WO2020189159A1 - Panneau à cristaux liquides et dispositif d'affichage à cristaux liquides - Google Patents

Panneau à cristaux liquides et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2020189159A1
WO2020189159A1 PCT/JP2020/006484 JP2020006484W WO2020189159A1 WO 2020189159 A1 WO2020189159 A1 WO 2020189159A1 JP 2020006484 W JP2020006484 W JP 2020006484W WO 2020189159 A1 WO2020189159 A1 WO 2020189159A1
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Prior art keywords
liquid crystal
adhesive layer
polarizing film
meth
layer
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PCT/JP2020/006484
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English (en)
Japanese (ja)
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寛大 小野
智之 木村
雄祐 外山
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日東電工株式会社
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Priority to KR1020217031888A priority Critical patent/KR20210142656A/ko
Priority to CN202080010737.5A priority patent/CN113348410B/zh
Publication of WO2020189159A1 publication Critical patent/WO2020189159A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

  • the present invention relates to a liquid crystal cell and a liquid crystal panel having a polarizing film with a predetermined adhesive layer on the visible side of the liquid crystal cell. Further, the present invention relates to a liquid crystal display device using the liquid crystal panel.
  • the liquid crystal display device using the liquid crystal panel of the present invention can be used together with an input device such as a touch panel applied on the visual side of the liquid crystal display device, and also as various input display devices as a liquid crystal display device with a touch sensing function. Can be used.
  • a liquid crystal display device has polarizing films bonded to both sides of a liquid crystal cell via an adhesive layer due to its image forming method. Further, a liquid crystal display device having a touch panel mounted on the display screen has been put into practical use. As the touch panel, there are various types such as a capacitance type, a resistance film type, an optical type, an ultrasonic type, and an electromagnetic induction type, but the capacitance type is widely adopted. In recent years, a liquid crystal display device with a touch sensing function having a built-in capacitance sensor has been used as a touch sensor unit.
  • the release film is peeled off from the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer. Electrostatic force is generated by peeling. In addition, static electricity is also generated when the surface protective film of the polarizing film attached to the liquid crystal cell is peeled off or when the surface protective film of the cover window is peeled off. The static electricity generated in this way affects the orientation of the liquid crystal layer inside the liquid crystal display device and causes defects. The generation of static electricity can be suppressed, for example, by forming an antistatic layer on the outer surface of the polarizing film.
  • the capacitance sensor in the liquid crystal display device with a touch sensing function detects the weak capacitance formed by the transparent electrode pattern and the finger when the user's finger approaches the surface thereof.
  • 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 becomes unstable. Will decrease, causing malfunction.
  • a liquid crystal display device with a touch sensing function is required to suppress the generation of static electricity and the malfunction of the capacitance sensor.
  • the surface resistance value is 1.0 ⁇ 10 9 to 1.0 ⁇ 10 11 ⁇ / ⁇ . It has been proposed to arrange a polarizing film having an antistatic layer on the visible side of the liquid crystal layer (Patent Document 1). Further, it has been proposed that the polarizing film to be arranged on the visual side is arranged via an adhesive layer containing an antistatic agent, an anchor layer containing a conductive polymer, and the like (Patent Documents 2 and 3).
  • Patent Document 1 According to the polarizing film having an 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 location where the antistatic layer is arranged is farther than the fundamental position where static electricity is generated, it is not effective as compared with the case where the adhesive layer is provided with the antistatic function. Further, in a liquid crystal display device with a touch sensing function, it is possible to impart 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, the conductive structure on the side surface is used. Since the contact area of the film is small, it has been found that sufficient conductivity cannot be obtained and conduction failure occurs.
  • the thicker the antistatic layer the lower the touch sensor sensitivity.
  • the antistatic layer provided on the outer surface of the polarizing film does not have sufficient conductivity due to the need for adhesion with the conductive structure provided on the side surface under humidification and humidification or a heating environment (after the humidification or heating reliability test). It turns out that defects occur.
  • liquid crystal panel using the polarizing film having the conductive pressure-sensitive adhesive layer or the like described in Patent Documents 2 and 3 static electricity unevenness can be suppressed as compared with Patent Document 1.
  • a liquid crystal panel in which a polarizing film with an adhesive layer is arranged on the visible side of the liquid crystal cell without a conductive layer is required to have high conductivity.
  • conductive characteristics in a high temperature range are required.
  • liquid crystal display devices for in-vehicle use are required to have durability in a high temperature range.
  • the present invention is a liquid crystal panel having a liquid crystal cell and a polarizing film with an adhesive layer applied to the visible side thereof, which has a good antistatic function and satisfies conduction reliability and durability in a high temperature range. It is an object of the present invention to provide a liquid crystal panel which can be used.
  • Another object of the present invention is to provide a liquid crystal display device using the liquid crystal panel.
  • the present invention includes a liquid crystal layer containing liquid crystal molecules homogenically oriented in the absence of an electric field, a liquid crystal cell having a first transparent substrate and a second transparent substrate sandwiching the liquid crystal layer on both sides.
  • a polarizing film with a pressure-sensitive adhesive layer is provided on the side of the first transparent substrate on the visible side of the liquid crystal cell via the first pressure-sensitive adhesive layer without using a conductive layer, and the polarized light with the pressure-sensitive adhesive layer is provided.
  • a liquid crystal panel having a conductive structure on the side surface of the film.
  • the polarizing film with an adhesive layer has a first polarizing film and a first adhesive layer in this order.
  • the polarizing film contains a polarizer having an iodine concentration of 6% by weight or less, and the polarizing film contains The liquid crystal is characterized in that the first pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B) having a cation component having a molecular weight of 210 or less. Regarding the panel.
  • the cation component is preferably lithium ion.
  • the ionic compound (B) is preferably contained in an amount of 1 to 13 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
  • the first polarizing film preferably contains a polarizer having a thickness of more than 10 ⁇ m.
  • the conduction structure changes the size of the polarizing film with an adhesive layer in the film surface direction when a dimensional shrinkage test of the polarizing film with an adhesive layer is performed in an environment of 85 ° C. for 500 hours. It is preferable that at least the point b on the side surface having an amount of 400 ⁇ m or less is provided.
  • the first polarizing film is preferably a double protective polarizing film having a protector and protective films on both sides of the polarizer.
  • an in-cell type liquid crystal cell having a touch sensor and a touch sensing electrode portion related to a touch drive function between the first transparent substrate and the second transparent substrate may be used. it can.
  • a second polarizing film arranged via a second pressure-sensitive adhesive layer can be provided on the side of the second transparent substrate of the liquid crystal cell.
  • the present invention also relates to a liquid crystal display device having the liquid crystal panel.
  • the polarizing film with an adhesive layer on the visual side in the liquid crystal panel of the present invention contains an ionic compound in the adhesive layer, and the antistatic performance can be improved by the adhesive layer, and the adhesive
  • the layered polarizing film is in contact with the conductive structure on the side surface. Therefore, even when the polarizing film with an adhesive layer is provided on the visible side of the liquid crystal cell without passing through the conductive layer, the conduction on the side surface of the polarizing film with the adhesive layer is ensured, and static electricity unevenness due to poor continuity is prevented. Occurrence can be suppressed.
  • the conductive properties can be improved by adding the ionic compound to the pressure-sensitive adhesive layer as described above, the hardness (paste deviation amount) of the pressure-sensitive adhesive layer differs depending on the type of the ionic compound to be added, and the pressure-sensitive adhesive layer is ionic. It was found that when the pressure-sensitive adhesive layer is softened by the addition of the compound, the amount of displacement of the pressure-sensitive adhesive layer is large, and conduction failure due to disconnection is likely to occur in an environment of high temperature (particularly, over 80 ° C.).
  • the heating shrinkage of the polarizing film can be controlled to be small by using a thin polarizing element, the influence of the disconnection can be reduced, but the thinner the polarizer, the higher the iodine concentration per thickness tends to be, and the thinner Since the iodine concentration is high in the polarizer, when a thin polarizer is used, polyene formation of the polarizer is likely to occur in a high temperature environment (particularly, above 80 ° C.), and the optical characteristics are not sufficient.
  • an ionic compound having a small molecular weight of a cation component can suppress the amount of displacement of the pressure-sensitive adhesive layer even in an environment of high temperature (particularly, over 80 ° C.), and therefore, as an ionic compound.
  • a cation component having a molecular weight of 210 or less is used.
  • a lithium salt was used as the cationic component of the ionic compound, the effect of suppressing the amount of deviation was excellent.
  • a polarizing film containing a polarizer having an iodine concentration of 6% by weight or less and providing the ionic compound having a molecular weight of a cation component of 210 or less by using a polarizing film containing a polarizer having an iodine concentration of 6% by weight or less and providing the ionic compound having a molecular weight of a cation component of 210 or less. It is possible to satisfy conduction reliability and durability in a high temperature region (particularly, over 80 ° C.).
  • the polarizing film A with an adhesive layer used on the visual side of the liquid crystal panel of the present invention has a first polarizing film 1 and a first adhesive layer 2. Further, the polarizing film A with an adhesive layer may have a surface treatment layer 4 on the visible side of the first polarizing film 1, and between the first polarizing film 1 and the first adhesive layer 2. It can have an anchor layer 3.
