming the second adhesive layer 12 . The adhesive used to form the second adhesive layer 12 may be the same as the first adhesive layer 2 or may be different. The thickness of the second adhesive layer 12 is not particularly limited, and is, for example, about 1 to 100 μm. It is preferably 2-50 μm, more preferably 2-40 μm, more preferably 5-35 μm.

Also, in the built-in liquid crystal panel C, conduction can be provided on the side of at least any one layer selected from the aforementioned surface treatment layer 4, the anchor layer 3, and the first adhesive layer 2 of the aforementioned polarizing film A attached to the adhesive layer. Structure 51 or 50. FIG. 2 exemplifies the case where a conduction structure 51 is provided on the side surfaces of the surface treatment layer 4 and the first polarizing film 1 . In addition, FIG. 2 exemplifies the case where the conduction structure 50 is provided on the side surfaces of the anchor layer 3 and the first polarizing film 2 . In addition, in FIG. 2 there are conducting structures 51 and 50, and the conducting structures can be provided on the side of at least any one layer selected from the surface treatment layer 4 containing an antistatic agent, the anchor layer 3, and the first adhesive layer 2. . For example, even if there are two layers containing antistatic agent, when the two layers of the anchor layer 3 and the first adhesive layer 2 have been endowed with conductivity, as long as the conductive structure 50 is provided, the conductive structure 51 may not be provided. The conduction structures 51 and 50 can be provided on all sides of at least one layer selected from the aforementioned surface treatment layer 4 , anchor layer 3 and first adhesive layer 2 , or partially. When the conduction structure is partially provided, in order to ensure the conduction on the side surface, the conduction structure should be provided at a ratio of more than 1 area % and ideally more than 3 area % of the area of the aforementioned side surface.

Through the above-mentioned conductive structures 51 and 50, the potential can be connected to other appropriate positions from the side of at least one layer selected from the above-mentioned surface treatment layer 4, anchor layer 3 and first adhesive layer 2, so as to suppress static electricity. occur. Materials for forming the conductive structures 51 and 50 include conductive pastes such as silver, gold, or other metal pastes, and other conductive adhesives and other appropriate conductive materials can also be used. The conductive structures 51 and 50 may also be formed in the form of lines extending from the side of at least any one layer selected from the aforementioned surface treatment layer 4 , anchor layer 3 , and first adhesive layer 2 .

In addition, the first polarizing film 1 arranged on the viewing side of the liquid crystal layer 20 and the second polarizing film 11 arranged on the opposite side of the viewing side of the liquid crystal layer 20 can be laminated with other optical films according to the suitability of each arrangement position. use. Also, the above-mentioned other optical films can be for example: reflective plates or anti-transmission plates, retardation plates (including 1/2 or 1/4 wavelength plates), visual compensation films, brightening films, etc., which can be used to form liquid crystal display devices, etc. optical layer. These can be used in 1 layer or 2 or more layers.

(Liquid Crystal Display Device) A liquid crystal display device with a built-in touch sensor function using the built-in liquid crystal panel C of the present invention can be suitably used in an illumination system using a backlight or a reflector as a member for forming a liquid crystal display device. Example

Hereinafter, the present invention will be described concretely with reference to manufacturing examples and examples, but the present invention is not limited by these examples. In addition, the parts and % in each example are based on weight. Below, all room temperature storage conditions not specified in particular are 23°C and 65%RH.

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

＜Making Polarizing Film＞ Place a polyvinyl alcohol film with a thickness of 80 μm between rollers with different speed ratios, dye it in 0.3% iodine solution at 30°C for 1 minute and extend it to 3 times at the same time. Thereafter, it was stretched while being immersed in an aqueous solution containing 4% boric acid and 10% potassium iodide at 60° C. for 0.5 minutes so that the total stretching ratio became 6 times. Next, it was immersed in an aqueous solution containing 1.5% potassium iodide at 30° C. for 10 seconds to clean it, and then dried at 50° C. for 4 minutes to obtain a polarizer with a thickness of 30 μm. A saponified 80 μm thick cellulose triacetate film was bonded to both sides of the polarizer with a polyvinyl alcohol-based adhesive to form a polarizing film.

