WO2020111232A1 - Film polarisant avec couche adhésive et dispositif d'affichage d'image - Google Patents

Film polarisant avec couche adhésive et dispositif d'affichage d'image Download PDF

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Publication number
WO2020111232A1
WO2020111232A1 PCT/JP2019/046788 JP2019046788W WO2020111232A1 WO 2020111232 A1 WO2020111232 A1 WO 2020111232A1 JP 2019046788 W JP2019046788 W JP 2019046788W WO 2020111232 A1 WO2020111232 A1 WO 2020111232A1
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Prior art keywords
group
adhesive layer
polarizing film
meth
pressure
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PCT/JP2019/046788
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English (en)
Japanese (ja)
Inventor
智之 木村
康隆 石原
翔 寳田
昌邦 藤田
雄祐 外山
聡司 三田
Original Assignee
日東電工株式会社
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Priority claimed from JP2019214309A external-priority patent/JP2020095263A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020217011181A priority Critical patent/KR20210096071A/ko
Priority to CN201980067253.1A priority patent/CN112840242B/zh
Publication of WO2020111232A1 publication Critical patent/WO2020111232A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • 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
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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 polarizing film with an adhesive layer. Further, the present invention relates to a laminate including a transparent conductive substrate to which the pressure-sensitive adhesive layer-attached polarizing film is applied. Furthermore, the present invention relates to an image display device using the laminate. Further, the present invention relates to an image display panel and an image display device using the above polarizing film with an adhesive layer.
  • An image display panel for example, a liquid crystal panel used in a liquid crystal display device or the like, usually has polarizing films laminated on both sides of a liquid crystal cell formed of a liquid crystal layer disposed between a pair of transparent substrates with an adhesive layer interposed therebetween. Has been done.
  • a pressure-sensitive adhesive layer is required to have high durability, and for example, in a durability test such as heating and humidification that is usually performed as an environment acceleration test, problems such as peeling and floating due to the pressure-sensitive adhesive layer may not occur. Desired.
  • Some transparent substrates such as an indium tin oxide (ITO) thin film or an organic conductive film using a conductive polymer, are formed on one transparent substrate of a liquid crystal cell that constitutes a liquid crystal panel.
  • the transparent conductive layer plays a role of preventing light leakage (uneven charging) caused by the alignment of the liquid crystal layer being disturbed by electrostatic charging. Further, when the liquid crystal display device is used for a touch panel, the transparent conductive layer functions as a shield electrode that separates the driving electric field in the liquid crystal cell from the touch panel. From the above circumstances, there is proposed a polarizing film with a pressure-sensitive adhesive layer that can maintain a stable surface resistance value in a humid environment even when it is attached to the transparent conductive layer (Patent Document 2).
  • the pressure-sensitive adhesive layer-attached polarizing film when a transparent protective film is provided only on one side of the polarizer, and a pressure-sensitive adhesive layer is provided on the other side without a transparent protective film, the adhesive layer is provided. There is.
  • the pressure-sensitive adhesive layer-attached one-sided protective polarizing film has a transparent protective film only on one side, so that the polarizing film can be made thinner than the case where the transparent protective film is provided on both sides, and the cost for one transparent protective film layer is still higher. It can be reduced.
  • the iodine-based polarizer is used as the polarizer. It has been found that iodine and/or iodine ions generated from the iodine-based polarizer may pass through the pressure-sensitive adhesive layer and corrode the transparent conductive layer. Further, when the transparent conductive layer is corroded, the surface resistance value is increased and display unevenness due to charging is likely to occur. Further, it has been found that when the liquid crystal display device is used for a touch panel, the shield function may be deteriorated and the touch panel may malfunction.
  • the present invention is a polarizing film with a pressure-sensitive adhesive layer in which a pressure-sensitive adhesive layer is provided on the polarizer of a one-sided protective polarizing film having a transparent protective film only on one surface of an iodine-based polarizer, and the pressure-sensitive adhesive layer is transparent.
  • An object of the present invention is to provide a pressure-sensitive adhesive layer-attached polarizing film capable of maintaining a stable surface resistance value of a transparent conductive layer even when it is attached to the conductive layer and placed in a humid environment.
  • Another object of the present invention is to provide a laminate including a transparent conductive substrate to which the polarizing film with an adhesive layer is applied. Furthermore, it is an object of the present invention to provide an image display panel and an image display device using the polarizing film with the pressure-sensitive adhesive layer or the laminate.
  • the present invention is Polarizer, a transparent protective film only on one side of the polarizer, and a transparent layer on the other side of the polarizer, and with an adhesive layer provided with an adhesive layer through the transparent layer A polarizing film
  • the polarizer is an iodine-based polarizer containing iodine and/or iodine ions
  • the polarizing film with the adhesive layer The change ratio of the surface resistance value represented by the general formula (1): R 250 /R i ⁇ 1.5 (where R i is a transparent conductive substrate having a transparent substrate and a transparent conductive layer).
  • the R 250 is a surface resistance value ( ⁇ / ⁇ ) of the transparent conductive layer after the autoclaved laminate is further subjected to high temperature and high humidity treatment at 65° C. and 95% RH for 250 hours. Respectively, respectively) are satisfied.
  • the polarizing film with the adhesive layer The change ratio of the surface resistance value represented by the general formula (2): R 500 /R 250 ⁇ 1.8 (wherein R 250 is a transparent conductive substrate having a transparent substrate and a transparent conductive layer).
  • the surface resistance value ( ⁇ / ⁇ ) of the transparent conductive layer after high-temperature and high-humidity treatment for 500 hours under conditions is the surface resistance value ( ⁇ / ⁇ ) of the transparent conductive layer after the autoclaved laminate is further subjected to a high temperature and high humidity treatment at 65° C. and 95% RH for 500 hours. Are respectively shown) are preferably satisfied.
  • the transparent layer is directly formed on the polarizer.
  • the transparent layer preferably has a thickness of 10 ⁇ m or less.
  • a cured product of a forming material containing a urethane prepolymer which is a reaction product of an isocyanate compound and a polyhydric alcohol, can be used as the transparent layer.
  • the isocyanate compound it is preferable to use at least one selected from tolylene diisocyanate and diphenylmethane diisocyanate.
  • the transparent layer may contain an epoxy resin.
  • X is a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group.
  • R 1 and R 2 are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or a substituent.
  • R 1 and R 2 may be linked to each other to form a ring
  • a polymer obtained by polymerizing and A resin composition comprising (b) an epoxy resin, A polymer in which the content ratio of the polymer (a) to the epoxy resin (b) is 95:5 to 60:40 or 40:60 to 1:99 by weight can be used.
  • the functional group represented by X in the general formula (1) is General formula (2): ZY- (wherein Z is a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde. Group and a functional group containing at least one reactive group selected from the group consisting of a carboxyl group, and Y represents an organic group).
  • the pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive composition containing a (meth)acrylic polymer (A) can be used.
  • the pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B) can be used.
  • the (meth)acrylic polymer (A) preferably contains an alkyl (meth)acrylate (a1) and an amide group-containing monomer (a2) as monomer units.
  • the amide group-containing monomer (a2) is preferably an N-vinyl group-containing lactam monomer.
  • the amide group-containing monomer (a2) is preferably contained as a monomer unit in the (meth)acrylic polymer (A) in an amount of 0.1% by weight or more.
  • the ionic compound (B) is preferably an alkali metal salt.
  • the ionic compound (B) is preferably contained in an amount of 0.01 parts by weight or more based on 100 parts by weight of the (meth)acrylic polymer (A).
  • the transparent conductive layer is preferably made of indium tin oxide.
  • the present invention also has a polarizing film with the pressure-sensitive adhesive layer, and a transparent conductive substrate having a transparent substrate and a transparent conductive layer, The laminated body, wherein the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film is bonded to the transparent conductive layer of the transparent conductive substrate.
  • the present invention relates to an image display device characterized by being bonded together as described above.
  • the present invention also relates to an image display panel comprising the above polarizing film with an adhesive layer.
  • the image display panel includes a transparent conductive substrate having a transparent conductive layer, the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer, the adhesive layer is bonded to the transparent conductive layer of the image display panel. Those that are suitable are preferred.
  • the present invention also relates to an image display device including the image display panel.
  • the polarizing film used for the pressure-sensitive adhesive layer-attached polarizing film of the present invention is a one-sided protective polarizing film having a transparent protective film on only one side of the polarizer, which is advantageous in terms of thinning and cost reduction.
  • an iodine-based polarizer is used as a polarizer, and when the pressure-sensitive adhesive layer is attached to a transparent conductive layer, the iodine-based Iodine and/or iodine ions generated from the polarizer may pass through the pressure-sensitive adhesive layer and corrode the transparent conductive layer.
  • the transparent layer since the transparent layer is provided between the polarizer and the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer-attached polarizing film, the transparent layer allows the pressure-sensitive adhesive layer of iodine and/or iodine ions in the polarizer to be changed. Can be suppressed. Therefore, even in a humid environment, corrosion of the transparent conductive layer due to the iodine and/or iodine ions can be suppressed, and the surface resistance value of the transparent conductive layer can be maintained within a desired value range for a long time, which is stable. It is considered that the optical characteristics could be satisfied. Further, it is considered that display unevenness due to charging could be suppressed, and occurrence of malfunction could be suppressed.
  • the pressure-sensitive adhesive layer-attached polarizing film of the present invention has good durability with respect to the transparent conductive layer even in a humid environment, and according to the present invention, the pressure-sensitive adhesive layer-attached polarizing film is applied to the transparent conductive layer. It is possible to provide a laminated body including a base material, and an image display panel and an image display device using the laminated body.
  • the polarizing film with an adhesive layer of the present invention is shown in FIG. 1, for example.
  • the polarizing film 1 with an adhesive layer has a polarizer a, a transparent protective film b only on one side of the polarizer a, and a transparent layer on the other side of the polarizer a.
  • the piece protective polarizing film 11 having c is used.
  • the pressure-sensitive adhesive layer 21 is provided on the one-sided protective polarizing film 11 via the transparent layer c. It is preferable that the transparent layer c is directly provided on the polarizer a in terms of suppressing an increase in water content of the polarizer under a high temperature and high humidity environment. The transparent layer c will be described later.
  • the pressure-sensitive adhesive layer-attached polarizing film 1 may have a conductive layer d between the transparent layer c and the pressure-sensitive adhesive layer 21, as shown in FIG.
  • the conductive layer d will be described later.