  • FIG. 1 illustrates a case where the surface treatment layer 4, the first polarizing film 1, the anchor layer 3, and the first pressure-sensitive adhesive layer 2 are provided in this order.
  • a separator can be provided in the first pressure-sensitive adhesive layer 2 of the polarizing film A with a pressure-sensitive adhesive layer of the present invention, and a surface protective film is provided in the surface treatment layer 4. Can be done.
  • the first polarizing film 1 a film having a protective film on one side or both sides of the polarizer is used, but from the viewpoint of optical durability, it is more than a single protective polarizing film having a protective film on only one side of the polarizer. It is preferable to use both protective polarizing films having protective films on both sides (no drawing).
  • the conductive structure is provided on the side surface of the polarizing film with the pressure-sensitive adhesive layer by selecting a portion where the heat shrinkage is small (that is, the amount of dimensional change is 400 ⁇ m or less), thereby providing a high temperature region (particularly, in particular). Conduction reliability and durability at (more than 80 ° C.) can be satisfied.
  • FIG. 2 shows a state of dimensional change before and after shrinkage in the film surface direction before and after charging when the polarizing film A with an adhesive layer was charged in an environment of 85 ° C. for 500 hours to perform a dimensional shrinkage test.
  • This is an example of a conceptual diagram in a plan view.
  • the polarizing film A with an adhesive layer before charging and the polarizing film A'with a pressure-sensitive adhesive layer shrunk after charging are shown.
  • the amount of dimensional change of the polarizing film A with an adhesive layer is a distance between a predetermined point on the side surface of the polarizing film A with an adhesive layer and a side surface of the polarizing film A ′ with an adhesive layer and a predetermined point.
  • At least a conductive structure is provided at the point b where the amount of dimensional change is 400 ⁇ m or less.
  • the amount of dimensional change is preferably 350 ⁇ m or less, more preferably 300 ⁇ m or less, further preferably 250 ⁇ m or less, and further preferably 200 ⁇ m or less.
  • point b will be described with respect to the relationship between the absorption axis direction and the direction orthogonal to the absorption axis (slow phase axis direction).
  • the distance between the point b1 on the side surface in the same direction in the absorption axis direction and the point b1'of the polarizing film A'with an adhesive layer (dimension change amount in the slow axis direction).
  • the dimensional change amount of 400 ⁇ m or less is satisfied.
  • the dimensional change amount of 400 ⁇ m or less is satisfied for the point b1, it is considered that the dimensional change amount of 400 ⁇ m or less is satisfied at each point of the side b.
  • the point b2'on the side surface of the curve connecting the side surfaces in the absorption axis direction and the slow phase axis direction for the deformed object having the rectangular corners processed.
  • the distance between the image and the point b2'of the polarizing film A'with an adhesive layer is exemplified as a case where the amount of dimensional change satisfies 400 ⁇ m or less.
  • the distance (the amount of dimensional change in the absorption axis direction) between the point a on the side surface in the slow axis direction and the point a of the polarizing film A'with an adhesive layer It is exemplified as a case where the dimensional change amount of 400 ⁇ m or less is not satisfied.
  • the polarizing film A with the pressure-sensitive adhesive layer of FIG. 3 if the dimensional change amount of 400 ⁇ m or less is satisfied at the point a, it is considered that the dimensional change amount of 400 ⁇ m or less is not satisfied at each point of the side a.
  • the ratio (b / a) of the dimensional change amount b ( ⁇ m) at the point b and the dimensional change amount a ( ⁇ m) in the absorption axis direction is 0. Satisfying the range of less than 8.8 is preferable from the viewpoint of maintaining the adhesion with the conductive structure provided on the side surface.
  • the ratio (b / a) is preferably 0.7 or less, more preferably 0.6 or less.
  • the size of the polarizing film (polarizing film A with an adhesive layer) used in the present invention is not particularly limited, but for example, a rectangular object having a length of 50 to 1500 mm and a width of 50 to 1500 mm is preferable.
  • the polarizing film A with the pressure-sensitive adhesive layer allows the pressure-sensitive adhesive layer 2 to visually recognize the liquid crystal cell B (in-cell type liquid crystal cell B in FIGS. 4 to 8) as shown in FIG. It is arranged on the side of the first transparent substrate 41 on the side without a conductive layer. Further, the liquid crystal panel C has a conductive structure 50 on the side surface of the polarizing film A with an adhesive layer.
  • the polarizing film A with an adhesive layer will be described below.
  • the polarizing film A with an adhesive layer of the present invention has a first polarizing film and a first adhesive layer.
  • the first polarizing film a polarizing element and a film having a protective film on one side or both sides of the polarizing element are generally used.
  • the polarizer is not particularly limited, and various polarizers can be used.
  • the polarizer include a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and an ethylene-vinyl acetate copolymer system partially saponified film, which is uniaxially stretched by adsorbing iodine. Can be mentioned.
  • a polarizer composed of a polyvinyl alcohol-based film and iodine is preferable.
  • the thickness of these polarizers is not particularly limited, but is generally about 80 ⁇ m or less.
  • a polarizing element having an iodine concentration of 6% by weight or less from the viewpoint of heat resistance.
  • the iodine concentration is preferably 5% by weight or less, more preferably 4% by weight or less, from the viewpoint of heat resistance.
  • the iodine concentration in the polarizer is preferably 1% by weight or more, more preferably 1.5% by weight or more, and further preferably 2% by weight or more. Is preferable.
  • the iodine concentration of the polarizer is high, the amount of dimensional change is large, and the poor adhesion of the conductive structure due to heat shrinkage tends to cause poor conduction. Therefore, it is preferable to adjust the iodine concentration of the polarizer within the above range.
  • a polarizing element having a thickness of more than 10 ⁇ m from the viewpoint of heat resistance.
  • the thickness is preferably more than 10 ⁇ m to 25 ⁇ m, more preferably 10 to 22 ⁇ m, and further preferably 10 to 20 ⁇ m.
  • the thicker the polarizer the larger the amount of dimensional change, and the insufficient adhesion of the conductive structure due to heat shrinkage tends to cause conduction failure. Therefore, it is preferable to adjust the thickness of the polarizing element within the above range.
  • thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture blocking property, isotropic property, etc.
  • thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, and cyclic resins.
  • examples thereof include polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
  • a protective film is attached to one side of the polarizer by an adhesive layer, but as a protective film on the other side, (meth) acrylic, urethane, acrylic urethane, epoxy, silicone, etc.
  • Thermosetting resin or ultraviolet curable resin can be used.
  • the protective film may contain one or more of any suitable additives.
  • a cellulose resin and a (meth) acrylic resin are preferable because the fluctuation of the surface resistance value of the pressure-sensitive adhesive layer can be controlled to be small.
  • the (meth) acrylic resin it is preferable to use a (meth) acrylic resin having a lactone ring structure.
  • the (meth) acrylic resin having a lactone ring structure include JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, JP-A-2002-254544, JP-A-2005 Examples thereof include (meth) acrylic resins having a lactone ring structure described in Japanese Patent Application Laid-Open No. 146084.
  • the cellulose resin is preferable to the (meth) acrylic resin in that it is effective in suppressing the polarizer crack, which is a problem in the single-protective polarizing film.
  • a retardation film, a diffusion film, or the like can also be used.
  • the retardation film include those having a frontal retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more.
  • the front phase difference is usually controlled in the range of 40 to 200 nm
  • the thickness direction phase difference is usually controlled in the range of 80 to 300 nm.
  • the retardation film also functions as a polarizer protective film, so that the thickness can be reduced.
  • the protective film and the polarizer are laminated via an intervening layer such as an adhesive layer, an adhesive layer, and an undercoat layer (primer layer). At this time, it is desirable that both are laminated without an air gap by an intervening layer.
  • the protective film and the polarizer are preferably laminated via an adhesive layer.
  • the adhesive used for bonding the polarizer and the protective film is not particularly limited as long as it is optically transparent, and various forms such as water-based, solvent-based, hot-melt-based, radical-curing type, and cation-curing type are used. However, water-based adhesives or radical curable adhesives are suitable.
  • the first pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B).
  • the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate as a main component as a monomer unit.
  • (meth) acrylate means acrylate and / or methacrylate, and has the same meaning as (meth) of the present invention.
  • alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (A) include those having a linear or branched alkyl group having 1 to 18 carbon atoms.
  • the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group and decyl.
  • Examples thereof include a group, an isodecyl group, a dodecyl group, an isomyristyl group, a lauryl group, a tridecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group and the like. These can be used alone or in combination.
  • the average carbon number of these alkyl groups is preferably 3 to 9.
  • the weight ratio of the alkyl (meth) acrylate is preferably 70% by weight or more in terms of the weight ratio of all the constituent monomers (100% by weight) constituting the (meth) acrylic polymer (A) as a monomer unit.
  • the weight ratio of the alkyl (meth) acrylate can be considered as the balance of the other copolymerized monomers. It is preferable to set the weight ratio of the alkyl (meth) acrylate in the above range in order to ensure adhesiveness.