<Formation of Surface Treatment Layer> In Examples 1, 2, and 10, one side of the polarizing film obtained above was adjusted so that the thickness after drying became the thickness shown in Table 1, and then ATO (antimony-doped UV-curable resin dispersion of tin oxide) particles (SUMITOMO OSAKA CEMENT Co., Ltd., ASHC-101) is used as a forming material for an antistatic hard coat layer, and then heated and dried at 80°C for 1 minute to form a coating film . Next, the coating film was irradiated with 300mJ/cm ² of ultraviolet rays by a metal halide lamp to harden the coating film to form an antistatic hard coat layer.

On the other hand, in Examples 3-9 and Comparative Examples 1 and 2, a hard coat layer not containing an antistatic agent was formed. The aforementioned coating solution for the hard coat layer containing no antistatic agent comprises 100 parts of ultraviolet curable acrylic resin (manufactured by DIC Co., UNIDIC 17-806), photopolymerization initiator (manufactured by Ciba Specialty Chemicals, IRGACURE 184 ) and 100 parts of toluene were mixed and prepared. Using this preparation solution, after drying, it adjusted so that the thickness may become the thickness shown in Table 1, and after coating with a wire bar, it heat-dried at 80 degreeC for 1 minute, and formed the coating film. Next, the coating film was irradiated with 300 mJ/cm ² of ultraviolet light with a metal halide lamp to harden the coating film to form a hard coat layer.

唑啉基丙烯酸聚合物之溶液(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%之錨定層形成用塗佈液。所得錨定層形成用塗佈液含有0.04重量%之聚噻吩系聚合物及0.25重量%之含

唑啉基丙烯酸聚合物。(Preparation of an anchor layer forming material) In Example 9, a solution containing 10 to 50% by weight of a thiophene polymer in terms of solid content (trade name: Denatron P-580W, manufactured by Nagase ChemteX Co., Ltd.) 8.6 servings, containing

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

Azoline-based acrylic polymer.

唑啉基丙烯酸聚合物。(Formation of Anchor Layer) The coating solution for forming an anchor layer was coated on one side of the above-mentioned polarizing film (the side not provided with a hard coat layer) so that the thickness after drying became the thickness shown in Table 1, and heated at 80° C. Dry for 2 minutes to form an anchor layer. The resulting anchor layer contains 8% by weight of thiophene polymer and 50% by weight of

Azoline-based acrylic polymer.

(Preparation of acrylic polymer) Feed the monomer mixture into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler. The monomer mixture contains 74.8 parts of butyl acrylate, 23 parts of phenoxyethyl acrylate 0.5 parts of N-vinyl-2-pyrrolidone (NVP), 0.3 parts of acrylic acid, and 0.4 parts of 4-hydroxybutyl acrylate. Next, feed 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator into 100 parts of the aforementioned monomer mixture (solid content) together with 100 parts of ethyl acetate, and introduce nitrogen gas while stirring slowly to carry out nitrogen substitution. Afterwards, the liquid temperature in the flask was kept at around 55° C. to carry out polymerization reaction for 8 hours to prepare an acrylic polymer solution with a weight average molecular weight (Mw) of 1.6 million and Mw/Mn=3.7.

(Preparation of adhesive composition) With respect to 100 parts of the solid content of the acrylic polymer solution obtained above, the ionic compound shown in Table 1 was blended in the amount shown in Table 1, and an isocyanate crosslinking agent (Mitsui Chemicals Takenate D160N manufactured by the company, 0.1 parts of trimethylolpropane hexamethylene diisocyanate), 0.3 parts of benzoyl peroxide (NYPER BMT manufactured by NOF Corporation), and γ-glycidoxypropylmethoxysilane (Shin-Etsu Chemical Co., Ltd. Industrial Co., Ltd.: KBM-403) 0.2 parts to prepare an acrylic adhesive composition solution.

(Formation of Adhesive Layer) Next, the above-mentioned acrylic adhesive composition solution was applied to the polyterephthalic acid treated with a silicone release agent so that the thickness of the adhesive layer after drying was as shown in Table 1. One side of an ethylene glycol ester film (separation film: manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) was dried at 155° C. for 1 minute to form an adhesive layer on the surface of the separation film. Then transfer the adhesive layer to the polarized film with the anchor layer or the polarized film without the anchor layer.