  • the conductive layer d can improve the antistatic performance. Since the conductive layer d is provided via the transparent layer c, the problem of decolorization of the end portion of the polarizer in a humid environment due to the conductive layer c being directly provided on the polarizer a is suppressed. it can.
  • the polarizing film with the pressure-sensitive adhesive layer of the present invention is applied to a transparent conductive substrate, and is used, for example, as a laminate L shown in FIG.
  • the pressure-sensitive adhesive layer 21 of the polarizing film with a pressure-sensitive adhesive layer 1 shown in FIG. 1 has the transparent conductive material F having the transparent conductive layer F1 on the transparent conductive material F2. The case of being laminated on the layer F1 is illustrated.
  • R i and R 250 which are surface resistance values ( ⁇ / ⁇ ) of the transparent conductive layer measured under the following conditions in the laminate, It is characterized by satisfying the change ratio of the surface resistance value represented by the general formula (1): R 250 /R i ⁇ 1.5.
  • the change ratio is preferably 1.3 or less, and more preferably 1.2 or less.
  • R 250 and R 500 which are surface resistance values ( ⁇ / ⁇ ) of the transparent conductive layer measured under the following conditions, It is preferable to satisfy the change ratio of the surface resistance value represented by the general formula (2): R 500 /R 250 ⁇ 1.8.
  • the change ratio is preferably 1.5 or less, and more preferably 1.2 or less.
  • R i is a laminated body in which the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film is bonded to the transparent conductive layer on the transparent conductive substrate having a transparent base and a transparent conductive layer at 50° C. under 5 atmospheres.
  • R 250 is the surface resistance value ( ⁇ / ⁇ ) of the transparent conductive layer after the autoclaved laminate was further subjected to high temperature and high humidity treatment at 65° C. and 95% RH for 250 hours.
  • R500 is the surface resistance value ( ⁇ / ⁇ ) of the transparent conductive layer after the autoclaved laminate was further subjected to high temperature and high humidity treatment at 65° C. and 95% RH for 500 hours.
  • the polarizer is not particularly limited, and various types can be used.
  • the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene/vinyl acetate copolymer partially saponified film, and dichroism of iodine or dichroic dye.
  • examples include polyene-oriented films such as those obtained by adsorbing a substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like.
  • a polarizer made of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
  • the thickness of these polarizers is not particularly limited, but is generally about 80 ⁇ m or less.
  • a thin polarizer having a thickness of 10 ⁇ m or less can be used as the polarizer. From the viewpoint of thinning, the thickness is preferably 1 to 7 ⁇ m. It is preferable that such a thin polarizer has little thickness unevenness, excellent visibility, and excellent durability due to small dimensional change, and that the thickness of the polarizing film can be reduced.
  • thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc.
  • a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc.
  • thermoplastic resin include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone 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 transparent protective film is attached to one side of the polarizer with an adhesive layer, while a transparent protective film is attached to the other side as a (meth)acrylic type, urethane type, acrylic urethane type, epoxy type, or silicone type.
  • a thermosetting resin such as a system or an ultraviolet curable resin can be used.
  • a cellulose resin or a (meth)acrylic resin is preferable because the change ratio of the surface resistance value of the transparent conductive layer to which the adhesive layer is attached 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, and JP-A-2005.
  • examples thereof include (meth)acrylic resins having a lactone ring structure described in Japanese Patent No. 146084.
  • the cellulose resin is preferable to the (meth)acrylic resin because it is more effective in suppressing the polarizer crack, which is a problem in the one-sided protective polarizing film.
  • a functional layer such as a hard coat layer, an antireflection layer, a sticking prevention layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered.
  • the adhesive used for bonding the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various types of water-based, solvent-based, hot-melt-based, radical-curable, and cation-curable types are used. However, a water-based adhesive or a radical curable adhesive is preferable.
  • the thickness of the transparent layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably 3 ⁇ m or less from the viewpoints of thinning and optical reliability, and further 1. It is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less. If the transparent layer is too thick, the thickness of the polarizing film becomes large, and further, the optical reliability of the polarizer may be deteriorated. On the other hand, the thickness of the transparent layer is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, further preferably 0.3 ⁇ m or more, from the viewpoint of suppressing the fluctuation ratio of the surface resistance value of the pressure-sensitive adhesive layer. Is preferred.
  • a material that is transparent and has a predetermined change ratio of the surface resistance value of the transparent conductive layer to which the adhesive layer is attached can be used.
  • examples of such a material include a forming material containing a urethane prepolymer (a) which is a reaction product of an isocyanate compound and a polyhydric alcohol.
  • a polyfunctional isocyanate compound for example, a polyfunctional isocyanate compound is preferable, and specifically, a polyfunctional aromatic isocyanate compound, an alicyclic isocyanate compound, an aliphatic isocyanate compound, or a dimer thereof can be mentioned.
  • polyfunctional aromatic isocyanate compound examples include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4 , 4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, methylenebis 4-phenyl isocyanate, p-phenylene diisocyanate and the like.
  • polyfunctional alicyclic isocyanate compound examples include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bisisocyanatomethylcyclohexane, isophorone diisocyanate, and hydrogen.
  • examples thereof include added diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethyl xylylene diisocyanate.
  • polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4. 4-trimethylhexamethylene diisocyanate and the like can be mentioned.
  • examples of the polyfunctional isocyanate compound include those having three or more isocyanate groups such as tris(6-incyanate hexyl) isocyanurate.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Examples thereof include methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and polypropylene glycol.
  • the urethane prepolymer (a) a rigid structure in which a cyclic structure (benzene ring, cyanurate ring, isocyanurate ring, etc.) occupies a large proportion in the structure is used in the present invention.
  • the polyfunctional isocyanate compounds may be used alone or in combination of two or more, and aromatic isocyanate compounds are preferable from the viewpoint of suppressing water contamination in the polarizer.
  • Other polyfunctional isocyanate compounds can be used in combination with the aromatic isocyanate compound.
  • urethane prepolymer (a) trimethylolpropane-tri-tolylene isocyanate and trimethylolpropane-tri-diphenylmethane diisocyanate are preferably used.
  • the urethane prepolymer (a) is a compound having a terminal isocyanate group, and can be obtained, for example, by mixing an isocyanate compound and a polyhydric alcohol, stirring and reacting them. Usually, it is preferable to mix the isocyanate compound and the polyhydric alcohol so that the isocyanate group becomes excessive with respect to the hydroxyl group of the polyhydric alcohol.
  • the urethane prepolymer (a) may have a terminal isocyanate group with a protecting group.
  • Protecting groups include oximes and lactams. When the isocyanate group is protected, the protective group is dissociated from the isocyanate group by heating and the isocyanate group reacts.
  • the forming material for forming the transparent layer may contain, in addition to the urethane prepolymer (a), a compound (b) having at least two functional groups having active hydrogen having reactivity with an isocyanate group.
  • the functional group having active hydrogen having reactivity with an isocyanate group include a hydroxyl group and an amino group.
  • the compound (b) preferably has a molecular weight divided by the number of the functional groups of 350 or less. By thus defining the relationship between the molecular weight and the number of functional groups, the reactivity between the compound (b) and the isocyanate group of the urethane prepolymer (a) can be ensured.
  • the molecular weight of the compound (b) is preferably 1000 or less.
  • the compound (b) having a molecular weight in the range of 1,000 or less is preferable in terms of compatibility with the urethane prepolymer (a) when the forming material is prepared as a solution.
  • Examples of the compound (b) include polyhydric alcohols, polyvalent amines, compounds having a hydroxyl group and an amino group in the molecule, and the like.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Bifunctional alcohols such as methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, polypropylene glycol; trifunctional alcohols such as glycerin and trimethylolpropane; tetrafunctional alcohols such as pentaerythritol, hexanetriol and
  • polyvalent amine examples include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, dimerdiamine and the like.
  • Examples of the compound having a hydroxyl group and an amino group in the molecule include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxy.
  • Diamines having a hydroxyl group in the molecule such as propylethylenediamine and di-2-hydroxypropylethylenediamine;
  • Alkanolamines such as ethanolamine, diethanolamine and triethanolamine can be mentioned.
  • the compound (b) it is preferable to use a polyhydric alcohol from the viewpoint of preventing the deterioration of the optical reliability of the polarizer.
  • a polyhydric alcohol from the viewpoint of preventing the deterioration of the optical reliability of the polarizer.
  • trimethylolpropane is preferable from the viewpoint of reactivity with the urethane prepolymer (a). preferable.
  • the forming material contains the urethane prepolymer (a) as a main component.
  • the urethane prepolymer (a) preferably contains 50% by weight or more of the solid content of the forming material.
  • the compounding ratio of the compound (b) to the urethane prepolymer (a) is 5% by weight or more based on the total 100% by weight (solid content ratio) of the urethane prepolymer (a) and the compound (b).
  • the compounding ratio of the compound (b) is preferably 10% by weight or more from the viewpoint of improving the film strength.
  • the compounding ratio of the compound (b) is 80% by weight or less, and further 50% by weight or less.
  • the compounding ratio of the compound (b) is 80% by weight or less, and further 50% by weight or less.
  • the above-mentioned forming material can use a reaction catalyst to further increase the reactivity of the isocyanate group.
  • the reaction catalyst is not particularly limited, but a tin-based catalyst or an amine-based catalyst is preferable.
  • As the reaction catalyst one kind or two or more kinds can be used.
  • the amount of the reaction catalyst used is usually 5 parts by weight or less based on 100 parts by weight of the urethane prepolymer (a). When the amount of the reaction catalyst is large, the crosslinking reaction rate is increased and foaming of the forming material occurs. Even if a forming material after foaming is used, sufficient adhesiveness cannot be obtained.
  • a reaction catalyst it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.
  • a reaction catalyst can be used to further increase the reactivity of the isocyanate group.
  • the reaction catalyst is not particularly limited, but a tin-based catalyst or an amine-based catalyst is preferable.
  • As the reaction catalyst one kind or two or more kinds can be used.
  • the amount of the reaction catalyst used is usually 5 parts by weight or less with respect to 100 parts by weight of the urethane prepolymer. When the amount of the reaction catalyst is large, the crosslinking reaction rate is increased and foaming of the forming material occurs. Even if a forming material after foaming is used, sufficient adhesiveness cannot be obtained.
  • a reaction catalyst it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.
  • the tin catalyst both inorganic and organic catalysts can be used, but organic catalysts are preferred.
  • the inorganic tin-based catalyst include stannous chloride and stannic chloride.