  • (meth) acrylic polymer (A) in addition to the above-mentioned alkyl (meth) acrylate monomer unit, unsaturated (meth) acryloyl group, vinyl group, etc. are used for the purpose of improving adhesiveness and heat resistance.
  • One or more types of copolymerizable monomers having a polymerizable functional group having a double bond can be introduced by copolymerization.
  • copolymerization monomer examples include functional group-containing monomers such as a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and an amide group-containing monomer.
  • the carboxyl group-containing monomer is a compound containing a carboxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl group.
  • Specific examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
  • acrylic acid is preferable from the viewpoint of copolymerizability, price, and adhesive properties.
  • the hydroxyl group-containing monomer is a compound containing a hydroxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyhexyl (meth) acrylate.
  • hydroxyalkyl (meth) acrylates such as hydroxyoctyl (meth) acrylates, 10-hydroxydecyl (meth) acrylates and 12-hydroxylauryl (meth) acrylates, and (4-hydroxymethylcyclohexyl) -methyl acrylates.
  • hydroxyl group-containing monomers 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, and 4-hydroxybutyl (meth) acrylate is particularly preferable, from the viewpoint of durability.
  • the carboxyl group-containing monomer and the hydroxyl group-containing monomer serve as reaction points with the cross-linking agent when the pressure-sensitive adhesive composition contains the cross-linking agent. Since the carboxyl group-containing monomer and the hydroxyl group-containing monomer are highly reactive with the intermolecular cross-linking agent, they are preferably used for improving the cohesiveness and heat resistance of the obtained first pressure-sensitive adhesive layer. Further, the carboxyl group-containing monomer is preferable in terms of achieving both durability and reworkability, and the hydroxyl group-containing monomer is preferable in terms of reworkability.
  • the weight ratio of the carboxyl group-containing monomer is preferably 10% by weight or less, more preferably 0.01 to 8% by weight, further preferably 0.05 to 6% by weight, and further preferably 0.1 to 0.1% by weight. 5% by weight is preferable. It is preferable that the weight ratio of the carboxyl group-containing monomer is 0.01% by weight or more from the viewpoint of durability. On the other hand, if it exceeds 10% by weight, it is not preferable from the viewpoint of reworkability.
  • the weight ratio of the hydroxyl group-containing monomer is preferably 3% by weight or less, more preferably 0.01 to 3% by weight, further preferably 0.1 to 2% by weight, and further 0.2 to 0.2 to 2% by weight. 2% by weight is preferable. It is preferable that the weight ratio of the hydroxyl group-containing monomer is 0.01% by weight or more from the viewpoint of cross-linking the first pressure-sensitive adhesive layer, durability and adhesive properties. On the other hand, if it exceeds 3% by weight, it is not preferable from the viewpoint of durability.
  • the amide group-containing monomer is a compound containing an amide group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl group.
  • Specific examples of the amide group-containing monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-methyl (meth) acrylamide, and N-.
  • the amide group-containing monomer is preferable in order to suppress an increase in the surface resistance value over time (particularly in a humid environment) and to satisfy the durability.
  • the N-vinyl group-containing lactam-based monomer suppresses an increase in the surface resistance value over time (particularly in a humid environment), and is a transparent conductive layer (touch sensor layer). It is preferable in terms of satisfying the durability against.
  • the weight ratio of the amide group-containing monomer increases, the anchoring property with respect to the optical film tends to decrease. Therefore, the weight ratio is preferably 10% by weight or less, more preferably 5% by weight or less. Especially preferable.
  • the weight ratio of the amide group-containing monomer is preferably 0.1% by weight or more from the viewpoint of suppressing an increase in the surface resistance value over time (particularly in a humid environment).
  • the weight ratio is preferably 0.3% by weight or more, more preferably 0.5% by weight or more.
  • the amide group-containing monomer is suitable in relation to the ionic compound (B) contained in the first pressure-sensitive adhesive layer of the present invention.
  • the amide group is said to be present. Due to the presence of the amide group, even in a humid environment, the surface resistance value of the first pressure-sensitive adhesive layer adjusted by blending the ionic compound (B) is suppressed from fluctuating and increasing, and the desired value can be obtained. It is preferable to keep it within the range.
  • phase of the (meth) acrylic polymer (A) and the ionic compound (B) due to the presence of an amide group introduced as a functional group of the copolymerization monomer in the side chain of the (meth) acrylic polymer (A). It is thought that the solubility will increase.
  • the first pressure-sensitive adhesive layer is a glass and a transparent conductive layer (ITO layer) when an amide group introduced into the side chain of the (meth) acrylic polymer (A) which is the base polymer is present. Etc.), and the durability is good, and it is possible to suppress the occurrence of peeling, floating, etc. in the state of being attached to the liquid crystal panel. Further, the durability can be satisfied even in a humidified environment (after the humidification reliability test).
  • ITO layer transparent conductive layer
  • an aromatic ring-containing (meth) acrylate As the copolymerization monomer, for example, an aromatic ring-containing (meth) acrylate can be used.
  • An aromatic ring-containing (meth) acrylate is a compound having an aromatic ring structure in its structure and containing a (meth) acryloyl group. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring.
  • aromatic ring-containing (meth) acrylate examples include, for example, benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxypropyl.
  • benzene ring such as acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, cresyl (meth) acrylate, polystyryl (meth) acrylate; hydroxyethylated ⁇ -naphthol acrylate, 2-naphthoethyl (meth) acrylate , 2-naphthoxyethyl acrylate, 2- (4-methoxy-1-naphthoxy) ethyl (meth) acrylate or the like having a naphthalene ring; examples thereof include
  • aromatic ring-containing (meth) acrylate benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable, and phenoxyethyl (meth) acrylate is particularly preferable, from the viewpoint of adhesive properties and durability.
  • the weight ratio of the aromatic ring-containing (meth) acrylate is preferably 25% by weight or less, more preferably 3 to 25% by weight, further preferably 10 to 22% by weight, and further preferably 14 to 20% by weight. Is preferable.
  • the weight ratio of the aromatic ring-containing (meth) acrylate is 3% by weight or more, it is preferable in order to suppress display unevenness. On the other hand, if it exceeds 25% by weight, the display unevenness is not sufficiently suppressed, and the durability tends to decrease.
  • copolymerization monomers other than the above include; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; allylsulfonic acid, 2- (meth) acrylamide-2. -Sulfonic acid group-containing monomers such as methylpropanesulfonic acid, (meth) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate; and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate.
  • acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride
  • caprolactone adducts of acrylic acid allylsulfonic acid, 2- (meth) acrylamide-2.
  • -Sulfonic acid group-containing monomers such as methylpropanesulfonic acid, (meth) acrylamide propanesulfonic acid, sulfo
  • alkylaminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl ( Alkoxyalkyl (meth) acrylates such as meta) acrylates; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, etc.
  • Succinimide-based monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide and N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N- Itaconimide-based monomers such as octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide are also mentioned as examples of monomers for modification purposes.
  • a vinyl-based monomer such as vinyl acetate and vinyl propionate; a cyanoacrylate-based monomer such as acrylonitrile and methacrylonitrile; an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate; and polyethylene glycol (meth).
  • Glycol-based (meth) acrylates such as acrylates, polypropylene glycol (meth) acrylates, methoxyethylene glycol (meth) acrylates, and methoxypolypropylene glycol (meth) acrylates; tetrahydrofurfuryl (meth) acrylates, fluorine (meth) acrylates, silicones (meth).
  • (Meta) acrylate monomers such as acrylate and 2-methoxyethyl acrylate can also be used. Further, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.
  • examples of copolymerizable monomers other than the above include silane-based monomers containing a silicon atom.
  • examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
  • 8-Vinyloctyloxydecyltriethoxysilane 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane and the like.
  • copolymerization monomer examples include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and neo.
  • the proportion of the other copolymerized monomer in the (meth) acrylic polymer (A) is about 0 to 10% by weight based on the weight ratio of all the constituent monomers (100% by weight) of the (meth) acrylic polymer (A). Further, it is preferably about 0 to 7% by weight, more preferably about 0 to 5% by weight.
  • the (meth) acrylic polymer (A) of the present invention usually preferably has a weight average molecular weight of 1 million to 2.5 million. Considering durability, particularly heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. When the weight average molecular weight is 1 million or more, it is preferable from the viewpoint of heat resistance. Further, when the weight average molecular weight is larger than 2.5 million, the adhesive tends to be hard and peeling is likely to occur.
  • the weight average molecular weight (Mw) / number average molecular weight (Mn) which indicates the molecular weight distribution, is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, and further 1.8 to. It is preferably 5.
  • the weight average molecular weight and the molecular weight distribution (Mw / Mn) are measured by GPC (gel permeation chromatography) and obtained from the values calculated by polystyrene conversion.
  • the obtained (meth) acrylic polymer (A) may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • solution polymerization for example, ethyl acetate, toluene and the like are used as the polymerization solvent.