Examples 1-10 and Comparative Examples 1 and 2 were combined as shown in Table 1 on one side of the polarizing film obtained above (the side not provided with a hard coat layer) to sequentially form an anchor layer and an adhesive layer to produce an adhesive layer The polarizing film.

In addition, no anchor layer was formed in Examples 1-8, 10 and Comparative Examples 1, 2. In addition, in Examples 1 and 2 and Comparative Example 1, no ionic compound was blended in the preparation of the adhesive composition.

The following evaluations were performed on the polarizing film with the adhesive layer obtained in the above examples and comparative examples. The evaluation results are shown in Table 1.

<Surface resistance value (Ω/□): conductivity> The surface resistance value was measured for the surface treatment layer, anchor layer, and adhesive layer. The surface resistance value of the surface treatment layer was measured with respect to the surface treatment layer of the polarizing film to which the adhesive layer was attached. The surface resistance value of the anchor layer is measured on the anchor layer side surface of the polarizing film with the anchor layer before the adhesive layer is formed. When the anchor layer was not formed, the surface resistance value of the surface of the polarizing film was measured. The surface resistance value of the adhesive layer was measured on the surface of the adhesive layer formed on the separation film.

<ESD Test> After peeling off the separation film from the polarizing film with the adhesive layer attached, it was attached to the viewing side of the built-in liquid crystal cell as shown in Fig. 2 . Next, a silver paste with a width of 5mm was coated on the sides of the laminated polarizing film to cover the hard coat layer, polarizing film, anchor layer, and adhesive layer, and connected to the external ground electrode. In addition, the wiring (not shown) around the transparent electrode pattern inside the built-in liquid crystal cell is connected to the controller IC (not shown) to manufacture a liquid crystal display device with built-in touch sensing function. An electrostatic discharge gun (Electrostatic discharge Gun) was fired on the polarizing film surface of the liquid crystal display device under an applied voltage of 10 kV, and the time for disappearance of the part with white spots due to electricity was measured, and judged according to the following criteria. However, in Example 1, no conductive structure was formed with silver paste. (Evaluation criteria) ⊚: Within 3 seconds. 〇: More than 3 seconds to less than 5 seconds. Δ: More than 5 seconds to less than 20 seconds. ×: more than 20 seconds.

<TSP Sensitivity> Observe with naked eyes in the state of using the input display device of the liquid crystal display device with built-in touch sensing function produced in the ESD test to confirm whether there is any failure. 〇: No failure. X: There is a malfunction.

<Continuity reliability: after ESD humidification test> The above-mentioned ESD test was carried out after treating the built-in liquid crystal cell with the silver paste coated on the side of the polarizing film for 500 hours in an atmosphere of 60°C/90%RH.

表1中，Li-TFSI表示雙(三氟甲烷磺醯基)醯亞胺鋰，MPP-TFSI表示雙(三氟甲烷磺醯基)醯亞胺甲基丙基吡咯啶鎓，EMI‐FSI表示雙(氟磺醯基)醯亞胺1-乙基-3-甲基咪唑啉鎓，EMP‐TFSI表示雙(三氟甲烷磺醯基)醯亞胺乙基甲基吡咯啶鎓。[Table 1]

In Table 1, Li-TFSI means lithium bis(trifluoromethanesulfonyl)imide, MPP-TFSI means bis(trifluoromethanesulfonyl)imidomethylpropylpyrrolidinium, and EMI-FSI means Bis(fluorosulfonyl)imide 1-ethyl-3-methylimidazolinium, EMP-TFSI stands for bis(trifluoromethanesulfonyl)imide ethylmethylpyrrolidinium.

1‧‧‧The first polarizing film 2‧‧‧The first adhesive layer 3‧‧‧anchor layer 4‧‧‧Surface treatment layer 11‧‧‧The second polarizing film 12‧‧‧The second adhesive layer 20‧‧‧LCD layer 31‧‧‧Touch sensor department 32‧‧‧Drive electrode and sensor part 41‧‧‧The first transparent substrate 42‧‧‧Second transparent substrate 50, 51‧‧‧conduction structure A‧‧‧Polarizing film with adhesive layer B‧‧‧Built-in LCD unit C‧‧‧Built-in LCD panel

FIG. 1 is a cross-sectional view showing an example of a polarizing film with an adhesive layer for a liquid crystal cell embedded with a touch sensing function of the present invention. FIG. 2 is a cross-sectional view showing an example of a liquid crystal panel (built-in type) with embedded touch sensing function according to the present invention.