  • the organic tin-based catalyst preferably has at least one organic group such as an aliphatic group or an alicyclic group having a skeleton such as a methyl group, an ethyl group, an ether group, or an ester group. Examples thereof include tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride and dibutyltin dilaurate.
  • the amine catalyst is not particularly limited.
  • those having at least one organic group such as alicyclic group such as quinoclidine, amidine and diazabicycloundecene are preferable.
  • Other examples of amine-based catalysts include triethylamine and the like.
  • reaction catalysts other than those mentioned above include cobalt naphthenate and benzyltrimethylammonium hydroxide.
  • the forming material is usually used as a solution containing the urethane prepolymer (a) and the compound (b).
  • the solution may be a solvent system or an aqueous system such as an emulsion, a colloidal dispersion or an aqueous solution.
  • the organic solvent is not particularly limited as long as it does not have a functional group having active hydrogen having reactivity with an isocyanate group and uniformly dissolves the urethane prepolymer (a) and the compound (b) constituting the forming material. Absent.
  • the organic solvent may be used alone or in combination of two or more.
  • different solvents can be used for the urethane prepolymer (a) and the compound (b).
  • the forming material can be prepared by mixing each solution after preparing each solution. Further, the viscosity of the forming material can be adjusted by further adding an organic solvent to the prepared forming material. Further, even in the case of a solvent-based solution dissolved in an organic solvent, alcohols, water and the like exemplified below can be contained as a solvent.
  • Organic solvents include aromatic hydrocarbons such as toluene and xylene); esters such as ethyl acetate and butyl acetate; aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane and methylcyclohexane; 1,2-dichloroethane And the like; ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and acetylacetone; and the like.
  • aromatic hydrocarbons such as toluene and xylene
  • esters such as ethyl acetate and butyl acetate
  • aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane and methylcyclohexane
  • 1,2-dichloroethane And the like ether
  • aqueous system for example, alcohols such as n-butyl alcohol and isopropyl alcohol, and ketones such as acetone can be mixed.
  • a dispersant is used, or urethane prepolymer is used as a functional group having low reactivity with isocyanate groups such as carboxylate, sulfonate, and quaternary ammonium salt, and water dispersibility such as polyethylene glycol. This can be done by introducing the components.
  • An epoxy resin can be used as a material for forming the transparent layer. Any appropriate epoxy resin can be used as the epoxy resin. An epoxy resin having an aromatic ring is preferably used as the epoxy resin. By using the epoxy resin, the surface resistance value of the pressure-sensitive adhesive layer can be prevented from changing over time, the adhesiveness with the polarizer can be further improved, and color loss from the end portion of the polarizer can be prevented. Further, when the pressure-sensitive adhesive layer is formed on the transparent layer, the anchoring force of the pressure-sensitive adhesive layer can be improved.
  • Examples of the epoxy resin having an aromatic ring include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac.
  • Novolak type epoxy resin such as epoxy resin; polyhydroxy type epoxy resin such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type Examples thereof include epoxy resin.
  • a bisphenol A type epoxy resin a biphenyl type epoxy resin, and a bisphenol F type epoxy resin are used.
  • these epoxy resins color loss from the end of the polarizer can be further prevented. Only one epoxy resin may be used, or two or more epoxy resins may be used in combination.
  • the weight average molecular weight (Mw) of the epoxy resin is preferably 20,000 or more, more preferably 30,000 or more, and further preferably 37,000 or more. When the weight average molecular weight of the epoxy resin is within the above range, it is possible to further prevent color loss from the end portion of the polarizer.
  • the weight average molecular weight can be measured, for example, by GPC.
  • the material for forming the transparent layer may be, for example, an acrylic monomer in an amount of more than 50 parts by weight and a monomer represented by the following general formula (1) in an amount of more than 0 parts by weight and less than 50 parts by weight. It is possible to use a composition containing a polymer (a) (hereinafter, also referred to as a polymer (a)) obtained by polymerizing the above and an epoxy resin (b).
  • a polymer (a) hereinafter, also referred to as a polymer (a) obtained by polymerizing the above and an epoxy resin (b).
  • the content ratio of the polymer (a) and the epoxy resin (b) is preferably 95:5 to 60:40, or 40:60 to 1:99 by weight.
  • X is a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. It represents a functional group containing at least one reactive group selected, and R 1 and R 2 are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or a substituent. Represents an optionally substituted aryl group or an optionally substituted heterocyclic group, and R 1 and R 2 may be linked to each other to form a ring).
  • the content ratio of the polymer (a) and the epoxy resin (b) in the composition is 95:5 to 60:40 by weight, or 40:60 to 1:99.
  • the content ratio of the polymer (a) and the epoxy resin (b) is within the above range, the surface resistance value of the pressure-sensitive adhesive layer is prevented from changing over time, the adhesiveness with the polarizer is excellent, and the end of the polarizer is obtained.
  • a resin composition for a transparent layer that can prevent color loss from a part is obtained. Further, when the content ratio of the polymer (a) and the epoxy resin (b) is within the above range, the anchoring force of the pressure-sensitive adhesive layer can be improved when the pressure-sensitive adhesive layer is formed on the transparent layer.
  • the content ratio of the polymer (a) and the epoxy resin (b) is preferably 95:5 to 80:20, or 20:80 to 5:95, and more preferably 90:10 to, by weight. 70:30 or 30:70 to 10:90. The closer the content ratio of the polymer (a) and the epoxy resin (b) is to the equal portion (50:50), the more likely the protective layer is whitened.
  • the polymer (a) is obtained by polymerizing more than 50 parts by weight of an acrylic monomer and more than 0 parts by weight and less than 50 parts by weight of the monomer represented by the general formula (1). can get.
  • the polymer (a) typically has a structure represented by the following formula.
  • the polymer (a) By polymerizing the monomer represented by the general formula (1) and an acrylic monomer component, the polymer (a) has a substituent containing a boron in the side chain (for example, repeating k in the following formula). Units). This can improve the adhesion between the polarizer and the layer (transparent layer) formed using the resin composition.
  • the substituent containing boron may be continuously contained in the polymer or may be randomly contained therein.
  • the polymer (a) may be used alone or in combination of two or more kinds. (In the formula, R 6 represents an arbitrary functional group, and j and k represent an integer of 1 or more).
  • the weight average molecular weight of the polymer (a) is preferably 10,000 or more, more preferably 20,000 or more, further preferably 35,000 or more, and particularly preferably 50,000 or more. ..
  • the weight average molecular weight of the polymer (a) is preferably 250,000 or less, more preferably 200,000 or less, still more preferably 150,000 or less.
  • the weight average molecular weight can be measured, for example, by GPC (solvent: dimethylformamide (DMF)).
  • the glass transition temperature of the polymer (a) is preferably 50° C. or higher, more preferably 60° C. or higher, even more preferably 80° C. or higher.
  • the glass transition temperature of the polymer (a) is preferably 300°C or lower. When the glass transition temperature is in the above range, the crack resistance of the layer (transparent layer) formed using the resin composition can be improved.
  • the polymer (a) includes an acrylic monomer in an amount of more than 50 parts by weight, an amount of the monomer represented by the formula (1) in an amount of more than 0 parts by weight and less than 50 parts by weight, and a polymerization initiator. It can be obtained by polymerizing the monomer composition containing the other monomer by any suitable polymerization method. Solution polymerization is preferably used as the polymerization method. By polymerizing the polymer (a) by solution polymerization, a higher molecular weight polymer can be obtained.
  • acrylic monomer Any appropriate acrylic monomer can be used as the acrylic monomer.
  • a (meth)acrylic acid ester-based monomer having a linear or branched structure and a (meth)acrylic acid ester-based monomer having a cyclic structure may be mentioned.
  • (meth)acrylic refers to acrylic and/or methacrylic.
  • Examples of the (meth)acrylic acid ester-based monomer having a linear or branched structure include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid.
  • Examples include isopropyl, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. ..
  • methyl (meth)acrylate is used.
  • the (meth)acrylic acid ester-based monomer may be used alone or in combination of two or more kinds.
  • Examples of the (meth)acrylic acid ester-based monomer having a cyclic structure include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, and ( Dicyclopentenyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, Dicyclopentanyl (meth)acrylate, Biphenyl (meth)acrylate, o-biphenyloxyethyl (meth)acrylate, o-biphenyloxyethoxy Ethyl (meth)acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth)acrylate, o-biphenyloxy-2-hydroxypropyl (meth)acrylate, p-biphenyloxy-2-hydroxypropyl (meth)acrylate
  • 1-adamantyl (meth)acrylate and dicyclopentanyl (meth)acrylate are used.
  • a polymer having a high glass transition temperature can be obtained.
  • monomers may be used alone or in combination of two or more.
  • (meth)acryloyl means an acryloyl group and/or a methacryloyl group.
  • a silsesquioxane compound having a (meth)acryloyl group may be used instead of the (meth)acrylic acid ester-based monomer.
  • an acrylic polymer having a high glass transition temperature can be obtained.
  • the silsesquioxane compound has various skeleton structures, for example, a skeleton structure such as a cage structure, a ladder structure, and a random structure.
  • the silsesquioxane compound may have only one type of these structures, or may have two or more types of these structures.
  • the silsesquioxane compound may be used alone or in combination of two or more kinds.
  • silsesquioxane compound having a (meth)acryloyl group for example, MAC grade and AC grade of SQ series of Toagosei Co., Ltd. can be used.
  • the MAC grade is a silsesquioxane compound containing a methacryloyl group, and specific examples thereof include MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM and the like.
  • AC grade is a silsesquioxane compound containing an acryloyl group, and specific examples thereof include AC-SQ TA-100 and AC-SQ SI-20.
  • Acrylic monomer is used in excess of 50 parts by weight.
  • the acrylic monomer is used so that the total amount of the acrylic monomer and the monomer represented by the general formula (1) is 100 parts by weight.
  • a substituent containing boron is introduced into the side chain of the polymer (a). Therefore, the adhesion between the polarizer typically composed of the PVA-based resin and the layer (transparent layer) formed using the resin composition can be improved. In addition, the water resistance of the layer (transparent layer) itself formed using the resin composition is also improved, and color loss from the end portion of the polarizer can be prevented.
  • the monomers may be used alone or in combination of two or more.
  • X is a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. It represents a functional group containing at least one reactive group selected, and R 1 and R 2 are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or a substituent. Represents an optionally substituted aryl group or an optionally substituted heterocyclic group, and R 1 and R 2 may be linked to each other to form a ring).
  • aliphatic hydrocarbon group a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cyclic alkyl group having 3 to 20 carbon atoms which may have a substituent.
  • alkenyl group having 2 to 20 carbon atoms.