  • the reaction is carried out under an inert gas stream such as nitrogen, a polymerization initiator is added, and usually at about 50 to 70 ° C. under reaction conditions of about 5 to 30 hours.
  • the polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not particularly limited and can be appropriately selected and used.
  • the weight average molecular weight of the (meth) acrylic polymer (A) can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types. To.
  • ionic compound (B) contained in the pressure-sensitive adhesive composition forming the first pressure-sensitive adhesive layer of the present invention a compound having a cation component with a molecular weight of 210 or less is used.
  • the molecular weight of the cation component is preferably 150 or less, more preferably 110 or less, and further preferably 50 or less. It is preferable, and more preferably 10 or less. The larger the molecular weight of the cation component, the more the (meth) acrylic polymers in the pressure-sensitive adhesive layer are prevented from being entangled with each other, and the physical properties of the pressure-sensitive adhesive layer tend to be softened.
  • an alkali metal salt and / or an organic cation-anionic salt can be preferably used.
  • the alkali metal salt organic salts and inorganic salts of alkali metals can be used.
  • the term "organic cation-anionic salt” as used in the present invention refers to an organic salt whose cation component is composed of an organic substance, and the anion component may be an organic substance or an inorganic substance. There may be.
  • the "organic cation-anionic salt” is also referred to as an ionic liquid or an ionic solid.
  • the surface resistance value of the first pressure-sensitive adhesive layer can be lowered to suppress the generation of static electricity, and the orientation of the liquid crystal layer due to electrification is disturbed. Therefore, it is possible to suppress the occurrence of light leakage (charge unevenness).
  • alkali metal ions constituting the cationic component of the alkali metal salt include lithium, sodium, and potassium ions. Among these alkali metal ions, lithium ions are preferable.
  • the anionic component of the alkali metal salt may be composed of an organic substance or an inorganic substance.
  • the anion components constituting the organic salt include CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 3 C ⁇ , C 4 F 9 SO 3 -, C 3 F 7 COO - , (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, PF 6 -, CO 3 2-, or the following general formula ( 1) to (4), (1) :( C n F 2n + 1 SO 2) 2 N - ( where, n is an integer of 0 to 10), (2): CF 2 (C m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10), (3): - O 3 S (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10), (4): (C p F
  • an anionic component containing a fluorine atom is preferably used because an ionic compound having good ionic dissociation property can be obtained.
  • the anionic component constituting the inorganic salts, Cl -, Br -, I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, (CN) 2 N -, and the like can be used.
  • anionic component (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, wherein represented by formula (1) etc., (perfluoroalkyl sulfonyl) imide are preferable, especially ( A (trifluoromethanesulfonyl) imide represented by CF 3 SO 2 ) 2 N ⁇ is preferred.
  • organic salt of the alkali metal examples include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, and Li (CF 3 SO 2).
  • Inorganic salts of alkali metals include lithium perchlorate and lithium iodide.
  • 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.
  • the cation component include pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, and dihydropyrimidinium cation.
  • Examples thereof include pyrazolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation and the like.
  • the anionic component e.g., Cl -, Br -, I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, (CN) 2 N -, C 4 F 9 SO 3 ⁇ , C 3 F 7 COO ⁇ , ((CF 3 SO 2 ) (CF 3 CO) N ⁇ , ⁇ O 3 S (CF 2 ) 3 SO 3 ⁇ , and the following general formulas (1) to (4) ), (1) :( C n F 2n + 1 SO 2) 2 N - ( where, n is an integer of 0 to 10), (2): CF 2 (C m F 2m SO 2) 2 N - ( where,
  • organic cation-anion salt a compound composed of a combination of the above cation component and an anion component is appropriately selected and used.
  • Preferred specific examples of the organic cation-anionic salt include, for example, methyltrioctylammonium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, and ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide. Fluorosulfonylimide). Of these, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide and ethyl methylimidazolium bis (fluorosulfonylimide) are more preferable.
  • inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferric chloride, ferric chloride and ammonium sulfate Can be mentioned.
  • alkali metal ions such as lithium, sodium, and potassium are cationic components having a molecular weight of 210 or less. Therefore, alkali metals containing these alkali metal ions as cationic components. Salt can be preferably used.
  • an organic salt of an alkali metal in which the anionic component of the alkali metal salt is composed of an organic substance is preferable.
  • the alkali metal ion lithium ion having the smallest molecular weight is preferable.
  • a lithium salt is preferable, and an organic salt of lithium is particularly preferable.
  • the ionic compound (B) is an organic cation-anion salt
  • a molecular weight of 210 or less can be selected and used from the above-exemplified cation components.
  • an organic cation-anion salt in which the anion component is composed of an organic substance is preferable.
  • the ionic compound (B) can be used alone or in combination of two or more in order to obtain a desired resistance value.
  • an alkali metal salt is used as the ionic compound (B). It is preferable in terms of enhancing the antistatic performance, and by using an alkali metal salt, a pressure-sensitive adhesive having a high antistatic performance can be obtained even with a small number of compounding parts.
  • the ionic compound (B) is an organic cation-anion.
  • the salt is preferable in that it enhances the antistatic performance, and by using the organic cation-ionic salt, a pressure-sensitive adhesive having a high antistatic performance can be obtained even with a smaller number of compounding parts.
  • the proportion of the ionic compound (B) in the pressure-sensitive adhesive composition of the present invention can be appropriately adjusted so as to satisfy the antistatic properties of the first pressure-sensitive adhesive layer and the sensitivity of the touch panel.
  • touch sensing while considering the type of protective film of the polarizing film so that the surface resistance value of the first pressure-sensitive adhesive layer is in the range of 1.0 ⁇ 10 8 to 1.0 ⁇ 10 12 ⁇ / ⁇ .
  • the initial surface resistance value of the first adhesive layer is controlled in the range of 1 ⁇ 10 8 to 1 ⁇ 10 11 ⁇ / ⁇ . Is preferable.
  • the surface resistance value of the first pressure-sensitive adhesive layer 2 is 1 ⁇ 10 8 to 1 ⁇ 10 from the viewpoint of antistatic function and touch sensor sensitivity. It is preferably 12 ⁇ / ⁇ , preferably 1 ⁇ 10 8 to 1 ⁇ 10 11 ⁇ / ⁇ , and more preferably 1 ⁇ 10 8 to 1 ⁇ 10 10 ⁇ .
  • the ratio of the ionic compound (B) is, for example, preferably 40 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer (A). Is preferable, and more preferably 13 parts by weight or less.
  • the ionic compound (B) is preferably 1 part by weight or more, more preferably 5 parts by weight or more.
  • the pressure-sensitive adhesive composition of the present invention can contain a cross-linking agent (C).
  • a cross-linking agent C
  • an organic cross-linking agent or a polyfunctional metal chelate can be used.
  • the organic cross-linking agent include isocyanate-based cross-linking agents, peroxide-based cross-linking agents, epoxy-based cross-linking agents, and imine-based cross-linking agents.
  • a polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinated to an organic compound.
  • Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti and the like. Can be mentioned.
  • Examples of the atom in the organic compound having a covalent bond or a coordination bond include an oxygen atom and the like, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound and a ketone compound.
  • cross-linking agent (C) an isocyanate-based cross-linking agent and / or a peroxide-based cross-linking agent is preferable.
  • isocyanate-based cross-linking agent (C) a compound having at least two isocyanate groups can be used.
  • known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, etc., which are generally used for urethanization reactions, are used.
  • any peroxide that generates radically active species by heating or light irradiation to promote cross-linking of the base polymer of the pressure-sensitive adhesive composition can be appropriately used, but in consideration of workability and stability. It is preferable to use a peroxide having a half-life temperature of 80 ° C. to 160 ° C. for 1 minute, and more preferably to use a peroxide having a half-life temperature of 90 ° C. to 140 ° C.
  • peroxide examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.) and di (4-t-butylcyclohexyl) peroxydicarbonate (1).
  • the amount of the cross-linking agent (C) used is preferably 3 parts by weight or less, more preferably 0.01 to 3 parts by weight, and further 0.02 with respect to 100 parts by weight of the (meth) acrylic polymer (A). It is preferably from 2 parts by weight, more preferably 0.03 to 1 part by weight. If the amount of the cross-linking agent (C) is less than 0.01 parts by weight, the first pressure-sensitive adhesive layer may be insufficiently cross-linked and the durability and adhesive properties may not be satisfied. On the other hand, if the amount is more than 3 parts by weight, the first pressure-sensitive adhesive layer may not be satisfied. There is a tendency for the pressure-sensitive adhesive layer to become too hard and reduce its durability.
  • the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent (D).
  • Durability can be improved by using the silane coupling agent (D).
  • Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3, 4-Epylcyclohexyl) Epyl group-containing silane coupling agent such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N- (1,3-dimethylbutylidene) propylamine and N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxy
  • Examples thereof include (meth) acrylic group-containing silane coupling agents such as ethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanuppropyltriethoxysilane.
  • an epoxy group-containing silane coupling agent is preferable.
  • silane coupling agent (D) one having a plurality of alkoxysilyl groups in the molecule can also be used.