1‧‧‧The first polarizing film

2‧‧‧The first adhesive layer

3‧‧‧anchor layer

4‧‧‧Surface treatment layer

11‧‧‧The second polarizing film

12‧‧‧The second adhesive layer

20‧‧‧LCD layer

31‧‧‧Touch sensor department

32‧‧‧Drive electrode and sensor part

41‧‧‧The first transparent substrate

42‧‧‧Second transparent substrate

50, 51‧‧‧conduction structure

A‧‧‧Polarizing film with adhesive layer

B‧‧‧Built-in LCD unit

C‧‧‧Built-in LCD panel

Claims (10)

A built-in liquid crystal panel, characterized by having: a built-in liquid crystal unit, which has a liquid crystal layer, a first transparent substrate and a second transparent substrate, a touch sensor part, and a drive electrode and sensor part, and the liquid crystal layer contains In the absence of an electric field, the liquid crystal molecules are aligned in parallel, the first transparent substrate and the second transparent substrate sandwich the liquid crystal layer from both sides, and the touch sensor part is provided between the liquid crystal layer and the first transparent substrate Between, the above-mentioned drive electrode and sensor part is arranged between the above-mentioned liquid crystal layer and the second transparent substrate; The first transparent substrate side of the viewing side of the unit; wherein, the aforementioned polarizing film with the adhesive layer has a surface treatment layer, the first polarizing film, and the first adhesive layer in sequence, or has a surface treatment layer and a first adhesive layer in sequence 1 Polarizing film, anchor layer, and first adhesive layer; at least one layer selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer contains an antistatic agent; the aforementioned first adhesive layer does not contain Antistatic agent with a surface resistance of 1×10 ¹⁴ Ω/□ or more, or an antistatic agent with a surface resistance of 1×10 ⁸ to 1×10 ¹¹ Ω/□; the aforementioned polarizing film with an adhesive layer The side surfaces of the antistatic agent-containing layer among the surface treatment layer, the anchor layer, and the first adhesive layer have conductive structures. The built-in liquid crystal panel according to claim 1, wherein at least one layer selected from the aforementioned surface treatment layer, the anchor layer and the first adhesive layer satisfies the following surface resistance value: the surface resistance value of the aforementioned surface treatment layer is 1 ×10 ⁷ ~1×10 ¹¹ Ω/□, the surface resistance value of the anchor layer is 1×10 ⁸ ~1×10 ¹¹ Ω/□, and the surface resistance value of the first adhesive layer is 1×10 ⁸ ~ 1×10 ¹¹ Ω/□. The built-in liquid crystal panel according to claim 1, wherein the first adhesive layer contains an antistatic agent. The built-in liquid crystal panel according to claim 3, wherein the antistatic agent is an alkali metal salt and/or an organic cation-anion salt. The built-in liquid crystal panel according to claim 1, wherein any two or more layers selected from the aforementioned surface treatment layer, anchor layer, and first adhesive layer contain an antistatic agent. The built-in liquid crystal panel according to claim 5, wherein the first adhesive layer contains at least an antistatic agent. The built-in liquid crystal panel as claimed in item 1, wherein the polarizing film with the adhesive layer has a surface treatment layer, a first polarizing film, an anchor layer, and a first adhesive layer in sequence, and the first polarizing film and the anchor The anchor layer, the aforementioned anchor layer and the aforementioned first adhesive layer are all in close contact. The built-in liquid crystal panel according to claim 1, wherein the surface treatment layer is provided on the first polarizing film. The built-in liquid crystal panel according to any one of claims 1 to 8, which has a transparent substrate on the second transparent substrate side of the aforementioned built-in liquid crystal unit. The second polarizing film configured in the second adhesive layer. A liquid crystal display device having a built-in liquid crystal panel according to claim 9.

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