  • the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent and a naphthyl group having 10 to 20 carbon atoms which may have a substituent.
  • heterocyclic group include a 5-membered ring group and a 6-membered ring group containing at least one hetero atom which may have a substituent.
  • R 1 and R 2 may be linked to each other to form a ring.
  • R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
  • the reactive group contained in the functional group represented by X is a vinyl group, a (meth)acrylic group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group. , And at least one selected from the group consisting of carboxyl groups.
  • the reactive groups are (meth)acrylic groups and/or (meth)acrylamide groups.
  • the functional group represented by X is represented by the general formula (2): ZY— (wherein Z is a vinyl group, a (meth)acryl group, a styryl group, a (meth)acrylamide group.
  • Z represents a functional group containing at least one reactive group selected from the group consisting of a vinyl ether group, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group
  • Y represents an organic group. It is preferable that it is a functional group represented by these.
  • the organic group specifically means an organic group having 1 to 20 carbon atoms which may have a substituent, and more specifically, for example, having a substituent having 1 to 20 carbon atoms.
  • organic group specifically means an organic group having 1 to 20 carbon atoms which may have a substituent, and more specifically, for example, having a substituent having 1 to 20 carbon atoms.
  • linear or branched alkylene group cyclic alkylene group having 3 to 20 carbon atoms which may have a substituent, phenylene group having 6 to 20 carbon atoms which may have a substituent, and 10 to 10 carbon atoms. Examples thereof include a naphthylene group which may have 20 substituents.
  • hydroxyethyl acrylamide and boric acid ester methylol acrylamide and boric acid ester, hydroxyethyl acrylate and boric acid ester, and An ester of (meth)acrylate and boric acid can be exemplified, such as an ester of hydroxybutyl acrylate and boric acid.
  • the content of the monomer represented by the general formula (1) is more than 0 parts by weight and less than 50 parts by weight. It is preferably 0.01 parts by weight or more and less than 50 parts by weight, more preferably 0.05 parts by weight to 20 parts by weight, and further preferably 0.1 parts by weight to 10 parts by weight. When the content of the monomer exceeds 50 parts by weight, color loss may easily occur from the edges.
  • peroxides such as benzoyl peroxide, lauroyl peroxide and sodium peroxide
  • hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide
  • azo compounds such as azobisisobutyronitrile
  • the content of the polymerization initiator may be any appropriate amount.
  • the content of the polymerization initiator is preferably 0.1 part by weight to 5 parts by weight, more preferably 0.3 part by weight to 2 parts by weight.
  • the polymer (a) is preferably obtained by solution polymerization of a monomer component such as an acrylic monomer and a monomer represented by the general formula (1).
  • a monomer component such as an acrylic monomer and a monomer represented by the general formula (1).
  • Any appropriate solvent can be used as the solvent used in the solution polymerization.
  • water alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-hexane; ester compounds such as ethyl acetate; ketones such as acetone and methyl ethyl ketone.
  • Cyclic ether compounds such as tetrahydrofuran and dioxane, etc. may be mentioned. These solvents may be used alone or in combination of two or more. Moreover, you may use together an organic solvent and water.
  • the polymerization reaction can be performed at any appropriate temperature and time.
  • the polymerization reaction can be carried out in the range of 50°C to 100°C, preferably 60°C to 80°C.
  • the reaction time is, for example, 1 hour to 8 hours, preferably 3 hours to 5 hours.
  • Epoxy resin (b) Any appropriate epoxy resin can be used as the epoxy resin (b).
  • An epoxy resin having an aromatic ring is preferably used as the epoxy resin (b).
  • an epoxy resin having an aromatic ring is preferably used as the epoxy resin (b).
  • Examples of the epoxy resin having an aromatic ring include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac.
  • Novolak type epoxy resin such as epoxy resin; polyhydroxy type epoxy resin such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinylphenol, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type Examples thereof include epoxy resin.
  • a bisphenol A type epoxy resin a biphenyl type epoxy resin, and a bisphenol F type epoxy resin are used.
  • these epoxy resins color loss from the end of the polarizer can be further prevented. Only one epoxy resin may be used, or two or more epoxy resins may be used in combination.
  • the epoxy resin (b) preferably has a weight average molecular weight (Mw) of 20,000 or more, more preferably 30,000 or more, still more preferably 37,000 or more.
  • Mw weight average molecular weight
  • the weight average molecular weight can be measured, for example, by GPC.
  • the resin composition for a transparent layer may contain any appropriate other component in addition to the epoxy resin, the polymer (a) and the epoxy resin (b).
  • Other components include, for example, a solvent and an additive.
  • a solvent a solvent that can be used in solution polymerization of the polymer (a) may be used, or another solvent may be used.
  • the other solvent ethyl acetate, toluene, methyl ethyl ketone, and cyclopentanone are preferably used. These solvents may be used alone or in combination of two or more.
  • any appropriate additive can be used as the additive.
  • surfactants for example, surfactants, ultraviolet absorbers, antioxidants, tackifiers and the like can be mentioned.
  • As the additive only one kind may be used, or two or more kinds may be used in combination. These additives can be used in any suitable amount.
  • the transparent layer resin composition can be prepared by any appropriate method. For example, it can be prepared by mixing the polymer (a), the epoxy resin (b), and, if necessary, any appropriate additive in any appropriate solvent. When the polymer (a) is polymerized by solution polymerization, it may be prepared by adding the epoxy resin (b) and any appropriate additive to the polymer solution of the polymer (a) and mixing them. Good.
  • the forming material containing the epoxy resin As a material for forming a transparent layer other than the forming material containing the urethane prepolymer (a), the forming material containing the epoxy resin, and the forming material of the composition containing the polymer (a) and the epoxy resin (b)
  • Examples include cyanoacrylate-based forming materials, epoxy-based forming materials, urethane acrylate-based forming materials, and the like.
  • the formation of the transparent layer can be appropriately selected depending on the type of the forming material.
  • the transparent layer can be formed by applying the forming material to a polarizer or the like and then curing it. It can be obtained as a layer. Usually, it is carried out by forming a cured layer by drying at about 30 to 100° C., preferably at 50 to 80° C. for about 0.5 to 15 minutes after the coating. Further, when the forming material contains an isocyanate component, an annealing treatment is performed at about 30 to 100° C., preferably at 50 to 80° C. for about 0.5 to 24 hours in order to accelerate the reaction. You can
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive.
  • various pressure-sensitive adhesives can be used, for example, rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, polyvinylpyrrolidone-based pressure-sensitive adhesives, Examples thereof include polyacrylamide adhesives and cellulose adhesives.
  • An adhesive base polymer is selected according to the type of the adhesive.
  • an acrylic pressure-sensitive adhesive is preferably used because it has excellent optical transparency, exhibits appropriate wettability, cohesiveness, and adhesive properties of adhesiveness and is excellent in weather resistance and heat resistance. It
  • the acrylic pressure-sensitive adhesive is prepared from a pressure-sensitive adhesive composition containing the (meth)acrylic polymer (A). Less than.
  • the pressure-sensitive adhesive composition will be described.
  • the (meth)acrylic polymer (A) contains, as a monomer unit, an alkyl (meth)acrylate (a1) as a main component.
  • (meth)acrylate refers to acrylate and/or methacrylate, and has the same meaning as (meth) of the present invention.
  • Examples of the alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an amyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group, and a decyl group.
  • 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 and an octadecyl group. These can be used alone or in combination.
  • the average carbon number of these alkyl groups is preferably 3-9.
  • the weight ratio of the alkyl (meth)acrylate (a1) is 70% by weight or more in the weight ratio of all the constituent monomers (100% by weight) constituting the (meth)acrylic polymer (A) as a monomer unit. preferable.
  • the weight ratio of the alkyl (meth)acrylate (a1) can be considered as the balance of the other copolymerization monomers. It is preferable to set the weight ratio of the alkyl (meth)acrylate (a1) within the above range in order to secure the adhesiveness.
  • (meth)acrylic polymer (A) in addition to the monomer unit of the alkyl (meth)acrylate (a1), a (meth)acryloyl group, a vinyl group or the like for the purpose of improving adhesiveness and heat resistance.
  • One or more copolymerizable monomers having a polymerizable functional group having an unsaturated double bond can be introduced by copolymerization.
  • Examples of the copolymerizable monomer include functional group-containing monomers such as amide group-containing monomers, carboxyl group-containing monomers, and hydroxyl group-containing monomers.
  • the amide group-containing monomer (a2) is suitable when the ionic compound (B) described below is blended.
  • the amide group introduced into the side chain in the (meth)acrylic polymer (A) as the base polymer when the amide group introduced into the side chain in the (meth)acrylic polymer (A) as the base polymer is present, the amide group
  • the presence of the composition prevents the surface resistance value of the pressure-sensitive adhesive layer adjusted by blending the ionic compound (B) from fluctuating and increasing even in a humid environment, and keeps it within a desired value range. It is preferable to Compatibility of the (meth)acrylic polymer (A) with the ionic compound (B) due to the presence of the amide group introduced as a functional group of the copolymerization monomer in the side chain of the (meth)acrylic polymer (A) Is expected to rise.
  • the pressure-sensitive adhesive layer has a glass and a transparent conductive layer (ITO layer or the like) when an amide group introduced into a side chain in a (meth)acrylic polymer (A) which is a base polymer is present. It has good durability against any of the above, and it is possible to suppress the occurrence of peeling, floating, etc. in the state of being attached to the liquid crystal panel. Further, the durability can be satisfied even in a humid environment (after a humidification reliability test).
  • the amide group-containing monomer (a2) is a compound containing an amide group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group or a vinyl group.
  • Specific examples of the amide group-containing monomer (a2) include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(meth)acrylamide.
  • the amide group-containing monomer (a2) is preferable for suppressing an increase in surface resistance value over time (particularly in a humid environment) and satisfying durability.
  • the amide group-containing monomers (a2) particularly the N-vinyl group-containing lactam-based monomer suppresses an increase in the surface resistance value over time (especially in a humid environment), or a transparent conductive layer (touch). It is preferable in satisfying the durability against the sensor layer).
  • the amide group-containing monomer having a hydroxyl group tends to have improved conductivity in combination with the ionic compound (B), and when the use ratio increases, a polarizing film ( It is preferably not used because there is a problem in anchoring force with the optical film) and reworkability with the transparent conductive layer (touch sensor layer).
  • the weight ratio of the amide group-containing monomer (a2) 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, and more preferably 0.5% by weight or more.