  • a silane coupling agent having a plurality of alkoxysilyl groups in these molecules is preferable because it is difficult to volatilize and has a plurality of alkoxysilyl groups, which is effective in improving durability.
  • the adherend of the optical film with the pressure-sensitive adhesive layer is a transparent conductive layer (for example, ITO or the like) in which the alkoxysilyl group is less likely to react than glass.
  • the silane coupling agent having a plurality of alkoxysilyl groups in the molecule preferably has an epoxy group in the molecule, and more preferably has a plurality of epoxy groups in the molecule.
  • a silane coupling agent having a plurality of alkoxysilyl groups in the molecule and having an epoxy group tends to have good durability even when the adherend is a transparent conductive layer (for example, ITO).
  • silane coupling agent having a plurality of alkoxysilyl groups in the molecule and having an epoxy group examples include X-41-1053, X-41-1059A, and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd.
  • X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. which has a high epoxy group content, is preferable.
  • the silane coupling agent (D) may be used alone or in combination of two or more, but the content as a whole is the (meth) acrylic polymer (A) 100. It is preferably 5 parts by weight or less, more preferably 0.001 to 5 parts by weight, further preferably 0.01 to 1 part by weight, still more preferably 0.02 to 1 part by weight, and further. Is preferably 0.05 to 0.6 parts by weight. It is an amount that improves durability.
  • the pressure-sensitive adhesive composition of the present invention may contain other known additives, for example, a polyether compound having a reactive silyl group, a polyether compound of polyalkylene glycol such as polypropylene glycol, and coloring. Powders of agents, pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization prohibited Agents, inorganic or organic fillers, metal powders, particles, foils and the like can be appropriately added depending on the intended use. Further, a redox system to which a reducing agent is added may be adopted within a controllable range. These additives are preferably used in a range of 5 parts by weight or less, further 3 parts by weight or less, and further 1 part by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (A).
  • a polyether compound having a reactive silyl group such as polypropylene glycol
  • the pressure-sensitive adhesive composition is applied to a peel-treated separator or the like, and a polymerization solvent or the like is dried and removed to form the first pressure-sensitive adhesive layer, and then an optical film (polarization) is formed. It is produced by a method of transferring to a film), or a method of applying the pressure-sensitive adhesive composition to an optical film (polarizing film) and drying and removing a polymerization solvent or the like to form a first pressure-sensitive adhesive layer on the optical film.
  • one or more solvents other than the polymerization solvent may be newly added as appropriate.
  • the thickness of the first pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100 ⁇ m. It is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and even more preferably 5 to 35 ⁇ m.
  • the thickness of the first pressure-sensitive adhesive layer 2 is preferably 5 to 100 ⁇ m, preferably 5 to 50 ⁇ m, and further 10 to 35 ⁇ m from the viewpoint of ensuring durability and securing a contact area with the conductive structure on the side surface. Is preferable.
  • the anchor layer can be formed of various materials.
  • the thickness of the anchor layer is preferably 0.01 to 0.5 ⁇ m, preferably 0.01 to 0.2 ⁇ m, and further preferably 0.01 to 0.1 ⁇ m.
  • the surface resistance value thereof is preferably 1 ⁇ 10 6 to 1 ⁇ 10 9 ⁇ / ⁇ from the viewpoint of the antistatic function.
  • the conductive anchor layer can be formed from various antistatic agent compositions.
  • an ionic surfactant system, a conductive polymer, conductive fine particles and the like are preferable.
  • the conductive polymer is preferably used from the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heat and humidification.
  • conductive polymers such as polyaniline and polythiophene are preferably used.
  • an organic solvent-soluble, water-soluble, or water-dispersible polymer can be appropriately used, but a water-soluble conductive polymer or a water-dispersible conductive polymer is preferably used.
  • the water-soluble conductive polymer and the water-dispersible conductive polymer can be prepared as an aqueous solution or an aqueous dispersion as a coating liquid for forming an antistatic layer, and the coating liquid does not need to use a non-aqueous organic solvent and is organic. This is because the deterioration of the optical film base material due to the solvent can be suppressed.
  • the aqueous solution or the aqueous dispersion can contain an aqueous solvent in addition to water.
  • -Alcohols such as propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and the like can be mentioned.
  • 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.
  • the hydrophilic functional group include a sulfon group, an amino group, an amide group, an imino group, a quaternary ammonium base, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate ester group, a phosphoric acid ester group, or a salt thereof. And so on.
  • a hydrophilic functional group in the molecule it becomes easy to be dissolved in water or dispersed in water in the form of fine particles, and the water-soluble conductive polymer or the water-dispersible conductive polymer can be easily prepared.
  • Examples of commercially available water-soluble conductive polymers include polyaniline sulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight of 150,000 in terms of polystyrene).
  • Examples of commercially available water-dispersible conductive polymers include polythiophene-based conductive polymers (manufactured by Nagase Chemtech, trade name, Denatron series).
  • a binder component can be added together with the antistatic agent for the purpose of improving the film-forming property of the antistatic agent and the adhesion to the optical film.
  • the antistatic agent is a water-soluble conductive polymer or a water-based material of the water-dispersible conductive polymer
  • a water-soluble or water-dispersible binder component is used.
  • binders include oxazoline group-containing polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone, polystyrene resins, polyethylene glycol, etc. Examples include pentaerythritol.
  • polyurethane-based resins, polyester-based resins, and acrylic-based resins are preferable.
  • One or two or more of these binders can be appropriately used according to the intended use.
  • the amount of the antistatic agent and the binder used depends on their types, but it is preferable to control the surface resistance value of the obtained anchor layer to be 1 ⁇ 10 6 to 1 ⁇ 10 9 ⁇ / ⁇ .
  • a functional layer such as a hard coat layer, an antiglare treatment layer, an antireflection layer, an antisticking layer or an antiglare layer can be provided.
  • the surface treatment layer can be provided on a surface of the protective film to which the polarizer is not adhered.
  • the surface resistance value of the surface treatment layer 4 is 1 ⁇ 10 7 to 1 ⁇ 10 11 ⁇ / ⁇ from the viewpoint of antistatic function and touch sensor sensitivity. It is preferably 1 ⁇ 10 7 to 1 ⁇ 10 10 ⁇ / ⁇ , and more preferably 1 ⁇ 10 7 to 1 ⁇ 10 9 ⁇ .
  • the surface treatment layer When imparting conductivity to the surface treatment layer, the surface treatment layer is preferably formed so that the surface resistance value is 1 ⁇ 10 7 to 1 ⁇ 10 11 ⁇ / ⁇ .
  • Conductivity can be imparted to the surface treatment layer by containing an antistatic agent.
  • the surface treatment layer can be provided on the protective film used for the first polarizing film, or can be provided separately from the protective film.
  • the antistatic agent used to impart conductivity to the surface treatment layer those exemplified above can be used, but at least one selected from an ionic surfactant, conductive fine particles and a conductive polymer. It is preferable to contain one type.
  • the antistatic agent used for the surface treatment layer is preferably conductive fine particles from the viewpoint of optical characteristics, appearance, antistatic effect, and stability of the antistatic effect during heat and humidification.
  • the surface treatment layer is preferably a hard coat layer.
  • a thermoplastic resin or a material that is cured by heat or radiation can be used as the material for forming the hard coat layer.
  • the material include radiation-curable resins such as thermosetting resins, ultraviolet curable resins, and electron beam curable resins.
  • 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.
  • these curable resins include various types such as polyester-based, acrylic-based, urethane-based, amide-based, silicone-based, epoxy-based, and melamine-based resins, and include these monomers, oligomers, and polymers.
  • a radiation-curable resin particularly an ultraviolet-curable resin
  • the ultraviolet curable resin preferably used include those having an ultraviolet polymerizable functional group, and among them, those containing an acrylic monomer or an oligomer component having 2 or more, particularly 3 to 6 of the functional groups. Further, the ultraviolet curable resin contains a photopolymerization initiator.
  • an antiglare treatment layer or an antireflection layer for the purpose of improving visibility can be provided.
  • an antiglare treatment layer and an antireflection layer can be provided on the hard coat layer.
  • the constituent material of the antiglare treatment 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 and the like are used.
  • a plurality of antireflection layers can be provided.
  • examples of the surface treatment layer include a sticking prevention layer and the like.
  • the thickness of the surface treatment layer can be appropriately set depending on the type of the surface treatment layer, but is generally preferably 0.1 to 100 ⁇ m.
  • the thickness of the hard coat layer is preferably 0.5 to 20 ⁇ m.
  • the thickness of the hard coat layer is not particularly limited, but if it is too thin, sufficient hardness as a hard coat layer cannot be obtained, while if it is too thick, cracks and peeling are likely to occur.
  • the thickness of the hard coat layer is more preferably 1 to 10 ⁇ m.
  • the amount of antistatic agent and binder (resin material, etc.) used in the surface treatment layer depends on their types, but the surface resistance value of the obtained surface treatment layer is 1 ⁇ 10 7 to 1 ⁇ 10 11 ⁇ / It is preferable to control so as to be ⁇ .
  • the amount of the binder is 1000 parts by weight or less, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the antistatic agent.
  • an easy-adhesive layer is provided on the surface of the first polarizing film on the side where the anchor layer is provided, and various easy-adhesion such as corona treatment and plasma treatment are performed. It can be processed.
  • liquid crystal cell B and the liquid crystal panel C will be described below.
  • the liquid crystal cell B includes a liquid crystal layer 20 containing liquid crystal molecules homogenically oriented in the absence of an electric field, a first transparent substrate 41 and a second transparent substrate 42 sandwiching the liquid crystal layer 20 on both sides. Have. In FIG. 3, the electrodes in the liquid crystal cell B are omitted.
  • liquid crystal layer 20 used in the liquid crystal cell B a liquid crystal layer containing liquid crystal molecules homogenically oriented in the absence of an electric field is used.
  • liquid crystal layer 20 for example, an IPS type liquid crystal layer is preferably used.
  • any type of liquid crystal layer such as TN type, STN type, ⁇ type, or VA type can be used.
  • the thickness of the liquid crystal layer 20 is, for example, about 1.5 ⁇ m to 4 ⁇ m.
  • Examples of the material for forming the transparent substrate include glass or a polymer film.
  • Examples of the polymer film include polyethylene terephthalate, polycycloolefin, polycarbonate and the like.
  • When the transparent substrate is made of glass its thickness is, for example, about 0.1 mm to 1 mm.
  • the transparent substrate may have an easy-adhesion layer or a hard coat layer on its surface.
  • the in-cell liquid crystal cell B As the liquid crystal cell B, the in-cell type liquid crystal cell B shown in FIGS. 4 to 8 can be used.
  • the in-cell liquid crystal cell B also has a touch sensor and a touch sensing electrode portion related to a touch drive function between the first transparent substrate 41 and the second transparent substrate 42.
  • the touch sensing electrode portion can be formed by the touch sensor electrode 31 and the touch drive electrode 32.
  • the touch sensor electrode referred to here refers to a touch detection (reception) electrode.
  • the touch sensor electrode 31 and the touch drive electrode 32 can be independently formed by various patterns. For example, when the in-cell type liquid crystal cell B is a flat surface, it can be arranged in a pattern that intersects at a right angle by a form provided independently in the X-axis direction and the Y-axis direction, respectively. Further, in FIGS. 4, 5, and 8, the touch sensor electrode 31 is arranged on the side (visual side) of the first transparent substrate 41 with respect to the touch drive electrode 32, but the opposite is true.
  • the touch drive electrode 32 may be arranged closer to the first transparent substrate 41 (visual recognition side) than the touch sensor electrode 31.
  • an electrode 33 in which a touch sensor electrode and a touch drive electrode are integrally formed can be used.
  • the touch sensing electrode portion can be arranged between the liquid crystal layer 20 and the first transparent substrate 41 or the second transparent substrate 42.
  • 4 and 6 show a case where the touch sensing electrode portion is arranged between the liquid crystal layer 20 and the first transparent substrate 41 (on the visual side of the liquid crystal layer 20).
  • 5 and 7 show a case where the touch sensing electrode portion is arranged between the liquid crystal layer 20 and the second transparent substrate 42 (on the backlight side of the liquid crystal layer 20).
  • the touch sensing electrode portion has a touch sensor electrode 31 between the liquid crystal layer 20 and the first transparent substrate 41, and the liquid crystal layer 20 and the second transparent substrate 42 A touch drive electrode 32 may be provided between them.
  • the drive electrode (the electrode 33 in which the touch drive electrode 32, the touch sensor electrode, and the touch drive electrode are integrally formed) in the touch sensing electrode portion can also be used as a common electrode for controlling the liquid crystal layer 20.
  • the in-cell type liquid crystal cell B has a touch sensor and a touch sensing electrode portion related to the touch drive function in the liquid crystal cell, and does not have a touch sensor electrode outside the liquid crystal cell. That is, the conductive layer (surface resistance value is 1 ⁇ 10 13 ⁇ /) is on the visible side of the in-cell liquid crystal cell B from the first transparent substrate 41 (on the liquid crystal cell side of the first adhesive layer 2 of the in-cell liquid crystal panel C). ⁇ Below) is not provided.
  • the in-cell liquid crystal panel C shown in FIGS. 4 to 8 shows the order of each configuration, the in-cell liquid crystal panel C may have other configurations as appropriate.
  • a color filter substrate can be provided on the liquid crystal cell (first transparent substrate 41).
  • the touch sensor electrode 31 (capacitance sensor), the touch drive electrode 32, or the electrode 33 in which the touch sensor electrode and the touch drive electrode are integrally formed, which form the touch sensing electrode portion, are formed as a transparent conductive layer.
  • the constituent material of the transparent conductive layer is not particularly limited, and for example, metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, and tungsten, and metals such as these metals. Examples include alloys.
  • Examples of the constituent material of the transparent conductive layer include metal oxides of indium, tin, zinc, gallium, antimony, zirconium, and cadmium, and specifically, indium oxide, tin oxide, titanium oxide, cadmium oxide, and these. Examples thereof include metal oxides composed of a mixture of the above. In addition, other metal compounds such as copper iodide are used. The metal oxide may further contain oxides of the metal atoms shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used. The ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
  • ITO indium oxide
  • the electrodes (touch sensor electrode 31, touch drive electrode 32, touch sensor electrode, and touch drive electrode 33 integrally formed) related to the touch sensing electrode portion are usually the first transparent substrate 41 and / or the second transparent electrode. It can be formed as a transparent electrode pattern on the inside of the substrate 42 (on the liquid crystal layer 20 side in the in-cell type liquid crystal cell B) by a conventional method.
  • the transparent electrode pattern is usually electrically connected to a routing wire (not shown) formed at the end of the transparent substrate, and the routing wire is connected to a controller IC (not shown).
  • a routing wire not shown
  • any shape such as a stripe shape or a rhombus shape can be adopted depending on the application.
  • the height of the transparent electrode pattern is, for example, 10 nm to 100 nm, and the width is 0.1 mm to 5 mm.
  • the liquid crystal panel C of the present invention may have the polarizing film A with an adhesive layer on the visible side of the liquid crystal cell B and the second polarizing film 11 on the opposite side.
  • FIGS. 4 to 8 show an in-cell type liquid crystal panel using the in-cell type liquid crystal cell B.
  • the polarizing film A with an adhesive layer is arranged on the side of the first transparent substrate 41 of the liquid crystal cell B via the first adhesive layer 2 without interposing a conductive layer.
  • the second polarizing film 11 is arranged on the side of the second transparent substrate 42 of the liquid crystal cell B via the second pressure-sensitive adhesive layer 12.
  • 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.
  • the second polarizing film 11 the one described in the first polarizing film 1 can be used.
  • the same one as the first polarizing film 1 may be used, or a different one may be used.
  • the pressure-sensitive adhesive described in the first pressure-sensitive adhesive layer 2 can be used for forming the second pressure-sensitive adhesive layer 12.
  • the same pressure-sensitive adhesive as the first pressure-sensitive adhesive layer 2 may be used, or a different pressure-sensitive adhesive may be used.
  • the thickness of the second pressure-sensitive adhesive layer 12 is not particularly limited, and is, for example, about 1 to 100 ⁇ m. It is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and even more preferably 5 to 35 ⁇ m.
  • a conductive structure 50 is provided on the side surface of the polarizing film A with an adhesive layer. If the conductive structure 50 is provided on the side surface of the first pressure-sensitive adhesive layer 2 containing an ionic compound, it is optional to provide the conductive structure on the side surface of the anchor layer 3. Further, in FIG. 3 (FIGS. 4 to 8), in addition to the conductive structure 50, a case where the conductive structure 51 is provided on the side surface of the surface treatment layer 4 and the first polarizing film 1 is illustrated, but the conductive structure 51 is provided. It is optional to provide the structure 51. The conductive structure is preferably provided when each layer has conductivity.
  • the conductive structures 51 and 50 may be provided on all of the side surfaces of the polarizing film A with an adhesive layer, or may be provided on a part of the side surfaces. When the conductive structure is partially provided, in order to ensure continuity on the side surface, 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. preferable. On the other hand, from the viewpoint of wiring, the conduction structure is preferably 99 area% or less of the side surface, and more preferably 95 area% or less.
  • the conductive structures 51 and 50 are preferably provided at least on the side surface of the polarizing film A with an adhesive layer at a point b (the amount of dimensional change of 400 ⁇ m or less) shown in FIG.
  • the generation of static electricity can be suppressed by connecting an electric potential from the side surface of the polarizing film A with an adhesive layer to another suitable location.
  • the material forming the conductive structures 51 and 50 include conductive pastes such as silver, gold and other metal pastes, and other conductive adhesives and any other suitable conductive material can be used. ..
  • the conductive structures 51 and 50 can also be formed in a linear shape extending from the side surface of the polarizing film A with an adhesive layer.
  • first polarizing film 1 arranged on the visible side of the liquid crystal layer 20 and the second polarizing film 11 arranged on the opposite side of the liquid crystal layer 20 on the visible side may be other depending on the suitability of the respective arrangement locations.