  • the weight ratio is preferably 35% by weight or less, and further 30% by weight or less. It is more preferably 25% by weight or less.
  • a carboxyl group-containing monomer is a compound that has a carboxyl group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group or 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 property.
  • a hydroxyl group-containing monomer is a compound that contains a hydroxyl group in its structure and also contains a polymerizable unsaturated double bond such as a (meth)acryloyl group and 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-.
  • hydroxyalkyl (meth)acrylates such as hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate.
  • 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 become reaction points with the crosslinking agent. Since the carboxyl group-containing monomer and the hydroxyl group-containing monomer have high reactivity with the intermolecular crosslinking agent, they are preferably used for improving the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer. Further, the carboxyl group-containing monomer is preferable from the viewpoint of achieving both durability and reworkability, and the hydroxyl group-containing monomer is preferable from the viewpoint of reworkability.
  • the above-mentioned weight ratio of the carboxyl group-containing monomer is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, further preferably 0.05 to 1.5% by weight, further preferably 0.1. It is preferably 1 to 1% by weight, and most preferably 0.1 to 0.5% by weight. It is preferable in terms of durability that the weight ratio of the carboxyl group-containing monomer be 0.01% by weight or more. On the other hand, if it exceeds 2% by weight, it is not preferable from the viewpoint of reworkability.
  • the carboxyl group-containing monomer does not have to be particularly used from the viewpoint of suppressing the corrosion of the transparent conductive layer.
  • 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 2% by weight is preferred. It is preferable that the weight ratio of the hydroxyl group-containing monomer is 0.01% by weight or more from the viewpoint of crosslinking the pressure-sensitive adhesive layer, durability and adhesive properties. On the other hand, if it exceeds 3% by weight, it is not preferable in terms of durability.
  • aromatic ring-containing (meth)acrylate As the copolymerization monomer, for example, aromatic ring-containing (meth)acrylate can be used.
  • the aromatic ring-containing (meth)acrylate is a compound containing an aromatic ring structure in its structure and a (meth)acryloyl group.
  • 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, phenoxypropyl.
  • 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, further 14 to 20% by weight. Is preferred.
  • the weight ratio of the aromatic ring-containing (meth)acrylate is 3% by weight or more, it is preferable for suppressing display unevenness. On the other hand, when it exceeds 25% by weight, uneven display is not sufficiently suppressed and durability tends to be deteriorated.
  • copolymerizable 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- Examples thereof include sulfonic acid group-containing monomers such as methyl propane sulfonic acid, (meth)acrylamide propane sulfonic acid and sulfopropyl (meth)acrylate; and phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl 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 methyl propane sulfonic acid, (meth)acrylamide propane sulfonic acid and sulfoprop
  • alkylaminoalkyl(meth)acrylates such as aminoethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, t-butylaminoethyl(meth)acrylate; methoxyethyl(meth)acrylate, ethoxyethyl( Alkoxyalkyl (meth)acrylates such as (meth)acrylate; N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyoctamethylenesuccinimide, etc.
  • Succinimide-based monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N- Examples of monomers for modification are also itaconimide-based monomers such as octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, and N-lauryl itaconimide.
  • vinyl-based monomers such as vinyl acetate and vinyl propionate; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate; polyethylene glycol (meth).
  • Glycol-based (meth)acrylates such as acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, silicone (meth) ) Acrylate and (meth)acrylate monomers such as 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, 8-vinyloctyltrimethoxysilane.
  • the copolymerization monomer tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , Polyfunctional having two or more unsaturated double bonds such as (meth)acryloyl group and vinyl group such as esterification products of (meth)acrylic acid such as caprolactone-modified dipentaerythritol hexa(meth)acrylate
  • the proportion of the other copolymerizable monomer in the (meth)acrylic polymer (A) is about 0 to 10% in 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%, more preferably about 0 to 5%.
  • the (meth)acrylic polymer (A) of the present invention usually preferably has a weight average molecular weight of 1,000,000 to 2,500,000. Considering durability, particularly heat resistance, the weight average molecular weight is preferably 1.2 to 2,000,000. A weight average molecular weight of 1,000,000 or more is preferable in terms of heat resistance. When the weight average molecular weight is more than 2.5 million, the pressure sensitive adhesive tends to be hard and peeling easily occurs.
  • the weight average molecular weight (Mw)/number average molecular weight (Mn) showing the molecular weight distribution is preferably 1.8 or more and 10 or less, further 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) can be obtained from the values calculated by polystyrene measurement by GPC (gel permeation chromatography).
  • the obtained (meth)acrylic polymer (A) may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • solution polymerization ethyl acetate, toluene, etc. are used as a polymerization solvent.
  • the reaction is usually carried out under a stream of an inert gas such as nitrogen and a polymerization initiator at about 50 to 70° C. for about 5 to 30 hours.
  • the polymerization initiator, chain transfer agent, emulsifier and the like 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 thereof can be adjusted appropriately according to these types. It
  • the pressure-sensitive adhesive composition of the present invention can contain an ionic compound (B).
  • an ionic compound (B) an alkali metal salt and/or an organic cation-anion salt can be preferably used.
  • organic and inorganic salts of alkali metal can be used.
  • the term “organic cation-anion salt” as used in the present invention means an organic salt in which the cation portion is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. It may be.
  • the “organic cation-anion salt” is also called an ionic liquid or an ionic solid.
  • the ionic compound (B) in the pressure-sensitive adhesive layer, it is possible to reduce the surface resistance value of the pressure-sensitive adhesive layer and suppress the generation of static electricity, and this occurs when the alignment of the liquid crystal layer is disturbed by charging. Light leakage (uneven charging) can be suppressed more efficiently.
  • alkali metal ion forming the cation portion of the alkali metal salt examples include lithium, sodium and potassium ions. Among these alkali metal ions, lithium ion is preferable.
  • the anion part of the alkali metal salt may be composed of an organic material or an inorganic material.
  • the anion moiety 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 ( A) to (D), (A): (C n F 2n+1 SO 2 ) 2 N ⁇ (where n is an integer of 10 to 10), (B): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (where m is an integer of 1 to 10), (C): - O 3 S (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10), (D
  • the anion moiety containing a fluorine atom is preferably used because an ionic compound having a good ion dissociation property can be obtained.
  • the anion moiety constituting the inorganic salt include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , AsF 6 ⁇ , SbF. 6 ⁇ , NbF 6 ⁇ , TaF 6 ⁇ , (CN) 2 N ⁇ , etc. are used.
  • organic salt of an alkali metal examples include sodium acetate, sodium alginate, sodium ligninsulfonate, sodium toluenesulfonate, LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N and Li(CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) 2 N, Li (CF 3 SO 2) 3 C, KO 3 S (CF 2) 3 SO 3 K, LiO 3 S (CF 2) 3 SO 3 K , and the like, among these LiCF 3 SO 3, Li (CF 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2) 2 N, Li (CF 3 SO 2) 3 C and the like are preferable, Li (CF 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C 4 F 9 SO 2 ) A fluorine-containing lithium imide salt that is a bis(fluorosulfonyl)imide lithium salt such as 2 N is more preferable, and
  • examples of 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 an organic substance.
  • the cation component specifically, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, Examples thereof include a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation.
  • anion component examples include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO.
  • organic cation-anion salt a compound comprising a combination of the above cation component and anion component is appropriately selected and used.
  • organic cation-anion salt include, for example, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, ethylmethylimidazolium bis( Fluorosulfonylimide).
  • 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide and ethylmethylimidazolium bis(fluorosulfonylimide) are more preferable.
  • ionic compound (B) in addition to the above-mentioned alkali metal salts and organic cation-anion salts, inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride and ammonium sulfate. Is mentioned.
  • the ionic compound (B) may be used alone or in combination in order to obtain a desired resistance value.
  • an alkali metal salt is an antistatic agent. It is preferable from the viewpoint of enhancing the performance, and by using the alkali metal salt, a pressure-sensitive adhesive having high antistatic performance can be obtained even with a small number of parts.
  • an organic cation-anion salt is used as the ionic compound (B). It is preferable in terms of enhancing antistatic performance, and by using an organic cation-anion salt, a pressure-sensitive adhesive having high antistatic performance can be obtained even with a smaller number of parts.
  • the ratio 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 property of the pressure-sensitive adhesive layer and the sensitivity of the touch panel.
  • the pressure-sensitive adhesive layer is preferably controlled to have an initial surface resistance value in the range of 1 ⁇ 10 8 to 1 ⁇ 10 10 ⁇ / ⁇ . ..
  • the adhesive layer has an initial surface resistance value of 1 ⁇ 10 10 to 1 ⁇ 10 12 ⁇ / It is preferable to control in the range of ⁇ .
  • the ratio of the ionic compound (B) is usually preferably 40 parts by weight or less, more preferably 30 parts by weight or less, relative to 100 parts by weight of the (meth)acrylic polymer (A). Further, it is preferably 20 parts by weight or less, and most preferably 10 parts by weight or less. On the other hand, in order to improve the antistatic performance, it is preferable to use 0.01 part by weight or more of the ionic compound (B). From this viewpoint, the ionic compound (B) is preferably 0.1 part by weight or more, and more preferably 0.5 part by weight or more. On the other hand, when the amount of the ionic compound (B) increases, the surface resistance value becomes too low and the baseline fluctuation (malfunction at the time of touch caused by the surface resistance value being too low) may reduce the sensitivity of the touch panel. There is.
  • the pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent (C).
  • An organic crosslinking agent or a polyfunctional metal chelate can be used as the crosslinking agent (C).
  • the organic crosslinking agent include isocyanate crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, imine crosslinking agents, and the like.
  • the polyfunctional metal chelate is a polyvalent metal having a covalent bond or a coordinate bond with an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn and Ti. Can be mentioned.
  • Examples of the atom in the organic compound that forms a covalent bond or a coordinate bond include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
  • crosslinking agent (C) an isocyanate crosslinking agent and/or a peroxide crosslinking agent are preferable.
  • isocyanate cross-linking agent (C) a compound having at least two isocyanate groups can be used.
  • known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like which are generally used for urethanization reaction are used.
  • the peroxide can be appropriately used as long as it generates a radical active species by heating or light irradiation to promote crosslinking of the base polymer of the pressure-sensitive adhesive composition, but in consideration of workability and stability. It is preferable to use a peroxide having a 1-minute half-life temperature of 80° C. to 160° C., and more preferably 90° C. to 140° C.