  • Optical films can be laminated and used. Examples of the other optical film include forming a liquid crystal display device such as a reflecting plate, an antitransmissive plate, a retardation film (including a wave plate such as 1/2 or 1/4), a visual compensation film, and a brightness improving film.
  • liquid crystal display device In the liquid crystal display device using the liquid crystal panel C of the present invention, a member forming the liquid crystal display device such as a lighting system using a backlight or a reflector can be appropriately used.
  • HLC-8120GPC manufactured by Tosoh Corporation -Column: Made by Tosoh, G7000H XL + GMH XL + GMH XL -Column size: 7.8 mm ⁇ x 30 cm each 90 cm in total -Column temperature: 40 ° C ⁇
  • ⁇ Manufacturing example 1> (Preparation of 40 ⁇ m TAC film with HC and 25 ⁇ m TAC film with HC) A solution in a resin solution (manufactured by DIC Co., Ltd., trade name: Unidic 17-806, solid content concentration: 80%) in which an ultraviolet curable resin monomer or oligomer containing urethane acrylate as a main component is dissolved in butyl acetate.
  • Add 5 parts of photopolymerization initiator BASF Co., Ltd., trade name: IRGACURE907
  • leveling agent DIC Co., Ltd., trade name: GRANDIC PC4100
  • cyclopentanone and propylene glycol monomethyl ether were added to the solution at a ratio of 45:55 so that the solid content concentration in the solution was 36% to prepare a hard coat layer forming material.
  • the produced hard coat layer forming material is applied onto TJ40UL (manufactured by Fujifilm, raw material: triacetyl cellulose-based polymer, thickness: 40 ⁇ m) so that the thickness of the hard coat layer after curing is 7 ⁇ m to form a coating film. did. Then, the coating film is dried at 90 ° C.
  • a 40 ⁇ m TAC film with HC was prepared.
  • ⁇ Manufacturing example 2> (Preparation of 30 ⁇ m acrylic film) 8,000 g of methyl methacrylate (MMA) and 2,000 g of methyl 2- (hydroxymethyl) acrylate (MHMA) in a 30 L pot-type reactor equipped with a stirrer, temperature sensor, cooling tube, and nitrogen introduction tube. ), 10,000 g of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK), and 5 g of n-dodecyl mercaptan were charged, and the temperature was raised to 105 ° C. and refluxed while passing nitrogen through the mixture.
  • MMA methyl methacrylate
  • MHMA methyl 2- (hydroxymethyl) acrylate
  • t-butylperoxyisopropyl carbonate (Kayacarboxylic BIC-7, manufactured by Kayaku Akzo Corporation) was added, and at the same time, a solution consisting of 10.0 g of t-butylperoxyisopropyl carbonate and 230 g of MIBK was added. Solution polymerization was carried out at about 105 to 120 ° C. under reflux while dropping over 4 hours, and aging was further carried out over 4 hours.
  • a stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added, and cyclization condensation was carried out at about 90 to 120 ° C. for 5 hours under reflux. The reaction was carried out.
  • the obtained polymer solution was subjected to a vent type screw twin-screw extruder having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a reduced pressure of 13.3 to 400 hPa (10 to 300 mmHg), one rear vent, and four fore vents.
  • the lactone ring-containing polymer had a weight average molecular weight of 133,000, a melt flow rate of 6.5 g / 10 min, and a glass transition temperature of 131 ° C.
  • the obtained pellets and acrylonitrile-styrene (AS) resin (Toyo SAS20, manufactured by Toyo Styrene Co., Ltd.) are kneaded and extruded at a mass ratio of 90/10 using a single-screw extruder (screw 30 mm ⁇ ). , Clear pellets were obtained.
  • the glass transition temperature of the obtained pellet was 127 ° C.
  • This pellet was melt-extruded from a coat hanger type T die having a width of 400 mm using a 50 mm ⁇ single-screw extruder to prepare a film having a thickness of 120 ⁇ m.
  • a stretched film (30 ⁇ m acrylic film) having a thickness of 30 ⁇ m is obtained by stretching the produced film 2.0 times in length and 2.0 times in width under a temperature condition of 150 ° C. using a biaxial stretching device. Obtained.
  • the total light transmittance was 93%
  • the in-plane retardation ⁇ nd was 0.8 nm
  • the thickness direction retardation Rth was 1.5 nm.
  • ⁇ Preparation of polarizing film (1)> A polyvinyl alcohol film having a thickness of 45 ⁇ m was dyed between rolls having different speed ratios in an iodine solution at 30 ° C. and a 0.3% concentration for 1 minute, and stretched up to 3 times. Then, the total stretching ratio was stretched to 6 times while being immersed in an aqueous solution containing boric acid having a concentration of 4% and potassium iodide at a concentration of 10% for 0.5 minutes at 60 ° C. Then, it was washed by immersing it in an aqueous solution containing potassium iodide having a concentration of 1.5% at 30 ° C. for 10 seconds, and then dried at 50 ° C.
  • a polarizing film (1) was prepared by laminating with an alcohol-based adhesive.
  • ⁇ Preparation of polarizing film (2)> (Preparation of thin polarizer A) Amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a water absorption rate of 0.75% and a Tg of 75 ° C. One side of the base material is subjected to corona treatment, and the corona treated surface is made of polyvinyl.
  • IPA copolymerized PET polyethylene terephthalate
  • a polyvinyl alcohol-based resin layer having a thickness of 11 ⁇ m was formed by applying and drying an aqueous solution containing the trade name “Gosephimmer Z200”) at a ratio of 9: 1 at 25 ° C. to prepare a laminate.
  • the obtained laminate was uniaxially stretched at the free end in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (aerial auxiliary stretching treatment).
  • the laminate was immersed in an insolubilizing bath at a liquid temperature of 30 ° C. (an aqueous boric acid solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
  • the polarizing plate was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance.
  • iodine 0.2 parts by weight of iodine was mixed with 100 parts by weight of water, and 1.0 part by weight of potassium iodide was mixed and immersed in the obtained iodine aqueous solution for 60 seconds (dyeing treatment). .. Next, it was immersed in a cross-linked bath at a liquid temperature of 30 ° C. (an aqueous boric acid solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds. (Crossing treatment). Then, the laminate is immersed in an aqueous solution of boric acid having a liquid temperature of 70 ° C.
  • UV curable adhesive 25 ⁇ m TAC with HC obtained in Production Example 1 while applying the ultraviolet curable adhesive to the surface of the polarizer A of the optical film laminate so that the thickness of the adhesive layer after curing is 1 ⁇ m.
  • ultraviolet rays were irradiated as active energy rays to cure the adhesive.
  • the amorphous PET substrate was peeled off to prepare a polarizing film (2) using a thin polarizer.
  • the optical characteristics of the obtained polarizing film were a simple substance transmittance of 42.8% and a degree of polarization of 99.99%.
  • the iodine concentration of the polarizer according to the polarizing film (1) obtained above was 3.2% by weight. Further, the iodine concentration of the polarizer according to the polarizing film (2) obtained above was 7.2% by weight.
  • the iodine concentration (% by weight) of the polarizer can be adjusted by immersing a polyvinyl alcohol-based film or a polyvinyl alcohol layer in an aqueous iodine solution having a predetermined concentration for a predetermined time during the production of the polarizer.
  • the iodine concentration of each polarizer of the polarizing film (1) shown in Table 2 was adjusted by changing the concentration of the iodine solution for dyeing the polyvinyl alcohol film when the polarizing film (1) was prepared.
  • ⁇ Polarizer film thickness The film thickness ( ⁇ m) of the polarizer was measured using a spectroscopic film thickness meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.).
  • the polarizer contained in the sample was taken out by immersing the sample in a solvent and dissolving the polarizing element protective film.
  • the solvent for example, dichloromethane was used when the polarizer protective film was a triacetyl cellulose film, and methyl ethyl ketone was used when the polarizer protective film was an acrylic film. If the resin of the polarizer protective film provided on one surface of the polarizer and the resin of the polarizer protective film provided on the other surface are different, the respective resins are used as the above-mentioned solvent. Was sequentially dissolved using.
  • the iodine concentration of the polarizer is measured by the following method.
  • the polarizer contained in the sample was taken out by immersing the sample in a solvent and dissolving the polarizer protective film in the same manner as when measuring the film thickness of the polarizer.
  • fluorescent X-ray measurement When measuring the iodine concentration of the polarizer, first, the iodine concentration was quantified using the calibration curve method of fluorescent X-ray analysis.
  • a fluorescent X-ray analyzer ZSX-PRIMUSIV manufactured by Rigaku Co., Ltd. was used as the apparatus.
  • the value directly obtained by the fluorescent X-ray analyzer is not the concentration of each element, but the fluorescent X-ray intensity (kcps) of the wavelength peculiar to each element. Therefore, in order to determine the iodine concentration contained in the polarizer, it is necessary to convert the fluorescent X-ray intensity into a concentration using a calibration curve.
  • the iodine concentration of the polarizer in the present specification and the like means the iodine concentration (% by weight) based on the weight of the polarizer.