  • peroxides examples include di(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6° C.), di(4-t-butylcyclohexyl)peroxydicarbonate (1 Minute half-life temperature: 92.1° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4° C.), t-butyl peroxy neodecanoate (1 minute half-life temperature: 103 0.5° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3° C.), dilauroyl peroxide ( 1-minute half-life temperature: 116.4°C), di-n-octanoyl peroxide (1-minute half-life temperature: 117.4°C), 1,1,3,3-tetramethylbutylperoxy-2-ethy
  • 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, further 0.02 parts by weight based on 100 parts by weight of the (meth)acrylic polymer (A).
  • the amount is preferably 2 to 2 parts by weight, more preferably 0.03 to 1 part by weight.
  • the pressure-sensitive adhesive composition of the present invention may contain a silane coupling agent (D).
  • the durability can be improved by using the silane coupling agent (D).
  • the silane coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3, Epoxy group-containing silane coupling agent such as 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N-(1,3-dimethylbutylidene)propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltri
  • silane coupling agent (D) one having a plurality of alkoxysilyl groups in the molecule can be used.
  • a silane coupling agent having a plurality of alkoxysilyl groups in these molecules does not easily volatilize, and since it has a plurality of alkoxysilyl groups, it is effective in improving durability and is preferable.
  • the durability is also suitable when the adherend of the optical film with the pressure-sensitive adhesive layer is a transparent conductive layer (for example, ITO) in which an 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.
  • the 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. 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 kinds, but the content as a whole is the (meth)acrylic polymer (A)100.
  • the amount 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, further preferably 0.02 to 1 part by weight, and further preferably Is preferably 0.05 to 0.6 parts by weight. This is the amount that improves durability.
  • a polyether compound (E) having a reactive silyl group can be added to the pressure-sensitive adhesive composition of the present invention.
  • the polyether compound (E) is preferable in that the reworkability can be improved.
  • the polyether compound (E) for example, those disclosed in JP 2010-275522A can be used.
  • the proportion of the polyether compound (E) in the pressure-sensitive adhesive composition of the present invention is preferably 10 parts by weight or less, and more preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the (meth)acrylic polymer (A). ..
  • the polyether compound (E) is preferably 0.01 part by weight or more, and more preferably 0.1 part by weight or more.
  • the polyether compound (E) is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less.
  • the ratio of the polyether compound (E) can be set to a preferable range by adopting the upper limit value or the lower limit value.
  • the pressure-sensitive adhesive composition of the present invention may contain other known additives, for example, polyether compounds of polyalkylene glycol such as polypropylene glycol, colorants, powders such as pigments, dyes, Surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metals 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 an amount of 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight or less with respect to 100 parts by weight of the (meth)acrylic polymer (A).
  • additives are preferably used in an amount of 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight
  • the pressure-sensitive adhesive composition is applied to a release-treated separator or the like, and a polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer, which is then transferred to an optical film (polarizing film).
  • a method of forming the pressure-sensitive adhesive layer on the optical film by coating the pressure-sensitive adhesive composition on an optical film (polarizing film) and drying and removing the polymerization solvent.
  • one or more solvents other than the polymerization solvent may be newly added as appropriate.
  • the thickness of the adhesive layer is not particularly limited and is, for example, about 1 to 100 ⁇ m.
  • the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and further preferably 5 to 35 ⁇ m.
  • the thickness of the conductive layer d is preferably 1 ⁇ m or less, more preferably 0.01 to 0.5 ⁇ m, from the viewpoint of the stability of the surface resistance value and the adhesiveness to the pressure-sensitive adhesive layer 21.
  • the thickness is preferably 01 to 0.2 ⁇ m, more preferably 0.01 to 0.1 ⁇ m.
  • the surface resistance value of the conductive layer d is preferably 1 ⁇ 10 8 to 1 ⁇ 10 12 ⁇ / ⁇ , from the viewpoint of the antistatic function, and 1 ⁇ 10 8 to 1 ⁇ 10 11 ⁇ / ⁇ . Is more preferable, and further preferably 1 ⁇ 10 8 to 1 ⁇ 10 10 ⁇ .
  • the conductive layer can be formed from various antistatic agent compositions.
  • an ionic surfactant system As the antistatic agent forming the conductive layer, an ionic surfactant system, a conductive polymer, conductive fine particles, carbon nanotubes, etc. can be used.
  • conductive polymers and carbon nanotubes are preferably used from the viewpoints of optical properties, appearance, antistatic effect, and stability of antistatic effect when heated and humidified.
  • conductive polymers such as polyaniline and polythiophene are preferably used.
  • the conductive polymer those soluble in an organic solvent, water-soluble and water-dispersible can be appropriately used, but a water-soluble conductive polymer or a water-dispersible conductive polymer is preferably used.
  • the water-soluble conductive polymer or the water-dispersible conductive polymer can be prepared as an aqueous solution or an aqueous dispersion of the coating liquid when forming the antistatic layer, the coating liquid does not need to use a non-aqueous organic solvent, This is because the deterioration of the optical film substrate due to the solvent can be suppressed.
  • the aqueous solution or aqueous dispersion may contain an aqueous solvent in addition to water.
  • alcohols such as -propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol.
  • the water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline or polythiophene preferably has a hydrophilic functional group in the molecule.
  • the hydrophilic functional group include a sulfone group, an amino group, an amide group, an imino group, a quaternary ammonium salt group, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate ester group, a phosphate ester group, or a salt thereof.
  • Etc By having a hydrophilic functional group in the molecule, it becomes easy to be dissolved in water or easily dispersed in water in the form of fine particles, so that 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 by polystyrene conversion) and the like.
  • Examples of commercially available water-dispersible conductive polymers include polythiophene-based conductive polymers (trade name, Denatron series, manufactured by Nagase Chemtech).
  • a binder component may be added together with the antistatic agent for the purpose of improving the film forming property of the antistatic agent, the adhesion to the optical film, and the like.
  • the antistatic agent is a water-based conductive polymer or water-dispersible conductive polymer aqueous material
  • a water-soluble or water-dispersible binder component is used.
  • the binder oxazoline group-containing polymer, polyurethane resin, polyester resin, acrylic resin, polyether resin, cellulose resin, polyvinyl alcohol resin, epoxy resin, polyvinylpyrrolidone, polystyrene resin, polyethylene glycol, Examples include pentaerythritol. Polyurethane resin, polyester resin, and acrylic resin are particularly preferable. These binders may be used alone or in combination of two or more as appropriate for their application.
  • the amount of the antistatic agent and the binder used depends on their types, but it is preferable to control the surface resistance value of the obtained conductive layer to be 1 ⁇ 10 8 to 1 ⁇ 10 12 ⁇ / ⁇ .
  • the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer is attached to the transparent conductive layer of the transparent conductive base material having the transparent conductive layer on the transparent base material, which is described above and shown in FIG. Explain the body.
  • the constituent material of the transparent conductive layer of the transparent conductive substrate is not particularly limited, and includes indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten.
  • a metal oxide of at least one metal selected from the group is used.
  • the metal oxide may further contain a metal atom shown in the above group, if necessary.
  • indium oxide (ITO) containing tin oxide and tin oxide containing antimony 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.
  • examples of the ITO include crystalline ITO and amorphous (amorphous) ITO, and any of them can be preferably used.
  • the transparent conductive layer of the transparent conductive base material may be a metal mesh formed by forming fine metal wires in a grid pattern, or one formed by coating fine metal particles.
  • Any appropriate metal (including an alloy substance) can be used as the metal material to be constituted as long as it is a metal having high conductivity.
  • at least one metal selected from the group consisting of gold, platinum, silver, aluminum, and copper is preferable, and from the viewpoint of conductivity, aluminum, silver, copper, or gold may be used. preferable.
  • the thickness of the transparent conductive layer is not particularly limited, but is preferably 10 nm to 1000 nm, and more preferably 50 to 400 nm.
  • the method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be adopted. Specifically, for example, a vacuum vapor deposition method, a sputtering method, and an ion plating method can be exemplified.
  • a coating liquid for example, a microgravure coating method, a roll coating method, a dipping coating method, a flow coating method, a spin coating method, a die coating method, a cast transfer method, a spray coating method and the like can be mentioned.
  • a photosensitive composition containing a silver salt (composition for forming a transparent conductive layer) is applied onto an adherend such as a release film, and then subjected to an exposure treatment and a development treatment, It can be obtained by forming fine metal wires in a predetermined pattern.
  • the transparent conductive layer can also be obtained by printing a paste containing fine metal particles (composition for forming a transparent conductive layer) in a predetermined pattern. Further, an appropriate method can be adopted depending on the required film thickness.
  • the transparent base material is not particularly limited as long as it is a transparent substrate, and examples thereof include glass and a transparent resin film base material.
  • examples of the transparent resin film base material include those mentioned above.
  • an undercoat layer, an oligomer prevention layer, etc. can be provided between the transparent conductive layer and the transparent substrate, if necessary.
  • the laminate of the present invention includes an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) equipped with an input device (touch panel, etc.), input device ( It can be preferably used in the production of a base material (member) constituting a device such as a touch panel or the like or a base material (member) used in these devices, but is particularly suitable in the production of an optical base material for a touch panel. Can be used. Further, it can be used regardless of the method such as the touch panel or the like such as the resistance film method or the electrostatic capacity method.
  • the polarizing film with an adhesive layer of the present invention can be applied to various image display parts to form an image display panel.
  • the pressure-sensitive adhesive layer-attached polarizing film of the present invention has a small variation ratio of the surface resistance value and is suitable for application to a liquid crystal panel with a touch sensing function.
  • an adhesive layer of the polarizing film with an adhesive layer of the present invention, and an image display panel comprising a transparent conductive substrate having a transparent conductive layer, the adhesive layer of the polarizing film with an adhesive layer, It is suitable to be applied to an image display panel that is attached to the transparent conductive layer.
  • the polarizing film with the adhesive layer and the transparent conductive substrate are as described above.
  • the image display panel preferably has the transparent conductive substrate, and forms a part of the image display device together with the adhesive-attached polarizing film.
  • a liquid crystal panel which is a typical embodiment of an image display panel to which the polarizing film with an adhesive layer of the present invention is applied, will be described.
  • the liquid crystal cell used for the liquid crystal panel is provided with a transparent conductive base material having a transparent conductive layer on a transparent base material.
  • the transparent conductive base material is usually provided on the surface of the liquid crystal cell on the visible side. .
  • the liquid crystal cell provided with the transparent conductive base material used in the present invention is composed of transparent conductive layer/transparent base material/liquid crystal layer/transparent base material.
  • the liquid crystal panel may be provided with an optical film such as a retardation film, a viewing angle compensation film, and a brightness enhancement film as appropriate.
  • an optical film such as a retardation film, a viewing angle compensation film, and a brightness enhancement film as appropriate.
  • the liquid crystal layer is not particularly limited, and may be of any type such as TN type, STN type, ⁇ type, VA type, IPS type, or any other type.
  • the transparent substrate 9 (light source side) is not particularly limited as long as it is a transparent substrate, and examples thereof include glass and a transparent resin film base material. Examples of the transparent resin film base material include those mentioned above.
  • a polarizing film with a pressure-sensitive adhesive layer which is conventionally used in this field, can be used on the light source side of the liquid crystal layer, and those described in the present specification can also be preferably used.
  • the image display device to which the image display panel can be applied include a liquid crystal display device, an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED: Field Emission Display), and the like. ..
  • the polarizing film with an adhesive layer of the present invention can be applied to various image display panels, and the image display panel can be applied to conventional image display devices. Other configurations of the image display device are the same as those of the conventional image display device.
  • the pressure-sensitive adhesive layer-carrying polarizing film of the present invention is particularly suitable for use in an image display device having a touch panel because it has features that it suppresses corrosion of the transparent conductive layer and does not impair the shielding function even after long-term use.
  • FIGS. 4 to 6 Specific examples of the liquid crystal panel with a built-in touch sensing function are shown in FIGS. 4 to 6, for example.
  • FIGS. 4 to 6 as the polarizing film with a pressure-sensitive adhesive layer of the present invention, the case where the polarizing film with a pressure-sensitive adhesive layer 1 shown in FIG. 1 is used on the viewing side of a liquid crystal cell is illustrated. That is, the piece protective polarizing film 11 and the pressure-sensitive adhesive layer 21 in FIG. 1 are shown as the first polarizing film 11 and the first pressure-sensitive adhesive layer 21 in FIGS. 4 to 6.
  • the polarizing film 1 with the pressure-sensitive adhesive layer shown in FIG. 2 can be similarly applied to the viewing side of the liquid crystal cell of FIGS. 4 to 6.
  • FIG. 4 shows a so-called in-cell type liquid crystal panel with a built-in touch sensing function, and from the viewing side, the first polarizing film 11, the first adhesive layer 21, the first transparent substrate 41, the touch sensor portion 5, the liquid crystal layer 3 and The drive electrode/sensor unit 6/second transparent substrate 42/second adhesive layer 22/second polarizing film 12 is configured.
  • the liquid crystal cell C includes the touch sensor unit 5 and the drive electrode/sensor in the first and second glass substrates 41 and 42 (in the liquid crystal cell) that sandwich the liquid crystal layer 3. It has a part 6.
  • FIG. 5 shows a modification of a so-called in-cell type (semi-in-cell type) liquid crystal panel with a touch sensing function, and from the viewer side, the first polarizing film 11, the first adhesive layer 21, the touch sensor section 5, and the 1 transparent substrate 41/liquid crystal layer 3/driving electrode/sensor section 6/second transparent substrate 42/second pressure-sensitive adhesive layer 22/second polarizing film 12.
  • the in-cell type liquid crystal panel with a touch sensing function of FIG. 5 for example, the liquid crystal cell C is outside the first transparent substrate 41, the touch sensor unit 5 is in direct contact with the first adhesive layer 21, and the liquid crystal layer 3 is sandwiched.
  • the first and second glass substrates 41, 42 (in the liquid crystal cell) have the drive electrode/sensor unit 6 on the side of the second transparent substrate 42.
  • FIG. 6 shows a so-called on-cell type liquid crystal panel with a built-in touch sensing function, and from the viewing side, the first polarizing film 11, the first adhesive layer 21, the touch sensor section 5, the drive electrode/sensor section 6 and the sixth section. 1 transparent substrate 41/liquid crystal layer 3/driving electrode 7/second transparent substrate 42/second adhesive layer 22/second polarizing film 12.
  • the liquid crystal cell C has the touch sensor unit 5 and the drive electrode/sensor unit 6 outside the first transparent substrate 41, and the touch sensor unit 5 is the first
  • the drive electrode 7 is provided on the side of the second transparent substrate 42 in the first and second glass substrates 41 and 42 (in the liquid crystal cell) that is in direct contact with the adhesive layer 21 and that sandwiches the liquid crystal layer 3.
  • the liquid crystal panel with a built-in touch sensing function when the touch sensor unit 5 of the liquid crystal cell C and the first adhesive layer 21 are in direct contact, the first adhesive layer 21 (containing an ionic compound) is prevented from being charged.
  • the function tends to deteriorate, especially in a humid environment. Therefore, the liquid crystal panel with a built-in touch sensing function of the present invention is preferably applied to the liquid crystal panel with a built-in touch sensing function of the in-cell type (modification) shown in FIG. 5 or the on-cell type shown in FIG.
  • the first polarizing film 11 arranged on the viewer side of the liquid crystal cell C and the second polarizing film 12 arranged on the opposite side of the viewer side are different optical films depending on the suitability of their respective locations. It can be used by stacking.
  • the other optical film for example, a liquid crystal display device such as a reflection plate, an anti-transmission plate, a retardation film (including a wavelength plate such as 1/2 or 1/4), a visual compensation film, and a brightness enhancement film is formed. Examples of the optical layer that can be used for These can be used in one layer or two or more layers. Even when these other optical films are used, it is preferable that the pressure-sensitive adhesive layer closest to the liquid crystal layer 3 is the first pressure-sensitive adhesive layer 21.
  • the liquid crystal layer 3 included in the liquid crystal cell C is a liquid crystal layer that is applied to a liquid crystal panel with a built-in touch sensing function and that includes liquid crystal molecules that are homogeneously aligned in the absence of an electric field.
  • the liquid crystal layer 3 for example, an IPS type liquid crystal layer is preferably used.
  • any type of liquid crystal layer of TN type, STN type, ⁇ type, VA type or the like can be used as the liquid crystal layer 3.
  • the thickness of the liquid crystal layer is, for example, about 1.5 ⁇ m to 4 ⁇ m.
  • the first transparent substrate 41 and the second transparent substrate 42 can form a liquid crystal cell with the liquid crystal layer 3 interposed therebetween.
  • a touch sensor unit 5, a drive electrode/sensor unit 6, a drive electrode 7 and the like are formed inside or outside the liquid crystal cell according to the form of the liquid crystal panel with a built-in touch sensing function. Further, a color filter substrate can be provided on the liquid crystal cell (first transparent substrate 41).
  • the material forming the transparent substrate is, for example, glass or polymer film.
  • the polymer film include polyethylene terephthalate, polycycloolefin, polycarbonate and the like.
  • the transparent substrate is made of glass, its thickness is, for example, about 0.3 mm to 1 mm.
  • the transparent substrate is formed of a polymer film, its thickness is, for example, about 10 ⁇ m to 200 ⁇ m.
  • the transparent substrate may have an easy adhesion layer or a hard coat layer on its surface.
  • the touch sensor unit 5 electrostatic capacitance sensor
  • the drive electrode/sensor unit 6, and the drive electrode 7 are formed as a transparent conductive layer.
  • the constituent material of the transparent conductive layer is not particularly limited, and examples thereof include metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, and tungsten, and 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.
  • the metal oxide may further contain an oxide of a metal atom shown in the above group, if necessary.
  • indium oxide (ITO) containing tin oxide and tin oxide containing antimony 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.
  • the touch sensor layer 5 is formed in the liquid crystal cell C, and the touch sensor layer 5 is formed according to the form of the liquid crystal panel with the touch sensing function.
  • the touch sensor layer 5 can be formed as a transparent electrode pattern on the first transparent substrate 41, for example.
  • a transparent electrode pattern can be formed according to a conventional method according to the form of the liquid crystal panel with a touch sensing function.
  • the transparent electrode pattern is usually electrically connected to a wiring line (not shown) formed at an end of the transparent substrate, and the wiring line is connected to a controller IC (not shown).
  • the shape of the transparent electrode pattern may be a comb shape, a stripe shape, a rhombus shape, or any other shape 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.
  • a member forming a liquid crystal display device such as a backlight or a reflection plate used for an illumination system can be appropriately used.
  • ⁇ Analyzer HLC-8120GPC manufactured by Tosoh Corporation ⁇ Column: manufactured by Tosoh Corporation, G7000H XL + GMH XL + GMH XL ⁇ Column size: Each 7.8 mm ⁇ 30 cm, total 90 cm ⁇ Column temperature: 40°C ⁇ Flow rate: 0.8 mL/min ⁇ Injection volume: 100 ⁇ L ⁇ Eluent: Tetrahydrofuran ⁇ Detector: Differential refractometer (RI) ⁇ Standard sample: polystyrene
  • Alcohol polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • aqueous solution containing the product name “Gosephimmer Z200”) in a ratio of 9:1 was applied and dried at 25° C. to form a PVA-based resin layer having a thickness of 11 ⁇ m to prepare a laminate.
  • the obtained laminate was uniaxially stretched by 2.0 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 120° C. (in-air auxiliary stretching treatment).
  • the laminated body was immersed in an insolubilizing bath having a liquid temperature of 30° C. (boric acid aqueous solution obtained by mixing 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.
  • a dyeing bath having a liquid temperature of 30° C.
  • iodine concentration 0.2 part by weight was added to 100 parts by weight of water, and 1.0 part by weight of potassium iodide was added, and the resultant was immersed in an aqueous iodine solution for 60 seconds (dyeing treatment). .. Then, it was immersed for 30 seconds in a crosslinking bath at a liquid temperature of 30° C.
  • Forming material A 75% ethyl acetate solution of urethane prepolymer consisting of tolylene diisocyanate (TDI) and trimethylolpropane (TMP) as a solution of urethane prepolymer (a) (Tosoh Corporation, trade name "Coronate L”) was used.
  • TTI tolylene diisocyanate
  • TMP trimethylolpropane
  • Forming material B Dioctyl tin dilaurate type catalyst (manufactured by Tokyo Fine Chemical Co., Ltd., trade name) 0.1 part of "Enbilizer OL-1" was added, and a urethane prepolymer coating solution was prepared with methyl isobutyl ketone as a solvent to a solid content concentration of 10%.
  • Forming material C 97.0 parts of methyl methacrylate, 3.0 parts of the monomer represented by the general formula (1) (monomer of the general formula (1e)), polymerization initiator (2,2′-) 0.2 part of azobis(isobutyronitrile) was dissolved in 200 parts of toluene. Then, a polymerization reaction was carried out for 5 hours while heating at 70° C. in a nitrogen atmosphere to obtain a polymer (a) (solid content concentration: 33% by weight). The weight average molecular weight of the obtained polymer (a) was 85,000.