  • the calibration curve was created by the following procedure. 1.
  • a known amount of potassium iodide was dissolved in a polyvinyl alcohol aqueous solution to prepare seven kinds of polyvinyl alcohol aqueous solutions containing iodine having a known concentration.
  • This polyvinyl alcohol aqueous solution was applied to polyethylene terephthalate, dried and then peeled off to prepare samples 1 to 7 of a polyvinyl alcohol film containing iodine having a known concentration.
  • the iodine concentration (% by weight) of the polyvinyl alcohol film is calculated by the following formula 1.
  • Iodine concentration ⁇ potassium iodide amount (g) / (potassium iodide amount (g) + polyvinyl alcohol weight (g)) ⁇ x (127/166) (Molecular weight of iodine: 127, molecular weight of potassium: 39)
  • the fluorescent X-ray intensity (kcps) corresponding to iodine was measured on the produced polyvinyl alcohol film using a fluorescent X-ray analyzer ZSX-PRIMUS IV (manufactured by Rigaku Co., Ltd.).
  • the fluorescent X-ray intensity (kcps) is the peak value of the fluorescent X-ray spectrum.
  • the film thickness of the produced polyvinyl alcohol film was measured using a spectroscopic film thickness meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.).
  • the fluorescent X-ray intensity is divided by the thickness of the polyvinyl alcohol film ( ⁇ m) to obtain the fluorescent X-ray intensity per unit thickness of the film (kcps / ⁇ m).
  • Table 1 shows the iodine concentration of each sample and the fluorescent X-ray intensity per unit thickness.
  • the fluorescent X-ray intensity obtained in the sample measurement is divided by the thickness to obtain the fluorescent X-ray intensity (kcps / ⁇ m) per unit thickness.
  • the iodine concentration is obtained by substituting the fluorescent X-ray intensity per unit thickness of each sample into Equation 2.
  • Example 1 (Preparation of acrylic polymer (A)) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, 77.9 parts of butyl acrylate, 16 parts of phenoxyethyl acrylate, 1 part of N-vinyl-2-pyrrolidone, 5 parts of acrylic acid, A monomer mixture containing 0.1 part of 4-hydroxybutyl acrylate was charged. Further, with respect to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator is charged together with 100 parts of ethyl acetate, and nitrogen gas is added while gently stirring.
  • the solution of the acrylic pressure-sensitive adhesive composition was applied to one side of a polyethylene terephthalate film (separator film: manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) treated with a silicone-based release agent, and the pressure-sensitive adhesive layer after drying was applied. It was applied so as to have a thickness of 20 ⁇ m and dried at 155 ° C. for 1 minute to form an adhesive layer on the surface of the separator film.
  • the pressure-sensitive adhesive layer formed on the separator film was transferred to the acrylic film side of the polarizing film (1) prepared above to prepare a polarizing film with a pressure-sensitive adhesive layer.
  • Example 2 Comparative Examples 1 to 3
  • the type of the polarizing film and the type of the ionic compound (B) used for preparing the pressure-sensitive adhesive composition were changed as shown in Table 2.
  • a polarizing film with an adhesive layer was produced in the same manner as in the above.
  • ⁇ Surface resistance value ( ⁇ / ⁇ ): Conductivity> The surface resistance value of the pressure-sensitive adhesive layer was measured on the surface of the pressure-sensitive adhesive layer formed on the separator film. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech.
  • a polarizing film with an adhesive layer was cut out in a size of 10 cm (absorption axis direction) ⁇ 10 cm (slow phase axis direction) and attached to non-alkali glass (manufactured by Corning Inc.) as a sample.
  • the sample was put into a heating tester at 85 ° C. After 500 hours, the sample was taken out, and the difference between the position of the polarizing film with the pressure-sensitive adhesive layer before the heating test was put in and the position of the polarizing film with the pressure-sensitive adhesive layer after the heating test was put in was measured and used as the amount of dimensional change.
  • the measurement is performed at point a: the center point of the side surface (contracted in the direction of the absorption axis) in the same direction in the slow axis direction of the rectangular sample and point b: the side surface in the same direction in the rectangular absorption axis direction (in the direction of the slow axis).
  • the center point of contraction was performed.
  • the polarizing film with the pressure-sensitive adhesive layer is stored at 85 ° C. or 95 ° C. for 120 hours, then taken out, and after the separator film is peeled off from the polarizing film with the pressure-sensitive adhesive layer, as shown in FIG. 7 (however, it does not have an anchor layer), the in-cell It was attached to the visible side of the type liquid crystal cell.
  • a silver paste having a width of 5 mm was applied to the side surface points b of the bonded polarizing film with the pressure-sensitive adhesive layer so as to cover each side surface of the hard coat layer, the polarizing film, and the pressure-sensitive adhesive layer, and an external ground electrode was applied. Connected with.
  • a liquid crystal display device with a built-in touch sensing function was manufactured by connecting a routing wiring (not shown) around the transparent electrode pattern inside the in-cell type liquid crystal cell to a controller IC (not shown).
  • an electrostatic discharge gun was fired on the polarizing film surface at an applied voltage of 15 kV, and the time until the white spots disappeared due to electricity was measured and judged according to the following criteria. .. (Evaluation criteria) ⁇ : Within 1 second. ⁇ : Over 1 second to within 10 seconds. ⁇ : Exceeding 10 seconds to within 30 seconds. X: Exceeds 30 seconds.
  • Polyene formation of polyvinyl alcohol is considered to occur when the dehydration reaction is promoted by heating with iodine (I 2 ) produced in a high temperature and high humidity environment (Chemical formula 1).
  • I 2 iodine
  • I 2 generated when the polyvinyl alcohol-polyiedo complex existing in the polarizer is broken by heating and the OH group in the polyvinyl alcohol form a charge transfer complex (HO ... I 2 ), and then pass through the OI group. It is thought that it will become polyene.
  • ⁇ Evaluation of polyeneization> The polarizing film with the pressure-sensitive adhesive layer was subjected to a heating test for 500 hours in an environment of 95 ° C., and the single transmittance of the sample was measured before and after that, and the amount of change ⁇ Ts of the single transmittance was determined by the following formula.
  • ⁇ Ts Ts (500) -Ts (0)
  • Ts (0) is the simple substance transmittance of the sample before heating
  • Ts (500) is the simple substance transmittance after heating for 500 hours in an environment of 105 ° C.
  • the sample was evaluated according to the following criteria. (Evaluation criteria) ⁇ : ⁇ Ts is 0 or more ⁇ : ⁇ Ts is less than 0
  • BA is butyl acrylate
  • PEA is phenoxyethyl acrylate
  • AA is acrylic acid
  • NVP N-vinyl-2-pyrrolidone
  • HBA 4-hydroxybutyl acrylate
  • the isocyanate type is an isocyanate cross-linking agent (Coronate L manufactured by Tosoh Corporation, trimethylolpropane tolylene diisocyanate)
  • BPO is benzoyl peroxide (NOF BMT manufactured by NOF Corporation)
  • Li-TFSI is bis (trifluoromethanesulfonyl) imide lithium
  • K-TFSI is bis (trifluoromethanesulfonyl) imide
  • EMP-TFSI is ethylmethylpyrrolidinium-bis (trifluorosulfonylimide)
  • TMPA-TFSI is trimethylpropylammonium-bis (trifluorosulfonylimide)
  • a Polarizing film with adhesive layer Liquid crystal cell (in-cell type liquid crystal cell) C liquid crystal panel (in-cell type liquid crystal panel) 1,11 1st and 2nd polarizing films 2,12 1st and 2nd adhesive layers 3 Anchor layers 4 Surface treatment layers 20 Liquid crystal layer 31 Touch sensor electrode 32 Touch drive electrode 33 Touch drive electrode and sensor electrode 41, 42 First and second transparent substrates

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Abstract

L'invention concerne un panneau à cristaux liquides qui a une bonne fonction antistatique et qui peut satisfaire une fiabilité de conduction dans une région à haute température.　Ce panneau à cristaux liquides (C) comprend une cellule à cristaux liquides (B) ayant un premier substrat transparent (41) et un second substrat transparent (42) pour encadrer chaque surface d'une couche de cristaux liquides (20) ; et un film polarisant (A) pourvu d'une couche adhésive, disposé sur le premier côté substrat transparent du panneau à cristaux liquides sur le côté visible de celui-ci; et ayant une structure de conduction (50) sur la surface du panneau à cristaux liquides sur le film polarisant pourvu d'un côté de couche adhésive de celui-ci ; le film polarisant comportant une couche adhésive ayant un premier film polarisant et une première couche adhésive dans cet ordre, le premier film polarisant contenant un polariseur ayant une concentration en iode de 6 % en poids ou moins et la première couche adhésive étant formée à partir d'une composition adhésive contenant un polymère (méth)acrylique (A) et un composé ionique (B) dans lequel le poids moléculaire d'un composant cationique de celui-ci est de 210 ou moins.
PCT/JP2020/006484 2019-03-20 2020-02-19 Panneau à cristaux liquides et dispositif d'affichage à cristaux liquides WO2020189159A1 (fr)

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