  • Forming material D A polyvinyl alcohol resin having a degree of polymerization of 2500 and a degree of saponification of 99.0% (trade name: JC-25, manufactured by Nippon Vineline Poval Co., Ltd.) is purely dissolved to prepare an aqueous solution having a solid content concentration of 4% by weight. Prepared.
  • Example 1 (Preparation of acrylic polymer (A)) A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser. Further, with respect to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged together with 100 parts of ethyl acetate, and nitrogen gas was added with gentle stirring.
  • ⁇ Preparation of one-sided protective polarizing film> The transparent protective film (triacetyl cellulose resin film) while applying the ultraviolet curable adhesive a on the surface of the polarizer A of the optical film laminate so that the thickness of the adhesive layer after curing becomes 1 ⁇ m. After bonding, was irradiated with ultraviolet rays as an active energy ray to cure the adhesive. Ultraviolet irradiation is performed using a gallium-encapsulated metal halide lamp, irradiation device: Fusion UV Systems, Inc. Light HAMMER10, bulb: V bulb, peak illuminance: 1600 mW/cm 2 , integrated irradiation amount 1000/mJ/cm 2 (wavelength 380 to 440 nm).
  • the amorphous PET substrate was peeled off to prepare a one-sided protective polarizing film using a thin polarizer.
  • the optical characteristics of the obtained one-sided protective polarizing film were a single substance transmittance of 42.8% and a polarization degree of 99.99%.
  • Example 2 to 17, Comparative Examples 1 to 4 In Example 1, as shown in Table 1, the composition of the monomer mixture used for the preparation of the acrylic polymer (A), the type of the ionic compound (B) used for the preparation of the pressure-sensitive adhesive composition (EMI-FSI or Li-TFSI) or its blending ratio, the thickness of the pressure-sensitive adhesive layer, the type of transparent layer forming material or the thickness thereof was changed as shown in Table 1, and the piece with a transparent layer was prepared in the same manner as in Example 1. A protective polarizing film and a one-sided protective polarizing film with an adhesive layer were produced.
  • Table 1 the composition of the monomer mixture used for the preparation of the acrylic polymer (A), the type of the ionic compound (B) used for the preparation of the pressure-sensitive adhesive composition (EMI-FSI or Li-TFSI) or its blending ratio, the thickness of the pressure-sensitive adhesive layer, the type of transparent layer forming material or the thickness thereof was changed as shown in Table 1, and the piece with a transparent layer was prepared in the same manner
  • the transparent layer forming material C was applied to the polarizer surface (polarizer surface not provided with the transparent protective film) of the one-sided protective polarizing film by a bar coater. After that, heat treatment was performed at 60° C. for 2 minutes to form a transparent layer having a thickness of 0.5 ⁇ m.
  • the transparent layer of Comparative Example 4 was formed by coating the surface of the polarizer of the one-sided protective polarizing film (the surface of the polarizer not provided with the transparent protective film) with the forming agent C using a bar coater, and then at 60° C. It was carried out by heating for 3 minutes to form a polyvinyl alcohol resin layer having a thickness of 1 ⁇ m. In Comparative Examples 1 to 3, no transparent layer was formed.
  • the blending amount of the ionic compound (B) is a value based on 100 parts of the solid content of the acrylic polymer solution.
  • ITO with sputter-deposited amorphous ITO on non-alkali glass with a thickness of 0.7 mm (trade name "EG-XG” manufactured by Corning Incorporated) Glass was used.
  • the ITO used had an Sn ratio of 3% by weight. The Sn ratio of ITO was calculated from the weight of Sn atoms/(weight of Sn atoms+weight of In atoms).
  • the ITO-coated glass was cut into 25 mm ⁇ 25 mm, and the pressure-sensitive adhesive layer-attached one-sided protective polarizing film obtained in Examples and Comparative Examples was 15 mm ⁇ in the center of the ITO-coated surface of the ITO-coated glass. After being cut to 15 mm and pasted together, an autoclave treatment was performed at 50° C. and 5 atm for 15 minutes to obtain an ITO corrosive evaluation sample. The value obtained by measuring the surface resistance value of the amorphous ITO layer before laminating the one-sided protective polarizing film with the pressure-sensitive adhesive layer was defined as “R i ”. After placing the measurement sample in an environment of a temperature of 60° C.
  • R 250 /R i 1.5 or less because the increase in resistance value due to heat and humidity is small and the corrosion resistance is good. Further, it is preferable that R 500 /R 250 is 1.8 or less, since the increase in resistance value due to wet heat is small and the corrosion resistance is good.
  • the amount of color loss at the edges is determined by measuring the distance of the straight line that connects the corner to the location closest to the center among the portions whose colors are lighter than the center on the diagonal lines of the four corners of the sample. ⁇ m) and the average value of the four corners was taken as the amount of edge color loss of the sample.
  • Device Olympus, MX-61L Measurement condition: Lens magnification: 5 times ISO: 200 Shutter speed: 1/100 Amount of reflected light: Scale 0
  • White balance Auto Transmitted light controller: LG-PS2 Amount of transmitted light: Scale 5 Polarization direction of transmitted light: Direction of crossed Nicols with respect to the transmission axis of the polarizing film
  • the variation ratio (b/a) in Table 1 is a value calculated from the "initial" surface resistance value (a) and the "after humidification” surface resistance value (b) (rounded to two decimal places). Value). Further, as an index less likely to cause "malfunction", a value with a small variation ratio is preferred and evaluated according to the following criteria.
  • C The fluctuation ratio is 10 or more.
  • BA is butyl acrylate
  • NVP is N-vinyl-2-pyrrolidone
  • HBA is 4-hydroxybutyl acrylate
  • AA is acrylic acid
  • EMI-FSI is ethylmethylimidazolium bis(fluorosulfonylimide)
  • Li-TFSI represents bis(trifluoromethanesulfonyl)imide lithium.
  • the transparent conductive layer is bonded to According to the example in which the pressure-sensitive adhesive layer is provided via the predetermined transparent layer, it can be seen that the stable surface resistance value of the transparent conductive layer can be maintained even in a humidified environment.
  • Polarizing film with an adhesive layer 11 One-sided protective polarizing film a Polarizer b Transparent protective film c Transparent layer d Conductive layer 21 Adhesive layer F Transparent conductive base material F1 Transparent conductive layer F2 Transparent base material L Laminated body 11, 12th 1, 2nd polarizing film 21, 22 1st, 2nd adhesive layer 3 Liquid crystal layer 41, 42 1st, 2nd transparent substrate 5 Touch sensor part 6 Drive electrode and sensor part 7 Drive electrode C Liquid crystal cell

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Abstract

Ce film polarisant avec une couche adhésive comprend un élément polarisant à base d'iode, un film protecteur transparent sur un seul côté de l'élément polarisant et une couche transparente sur l'autre côté de l'élément polarisant. Il comprend une couche adhésive avec la couche transparente susmentionnée entre elles. La couche adhésive est utilisée liée sur une couche conductrice transparente d'un substrat conducteur transparent, qui comprend un substrat transparent et ladite couche conductrice transparente. Le rapport de changement de la valeur de résistance du film polarisant avec la couche adhésive à celle de la couche conductrice transparente est un rapport de changement prescrit. Même dans le cas où la couche adhésive est liée à la couche conductrice transparente et placée dans un environnement humidifié, il est possible de maintenir une valeur de résistance de surface stable de la couche conductrice transparente.
PCT/JP2019/046788 2018-11-29 2019-11-29 Film polarisant avec couche adhésive et dispositif d'affichage d'image WO2020111232A1 (fr)

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WO2021149312A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation équipée d'une couche de retard et dispositif d'affichage d'image l'utilisant
WO2021149311A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation équipée d'une couche de retard et dispositif d'affichage d'image l'utilisant
WO2021149314A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation, plaque de polarisation avec couche de retard et dispositif d'affichage d'image utilisant lesdites plaques
WO2021149313A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation et plaque de polarisation équipée d'une couche de différence de phase, et dispositif d'affichage d'image l'utilisant
WO2022034774A1 (fr) * 2020-08-11 2022-02-17 日東電工株式会社 Plaque de polarisation équipée d'une couche de retard et dispositif d'affichage d'image l'utilisant
KR20220033996A (ko) 2020-09-10 2022-03-17 스미또모 가가꾸 가부시키가이샤 광학 적층체
CN115248472A (zh) * 2021-04-28 2022-10-28 日东电工株式会社 带粘合剂层的偏光板及使用其的图像显示装置
WO2023234100A1 (fr) * 2022-05-31 2023-12-07 日東電工株式会社 Plaque de polarisation avec une couche de retard et dispositif d'affichage d'image

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JP2016170412A (ja) * 2015-03-12 2016-09-23 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムならびに画像表示装置

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WO2021149312A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation équipée d'une couche de retard et dispositif d'affichage d'image l'utilisant
WO2021149311A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation équipée d'une couche de retard et dispositif d'affichage d'image l'utilisant
WO2021149314A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation, plaque de polarisation avec couche de retard et dispositif d'affichage d'image utilisant lesdites plaques
WO2021149313A1 (fr) * 2020-01-24 2021-07-29 日東電工株式会社 Plaque de polarisation et plaque de polarisation équipée d'une couche de différence de phase, et dispositif d'affichage d'image l'utilisant
WO2022034774A1 (fr) * 2020-08-11 2022-02-17 日東電工株式会社 Plaque de polarisation équipée d'une couche de retard et dispositif d'affichage d'image l'utilisant
JP2022032081A (ja) * 2020-08-11 2022-02-25 日東電工株式会社 位相差層付偏光板およびそれを用いた画像表示装置
JP7258829B2 (ja) 2020-08-11 2023-04-17 日東電工株式会社 位相差層付偏光板およびそれを用いた画像表示装置
KR20220033996A (ko) 2020-09-10 2022-03-17 스미또모 가가꾸 가부시키가이샤 광학 적층체
JP2022046029A (ja) * 2020-09-10 2022-03-23 住友化学株式会社 光学積層体
CN115248472A (zh) * 2021-04-28 2022-10-28 日东电工株式会社 带粘合剂层的偏光板及使用其的图像显示装置
WO2023234100A1 (fr) * 2022-05-31 2023-12-07 日東電工株式会社 Plaque de polarisation avec une couche de retard et dispositif d'affichage d'image

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